JP2024051657A - Porous insulating layer applied for adhesion of electrochemical element members, laminate, electrode, electrochemical element, method for manufacturing laminate, method for manufacturing electrode, and method for manufacturing electrochemical element - Google Patents

Abstract

To provide a porous insulation layer imparting substance for bonding a member for an electrochemical element which enables manufacture of an electrochemical element that is excellent in flexibility and ion permeability of an insulation layer, can reduce occurrence of lamination deviation of an electrode, and is excellent in battery characteristics.SOLUTION: A porous insulation layer imparting substance for bonding a member for an electrochemical element has base materials, and adhesive porous insulation layers provided on the base materials, wherein the adhesive porous insulation layer is a porous structure as a co-continuous structure containing a resin as a skeleton, the resin is a crosslinked resin, the adhesive porous insulation layers are provided on the entire one surfaces of the two base materials of 30 mm×100 mm, and peel strength by a peel measurement method using an element for peel strength measurement which is obtained by heat bonding the adhesive porous insulation layers that are made to face each other under the conditions of a temperature of 140°C, air cylinder thrust of 500 N and 1 second is 2 N/m or more.SELECTED DRAWING: Figure 2

Description

The present invention relates to a porous insulating layer for bonding electrochemical element members, a laminate, an electrode, an electrochemical element, a method for manufacturing a laminate, a method for manufacturing an electrode, and a method for manufacturing an electrochemical element.

In recent years, smartphones and laptops have become commonplace in everyday life, and electric vehicles, which do not have internal combustion engines, are beginning to attract attention around the world in an effort to move toward a carbon-free society. These electronic devices are equipped with lithium-ion secondary batteries, which have the characteristics of high output and high energy density.

In many current common batteries, the electrodes are not fixed together, which creates the problem of electrodes easily becoming misaligned when stacked. If electrode stacking misalignment occurs inside a battery, it can lead to a deterioration in good battery characteristics and safety, so it is important to prevent electrode stacking misalignment.

To date, a secondary battery in which peeling of resin particles in an insulating layer laminated on an electrode active material layer is suppressed has been reported, which includes a porous insulating layer bonded to and laminated on a surface of at least one of a positive electrode active material layer and a negative electrode active material layer so as to cover at least one of the positive electrode active material layer and the negative electrode active material layer, and a molten portion formed on an edge of the insulating layer and solidified in a state in which pores have disappeared due to melting of the resin particles in the insulating layer (see, for example, Patent Document 1).
Also, a power storage device has been reported that has an electrolyte and a power storage unit including a first insulating layer that is adhered to a part of a surface of a positive electrode and a part of a surface of a negative electrode to separate the positive electrode and the negative electrode, and a region that is closed by the first insulating layer in a plan view and that is for holding an electrolyte between the positive electrode and the negative electrode, wherein the air permeability of the first insulating layer is more than 1250 sec/100 cc and less than 95000 sec/100 cc (see, for example, Patent Document 2).

The present invention aims to provide a porous insulating layer for bonding electrochemical element members that has excellent insulating layer flexibility and ion permeability, can reduce the occurrence of electrode lamination misalignment, and can produce electrochemical elements with excellent battery characteristics.

The adhesive porous insulating layer imparted to the electrochemical element member of the present invention as a means for solving the above problem comprises a substrate and an adhesive porous insulating layer provided on the substrate, the adhesive porous insulating layer being a porous structure having a co-continuous structure with a resin skeleton, the resin being a cross-linked resin, the adhesive porous insulating layer being provided on the entire surface of one side of each of two substrates measuring 30 mm x 100 mm, the adhesive porous insulating layers being opposed to each other, and the peel strength measured by the peel measurement method when a peel strength measuring element is used that is thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second, is 2 N/m or more.

The present invention provides a porous insulating layer for bonding electrochemical element members that has excellent insulating layer flexibility and ion permeability, reduces the occurrence of electrode lamination misalignment, and can produce electrochemical elements with excellent battery characteristics.

FIG. 1 is a schematic plan view showing an example of a coating region of a porous insulating layer according to the present embodiment. FIG. 2 is a schematic cross-sectional view showing an example of an electrode according to the present embodiment. FIG. 3 is a schematic cross-sectional view showing an example of the laminate of the present embodiment. FIG. 4 is a schematic cross-sectional view showing an example of an electrode according to the present embodiment. FIG. 5 is a schematic cross-sectional view showing another example of the laminate of the present embodiment. FIG. 6 is a schematic cross-sectional view showing another example of the laminate of the present embodiment. FIG. 7 is a schematic plan view showing an example of a coating region of the porous insulating layer of this embodiment. FIG. 8 is a schematic plan view showing an example of a coating region of the porous insulating layer of this embodiment. FIG. 9 is a schematic cross-sectional view showing another example of the electrode of the present embodiment. FIG. 10 is a schematic cross-sectional view showing another example of the electrode of the present embodiment. FIG. 11 is a schematic cross-sectional view showing another example of the electrode of the present embodiment. FIG. 12 is a schematic cross-sectional view showing another example of the laminate of the present embodiment. FIG. 13 is a schematic cross-sectional view showing another example of the laminate of the present embodiment. FIG. 14 is a schematic cross-sectional view showing another example of the laminate of the present embodiment. FIG. 15 is a schematic cross-sectional view showing another example of the laminate of the present embodiment. FIG. 16A is a plan view that typically illustrates a porous insulating layer. FIG. 16B is a cross-sectional view that illustrates a schematic view of the porous insulating layer. FIG. 17 is a schematic diagram showing an example of an apparatus for manufacturing the adhesive porous insulating layer of this embodiment. FIG. 18 is a schematic diagram showing a modification of the liquid ejection device of FIG. FIG. 19 is a schematic diagram showing another example of an apparatus for manufacturing an adhesive porous insulating layer of this embodiment. FIG. 20 is a schematic diagram showing another example of a liquid ejection apparatus which is a manufacturing apparatus for the adhesive porous insulating layer of this embodiment. FIG. 21 is a schematic diagram showing a modification of the liquid ejection device of FIG. FIG. 22 is a configuration diagram showing an example of a printing unit using a drum-shaped intermediate transfer body as a manufacturing apparatus for the adhesive porous insulating layer of this embodiment. FIG. 23 is a configuration diagram showing an example of a printing unit using an endless belt-like intermediate transfer body as a manufacturing apparatus for an adhesive porous insulating layer of this embodiment.

(Product with porous insulating layer for bonding electrochemical element members)
The adhesive porous insulating layer-imparting product of the electrochemical element member of the present invention has a substrate and an adhesive porous insulating layer provided on the substrate, the adhesive porous insulating layer being a porous structure which is a co-continuous structure having a resin skeleton, the resin being a crosslinked resin, the adhesive porous insulating layer being provided on the entirety of one surface of each of two substrates measuring 30 mm x 100 mm, the adhesive porous insulating layers being opposed to each other, and the peel strength measured using a peel strength measurement element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second is 2 N/m or more.
The adhesive porous insulating layer-imparted product for electrochemical element members is used for bonding electrochemical element members, and has an adhesive insulating layer.

The adhesive porous insulating layer-imparted product for an electrochemical device member of the present invention is an invention based on the fact that the present inventors have found the following problems in the prior art.
That is, conventionally, battery electrodes have been known in which an insulating adhesive is applied to prevent peeling of the resin particles in the insulating layer (see Patent Document 1, etc.). However, when a material that adheres by thermal welding is used, the resin particles in the insulating layer melt, causing the pores to disappear, resulting in a decrease in porosity and a decrease in the insulating properties of the insulating layer.
In addition, the insulating adhesive is preferably porous with a high porosity so as not to impede the circulation of the electrolyte inside the cell. However, for example, when the insulating layer has a high air permeability (porosity), as in the electricity storage device of Patent Document 2, there is a problem in that the strength of the insulating layer decreases.

In particular, in battery applications such as power storage elements such as batteries and power generation elements such as fuel cells, when the porous structure of the conventional technology is formed on an electrode as a substrate and used as an insulating layer, there is a problem that a decrease in the porosity of the porous structure makes it difficult to obtain sufficient substance permeability and makes it difficult to ensure ion permeability, leading to a decrease in battery performance.
In addition, if electrode stacking misalignment occurs inside a battery, it will lead to a deterioration in good battery characteristics and safety, so it is desirable to reduce the occurrence of electrode stacking misalignment. However, it has been found that it is important to balance the trade-off between the ion permeability (porosity) of the insulating layer and the strength of the insulating layer, and that the insulating layer has sufficient flexibility in addition to strength against electrode stacking misalignment.
As a result of intensive research to achieve the above object, the inventors have found that the porous insulating layer-added adhesive product of the present invention for electrochemical element members has excellent insulating layer flexibility and ion permeability, can reduce the occurrence of electrode lamination misalignment, and can provide an electrochemical element with excellent battery characteristics, thereby completing the present invention.

<Substrate>
The substrate may be any material, transparent or opaque, and may be appropriately selected depending on the purpose.
Examples of the transparent substrate include glass substrates, resin film substrates such as various plastic films, and composite substrates of these.
Examples of opaque substrates include silicon substrates; metal substrates such as stainless steel, aluminum, and copper; recording media; and substrates made by laminating these.
The recording medium may be plain paper, glossy paper, special paper, cloth, etc., or may be a low-permeability substrate (low-absorbency substrate). The low-permeability substrate means a substrate having a surface with low water permeability, absorbency, or adsorption, and includes materials that have many cavities inside but are not open to the outside. Examples of low-permeability substrates include recording media such as coated paper used in commercial printing and paperboard coated on the surface with recycled paper pulp in the middle layer and back layer.
The substrate may be a porous insulating layer such as a porous resin sheet used as an insulating layer for an electrochemical element, a paper separator containing cellulose fibers, an electrode substrate for an electrochemical element, or an electrode mixture layer provided on an electrode substrate.
The shape of the substrate may be curved or may have an uneven shape, and a substrate applicable to the application means and polymerization means of the laminate manufacturing apparatus can be appropriately selected and used.

<Adhesive Porous Insulating Layer>
The adhesive porous insulating layer is provided on the substrate.
The adhesive porous insulating layer is a porous structure that is a co-continuous structure having a resin skeleton, has a peel strength of 2 N/m or more, and has thermal adhesiveness.
In the present specification and claims, "thermal adhesiveness" refers to the development of adhesiveness to another substance by heating. One example of the development of adhesiveness is the improvement of peel strength between a structure having thermal adhesiveness by heating and another substance.
The specific volume resistivity of the adhesive porous insulating layer is preferably 1×10 ¹² (Ω·cm) or more.

-Porous structure-
The porous structure (hereinafter, sometimes referred to as a porous resin) has a bicontinuous structure with a resin as a skeleton.
The resin is preferably a crosslinked resin, and is a polymer of a polymerizable compound that can be polymerized by energy irradiation.
Here, the term "co-continuous structure" refers to a structure in which two or more substances or phases each have a continuous structure and do not form an interface, and in this embodiment, refers to a structure in which both the resin phase and the pore phase are three-dimensional branched network continuous phases. Such a structure can be formed, for example, by polymerizing the liquid composition described below by a polymerization induced phase separation method.

[Glass transition temperature]
Since the resin is a crosslinked resin, when the adhesiveness is developed by heating and the resin is bonded to another substance, the crosslinked resin does not melt and is unlikely to cause a large change in shape, so that the adhesive porous insulating layer can maintain good insulating properties before and after heat bonding.
In order for the adhesive porous insulating layer to function as an adhesive layer, the glass transition point (Tg) of the crosslinked resin that constitutes the skeleton is important.
The glass transition point (Tg) of the adhesive porous insulating layer is preferably 0° C. or higher and 100° C. or lower, and more preferably 25° C. or higher and 60° C. or lower.
If the Tg is less than 0° C., tackiness appears on the surface of the crosslinked resin at room temperature, making handling difficult after the adhesive porous insulating layer is formed, which is undesirable.
If the Tg exceeds 100° C., it is difficult to obtain good adhesion after heat bonding, and the high temperature required for heat bonding is likely to have adverse effects due to overheating on other surrounding substrates, which is undesirable. On the other hand, if the Tg is 0° C. or more and 100° C. or less, it is advantageous in that handling before and after heat bonding is good, good adhesion is obtained after heat bonding, and no adverse effects due to overheating occur.

The porous structure has a bicontinuous structure with a three-dimensional branched network structure as the skeleton, so that it is possible to realize a porous structure with high porosity and high strength.
That is, as shown in Figures 16A and 16B, the adhesive porous insulating layer 10b has a large number of voids 10x, and each void 10x has connectivity with other voids 10x surrounding it and spreads out three-dimensionally.

The porous structure has a bicontinuous structure in which the pores are interconnected, allowing sufficient infiltration of the electrolyte and not impeding the movement of ions.
A method for confirming that the porous structure has a bicontinuous structure and that the pores are interconnected can be, for example, a method for observing an image of a cross section of the porous structure using a scanning electron microscope (SEM) or the like to confirm that the pores are interconnected. In addition, air permeability can be mentioned as one of the physical properties obtained by interconnecting pores.

[Image Observation Using a Scanning Electron Microscope (SEM) and Measurement of Porosity]
The porosity of the porous structure is preferably 30% or more, more preferably 50% or more, and is preferably 90% or less, more preferably 85% or less.
By setting the porosity to 30% or more, the porous structure can be permeated sufficiently with liquids and gases, and functions such as substance separation and reaction field can be efficiently realized. In addition, when the porous structure is used as an insulating layer in an electric storage element, the permeability of the electrolyte and the permeability of ions are improved, and the reaction inside the electric storage element progresses efficiently. In addition, by setting the porosity to 90% or less, the strength of the porous structure is improved.
The method for evaluating the porosity of the porous structure is not particularly limited and can be appropriately selected depending on the purpose. For example, a method in which the porous structure is stained with osmium, the internal cross-sectional structure is cut out with a focused ion beam (FIB), and the porosity is measured using a scanning electron microscope (SEM) can be mentioned.

Specifically, the porosity can be measured by the following procedure.
That is, the porous structure is cut into a size of 5 mm x 10 mm and stained with osmium (VIII) tetroxide (manufactured by EM Corporation). The cut-out adhesive porous insulating layer is placed in a bottle containing a small amount of the aqueous solution without touching the aqueous solution, and the layer is left to stand in the sealed bottle for 30 minutes for staining. The layer is then dried in a draft for 1 hour to obtain a stained sample.
After sufficient drying, the specimen is vacuum-impregnated with a two-liquid mixed epoxy resin (manufactured by ITW Performance Polymers & Fluids Japan). Then, a cross section is cut out at 5.0 kV using a cross section polisher (manufactured by JEOL Ltd.) and observed using a cryo-FIB/SEM (manufactured by Nippon FEI Co., Ltd.).
The observed image is binarized, and the proportion of voids in the observed area is determined, thereby calculating the porosity of the porous structure.

[Air permeability]
The air permeability of the porous structure is preferably 1,000 sec/100 mL or less, more preferably 500 sec/100 mL or less, and even more preferably 300 sec/100 mL or less.
The air permeability is measured in accordance with JIS P8117, and can be measured, for example, by using a Gurley densometer (manufactured by Toyo Seiki Seisakusho, Ltd.).
As an example, it may be determined that the pores are interconnected when the air permeability is 1,000 sec/100 mL or less.

