KR20250033137A - Film-type adhesive with dicing film, electronic component using the same, and method for manufacturing the same - Google Patents

Abstract

A film-type adhesive having a dicing film having a substrate and an adhesive layer, and a film-type adhesive disposed on the adhesive layer, wherein a storage elastic modulus E1 (MPa) of the film-type adhesive at 60°C and a storage elastic modulus E2 (MPa) of the dicing film at 60°C satisfy E1×E2≥7.0, and a cured product of the film-type adhesive has a light transmittance of 60% or more.

Description

Film-type adhesive with dicing film, electronic component using the same, and method for manufacturing the same

The present invention relates to a film-type adhesive having a dicing film, an electronic component using the same, and a method for manufacturing the same.

Digital still cameras and digital video cameras, etc., have built-in image sensors (imaging elements) such as CMOS (Complementary Metal Oxide Semiconductor) image sensors and CCD (Charge Coupled Device) image sensors. The image sensor converts incident light into an electric signal by photoelectric conversion using a photodiode, and a digital image is formed through signal processing. Color filters, micro lenses, etc. are arranged on the surface of the photodiode as necessary, and a transparent protective film such as a glass plate is usually arranged on the surface. Such transparent protective films are fixed using a film-type adhesive, etc. The adhesive used to adhere and fix the transparent protective film of the image sensor is required to have transparency that sufficiently transmits light at least after the curing reaction.

Film-type adhesives themselves are known to come in various compositions and are widely used not only in image sensors but also in the manufacture of electronic devices and their components. For example, in the manufacturing process of semiconductor chips, film-type adhesives are used as die-attach films.

It has been proposed to use a film-like adhesive that exhibits sufficiently high transparency at least after a curing reaction as a laminated structure with a dicing film (a film-like adhesive with a dicing film), in the manufacture of electronic components. For example, Patent Document 1 describes a method for manufacturing an electronic component, including a first step of obtaining a laminated structure in which a transparent film-like member, a film-like adhesive that exhibits sufficiently high transparency after a curing reaction, and a dicing film are laminated in this order, a second step of integrally dicing the transparent film-like member and the film-like adhesive to obtain a transparent film-like chip with an adhesive layer on the dicing film, a third step of removing the dicing film from the adhesive layer and thermally compressing the transparent film-like chip with an adhesive layer and another member constituting the electronic component via the adhesive layer, and a fourth step of thermally curing the adhesive layer. As the transparent film-type member, a glass substrate or transparent resin can be exemplified, and a transparent film-type chip with an adhesive layer obtained by dicing the transparent film-type member into a desired shape as described above can be embedded in an electronic component through a cured product of the adhesive layer, for example, as a protective film for a photodiode.

In addition, the above-described dicing film-attached film-type adhesive can also be used as a dicing die attach film for dicing a semiconductor wafer and providing an adhesive to semiconductor chips divided into pieces by dicing in a semiconductor chip manufacturing process.

International Publication No. 2023/026584

In the above-mentioned dicing process, there is a possibility that chips broken up by dicing may not occur infrequently, in which the chips are separated from the film-type adhesive during dicing (chip dropout). The inventor of the present invention has conducted repeated studies and found that when the amount of fine particle additives such as fillers is reduced in order to increase the transparency of the film-type adhesive, chip dropout in the dicing process becomes more likely to occur.

The present invention aims to provide a film-type adhesive having a dicing film, which exhibits sufficiently high transparency at least after a curing reaction and can effectively suppress chip detachment in a dicing process. The present invention also aims to provide a method for manufacturing an electronic component using the film-type adhesive having the dicing film.

The above-mentioned problem of the present invention is solved by the following means.

[1]

A dicing film having a substrate and an adhesive layer, and a film-type adhesive placed on the adhesive layer,

The storage elastic modulus E1 (MPa) of the film-type adhesive at 60°C and the storage elastic modulus E2 (MPa) of the dicing film at 60°C satisfy E1×E2≥7.0,

A film-type adhesive having a dicing film, wherein the light transmittance of the cured product of the film-type adhesive is 60% or more.

[2]

A film-type adhesive with a dicing film as described in [1], wherein the film-type adhesive contains an epoxy resin and a phenoxy resin.

[3]

A film-type adhesive with a dicing film as described in [1] or [2], wherein the film-type adhesive contains a filler, and the content of the filler is 10 mass% or less of the total solid content of the film-type adhesive.

[4]

A film-type adhesive with a dicing film as described in [3], wherein the average particle size (d50) of the filler is 500 nm or less.

[5]

A film-type adhesive with a dicing film according to any one of [1] to [4], wherein the film-type adhesive contains a curing agent, and the curing agent is a thermal cationic polymerization initiator.

[6]

A film-type adhesive having a dicing film as described in any one of [1] to [5], wherein E1 is 0.1 to 1.0 MPa and E2 is 10 to 70 MPa.

[7]

A method for manufacturing electronic components,

A first step for obtaining a laminate in which a transparent film-type member and a film-type adhesive with a dicing film described in any one of [1] to [6] are laminated in this order,

A second process of obtaining a transparent film-type chip with an adhesive layer on the dicing film by integrally dicing the transparent film-type member and the film-type adhesive;

A third process of removing the dicing film from the adhesive layer and thermally compressing a transparent film-type chip and other components forming an electronic component with the adhesive layer attached thereto through the adhesive layer;

The fourth process of heat-curing the above adhesive layer

A method for manufacturing an electronic component comprising:

[8]

A method for manufacturing an electronic component as described in [7], wherein the electronic component is an image sensor.

[9]

A method for manufacturing an electronic component as described in [8], wherein the electronic component has a structure in which the transparent film-type chip is embedded as a protective film for a photodiode.

In the present invention, the numerical range indicated using “to” means a range that includes the numerical values described before and after “to” as the lower limit and the upper limit.

In the present invention, the term "∼compound" means "a compound having ∼ skeleton." For example, the term "dicyandiamide compound" includes not only dicyandiamide itself but also a form in which at least a portion of the hydrogen atoms of dicyandiamide are substituted.

The film-type adhesive having a dicing film of the present invention exhibits sufficiently high transparency at least after a curing reaction, and can effectively suppress chip detachment when applied to a dicing process. In addition, according to the method for manufacturing an electronic component of the present invention, chip detachment of a transparent film-type chip obtained in a dicing process can be effectively suppressed, and as a result, an electronic component having a transparent film-type chip built into it can be obtained with high productivity through a transparent cured product of the film-type adhesive.

Figure 1 is a cross-sectional view schematically illustrating the structure of a film-type adhesive with a peeling film prepared in an embodiment.

The film-type adhesive having a dicing film of the present invention has a dicing film having a base material and an adhesive layer, and a film-type adhesive arranged on the adhesive layer. Furthermore, the storage elastic modulus E1 (MPa) of the film-type adhesive at 60°C and the storage elastic modulus E2 (MPa) of the dicing film at 60°C satisfy E1×E2≥7.0, and the light transmittance after curing of the film-type adhesive is 60% or more.

