JP4419809B2 - Manufacturing method of laminate - Google Patents

Description

  The present invention relates to a method for producing a laminate and a laminate obtained thereby, and more particularly to a method for producing a laminate capable of forming two or more layers from one coating film.

  Currently, with the development of multimedia, various developments have been seen in various display devices (display devices). Among various types of display devices, especially those used outdoors, mainly for portable use, the improvement in visibility has become increasingly important, and even in large display devices, it is easier to see. This is a technical issue as it is required by consumers.

  Conventionally, as one means for improving the visibility of a display device, an antireflection film made of a low refractive index material is coated on a substrate of the display device, and a method of forming the antireflection film For example, a method of forming a fluorine compound thin film by a vapor deposition method is known. However, in recent years, there has been a demand for a technique capable of forming an antireflection film for a large display device at a low cost centering on a liquid crystal display device. However, in the case of the vapor deposition method, it is difficult to form a high-efficiency and uniform antireflection film on a large-area substrate, and a vacuum apparatus is required, so that the cost can be reduced. Have difficulty.

  Under such circumstances, a method of forming an antireflection film by preparing a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent and applying it to the surface of a substrate has been studied. Yes. For example, it has been proposed to apply a fluorinated alkylsilane to the surface of a substrate (see, for example, Patent Document 1 and Patent Document 2). In addition, a method of applying a fluorine-based polymer having a specific structure has been proposed (see, for example, Patent Document 3).

JP 61-40845 A Japanese Examined Patent Publication No. 6-98703 Japanese Patent Application Laid-Open No. 6-1115023

These conventional antireflection films are often laminates in which layers having different refractive indexes, antistatic layers, hard coat layers and the like are formed on a substrate. In the conventional manufacturing method, the process of apply | coating each layer on a base material was repeated.
The present invention has been made in the background as described above, and the object thereof is a method for producing a laminate capable of forming two or more layers from one coating film obtained by applying the composition, and the method thereof. It is providing the laminated body obtained by these. Another object of the present invention is to provide a method for producing a laminate having a good antireflection effect and a laminate obtained thereby. Furthermore, the other object of this invention is to provide the manufacturing method of the laminated body which is excellent in the adhesiveness with respect to a base material, and is high in abrasion resistance, and the laminated body obtained by it.

According to the present invention, the following laminate manufacturing method and laminate obtained thereby can be provided.
1. A substrate and a method for producing a laminate having a multilayer structure thereon,
On the base material or the layer formed on the base material, a liquid curable resin composition containing the following components (A) to (F) is applied to form a coating film,
A method for producing a laminate, wherein two or more layers are formed by evaporating a solvent from the coating film of 1.
[Liquid curable resin composition]
(A) Fluoropolymer having a hydroxyl group in the molecule (B) One or two or more metal oxide particles (hereinafter referred to as “a”) having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more. (B) Metal oxide particles ”
(C) (A) One or two or more solvents (hereinafter referred to as “(C) fast volatile solvent”) having high solubility in a fluorine-containing polymer having a hydroxyl group in the molecule
(D) (B) one or two or more solvents (hereinafter referred to as “(D) slow volatile solvent”) having high dispersion stability with respect to the metal oxide particles and being compatible with (C) the fast volatile solvent. Called)
(E) Curable compound (F) Thermal acid generator and (C) Relative evaporation rate of fast volatile solvent is higher than (D) Relative evaporation rate of slow volatile solvent. Each of the two or more layers is a layer in which metal oxide particles are present in a high density or a layer in which metal oxide particles are not substantially present, and at least one layer has metal oxide particles in a high density. 2. The method for producing a laminate according to 1, wherein the laminate is a layer.
3. The method for producing a laminate according to 2, wherein the two or more layers are two layers.
4). Furthermore, the said 2 or more layer is hardened by heating, The manufacturing method of the laminated body in any one of 1-3 characterized by the above-mentioned.
5). The method for producing a laminate according to any one of 1 to 4, wherein the laminate is an optical component.
6). The method for producing a laminate according to any one of 1 to 4, wherein the laminate is an antireflection film.
7). The laminated body is an antireflection film in which at least a high refractive index layer and a low refractive index layer are laminated in this order from the side close to the base material on the base material, and the two layers according to 3,
4. The method for producing a laminate according to 3, comprising a high refractive index layer and a low refractive index layer.
8). The refractive index at 589 nm of the low refractive index layer is 1.20 to 1.55,
8. The method for producing a laminate according to 7, wherein the refractive index at 589 nm of the high refractive index layer is 1.50 to 2.20, which is higher than the refractive index of the low refractive index layer.
9. The laminate is an antireflection film in which at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order from the side close to the base material on the base material. The method for producing a laminate according to 3, wherein the two layers are a high refractive index layer and a low refractive index layer.
10. The refractive index at 589 nm of the low refractive index layer is 1.20 to 1.55,
The refractive index at 589 nm of the middle refractive index layer is 1.50 to 1.90, which is higher than the refractive index of the low refractive index layer,
10. The method for producing a laminate according to 9, wherein the high refractive index layer has a refractive index at 589 nm of 1.51 to 2.20, which is higher than the refractive index of the medium refractive index layer.
11. Furthermore, the manufacturing method of the laminated body in any one of 7-10 characterized by forming a hard-coat layer and / or an antistatic layer on a base material.
12 The (C) fast volatile solvent of the liquid curable resin composition is one or more solvents having low dispersion stability with respect to (B) metal oxide particles, and (D) the slow volatile solvent is (A) The method for producing a laminate according to any one of 1 to 11, which is one or more solvents having low solubility in a fluoropolymer having a hydroxyl group in the molecule.
13. The (B) metal oxide particles of the liquid curable resin composition are titanium oxide, zirconium oxide, antimony-containing tin oxide, tin-containing indium oxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide, antimony-containing zinc oxide and indium. The method for producing a laminate according to any one of 1 to 12, which is a particle mainly composed of one or more metal oxides selected from contained zinc oxide.
14 14. The method for producing a laminate according to any one of 13, wherein the (B) metal oxide particles of the liquid curable resin composition are particles mainly composed of titanium oxide.
15. The method for producing a laminate according to any one of 1 to 14, wherein the (B) metal oxide particles of the liquid curable resin composition are metal oxide particles having a multilayer structure.
16. A laminate produced by the laminate production method described in any one of 16.1 to 15.

  Since the manufacturing method of the laminated body of this invention can form two or more layers from one coating film obtained by apply | coating a composition, the manufacturing process of the laminated body which has a multilayer structure can be simplified. Therefore, the method for producing a laminate of the present invention can be advantageously used particularly for forming an optical material such as an antireflection film and an optical filter. Moreover, the laminated body of this invention can be conveniently used as a coating material, a weather resistant film, a coating, etc. with respect to the base material which requires a weather resistance using the high fluorine content. And the said laminated body provides a favorable antireflection effect by providing a low-refractive-index layer in the outermost layer (layer farthest from the base material). Moreover, according to this invention, the laminated body which is excellent in the adhesiveness with respect to a base material and has high abrasion resistance is obtained. From these facts, the laminate of the present invention is extremely useful as an antireflection film, and its visibility can be improved by applying it to various display devices.

  The present invention is a substrate, a method for producing a laminate having a multilayer structure of two or more layers thereon, and a laminate obtained thereby. Specifically, in the production method of the present invention, a solvent is formed from one coating film obtained by applying a predetermined liquid curable resin composition to be described later on a substrate or a layer formed on the substrate. Is evaporated (hereinafter, evaporation of the solvent may be referred to as “drying”) to form two or more layers. It should be noted that the solvent may not be completely removed after drying, and the solvent may remain within a range where the properties as a cured film can be obtained. Moreover, in this invention, formation of two or more layers from one coating film can be implemented twice or more.

When a specific liquid curable resin composition is applied by a usual method and then dried, it is separated into two or more layers. Here, the two or more layers may be two or more layers including both “a layer in which metal oxide particles are present at high density” and “a layer in which metal oxide particles are not substantially present”. In addition, there may be two or more layers consisting only of “a layer in which metal oxide particles are present at a high density”.
Hereinafter, using the drawings, “each of the two or more layers is a layer in which metal oxide particles are present in high density or a layer in which metal oxide particles are substantially absent, and at least one layer is metal oxide particles. Will be described. FIG. 1A shows a case where two or more layers are “layer 1 in which metal oxide particles are present at high density” and “layer 3 in which metal oxide particles are not substantially present”. FIG. 1B shows a case where two or more layers are “layers 1 and 1a in which metal oxide particles are present in high density”. FIG. 1C shows a case where two or more layers are “layers 1 and 1a in which metal oxide particles are present in high density” and “layer 3 in which metal oxide particles are not substantially present”. . FIG. 1D shows a case where two or more layers are “layers 1 and 1a in which metal oxide particles are present in high density” and “layer 3 in which metal oxide particles are substantially absent”. . FIG. 1E shows a case where two or more layers are “layer 1b in which metal oxide particles are present at high density” and “layer 3 in which metal oxide particles are not substantially present”.
When the liquid curable resin composition contains two or more kinds of metal oxide particles, as shown in FIGS. 1B, 1C, and 1D, two or more types of “layers in which the metal oxide particles exist at high density” are formed. obtain.

