JP4839703B2 - Manufacturing method of laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a laminate, capable of forming two or more layers from one coated film and to provide the laminate by using the method. <P>SOLUTION: The method for producing the laminate has a base material 30 and multilayer structures 40 and 50 arranged on the base material. The method for producing the laminate comprises applying a liquid curable resin composition containing a fluorine-containing polymer, a thermosetting compound, a curing catalyst, metal oxide particles, a highly volatile solvent, a less volatile solvent and an active energy ray-curable compound onto the base material 30 or a layer formed on the base material 30 to form a coated film and forming two or more layers 40 and 50 by evaporating a solvent from the single coated film. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

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, the following components (A), (B), (C), (D), (E-1), (E-2) and (F) A liquid curable resin composition containing 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) fluorinated polymer (B) thermosetting compound (C) curing catalyst (D) metal oxide particles having a number average particle diameter of 100 nm or less (hereinafter referred to as “(D) metal oxide particles”)
(E-1) (A) One type or two or more types of solvents having high solubility of the fluoropolymer (hereinafter referred to as “(C) fast volatile solvent”)
(E-2) (D) One or two or more solvents (hereinafter referred to as “(E-)” which have high dispersion stability of metal oxide particles and are compatible with (E-1) fast volatile solvents. 2) Slow volatile solvent ")
1. (F) The relative evaporation rate of the active energy ray-curable compound and (E-1) fast volatile solvent is greater than the relative evaporation rate of (E-2) 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, it hardens | cures by heating the said 2 or more layer and / or irradiating a radiation, 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 In 100 mass% of the total amount of components other than (E-1) fast volatile solvent and (E-2) slow volatile solvent (hereinafter referred to as “(E) solvent”) in the liquid curable resin composition. ,
(C) 0.1-20 mass% of component
The manufacturing method of the laminated body as described in any one of Claims 1-11 characterized by the above-mentioned.
13. The laminate according to any one of 1 to 12, wherein 5 to 80% by mass of the component (B) is contained in 100% by mass of the total amount of components other than the solvent (E) in the liquid curable resin composition. Manufacturing method.
14 (D) metal oxide particles of the liquid curable resin composition contain titanium oxide, zirconium oxide, antimony-containing tin oxide, tin oxide-containing indium, silicon dioxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide, antimony 14. The method for producing a laminate according to any one of 1 to 13, which is a particle mainly composed of one or two or more metal oxides selected from zinc oxide and indium-containing zinc oxide.
15. The method for producing a laminate according to any one of 1 to 14, wherein (D) the metal oxide particles of the liquid curable resin composition are metal oxide particles having a multilayer structure.
16. (D) The metal oxide particle of the said liquid curable resin composition is couple | bonded with the organic compound which has a polymerizable unsaturated group, The manufacturing method of the laminated body in any one of 1-15 characterized by the above-mentioned. .
The laminated body manufactured by the manufacturing method of the laminated body described in any one of 17.1-16.

  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 and / or irradiation. 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
Examples thereof include coated TiO ₂ particles and CeO ₂ particles. 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
Examples thereof include coated TiO ₂ particles and CeO ₂ particles. 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), (B), (C), (D), (E-1), (E-2), and (F).
(A) Fluoropolymer (B) Thermosetting Compound (C) Curing Catalyst (D) Metal Oxide Particles with Number Average Particle Diameter of 100 nm or Less (E-1) (A) Solubility of Fluoropolymer 1 type or 2 or more types of solvent (henceforth "(C) fast volatile solvent") with high
(E-2) (D) One or two or more solvents (hereinafter referred to as “(E-)” which have high dispersion stability of metal oxide particles and are compatible with (E-1) fast volatile solvents. 2) Slow volatile solvent ")
(F) Active energy ray-curable compound These components will be described below.

(A) Fluoropolymer The fluoropolymer is a polymer having a carbon-fluorine bond in the molecule, and the fluorine content is 30% by mass or more. As the fluorine-containing polymer, if it is a fluorine-containing polymer having a hydroxyl group in the molecule (hereinafter sometimes referred to as “hydroxyl group-containing fluorine-containing polymer” or simply “fluorine-containing polymer”), it is preferably used. Can do. Here, the fluorine content is a value measured by the alizarin complexone method.