The cross-sectional shape of the pores of the porous resin may be various shapes and sizes, such as a substantially circular shape, a substantially elliptical shape, a substantially polygonal shape, etc. Here, the size of the pores refers to the length of the longest part in the cross-sectional shape. The size of the pores can be obtained from a cross-sectional photograph taken with a scanning electron microscope (SEM).
The size of the pores of the porous resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01 μm or more and 10 μm or less from the viewpoint of liquid or gas permeability. When the pore size is 0.1 μm or more and 10 μm or less, the liquid or gas can be sufficiently infiltrated into the porous structure, and functions such as material separation and reaction field can be efficiently exhibited. In addition, as described later, when the porous structure is used as an insulating layer of an electric storage element, a pore size of 10 μm or less can prevent a short circuit between the positive electrode and the negative electrode due to lithium dendrites generated inside the electric storage element, thereby improving safety.
The method for adjusting the pore size and porosity of the porous resin to fall within these ranges is not particularly limited, and examples thereof include a method of adjusting the content of the polymerizable compound in the liquid composition to fall within the above-mentioned range, a method of adjusting the content of the porogen in the liquid composition to fall within the above-mentioned range, and a method of adjusting the irradiation conditions of active energy rays.

The average thickness of the adhesive porous insulating layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.0 μm to 150.0 μm, more preferably 10.0 μm to 100.0 μm. When the average thickness is 10.0 μm or more, good adhesive strength can be obtained when thermally bonding with other electrodes, and when the average thickness is 100.0 μm or less, a flexible adhesive porous insulating layer can be obtained.
The average thickness is appropriately adjusted depending on the application of the porous resin.
It is most preferable that the average thickness is adjusted according to the thickness of the counter electrode, and it is preferable that the space thickness formed by the adhesive layer is approximately the same as the film thickness of the counter electrode in the cross-sectional structure after cell formation as shown in Fig. 13. This makes it possible to suppress distortion occurring at the end of the stacked electrodes after battery stacking.
The average thickness can be determined by measuring the thickness at any three or more points and calculating the average.
In this case, the thickness refers to the thickness of only the porous resin layer, and does not include the thickness of the layer including the porous resin layer and the substrate, for example, if the porous resin layer penetrates into the substrate.

The adhesive porous insulating layer enables, for example, thermal bonding when an electrode coated with the adhesive porous insulating layer is combined with another electrode, and can suppress the misalignment of the electrode stack that occurs during stacking of the battery or during processes after stacking. Therefore, the location where the adhesive porous insulating layer is formed is not particularly limited as long as it is a location where the above-mentioned adhesive effect can be exerted, and it can be formed at any location such as on the electrode substrate, on the electrode mixture layer, or on the porous insulating layer. However, when it is placed on the surface facing the counter electrode, it can exert these functions, but it is preferable to form it in an area that does not face the counter electrode so as not to hinder ion permeability between the electrodes.

[Peel strength]
The peel strength of the adhesive porous insulating layer is a peel strength measured by a peel measurement method at room temperature (25° C.) using the peel strength measuring element.
The peel strength of the adhesive porous insulating layer is 2 N/m or more, preferably 5 N/m or more, and more preferably 25 N/m or more.
The peel strength measurement element is prepared by providing the adhesive porous insulating layer on the entire surface of one side of each of two substrates measuring 30 mm x 100 mm, arranging the adhesive porous insulating layers facing each other, and thermally bonding them under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second.

The peel strength can be measured, for example, using an adhesive/coating peeling analyzer Versatile Peel Analyzer (manufactured by Kyowa Interface Science Co., Ltd.) as a peel strength measuring device, and specifically, the peel strength can be measured by the following procedure.
The surface of the substrate a of the peel strength measuring element opposite to the surface on which the adhesive porous insulating layer is formed is fixed to the sample fixing surface of the peel strength measuring device with a thin double-sided tape. Next, the surface of the substrate b of the peel strength measuring element opposite to the surface on which the adhesive porous insulating layer is formed is fixed to the tensile indenter of the peel strength measuring device with tape. The peel strength is measured under the measurement conditions shown below.

- Peel strength measurement conditions -
Peel strength measuring device: Versatile Peel Analyzer (manufactured by Kyowa Interface Science Co., Ltd.)
Thin double-sided tape: No. 5000NS (width 20 mm, manufactured by Nitto Denko Corporation)
Tape: No. 29 (width 18 mm, manufactured by Nitto Denko Corporation)
Measurement speed: 30 mm/min
Peel angle: 90°
Peeling distance: 75 mm
The peel distance may be any value since it does not significantly affect the peel strength. The thin double-sided tape and tape used to fix the element for measuring the peel strength may be appropriately selected from those that have a peel strength sufficiently higher than the peel strength of the adhesive porous insulating layer and do not peel off during the measurement.

(Laminate)
The laminate in the first embodiment of the present invention has the adhesive porous insulating layer-imparted product of the electrochemical element member of the present invention described above, and another substrate adhered via at least a portion of the adhesive porous insulating layer.

In addition, a laminate in a second embodiment of the present invention includes a first substrate and a second substrate, the first substrate having a first adhesive porous insulating layer, the first substrate and the second substrate being bonded via the first adhesive porous insulating layer, the first adhesive porous insulating layer being a porous structure having a co-continuous structure with a resin skeleton, the resin being a cross-linked resin, the first adhesive porous insulating layer being provided on one entire surface of the first substrate of 30 mm x 100 mm and on one entire surface of the second substrate of 30 mm x 100 mm, respectively, the first adhesive porous insulating layers being opposed to each other, and the peel strength measured by a peel measurement method using a peel strength measuring element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second is 2 N/m or more.
It is preferable that the second substrate has a second adhesive porous insulating layer, and that the first substrate and the second substrate are laminated so that the first adhesive porous insulating layer and the second adhesive porous insulating layer face each other.
The laminate may be in an embodiment in which the first substrate is an electrode and the second substrate is a film separator, or in which the first substrate is an electrode and the second substrate is an electrode, and either embodiment can be suitably adopted.

Since these adhesive porous insulating layers have a peel strength of 2 N/m or more and are excellent in adhesion, it is possible to suppress the binder content of the first adhesive porous insulating layer to the second adhesive porous insulating layer while ensuring sufficient adhesion at the interface between the first adhesive porous insulating layer and each substrate, and at the interface between the second adhesive porous insulating layer and the second substrate when a second adhesive porous insulating layer is present, and at the interface between the first adhesive porous insulating layer and the second adhesive porous insulating layer. If the first adhesive porous insulating layer to the second adhesive porous insulating layer contain a binder, the binder melts and blocks the pores of the first adhesive porous insulating layer to the second adhesive porous insulating layer, making it impossible to maintain porosity, resulting in a decrease in battery characteristics.
The binder content in the first adhesive porous insulating layer is preferably 0% by mass or more and 30% by mass or less, relative to the total amount of the first adhesive porous insulating layer, more preferably 0% by mass or more and 10% by mass or less, so that the binder is substantially not contained, even more preferably 0% by mass or more and 5% by mass or less, and even more preferably 0% by mass.
When a second adhesive porous insulating layer is provided, the content of the binder is defined relative to the total amount of the first adhesive porous insulating layer and the second adhesive porous insulating layer.

<Another Substrate, First Substrate, Second Substrate>
The other substrate, the first substrate, and the second substrate can each be appropriately selected from the items described above for the substrate.
The substrate may be a porous resin sheet or a porous insulating layer used as an insulating layer for an electrochemical element, a paper separator containing cellulose fibers, an electrode substrate for an electrochemical element, or an electrode mixture layer provided on an electrode substrate.

<<Porous insulating layer>>
The porous insulating layer can be provided on the active material or on the electrode substrate so as to be adjacent to the active material, for the purpose of suppressing short circuits while ensuring battery characteristics.
The porous insulating layer is not particularly limited, and a layer of a porous body having a structure with a plurality of pores and a volume resistivity of 1×10 ¹² (Ω·cm) or more can be appropriately selected depending on the purpose. Examples of the porous insulating layer include a sheet-like insulating layer mainly made of a material such as polyolefin or cellulose, and an insulating layer integral with a substrate such as an electrode that is formed on the substrate.

Among the above-mentioned porous insulating layers, a porous structure that is a co-continuous structure having a crosslinkable resin skeleton and that has the peel strength of less than 2 N/m is preferred.
As for the porous structure in the porous insulating layer, the characteristics other than the peel strength and the glass transition point can be appropriately selected from the items explained in the porous structure in the adhesive porous insulating layer.
The peel strength of the porous structure is not particularly limited as long as it is less than 2 N/m, and can be appropriately selected depending on the purpose.
The glass transition point of the porous structure is not particularly limited and can be appropriately selected depending on the purpose.
The method for producing the porous structure in the porous insulating layer can be appropriately selected from the liquid composition, polymerizable compound, liquid, polymerization induced phase separation method, etc. described for the porous structure in the adhesive porous insulating layer.

The average thickness of the porous resin is not particularly limited and can be appropriately selected according to the purpose, but in terms of the uniformity of hardening during polymerization, it is preferably 0.01 μm or more and 500 μm or less, more preferably 0.01 μm or more and 100 μm or less, even more preferably 1 μm or more and 50 μm or less, and particularly preferably 10 μm or more and 20 μm or less. By having an average thickness of 0.01 μm or more, the surface area of the obtained porous resin is increased, and the function of the porous resin can be fully obtained. In addition, by having an average thickness of 500 μm or less, unevenness of light and heat used during polymerization in the film thickness direction is suppressed, and a uniform porous resin in the film thickness direction can be obtained. By producing a uniform porous resin in the film thickness direction, the structural unevenness of the porous resin can be suppressed, and the decrease in permeability of liquids and gases can be suppressed.
When the porous resin is used as an insulating layer for an electrochemical element, the average thickness of the porous insulating layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.0 μm to 50.0 μm, more preferably 5.0 μm to 20.0 μm. When the average thickness is 5.0 μm or more, short circuits due to unevenness of the active material are unlikely to occur, and when it is 20.0 μm or less, good battery characteristics can be obtained.
The porous insulating layer is mainly disposed in the region where the first electrode and the second electrode face each other, that is, in the region where ions react in the secondary battery, and the thinner the porous insulating layer formed, the better the battery characteristics can be obtained.
In this case, the thickness refers to the thickness of only the porous resin layer, and does not include the thickness of the layer including the porous resin layer and the substrate, for example, if the porous resin layer penetrates into the substrate.

1 to 3 show an example of an adhesive porous insulating layer applied product (electrode) and a laminate (electrochemical element) of an electrochemical element member in this embodiment. Fig. 1 and Fig. 2 show a plan view and a cross-sectional view of this embodiment, respectively, and Fig. 1 shows a coating area of an adhesive porous insulating layer 10b. In this embodiment, a porous insulating layer 10a is provided on one surface (on the first electrode mixture layer 9) of a base material having a first electrode substrate 8 and a first electrode mixture layer 9 provided on both sides thereof, and an adhesive porous insulating layer 10b is provided in the margin around the porous insulating layer 10a on the base material.
Fig. 3 shows a cross-sectional view of a laminate (electrochemical element) having the electrodes shown in Fig. 1 and Fig. 2. In the laminate of Fig. 3, a second electrode having second electrode mixture layers 12 provided on both sides of a second electrode substrate 11 is sandwiched between the electrode (first electrode) shown in Fig. 1 and Fig. 2 and an electrode (first electrode) having a similar configuration, and two separated first electrode mixture layers 9 are bonded via an adhesive porous insulating layer 10b.
The adhesive porous insulating layer 10b is provided on the outermost layer of the electrode, in other words, on the portion exposed on the surface of the electrode, and in this embodiment, is provided on at least a portion of the outer periphery of the side surface of the electrode. The adhesive porous insulating layer 10b has excellent ion permeability so as not to impede the circulation of the electrolyte inside the cell, and has excellent flexibility as an insulating layer so as to reduce the occurrence of electrode lamination misalignment, thereby obtaining good battery characteristics and safety.

An example of an adhesive porous insulating layer applied product (electrode) and a laminate (electrochemical element) of an electrochemical element member in another embodiment is shown in Fig. 1 and Fig. 4, respectively showing a plan view and a cross-sectional view of this embodiment, and Fig. 1 shows a coating area of an adhesive porous insulating layer 10b. In this embodiment, a porous insulating layer 10a is provided on the entire surface of one surface (on the first electrode mixture layer 9) of a base material having a first electrode substrate 8 and a first electrode mixture layer 9 provided on both surfaces thereof, and an adhesive porous insulating layer 10b is provided around the porous insulating layer 10a.
Fig. 5 shows a cross-sectional view of a laminate (electrochemical element) having the electrodes shown in Fig. 1 and Fig. 4. In the laminate of Fig. 5, a second electrode is sandwiched between the electrode (first electrode) shown in Fig. 1 and Fig. 4 and an electrode (first electrode) having a similar configuration, and two separated first electrode mixture layers 9 are bonded via an adhesive porous insulating layer 10b.
The laminate shown in Fig. 6 is a modified example of the laminate shown in Fig. 5, and compared to the laminate shown in Fig. 5, the end of the second electrode substrate 11 extends beyond the end of the second electrode mixture layer 12, and the second electrode substrate 11 and the first electrode mixture layer 9 are bonded via an adhesive porous insulating layer 10b. Similarly, the other first electrode mixture layer 9 is also bonded to the other surface of the second electrode substrate 11 via an adhesive porous insulating layer 10b.

7 to 11 show examples of an article (electrode) with a porous insulating layer for adhesion and a laminate (electrochemical element) of an electrochemical element member in still another embodiment.
As shown in the plan views of Figures 7 and 8, which show other modified examples of the application region of the adhesive porous insulating layer 10b, an adhesive porous insulating layer 10b may be provided on the first electrode mixture layer 9 (substrate) without providing a porous insulating layer 10a (Figure 7), and then a sheet separator 13 may be provided instead of the porous insulating layer 10a (Figure 8). Figure 9 is a cross-sectional view corresponding to Figure 7, Figure 10 is a cross-sectional view corresponding to Figure 8, and Figure 11 shows a cross-sectional view of a laminate (electrochemical element) having the electrodes shown in Figures 8 and 10.

12 to 13 and 14 to 15 show an example of an article (electrode) to which an adhesive porous insulating layer is applied and a laminate (electrochemical element) of an electrochemical element member in still another embodiment.
As shown in Figures 12 to 13 and Figures 14 to 15, a first electrode mixture layer 9 is provided on both sides of a first electrode substrate 8, but the peripheral portion of the first electrode substrate 8 is exposed, and an adhesive porous insulating layer 10b may be provided on the exposed first electrode substrate 8.
Fig. 12 and Fig. 13 show an embodiment having a sheet separator 13 as an insulating layer, and Fig. 14 and Fig. 15 show an embodiment having a porous insulating layer 10a as an insulating layer. Fig. 13 shows a cross-sectional view of a laminate (electrochemical element) having the electrodes shown in Fig. 12, and Fig. 15 shows a cross-sectional view of a laminate (electrochemical element) having the electrodes shown in Fig. 14.
The laminates in Figures 3, 5, 6, 11, 13, and 15 all include a first electrode and a second electrode insulated from the first electrode, and are electrochemical elements in which the first electrode and the second electrode are laminated.

(Laminate manufacturing method and laminate manufacturing device)
The method for producing a laminate of the present invention comprises an adhesive porous insulating layer forming step, a laminating step, and a bonding step, and further comprises other steps as necessary.
The laminate manufacturing apparatus of the present invention comprises an adhesive porous insulating layer forming means, a laminating means, and an adhesive means, and further comprises other means as required.

<Adhesive Porous Insulating Layer Forming Step and Adhesive Porous Insulating Layer Forming Means>
[Method of manufacturing an article having a porous insulating layer for adhesion of an electrochemical element member]
The adhesive porous insulating layer forming step is a step of forming a first adhesive porous insulating layer on a first base material, and can be suitably carried out by an adhesive porous insulating layer forming means.
The adhesive porous insulating layer forming means is a means for forming a first adhesive porous insulating layer on a first substrate.
The first adhesive porous insulating layer is a porous structure which is a co-continuous structure having a resin skeleton, the resin being a cross-linked resin, and the first adhesive porous insulating layer is provided on one entire surface of the first substrate measuring 30 mm x 100 mm, and on one entire surface of the second substrate measuring 30 mm x 100 mm, respectively, and the first adhesive porous insulating layers are placed opposite each other, and the peel strength measured using a peel strength measuring element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second is 2 N/m or more.
The adhesive porous insulating layer forming step can suitably produce the above-mentioned member for electrochemical devices of the present invention to which an adhesive porous insulating layer is applied.