  Furthermore, the “metal oxide particles” of the “layer in which metal oxide particles are present at high density” means at least one, that is, one or more “metal oxide particles”. When the liquid curable resin composition contains two or more kinds of metal oxide particles, the “layer in which the metal oxide particles exist at high density” may be composed of two or more kinds of metal oxide particles (for example, FIG. 1E). In FIG. 1E, the “layer 1b in which metal oxide particles are present at high density” is composed of particles X and particles Y. Since the particle Y is larger than the thickness of the “layer 1b in which the metal oxide particles are present in high density”, the particle Y protrudes into the “layer 3 in which the metal oxide particles are substantially not present”. It is contained in the layer 1b "in which oxide particles are present in high density.

  In FIGS. 1A to 1E, the “layer 3 substantially free of metal oxide particles” usually contains no metal oxide particles, but is included in a range that does not impair the effects of the present invention. Also good. Similarly, the “layers 1, 1 a, 1 b in which the metal oxide particles are present at high density” may also contain other substances other than the metal oxide particles.

As a coating method of the liquid curable resin composition, a known coating method can be used, and in particular, various methods such as a dipping method, a coater method, and a printing method can be applied.
Drying is usually performed for about 1 to 60 minutes by heating from room temperature to about 100 ° C.
Preferably, these two or more layers are cured by heating. Specific curing conditions will be described later.

In this invention, a liquid curable resin composition is apply | coated to various base materials with a solution form, and the obtained coating film can be dried / cured and a laminated body can be obtained. For example, when the substrate is a transparent substrate, an excellent antireflection film is formed by providing a low refractive index layer as the outermost layer.
The specific structure of the antireflection film is usually a base material and a low refractive index film, or a base material, a high refractive index film and a low refractive index film laminated in this order. In addition, other layers may be interposed between the base material, the high refractive index film, and the low refractive index film. For example, a hard coat layer, an antistatic layer, a middle refractive index layer, a low refractive index layer, a high refractive index layer, Layers such as a combination of refractive index layers can be provided.

FIG. 2 shows an antireflection film in which a high refractive index layer 40 and a low refractive index layer 50 are laminated in this order on a substrate 10.
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

FIG. 3 shows an antireflection film in which a hard coat layer 20, an antistatic layer 30, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10.
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

FIG. 4 shows an antireflection film in which an antistatic layer 30, a hard coat layer 20, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10.
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

FIG. 5 shows an antireflection film in which a hard coat layer 20, an antistatic layer 30, a middle refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10. .
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Alternatively, each of the medium refractive index layer 60 and the high refractive index layer 40 corresponds to a layer in which metal oxide particles exist at high density, or the medium refractive index layer 60 has high density in metal oxide particles. In the existing layer, the high refractive index layer 40 corresponds to a layer substantially free of metal oxide particles.
According to the present invention, the middle refractive index layer 60 and the high refractive index layer 40 or the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.

FIG. 6 shows an antireflection film in which an antistatic layer 30, a hard coat layer 20, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10. .
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Alternatively, each of the medium refractive index layer 60 and the high refractive index layer 40 corresponds to a layer in which metal oxide particles exist at high density, or the medium refractive index layer 60 has high density in metal oxide particles. In the existing layer, the high refractive index layer 40 corresponds to a layer substantially free of metal oxide particles.
According to the present invention, the middle refractive index layer 60 and the high refractive index layer 40 or the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.

FIG. 7 shows an antireflection film in which a hard coat layer 20, a high refractive index layer 40, and a low refractive index layer 50 are laminated on the base material 10 in this order.
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

FIG. 8 shows an antireflection film in which a hard coat layer 20, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated on the substrate 10 in this order.
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Alternatively, each of the medium refractive index layer 60 and the high refractive index layer 40 corresponds to a layer in which metal oxide particles exist at high density, or the medium refractive index layer 60 has high density in metal oxide particles. In the existing layer, the high refractive index layer 40 corresponds to a layer substantially free of metal oxide particles.
According to the present invention, the middle refractive index layer 60 and the high refractive index layer 40 or the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.

FIG. 9 shows an antireflection film in which an antistatic layer 30, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10.
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present.
According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

FIG. 10 shows an antireflection film in which an antistatic layer 30, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate 10.
In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Alternatively, each of the medium refractive index layer 60 and the high refractive index layer 40 corresponds to a layer in which metal oxide particles exist at high density, or the medium refractive index layer 60 has high density in metal oxide particles. In the existing layer, the high refractive index layer 40 corresponds to a layer substantially free of metal oxide particles.
According to the present invention, the middle refractive index layer 60 and the high refractive index layer 40 or the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.

  In the above antireflection film, the addition of conductive particles such as antimony-doped tin oxide (ATO) particles as the metal oxide contained in the liquid curable resin composition to be used increases the resulting metal oxide. The layer included in the density becomes a film having antistatic properties. Therefore, for example, if the high refractive index layer or the middle refractive index layer is formed as a layer containing a metal oxide having such an antistatic property at a high density, the high refractive index layer or the middle refractive index layer is antistatic. It can be set as the film | membrane which served as. In this case, the formation of the antistatic film can be omitted.

Next, each layer of the antireflection film will be described.
(1) Substrate The type of the substrate used for the antireflection film of the present invention is not particularly limited, but specific examples of the substrate include, for example, triacetyl cellulose, polyethylene terephthalate resin (manufactured by Toray Industries, Inc.). Lumirror, etc.), glass, polycarbonate resin, acrylic resin, styryl resin, arylate resin, norbornene resin (Arton manufactured by JSR Co., Ltd., Zeonex manufactured by Nippon Zeon Co., Ltd.), methyl methacrylate / styrene copolymer resin, polyolefin resin And various transparent plastic plates and films. Preferable examples include triacetyl cellulose, polyethylene terephthalate resin (such as Lumirror manufactured by Toray Industries, Inc.), norbornene resin (such as Arton manufactured by JSR Corporation), and the like.

(2) Low refractive index layer The low refractive index layer represents a layer having a refractive index of 1.20 to 1.55 for light having a wavelength of 589 nm.
The material used for the low refractive index layer is not particularly limited as long as the desired properties are obtained. For example, a curable composition containing a fluorine-containing polymer, an acrylic monomer, and a fluorine-containing acrylic monomer. And cured products such as epoxy group-containing compounds and fluorine-containing epoxy group-containing compounds. Moreover, in order to raise the intensity | strength of a low refractive index layer, a silica fine particle etc. can also be mix | blended.

(3) High Refractive Index Layer The high refractive index layer represents a layer having a refractive index of light having a wavelength of 589 nm of 1.50 to 2.20 and a higher refractive index than the low refractive index layer.
In order to form a high refractive index layer, high refractive index inorganic particles, such as metal oxide particles, can be blended.
Specific examples of metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, ZnO particles, antimony-doped ZnO, Al-doped ZnO particles, ZrO ₂ particles, TiO ₂ particles, silica coating TiO ₂ particles, Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles, CeO ₂ particles and the like can be mentioned. Antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, Al-doped ZnO particles, and Al ₂ O ₃ / ZrO ₂ -coated TiO ₂ particles are preferable. These metal oxide particles can be used singly or in combination of two or more.
Moreover, the function of a hard coat layer or an antistatic layer can be given to the high refractive index layer.

(4) Medium Refractive Index Layer When combining layers having three or more refractive indexes, the refractive index of light with a wavelength of 589 nm is 1.50 to 1.90, which is higher than the low refractive index layer and has a high refractive index. A layer having a lower refractive index than the layer is referred to as a middle refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.80, more preferably 1.50 to 1.75.
In order to form the middle refractive index layer, inorganic particles having a high refractive index, for example, metal oxide particles can be blended.
Specific examples of metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, ZnO particles, antimony-doped ZnO, Al-doped ZnO particles, ZrO ₂ particles, TiO ₂ particles, silica coating TiO ₂ particles, Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles, CeO ₂ particles and the like can be mentioned. Antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, Al-doped ZnO particles, and ZrO ₂ particles are preferable. These metal oxide particles can be used singly or in combination of two or more.
Further, the medium refractive index layer can have a function of a hard coat layer or an antistatic layer.

  The reflectance can be lowered by combining the low refractive index layer and the high refractive index layer, and the reflectance can be lowered by combining the low refractive index layer, the high refractive index layer, and the middle refractive index layer. As well as being able to reduce color.

(5) Hard coat layer As a specific example of the hard coat layer, it is preferable that the hard coat layer is composed of a material such as SiO ₂ , an epoxy resin, an acrylic resin, or a melamine resin. Moreover, you may mix | blend a silica particle with these resin.
The hard coat layer has the effect of increasing the mechanical strength of the laminate.

(6) Antistatic layer Specific examples of the antistatic layer include conductive metal oxide particles such as antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, and Al-doped ZnO particles, or organic Or a curable film to which an inorganic conductive compound is added, a metal oxide film obtained by vapor deposition or sputtering of the metal oxide, or a film made of a conductive organic polymer. Examples of the conductive organic polymer include polyacetylene conductive polymer, polyaniline conductive polymer, polythiophene conductive polymer, polypyrrole conductive polymer, polyphenylene vinylene conductive polymer, and the like. . In addition, as described above, if conductive particles such as ATO particles, ITO particles, antimony-doped ZnO, Al-doped ZnO particles are added as the metal oxide contained in the liquid curable resin composition used in the present invention, The resulting layer containing the metal oxide at a high density becomes a film having antistatic properties. In this case, the formation of a separate antistatic film can be omitted.
The antistatic layer imparts conductivity to the laminate, and prevents static electricity from being generated and dust and the like from adhering thereto.