Since the storage moduli E1 and E2 satisfy the above relationship, even when the film-type adhesive with the dicing film of the present invention is locally heated (can be heated to about 60°C) by the frictional heat of the blade during dicing, the rigidity of the entire film-type adhesive with the dicing film of the present invention is secured, so that chip drop-off can be effectively suppressed, and further, since it exhibits high transparency after the curing reaction, it exhibits excellent optical properties as an adhesive when embedding a transparent film-type member into electronic components, etc. In order to control the storage modulus of the entire dicing film and film-type adhesive, it is thought that even when a film-type adhesive layer with a relatively small storage modulus is used by reducing the blending amount of the fine particle additive, the storage modulus of the entire dicing film is appropriately controlled, so that vibration, etc. during dicing can be suppressed.

In the present invention, the storage elastic modulus E1 (MPa) of the film-shaped adhesive at 60°C and the storage elastic modulus E2 (MPa) of the dicing film at 60°C are, from the viewpoint of suppressing chip dropout, preferably E1 × E2 ≥ 10.0, more preferably E1 × E2 ≥ 11.0, still more preferably E1 × E2 ≥ 12.0, and particularly preferably E1 × E2 ≥ 15.0. The upper limit is not particularly limited, and usually 50.0 ≥ E1 × E2, and 40.0 ≥ E1 × E2 is practical. Therefore, 50.0≥E1×E2≥7.0 is preferable, 50.0≥E1×E2≥10.0 is more preferable, 50.0≥E1×E2≥11.0 is further preferable, 50.0≥E1×E2≥12.0 is still more preferable, and 40.0≥E1×E2≥15.0 is particularly preferable.

The storage elastic modulus E1 of the above film-type adhesive at 60°C is not particularly limited as long as the relationship between E1 and E2 is satisfied. E1 is preferably 0.1 to 1.5 MPa, more preferably 0.1 to 1.0 MPa, still more preferably 0.2 to 1.0 MPa, still more preferably 0.3 to 0.9 MPa, and still more preferably 0.3 to 0.8 MPa.

The storage elastic modulus E2 of the above dicing film at 60°C is not particularly limited as long as the relationship between E1 and E2 is satisfied. E2 is preferably 10 to 80 MPa, more preferably 10 to 70 MPa, still more preferably 20 to 70 MPa, still more preferably 25 to 60 MPa, and still more preferably 30 to 50 MPa.

The storage elastic modulus E1 at 60°C of the above film-type adhesive can be controlled by the type and content of components (resin, curing agent, filler, etc.) constituting the film-type adhesive.

The storage elastic modulus E2 of the above-mentioned dicing film at 60°C can be controlled by the types and contents of the components constituting the dicing film (resin constituting the adhesive layer and the substrate), the thickness of the adhesive layer and the substrate, etc. Normally, since the substrate has a thicker thickness than the adhesive layer, E2 tends to be greatly affected by the characteristics of the substrate. From this viewpoint, the storage elastic modulus E3 of the substrate of the dicing film at 60°C is preferably 10 to 80 MPa, more preferably 10 to 70 MPa, still more preferably 20 to 70 MPa, still more preferably 30 to 60 MPa, and still more preferably 30 to 50 MPa.

The storage elastic modulus E1 of the film-type adhesive at 60°C and the storage elastic modulus E2 of the dicing film at 60°C can each be determined by the method described in the Examples. In addition, the storage elastic modulus E3 of the substrate at 60°C can also be determined in accordance with the method for determining the storage elastic modulus E2 of the dicing film at 60°C.

The film-type adhesive constituting the film-type adhesive including the dicing film of the present invention has a light transmittance of 60% or more after curing. Since the light transmittance after curing is 60% or more, transparency can be secured after curing, and optical properties suitable for bonding transparent film-type members, etc. can be exhibited. Here, in the present invention, "a light transmittance of 60% or more" means that the light transmittance at a wavelength of 400 nm is 60% or more. The light transmittance at a wavelength of 400 nm represents the light transmittance at wavelengths in all visible light ranges.

The term "cured film adhesive" means a cured product obtained by treating a film adhesive at 150°C for 1 hour and curing it. In addition, in the present invention or the specification, when simply referring to a "film adhesive" in the description of the properties of a film adhesive, it means a film adhesive before heat curing. Specifically, it means a film adhesive that is not exposed to a temperature higher than the temperature at which an epoxy resin is heat cured after the film adhesive is prepared. Preferably, it is a film adhesive that is not exposed under a temperature condition of 25°C or higher after the film adhesive is prepared. In addition, the above description is intended to clarify the properties of the film adhesive, and the film adhesive with a dicing film of the present invention is not limited to a film adhesive that is not exposed under a temperature condition of 25°C or higher.

The light transmittance of the cured product of the above film-type adhesive is preferably 70% or more, more preferably 80% or more, and more preferably 85% or more. The light transmittance of the cured product of the above film-type adhesive is preferably 70 to 95%, more preferably 80 to 92%, and more preferably 85 to 90%.

The light transmittance of the cured product of the above film-type adhesive is determined by the method described in the examples.

The light transmittance of the cured product of the above film-type adhesive can be controlled by the type and content of the components (resin, curing agent, filler, etc.) of the film-type adhesive. The filler can affect the light transmittance not only by the content but also by its particle size.

The transparency of the film-type adhesive before curing is not limited, and may be transparent or opaque. Accordingly, the light transmittance of the film-type adhesive before curing at a wavelength of 400 nm may be 60% or more, or may be less than 60%.

Below, the film-type adhesive with a dicing film of the present invention is described in more detail.

＜Dicing Film＞

The dicing film constituting the film-type adhesive having the dicing film of the present invention has a substrate and an adhesive layer.

The substrate and adhesive layers are not particularly limited in material or composition, as long as they satisfy E1 and E2 when laminated to form a dicing film and then combined with a film-type adhesive.

-Material-

The substrate can be composed of various resin materials. Among them, it is preferable to be composed of a resin material selected from polyolefin resin and polyvinyl chloride resin. It is also preferable that these resin materials have a crosslinked structure. The bond contributing to the formation of the crosslinked structure may be a covalent bond, a bond based on ionic interaction, or a hydrogen bond.

Examples of the above polyolefin resin include resins of homopolymers or copolymers of α-olefins, or mixtures thereof, such as polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid alkyl ester copolymer (ethylene-ethyl acrylic acid copolymer, ethylene-methyl acrylic acid copolymer, ethylene-methyl methacrylate copolymer, etc.), ethylene-(meth)acrylic acid copolymer, and ionomer resins.

In particular, an ionomer resin, which is a synthetic resin that aggregates polymers by utilizing the cohesive force of metal ions, is preferable, and examples thereof include an ionomer resin crosslinked with a metal ion, such as an ethylene-(meth)acrylic acid binary copolymer or an ethylene-(meth)acrylic acid-(meth)acrylic acid alkyl ester terpolymer. These are suitable for an expand process in terms of uniform expandability. The metal ion contained in the ionomer resin is not particularly limited, and examples thereof include zinc ion, sodium ion, and the like. Zinc ion is preferable in terms of low solubility and low contamination.