The adhesive porous insulating layer forming process includes an application process of applying a liquid composition onto a first substrate, and a polymerization process of polymerizing the liquid composition by applying heat or light, and further includes other processes as necessary.
The adhesive porous insulating layer forming means has a container for storing a liquid composition, an application section for applying the liquid composition contained in the container onto a substrate, and a polymerization section for applying heat or light to the liquid composition to polymerize it, and further has other sections as necessary.

--Liquid composition--
The liquid composition contains a polymerizable compound and a liquid, and further contains other components such as a polymerization initiator, if necessary.
The liquid composition forms a porous resin, and the light transmittance at a wavelength of 550 nm, measured while stirring the liquid composition, is 30% or more, and the increase rate of the haze value in a haze measurement element produced by polymerizing the liquid composition is 1.0% or more.

The liquid composition forms a porous structure, that is, a resin structure having a porous structure with a resin skeleton (also referred to as a "porous resin" or a "porous structure") is formed by polymerization and curing of the polymerizable compound in the liquid composition.
When the peel strength of the insulating layer made of the porous structure is 2 N/m or more, the insulating layer corresponds to the adhesive porous insulating layer in the adhesive porous insulating layer attachment of the electrochemical element member of the present invention, and also corresponds to the first adhesive porous insulating layer in the laminate of the present invention.
When the peel strength of the insulating layer made of the porous structure is less than 2 N/m, the porous insulating layer corresponds to other porous insulating layers.
Here, "the liquid composition forms a porous resin" refers not only to the case where a porous resin is formed in the liquid composition, but also to the case where a precursor of the porous resin (e.g., the skeletal part of the porous resin) is formed in the liquid composition, and the porous resin is formed by subsequent treatment (e.g., heat treatment, etc.).

--Polymerizable compound--
The polymerizable compound forms a resin by polymerization, and forms a porous resin depending on the composition and characteristics of the liquid composition.
The polymerizable compound is not particularly limited as long as it forms a polymer (resin) by polymerization, and any known polymerizable compound can be appropriately selected depending on the purpose. However, it is preferable that the polymerizable compound has at least one radically polymerizable functional group.
Suitable examples of the polymerizable compound include radical polymerizable compounds such as monofunctional, bifunctional, trifunctional or higher functional radical polymerizable monomers and oligomers; functional monomers and oligomers having a functional group other than the polymerizable functional group, etc. Among these, bifunctional or higher functional radical polymerizable compounds are preferred.
The polymerizable group of the polymerizable compound is preferably at least one of a (meth)acryloyl group and a vinyl group, and more preferably a (meth)acryloyl group.
The polymerizable compound is preferably polymerizable by energy irradiation, and more preferably polymerizable by heat or light.

The resin formed from the polymerizable compound is preferably a resin having a network structure formed by application of active energy rays (for example, by irradiation with light or heating), etc. Suitable examples thereof include acrylate resins, methacrylate resins, urethane acrylate resins, vinyl ester resins, unsaturated polyester resins, epoxy resins, oxetane resins, vinyl ether resins, and resins formed by ene-thiol reactions.
Among these, acrylate resins, methacrylate resins, and urethane acrylate resins, which are resins formed from a polymerizable compound having a (meth)acryloyl group, are more preferred because they can be easily used to form a structure by utilizing highly reactive radical polymerization, and vinyl ester resins, which are resins formed from a polymerizable compound having a vinyl group, are more preferred from the viewpoint of productivity.
These may be used alone or in combination of two or more. When using two or more, the combination of polymerizable compounds is not particularly limited and can be appropriately selected according to the purpose, but for example, in order to impart flexibility, it is preferable to mix other resins with urethane acrylate resin as the main component. Note that a polymerizable compound having at least one of an acryloyl group and a methacryloyl group is referred to as a polymerizable compound having a (meth)acryloyl group.

The active energy rays are not particularly limited as long as they can impart the energy necessary to advance the polymerization reaction of the polymerizable compound in the liquid composition, and can be appropriately selected depending on the purpose. Examples of the active energy rays include ultraviolet rays, electron beams, α rays, β rays, γ rays, and X-rays. Among these, ultraviolet rays are preferred. When a particularly high-energy light source is used, the polymerization reaction can be advanced without using a polymerization initiator.

Examples of the monofunctional radical polymerizable compound include 2-(2-ethoxyethoxy)ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, and styrene monomer. These may be used alone or in combination of two or more.

Examples of the bifunctional radical polymerizable compound include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, neopentyl glycol diacrylate, and tricyclodecane dimethanol diacrylate. These may be used alone or in combination of two or more.

Examples of the trifunctional or higher radical polymerizable compounds include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate, PO-modified glycerol triacrylate, and trimethylolpropane triacrylate. Examples of such compounds include thi(acryloxyethyl)isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxy tetraacrylate, EO-modified phosphoric acid triacrylate, and 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate. These compounds may be used alone or in combination of two or more.

The content of the polymerizable compound is preferably from 5.0% by mass to 70.0% by mass, more preferably from 10.0% by mass to 50.0% by mass, and even more preferably from 20.0% by mass to 40.0% by mass, based on the total amount of the liquid composition.
When the content is 70.0% by mass or less, the size of the pores of the obtained porous body is not too small, such as a few nm or less, and the porous body has an appropriate porosity, which is preferable because it can suppress the tendency for liquid or gas to penetrate easily. Also, when the content is 5.0% by mass or more, the three-dimensional network structure of the resin is sufficiently formed, the porous structure is sufficiently obtained, and the strength of the obtained porous structure also tends to be improved, which is preferable.

--liquid--
The liquid contains a porogen and, if necessary, further contains other liquids other than the porogen.
The porogen is a liquid that is compatible with the polymerizable compound and becomes incompatible with the polymer (resin) (causes phase separation) during the polymerization of the polymerizable compound in the liquid composition. By including a porogen in the liquid composition, a porous resin is formed when the polymerizable compound is polymerized. In addition, it is preferable that the porogen can dissolve a compound that generates a radical or an acid by light or heat (a polymerization initiator described later).
The liquid or porogen may be used alone or in combination of two or more kinds.
In this embodiment, the liquid is not polymerizable.

The boiling point of one type of porogen alone or two or more types in combination is preferably 50°C to 250°C, more preferably 70°C to 200°C, and even more preferably 120°C to 190°C at normal pressure. By having a boiling point of 50°C or higher, vaporization of the porogen at around room temperature is suppressed, making the liquid composition easier to handle and facilitating control of the porogen content in the liquid composition. In addition, by having a boiling point of 250°C or lower, the time required for the process of removing the porogen after polymerization is shortened, improving the productivity of the porous resin. In addition, since the amount of porogen remaining inside the porous resin can be suppressed, the quality is improved when the porous resin is used as a functional layer such as a material separation layer that separates substances or a reaction layer as a reaction field.

Examples of porogens include ethylene glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, and dipropylene glycol monomethyl ether; esters such as gamma-butyrolactone and propylene carbonate; and amides such as N,N-dimethylacetamide. Other examples include liquids with relatively large molecular weights such as methyl tetradecanoate, methyl decanoate, methyl myristate, and tetradecane. Other examples include liquids such as acetone, 2-ethylhexanol, and 1-bromonaphthalene.

It should be noted that not all of the above-listed liquids are porogens.
As described above, a porogen is a liquid that is compatible with a polymerizable compound and is incompatible with (substances are separated from) a polymer (resin) produced in the course of polymerization of the polymerizable compound in the liquid composition. In other words, whether or not a liquid corresponds to a porogen is determined by the relationship between the liquid and the polymerizable compound and the polymer (resin formed by polymerization of the polymerizable compound).
In addition, since the liquid composition only needs to contain at least one type of porogen having the above-mentioned specific relationship with the polymerizable compound, the range of material selection when preparing the liquid composition is broadened, and the liquid composition can be easily designed. By broadening the range of material selection when preparing the liquid composition, the range of response is broadened when there are characteristics required for the liquid composition from a viewpoint other than the formation of a porous structure. For example, when the liquid composition is discharged by the inkjet method, the liquid composition is required to have discharge stability and the like from a viewpoint other than the formation of a porous structure, and the wide range of material selection makes it easy to design the liquid composition.

The content of the liquid or porogen is preferably 30.0% by mass or more and 95.0% by mass or less, more preferably 50.0% by mass or more and 90.0% by mass or less, and even more preferably 60.0% by mass or more and 80.0% by mass or less, based on the total amount of the liquid composition.
When the content of the liquid or porogen is 30.0% by mass or more, the size of the pores in the obtained porous body is not too small, such as several nm or less, and the porous body has an appropriate porosity, which is preferable because it is possible to suppress the tendency for liquid or gas to penetrate less easily. Also, when the content of the liquid or porogen is 95.0% by mass or less, a three-dimensional network structure of the resin is sufficiently formed, a porous structure is sufficiently obtained, and the strength of the obtained porous structure also tends to be improved, which is preferable.

As described above, the liquid composition is required to contain at least one type of porogen having the above-mentioned specific relationship with the polymerizable compound, and therefore may additionally contain other liquids (liquids that are not porogens) that do not have the above-mentioned specific relationship with the polymerizable compound.
The content of the other liquids is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, still more preferably 1.0% by mass or less, and particularly preferably 0% by mass (not included), based on the total amount of the liquid composition.

The mass ratio of the polymerizable compound content to the porogen content in the liquid composition (polymerizable compound:porogen) is preferably 1.0:0.4 to 1.0:19.0, more preferably 1.0:1.0 to 1.0:9.0, and even more preferably 1.0:1.5 to 1.0:4.0.

--Other ingredients--
---Polymerization initiator---
The liquid composition may contain other components, such as a polymerization initiator.
The polymerization initiator is a material capable of generating active species such as radicals and cations by energy such as light and heat, and initiating polymerization of a polymerizable compound. Examples of the polymerization initiator include known radical polymerization initiators, cationic polymerization initiators, and base generators. These may be used alone or in combination of two or more. Among these, photoradical polymerization initiators are preferred.

The photoradical polymerization initiator is not particularly limited, and a known photoradical generator can be appropriately selected depending on the purpose. Examples of the photoradical polymerization initiator include Michler's ketone and benzophenone, known under the trade names Irgacure and Darocur, and acetophenone derivatives.
Specific examples of the compounds include α-hydroxy-acetophenone, α-aminoacetophenone, 4-aroyl-1,3-dioxolane, benzil ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, pp'-dichlorobenzophenone, pp'-bisdiethylaminobenzophenone, Michler's ketone, benzil, benzoin, benzil dimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthio Oxanthone, azobisisobutyronitrile, benzoin peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate, benzoin isopropyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin n-propyl, 1-hydroxy-cyclohexyl cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-cyclohexyl-phenyl-ketone, hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one monoacylphosphine oxide, bisacylphosphine oxide; titanocene, fluorescein, anthraquinone, thioxanthone; xanthone, lophine dimer, trihalomethyl compounds; dihalomethyl compounds, active ester compounds, and organic boron compounds.

In addition, a photocrosslinking radical generator such as a bisazide compound may be simultaneously contained. In addition, when polymerization is performed by heat alone, a thermal polymerization initiator such as azobisisobutyronitrile (AIBN), which is a typical radical generator, can be used.

The content of the polymerization initiator is preferably 0.05% by mass or more and 10.0% by mass or less, and more preferably 0.5% by mass or more and 5.0% by mass or less, when the total mass of the polymerizable compounds is taken as 100.0% by mass, in order to obtain a sufficient curing speed.

The liquid composition may be a non-dispersion type composition that does not contain any dispersing matter in the liquid composition, or a dispersion type composition that contains a dispersing matter in the liquid composition, but is preferably a non-dispersion type composition.

Polymerization-induced phase separation
Porous resins are formed by polymerization-induced phase separation. Polymerization-induced phase separation refers to a state in which a polymerizable compound and a porogen are compatible with each other, but the polymer (resin) and porogen that are generated during the polymerization of the polymerizable compound are not compatible with each other (phase separation occurs). Although there are other methods for obtaining a porous body by phase separation, the polymerization-induced phase separation method can form a porous body with a network structure, which is expected to be highly resistant to chemicals and heat. In addition, compared to other methods, it has the advantages of a shorter process time and easier surface modification.

Next, a process for forming a porous resin using polymerization-induced phase separation with a liquid composition containing a polymerizable compound will be described. The polymerizable compound undergoes a polymerization reaction by irradiation with light or the like to form a resin. During this process, the solubility of the porogen in the growing resin decreases, and phase separation occurs between the resin and the porogen. Finally, the resin forms a porous structure with a co-continuous structure due to the resin skeleton, with the porogen filling the pores. When this is dried, the porogen is removed, leaving a porous resin with a co-continuous structure of a three-dimensional network structure. Therefore, in order to form a porous resin with an appropriate porosity, the compatibility of the porogen with the polymerizable compound and the compatibility of the porogen with the resin formed by polymerization of the polymerizable compound are examined.

[Light transmittance]
The liquid composition has a light transmittance of 30% or more at a wavelength of 550 nm, as measured while being stirred.
The compatibility between the porogen and the polymerizable compound can be judged by the light transmittance.
When the light transmittance is 30% or more, it is determined that the liquid contains porogen and that the polymerizable compound and the porogen are in a compatible state, and when the light transmittance is less than 30%, it is determined that the polymerizable compound and the liquid are in an incompatible state.

Specifically, the light transmittance can be measured by the following method.
First, the liquid composition is poured into a quartz cell, and while stirring with a stirrer at 300 rpm, the transmittance of the liquid composition to light (visible light) at a wavelength of 550 nm is measured under the following conditions.
Quartz cell: Special microcell with screw cap (product name: M25-UV-2, manufactured by GL Sciences Inc.)
Transmittance measuring device: USB4000 manufactured by Ocean Optics
Stirring speed: 300 rpm
Measurement wavelength: 550 nm
Reference: Obtained by measuring the transmittance of light at a wavelength of 550 nm when the quartz cell is filled with air (transmittance: 100%)

[Rate of increase in haze value]
The increase rate of the haze value in a haze measuring element prepared by polymerizing the liquid composition is 1.0% or more.
The compatibility between the porogen and the resin formed by polymerization of the polymerizable compound can be judged by the rate of increase in the haze value.
When the rate of increase in the haze value is 1.0% or more, it is determined that the liquid contains porogen and that the resin and the porogen are incompatible with each other, and when the rate of increase in the haze value is less than 1.0%, it is determined that the resin and the liquid are compatible with each other.
The haze value in the haze measuring element increases as the compatibility between the porogen and the resin formed by polymerization of the polymerizable compound decreases, and decreases as the compatibility increases. Also, the higher the haze value, the easier it is for the resin formed by polymerization of the polymerizable compound to form a porous structure.