Only one of these layers may be formed, or two or more different layers may be formed.
The film thickness of the low, medium and high refractive index layers is usually 60 to 150 nm, the film thickness of the antistatic layer is usually 0.05 to 3 μm, and the film thickness of the hard coat layer is usually 1 to 20 μm.

  In the present invention, any two or more continuous layers of the laminate can be formed by the production method of the present invention, but the layer production method not based on the production method of the present invention is known coating and curing, vapor deposition, sputtering, etc. It can manufacture by the method of.

  In addition, the layer made of the liquid curable resin composition according to the present invention is particularly preferably given a heat history by heating in order to form a cured film having excellent optical properties and durability. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time, and the desired cured film is formed. However, in practice, curing by heating is effective in reducing the required time. Is. Moreover, the curing reaction can be further promoted by adding a thermal acid generator as a curing catalyst. The curing catalyst is not particularly limited, and various acids and salts used as curing agents for general urea resins and melamine resins can be used. In particular, ammonium salts can be preferably used. . The heating conditions for the curing reaction can be selected as appropriate, but the heating temperature needs to be equal to or lower than the heat resistant limit temperature of the substrate to be coated.

According to the present invention, since two or more layers can be formed from one coating film, the manufacturing process of the laminate can be simplified.
Further, by making the metal oxide particles unevenly distributed, the scratch resistance of the laminate can be improved.
In addition to the antireflection film, the laminate of the present invention can be used for optical parts such as a lens and a selective transmission film filter.

Next, the liquid curable resin composition used in the present invention will be described.
The liquid curable resin composition contains the following components (A) to (F).
(A) Fluoropolymer having a hydroxyl group in the molecule (B) One or two or more metal oxide particles (hereinafter referred to as “a”) having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more. (B) Metal oxide particles ”
(C) (A) One or two or more solvents (hereinafter referred to as “(C) fast volatile solvent”) having high solubility in a fluorine-containing polymer having a hydroxyl group in the molecule
(D) (B) one or two or more solvents (hereinafter referred to as “(D) slow volatile solvent”) having high dispersion stability with respect to the metal oxide particles and being compatible with (C) the fast volatile solvent. Called)
(E) Curable compound (F) Thermal acid generator Hereinafter, these components will be described individually.

(A) Fluorinated polymer having a hydroxyl group in the molecule The fluorinated polymer is a polymer having a carbon-fluorine bond in the molecule, and the fluorine content is preferably 30% by mass or more. It is preferable that the number average molecular weight by polystyrene conversion obtained by permeation chromatography is 5000 or more. Here, the fluorine content is a value measured by the alizarin complexone method, and the number average molecular weight is a value when tetrahydrofuran is used as a developing solvent.

  An example of the fluoropolymer used in the present invention is a fluoropolymer having a hydroxyl group in the molecule (hereinafter referred to as “hydroxyl group-containing fluoropolymer”). Preferable examples of the hydroxyl group-containing fluoropolymer include those having a polysiloxane segment in the main chain, which contains 10 mol% to 50 mol% of a structural unit derived from a monomer containing a hydroxyl group. The hydroxyl group-containing fluoropolymer is an olefin polymer having a polysiloxane segment represented by the following general formula (1) in the main chain, and the ratio of the polysiloxane segment in the fluoropolymer is usually 0. It is preferable that it is 1-20 mol%.

In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.

  Further, the hydroxyl group-containing fluoropolymer preferably has a fluorine content of 30% by mass or more, more preferably 40-60% by mass, and the number average molecular weight in terms of polystyrene obtained by gel permeation chromatography, Preferably it is 5000 or more, More preferably, it is 10000-500000.

  The hydroxyl group-containing fluoropolymer includes (a) a fluorine-containing olefin compound (hereinafter referred to as “component (a)”), (b) a monomer compound containing a hydroxyl group copolymerizable with the component (a) (hereinafter referred to as “component (a)”). (Referred to as “component (b)”) and (c) an azo group-containing polysiloxane compound (hereinafter referred to as “component (c)”) and, if necessary, (d) a reactive emulsifier (hereinafter referred to as “(d ) Component)) and / or (e) It can be obtained by reacting a monomer compound other than the component (b) copolymerizable with the component (a).

  Examples of the fluorine-containing olefin compound as component (a) include compounds having at least one polymerizable unsaturated double bond and at least one fluorine atom. Specific examples thereof include, for example, (1) fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene; (2) perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether); (3) perfluoro (methyl) (4) perfluoro (propoxypropyl vinyl), perfluoro (alkyl vinyl ether) such as vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); Ether) such as perfluoro (alkoxyalkyl vinyl ethers); other can be exemplified. These compounds can be used alone or in combination of two or more. Among these, hexafluoropropylene, perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) is particularly preferable, and a combination thereof is preferably used.

  Examples of the monomer compound containing a hydroxyl group as component (b) include (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl. Hydroxyl group-containing vinyl ethers such as vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; (2) hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; 3) allyl alcohol; (4) hydroxyethyl (meth) acrylate; These compounds can be used alone or in combination of two or more. Preferred are hydroxyl-containing alkyl vinyl ethers.

  As the azo group-containing polysiloxane compound of component (c), a compound having a polysiloxane segment represented by the above general formula (1) while containing an azo group which is easily thermally cleaved represented by -N = N- For example, it can be manufactured by the method described in JP-A-6-93100. Specific examples of the component (c) include compounds represented by the following general formula (2).

In the formula, y = 10 to 500 and z = 1 to 50.

  Preferred combinations of the components (a), (b) and (c) are, for example, (1) fluoroolefin / hydroxyl group-containing alkyl vinyl ether / polydimethylsiloxane unit, (2) fluoroolefin / perfluoro (alkyl vinyl ether) / Hydroxyl group-containing alkyl vinyl ether / polydimethylsiloxane unit, (3) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether / polydimethylsiloxane unit, (4) fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether / Polydimethylsiloxane unit, (5) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether / polydimethylsiloxane It is a down unit.

  In the hydroxyl group-containing fluoropolymer, the structural unit derived from the component (a) is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, and particularly preferably 30 to 60 mol%. When the proportion of the structural unit derived from the component (a) is less than 20 mol%, the fluorine content in the resulting fluoropolymer tends to be excessive, and the cured product of the resulting liquid curable resin composition has a sufficient refractive index. It is hard to be low. On the other hand, when the proportion of the structural unit derived from the component (a) exceeds 70 mol%, the solubility of the obtained fluoropolymer in an organic solvent is remarkably lowered, and the obtained liquid curable resin composition is: The transparency and adhesion to the substrate are small.

  In the hydroxyl group-containing fluoropolymer, the structural unit derived from the component (b) is preferably 10 to 50 mol%. More preferably, the lower limit is 13 mol% or more, more preferably more than 20 mol% and 21 mol% or more, and preferably the upper limit is 45 mol% or less, more preferably 35 mol% or less. It is. By constituting a liquid curable resin composition using such a fluorine-containing polymer containing a predetermined amount of component (b), it is possible to achieve good scratch resistance and dust wiping in the cured product. it can. On the other hand, when the proportion of the structural unit derived from the component (b) is less than 10 mol%, the fluoropolymer has poor solubility in an organic solvent, and when it exceeds 50 mol%, the liquid curable resin composition The cured product of the product has deteriorated optical properties such as transparency and low reflectance.

  The component (c) azo group-containing polysiloxane compound itself is a thermal radical generator, and has a function as a polymerization initiator in a polymerization reaction for obtaining a fluorinated polymer. It can also be used together. The proportion of the structural unit derived from the component (c) in the fluoropolymer is preferably 0.1 to 20 mol%, more preferably 0.1 to 15 in the polysiloxane segment represented by the general formula (1). The proportion is such that it is mol%, particularly preferably 0.1 to 10 mol%, particularly preferably 0.1 to 5 mol%. When the proportion of the polysiloxane segment represented by the general formula (1) exceeds 20 mol%, the resulting hydroxyl group-containing fluoropolymer is inferior in transparency, and when used as a coating agent. , Repelling and the like are likely to occur during application.

  In addition to the components (a) to (c), a reactive emulsifier is preferably used as the monomer component as the component (d). By using this (d) component, when using a hydroxyl-containing fluoropolymer as a coating agent, favorable coating property and leveling property can be obtained. As the reactive emulsifier, it is particularly preferable to use a nonionic reactive emulsifier. Specific examples of the nonionic reactive emulsifier include compounds represented by the following general formula (3) or general formula (4).

In the formula, n = 1 to 20, m and s represent repeating units, and m = 0 to 4 and s = 3 to 50.

In the formula, m and s are the same as those in the general formula (3). R ³ is an alkyl group which may be linear or branched, and is preferably an alkyl group having 1 to 40 carbon atoms.

  In the hydroxyl group-containing fluoropolymer, the proportion of the structural unit derived from the component (d) is preferably 0 to 10 mol%, more preferably 0.1 to 5 mol%, particularly preferably 0.1 to 1 mol. %. When this ratio exceeds 10 mol%, the liquid curable resin composition obtained becomes sticky, so that handling becomes difficult, and moisture resistance decreases when used as a coating agent.