Examples of a preferred 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 preferably has a fluorine content of 30% by mass or more, more preferably 40 to 60% by mass, and the number in terms of polystyrene when tetrahydrofuran is used as a developing solvent by gel permeation chromatography. The average molecular weight is 5000 or more, more preferably 10,000 to 500,000.
Such a 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 hydroxyl group-containing fluoropolymer is: Usually, it is 0.1 to 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.

  The fluorine-containing polymer includes (a) a fluorine-containing olefin compound (hereinafter referred to as “(a) component”), (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 this fluoropolymer, the structural unit derived from the component (a) is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, 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 obtained 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 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 obtained fluoropolymer is inferior in transparency, and when used as a coating agent, it is coated. Occasionally repelling or the like occurs.

  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 component (d), good coating properties and leveling properties can be obtained when the fluoropolymer is used as a coating agent. 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 formula, n is 1-20, m and s show a repeating unit, and are m = 0-4 and s = 3-50.

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 fluorinated polymer, 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%. is there. 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, (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 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 the 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. An appropriate one can be selected from batch, semi-continuous or continuous operations.

  The polymerization reaction for obtaining the 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.

  Although the fluoropolymer obtained as described above may be able to use the reaction solution obtained by the polymerization reaction as it is as the liquid curable resin composition, Post-processing is also free. As this post-treatment, for example, a general reprecipitation treatment represented by a purification method in which the polymerization reaction solution is added dropwise to an insolubilizing solvent for the fluoropolymer made of alcohol or the like to solidify the fluoropolymer. Next, a solution of the fluoropolymer can be prepared by dissolving the obtained solid copolymer in a solvent. Moreover, what removed the residual monomer from the polymerization reaction solution can also be used as a solution of a fluoropolymer as it is.

  The blending ratio of the (A) fluoropolymer in 100% by mass of the total component other than the solvent (E) in the liquid curable resin composition is usually in the range of 5 to 80% by mass, preferably 10 to 80% by mass. %, More preferably in the range of 15 to 80% by mass. Outside this range, the antireflection effect is impaired and the coating film strength is lowered, which is not preferable.

(B) Thermosetting compound In the liquid curable resin composition, the thermosetting compound may be included by simply mixing with the (A) fluorine-containing polymer, or between the fluorine-containing polymer and the thermosetting compound. You may include the thing which made the reaction product which made all react, or only those parts reacted.

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

  The amino compound used as the thermosetting compound is an amino group capable of reacting with a hydroxyl group present in the fluoropolymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total of 2 or more. 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 thermosetting compound. For example, the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun) It is also possible to use various resinous materials obtained.

  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 usage-amount of the thermosetting compound contained in 100 mass% of component total amounts other than the (E) solvent in a liquid curable resin composition is the range of 5-80 mass%, Preferably it is 5-70 mass%, More preferably, it is the range of 10-50 mass%. If the amount of the thermosetting compound used is too small, the durability of the thin film formed by the liquid curable resin composition obtained may be insufficient. If the amount exceeds 80% by mass, In this reaction, it is difficult to avoid gelation, and the cured product may be brittle.

  The reaction between the fluoropolymer and the thermosetting compound can be achieved, for example, by adding the thermosetting compound to an organic solvent solution in which the fluoropolymer is dissolved, and uniformizing the reaction system by heating, stirring, etc. for an appropriate time. Just do it. 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 crosslinking reaction is caused by the reaction between methylol groups and alkoxylated methyl groups in the thermosetting compound. Is generated and a gel is formed, which is not preferable. 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.

  For the reaction between the fluoropolymer and the thermosetting compound, it is preferable to use the same organic solvent as that used in the production of the fluoropolymer, for example. In the present invention, the reaction solution obtained by the fluoropolymer and the thermosetting compound thus obtained can be used as it is as a solution of the liquid curable resin composition, and various additives can be used as necessary. It can also be used after blending.