Specifically, the rate of increase in haze value is the rate of increase in haze value before and after polymerization of a haze measurement element having an average thickness of 100 μm produced by polymerizing the liquid composition, and can be measured by the following method.
- Preparation of element for haze measurement -
First, resin particles as a gap agent are uniformly dispersed on a non-alkali glass substrate by spin coating. Then, the substrate coated with the gap agent is bonded to a non-alkali glass substrate not coated with the gap agent, with the surfaces coated with the gap agent sandwiched between them. Next, the liquid composition is filled between the bonded substrates by utilizing capillary action to prepare a "pre-UV haze measurement element". Next, the pre-UV haze measurement element is irradiated with UV light to harden the liquid composition. Finally, the periphery of the substrate is sealed with a sealant to prepare a "haze measurement element". The size of the gap agent (average particle diameter 100 μm) corresponds to the average thickness of the haze measurement element. The various conditions during preparation are shown below.
Non-alkali glass substrate: Nippon Electric Glass Co., Ltd., 40 mm, t=0.7 mm, OA-10G
Gap agent: Sekisui Chemical Co., Ltd., resin microparticle Micropearl GS-L100, average particle size 100 μm
Spin coating conditions: Dispersion liquid drop amount 150 μL, rotation speed 1000 rpm, rotation time 30 s
Amount of liquid composition filled: 160 μL
UV irradiation conditions: UV-LED was used as the light source, light source wavelength was 365 nm, irradiation intensity was 30 mW/cm ² , and irradiation time was 20 s.
Sealant: TB3035B (manufactured by Three Bond)

- Haze value (cloudiness) measurement -
Next, the haze value (cloudiness) is measured using the prepared haze measuring element before UV irradiation and the haze measuring element. The measured value in the haze measuring element before UV irradiation is set as a reference (haze value 0), and the increase rate of the measured value (haze value) in the haze measuring element relative to the measured value in the haze measuring element before UV irradiation is calculated.
The equipment used for the measurements is shown below.
Haze measuring device: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

[viscosity]
The viscosity of the liquid composition is preferably 1.0 mPa·s or more and 150.0 mPa·s or less, more preferably 1.0 mPa·s or more and 30.0 mPa·s or less, and particularly preferably 1.0 mPa·s or more and 25.0 mPa·s or less, at 25° C., from the viewpoint of workability when applying the liquid composition. By having the viscosity of the liquid composition be 1.0 mPa·s or more and 30.0 mPa·s or less, good ejection properties can be obtained even when the liquid composition is applied to an inkjet method. Here, the viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.) or the like.

[Hansen Solubility Parameter (HSP)]
The compatibility between the porogen and the polymerizable compound, and the compatibility between the porogen and the resin formed by polymerization of the polymerizable compound, can be predicted through Hansen Solubility Parameter (HSP).
Hansen solubility parameter (HSP) is a useful tool for predicting the compatibility of two substances, and is a parameter discovered by Charles M. Hansen. Hansen solubility parameter (HSP) is expressed by combining the following three parameters (δD, δP, and δH) derived experimentally and theoretically. The unit of Hansen solubility parameter (HSP) is MPa0.5 or (J/ ^cm3 ) ^0.5 . In this embodiment, (J/ ^cm3 ) ^0.5 is used.
δD: Energy derived from London dispersion forces.
δP: Energy resulting from dipole-dipole interactions.
δH: Energy derived from hydrogen bonding forces.

The Hansen solubility parameter (HSP) is a vector quantity expressed as (δD, δP, δH), and is plotted in a three-dimensional space (Hansen space) with the three parameters as the coordinate axes. The Hansen solubility parameters (HSP) of commonly used substances are available from publicly known information sources such as databases, so the Hansen solubility parameter (HSP) of a desired substance can be obtained, for example, by referring to the database. For substances whose Hansen solubility parameters (HSP) are not registered in the database, the Hansen solubility parameter (HSP) can be calculated from the chemical structure of the substance or the Hansen solubility sphere method described below, for example, by using computer software such as Hansen Solubility Parameters in Practice (HSPiP). The Hansen solubility parameter (HSP) of a mixture containing two or more substances is calculated as the vector sum of the Hansen solubility parameters (HSP) of each substance multiplied by the volume ratio of each substance to the entire mixture. In this embodiment, the Hansen solubility parameter (HSP) of a liquid (porogen) obtained based on a publicly known information source such as a database is referred to as the "Hansen solubility parameter of the liquid."

上記式中、Ｒａは、溶質のハンセン溶解度パラメータ（ＨＳＰ）と溶液のハンセン溶解度パラメータ（ＨＳＰ）との相互作用間距離を示し、Ｒｏは、溶質の相互作用半径を示す。ハンセン溶解度パラメータ（ＨＳＰ）間の相互作用間距離（Ｒａ）は２種の物質の距離を示す。その値が小さいほど、３次元空間（ハンセン空間）内で、２種の物質がより接近することを意味し、互いに溶解する（相溶する）可能性がより高くなることを示す。
２種の物質（溶質Ａ及び溶液Ｂ）に対するそれぞれのハンセン溶解度パラメータ（ＨＳＰ）が下記のようであると仮定すれば、Ｒａは下記のように計算することができる。
・ＨＳＰ^Ａ＝（δＤ^Ａ、δＰ^Ａ、δＨ^Ａ）
・ＨＳＰ^Ｂ＝（δＤ^Ｂ、δＰ^Ｂ、δＨ^Ｂ）
・Ｒａ＝［４×（δＤ^Ａ－δＤ^Ｂ）^２＋（δＰ^Ａ－δＰ^Ｂ）^２＋（δＨ^Ａ－δＨ^Ｂ）^２］^１／２
Ｒｏ（溶質の相互作用半径）は、例えば、次に説明するハンセン溶解球法により決定することができる。 In addition, the relative energy difference (RED) based on the Hansen solubility parameters (HSP) of a solute and the Hansen solubility parameters (HSP) of a solution is expressed by the following formula.

In the above formula, Ra indicates the interaction distance between the Hansen Solubility Parameter (HSP) of the solute and the Hansen Solubility Parameter (HSP) of the solution, and Ro indicates the interaction radius of the solute. The interaction distance (Ra) between the Hansen Solubility Parameter (HSP) indicates the distance between two substances. The smaller the value, the closer the two substances are in the three-dimensional space (Hansen space), and the higher the possibility of dissolving (being compatible) with each other.
Assuming that the Hansen Solubility Parameters (HSP) for two substances (solute A and solution B) are as follows, Ra can be calculated as follows:
HSP ^A = (δD ^A , δP ^A , δH ^A )
HSP ^B = (δD ^B , δP ^B , δH ^B )
Ra = [4 x (δD ^A - δD ^B ) ² + (δP ^A - δP ^B ) ² + (δH ^A - δH ^B ) ² ] ^1/2
Ro (the interaction radius of a solute) can be determined, for example, by the Hansen dissolved sphere method described below.

-Hansen dissolving ball method-
First, a substance for which Ro is to be obtained and several dozen types of evaluation liquids (liquids whose meaning is different from the above-mentioned "liquid (porogen)") whose Hansen solubility parameters (HSP) are known are prepared, and a compatibility test of the target substance with each evaluation liquid is performed. In the compatibility test, the Hansen solubility parameters (HSP) of the evaluation liquids that showed compatibility and the Hansen solubility parameters (HSP) of the evaluation liquids that did not show compatibility are plotted on the Hansen space. Based on the plotted Hansen solubility parameters (HSP) of each evaluation liquid, a virtual sphere (Hansen sphere) is created on the Hansen space so as to include the Hansen solubility parameters (HSP) of the evaluation liquid group that showed compatibility and not include the Hansen solubility parameters (HSP) of the evaluation liquid group that did not show compatibility. The radius of the Hansen sphere is the interaction radius R ₀ of the substance, and the center is the Hansen solubility parameter (HSP) of the substance. The evaluation criteria for compatibility (criteria for determining whether or not compatibility exists) between a substance for which the interaction radius _R0 and Hansen solubility parameter (HSP) are to be calculated and a liquid for evaluation having a known Hansen solubility parameter (HSP) is set by the evaluator himself/herself. The evaluation criteria in this embodiment will be described later.

- Hansen Solubility Parameter (HSP) and Interaction Radius of Polymerizable Compounds -
The Hansen solubility parameter (HSP) of the polymerizable compound in this embodiment and the interaction radius of the polymerizable compound are determined by the Hansen dissolved ball method. As described above, the evaluation criteria for compatibility in the Hansen dissolved ball method are set by the evaluator himself, so the Hansen solubility parameter (HSP) of the polymerizable compound in this embodiment obtained by the following criteria is represented as the "Hansen solubility parameter C of the polymerizable compound", and the interaction radius of the polymerizable compound is represented as the "interaction radius D of the polymerizable compound". In other words, the "Hansen solubility parameter C of the polymerizable compound" and the "interaction radius D of the polymerizable compound" are obtained based on the Hansen solubility parameter C of the polymerizable compound, which is different from the "Hansen solubility parameter of the liquid" obtained based on a known information source such as a database, and are obtained based on the Hansen dissolved ball method including the evaluation criteria for compatibility set by the evaluator himself.

The Hansen solubility parameter C and the interaction radius D of the polymerizable compound are determined by evaluating the compatibility of the polymerizable compound with the evaluation liquid (based on the "transmittance of light at a wavelength of 550 nm of the transmittance measurement composition, which is measured while stirring the transmittance measurement composition containing the polymerizable compound and the evaluation liquid") according to the following [1-1] and the above-mentioned method for measuring light transmittance.

[1-1] Preparation of composition for measuring transmittance First, prepare a polymerizable compound for which the Hansen solubility parameter (HSP) is to be determined and several dozen types of evaluation liquids with known Hansen solubility parameters (HSP), and mix the polymerizable compound, each evaluation liquid, and polymerization initiator in the ratio shown below to prepare a composition for measuring transmittance. As several dozen types of evaluation liquids with known Hansen solubility parameters (HSP), the following 21 types of evaluation liquids are used.
~Composition ratio for transmittance measurement~
Polymerizable compound for which Hansen solubility parameter (HSP) is to be calculated: 28.0% by mass
Liquid for evaluation with known Hansen solubility parameter (HSP): 70.0% by mass
Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0% by mass
~Evaluation liquid group (21 types)~
Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene

-Hansen solubility parameter (HSP) and interaction radius of resin formed by polymerization of polymerizable compound-
The Hansen solubility parameter (HSP) of the resin formed by polymerization of the polymerizable compound and the interaction radius of the resin formed by polymerization of the polymerizable compound are determined by the Hansen sphere method. As described above, the evaluation criteria for compatibility in the Hansen sphere method are set by the evaluator himself, so the Hansen solubility parameter (HSP) of the resin formed by polymerization of the polymerizable compound in this embodiment obtained by the following criteria is represented as "Hansen solubility parameter A of the resin", and the interaction radius of the resin formed by polymerization of the polymerizable compound is represented as "interaction radius B of the resin". In other words, "Hansen solubility parameter A of the resin" and "interaction radius B of the resin" are obtained based on the Hansen solubility parameter of the liquid, which is obtained based on a known information source such as a database, and are obtained based on the Hansen sphere method including the evaluation criteria for compatibility set by the evaluator himself.

The Hansen solubility parameter A and interaction radius B of the resin are determined by evaluating the compatibility of the resin with the evaluation liquid (based on the "rate of increase in haze value (cloudiness) in a haze measurement element prepared using a haze measurement composition containing a polymerizable compound and an evaluation liquid") according to [2-1] below and the method for measuring the rate of increase in haze value described above.

[2-1] Preparation of a composition for measuring haze First, a precursor (polymerizable compound) of a resin for which the Hansen Solubility Parameter (HSP) is to be determined and several dozen types of evaluation liquids with known Hansen Solubility Parameters (HSP) are prepared, and the polymerizable compound, each evaluation liquid, and polymerization initiator are mixed in the ratio shown below to prepare a composition for measuring haze. As several dozen types of evaluation liquids with known Hansen Solubility Parameters (HSP), the following 21 types of evaluation liquids are used.
~Composition ratio for haze measurement~
Precursor of the resin for which the Hansen solubility parameter (HSP) is to be calculated (polymerizable compound): 28.0% by mass
Liquid for evaluation with known Hansen solubility parameter (HSP): 70.0% by mass
Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0% by mass
~Evaluation liquid group (21 types)~
Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene

- Relative Energy Difference (RED) based on Hansen Solubility Parameters (HSP) of resin and liquid (porogen) -
As described above, the relative energy difference (RED) calculated based on the Hansen solubility parameter A of a resin formed by polymerization of a polymerizable compound, which is determined based on the rate of increase in the haze value (cloudiness) in a haze measurement element prepared using a composition for haze measurement containing a polymerizable compound and an evaluation liquid, the interaction radius B of the resin, and the Hansen solubility parameter of the porogen according to the following formula 1, is preferably 1.00 or more, more preferably 1.10 or more, even more preferably 1.20 or more, and particularly preferably 1.30 or more.
When the relative energy difference (RED) based on the Hansen solubility parameter (HSP) between the resin and the porogen is 1.00 or more, the resin and the porogen formed by polymerization of the polymerizable compound in the liquid composition are more likely to undergo phase separation, which is preferable because it makes it easier to form a porous resin.

- Relative Energy Difference (RED) based on Hansen Solubility Parameters (HSP) of Polymerizable Compound and Liquid (Porogen) -
As described above, the relative energy difference (RED) calculated based on the Hansen solubility parameter C of the polymerizable compound, which is determined based on the transmittance of light at a wavelength of 550 nm of the transmittance measurement composition, which is measured while stirring the transmittance measurement composition containing the polymerizable compound and the evaluation liquid, the interaction radius D of the polymerizable compound, which is determined based on the compatibility between the polymerizable compound and the evaluation liquid, and the Hansen solubility parameter of the liquid, based on the following formula 2, is preferably 1.05 or less, more preferably 0.90 or less, even more preferably 0.80 or less, and particularly preferably 0.70 or less.
When the relative energy difference (RED) based on the Hansen solubility parameter (HSP) between the polymerizable compound and the porogen is 1.05 or less, the polymerizable compound and the porogen are more likely to exhibit compatibility, and as the RED approaches 0, the compatibility is more pronounced. Therefore, when the relative energy difference (RED) is 1.05 or less, a liquid composition is obtained that exhibits high dissolution stability such that the polymerizable compound does not precipitate over time after dissolving the polymerizable compound in the porogen. Since the polymerizable compound has high solubility in the porogen, the ejection stability of the liquid composition can be maintained, and the liquid composition of this embodiment can be suitably applied to a method of ejecting the liquid composition, such as an inkjet method. In addition, when the relative energy difference (RED) is 1.05 or less, separation between the polymerizable compound and the porogen is suppressed in the state of the liquid composition before the start of the polymerization reaction, and the formation of an irregular or non-uniform porous resin is suppressed.

[Method of producing liquid composition]
The method for producing the liquid composition is not particularly limited and can be appropriately selected depending on the purpose. However, it is preferable to produce the liquid composition through a step of dissolving a polymerization initiator in a polymerizable compound, a step of further dissolving a porogen and other components, and a step of stirring to obtain a homogeneous solution.

<<Storage container>>
The storage vessel includes the liquid composition and a container, and the liquid composition is stored in the container.
Examples of containers include glass bottles, plastic containers, plastic bottles, stainless steel bottles, one-gallon cans, drums, and the like.

<<Assignment process, assignment unit>>
The application process is a process of applying the liquid composition contained in the container onto a substrate, and can be suitably performed by an application section.
The ejection section is a section that applies the liquid composition onto a substrate.

The application process and application unit are not particularly limited as long as they can apply the liquid composition, and can be appropriately selected depending on the purpose. For example, any printing device can be used according to various printing methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing. Among these, inkjet printing is preferred.

<<Polymerization treatment, polymerization section>>
The polymerization treatment is a treatment in which heat or light is applied to the liquid composition to polymerize it, and can be suitably carried out by a polymerization section.
The polymerization section is a section in which heat or light is applied to the liquid composition to polymerize it.
The polymerization causes the polymer compound in the liquid composition to polymerize, and a porous resin is formed by polymerization-induced phase separation, thereby producing a laminate having a substrate and a porous resin on the substrate.
The polymerization treatment and polymerization part are not particularly limited and can be appropriately selected depending on the purpose such as the polymerization initiator used and the polymerization mode. For example, in the case of photopolymerization, a light irradiation treatment and a light irradiation method in which ultraviolet rays having a wavelength of 365 nm are irradiated for 3 seconds, and in the case of thermal polymerization, a heat treatment and a heating method in which heating is performed in a vacuum drying at 150° C. for 12 hours can be mentioned.