In general, ionomer resins have greater tensile resilience than resins without metal ions, and have greater shrinkage stress when heat is applied to the stretched state after the expanding process. Therefore, ionomer resins are preferable in that they can be used in a heat shrink process that removes slack in the tape after the expanding process by heat shrinkage and stably maintains the gap between individual wafer chips by tensioning the tape.

In addition, in addition to the above ionomer resin, a thermoplastic cross-linked resin cross-linked with a resin selected from low-density polyethylene having a specific gravity of 0.910 or more and less than 0.930, ultra-low-density polyethylene having a specific gravity of less than 0.910, and an ethylene-vinyl acetate copolymer is also suitable.

As a crosslinking method, a method of irradiating the resin with energy rays such as electron rays can be exemplified. Such a thermoplastic crosslinked resin has a certain uniform expandability since crosslinked portions and non-crosslinked portions coexist in the resin. In addition, such a thermoplastic crosslinked resin contains almost no chlorine atoms in the composition of the molecular chain, so even if the tape that has become unnecessary after use is incinerated, it does not generate chlorinated aromatic hydrocarbons such as dioxin or its analogues, and the environmental load is also small. By appropriately adjusting the amount of energy rays irradiated to the polyethylene or ethylene-vinyl acetate copolymer, it is possible to obtain a resin having sufficient uniform expandability.

The substrate may be single-layer or multi-layer.

The material is preferably an ionomer resin of an ethylene-(meth)acrylic acid copolymer.

There is no particular limitation on the thickness of the substrate, but a thickness of 50 to 200 ㎛ is preferable, 60 to 160 ㎛ is more preferable, and 70 to 150 ㎛ is still more preferable.

-Adhesive layer-

The adhesive layer constituting the adhesive tape of the present invention is not particularly limited as long as it has a property of maintaining the integrity of the laminate of the transparent film-type member (adherent) and the film-type adhesive described later so as not to cause peeling during the dicing process, and a property of allowing peeling from the transparent film-type chip with adhesive attached during pick-up.

The adhesive constituting the adhesive layer is not particularly limited as long as it exhibits the above characteristics, and general adhesives used for dicing film purposes, such as acrylic adhesives and rubber adhesives, can be appropriately used. Among these, an energy-ray-curable adhesive is preferable. If it is an energy-ray-curable adhesive, pickup becomes easy by curing it before the pickup process. Here, the energy ray refers to light such as ultraviolet rays or ionizing radiation such as electron beams.

As the adhesive constituting the adhesive layer, a common adhesive used as an adhesive for adhesive tapes for dicing can be used without particular limitation. As for the components, properties, and manufacturing methods of the adhesive, reference can be made to, for example, the descriptions in paragraphs [0039] to [0076] of Japanese Patent No. 6928852, paragraphs [0033] to [0052] of Japanese Patent No. 6989561, paragraphs [0031] to [0057] of Japanese Unexamined Patent Publication No. 2023-13022, etc.

The adhesive constituting the adhesive layer is preferably an acrylic adhesive containing a (meth)acrylic resin as a base polymer, and more preferably an acrylic adhesive containing at least one of a (meth)acrylic acid alkyl ester and (meth)acrylic acid as a constituent component. The (meth)acrylic acid alkyl ester preferably has a radiation-curable group introduced into a side chain, and more preferably has a (meth)acrylic acid ester having an isocyanate group added thereto. The adhesive may further contain a radiation-curable oligomer, and for example, may contain a urethane (meth)acrylate oligomer or the like.

The adhesive layer may contain a curing agent. Examples of the curing agent include polyisocyanate compounds.

Additionally, the adhesive layer may contain a photopolymerization initiator.

There is no particular limitation on the thickness of the adhesive layer, but a thickness of 2 to 35 ㎛ is preferable, 5 to 30 ㎛ is more preferable, and 5 to 20 ㎛ is still more preferable.

＜Film type adhesive＞

A film-type adhesive constituting the film-type adhesive including the dicing film of the present invention is described.

A film-type adhesive can be used if it satisfies E1 and E2 above when combined with a dicing film, and further, the light transmittance of the cured product of the film-type adhesive is 60% or higher.

The film-type adhesive preferably contains an epoxy resin and a polymer component, more preferably contains an epoxy resin and a urethane resin, or an epoxy resin and a phenoxy resin, and even more preferably contains an epoxy resin and a phenoxy resin.

The film-type adhesive may contain a filler. However, from the viewpoint of increasing light transmittance, when the film-type adhesive contains a filler, the content of the filler is preferably 30 mass% or less of the total solid content of the film-type adhesive, more preferably 20 mass% or less, still more preferably 10 mass% or less, and still more preferably 5 mass% or less.

Film adhesives usually contain a hardener.

In a preferred embodiment of the present invention, the film-type adhesive preferably contains an epoxy resin, a polymer component, and a curing agent. In this case, as described above, a filler may be contained. Each component is described below.

-Epoxy resin-

The above epoxy resin is a thermosetting resin having an epoxy group, and has an epoxy equivalent of 1000 g/eq or less. The epoxy resin may be a liquid, a solid, or a semi-solid. In the present invention, a liquid means one having a softening point of less than 25°C, a solid means one having a softening point of 60°C or more, and a semi-solid means one having a softening point between the softening point of the liquid and the softening point of the solid (25°C or more and less than 60°C). The epoxy resin used in the present invention preferably has a softening point of 100°C or less from the viewpoint of obtaining a film-type adhesive capable of reaching a low melting viscosity in a suitable temperature range (for example, 60 to 120°C). In addition, in the present invention, the softening point is a value measured by a softening point test (ring and ball type) method (measurement conditions: based on JIS-K7234, 1986).

In the epoxy resin used in the present invention, from the viewpoint of increasing the crosslinking density of the thermosetting body, the epoxy equivalent is preferably 150 to 800 g/eq. In addition, in the present invention, the epoxy equivalent refers to the number of grams (g/eq) of the resin containing 1 gram equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is usually preferably less than 10,000, more preferably less than 5,000. There is no particular restriction on the lower limit, but 300 or more is practical.

The weight average molecular weight is a value obtained through GPC (Gel Permeation Chromatography) analysis.

As the epoxy resin skeleton, there may be mentioned, for example, phenol novolac type, orthocresol novolac type, cresol novolac type, dicyclopentadiene type, biphenyl type, fluorenebisphenol type, triazine type, naphthol type, naphthalenediol type, triphenylmethane type, tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, and trimethylolmethane type. Among these, from the viewpoint of obtaining a film-shaped adhesive having low resin crystallinity and good appearance, triphenylmethane type, bisphenol A type, cresol novolac type, or orthocresol novolac type is preferable. These may be used singly or in combination of two or more, and a combination of triphenylmethane type and bisphenol A type is preferable.