  (E) As a monomer compound other than the component (b) that can be copolymerized with the component (a), (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, Alkyl vinyl ethers or cycloalkyl vinyl ethers such as isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; (2) vinyl acetate , Vinyl carboxylates such as vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate; ) Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n- (Meth) acrylic acid esters such as propoxy) ethyl (meth) acrylate; (4) carboxyl group-containing monomer compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. The thing which does not contain a hydroxyl group can be mentioned. Alkyl vinyl ether is preferable.

  In the hydroxyl group-containing fluoropolymer, the proportion of the structural unit derived from the component (e) is preferably 0 to 70 mol%, more preferably 5 to 35 mol%. When this ratio exceeds 70 mol%, the resulting liquid curable resin composition becomes tacky and difficult to handle, and moisture resistance decreases when used as a coating agent.

When the component (d) is contained, preferred combinations of the component (a), the component (b), the component (c), the component (d), and the component (e) are as follows.
(1) fluoroolefin / hydroxyl group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (2) fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / Alkyl vinyl ether, (3) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / hydroxyl group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (4) fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group-containing vinyl ether / Polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (5) fluoroolefin / perfluoro (A) Job Shi alkyl vinyl ether) / hydroxyl group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether.

  Examples of radical polymerization initiators that can be used in combination with component (c) include (1) diacyl peroxides such as acetyl peroxide and benzoyl peroxide; (2) ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide. (3) Hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; (4) Di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc. Dialkyl peroxides; (5) peroxyesters such as tert-butylperoxyacetate and tert-butylperoxypivalate; and (6) azo-based compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Compounds like; (7) ammonium persulfate, sodium persulfate, persulfates such as potassium persulfate; Other can be exemplified.

  Specific examples other than the above radical polymerization initiator include, for example, perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (Perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro 2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane And iodine-containing fluorine compounds. The iodine-containing fluorine compound can be used alone or in combination with the organic peroxide, azo compound or persulfate.

  As a polymerization mode for producing a hydroxyl group-containing fluoropolymer, any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method using a radical polymerization initiator can be used. However, an appropriate one can be selected from batch, semi-continuous or continuous operations.

  The polymerization reaction for obtaining the hydroxyl group-containing fluoropolymer is preferably carried out in a solvent system using a solvent. Examples of preferable organic solvents include (1) esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and cellosolve; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; (3) Cyclic ethers such as tetrahydrofuran and dioxane; (4) Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; (5) Aromatic hydrocarbons such as toluene and xylene; be able to. Further, if necessary, alcohols, aliphatic hydrocarbons and the like can be mixed and used.

  The hydroxyl group-containing fluoropolymer obtained as described above may be able to use the reaction solution obtained by the polymerization reaction as it is as a liquid curable resin composition as it is. Appropriate post-processing can also be performed. As this post-treatment, for example, a general method represented by a purification method in which a polymerization reaction solution is added dropwise to an insolubilizing solvent for the hydroxyl group-containing fluoropolymer made of alcohol or the like to coagulate the hydroxyl group-containing fluoropolymer. Reprecipitation treatment can be performed, and then the resulting solid copolymer is dissolved in a solvent to prepare a hydroxyl group-containing fluoropolymer solution. Moreover, what remove | eliminated the residual monomer from the polymerization reaction solution can also be used as a solution of a hydroxyl-containing fluoropolymer as it is.

  The blending ratio of the (A) hydroxyl group-containing fluoropolymer in the solid content of 100% by mass of the liquid curable resin composition is usually 7 to 70% by mass, preferably 10 to 50% by mass. The transparency of the film is improved.

(B) Metal oxide particles The (B) metal oxide particles used in the present invention are metal oxide particles having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more. When the number average particle diameter exceeds 100 nm, it may be difficult to uniformly disperse the metal oxide particles. In addition, the metal oxide particles are liable to settle and lack storage stability. Furthermore, the transparency of the obtained cured film may decrease, or turbidity (Haze value) may increase.
The number average particle diameter is more preferably from 10 to 80 nm, further preferably from 20 to 50 nm.
The “number average particle size” is the number average particle size measured by electron microscopy. When the metal oxide particles are aggregated, it is the primary particle size, and when the metal oxide particles are not spherical ( For example, acicular ATO or the like), the average of the long diameter (longitudinal) and the short diameter (horizontal). Further, when the particle shape is a rod shape (refers to a shape having an aspect ratio of more than 1 and 10 or less), the minor axis is defined as the particle diameter.

  The metal oxide particles preferably include titanium oxide, zirconium oxide (zirconia), antimony-containing tin oxide, tin-containing indium oxide, aluminum oxide (alumina), cerium oxide, zinc oxide, tin oxide, antimony-containing zinc oxide and indium. Particles based on one or more metal oxides selected from zinc oxide can be used.

  Here, metal oxide particles having a multilayer structure in which the metal oxide particles are coated with the one or more metal oxides other than the metal oxide can also be used. Specific examples of the metal oxide particles having a multilayer structure include silica-coated titanium oxide particles, alumina-coated titanium oxide particles, zirconia-coated titanium oxide particles, alumina, and zirconia-coated titanium oxide particles. Among such metal oxide particles, particles mainly composed of titanium oxide or alumina / zirconia-coated titanium oxide particles are particularly preferable.

  By using metal oxide particles having a multilayer structure, the photocatalytic activity of titanium oxide can be suppressed, and decomposition of the cured product can be suppressed. As a result, a cured film having a high refractive index and excellent light resistance can be obtained.

  Moreover, antistatic property can be provided to the cured film by using antimony-containing tin oxide particles (ATO) or the like. In this case, as will be described later, since ATO particles are unevenly distributed, effective antistatic properties and good transparency can be achieved with a smaller amount of added particles.

  As particles mainly composed of titanium oxide, known particles can be used, and the shape thereof may be hollow particles, porous particles, core-shell type particles, and the like. Further, the shape is not limited to a spherical shape, and may be a rod-like shape (referring to a shape having an aspect ratio exceeding 1 and not more than 10) or an irregular shape, and a rod-like shape is preferable. The number average particle size determined by electron microscopy is preferably 1 to 100 nm.

  The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.

  As a commercial item of the particle | grains which have a titanium oxide as a main component, the product etc. by Teika Co., Ltd. and CI Kasei Co., Ltd. can be mentioned, for example.

  The blending ratio of the (B) metal oxide particles with respect to 100% by mass of the solid content of the liquid curable resin composition is usually 10 to 90% by mass, preferably 20 to 80% by mass.

(C) Fast volatile solvent The (C) fast volatile solvent contained in the liquid curable resin composition is one or more solvents having high solubility in the above (A) hydroxyl group-containing fluoropolymer. Here, the high solubility in the hydroxyl group-containing fluoropolymer means that (A) the hydroxyl group-containing fluoropolymer is added to each solvent so as to be 50% by mass and stirred visually at room temperature for 8 hours. A uniform solution. The relative evaporation rate of the (C) fast volatile solvent needs to be larger than the relative evaporation rate of the later-described (D) slow volatile solvent. Here, “relative evaporation rate” refers to the relative value of evaporation rate based on the time required for 90% by mass of butyl acetate to evaporate. For details, see TECHNIQUES OF CHEMISTRY VOL.2 ORGANIC SOLVENTS Physical Properties and
methods of purification 4th ed. (Interscience Publishers, Inc. 1986 page 62). The (C) fast volatile solvent preferably has low dispersion stability with respect to the (B) metal oxide particles. (C) The fast volatile solvent has a relative evaporation rate higher than (D), (A) high solubility in a hydroxyl group-containing fluoropolymer, and (B) low dispersion stability in metal oxide particles. Thus, in the process of applying the liquid curable resin composition to the base material and evaporating the solvents (C) and (D), (B) the metal oxide particles can be unevenly distributed.

  The solvent that can be used as the (C) fast volatile solvent in the present invention is a solvent having a relative evaporation rate of about 1.7 or more. Specifically, methyl ethyl ketone (MEK; relative evaporation rate 3.8), isopropanol (IPA; 1.7), methyl isobutyl ketone (MIBK; relative evaporation rate 1.6), methyl amyl ketone (MAK; 0.3), acetone, methyl propyl ketone and the like.

(D) Slow volatile solvent The (D) slow volatile solvent contained in the liquid curable resin composition is one or more solvents having high dispersion stability with respect to the metal oxide particles (B). Here, (B) that the dispersion stability with respect to the metal oxide particles is high means that (B) the metal oxide particles are adhered to the glass wall by immersing the glass plate in an isopropanol dispersion of the metal oxide particles. When (B) the glass plate to which the metal oxide particles are adhered is immersed in each solvent, (B) the metal oxide particles are visually dispersed uniformly in the solvent. The (D) slow volatile solvent preferably has low solubility in the above (A) hydroxyl group-containing fluoropolymer.

  The solvent that can be used as the (D) slow volatile solvent in the present invention is a solvent having a relative evaporation rate of about 1.7 or less, specifically, methanol (relative evaporation rate 2.1), isopropanol (IPA). 1.7), n-butanol (n-BuOH; 0.5), tert-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl cellosolve, propyl cellosolve, butyl cellosolve, etc. It is done.