<<Other Processing, Other Parts>>
Other treatments in the laminate manufacturing apparatus are not particularly limited as long as they do not impair the effects of the present invention and can be appropriately selected depending on the purpose. For example, a removal treatment can be included.
The other portion in the method for producing the laminate is not particularly limited as long as it does not impair the effects of the present invention and may be appropriately selected depending on the purpose. For example, a removed portion may be mentioned.

<<<<Removal process, removal unit>>>
The removal treatment is a treatment for removing liquid from the porous resin formed by polymerizing the liquid composition in the polymerization treatment, and can be suitably performed by a removal unit.
The removal section is a section for removing liquid from the porous resin formed by polymerization of the liquid composition in the polymerization section.
The method for removing the liquid is not particularly limited, and examples thereof include a method of removing liquid such as a solvent or dispersion liquid from a porous resin by heating. In this case, heating under reduced pressure is preferable because it can further promote the removal of the liquid and suppress the liquid from remaining in the formed insulating layer.

<Lamination process and lamination means>
The lamination process is a process of laminating the first substrate, on which the first adhesive porous insulating layer is formed, and a second substrate so that the first adhesive porous insulating layer faces the second substrate, and can be suitably carried out by a lamination means.
The lamination means is a means for laminating the first substrate on which the first adhesive porous insulating layer is formed and a second substrate so that the first adhesive porous insulating layer and the second substrate face each other.
The first substrate may be an electrode and the second substrate may be a film separator, or the first substrate may be an electrode and the second substrate may be an electrode, and either of these substrates may be suitably adopted. The electrode on which the adhesive porous insulating layer is formed may be on an electrode substrate, or on an electrode mixture layer provided on an electrode substrate.

<Bonding step and bonding means>
The bonding step is a step of bonding the laminated first base material and second base material via the first adhesive porous insulating layer, and can be suitably carried out by an adhesive means.
The bonding means is a means for bonding the laminated first base material and second base material via the first adhesive porous insulating layer.
The bonding method includes a thermal bonding method under conditions of a temperature of 50° C. to 300° C., an air cylinder thrust of 50 N to 1,000 N, and a time of 0.5 seconds to 10 seconds.
The bonding means is not particularly limited and can be appropriately selected depending on the purpose. For example, a hot plate sealer (manufactured by Ishizaki Electric Works, Ltd.) can be used.

[Embodiments in which an adhesive porous insulating layer or a laminate is formed by directly applying a liquid composition to a substrate]
FIG. 17 is a schematic diagram showing an example of an adhesive porous insulating layer manufacturing apparatus (liquid ejection apparatus) for realizing the method for manufacturing an adhesive porous insulating layer imparted to an electrochemical element member of this embodiment and a laminate.
The adhesive porous insulating layer manufacturing apparatus 500 is an apparatus for manufacturing an adhesive porous insulating layer using the above-mentioned liquid composition. The adhesive porous insulating layer manufacturing apparatus includes a printing section 100 for carrying out an application process of applying a liquid composition onto a printing substrate 4 to form a liquid composition layer, a polymerization section 200 for carrying out a polymerization process of applying heat or light to the liquid composition layer to polymerize it, and a removal section 300 for carrying out a removal process of heating a porous resin precursor 6 and removing the solvent in the pores to obtain a porous resin. The adhesive porous insulating layer manufacturing apparatus includes a transport section 5 for transporting the printing substrate 4, and the transport section 5 transports the printing substrate 4 at a preset speed in the order of the printing section 100, the polymerization section 200, and the heating section 300.

--Printing unit 100--
The printing unit 100 includes a printing device 1a, which is an example of an application means for realizing an application process of applying a liquid composition for forming an adhesive porous insulating layer on the printing substrate 4, a storage container 1b for storing the liquid composition, and a supply tube 1c for supplying the liquid composition stored in the storage container 1b to the printing device 1a.
The storage container 1b stores the liquid composition 7, and the printing unit 100 ejects the liquid composition 7 from the printing device 1a and applies the liquid composition 7 onto the printing substrate 4 to form a thin film of the liquid composition layer. The storage container 1b may be integrated with the laminate manufacturing device, or may be removable from the laminate manufacturing device. Alternatively, the storage container 1b may be a container used for adding to a storage container integrated with the laminate manufacturing device or a storage container removable from the laminate manufacturing device.
The container 1b and the supply tube 1c may be selected arbitrarily as long as they can stably store and supply the liquid composition 7. The materials constituting the container 1b and the supply tube 1c preferably have a light-shielding property in the relatively short wavelength region of ultraviolet and visible light. This prevents the liquid composition 7 from being polymerized by external light.

--Polymerization section 200--
As shown in FIG. 17 , in the case of photopolymerization, the polymerization unit 200 has a light irradiation device 2a, which is an example of a polymerization means for carrying out a polymerization process, and a polymerization inert gas circulation device 2b for circulating a polymerization inert gas. The light irradiation device 2a irradiates the liquid composition layer formed by the printing unit 100 with light in the presence of the polymerization inert gas, and photopolymerizes the liquid composition to obtain a porous resin precursor 6.
The light irradiation device 2a is appropriately selected according to the absorption wavelength of the photopolymerization initiator contained in the liquid composition layer, and is not particularly limited as long as it can initiate and advance the polymerization of the compound in the liquid composition layer, and examples thereof include ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and LEDs. However, since light with a shorter wavelength generally tends to reach deeper parts, it is preferable to select a light source according to the thickness of the porous film to be formed.
Next, regarding the irradiation intensity of the light source of the light irradiation device 2a, if the irradiation intensity is too strong, polymerization will proceed rapidly before phase separation occurs sufficiently, so that it is difficult to obtain a porous structure. If the irradiation intensity is too weak, phase separation will proceed to a microscale or greater, and porosity variations and coarsening will occur easily. In addition, the irradiation time will be longer, and productivity will tend to decrease. Therefore, the irradiation intensity is preferably 10 mW/cm ² or more and 1 W/cm ² or less, and more preferably 30 mW/cm ² or more and 300 mW/cm ² or less.

The polymerization inert gas circulation device 2b plays a role of lowering the concentration of polymerization active oxygen contained in the atmosphere and allowing the polymerization reaction of the polymerizable compound near the surface of the liquid composition layer to proceed without being hindered. Therefore, the polymerization inert gas used is not particularly limited as long as it satisfies the above-mentioned functions, and examples thereof include nitrogen, carbon dioxide, and argon.
The _O2 concentration of the polymerization inert gas is preferably less than 20% (an environment with a lower oxygen concentration than the atmosphere) in consideration of the effective inhibition reduction effect, more preferably 0% to 15%, and even more preferably 0% to 5%. In addition, the polymerization inert gas circulation device 2b is preferably provided with a temperature control means capable of controlling the temperature in order to realize stable polymerization progress conditions.

In the case of thermal polymerization, the polymerization section 200 may be a heating device. The heating device is not particularly limited and may be appropriately selected depending on the purpose. Examples of the heating device include a substrate heater (e.g., a hot plate), an IR heater, and a hot air heater, and these may be combined.
The heating temperature, time, and light irradiation conditions can be appropriately selected depending on the polymerizable compound contained in the liquid composition 7 and the thickness of the formed film.

--Removal Unit 300--
17, the removal section 300 has a heating device 3a and performs a liquid removal step in which the porous resin precursor 6 formed in the polymerization section 200 is heated by the heating device 3a to dry and remove the remaining liquid. This makes it possible to form a porous resin. The removal section 300 may remove the liquid under reduced pressure.
The removal unit 300 also performs a polymerization promotion step in which the porous film precursor 6 is heated by the heating device 3a to further promote the polymerization reaction carried out in the polymerization unit 200, and an initiator removal step in which the photopolymerization initiator remaining in the porous film precursor 6 is heated by the heating device 3a, dried, and removed. Note that these polymerization promotion step and initiator removal step may be performed before or after the liquid removal step, rather than simultaneously with the liquid removal step.
Furthermore, the removal unit 300 performs a polymerization completion step of heating the porous material under reduced pressure after the liquid removal step. There are no particular limitations on the heating device 3a as long as it satisfies the above-mentioned functions, and examples of the heating device include an IR heater and a hot air heater.
The heating temperature and time can be appropriately selected depending on the boiling point of the liquid contained in the porous film precursor 6 and the thickness of the formed film.

As shown in FIG. 18, the adhesive porous insulating layer manufacturing apparatus of FIG. 17 may further include an additional printing unit 100'. The adhesive porous insulating layer manufacturing apparatus of FIG. 18 includes an additional printing unit 100' that applies a liquid composition for forming a porous insulating layer on the printing substrate 4 in addition to the printing unit 100 that applies a liquid composition for forming an adhesive porous insulating layer on the printing substrate 4. By applying different liquid compositions to multiple areas on the printing substrate 4, the adhesive porous insulating layer and the porous insulating layer can be formed by the subsequent polymerization unit 200 and removal unit 300, respectively.

FIG. 19 is a schematic diagram showing another example of an adhesive porous insulating layer manufacturing apparatus (liquid ejection apparatus) for realizing the method for manufacturing the adhesive porous insulating layer-added article and laminate of the electrochemical element member of this embodiment.
The liquid ejection device 300 ′ is capable of circulating the liquid composition through the liquid ejection head 306 , the tank 307 , and the tube 308 by controlling the pump 310 and the valves 311 and 312 .
In addition, the liquid ejection device 300' is provided with an external tank 313, and when the liquid composition in the tank 307 decreases, it is also possible to supply the liquid composition from the external tank 313 to the tank 307 by controlling the pump 310 and the valves 311, 312, and 314.
By using the adhesive porous insulating layer manufacturing apparatus, the liquid composition can be discharged to a targeted location on an object to which the composition is to be applied.

Another example of the method for producing the adhesive porous insulating layer and the laminate of this embodiment is shown in FIG.
The method for producing the applied object 210 in which an adhesive porous resin is applied onto a substrate includes a step of sequentially discharging the liquid composition 12A onto a substrate 211 using a liquid discharge device 300'.
First, an elongated substrate 211 is prepared. Then, the substrate 211 is wound around a cylindrical core, and set on a feed roller 304 and a take-up roller 305 so that the side on which the adhesive porous resin 212 is formed is the upper side in FIG. 20. Here, the feed roller 304 and the take-up roller 305 rotate counterclockwise, and the substrate 211 is transported from right to left in FIG. 20. Then, droplets of the liquid composition 12A are ejected from a liquid ejection head 306 installed above the substrate 211 between the feed roller 304 and the take-up roller 305, in the same manner as in FIG. 16, onto the substrate 211 which is being transported in sequence.
A plurality of liquid ejection heads 306 may be installed in a direction substantially parallel to or substantially perpendicular to the transport direction of the substrate 211. Next, the substrate 211 onto which the droplets of the liquid composition 12A have been ejected is transported to a polymerization section 309 by a delivery roller 304 and a take-up roller 305. As a result, an adhesive porous resin 212 is formed, and an applied object 210 in which the adhesive porous resin is provided on the substrate is obtained. Thereafter, the applied object 210 to which the adhesive porous resin has been applied is cut to a desired size by punching or the like.
The overlapping portion 309 may be provided on either the top or bottom of the base material 211, or a plurality of overlapping portions may be provided.
The polymerization section 309 is not particularly limited as long as it does not come into direct contact with the liquid composition 12A, and examples of the polymerization section 309 include a resistance heater, an infrared heater, a fan heater, etc. in the case of thermal polymerization, and an ultraviolet ray irradiation device, etc. in the case of photopolymerization. A plurality of polymerization sections 309 may be provided.

The conditions for heating or light irradiation are not particularly limited and can be appropriately selected depending on the purpose. The liquid composition 12A is polymerized by polymerization to form an adhesive porous resin.
As shown in FIG. 21, the tank 307A may be supplied with the liquid composition from a tank 313A connected to the tank 307A, and the liquid ejection head 306 may have a plurality of liquid ejection heads 306A and 306B.

[Embodiments in which an adhesive porous insulating layer or a laminate is formed by indirectly applying a liquid composition to a substrate]
Figures 22 and 23 are configuration diagrams showing an example of a printing unit that employs an inkjet method and a transfer method as an application method in a manufacturing apparatus for an adhesive porous insulating layer of this embodiment, where Figure 22 is a configuration diagram showing a printing unit that uses a drum-shaped intermediate transfer body, and Figure 23 is a configuration diagram showing a printing unit that uses an endless belt-shaped intermediate transfer body.
The printing unit 400 ′ shown in FIG. 22 is an inkjet printer that transfers a liquid composition or a porous resin to a substrate via an intermediate transfer body 4001 to form a porous resin on the substrate.

The printing section 400 ′ includes an inkjet section 420 , a transfer drum 4000 , a pre-treatment unit 4002 , an absorbing unit 4003 , a heating unit 4004 and a cleaning unit 4005 .
The inkjet unit 420 includes a head module 422 that holds a plurality of heads 101. The heads 101 eject a liquid composition onto an intermediate transfer body 4001 supported by a transfer drum 4000, and form a liquid composition layer on the intermediate transfer body 4001. Each head 101 is a line head, and nozzles are arranged in a range that covers the width of the recording area of a substrate of the maximum size that can be used. The head 101 has a nozzle surface on its lower surface on which nozzles are formed, and the nozzle surface faces the surface of the intermediate transfer body 4001 via a minute gap. In the case of this embodiment, the intermediate transfer body 4001 is configured to circulate on a circular orbit, so the plurality of heads 101 are arranged radially.

The transfer drum 4000 faces the pressure cylinder 621 and forms a transfer nip. The pretreatment unit 4002 applies, for example, a reaction liquid for increasing the viscosity of the liquid composition onto the intermediate transfer body 4001 before the liquid composition is discharged by the head 101. The absorption unit 4003 absorbs liquid components from the liquid composition layer on the intermediate transfer body 4001 before transfer. The heating unit 4004 heats the ink layer on the intermediate transfer body 4001 before transfer. By heating the liquid composition layer, the liquid composition is thermally polymerized to form a porous resin. In addition, the liquid is removed, improving the transferability to the substrate. The cleaning unit 4005 cleans the intermediate transfer body 4001 after transfer and removes foreign matter such as ink and dust remaining on the intermediate transfer body 4001.
The outer peripheral surface of the pressure drum 621 is in pressure contact with the intermediate transfer body 4001, and the porous resin on the intermediate transfer body 4001 is transferred to the substrate when the substrate passes through a transfer nip between the pressure drum 621 and the intermediate transfer body 4001. The pressure drum 621 may be configured to have at least one gripping mechanism for holding the leading end of the substrate on its outer peripheral surface.

The printing unit 400 ″ shown in FIG. 23 is an inkjet printer that transfers a liquid composition or a porous resin onto a substrate via an intermediate transfer belt 4006 to form a porous resin on the substrate.
The printing unit 400'' ejects droplets of the liquid composition from a plurality of heads 101 provided in the inkjet unit 420 to form a liquid composition layer on the outer circumferential surface of the intermediate transfer belt 4006. The liquid composition layer formed on the intermediate transfer belt 4006 is heated by a heating unit 4007 and thermally polymerized to form a porous resin, which is then turned into a film on the intermediate transfer belt 4006.

The porous resin film on the intermediate transfer belt 4006 is transferred to the substrate in the transfer nip where the intermediate transfer belt 4006 faces the transfer roller 622. The surface of the intermediate transfer belt 4006 after transfer is cleaned by a cleaning roller 4008.
The intermediate transfer belt 4006 is stretched over a drive roller 4009a, an opposing roller 4009b, a plurality of (four in this example) shape maintaining rollers 4009c, 4009d, 4009e, and 4009f, and a plurality of (four in this example) support rollers 4009g, and moves in the direction of the arrow in the figure. The support roller 4009g, which is provided opposite the head 101, maintains the tension state of the intermediate transfer belt 4006 when ink droplets are ejected from the head 101.