The content of the epoxy resin is preferably 25 to 80 parts by mass, more preferably 30 to 80 parts by mass, still more preferably 30 to 70 parts by mass, and still more preferably 40 to 70 parts by mass, based on 100 parts by mass of the total content of the components constituting the film-type adhesive (specifically, components other than the solvent, i.e., the solid content). By setting the content within the above preferred range, the preservation stability and transparency can be improved. In addition, by setting it to be equal to or lower than the above preferred upper limit, the production of an oligomer component can be suppressed, and it can be made difficult for a change in the film state (film tackiness, etc.) to occur with a slight temperature change.

The content of the epoxy resin is preferably 30 to 70 parts by mass, more preferably 30 to 60 parts by mass, based on 100 parts by mass of the total content of the epoxy resin and the polymer component.

-Polymer components-

As the above polymer component, any component that suppresses the film tackiness (a property in which the film state is likely to change even with a slight temperature change) at room temperature (25°C) when forming a film-type adhesive and provides sufficient adhesiveness and film-forming properties (film-forming properties) may be used. Examples thereof include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resins such as 6-nylon or 6,6-nylon, phenoxy resin, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamideimide resin, fluorine resin, polyurethane resin, etc. These polymer components may be used alone or in combination of two or more. Examples of the polymer components include phenoxy resin and polyurethane. At least one type of resin is preferred.

The weight average molecular weight of the polymer component is 10,000 or more. There is no specific upper limit, but 5,000,000 or less is practical.

The weight average molecular weight of the above polymer component is a value obtained by converting it to polystyrene using GPC (Gel Permeation Chromatography). Hereafter, the value of the weight average molecular weight of a specific polymer component has the same meaning.

In addition, the glass transition temperature (Tg) of the polymer component is preferably less than 100°C, and more preferably less than 90°C. The lower limit is preferably 0°C or higher, and more preferably 10°C or higher. Therefore, the glass transition temperature (Tg) of the polymer component is preferably 0°C or higher and less than 100°C.

The glass transition temperature of the above polymer component is the glass transition temperature measured by differential scanning calorimetry (DSC) at a heating rate of 0.1°C min. More specifically, the temperature was increased from -100°C to 100°C at a heating rate of 0.1°C min, and the extrapolated glass transition onset temperature of JIS K7121: 2012 "Method for Measuring Transition Temperature of Plastics" was taken as the glass transition temperature. Hereinafter, the values of the glass transition temperatures of specific polymer components have the same meaning.

In addition, in the present invention, among the epoxy resin and polymer components, the resin that can have an epoxy group such as a phenoxy resin is classified as an epoxy resin if the epoxy equivalent is 1000 g/eq or less, and as a polymer component if the epoxy equivalent is more than 1000 g/eq.

(phenoxy resin)

Phenoxy resin is preferable as a polymer component because it has good compatibility with epoxy resin due to its similar structure. If phenoxy resin is included, excellent adhesive properties can also be achieved.

Phenoxy resins can be obtained by commercial methods. For example, phenoxy resins can be obtained by the reaction of bisphenol or biphenol compounds with epihalohydrin such as epichlorohydrin, or by the reaction of liquid epoxy resins with bisphenol or biphenol compounds.

The weight average molecular weight of the phenoxy resin is preferably 10,000 or more, more preferably 10,000 to 100,000.

In addition, the amount of epoxy groups remaining slightly in the phenoxy resin is preferably 5000 g/eq or more in epoxy equivalent weight.

The glass transition temperature (Tg) of the phenoxy resin is preferably less than 100°C, more preferably less than 90°C. The lower limit is preferably 0°C or higher, more preferably 10°C or higher. Therefore, the glass transition temperature (Tg) of the phenoxy resin is preferably 0°C or higher and less than 100°C.

(polyurethane resin)

Polyurethane (polyurethane) resin is a polymer having a urethane (carbamic acid ester) bond in the main chain. Polyurethane resin has a constituent unit derived from polyol, a constituent unit derived from polyisocyanate, and may further have a constituent unit derived from polycarboxylic acid. Polyurethane resin may be used alone or in combination of two or more types.

The Tg of polyurethane resin is usually 100°C or lower, preferably 60°C or lower, more preferably 50°C or lower, and also preferably 45°C or lower.

The weight average molecular weight of polyurethane resin is not particularly limited, and is usually used within the range of 5,000 to 500,000.

Polyurethane resins can be synthesized by commercial methods, and can also be obtained on the market. Commercially available products that can be used as polyurethane resins include Dynaleo VA-9320M, Dynaleo VA-9310MF, and Dynaleo VA-9303MF (all manufactured by TOYOCHEM CO., LTD.).

The content of the polymer component relative to 100 parts by mass of the epoxy resin is preferably 1 to 250 parts by mass, more preferably 10 to 180 parts by mass, and even more preferably 40 to 150 parts by mass. By setting the content within this range, the rigidity and flexibility of the film-type adhesive before curing can be adjusted. The film state becomes good (film tackiness is reduced), and film brittleness can also be suppressed.

The content of the polymer component is preferably 30 to 70 parts by mass, more preferably 40 to 70 parts by mass, based on 100 parts by mass of the total content of the epoxy resin and the polymer component.

- Hardener -

The curing agent is a component that affects the control of the above-mentioned light transmittance stipulated in the present invention. It is preferable to select the above-mentioned curing agent in consideration of the control of the above-mentioned light transmittance.

As the curing agent, for example, amines, acid anhydrides, and polyhydric phenols can be mentioned. From the viewpoint of the preservation stability of the film-type adhesive, it is preferable to use a latent curing agent. As the latent curing agent, for example, dicyandiamide compounds, imidazole compounds, curing catalyst complex-type polyhydric phenol compounds, hydrazide compounds, boron trifluoride-amine complexes, amine imide compounds, polyamine salts, and modified products or microcapsules thereof can be mentioned. These may be used singly or in combination of two or more. Among them, it is preferable to use at least one of a dicyandiamide compound, an imidazole compound, and a hydrazide compound.

The latent curing agent may be a thermal cationic polymerization initiator, and a thermal cationic polymerization initiator having a sulfonium cation as the cation component and SbF ₆ ^- or PF ₆ ^- as the anion component is more preferable.

The content of the curing agent relative to 100 parts by mass of the epoxy resin is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, further preferably 1 to 30 parts by mass, still more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass, from the viewpoint of ensuring transparency after curing while exhibiting a sufficient curing speed.

-filling-

As for the filler, any filler that can be commonly used in film-type adhesives can be used without particular limitation, as long as it can achieve the above-mentioned light transmittance. The filler is preferably an inorganic filler.

Examples of inorganic fillers include ceramics such as silica, clay, gypsum, calcium carbonate, barium sulfate, alumina (aluminum oxide), beryllium oxide, magnesium oxide, silicon carbide, silicon nitride, aluminum nitride, and boron nitride; metals such as aluminum, copper, silver, gold, nickel, chromium, lead, tin, zinc, palladium, and solder; alloys; and various inorganic powders such as carbon nanotubes and graphene.

Silica is preferred as a filler.