(C) Curing catalyst As a curing catalyst used by this invention, a thermal acid generator can be mentioned, for example. The thermal acid generator is a substance that can accelerate the curing reaction when the coating film of the liquid curable resin composition is cured by heating, and the heating condition is improved to be milder. It is a substance that can do. There is no restriction | limiting in particular as this thermal acid generator, The various acids currently used as a hardening | curing agent for general urea resin, melamine resin, etc. and its salt can be utilized. Specific examples 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, various aromatic carboxylic acids and salts thereof such as benzoic acid and phthalic acid, Examples thereof include alkylbenzenesulfonic acid and its ammonium salt, various metal salts, phosphoric acid and phosphoric acid esters of organic acids.

  The use amount of the curing catalyst contained in 100% by mass of the total amount of components other than the solvent (E) in the liquid curable resin composition is usually in the range of 0.1 to 20% by mass, preferably 0.1 to 10%. It is in the range of 3% by mass, more preferably 3-8% by mass. If the amount of the curing catalyst used is too small, sufficient mechanical strength and chemical resistance cannot be obtained. If this ratio is excessive, the catalyst acts as a plasticizer in the cured film, which is not preferable because the transparency of the coating film is impaired or sufficient mechanical strength cannot be obtained.

  In the liquid curable resin composition, the cured film obtained by curing the liquid curable resin composition by setting the addition amount of the thermosetting compound (B) and the curing catalyst (C) within the specific range. Properties, particularly scratch and chemical resistance, can be improved.

(D) Metal oxide particles having a number average particle diameter of 100 nm or less As metal oxide particles, preferably titanium oxide, zirconium oxide (zirconia), antimony-containing tin oxide, tin oxide-containing indium, silicon dioxide (silica), Particles based on one or more metal oxides selected from aluminum oxide (alumina), cerium oxide, zinc oxide, tin oxide, antimony-containing zinc oxide and indium-containing 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, and zirconia-coated titanium oxide particles. Among such metal oxide particles, particles mainly composed of silica, particles mainly composed of titanium oxide or silica-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 silica, known particles can be used, and if the shape is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, core / shell type particles, etc. It does not matter. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a number average particle size of 1 to 100 nm, solid content of 10 to 40% by mass, and pH of 2.0 to 6.5 determined by dynamic light scattering or electron microscope observation is preferable.

  By using metal oxide particles having a refractive index of 1.5 or more at a wavelength of 589 nm as the metal oxide particles, the metal oxide particles constituting the cured film having two or more layers have a high density. Since the refractive index can be increased, it is suitable as an antireflection layer. For such purposes, silica (refractive index about 1.45) particles are not suitable.

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 product of particles mainly composed of silica, for example, Snowtex O (manufactured by Nissan Chemical Industries, Ltd.) (number average particle diameter determined by dynamic light scattering method 7 nm, solid content 20 mass%, pH 2.7) ), Snowtex OL (number average particle diameter determined by dynamic light scattering method: 15 nm, solid content: 20% by mass, pH 2.5), and the like.

  In addition, the (D) metal oxide particles used in the present invention include the following organic compound (Ab) having a polymerizable unsaturated group, hydrolyzable silicon compound having one or more alkyl groups in the molecule, or hydrolysis thereof. And a method of reacting a product containing a product (hereinafter referred to as “organic compound (Ac)”). However, the reaction here includes non-covalent bonds such as physical adsorption in addition to covalent bonds. In this case, the metal oxide particles not bonded to the organic compound (Ab) (hereinafter referred to as metal oxide particles (Aa)) and the particles bonded to the organic compound (Ab) or (Ac) are reacted with each other. It is called particle (Dab) or (Dac).

  By making the reactive particles (Dab) or (Dac) in which the metal oxide particles (Ab) are bonded to the organic compound (Ab) or (Ac) having a polymerizable unsaturated group, (D) the metal oxide The particle component can have a polymerizable unsaturated group to form a strong covalent bond with another polymerizable component, and the scratch resistance of the resulting cured film can be improved.

(1) Chemical modification with an organic compound (Ab) having a polymerizable unsaturated group The organic compound (Ab) used in the present invention is a compound having a polymerizable unsaturated group, and is further represented by the following formula (5). An organic compound containing a group is preferred. Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least 1 of these is included. Moreover, it is preferable that this organic compound (Ab) is a compound which has a silanol group in a molecule | numerator, or a compound which produces | generates a silanol group by hydrolysis.