As the (C) fast volatile solvent and / or (D) slow volatile solvent used in the present invention, the solvent used in the production of the (A) hydroxyl group-containing fluoropolymer can be used as it is.
The (C) fast volatile solvent and (D) slow volatile solvent used in the present invention must be compatible. The compatibility is sufficient if the specific composition of the composition has such a degree of compatibility that (C) the fast volatile solvent and (D) the slow volatile solvent are not separated.
Here, whether the selected solvent corresponds to (C) fast volatile solvent or (D) slow volatile solvent used in the present invention is relatively determined among a plurality of selected solvent types. Therefore, isopropanol having a relative evaporation rate of 1.7 may be used as (C) a fast volatile solvent or (D) a slow volatile solvent.

  Moreover, in a liquid curable resin composition, a solvent mix | blends solvents other than the said (C) fast volatile solvent and (D) slow volatile solvent for the purpose of improving the applicability | paintability of a composition, etc. be able to. Examples of the solvent blended for such purposes include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and esters such as ethyl acetate and butyl acetate. Further, a solvent that cannot dissolve the fluoropolymer, for example, a poor solvent such as water, alcohols, or ethers, is used in the liquid curable resin composition solution as long as the fluoropolymer does not precipitate. be able to. Thereby, the solution of the fluoropolymer may have good storage properties and preferable coating properties. Examples of such a poor solvent include ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, ethyl cellosolve, and butyl cellosolve.

  The total amount of the solvent (C) and the solvent (D) is usually 300 to 5000 with respect to 100 parts by mass of the total amount of the components other than the solvent (including the components (C) and (D)) in the liquid curable resin composition. Part by mass, preferably 300 to 4000 parts by mass, more preferably 300 to 3000 parts by mass is used. The mixing ratio (mass ratio) of the solvent (C) and the solvent (D) may be arbitrary in the range of 1:99 to 99: 1.

(E) Curable compound (E) A curable compound is a component which superposes | polymerizes by heating etc. and provides sclerosis | hardenability to this-application composition.

  Examples of the curable compound include various amino compounds, various hydroxyl-containing compounds such as pentaerythritol, polyphenol, and glycol, and others.

  The amino compound used as the curable compound is an amino group capable of reacting with the hydroxyl group in the hydroxyl group-containing fluoropolymer (A), for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total. A compound containing two or more, and specific examples include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine obtained by reacting melamine and formaldehyde under basic conditions, alkoxylated methylmelamine, or a derivative thereof is preferable, and in particular, liquid curable resin compositions have good storage stability. Alkoxylated methyl melamine is preferred in that it is obtained and good reactivity is obtained. There are no particular limitations on the methylolated melamine and the alkoxylated methylmelamine used as the curable compound. For example, it can be obtained by the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun) Various resinous materials can be used.

  In addition to urea, examples of the urea compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, and alkoxylated methyluron. And also about compounds, such as a urea derivative, the use of the various resinous materials described in said literature is possible.

  The compounding ratio of the curable compound contained in the solid content of 100% by mass of the liquid curable resin composition is usually 3 to 70% by mass, preferably 3 to 50% by mass, more preferably 5 to 30% by mass. is there. If the amount of the curable compound used is too small, the durability of the thin film formed by the resulting liquid curable resin composition may be insufficient, and if it is out of the range of 3 to 70% by mass, fluorine-containing In the reaction with the polymer, it is difficult to avoid gelation, and the cured product may become brittle.

  (A) The reaction between the hydroxyl group-containing fluoropolymer and the (E) curable compound is, for example, adding a curable compound to a solution of an organic solvent in which the hydroxyl group-containing fluoropolymer is dissolved, and heating for an appropriate time. What is necessary is just to carry out, making a reaction system uniform by stirring etc. The heating temperature for this reaction is preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 120 ° C. If the heating temperature is less than 30 ° C., the reaction proceeds very slowly. If the heating temperature exceeds 150 ° C., in addition to the intended reaction, a cross-linking reaction is caused by a reaction between methylol groups or alkoxylated methyl groups in the curable compound. This is not preferable because a gel is formed. The progress of the reaction is quantitative by measuring the amount of methylol group or alkoxylated methyl group by infrared spectroscopic analysis or by collecting the dissolved polymer by reprecipitation method and measuring the increase. Can be confirmed.

  In addition, it is preferable to use the same organic solvent as that used in the production of the hydroxyl group-containing fluoropolymer for the reaction of (A) the hydroxyl group-containing fluoropolymer and (E) the curable compound. In the present invention, the reaction solution obtained by the hydroxyl group-containing fluoropolymer and the curable compound thus obtained can be used as it is as a solution of the liquid curable resin composition, and various additions can be made as necessary. It can also be used after blending an agent.

(F) Thermal acid generator When the thermal acid generator that can be blended in the liquid curable resin composition is cured by heating the coating film of the liquid curable resin composition, the heating conditions are: It is a substance that can be improved to a milder one. Specific examples of the thermal acid generator include, for example, various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid, and maleic acid, and various aromatic acids such as benzoic acid and phthalic acid. Examples thereof include carboxylic acids and salts thereof, alkylbenzene sulfonic acids and ammonium salts thereof, various metal salts, phosphoric acid and organic acid phosphoric esters.
The ratio of the thermal acid generator used in the solid content of 100% by mass of the liquid curable resin composition is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass. When this ratio is excessive, the storage stability of the liquid curable resin composition is deteriorated, which is not preferable.

(G) Additive The liquid curable resin composition includes, for example, a hydroxyl group for the purpose of improving the coating properties of the liquid curable resin composition and the properties of the thin film after curing, and imparting photosensitivity to the coating film. Contains various additives such as colorants such as various polymers and monomers, pigments or dyes, stabilizers such as anti-aging agents and UV absorbers, photosensitive acid generators, surfactants, and polymerization inhibitors Can be made. In particular, it is preferable to add a thermal acid generator or a photoacid generator for the purpose of improving the hardness and durability of the formed cured film, and in particular, the transparency after curing of the liquid curable resin composition is reduced. It is preferable to select and use one that is not dissolved and that dissolves uniformly in the solution.

(1) Polymer having a hydroxyl group Examples of the polymer having a hydroxyl group that can be blended in a liquid curable resin composition are obtained by copolymerizing a hydroxyl group-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate. Examples of the polymer, novolak resin or resol resin that can be used include resins having a known phenol skeleton.

(2) Colorant such as pigment or dye Examples of the colorant that can be blended in the liquid curable resin composition include (1) extender pigments such as alumina white, clay, barium carbonate, barium sulfate; Inorganic pigments such as zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black; (3) Brilliant Carmine 6B, Permanent Red 6B, Permanent Red R, Benzidine Yellow, Organic pigments such as phthalocyanine blue and phthalocyanine green; (4) basic dyes such as magenta and rhodamine; (5) direct dyes such as direct scarlet and direct orange; (6) acidic dyes such as low serine and metanyl yellow; Can be mentioned.

(3) Stabilizers such as anti-aging agents and UV absorbers As anti-aging agents and UV absorbers that can be added to the liquid curable resin composition, known ones can be used.
Specific examples of the antioxidant include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone Monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole, and the like.

  Specific examples of ultraviolet absorbers include, for example, salicylic acid ultraviolet absorbers represented by phenyl salicylate, benzophenone ultraviolet absorbers such as dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and benzotriazole ultraviolet absorbers. Ultraviolet absorbers used as additives for various plastics such as cyanoacrylate-based ultraviolet absorbers can be used.

(4) Photosensitive acid generator The photosensitive acid generator that can be blended in the liquid curable resin composition imparts photosensitivity to the coating film of the liquid curable resin composition, for example, radiation such as light. Is a substance that enables the coating film to be photocured by irradiation. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt; (2) β-ketoester, β-sulfonylsulfone and these Sulfone compounds such as α-diazo compounds of (3); (3) sulfonic acid esters such as alkyl sulfonates, haloalkyl sulfonates, aryl sulfonates, and imino sulfonates; (4) sulfones represented by the following general formula (5) Imide compounds; (5) Diazomethane compounds represented by the following general formula (6);

In the formula, X represents a divalent group such as an alkylene group, an arylene group or an alkoxylene group, and R ⁴ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group. Show.

In the formula, R ⁵ and R ⁶ may be the same as or different from each other, and represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

  The photosensitive acid generator can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generator. The use ratio of the photosensitive acid generator in 100 parts by mass of the solid content of the liquid curable resin composition is preferably 0 to 20 parts by mass, more preferably 0.1 to 10 parts by mass. When this ratio is excessive, the strength of the cured film becomes inferior and the transparency is also lowered, which is not preferable.

(5) Surfactant A surfactant can be added to the liquid curable resin composition for the purpose of improving the applicability of the liquid curable resin composition. As this surfactant, known ones can be used. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used. In particular, a cationic surfactant is preferably used so that the cured film has excellent strength and good optical properties. Furthermore, a quaternary ammonium salt is preferable, and among them, the use of a quaternary polyether ammonium salt is particularly preferable because dust wiping property is further improved. Examples of cationic surfactants that are quaternary polyether ammonium salts include Adekacol CC-15, CC-36, and CC-42 manufactured by Asahi Denka Kogyo Co., Ltd. The use ratio of the surfactant is preferably 5 parts by mass or less with respect to 100 parts by mass of the solid content of the liquid curable resin composition.