The particle size (d50) of the filler is not particularly limited, and from the viewpoint of increasing light transmittance, it is preferably 500 nm or less. The particle size is preferably 1 to 500 nm, more preferably 10 to 500 nm, still more preferably 10 to 499 nm, still more preferably 10 to 450 nm, still more preferably 10 to 350 nm, still more preferably 10 to 200 nm, and still more preferably 10 to 100 nm. The particle size (d50) is the so-called median diameter, and means the particle size when the particle size distribution is measured by a laser diffraction/scattering method, and when the entire particle volume in the cumulative distribution is 100%, 50% of the accumulation occurs.

-Other ingredients-

The film-type adhesive may further contain, in addition to the epoxy resin, curing agent, polymer component, and filler, an ion trap agent, a curing catalyst, a viscosity modifier, an antioxidant, a flame retardant, and a colorant, within a range that does not impair (or weaken) the effects of the present invention. For example, it may contain other additives of International Publication No. 2017/158994.

In addition, from the viewpoint of adhesive reliability, it is preferable that the film-type adhesive does not contain coloring agents such as dyes or pigments. It is also preferable that it is in a form that does not contain fillers.

The total content of the epoxy resin and polymer component included in the film-type adhesive is preferably 50 mass% or more, more preferably 60 mass% or more, still more preferably 70 mass% or more, and also preferably 80 mass% or more.

-Thickness of film-type adhesive-

The thickness of the film-type adhesive is not particularly limited and can be appropriately set depending on the purpose. The film-type adhesive can have a thickness of, for example, 1 to 30 ㎛, preferably 1 to 25 ㎛, preferably 1 to 20 ㎛, preferably 2 to 20 ㎛, preferably 3 to 20 ㎛, or preferably 4 to 20 ㎛. The thickness of the film-type adhesive can be measured by a contact/linear gauge method (table-top contact-type thickness measuring device).

＜Manufacture of film-type adhesive with dicing film＞

The method for manufacturing a film-type adhesive having a dicing film is not particularly limited as long as it can have a structure in which the dicing film and the film-type adhesive are laminated.

For example, a coating solution containing an adhesive is applied onto a release liner that has undergone a release process, and by drying, an adhesive layer is formed, and by bonding the adhesive layer and the substrate, a laminated body in which the substrate, the adhesive layer, and the release liner are laminated in that order is obtained. Separately from this, a composition for forming a film-like adhesive is applied onto a release film (which has the same meaning as the release liner, but for convenience, the expression is changed here), and by drying, a film-like adhesive is formed on the release film. Then, the release liner is peeled off to expose the adhesive layer, and the dicing film and the film adhesive are brought into contact, thereby bonding the dicing film and the film adhesive, whereby a film-like adhesive with a dicing film in which the substrate, the adhesive layer, the film adhesive, and the release film are laminated in that order can be obtained.

It is preferable that the bonding of the above-mentioned dicing film and die attach film be performed under pressurized conditions.

In the bonding of the above-described dicing film and film-like adhesive, the shape of the dicing film is not particularly limited as long as it can cover the opening of the ring frame, and is preferably circular. The shape of the film-like adhesive is also not particularly limited as long as it can cover the back surface of the wafer, and is preferably circular. The dicing film is preferably larger than the film-like adhesive and has a portion in which the adhesive layer is exposed around the adhesive layer. In this way, it is preferable to bond the dicing film and the film-like adhesive cut into a desired shape.

The film-type adhesive with dicing film manufactured as described above is used by peeling off the peeling film when in use.

Further explanation is given regarding the formation of film-type adhesives.

The film-type adhesive can be obtained by forming a film using a composition (film-type adhesive forming composition (varnish)) in which each component constituting the film-type adhesive is mixed at a temperature at which the epoxy resin does not substantially heat-cured. The order of mixing is not particularly limited. For example, resin components such as epoxy resin and polymer components may be mixed with a solvent as necessary, and then a curing agent may be mixed. In this case, mixing in the presence of the curing agent may be performed at a temperature at which the epoxy resin does not substantially heat-cured, and mixing of the resin components in the absence of the curing agent may be performed at a higher temperature.

A film formed using the composition for forming the above-mentioned film-type adhesive can be formed, for example, by applying the composition for forming the film-type adhesive on a release-treated substrate (also called a release film or a peeling film) and drying it as necessary.

As the release film, any film that functions as a cover film for the resulting film-type adhesive may be used, and a conventional one may be appropriately employed. Examples thereof include release-treated polypropylene (PP), release-treated polyethylene (PE), and release-treated polyethylene terephthalate (PET).

As a coating method, a conventional method can be appropriately adopted, and examples thereof include methods using a roll knife coater, a gravure coater, a die coater, and a reverse coater.

Drying is performed when the epoxy resin is not substantially cured and the organic solvent is removed from the composition for forming a film-type adhesive to obtain a film-type adhesive, and can be performed, for example, by preserving it at a temperature of 80 to 150°C for 1 to 20 minutes.

The film-type adhesive can be formed in a form in which the above-described release film, etc. is bonded to at least one surface. In this case, the release film does not constitute the film-type adhesive, but is treated as being laminated to the film-type adhesive. In other words, in a form in which the above-described release film, etc. is bonded to at least one surface of the film-type adhesive, when the thickness of the film-type adhesive is described, the thickness of the release film, etc. is not included in the thickness. That is, in the present invention, the thickness of the film-type adhesive is the thickness of the layer derived from the composition for forming the film-type adhesive.

From the viewpoint of more reliably suppressing heat curing of epoxy resin, it is preferable to store film-type adhesives under temperature conditions below 10℃ before use.

The film-type adhesive having a dicing film of the present invention may additionally have a release film or the like laminated thereon.

The film-type adhesive with a dicing film of the present invention, by forming a laminated film as described above, makes it possible to adhere a transparent film-type member (adherent), such as a transparent protective film, to the film-type adhesive side of the laminated film, fix this via the dicing film, and cut (dicing) the transparent film-type member together with the film-type adhesive into a desired size. As a result, a transparent film-type chip with an adhesive layer cut into a desired size can be obtained on the dicing film. Next, the transparent film-type chip with an adhesive layer can be peeled off from the dicing film, and the transparent film-type chip can be embedded in an electronic component via the adhesive layer. This embedding into an electronic component is performed by thermocompression bonding or the like, and then the adhesive layer is thermally cured, so that, accompanying the curing reaction, for example, a solid curing agent reacts, and it becomes possible to increase the transparency of the adhesive.

The above conditions for thermal compression are performed at a temperature at which the epoxy resin does not actually undergo thermal curing. For example, conditions of 70°C and pressure of approximately 0.3 MPa can be cited.

The above-mentioned thermal curing reaction may be carried out at a temperature higher than the thermal curing initiation temperature of the film-type adhesive. The thermal curing initiation temperature varies depending on the type of epoxy resin, polymer component, and epoxy curing agent used, and cannot be stated uniformly, but is preferably 100 to 180°C, and from the viewpoint of realizing short-term curing, is more preferably 140 to 180°C. If the temperature is lower than the thermal curing initiation temperature, the thermal curing reaction does not proceed sufficiently, and the strength of the adhesive layer tends to decrease. On the other hand, if the temperature of the curing reaction is too high, the curing agent and additives in the film-type adhesive tend to volatilize during the curing reaction, which makes it easy for foaming to occur. In addition, the time for the curing treatment is preferably 10 to 120 minutes, for example.