[Uses of the porous insulating layer-added product for adhesion of electrochemical element members and the laminate]
<Electrochemical element applications>
The uses of the adhesive porous insulating layer applied to the electrochemical element member and the laminate are not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the adhesive porous insulating layer is an adhesive porous insulating layer for bonding electrochemical element members.
When used for these applications, it is preferable to form an insulating layer (separator) by applying the liquid composition onto an electrode mixture layer that has been previously formed on an electrode substrate as a base material, for example.
When the substrate is an electrode used in an electricity storage element such as a battery or a power generation element such as a fuel cell, if the adhesion between the insulating layer, which is a porous structure, and the substrate is low, there is a concern that a gap will occur between the porous structure and the substrate when the structure is deformed by an external impact or when a foreign object such as a metal piece penetrates the substrate, resulting in a short circuit.
According to the adhesive porous insulating layer additive and laminate of the electrochemical element member of this embodiment, an adhesive porous resin having adhesive properties and excellent insulating layer flexibility and ion permeability can be formed on a substrate, and the occurrence of electrode stacking misalignment and the occurrence of short circuits can be reduced.
As an insulating layer for an electrochemical element, for example, a film-like porous insulating layer having a predetermined size of pores or porosity is known to be used. On the other hand, when the liquid composition is used, the pores or porosity can be appropriately changed by appropriately adjusting the content of the polymerizable compound, the content of the porogen, the irradiation conditions of the active energy rays, etc., and the design freedom in terms of the performance of the electrochemical element can be improved. In addition, since the liquid composition can be applied in various ways, for example, it can be applied by an inkjet method, and the design freedom in terms of the shape of the electrochemical element can be improved.
The insulating layer is a member that separates the positive electrode from the negative electrode and ensures ion conductivity between the positive electrode and the negative electrode. In the present disclosure, the insulating layer is not limited to a layered shape.

The substrate may be an insulating layer (film separator) for an electrochemical element, or may be a porous insulating layer different from the adhesive porous insulating layer. By forming the adhesive porous resin on the porous insulating layer, it is possible to add or improve various functions of the insulating layer as a whole, such as heat resistance, impact resistance, and high-temperature shrinkage resistance.

(electrode)
The electrode of the present invention comprises the adhesive porous insulating layer imparted product of the electrochemical device member of the present invention described above, the substrate comprises an electrode substrate, and the electrode comprises the adhesive porous insulating layer as the outermost layer.

(Electrode manufacturing method and electrode manufacturing device)
The method for producing an electrode of the present invention comprises a step of forming an adhesive porous insulating layer on a substrate having an electrode base, and further comprises other steps as necessary.
The electrode manufacturing apparatus of the present invention has an adhesive porous insulating layer forming means for forming an adhesive porous insulating layer on a substrate having an electrode substrate, and further has other means as required.
The adhesive porous insulating layer is a porous structure which is a co-continuous structure having a resin skeleton, the resin being a cross-linked resin, and the adhesive porous insulating layer is provided on the entirety of one side of each of the two 30 mm x 100 mm substrates. The adhesive porous insulating layers are placed facing each other, and the peel strength of the adhesive porous insulating layer is 2 N/m or more when measured using a peel strength measuring element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second.
As for the adhesive porous insulating layer forming process and means, except that the substrate has an electrode substrate, the items described in the adhesive porous insulating layer forming process in the laminate manufacturing method and manufacturing apparatus of the present invention can be appropriately selected.

<Electrodes (First Electrode, Second Electrode)>
The electrode includes an electrode substrate and an adhesive porous insulating layer, and may further include at least one of an electrode mixture layer and a porous insulating layer on the electrode substrate, as necessary.
The negative electrode and positive electrode are collectively referred to as "electrodes", the negative electrode substrate and positive electrode substrate are collectively referred to as "electrode substrate", and the negative electrode mixture layer and positive electrode mixture layer are collectively referred to as "electrode mixture layer".
Moreover, when the first electrode is a negative electrode, the second electrode refers to a positive electrode, and when the first electrode is a positive electrode, the second electrode refers to a negative electrode.
The positive and negative electrodes may be provided with an electrode mixture layer, but if the reaction occurs sufficiently inside the battery, the electrode mixture layer can be omitted.
Furthermore, for the purpose of suppressing short circuits while maintaining the battery characteristics, a porous insulating layer different from the adhesive porous insulating layer may be provided.

<Electrode Substrate>
The electrode substrate is not particularly limited as long as it is a conductive substrate, and examples thereof include aluminum foil, copper foil, stainless steel foil, titanium foil, and etched foils in which fine holes are formed by etching these, as well as perforated electrode substrates used in lithium ion capacitors, etc. Such electrode substrates can be suitably used in general electricity storage devices such as secondary batteries and capacitors, and among these, they can be suitably used in lithium ion secondary batteries.
Also usable are non-woven or woven flat carbon paper fibrous electrodes used in power generation devices such as fuel cells, and the above-mentioned perforated electrode substrates with fine holes. Furthermore, in the case of solar devices, in addition to the above-mentioned electrodes, a transparent semiconductor thin film such as an indium-titanium oxide or zinc oxide formed on a flat substrate such as glass or plastic, or a thin conductive electrode film deposited by vapor deposition can be used.

<Electrode mixture layer>
The electrode mixture layer (hereinafter, sometimes referred to as "active material layer") is not particularly limited and can be appropriately selected depending on the purpose. For example, it contains an active material (negative electrode active material or positive electrode active material) and may further contain a binder (binding agent), a thickener, a conductive agent, etc., as necessary.
The negative electrode mixture layer and the positive electrode mixture layer are formed by dispersing a powdered active material, a binder, a conductive material, etc. in a liquid, applying the liquid onto an electrode substrate, fixing the liquid, and drying the liquid. The application method is by a spray, a dispenser, a die coater, lift-up coating, etc.
The electrode mixture layer is formed by dispersing a powdered active substance or catalyst composition in a liquid, applying the liquid onto the electrode substrate, fixing the liquid, and drying the liquid. Usually, printing using a spray, dispenser, die coater, or pull-up coating is used, and the electrode mixture layer is formed by applying the liquid and then drying the liquid.

<<Active material>>
The positive electrode active material is not particularly limited as long as it is a material that can reversibly absorb and release alkali metal ions. Typically, an alkali metal-containing transition metal compound can be used as the positive electrode active material. Examples of lithium-containing transition metal compounds include composite oxides containing at least one element selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium and lithium. Examples of lithium-containing transition metal compounds include lithium cobaltate, lithium nickelate, and lithium manganate, olivine-type lithium salts such as _LiFePO4 , chalcogen compounds such as titanium disulfide and molybdenum disulfide, and manganese dioxide. The lithium-containing transition metal oxide is a metal oxide containing lithium and a transition metal, or a metal oxide in which a part of the transition metal in the metal oxide is replaced by a different element. Examples of different elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B, and among these, Mn, Al, Co, Ni, and Mg are preferred. The different elements may be one kind or two or more kinds. These positive electrode active materials may be used alone or in combination of two or more kinds. The active material in the nickel-metal hydride battery may be nickel hydroxide.

The negative electrode active material is not particularly limited as long as it is a material that can reversibly absorb and release alkali metal ions. Typically, a carbon material containing graphite having a graphite crystal structure can be used as the negative electrode active material. Examples of such carbon materials include natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), and easily graphitizable carbon (soft carbon). Examples of materials other than carbon materials include lithium titanate. In addition, from the viewpoint of increasing the energy density of lithium ion batteries, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, and tin oxide can also be suitably used as the negative electrode active material.

As the active material in nickel-metal hydride batteries, examples of hydrogen storage alloys include AB2-based or A2B-based hydrogen storage alloys.

<<Binding agent>>
As the binder for the positive or negative electrode, for example, PVDF, PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene butadiene rubber, carboxymethyl cellulose, etc. can be used. In addition, a copolymer of two or more materials selected from tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene may be used. In addition, two or more selected from these may be mixed and used. Examples of the conductive agent contained in the electrode include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black, conductive fibers such as carbon fiber and metal fiber, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenylene derivatives and graphene derivatives.

In fuel cells, active materials are generally used as catalysts for cathode and anode electrodes, in which metal particles such as platinum, ruthenium, or platinum alloy are supported on a catalyst carrier such as carbon. To support catalyst particles on the surface of a catalyst carrier, for example, the catalyst carrier is suspended in water, and a catalyst particle precursor (containing alloy components such as chloroplatinic acid, dinitrodiamino platinum, platinic chloride, platinous chloride, bisacetylacetonato platinum, dichlorodiammine platinum, dichlorotetramine platinum, platinic sulfate chlororuthenic acid, chloroiridic acid, chlororhodium acid, ferric chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nickel nitrate, ferrous sulfate, and copper chloride) is added and dissolved in the suspension, and an alkali is added to generate metal hydroxides and obtain a catalyst carrier supported on the surface of the catalyst carrier. Such a catalyst carrier is applied to an electrode and reduced under a hydrogen atmosphere, etc., to obtain an electrode with catalyst particles (active material) applied to its surface.

In the case of solar cells and the like, examples of the active material include tungsten oxide powder, titanium oxide powder, and oxide semiconductor layers such as _SnO2 , _ZnO , _ZrO2 , _Nb2O5 , _CeO2 , _SiO2 , and _{Al2O3 ,} and the semiconductor layer is supported with a dye, such as a ruthenium-tris type transition metal complex, a ruthenium-bis type transition metal complex, an osmium-tris type transition metal complex, an osmium-bis type transition metal complex, a ruthenium-cis-diaqua-bipyridyl complex, phthalocyanine and porphyrin, and an organic-inorganic perovskite crystal.

<<Conductive agent>>
Examples of the conductive agent include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black, conductive fibers such as carbon fiber and metal fiber, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenylene derivatives and graphene derivatives.

(Electrochemical element)
The electrochemical element in the first embodiment of the present invention includes a first electrode and a second electrode insulated from the first electrode, and is an electrochemical element in which the first electrode and the second electrode are stacked, and at least one of the first electrode and the second electrode is the electrode of the present invention described above.
An electrochemical device according to a second embodiment of the present invention has the laminate of the present invention described above, in which the first substrate has an electrode substrate, and the second substrate has an electrode substrate.
The electrochemical element to which this embodiment can be applied is not particularly limited, and examples thereof include secondary batteries and capacitors, which are generally electric storage elements, and among these, lithium ion secondary batteries are preferred.
In addition, in the electrochemical element member according to this embodiment, it is preferable that the first electrode is disposed on the outside of the second electrode and is adhered to the second electrode via the adhesive porous insulating layer.
For example, the structure includes a structure in which the negative electrode is disposed outside the positive electrode, the negative electrode and the positive electrode are laminated with an insulating layer sandwiched therebetween and bonded via the adhesive porous insulating layer, and the negative electrode and the positive electrode are insulated from each other by the insulating layer. A battery is formed by an electrochemical device member, an electrolyte injected into the electrochemical device member, an exterior that seals the electrochemical device member and the electrolyte, and the like.

<Electrolytes>
The electrolyte may be composed of an electrolytic solution or a solid electrolyte. When the electrolyte layer is composed of an electrolytic solution, it is preferable that the electrolyte solution is a non-aqueous electrolytic solution obtained by dissolving an electrolyte salt in a non-aqueous solvent.

--Non-aqueous solvent--
The non-aqueous solvent is preferably an aprotic organic solvent.
Examples of the aprotic organic solvent include carbonate-based organic solvents, ester-based organic solvents, and ether-based organic solvents, and low-viscosity solvents are preferred.
Examples of the carbonate-based organic solvent include chain carbonates, cyclic carbonates, etc. These may be used alone or in combination of two or more.
Among these, the chain carbonates are preferred because they have a high ability to dissolve electrolyte salts.

Examples of the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (EMC). These may be used alone or in combination of two or more. Among these, dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) are preferred.
When a mixed solvent of dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) is used, the mixing ratio of dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) is not particularly limited and can be appropriately selected depending on the purpose.

Examples of the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), and fluoroethylene carbonate (FEC). These may be used alone or in combination of two or more. Among these, propylene carbonate (PC) and ethylene carbonate (EC) are preferred.
When a mixed solvent combining ethylene carbonate (EC) as a cyclic carbonate and dimethyl carbonate (DMC) as a chain carbonate is used, the mixing ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) is not particularly limited and can be appropriately selected depending on the purpose.

Examples of the ester-based organic solvent include cyclic esters and chain esters.
Examples of cyclic esters include γ-butyrolactone (γBL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, γ-valerolactone, etc. Examples of chain esters include alkyl propionate, dialkyl malonate, alkyl acetate, alkyl formate, etc.
Examples of the alkyl acetate include methyl acetate (MA) and ethyl acetate.
Examples of the alkyl formate include methyl formate (MF) and ethyl formate.

Examples of the ether-based organic solvent include cyclic ethers and chain ethers.
Examples of the cyclic ether include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, and 1,4-dioxolane.
Examples of the chain ether include 1,2-dimethoxyethane (DME), ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, and tetraethylene glycol dialkyl ether.

-Electrolyte salt-
The electrolyte salt used in the non-aqueous electrolyte solution is preferably a lithium salt.
The lithium salt is not particularly limited as long as it dissolves in a non-aqueous solvent and exhibits high ionic conductivity, and can be appropriately selected according to the purpose, and examples thereof include lithium hexafluorophosphate (LiPF ₆ ), lithium perchlorate (LiClO ₄ ), lithium chloride (LiCl), lithium borofluoride (LiBF ₄ ), lithium arsenic hexafluoride (LiAsF ₆ ), lithium trifluoromethansulfonate (LiCF ₃ SO ₃ ), lithium bistrifluoromethanesulfonylimide (LiN(SO ₂ CF ₃ ) ₂ ), lithium bisperfluoroethylsulfonylimide (LiN(SO ₂ C ₂ F ₅ ) ₂ ), and lithium bisfluorosulfonylimide (LiN(SO ₂ F) ₂ ). These may be used alone or in combination of two or more. Among these, LiPF ₆ , LiBF ₄ and LiN(SO ₂ F) ₂ are preferred from the viewpoint of the amount of anions absorbed into the electrode.
The concentration of the electrolyte salt is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of achieving both discharge capacity and output, the concentration is preferably 1.0 mol/L or more and 6 mol/L or less, and more preferably 1.5 mol/L or more and 4 mol/L or less, in the nonaqueous solvent.

-Solid electrolyte-
Examples of solid electrolyte particles that can be used as the solid electrolyte include sulfide-based amorphous solid electrolyte particles, oxide-based amorphous solid electrolyte particles, and crystalline oxide particles.

(Method of manufacturing electrochemical device and apparatus for manufacturing electrochemical device)
The method for manufacturing an electrochemical device of the present invention includes an electrode manufacturing step of manufacturing an electrode by the above-mentioned electrode manufacturing method of the present invention, and an element fabrication step of manufacturing an electrochemical device using the electrode, and may further include other steps as necessary.
The electrochemical element manufacturing apparatus of the present invention has an electrode manufacturing section that manufactures electrodes using the above-mentioned electrode manufacturing apparatus of the present invention, and an element production section that manufactures electrochemical elements using the electrodes, and may further have other means as necessary.