(6) Polymerization inhibitor Thermal polymerization inhibitors that can be incorporated into the liquid curable resin composition include, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amino Loxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1 , 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and the like. This thermal polymerization inhibitor is preferably used in an amount of 5 parts by mass or less with respect to 100 parts by mass of the solid content of the liquid curable resin composition.

(7) Solvents other than components (C) and (D) A solvent other than components (C) and (D) can be added to the liquid curable resin composition. Such a kind and compounding quantity of a solvent can be freely selected in the range which does not impair the effect of this invention.

  The cured film is obtained by curing the liquid curable resin composition, and has a multilayer structure of two or more layers. In particular, it has a layer structure of two or more layers consisting of (B) one or more layers in which the metal oxide particles are present in high density and one or less layers in which the (B) metal oxide particles are substantially absent. It is preferable.

  When forming a cured film from said liquid curable resin composition, it is preferable to coat with respect to a base material (application member). As such a coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, an ink jet method, or the like can be used.

  The means for curing the liquid curable resin composition is not particularly limited, but for example, heating is preferable. In this case, it is preferable to heat at 30 to 200 ° C. for 1 to 180 minutes. By heating in this way, a cured film excellent in antireflection properties can be obtained more efficiently without damaging the substrate and the formed cured film. Preferably, it heats at 50-180 degreeC for 1 to 120 minutes, More preferably, it heats at 80-150 degreeC for 1 to 60 minutes.

Moreover, it can also be hardened | cured by irradiating a radiation by adding the above-mentioned photo-acid generator. In this case, for example, an ultraviolet irradiation device (a metal halide lamp, a high-pressure mercury lamp, or the like) can be used under a light irradiation condition of 0.001 to 10 J / cm ² , but the irradiation condition is not limited to this. . 0.01-5 J / cm ² is more preferable, and 0.1-3 J / cm ² is more preferable.

  In addition, the degree of cure of the cured film is, for example, when using a melamine compound as the curable compound, infrared spectroscopy analysis of the amount of methylol group or alkoxylated methyl group of the melamine compound, or the gelation rate, It can be confirmed quantitatively by measuring using a Soxhlet extractor.

  In the process of evaporating the solvent (C) and the solvent (D) in the composition after applying the liquid curable resin composition, (B) the metal oxide particles are applied on the coating base side (near the boundary with the adjacent layer) or its It is unevenly distributed on the opposite side. Therefore, (B) metal oxide particles are present at high density near one interface of the cured film, and (B) metal oxide particles are substantially absent near the other interface of the cured film. A resin layer having a refractive index is formed. Therefore, a cured film having a layer structure of two or more layers can be obtained by curing one coating film made of the liquid curable resin composition. Each layer formed by separation can be confirmed, for example, by observing a cross section of the obtained film with an electron microscope. (B) The layer in which the metal oxide particles are present at a high density is a concept indicating a portion where the metal oxide particles are aggregated, and is a layer substantially composed of the metal oxide particles as a main component. However, the component (A) may coexist in the layer. On the other hand, the layer substantially free of metal oxide particles is a concept indicating a portion where metal oxide particles are not present, but may be included a little as long as the effect of the present invention is not impaired. This layer is a layer substantially composed of components other than metal oxide particles such as a cured product of component (A) and component (E). In many cases, the cured film has a two-layer structure in which a layer in which metal oxide particles are present at a high density and a layer in which metal oxide particles are not substantially present form a continuous layer. When a PET resin (including a PET resin having an easy-adhesion layer) or the like is used for the base material, the layer that is the base material, the layer in which metal oxide particles are present at a high density, and the metal oxide particles are substantially Layers not present in are formed adjacent in this order.

The obtained cured film preferably has a refractive index of 0.05 to 0.8, more preferably 0.1 to 0.6, in the film thickness direction. Further, it is preferable that the refractive index change has a main change in the vicinity of the boundary of the substantial two-layer structure.
The degree of change in refractive index can be adjusted by (B) content and type of metal oxide particles, (A) content and composition of fluoropolymer, and (E) content and type of curable compound. .
Moreover, the refractive index in the low refractive index part of a cured film is 1.3-1.5, for example, and the refractive index in a high refractive index part is 1.6-2.2.

In the following description, “part” or “%” means “part by mass” or “% by mass” unless otherwise specified.
Production Example 1
(1) Synthesis of an organic compound having a polymerizable unsaturated group To a mixed solution of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in a vessel equipped with a stirrer, 222 parts of isophorone diisocyanate was added in dry air at 50 ° C. After dropwise addition over 1 hour, the mixture was further stirred at 70 ° C. for 3 hours.
Subsequently, NK ester A-TMM-3LM-N (made of 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., is involved in the reaction. (Only pentaerythritol triacrylate having a hydroxyl group.) 549 parts were added dropwise at 30 ° C. over 1 hour, and then stirred at 60 ° C. for 10 hours to obtain a reaction solution.
The product in this reaction solution, that is, the amount of residual isocyanate in the organic compound having a polymerizable unsaturated group was measured by FT-IR and found to be 0.1% by mass or less, and each reaction was performed almost quantitatively. I confirmed that. As described above, a composition (A-1) of 773 parts of a compound having thiourethane bond, urethane bond, alkoxysilyl group, and polymerizable unsaturated group and 220 parts of pentaerythritol tetraacrylate not involved in the reaction was obtained. Obtained.

Production Example 2
(2) Synthesis of urethane acrylate To a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer, NK ester A-TMM-3LM-N (reaction made by Shin-Nakamura Chemical) (Only pentaerythritol triacrylate having a hydroxyl group is involved in the reaction.) After 93 parts were added dropwise at 10 ° C. for 1 hour, the reaction solution was stirred at 60 ° C. for 6 hours.
The product in this reaction solution, that is, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 1, and was 0.1% by mass or less, confirming that the reaction was carried out almost quantitatively. did. Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator.
As a result, 75 parts of a urethane hexaacrylate compound was obtained, and a composition (A-2) in which 37 parts of pentaerythritol tetraacrylate that was not involved in the reaction was mixed was obtained.

Production Example 3
[Preparation of silica particle-containing composition for hard coat layer]
2.32 parts of composition (A-1) containing a polymerizable unsaturated group produced in Production Example 1, silica particle sol (methyl ethyl ketone silica sol, MEK-ST manufactured by Nissan Chemical Industries, Ltd., number average particle size 0.022 μm) , Silica concentration 30%) 91.3 parts (27 parts as silica particles), 0.12 part of ion-exchanged water, and 0.01 part of p-hydroxyphenyl monomethyl ether were stirred at 60 ° C. for 4 hours, Reactive particles (dispersion liquid (A-3)) were obtained by adding 1.36 parts of orthoformate methyl ester and further heating and stirring at the same temperature for 1 hour. When 2 g of this dispersion (A-3) was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour and weighed to determine the solid content, it was 30.7%. Further, 2 g of the dispersion (A-3) was weighed in a magnetic crucible, preliminarily dried on a hot plate at 80 ° C. for 30 minutes, and baked in a muffle furnace at 750 ° C. for 1 hour. The inorganic content was determined to be 90%.

  98.6 g of this dispersion (A-3), 3.4 g of composition (A-2), 2.1 g of 1-hydroxycyclohexyl phenyl ketone, IRGACURE907 (2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals) 1.2 g, dipentaerythritol hexaacrylate (DPHA) 33.2 g, and cyclohexanone 7 g were mixed and stirred to prepare a silica particle-containing hard coat layer composition (solid) 145 g of 50% fractional concentration was obtained.

Production Example 4
[Preparation of zirconia particle-containing composition]
300 parts of UEP-100 (primary particle size 10-30 nm) manufactured by Daiichi Rare Chemicals Co., Ltd. are added to 700 parts of methyl ethyl ketone (MEK), and dispersed for 168 hours with glass beads to remove the glass beads. As a result, 950 parts of a zirconia dispersed sol was obtained. After weighing 2 g of the zirconia-dispersed sol in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 30%. To 100 g of this zirconia dispersion sol, 0.86 g of the composition (A-1) synthesized in Production Example 1, 13.4 g of dipentaerythritol hexaacrylate (DPHA), 0.016 g of p-methoxyphenol, 0.033 g of ion-exchanged water. The mixture was stirred at 60 ° C. for 3 hours, 0.332 g of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain 116 g of a dispersion of surface-modified zirconia particles. 116 g of this dispersion, 1.34 g of composition (A-2), 1.26 g of 1-hydroxycyclohexyl phenyl ketone, IRGACURE907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, manufactured by Ciba Specialty Chemicals) 0.76 g and 2846 g of MEK were mixed and stirred to obtain 2964 g of a zirconia particle-containing composition (solid content concentration 4%).

Production Example 5
[Preparation of composition containing tin-doped indium oxide (ITO) particles]
700 g ITO sol (10 wt% IPA sol) manufactured by Fuji Chemical Co., Ltd., 29.5 g DPHA, 1 g 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, isopropyl alcohol (IPA) 1769 0.5 g was mixed to obtain an ITO particle-containing composition having a solid content concentration of 4%.