With respect to the above-described embodiment, according to the present invention, a method for manufacturing an electronic component as shown below is provided.

A method for manufacturing electronic components,

A first step of obtaining a laminate in which a transparent film-type member and a film-type adhesive with a dicing film of the present invention are laminated in this order;

A second process of obtaining a transparent film-type chip with an adhesive layer on the dicing film by integrally dicing the transparent film-type member and the film-type adhesive;

A third process of removing the dicing film from the adhesive layer and thermally compressing a transparent film-type chip and other components forming an electronic component with the adhesive layer attached thereto through the adhesive layer;

The fourth process of heat-curing the above adhesive layer

A method for manufacturing an electronic component comprising:

An electronic component obtained by the above manufacturing method includes a structure in which a transparent film-type chip is embedded in the electronic component through a heat-curing agent of a film-type adhesive.

In the present invention, the "transparent film-type chip" means a transparent film processed into a desired shape. Typically, it is a transparent film-type member such as a glass substrate or transparent resin cut into a desired shape for embedding in an electronic component.

As an example of the above-mentioned electronic component, an image sensor (image pickup element) can be mentioned. In this case, it is preferable that the transparent film-type chip built into the above-mentioned electronic component is a protective film for a photodiode.

In addition, the above has described a preferred embodiment of a transparent film-type member, and the present invention is not limited to these embodiments at all, except as stipulated in the present invention. For example, as the electronic component, members used in optical devices such as optical lenses, optical fibers, optical waveguides, optical isolators, and semiconductor lasers can also be preferably mentioned.

Example

The present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following embodiments.

In the description below, room temperature means 25℃. Also, "MEK" is methyl ethyl ketone, and "PET" is polyethylene terephthalate.

As each exemplary embodiment and comparative example, a film-type adhesive with a peeling film as shown in Fig. 1 was prepared.

[Production of dicing film]

＜Preparation of materials＞

(Not described X)

Zinc ionomer resin of ethylene-methacrylic acid copolymer (trade name: Himilan 1855, manufactured by Mitsui DuPont Chemical Co., Ltd.) was melted at 200°C, and a substrate X having a thickness of 90 μm was produced using an extruder. One side of the substrate X was subjected to corona treatment.

(Reported by Y)

Zinc ionomer resin of ethylene-methacrylic acid copolymer (trade name: Hymilan AM7326, manufactured by Mitsui DuPont Chemical Co., Ltd.) was melted at 200°C, and a substrate Y having a thickness of 90 μm was produced using an extruder. One side of the substrate Y was subjected to corona treatment.

(Reporter Z)

An ethylene-methacrylic acid copolymer (trade name: NUCREL N0200H, manufactured by DuPont Mitsui Chemical Co., Ltd.) was melted at 200°C, and a substrate Z having a thickness of 90 μm was produced using an extruder. One side of the substrate Z was subjected to corona treatment.

＜Dicing Film A＞

65 parts by mass of butyl acrylate, 25 parts by mass of 2-hydroxyethyl acrylate, and 10 parts by mass of acrylic acid were radically polymerized, and further 2-isocyanateethyl methacrylate was added dropwise to cause a reaction, thereby obtaining an acrylic copolymer having a weight average molecular weight of 800,000. To 100 parts by mass of this acrylic copolymer, 3 parts by mass of polyisocyanate as a curing agent and 1 part by mass of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator were added and mixed, thereby obtaining an adhesive layer composition.

Next, the adhesive layer composition was applied to a release liner that had been subjected to mold release treatment so that the dry film thickness was 10 ㎛, and dried at 120° C. for 3 minutes to obtain an adhesive layer. This adhesive layer was bonded to the corona-treated surface of the substrate X to produce a dicing film A having a substrate and an adhesive layer, with a release liner attached.

＜Dicing Film B＞

Dicing film B was produced in the same manner as dicing film A, except that the base material used was changed to Y.

＜Dicing Film C＞

Dicing film C was produced in the same way as dicing film A, except that the substrate used was changed to substrate Z.

[Production of film-type adhesive with dicing film]

The ingredients used in the preparation of the film-type adhesive are shown below.

＜Materials used＞

(epoxy resin)

·828 (Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 190 g/eq, specific gravity 1.17)

·ST-3000 (hydrogenated bisphenol A type epoxy resin, manufactured by Nittesu Chemical & Materials Co., Ltd.)

·YDCN－703 (cresol novolac type epoxy resin, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210 g/eq, molecular weight 1200, softening point 80℃)

(phenoxy resin)

·1256 (Phenoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 7500 g/eq)

(urethane resin)

·Dynareo VA-9320M (urethane resin solution, weight average molecular weight: 120,000, Tg: 39℃, elastic modulus at room temperature: 594 MPa, solvent: MEK/IPA mixed solvent, manufactured by Toyochem Co., Ltd.) (in the table, it is written as VA-9320M)

(Acrylic resin)

·SG-P3 (Acrylic resin, manufactured by Nagase Chemtec Co., Ltd., weight average molecular weight 850,000, glass transition temperature 10℃)

(hardener)

·2PHZ-PW (imidazole-based curing agent, manufactured by Shikoku Kasei Co., Ltd.)

·SI-150 (thermal cationic polymerization initiator, manufactured by Sanshin Chemical Co., Ltd.)

(Phenol resin)

·Milex XLC-LL (phenol resin, manufactured by Mitsui Kagaku Co., Ltd., hydroxyl equivalent 175 g/eq)

(filling)

·RY-200 (Nano silica filler, manufactured by Nippon Aerosil Co., Ltd., particle size (d50): 12 nm, Mohs hardness: 7 Mohs, thermal conductivity: 1 W/m·K)

·S0－C2 (Silica filler, manufactured by Adoma Fine Co., Ltd., specific gravity 2.2 g/cm2, Mohs hardness: 7 Mohs, particle size (d50) 500 nm, specific surface area 6.0 ㎡/g)

＜Example 1＞

(Production of film-type adhesive)

50 parts by mass of an epoxy resin (trade name: 828, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 190 g/eq, specific gravity 1.17) and 50 parts by mass of a phenoxy resin (trade name: 1256, manufactured by Mitsubishi Chemical Corporation, bisphenol A type phenoxy resin, epoxy equivalent 7500 g/eq) were heated and stirred with MEK in a 1000 mL separable flask at 110°C for 2 hours to obtain a resin varnish. Next, this resin varnish was transferred to a separate flask container, and 1 part by mass of a curing agent (trade name: 2PHZ-PW, imidazole-based curing agent, manufactured by Shikoku Kasei Co., Ltd.) was added, stirred and mixed at room temperature for 1 hour, and then vacuum defoamed to obtain a mixed varnish. In addition, the obtained mixed varnish was applied onto a 38 ㎛ thick PET film (release film) that had been subjected to a release treatment, and dried by heating at 130° C. for 10 minutes to form a film-shaped adhesive layer having a length of 300 mm, a width of 300 mm, and a thickness of 20 ㎛. The obtained film-shaped adhesive with a release film was stored at 10° C. or lower. After the drying, the epoxy resin was not cured (hereinafter, unless otherwise specified, the same applies to other Examples and Comparative Examples).