[Wherein U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, and ethynyl. Preferred examples include a group, a cinnamoyl group, a maleate group and an acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (5) The group [—UC— (V) —NH—] represented by the formula (5) contained in the organic compound is specifically represented by [—O—C ( = O) -NH-], [-O-C (= S) -NH-], [-S-C (= O) -NH-], [-NH-C (= O) -NH-], Six types of [—NH—C (═S) —NH—] and [—S—C (═S) —NH—]. These groups can be used alone or in combination of two or more. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [—UC— (V) —NH—] represented by the formula (5) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion and heat resistance to adjacent layers such as materials and high refractive index layers.

(Iii) Silanol group or group that generates a silanol group by hydrolysis The organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Examples of the compound that generates such a silanol group include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. A compound having a group bonded thereto, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the oxide particles (Aa) by a condensation reaction that occurs following a condensation reaction or hydrolysis.

(Iv) Preferred Embodiment Specific examples of the organic compound (Ab) include a compound represented by the following formula (6).

In formula, R < ⁶ >, R <^7> may be same or different, and is a hydrogen atom or a C1-C8 alkyl group or an aryl group, for example, methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl Groups and the like. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ⁶ O) _j R ⁷ _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ⁸ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
R ⁹ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
R ¹⁰ is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

Specific examples of the compound represented by the formula (6) include compounds represented by the following formulas (7-1) and (7-2).
[Wherein “Acryl” represents an acryloyl group. “Me” represents a methyl group. ]

  For the synthesis of the organic compound (Ab) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent.

(V) Reactive particles (Dab)
The organic compound (Ab) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with the metal oxide particles (Aa), hydrolyzed, and bonded together. The ratio of the organic polymer component, that is, the hydrolyzate and condensate of hydrolyzable silane in the resulting reactive particles (Dab) is usually the mass loss% when the dry powder is completely burned in air. The constant value can be obtained, for example, by thermal mass spectrometry from room temperature to usually 800 ° C. in air.

  The binding amount of the organic compound (Ab) to the metal oxide particles (Aa) is preferably 100% by mass of the reactive particles (Dab) (the total of the metal oxide particles (Aa) and the organic compound (Ab)). 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more. When the amount of the organic compound (Ab) bonded to the metal oxide particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (Dab) in the composition is not sufficient, and the resulting cured product The transparency and scratch resistance of the object may not be sufficient. Moreover, the compounding ratio of the metal oxide particles (Aa) in the raw material during the production of the reactive particles (Dab) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass. The content of the metal oxide particles (Aa) constituting the reactive particles (Dab) is preferably 65 to 95% by mass of the reactive particles (Dab).

(2) Chemical modification with a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof (organic compound (Ac)), etc. A hydrolyzable silicon compound having one or more alkyl groups therein or a substance containing the hydrolyzate thereof (organic compound (Ac)) can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane or the like having an OH group, bis (2-hydroxyethyl) -3-aminotripropylmethoxysilane or the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane or the like having a thiocyanate group As those having an thiol group such as (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like having an epoxy group such as 3-thiocyanate propyltrimethoxysilane, 3-mercaptopropyltrimeth Examples include xylsilane. A preferred compound is 3-mercaptopropyltrimethoxysilane.

  Ratio of use of (D) metal oxide particles (including reactive particles (Dab) and (Dac)) contained in 100% by mass of the total amount of components other than (E) solvent in the liquid curable resin composition Is usually in the range of 5 to 80 mass%, preferably 10 to 80 mass%, more preferably 20 to 70 mass%. Outside this range, the antireflection effect is impaired and the coating film strength is lowered, which is not preferable.

The number average particle diameter of the metal oxide particles is 100 nm or less. 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 diameter” is the primary particle diameter when the metal oxide particles are agglomerated, and when the metal oxide particles are not spherical (for example, acicular ATO), the long diameter (longitudinal) It is the average of the minor axis (horizontal length). The number average particle diameter is the number average particle diameter measured by electron microscopy.