Production Example 6
[Preparation of antimony-doped tin oxide (ATO) particle-containing composition]
ATO particles (Ishihara Techno Co., Ltd., SN-100P, primary particle size 10-30 nm), dispersant (Asahi Denka Kogyo Co., Ltd., Adeka Pluronic TR-701), and methanol were mixed in 90 / 2.78 / 211 (weight ratio) was mixed (total solid content 31%, total inorganic content 29.6%). In a 50 ml plastic shaker of a paint shaker, 40 g of glass beads (manufactured by TOSHINRIKO, BZ-01) (bead diameter: 0.1 mm) (volume: about 16 ml) and the above mixed solution (30 g) were dispersed for 3 hours, and the median diameter was 80 nm. A dispersed sol was obtained. To sol 304 g, a mixed solution of 5.7 g of the composition (A-1), 0.01 g of p-methoxyphenol and 0.12 g of ion exchange water was stirred at 60 ° C. for 3 hours, and then 1.3 g of methyl orthoformate was added. Then, by further heating and stirring at the same temperature for 1 hour, 311 g of a dispersion of surface-modified ATO particles was obtained. 278.3 g of this dispersion, 1.7 g of composition (A-2), 8.59 g of pentaerythritol triacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 0 .88 g, methanol 33 g, and propylene glycol monomethyl ether 1675 were mixed and stirred to obtain 2000 g of an ATO particle-containing composition (solid content concentration 5%).

Production Example 7
[Preparation of Al-doped ZnO particle-containing composition]
Zinc oxide particles (Al-doped ZnO particles manufactured by Sakai Kagaku, primary particle size 10 to 20 nm), dispersant (manufactured by Enomoto Kasei Co., Ltd., Hyprad ED151) and propylene glycol monomethyl ether were mixed with 27.6 / 4.8 / 67. 6 (weight ratio) was mixed (total solid content 30%, total inorganic content 27.6%). Into a 50 ml plastic bottle of a paint shaker, 40 g of zirconia beads (bead diameter 0.1 mm) and the above mixed solution (30 g) were placed and dispersed for 8 hours to obtain a dispersion sol having a median diameter of 40 nm. To 290 g of this sol, 10 g of pentaerythritol triacrylate, 0.5 g of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and 2138 g of propylene glycol monomethyl ether were added and mixed and stirred. 2438 g of a particle-containing composition (solid content concentration 4%) was obtained.

Production Example 8
[Production of fluoropolymer]
A stainless steel autoclave with an electromagnetic stirrer with an internal volume of 1.5 L was sufficiently replaced with nitrogen gas, and then 500 g of ethyl acetate, 43.2 g of perfluoro (propyl vinyl ether), 41.2 g of ethyl vinyl ether, 21.5 g of hydroxyethyl vinyl ether, nonionic properties 40.5 g of “Adekaria soap NE-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) as a reactive emulsifier, 6.0 g of “VPS-1001” (manufactured by Wako Pure Chemical Industries, Ltd.) as an azo group-containing polydimethylsiloxane, and excess After adding 1.25 g of lauroyl oxide and cooling to −50 ° C. with dry ice-methanol, oxygen in the system was removed again with nitrogen gas.

Next, 97.4 g of hexafluoropropylene was added, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a fluoropolymer.

  The obtained polymer had a polystyrene-reduced number average molecular weight (Mn) of 48000 by gel permeation chromatography, a glass transition temperature (Tg) of 26.8 ° C. by DSC, and a fluorine content of 50.3% by the alizarin complexone method. It was confirmed that.

Production Example 9
[Silica-coated TiO ₂ particle dispersion]
Add 350 parts by mass of silica-coated titanium oxide fine powder, 80 parts by mass of ethylene oxide-propylene oxide copolymer (average polymerization degree: about 20), 1000 parts by mass of isopropyl alcohol, and 1000 parts by mass of butyl cellosolve. After time dispersion, the glass beads were removed to obtain 2430 parts by mass of silica-coated titanium oxide particle dispersion. Here, when the obtained silica-coated TiO ₂ particle dispersion was weighed on an aluminum dish and dried on a hot plate at 120 ° C. for 1 hour to obtain the total solid concentration, it was 17% by mass. Further, this silica-coated TiO ₂ particle dispersion-1 was weighed in a magnetic crucible, pre-dried on a hot plate at 80 ° C. for 30 minutes, and then fired in a muffle furnace at 750 ° C. for 1 hour. It was 82 mass% when the inorganic content in total solid content was calculated | required from the amount of residue and total solid content concentration.

Production Example 10
(1) Production of liquid curable resin composition (Compositions 1 to 5) 24 g of silica-coated titanium oxide dispersion obtained in Production Example 9 (solid content: 4.08 g), fluorinated polymer obtained in Production Example 8 2 g, 1.2 g of methoxylated methylmelamine “Cymel 303” (Mitsui Cytec Co., Ltd.) as a crosslinkable compound and 0.68 g of catalyst 4050 (Mitsui Cytec Co., Ltd., aromatic sulfonic acid compound) as a curing catalyst Was dissolved in 32 g of methyl ethyl ketone, 24 g of methyl isobutyl ketone, and 16 g of tertiary butanol to obtain composition 1. When the total solid content concentration in the liquid resin composition was measured in the same manner as in Production Example 9, it was 7.5% by mass.
Similarly, each component was mix | blended so that it might become a mixture ratio shown in following Table 1, and the compositions 2-5 were obtained. In compositions 2 to 5, normal butanol (n-BuOH) was used instead of tertiary butanol, and the composition of the solvent was methyl ethyl ketone (MEK) / isopropanol (IPA) / methyl isobutyl ketone (MIBK) / normal butanol (n -BuOH) = 40/20/30/10 was used.

(2) Production of Liquid Curable Resin Composition (Composition 6) Instead of the fluoropolymer obtained in Production Example 8, Kyner ADS (manufactured by Elf Atchem Japan Co., Ltd. Propylene hexafluoride, 4 fluoropolymer) A liquid curable resin in the same manner as in the production of the liquid curable resin composition (Composition 1) except that a copolymer of ethylene fluoride and ethylene difluoride (having no hydroxyl group or polymerizable unsaturated group) is used. A resin composition (Composition 6) was obtained.

Example 1 and Comparative Example 1
[Production of laminate]
(1) Production of hard coat layer The silica particle-containing composition for hard coat layer (solid content concentration 50%) prepared in Production Example 3 was used to prepare a triacetyl cellulose film (manufactured by LOFO) using a wire bar coater (# 12). And then dried in an oven at 80 ° C. for 1 minute. Then, the cured film layer was formed by irradiating an ultraviolet-ray on the light irradiation conditions of 0.6 J / cm < ² > using the high pressure mercury lamp in air. It was 5 micrometers when the film thickness of the cured film layer was measured with the stylus type film thickness meter.

(2) Production of Medium Refractive Index Layer On the hard coat layer produced in (1) using the zirconia particle-containing composition (solid content concentration 4%) prepared in Production Example 4 using a wire bar coater (# 3) And then dried in an oven at 80 ° C. for 1 minute. Subsequently, a cured film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.6 J / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere. It was 65 nm when the film thickness of the cured film layer was computed with the reflection spectrometer.

(3) Production of High Refractive Index Layer and Low Refractive Index Layer Using the wire bar coater (# 3), each of the liquid curable resin compositions of Compositions 1 to 6 obtained in Production Example 10 (2) After coating on the medium refractive index layer prepared in step 1, a cured film layer having a thickness of 0.2 μm was formed by heating in an oven at 120 ° C. for 10 minutes.

Example 2 and Comparative Example 2
[Production of laminate]
(1) Production of Hard Coat Layer It was produced in the same manner as Example 1 (1).
(2) Preparation of antistatic layer The ITO particle-containing composition (solid content concentration 4%) prepared in Production Example 5 was applied to the hard coat layer prepared in (1) using a wire bar coater (# 3). After coating, it was dried in an oven at 80 ° C. for 1 minute. Subsequently, a cured film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.6 J / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere. It was 65 nm when the film thickness of the cured film layer was computed with the reflection spectrometer.
(3) Production of medium refractive index layer It was produced in the same manner as Example 1 (2).
(4) Production of High Refractive Index Layer and Low Refractive Index Layer Using the wire bar coater (# 3), each of the liquid curable resin compositions of Compositions 1 to 6 obtained in Production Example 10 (3) After coating on the medium refractive index layer prepared in step 1, a cured film layer having a thickness of 0.2 μm was formed by heating in an oven at 120 ° C. for 10 minutes.

Examples 3 and 4 and Comparative Examples 3 and 4
[Production of laminate]
(1) Preparation of antistatic layer Instead of ITO particles prepared in Production Example 5, ATO particle-containing composition (solid content concentration 5%) prepared in Production Example 6 or 7 or Al-doped ZnO particle-containing composition (solid) After coating a triacetylcellulose film (made by LOFO, film thickness 80 μm) using a wire bar coater (# 3), it was dried in an oven at 80 ° C. for 1 minute. Subsequently, a cured film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.6 J / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere. It was 65 nm when the film thickness of the cured film layer was computed with the reflection spectrometer.
(2) Production of Hard Coat Layer After coating the silica particle-containing hard coat layer composition prepared in Production Example 3 (solid content concentration 50%) using a wire bar coater (# 12), in an oven Dry at 80 ° C. for 1 minute. Then, the cured film layer was formed by irradiating an ultraviolet-ray on the light irradiation conditions of 0.6 J / cm < ² > using the high pressure mercury lamp in air.
(3) Production of medium refractive index layer It was produced in the same manner as Example 1 (2).
(4) Production of High Refractive Index Layer and Low Refractive Index Layer Using the wire bar coater (# 3), each of the liquid curable resin compositions of Compositions 1 to 6 obtained in Production Example 10 (3) After coating on the medium refractive index layer prepared in step 1, a cured film layer having a thickness of 0.2 μm was formed by heating in an oven at 120 ° C. for 10 minutes.