(Production of film-type adhesive with dicing film)

Next, the dicing film B with the above-described peeling liner was cut into a circular shape that could be laminated to cover the opening of the ring frame. In addition, the film-type adhesive with the above-described peeling film was cut into a circular shape that could cover the back surface of the wafer.

As described above, a dicing film B with a release liner is peeled off and exposed, and a film-type adhesive with a release film cut as described above are laminated using a roll press under the conditions of a load of 0.4 MPa and a speed of 1.0 m/min, to produce a film-type adhesive with a dicing film in which a substrate, an adhesive layer, a film-type adhesive, and a release film are laminated in this order. In this film-type adhesive with a dicing film, the film-type adhesive is formed on the adhesive layer of a dicing film having a substrate and an adhesive layer. In addition, in this film-type adhesive with a dicing film, the dicing film is larger than the film-type adhesive, and has a portion in which the dicing film is exposed around the film-type adhesive.

＜Example 2＞

In the production of the film-type adhesive of Example 1, 1 part by mass of SI-150 was used instead of 2PHZ-PW as the curing agent, and 3 parts by mass of RY-200 was added as a filler to the mixed varnish, and the same procedure as Example 1 was performed to obtain a film-type adhesive with a peeling film and a film-type adhesive with a dicing film.

＜Example 3＞

In the production of the film-type adhesive of Example 1, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 1, except that 11 parts by mass of RY-200 was added as a filler to the mixed varnish.

＜Example 4＞

In the production of the film-type adhesive of Example 2, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 2, except that 5 parts by mass of S0-C2 was added as a filler instead of RY-200 in the mixed varnish.

＜Example 5＞

In the production of a film-type adhesive with a dicing film of Example 2, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 2, except that dicing film A was used as the dicing film.

＜Example 6＞

In the production of a film-type adhesive with a dicing film of Example 3, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 3, except that dicing film A was used as the dicing film.

＜Example 7＞

In the production of a film-type adhesive with a dicing film of Example 4, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 4, except that dicing film A was used as the dicing film.

＜Example 8＞

In the production of a film-type adhesive of Example 5, 150 parts by mass of a urethane (urethane) resin solution (VA-9320M) (50 parts by mass of the heavy urethane resin) was used instead of the phenoxy resin (1256) as the polymer component, 1 part by mass of 2PHZ-PW was used as the curing agent in the mixed varnish, and 35 parts by mass of RY-200 was added as the filler, respectively, in the same manner as Example 5, to obtain a film-type adhesive with a peeling film and a film-type adhesive with a dicing film.

＜Example 9＞

In the production of the film-type adhesive of Example 5, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 5, except that 50 parts by mass of ST-3000 was used instead of 828 as the epoxy resin.

＜Example 10＞

In the production of the film-type adhesive of Example 5, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 5, except that 20 parts by mass of RY-200 was added as a filler in the mixed varnish.

＜Example 11＞

In the production of the film-type adhesive of Example 5, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 5, except that the blending amount of 828 in the resin varnish was changed to 30 parts by mass and the blending amount of 1256 was changed to 70 parts by mass.

＜Example 12＞

In the production of the film-type adhesive of Example 2, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 2, except that the blending amount of 828 in the resin varnish was changed to 60 parts by mass and the blending amount of 1256 was changed to 40 parts by mass.

＜Comparative Example 1＞

In the production of a film-type adhesive with a dicing film of Example 1, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 1, except that dicing film A was used as the dicing film.

＜Comparative Example 2＞

In the production of the film-type adhesive of Comparative Example 1, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as in Comparative Example 1, except that 80 parts by mass of S0-C2 was added as a filler in the mixed varnish.

＜Comparative Example 3＞

In the production of the film-type adhesive of Example 1, 18 parts by mass of YDCN-703 was used instead of 828 as the epoxy resin, 100 parts by mass of an acrylic resin (SG-P3) was used instead of phenoxy resin (1256) as the polymer component, and 1 part by mass of 2PHZ-PW and 15 parts by mass of MILLEX XLC-LL were used as the curing agent, respectively, in the same manner as Example 1, to obtain a film-type adhesive with a peeling film and a film-type adhesive with a dicing film.

＜Comparative Example 4＞

In the production of the film-type adhesive of Comparative Example 3, the blending amount of YDCN-703 was set to 50 parts by mass, the blending amount of SG-P3 was set to 250 parts by mass, 50 parts by mass of Milex XLC-LL was used as the hardener instead of blending 2PHZ-PW, and 35 parts by mass of S0-C2 was added as a filler to the mixed varnish, except that the same procedure as Comparative Example 3 was performed to obtain a film-type adhesive with a peeling film and a film-type adhesive with a dicing film.

＜Comparative Example 5＞

In the production of a film-type adhesive with a dicing film of Example 2, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 2, except that dicing film C was used as the dicing film.

＜Comparative Example 6＞

In the production of a film-type adhesive with a dicing film of Example 3, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 3, except that dicing film C was used as the dicing film.

＜Comparative Example 7＞

In the production of a film-type adhesive with a dicing film of Example 4, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 4, except that dicing film C was used as the dicing film.

＜Comparative Example 8＞

In the production of a film-type adhesive with a dicing film of Example 8, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 8, except that dicing film C was used as the dicing film.

＜Comparative Example 9＞

In the production of a film-type adhesive with a dicing film of Example 9, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 9, except that dicing film C was used as the dicing film.

＜Comparative Example 10＞

In the production of a film-type adhesive with a dicing film of Example 10, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 10, except that dicing film C was used as the dicing film.

＜Comparative Example 11＞

In the production of a film-type adhesive with a dicing film of Example 11, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 11, except that dicing film C was used as the dicing film.

＜Comparative Example 12＞

In the production of a film-type adhesive with a dicing film of Example 12, a film-type adhesive with a peeling film and a film-type adhesive with a dicing film were obtained in the same manner as Example 12, except that dicing film C was used as the dicing film.

For the film-type adhesives and dicing films A to C with peeling films obtained in each of the above-mentioned examples and comparative examples, the storage elastic modulus at 60°C of the film-type adhesives and the storage elastic modulus at 60°C of the dicing films were determined as follows.

[Measurement of storage modulus of film-type adhesive]

In each of the embodiments and comparative examples, the release film was peeled off from the obtained film-type adhesive with a release film, and the film-type adhesive was laminated using a laminator at 70°C until the thickness became 0.5 mm. This laminated body was cut into a width of 5 mm and used as a measurement sample. Using a dynamic viscoelasticity measuring device RSAⅢ Instrument (manufactured by TA Instruments), the viscoelastic behavior of the film-type adhesive when the temperature was increased from 25°C to 80°C at a heating rate of 5°C/min under tensile conditions of a chuck distance of 20 mm and a frequency of 10 Hz was measured, and the storage modulus E1 at 60°C was obtained.