<Electrode manufacturing process and electrode manufacturing department>
The electrode manufacturing process can be appropriately selected from the items described in the electrode manufacturing method of the present invention described above, and includes an adhesive porous insulating layer forming process, and further includes other processes such as an electrode processing process, as necessary.
The electrode manufacturing section can appropriately select the items described in the electrode manufacturing apparatus of the present invention described above, and has an adhesive porous insulating layer forming means, and further has other means such as an electrode processing means, if necessary.
The electrode manufacturing process and the electrode manufacturing unit can manufacture an electrode having an electrode substrate and an adhesive porous insulating layer on the electrode substrate. The electrode may be a laminated electrode having an electrolyte layer, or an electrolyte layer-integrated laminated electrode in which an electrode mixture layer provided on an electrode substrate and the porous resin are integrated.
The application process and application unit can be appropriately selected from the items described in the laminate manufacturing method and laminate manufacturing apparatus.
The polymerization treatment and the polymerization section can be appropriately selected from the items explained in the laminate production apparatus and the laminate production method.

<Device Formation Step and Device Formation Division>
The device fabrication step is a step of manufacturing an electrochemical device using the laminated battery.
The device production section is a means for producing an electrochemical device using the laminated battery.
The method for producing an electrochemical element using a battery is not particularly limited, and a publicly known method for producing an electrochemical element can be appropriately selected depending on the purpose. For example, a method for producing an energy storage element can be mentioned in which at least one of providing a counter electrode, rolling or stacking, and housing in a container is performed.
The element fabrication step does not need to include all steps of element fabrication, and may include only a part of the steps.

<Electrode processing step and electrode processing section>
The electrode processing unit processes the laminated electrode on which the resin layer is formed downstream of the application unit. The electrode processing unit may perform at least one of cutting, folding, and lamination. The laminated electrode processing unit can, for example, cut the laminated electrode on which the resin layer is formed to produce a laminate of laminated electrodes. The electrode processing unit can wind or stack the laminated electrode on which the resin layer is formed.
The electrode processing section has, for example, an electrode processing device, and cuts, folds, stacks, or winds the laminated electrode on which the porous resin layer is formed, according to the desired battery form.
The electrode processing step performed by the electrode processing unit is, for example, a step of processing a laminated electrode on which a resin layer has been formed downstream of the application step. The electrode processing step may include at least one of a cutting step, a folding step, and a bonding step.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

<Preparation of Liquid Composition for Forming Resin>
Liquid compositions 1 to 4 for forming resins 1 to 4 were prepared by mixing the materials in the ratios shown below.
--Preparation of Liquid Composition 1 for Forming Resin 1--
A liquid composition 1 for forming resin 1, which is another porous resin, was obtained by mixing 29.0 mass% of tricyclodecane dimethanol diacrylate (EBECRYL130, manufactured by Daicel Allnex Corporation) as a polymerizable compound, 70.0 mass% of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Industry Co., Ltd.) as a porogen, and 1.0 mass% of Irgacure 184 (manufactured by BASF Corporation) as a polymerization initiator.

--Preparation of Liquid Composition 2 for Forming Resin 2--
A liquid composition 2 for forming resin 2, which is an adhesive porous resin, was obtained by mixing 29.0 mass% of KAYARAD PEG400DA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 70.0 mass% of methyl decanoate (manufactured by Kanto Chemical Industry Co., Ltd.) as a porogen, and 1.0 mass% of Irgacure 819 (manufactured by BASF Corporation) as a polymerization initiator.

--Preparation of Liquid Composition 3 for Forming Resin 3--
A liquid composition 3 for forming resin 3, which is a comparative thermoplastic resin, was obtained by mixing 29.0 mass% of W#9100 (manufactured by Kureha Corporation) as a thermoplastic resin, 70.0 mass% of NMP (manufactured by Mitsubishi Chemical Corporation) as a solvent, and 1.0 mass% of Irgacure 819 (manufactured by BASF) as a polymerization initiator.

--Preparation of Liquid Composition 4 for Forming Resin 4--
A liquid composition 4 for forming a resin 4, which is an adhesive porous resin, was obtained by mixing 29.0 mass% of SR502 NS (ethoxylated (9) trimethylolpropane triacrylate, manufactured by SARTOMER) as a polymerizable compound, 70.0 mass% of methyl decanoate (manufactured by Kanto Chemical Industry Co., Ltd.) as a porogen, and 1.0 mass% of Irgacure 819 (manufactured by BASF Corporation) as a polymerization initiator.

<Preparation of Liquid Composition for Forming Inorganic Solid Layer>
A pre-dispersion in which materials were mixed in the ratios shown below was prepared, and then dispersed in the following manner to prepare a liquid composition for forming an inorganic solid layer.
--Liquid composition for forming inorganic solid layer--
A pre-dispersion was prepared by mixing 40.0 mass% of α-alumina (primary particle size (D50): 0.5 μm, specific surface area: 7.8 g/m ² ) as an inorganic solid, 58.0 mass% of a mixed solution of dimethyl sulfoxide and ethylene glycol (DMSO-EG, mass ratio: 3:4), and 2.0 mass% of Marialim HKM-150A (manufactured by NOF Corporation) as a dispersant. This pre-dispersion was placed in a container together with zirconia beads (Φ2 mm) and subjected to a dispersion treatment at 1,500 rpm for 3 minutes using a frozen nano-pulverizer NP-100 (manufactured by Thinky Corporation) to obtain a dispersion. The zirconia beads were removed from the obtained dispersion using a 25 μm mesh filter to prepare a liquid composition for forming an inorganic solid layer.

<Preparation of negative electrode>
- Preparation of negative electrode paint -
For forming a negative electrode composite layer, 97.0 mass % of graphite, 1.0 mass % of a thickener (carboxymethyl cellulose), 2.0 mass % of a polymer (styrene butadiene rubber), and 100.0 mass % of water as a solvent were mixed to prepare a negative electrode coating material.

- Preparation of the negative electrode -
As shown in Fig. 9, the negative electrode paint was applied to the entire surfaces of both sides of the copper foil substrate (the area of the first electrode mixture layer 9) and then dried to form a negative electrode mixture layer with a basis weight of 9.0 mg/ ^cm2 on one side. Next, the electrode was pressed with a roll press machine so that the deposition density of the electrode was 1.6 g/ ^cm3 to prepare a negative electrode. The average thickness of the negative electrode at this time was 112.0 µm.

<Preparation of Positive Electrode>
- Preparation of positive electrode paint -
A positive electrode coating material was prepared by dispersing 92.0 mass % of lithium nickel oxide (NCA) as the positive electrode active material, 3.0 mass % of acetylene black as the conductive material, and 5.0 mass % of polyvinylidene fluoride (PVDF) as the binder in N-methylpyrrolidone (NMP).

- Preparation of the positive electrode -
The positive electrode paint was applied to both sides of the aluminum foil substrate and then dried to obtain a positive electrode having a positive electrode composite layer with a weight per surface area of 15.0 mg/ ^cm2 on one side. Next, the electrode was pressed with a roll press machine so that the volume density of the electrode was 2.8 g/ ^cm3 to obtain a positive electrode. The average thickness of the positive electrode at this time was 132.0 μm.

Example 1
<Production of negative electrode laminate>
1 and 2, liquid composition 1 for resin 1 was filled into an inkjet discharger equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The discharge amount of liquid composition 1 was controlled for the negative electrode mixture layer of the negative electrode, and a coating region was formed so that the average thickness of the porous insulating layer 10a was 20.0 μm.
Immediately afterwards, the coating area was irradiated with UV light (light source: UV-LED (manufactured by _Phoseon , product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a N 2 atmosphere to harden the coating. Next, the cured product was heated at 130° C. for 1 minute using a hot plate to remove the porogen, and a porous insulating layer 10a was obtained.

Next, liquid composition 2 for resin 2 was filled into an inkjet discharger equipped with a GEN5 head, and liquid composition 2 was discharged into the region shown in adhesive porous insulating layer 10b as shown in Figures 1 and 2 to form a coating region with an average thickness of 100.0 µm. Immediately after that, the coating region was irradiated with _UV (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a N 2 atmosphere to cure. After curing, the cured product was heated at 130°C for 1 minute using a hot plate to remove the porogen, and adhesive porous insulating layer 10b was obtained.
As a result of the above, as shown in Figures 1 and 2, a negative electrode laminate of Example 1 was manufactured as a first electrode in which a porous insulating layer 10a was formed on the first electrode mixture layer 9 using resin 1, and an adhesive porous insulating layer 10b was formed on the three peripheral sides of the porous insulating layer 10a on the first electrode mixture layer 9 using resin 2.

<Preparation of electrochemical element>
3, a negative electrode as a first electrode having a porous insulating layer 10a and an adhesive porous insulating layer 10b formed thereon and a positive electrode as a second electrode were laminated facing each other, and the adhesive porous insulating layer 10b was thermally bonded at a temperature of 140° C. with an air cylinder thrust of 500 N for 1 s. After that, vacuum drying was performed at 150° C. to remove residual moisture.
Thereafter, an electrolyte solution was poured into the container, and the container was sealed using a laminate exterior material as an exterior, thereby producing the electrochemical element (electricity storage element) of Example 1.
As the electrolyte, a solution was used in which an electrolyte, LiPF ₆ , was added to a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (a mixture of EC:DMC = 1:1 (mass ratio)) so that the concentration was 1.5 mol/L.

<Evaluation>
The peel strength, flexibility, and ion permeability of the adhesive porous insulating layer were evaluated by the following procedures.

<<Measurement of peel strength of insulating layer>>
- Preparation of elements for measuring peel strength -
Two electrodes were prepared by applying the liquid composition 1 to the entire surface of one side of two electrodes measuring 30 mm x 100 mm and curing the liquid composition 1 to form an adhesive porous insulating layer 10b. The two electrodes were designated as test electrodes a and b. The two electrodes were then placed facing each other with the adhesive porous insulating layer 10b applied thereto, and thermally bonded together at a temperature of 140°C, an air cylinder thrust of 500 N, and for 1 second to prepare a "peel strength measurement element."
The thickness of the adhesive porous insulating layer 10b was evaluated at the thickness described in each of the examples and comparative examples.

- Peel strength measurement -
The surface of the electrode substrate of the test electrode a of the peel strength measuring element, which faces the surface on which the adhesive porous insulating layer is formed, was fixed to the sample fixing surface of the peel strength measuring device with a thin double-sided tape. Next, the surface of the electrode substrate of the test electrode b of the peel strength measuring element, which faces the surface on which the adhesive porous insulating layer is formed, was fixed to the tensile indenter of the peel strength measuring device with tape. The peel strength was measured under the measurement conditions shown below.

- Peel strength measurement conditions -
Peel strength measuring device: Versatile Peel Analyzer (manufactured by Kyowa Interface Science Co., Ltd.)
Thin double-sided tape: No. 5000NS (width 20 mm, manufactured by Nitto Denko Corporation)
Tape: No. 29 (width 18 mm, manufactured by Nitto Denko Corporation)
Measurement speed: 30 mm/min
Peel angle: 90°
Peeling distance: 75 mm

<<Evaluation of the flexibility of the insulating layer>>
An electrode prepared in the same manner as the test electrode a used in measuring the peel strength of the insulating layer was cut into a 100 mm square, and a bending test was carried out using a cylindrical mandrel bending tester (manufactured by Cortec Co., Ltd.) equipped with a cylindrical mandrel having a diameter of 4 mm. The insulating layer was then observed for the presence or absence of cracks before and after the bending test.
- Flexibility measurement conditions -
Test equipment name: Cylindrical mandrel bending tester stand (manufactured by Coatec Co., Ltd. and Allgood Co., Ltd.)
・Necessary jig: Mandrel rod, diameter 4 mm (same as above)

The presence or absence of cracks in the insulating layer was evaluated visually and using an optical microscope. Note that the fewer cracks in the insulating layer, the more excellent the bending properties.
[Evaluation criteria]
◯: No cracks in the insulating layer.
×: Cracks were found in the insulating layer.

<<Evaluation of ion permeability of insulating layer>>
The ion permeability of the insulating layer was evaluated by observing images using a scanning electron microscope (SEM) and measuring the porosity.
The adhesive porous insulating layer 10b was cut into a size of 5 mm x 10 mm and stained with osmium (VIII) tetroxide (manufactured by EM Corporation). Specifically, the cut adhesive porous insulating layer was placed in a bottle containing a small amount of the aqueous solution without touching the aqueous solution, and left to stand in the sealed bottle for 30 minutes for staining. The sample was then dried in a draft for 1 hour to obtain a stained sample.
After sufficient drying, the sample was vacuum-impregnated with a two-liquid mixed epoxy resin (manufactured by ITW Performance Polymers & Fluids Japan). Then, a cross section was cut out at 5.0 kV using a cross-section polisher (manufactured by JEOL Ltd.) and observed using a cryo-FIB/SEM (manufactured by Nippon FEI Co., Ltd.).
The observed image was binarized, and the ratio of the voids to the observed area was calculated to calculate the porosity of the adhesive porous insulating layer 11b. The ion permeability was evaluated based on the calculated porosity.
[Evaluation criteria]
○: Porosity less than 30% ×: Porosity 30% or more

Example 2
1 and 4, the liquid composition for resin 1 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The amount of the liquid composition ejected was controlled for the negative electrode mixture layer of the negative electrode, and a coating region was formed so that the porous insulating layer 11a had a film thickness of 20.0 μm.
Immediately afterwards, the coating area was irradiated with UV light (light source: UV-LED (manufactured by _Phoseon , product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a N 2 atmosphere to harden the coating. Next, the cured product was heated at 130° C. for 1 minute using a hot plate to remove the porogen, and a porous insulating layer 10a was obtained.

Next, the liquid composition for resin 2 was filled into an inkjet discharger equipped with a GEN5 head, and the liquid composition was discharged onto the porous insulating layer 11a on the negative electrode on which 20.0 μm of resin 1 was formed, forming a coating region with a film thickness of 65.0 μm in the region shown in the adhesive porous insulating layer 10b as shown in Figures 1 and _4. Thereafter, the coating region was immediately irradiated with UV (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in an N 2 atmosphere to cure. After curing, the cured product was heated at 130°C for 1 minute using a hot plate to remove the porogen, and an adhesive porous insulating layer 10b was obtained.
As a result, a negative electrode laminate of Example 2 was produced, in which the first electrode substrate 8, the first electrode mixture layer 9, the porous insulating layer 10a, and the adhesive porous insulating layer 10b were laminated in this order, as shown in Fig. 4. Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.
An electrochemical element of Example 2 was produced in the same manner as in Example 1, except that the negative electrode laminate of Example 2 was used.

Example 3
As shown in Figures 7 and 8, the liquid composition for resin 2 was filled into an inkjet discharger equipped with a GEN5 head, and the liquid composition was discharged onto the negative electrode active material in the region without the negative electrode film separator to form a pattern image-like coating region with a film thickness of 90.0 μm in the region shown in the adhesive porous insulating layer _10b . Thereafter, the coating region was immediately irradiated with UV (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in an N 2 atmosphere to cure. After curing, the cured product was heated at 130°C for 1 minute using a hot plate to remove the porogen, and the adhesive porous insulating layer 10b was obtained.
Subsequently, a separator made of a microporous polypropylene film (SETELA (F20BHE), manufactured by Toray Industries, Inc., thickness: 20 μm) was placed on the negative electrode active material in the region of the adhesive porous insulating layer 10b shown in FIGS.

Example 4
1 and 2, the liquid composition for resin 1 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The amount of the liquid composition ejected was controlled for the negative electrode mixture layer of the negative electrode, and a coating region was formed so that the porous insulating layer 10a had a film thickness of 20.0 μm.
Immediately afterwards, the coating area was irradiated with UV light (light source: UV-LED (manufactured by _Phoseon , product name: FJ800), wavelength: 362 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a N 2 atmosphere to harden the coating. Next, the cured product was heated at 130° C. for 1 minute using a hot plate to remove the porogen, and a porous insulating layer 10a was obtained.