Example 5, Comparative Example 5
[Production of laminate]
(1) Production of Hard Coat Layer It was produced in the same manner as Example 1 (1).
(2) Production of High Refractive Index Layer and Low Refractive Index Layer Using the wire bar coater (# 3), each of the liquid curable resin compositions of Compositions 1 to 6 obtained in Production Example (1) After coating on the hard coat layer prepared in step 1, a cured film layer having a thickness of 0.2 μm was formed by heating in an oven at 120 ° C. for 10 minutes.

Evaluation Example 1
[Evaluation of laminate]
When the cross sections of the laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were observed with a transmission electron microscope, in the laminate using the compositions 1, 2, 3, and 5, the low refractive index layer was used. It was confirmed that the high refractive index layer was separated into two layers. At this time, the low refractive index layer was a layer in which metal oxide particles were not substantially present, and the high refractive index layer was a layer in which metal oxide particles were present at high density. In the laminate using the composition 4, the high refractive index layer and the low refractive index layer had a uniform structure and were not separated. In the laminate using the composition 6, the high refractive index layer and the low refractive index layer were partially aggregated and the layers were not separated.
FIG. 11 shows the concept of each state of two-layer separation, no separation (partial aggregation), and uniform structure.
The antireflection property of the antireflection laminate using the compositions 1, 2, 3, and 5 was measured using a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, Hitachi (Manufactured by Seisakusho Co., Ltd.), the reflectance at a wavelength of 550 nm was measured and evaluated. Specifically, the reflectance of the antireflection laminate (antireflection film) was measured using the reflectance of the deposited aluminum film as a reference (100%). As a result, all the laminates had a reflectance of 1% or less at a wavelength of 550 nm.

Abbreviations in Table 1 represent the following.
(A) Fluoropolymer: The fluoropolymer produced in Production Example 1 above.
Kyner ADS: Elf Atchem Japan Co., Ltd .; copolymer of hexafluoropropylene, tetrafluoroethylene and difluoroethylene. It does not have a hydroxyl group or a polymerizable unsaturated group.
(B) Metal oxide particles Alumina, zirconia-coated TiO ₂ particle dispersion: manufactured by Teika Co., Ltd. Total solid content concentration 28%, particle concentration 24%, number average particle diameter 20 nm
Silica-coated TiO ₂ particle dispersion: produced in Production Example 2.
(E) Cymel 303: Methoxylated methylmelamine, manufactured by Mitsui Cytec Co., Ltd. (F) Catalyst 4050: manufactured by Mitsui Cytech Co., Ltd., aromatic sulfonic acid compound

  Since the manufacturing method of the laminated body of this invention can form two or more layers from one coating film, it can simplify the manufacturing process of the laminated body which has a multilayer structure of two or more layers. Therefore, the method for producing a laminate of the present invention can be advantageously used particularly for the formation of optical materials such as antireflection films, lenses, and selective transmission film filters. Moreover, the obtained laminated body can be suitably used as a paint, a weather resistant film, a coating, etc. for a substrate requiring weather resistance by utilizing the fact that a layer having a high fluorine content can be included. Moreover, since the laminate is excellent in adhesion to the substrate, has high scratch resistance, and imparts a good antireflection effect, it is extremely useful as an antireflection film and can be applied to various display devices. The visibility can be improved.

It is a figure for demonstrating "two or more layers formed from one coating film." It is a figure for demonstrating "two or more layers formed from one coating film." It is a figure for demonstrating "two or more layers formed from one coating film." It is a figure for demonstrating "two or more layers formed from one coating film." It is a figure for demonstrating "two or more layers formed from one coating film." It is sectional drawing of the anti-reflective film which is one Embodiment which concerns on this invention. It is sectional drawing of the antireflection film which is other embodiment which concerns on this invention. It is sectional drawing of the antireflection film which is other embodiment which concerns on this invention. It is sectional drawing of the antireflection film which is other embodiment which concerns on this invention. It is sectional drawing of the antireflection film which is other embodiment which concerns on this invention. It is sectional drawing of the antireflection film which is other embodiment which concerns on this invention. It is sectional drawing of the antireflection film which is other embodiment which concerns on this invention. It is sectional drawing of the antireflection film which is other embodiment which concerns on this invention. It is sectional drawing of the antireflection film which is other embodiment which concerns on this invention. It is an electron micrograph which shows the concept of each state of bilayer separation, not isolate | separating (partial aggregation), and a uniform structure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Base material 20 Hard-coat layer 30 Antistatic layer 40 High refractive index layer 50 Low refractive index layer 60 Medium refractive index layer

Claims (16)

A substrate and a method for producing a laminate having a multilayer structure thereon,
On the base material or the layer formed on the base material, a liquid curable resin composition containing the following components (A) to (F) is applied to form a coating film,
A method for producing a laminate, wherein two or more layers are formed by evaporating a solvent from the coating film of 1.
[Liquid curable resin composition]
(A) a hydroxyl group have a in the molecule, was mainly fluorine-containing polymer in the chain having a polysiloxane segment (B) Number-average particle diameter of 100nm or less and a refractive index of 1.50 or more one or More than seed metal oxide particles (hereinafter referred to as “(B) metal oxide particles”)
(C) (A) One or two or more solvents (hereinafter referred to as “(C) fast volatile solvent”) having high solubility in a fluorine-containing polymer having a hydroxyl group in the molecule
(D) (B) one or two or more solvents (hereinafter referred to as “(D) slow volatile solvent”) having high dispersion stability with respect to the metal oxide particles and being compatible with (C) the fast volatile solvent. Called)
(E) curable compound (F) thermal acid generator and (C) relative evaporation rate of fast volatile solvent is greater than (D) relative evaporation rate of slow volatile solvent   Each of the two or more layers is a layer in which metal oxide particles are present in a high density or a layer in which metal oxide particles are not substantially present, and at least one layer has metal oxide particles in a high density. It is a layer, The manufacturing method of the laminated body of Claim 1 characterized by the above-mentioned.   The method for producing a laminate according to claim 2, wherein the two or more layers are two layers.   Furthermore, the said 2 or more layer is hardened by heating, The manufacturing method of the laminated body as described in any one of Claims 1-3 characterized by the above-mentioned.   The method for producing a laminate according to any one of claims 1 to 4, wherein the laminate is an optical component.   The method for producing a laminate according to any one of claims 1 to 4, wherein the laminate is an antireflection film. The layered product is an antireflection film in which at least a high-refractive index layer and a low-refractive index layer are stacked in this order from the side close to the substrate on the substrate, and the two layers according to claim 3 ,
It consists of a high refractive index layer and a low refractive index layer, The manufacturing method of the laminated body of Claim 3 characterized by the above-mentioned. The refractive index at 589 nm of the low refractive index layer is 1.20 to 1.55,
The method for producing a laminate according to claim 7, wherein the refractive index at 589 nm of the high refractive index layer is 1.50 to 2.20, which is higher than the refractive index of the low refractive index layer. The laminated body is an antireflection film in which at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order from the side close to the base material on the base material. The method for producing a laminate according to claim 3, wherein the two layers are composed of a high refractive index layer and a low refractive index layer. The refractive index at 589 nm of the low refractive index layer is 1.20 to 1.55,
The refractive index at 589 nm of the middle refractive index layer is 1.50 to 1.90, which is higher than the refractive index of the low refractive index layer,
The method for producing a laminate according to claim 9, wherein the refractive index at 589 nm of the high refractive index layer is 1.51 to 2.20, which is higher than the refractive index of the medium refractive index layer.   Furthermore, a hard-coat layer and / or an antistatic layer are formed on a base material, The manufacturing method of the laminated body as described in any one of Claims 7-10 characterized by the above-mentioned. The (C) fast volatile solvent of the liquid curable resin composition is one or more solvents having low dispersion stability with respect to (B) metal oxide particles, and (D) the slow volatile solvent is (A) ) have a hydroxyl group in the molecule, low solubility fluoropolymer having a polysiloxane segment in the main chain, one of the claims 1 to 11, characterized in that the one or more solvents The manufacturing method of the laminated body as described in any one.   The (B) metal oxide particles of the liquid curable resin composition are titanium oxide, zirconium oxide, antimony-containing tin oxide, tin-containing indium oxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide, antimony-containing zinc oxide and indium. It is a particle | grain which has 1 type, or 2 or more types of metal oxides selected from a contained zinc oxide as a main component, The manufacturing method of the laminated body as described in any one of Claims 1-12 characterized by the above-mentioned.   The method for producing a laminate according to claim 13, wherein the (B) metal oxide particles of the liquid curable resin composition are particles mainly composed of titanium oxide.   The method for producing a laminate according to any one of claims 1 to 14, wherein the (B) metal oxide particles of the liquid curable resin composition are metal oxide particles having a multilayer structure.   The laminated body manufactured by the manufacturing method of the laminated body as described in any one of Claims 1-15.