[Measurement of storage modulus of dicing film]

Dicing films A to C were each cut into 5 mm widths to serve as measurement samples. Using a dynamic viscoelasticity measuring device (RSAⅢ Instruments), the viscoelastic behavior of the dicing films was measured when the temperature was increased from 25°C to 80°C at a heating rate of 5°C/min under tensile conditions of a chuck distance of 20 mm and a frequency of 10 Hz, and the storage modulus E2 at 60°C was obtained.

In addition, when the storage elastic modulus of the substrate was measured at 60℃, it was almost the same as the storage elastic modulus of the dicing film.

For the film-type adhesives with dicing films obtained in each of the above-mentioned examples and comparative examples, the light transmittance and chip detachment after curing of the film-type adhesives were evaluated as follows.

[Measurement of light transmittance of cured film adhesive]

After the film-type adhesive with the dicing film was heat-cured at 150°C for 1 hour, the dicing film was peeled off, and the parallel line transmittance of the film-type adhesive alone was measured using a spectrophotometer (Hitachi High-Technologies Corporation, Spectrophotometer U-4100 Type Solid State Data Measurement System) over a wavelength range of 200 to 1100 nm, and the parallel line transmittance at a wavelength of 400 nm was used for evaluation.

[Chip drop evaluation]

In each of the embodiments and comparative examples, the obtained film-type adhesive with a dicing film was first bonded to one side of a glass wafer (material D263, 10 cm square with a side of 10 cm, thickness 100 µm) using a manual laminator (trade name: FM-114, manufactured by TECHNOVISION, INC.) at a temperature of 70°C and a pressure of 0.3 MPa so that the film-type adhesive layer was in contact therewith. Thereafter, using the same manual laminator, a dicing frame (trade name: DTF2-8-1H001, manufactured by DISCO Corporation) was bonded to the area where the glass wafer was not bonded with the film-type adhesive at room temperature and a pressure of 0.3 MPa. Next, using a dicing device (product name: DFD-6340, manufactured by DISCO) equipped with a two-axis dicing blade (Z1: NBC-ZH2050 (27HEDD), manufactured by DISCO; Z2: NBC-ZH127F-SE (BC), manufactured by DISCO), dicing was performed from the glass wafer side to a size of 2 mm x 2 mm. By this dicing, 2,500 chips were obtained. In the sample after dicing, the number of chips that had fallen off (peeled) was counted, and the chip fall-off rate with respect to the total number of chips (number of chips that had fallen off/total number x 100) was calculated. The obtained chip fall-off rate was evaluated by applying it to the following evaluation criteria.

-metewand-

AA: Chip drop rate is 0%

A: The chip dropout rate is less than 1% of all chips.

B: Chip dropout rate is 1% or more and less than 3% of all chips

C: Chip dropout rate is 3% or more of all chips

The above results are summarized in the table below. In the table below, the numerical values indicating the mixing amounts of epoxy resin, polymer components, hardeners, and fillers are in mass parts. A blank space indicates that the component is not contained. The column for “filler content” indicates the content of filler in the total solid content of the film-type adhesive.

[Table 1-1]

[Table 1-2]

The film-type adhesive with a dicing film of Comparative Example 1 does not satisfy the relationship of storage elastic modulus E1×E2≥7.0. In the film-type adhesive with a dicing film of Comparative Example 1, chip detachment occurred during dicing.

The film-type adhesives with dicing films of Comparative Examples 2 to 4 had a light transmittance of 35% or less of the cured product of the film-type adhesives and did not exhibit sufficient transparency. It is thought that one of the factors was that the amount of filler in Comparative Example 2 was too much, and that in Comparative Examples 3 and 4, the acrylic resin was not compatible with the epoxy resin.

The film-type adhesive with the dicing film of Comparative Examples 5 to 12 has a relationship of storage elastic modulus E1×E2≥7.0

The film-type adhesives with dicing films of these comparative examples 5 to 12 had chip detachment during dicing.

In comparison, the film-type adhesives with dicing films of Examples 1 to 12 satisfying the provisions of the present invention satisfied E1×E2≥7.0, and the light transmittance of the cured product of the film-type adhesives was 60% or more. It can be seen that the use of these film-type adhesives with dicing films can effectively suppress chip detachment in the dicing process, and also exhibit sufficiently high transparency after the curing reaction.

While the present invention has been described in detail with respect to embodiments thereof, it is to be understood that the invention is not limited in any detail of the description unless otherwise specified, and should be broadly construed without being contrary to the spirit and scope of the invention as set forth in the appended claims.

This application claims priority based on Japanese patent application No. 2023-074875 filed on April 28, 2023, the contents of which are incorporated herein by reference as if they were part of the description of this application.

10: Dicing film
11: Description
12: Adhesive layer
20: Film type adhesive

Claims (9)

A dicing film having a substrate and an adhesive layer, and a film-type adhesive disposed on the adhesive layer,
The storage elastic modulus E1 (MPa) of the film-type adhesive at 60°C and the storage elastic modulus E2 (MPa) of the dicing film at 60°C satisfy E1×E2≥7.0,
A film-type adhesive having a dicing film, wherein the light transmittance of the cured product of the above film-type adhesive is 60% or more. In the first paragraph,
A film-type adhesive with a dicing film, wherein the film-type adhesive contains an epoxy resin and a phenoxy resin. In paragraph 1 or 2,
A film-type adhesive with a dicing film, wherein the film-type adhesive contains a filler, and the content of the filler is 10 mass% or less of the total solid content of the film-type adhesive. In the third paragraph,
A film-type adhesive having a dicing film, wherein the particle size (d50) of the above-mentioned filler is 500 nm or less. In any one of claims 1 to 4,
A film-type adhesive with a dicing film, wherein the film-type adhesive contains a curing agent, and the curing agent is a thermal cationic polymerization initiator. In any one of paragraphs 1 to 5,
A film-type adhesive having a dicing film, wherein E1 is 0.1 to 1.0 MPa and E2 is 10 to 70 MPa. A method for manufacturing electronic components,
A first step for obtaining a laminate in which a transparent film-type member and a film-type adhesive with a dicing film described in any one of claims 1 to 6 are laminated in this order;
A second process of obtaining a transparent film-type chip with an adhesive layer on the dicing film by integrally dicing the transparent film-type member and the film-type adhesive;
A third process of removing the dicing film from the adhesive layer and thermally compressing a transparent film-type chip and other components forming an electronic component with the adhesive layer attached thereto through the adhesive layer;
The fourth process of heat-curing the above adhesive layer
A method for manufacturing an electronic component comprising: In Article 7,
A method for manufacturing an electronic component, wherein the electronic component is an image sensor. In Article 8,
A method for manufacturing an electronic component, wherein the electronic component has a structure in which the transparent film-type chip is embedded as a protective film for a photodiode.