Next, the liquid composition for resin 4 was filled into an inkjet discharger equipped with a GEN5 head, and the liquid composition was discharged onto the porous insulating layer 10a on the negative electrode on which 20.0 μm of resin 1 had been formed, forming a coating region with a film thickness of 65.0 μm in the region shown in the adhesive porous insulating layer 10b as shown in Figures 1 and _4. Thereafter, the coating region was immediately irradiated with UV (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 362 Nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in an N 2 atmosphere to cure. After curing, the cured product was heated at 130°C for 1 minute using a hot plate to remove the porogen, and an adhesive porous insulating layer 10b was obtained.
As a result, a negative electrode laminate of Example 4 was produced, in which the first electrode substrate 8, the first electrode mixture layer 9, the porous insulating layer 10a, and the adhesive porous insulating layer 10b were laminated in this order, as shown in Fig. 3. Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.
An electrochemical element of Example 4 was produced in the same manner as in Example 1, except that the negative electrode laminate of Example 4 was used.

(Comparative Example 1)
1 and 2, the liquid composition for resin 1 was filled into an inkjet discharger equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The discharge amount of the liquid composition was controlled relative to the negative electrode active material of the negative electrode, and a coating region was formed so that the porous insulating layer 10a had a film thickness of 20.0 μm.
Immediately afterwards, the coating area was irradiated with UV light (light source: UV-LED (manufactured by _Phoseon , product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a N 2 atmosphere to harden the coating. Next, the cured product was heated at 130° C. for 1 minute using a hot plate to remove the porogen, and a porous insulating layer 10a was obtained.

Next, the liquid composition for resin 3 was filled into an inkjet discharger equipped with a GEN5 head, and the liquid composition was discharged onto the negative electrode active material of the negative electrode to form a pattern image-like coating region in which the film thickness of the region shown in the adhesive porous insulating layer 10b was 85.0 μm as shown in Figures 1 and _2. Thereafter, the coating region was immediately irradiated with UV (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in an N 2 atmosphere to cure. After curing, the cured product was heated at 130°C for 1 minute using a hot plate to remove the solvent, and an adhesive porous insulating layer 10b made of resin 3 (thermoplastic resin) was obtained.
Since the adhesive porous insulating layer 10b is made of a thermoplastic resin, its porosity is lost due to the heating for removing the solvent.

(Comparative Example 2)
1 and 2, the liquid composition for resin 1 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The amount of the liquid composition ejected was controlled relative to the negative electrode active material of the negative electrode, and a coating region was formed so that the porous insulating layer 11a had a film thickness of 20.0 μm.
Immediately afterwards, the coating area was irradiated with UV light (light source: UV-LED (manufactured by _Phoseon , product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a N 2 atmosphere to harden the coating. Next, the cured product was heated at 130° C. for 1 minute using a hot plate to remove the porogen, and a porous insulating layer 10a was obtained.

Next, the liquid composition for inorganic solids was filled into an inkjet discharger equipped with a GEN5 head, and the liquid composition was discharged onto the negative electrode active material of the negative electrode to form a pattern image-like coating region in which the thickness of the region shown in the adhesive porous insulating layer 10b was 85.0 μm as shown in Figures 1 and _2. Thereafter, the coating region was immediately irradiated with UV (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in an N 2 atmosphere to cure. After curing, the cured product was heated at 130°C for 1 minute using a hot plate to remove the porogen, and an adhesive porous insulating layer 10b made of inorganic solids was obtained.

(Comparative Example 3)
1 and 2, the liquid composition for resin 1 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The amount of the liquid composition ejected was controlled relative to the negative electrode active material of the negative electrode, and a coating region was formed so that the porous insulating layer 11a had a film thickness of 20.0 μm.
Immediately afterwards, the coating area was irradiated with UV light (light source: UV-LED (manufactured by _Phoseon , product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a N 2 atmosphere to harden the coating. Next, the cured product was heated at 130° C. for 1 minute using a hot plate to remove the porogen, and a porous insulating layer 10a was obtained.

Next, the liquid composition for resin 1 was discharged onto the negative electrode active material of the negative electrode to form a pattern image-like coating region in which the thickness of the region shown in the adhesive porous insulating layer 10b was 85.0 μm as shown in FIG. ₁ and FIG. 2. Thereafter, the coating region was immediately irradiated with UV light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW/cm ² , irradiation time: 20 s) in a N 2 atmosphere to cure. After curing, the cured product was heated at 130° C. for 1 minute using a hot plate to remove the porogen, and an adhesive porous insulating layer 10b made of resin 1 was obtained. The glass transition point (Tg) of resin 1 was 190° C.

The results are shown in Table 1.
In the case of Comparative Example 3, when a material with strong cross-linking or a resin with high Tg (Resin 1) is used as the insulating layer 10b for bonding the negative electrode composite layers, such a resin lacks elasticity, and therefore the strength of the insulating layer is high but the flexibility is poor. In Comparative Example 2, in which an inorganic solid layer is used, the flexibility of the insulating layer 10b is also poor. In Comparative Example 1, in which a thermoplastic resin (Resin 3) is used, the chain molecular structure melts when heat is applied, and the porosity is crushed, so that the ion permeability is almost lost.
On the other hand, in Examples 1 to 4, it was found that by using a substrate and an adhesive porous insulating layer provided on the substrate and having a peel strength of 2 N/m or more, the flexibility and ion permeability of the insulating layer are excellent, the occurrence of electrode lamination misalignment can be reduced, and an electrochemical element with excellent battery characteristics can be produced.

For example, aspects of the present invention are as follows.
<1> A substrate,
an adhesive porous insulating layer provided on the substrate;
the adhesive porous insulating layer is a porous structure having a bicontinuous structure with a resin skeleton,
The resin is a crosslinked resin,
The adhesive porous insulating layer is provided on one entire surface of each of two substrates measuring 30 mm x 100 mm, and the adhesive porous insulating layers are placed facing each other. When a peel strength measurement element is used, the peel strength measurement element is thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second, and the peel strength is 2 N/m or more as measured by a peel measurement method.
<2> The article for providing a porous insulating layer for adhesion of an electrochemical element member according to <1>, wherein the resin is a polymer of a polymerizable compound that can be polymerized by energy irradiation.
<3> The material for imparting a porous insulating layer for adhesion to an electrochemical element member according to <2>, wherein the polymerizable compound has a (meth)acryloyl group.
<4> An article for providing an adhesive porous insulating layer for an electrochemical element member according to any one of <1> to <3>,
and another substrate bonded via at least a portion of the adhesive porous insulating layer.
<5> The electrochemical element member according to any one of <1> to <3>, comprising an adhesive porous insulating layer-imparted product,
The substrate has an electrode substrate,
The electrode is characterized by having the adhesive porous insulating layer as the outermost layer.
<6> An electrochemical element including a first electrode and a second electrode insulated from the first electrode, the first electrode and the second electrode being stacked,
The electrochemical element is characterized in that at least one of the first electrode and the second electrode is the electrode described in <5> above.
<7> The electrochemical element according to <6>, wherein at least a portion of the adhesive porous insulating layer is adhered to a surface of another substrate.
<8> The electrochemical element according to any one of <6> to <7>, wherein the first electrode is disposed on an outer side of the second electrode and is adhered to the second electrode via the adhesive porous insulating layer.
<9> The electrochemical element according to any one of <6> to <8>, which is a lithium ion secondary battery.
<10> A first substrate;
A second substrate,
the first substrate having a first adhesive porous insulating layer;
the first substrate and the second substrate are bonded via the first adhesive porous insulating layer;
the first adhesive porous insulating layer is a porous structure having a bicontinuous structure with a resin skeleton;
The resin is a crosslinked resin,
The laminate is characterized in that the first adhesive porous insulating layer is provided on one entire surface of the first substrate measuring 30 mm x 100 mm, and on one entire surface of the second substrate measuring 30 mm x 100 mm, and the first adhesive porous insulating layers are arranged facing each other, and the peel strength measured using a peel strength measuring element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second is 2 N/m or more.
<11> The second base material has a second adhesive porous insulating layer,
The laminate described in <10> above, wherein the first base material and the second base material are laminated so that the first adhesive porous insulating layer and the second adhesive porous insulating layer face each other.
<12> The first substrate is an electrode,
The laminate according to any one of <10> to <11>, wherein the second base material is a film separator.
<13> The first substrate is an electrode,
The laminate according to any one of <10> to <11>, wherein the second base material is an electrode.
<14> The laminate according to any one of <10> to <13>, wherein the first adhesive porous insulating layer has a binder content of 0 mass % or more and 30 mass % or less.
<15> An adhesive porous insulating layer forming step of forming a first adhesive porous insulating layer on a first base material;
a lamination step of laminating the first base material on which the first adhesive porous insulating layer is formed and a second base material such that the first adhesive porous insulating layer and the second base material face each other;
a bonding step of bonding the laminated first base material and second base material together via the first adhesive porous insulating layer;
having
the first adhesive porous insulating layer is a porous structure having a bicontinuous structure with a resin skeleton;
The resin is a crosslinked resin,
This is a method for producing a laminate, characterized in that the first adhesive porous insulating layer is provided on one entire surface of the first substrate measuring 30 mm x 100 mm, and on one entire surface of the second substrate measuring 30 mm x 100 mm, the first adhesive porous insulating layers are arranged facing each other, and the peel strength measured using a peel strength measuring element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second is 2 N/m or more.
<16> A laminate according to any one of <10> to <13>,
the first substrate has an electrode substrate;
The electrochemical device is characterized in that the second substrate has an electrode substrate.
<17> An adhesive porous insulating layer forming step of forming an adhesive porous insulating layer on a substrate having an electrode substrate,
The adhesive porous insulating layer is a porous structure having a bicontinuous structure with a resin skeleton,
The resin is a crosslinked resin,
This is a method for manufacturing an electrode, characterized in that the adhesive porous insulating layer is provided on the entire surface of one side of each of two substrates measuring 30 mm x 100 mm, the adhesive porous insulating layers are placed facing each other, and the peel strength of the adhesive porous insulating layer is 2 N/m or more when measured using a peel strength measuring element that is thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second.
<18> An electrode manufacturing process for manufacturing an electrode by the electrode manufacturing method according to <17>;
and a device forming step of manufacturing an electrochemical device using the electrode.

The porous insulating layer-added material for adhesion of the electrochemical element member described in any one of <1> to <3>, the laminate described in any one of <4> and <10> to <14>, the electrode described in <5>, the electrochemical element described in any one of <6> to <9> and <16>, the method for manufacturing the laminate described in <15>, the method for manufacturing the electrode described in <17>, and the method for manufacturing the electrochemical element described in <18> can solve the above-mentioned problems in the past and achieve the object of the present invention.

Description of the Reference Numerals 1a: Inkjet device 1b: Ink container 1c: Ink supply tube 2a: Light irradiation device 2b: Polymerizable inert gas flow device 3a: Heating device 4: First electrode 5: Transport unit 6: Porous film precursor 7: Liquid composition 8: First electrode substrate 9: First electrode mixture layer 10a: Porous insulating layer 10b: Adhesive porous insulating layer 11: Second electrode substrate 12: Second electrode mixture layer 13: Sheet separator 100: Printing unit (adhesive porous insulating layer liquid application means)
100': Additional printing unit (porous insulating layer liquid application unit)
200: Polymerization section 300: Removal section 500: Apparatus for manufacturing adhesive porous insulating layer

JP 2016-33930 A International Publication No. 2013-002138

Claims (18)

A substrate;
an adhesive porous insulating layer provided on the substrate;
the adhesive porous insulating layer is a porous structure having a bicontinuous structure with a resin skeleton,
The resin is a crosslinked resin,
The adhesive porous insulating layer is provided on the entire surface of one side of each of two substrates measuring 30 mm x 100 mm, and the adhesive porous insulating layers are placed facing each other. When a peel strength measurement element is used, the peel strength measurement element is thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second, and the peel strength is 2 N/m or more as measured by a peel measurement method. The porous insulating layer-imparting material for bonding electrochemical element members according to claim 1, wherein the resin is a polymer of a polymerizable compound that can be polymerized by energy irradiation. The porous insulating layer for adhesion of electrochemical element members according to claim 2, wherein the polymerizable compound has a (meth)acryloyl group. The electrochemical element member according to claim 1 ,
and another substrate bonded via at least a portion of the adhesive porous insulating layer. The electrochemical element member according to claim 1 has a porous insulating layer for adhesion,
The substrate has an electrode substrate,
An electrode comprising the adhesive porous insulating layer as described above as an outermost layer. An electrochemical element including a first electrode and a second electrode insulated from the first electrode, the first electrode and the second electrode being stacked,
6. An electrochemical element, wherein at least one of the first electrode and the second electrode is the electrode according to claim 5. The electrochemical element according to claim 6, wherein at least a portion of the adhesive porous insulating layer is adhered to the surface of another substrate. The electrochemical element according to claim 6, wherein the first electrode is disposed outside the second electrode and is adhered to the second electrode via the adhesive porous insulating layer. The electrochemical element according to any one of claims 6 to 8, which is a lithium ion secondary battery. A first substrate;
A second substrate,
the first substrate having a first adhesive porous insulating layer;
the first substrate and the second substrate are bonded via the first adhesive porous insulating layer;
the first adhesive porous insulating layer is a porous structure having a bicontinuous structure with a resin skeleton;
The resin is a crosslinked resin,
A laminate characterized in that the first adhesive porous insulating layer is provided on one entire surface of the first substrate measuring 30 mm x 100 mm, and on one entire surface of the second substrate measuring 30 mm x 100 mm, and the first adhesive porous insulating layers are arranged facing each other, and the peel strength measured using a peel strength measuring element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second is 2 N/m or more. the second substrate having a second adhesive porous insulating layer;
The laminate according to claim 10 , wherein the first substrate and the second substrate are laminated such that the first adhesive porous insulating layer and the second adhesive porous insulating layer face each other. the first substrate is an electrode,
The laminate of claim 10 , wherein the second substrate is a film separator. the first substrate is an electrode,
The laminate according to claim 10 , wherein the second substrate is an electrode. The laminate according to claim 10, wherein the binder content in the first adhesive porous insulating layer is 0% by mass or more and 30% by mass or less. an adhesive porous insulating layer forming step of forming a first adhesive porous insulating layer on a first substrate;
a lamination step of laminating the first base material on which the first adhesive porous insulating layer is formed and a second base material such that the first adhesive porous insulating layer and the second base material face each other;
a bonding step of bonding the laminated first base material and second base material together via the first adhesive porous insulating layer;
having
the first adhesive porous insulating layer is a porous structure having a bicontinuous structure with a resin skeleton;
The resin is a crosslinked resin,
A method for producing a laminate, characterized in that the first adhesive porous insulating layer is provided on one entire surface of the first substrate measuring 30 mm x 100 mm, and on one entire surface of the second substrate measuring 30 mm x 100 mm, the first adhesive porous insulating layers are faced to each other, and the peel strength measured using a peel strength measuring element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second is 2 N/m or more. The laminate according to claim 10,
the first substrate has an electrode substrate;
An electrochemical device, wherein the second substrate has an electrode substrate. An adhesive porous insulating layer forming step of forming an adhesive porous insulating layer on a substrate having an electrode substrate,
the adhesive porous insulating layer is a porous structure having a bicontinuous structure with a resin skeleton,
The resin is a crosslinked resin,
A method for manufacturing an electrode, characterized in that the adhesive porous insulating layer is provided over the entire surface of one side of each of two substrates measuring 30 mm x 100 mm, the adhesive porous insulating layers are placed facing each other, and the peel strength of the adhesive porous insulating layer is 2 N/m or more when measured using a peel strength measuring element thermally bonded under conditions of a temperature of 140°C, an air cylinder thrust of 500 N, and a time of 1 second. An electrode manufacturing process for manufacturing an electrode by the electrode manufacturing method according to claim 17;
and producing an electrochemical element using the electrode.