(E) Solvent In the liquid curable resin composition, it is necessary to blend two types of solvents, (E-1) fast volatile solvent and (E-2) slow volatile solvent, in order to cause layer separation. One or more of the solvents (E-1) and (E-2) are used.
(E-1) Fast volatile solvent (E-1) Fast volatile solvent contained in the liquid curable resin composition is one or more solvents having high solubility of the (A) fluoropolymer. . Here, the high solubility of the fluorinated polymer means that (A) the fluorinated polymer is added to each solvent so as to be 50% by mass, and when stirred at room temperature for 8 hours, Say that. The relative evaporation rate of the (E-1) fast volatile solvent needs to be larger than the relative evaporation rate of the later-described (E-2) 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 (E-1) fast volatile solvent preferably has a low dispersion stability of the metal oxide particles (D). (E-1) The fast volatile solvent has a relative evaporation rate larger than that of (E-2), (A) the solubility of the fluoropolymer is high, and (D) the dispersion stability of the metal oxide particles. By being low, in the process of applying the liquid curable resin composition to the substrate and evaporating the solvents (E-1) and (E-2), (D) the metal oxide particles can be unevenly distributed. .

  The solvent that can be used as the (E-1) 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.

(E-2) Slow volatile solvent (E-2) Slow volatile solvent contained in the liquid curable resin composition is one or more solvents having high dispersion stability of the metal oxide particles (D). It is. Here, (D) that the dispersion stability of the metal oxide particles is low means that (D) a metal plate is immersed in the metal oxide particle dispersion and (D) the metal oxide particles are adhered to the glass wall. (B) When the glass plate to which the metal oxide particles are adhered is immersed in each solvent, (D) means that the metal oxide particles are not visually dispersed uniformly in the solvent. Moreover, it is preferable that the (E-2) slow volatile solvent has low solubility of the (A) fluoropolymer.

  The solvent that can be used as the slow volatile solvent (E-2) 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.

  As the (E-1) fast volatile solvent and / or (E-2) slow volatile solvent used in the present invention, the solvent used in the production of the (A) fluoropolymer can be used as it is.

The (E-1) fast volatile solvent and (E-2) slow volatile solvent used in the present invention must be compatible. It is sufficient that the compatibility is such that (E-1) the fast volatile solvent and (E-2) the slow volatile solvent are not separated in the specific configuration of the composition.
Here, whether the selected solvent corresponds to (E-1) fast volatile solvent or (E-2) slow volatile solvent used in the present invention is relative among the selected solvent types. Therefore, isopropanol having a relative evaporation rate of 1.7 may be used as (E-1) fast volatile solvent or (E-2) as slow volatile solvent. .

  With respect to 100 parts by mass of the total amount of the components other than the solvent (including the (E-1) component and the (E-2) component) in the liquid curable resin composition, the solvent (E-1) and the solvent (E-2) The total amount is usually 300 to 5000 parts by mass, preferably 300 to 4000 parts by mass, more preferably 300 to 3000 parts by mass. The compounding ratio of the solvent (E-1) and the solvent (E-2) can be arbitrarily selected in the range of 1:99 to 99: 1.

(F) Active energy ray-curable compound The active energy ray-curable compound used in the present invention is a compound containing two or more polymerizable unsaturated groups in the molecule. This compound is suitably used to enhance the film formability of the composition, and is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule. For example, melamine acrylates, (meth) acrylic Examples include esters and vinyl compounds. Of these, (meth) acrylic esters are preferred.

Specific examples of the component (F) used in the present invention are listed below.
(Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and starting alcohols thereof Poly (meth) acrylates of adducts with ethylene oxide or propylene oxide, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meth) acrylates, oligourethanes (meth) In addition to acrylates and oligoepoxy (meth) acrylates, examples include compounds represented by the following formula (8). Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and a compound represented by the following formula (8) are preferable. .
[Wherein “Acryl” represents an acryloyl group. ]

  Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  As a commercial item of such (F) component, for example, Sanwa Chemical Co., Ltd. product name: Nicarak MX-302, Toagosei Co., Ltd. product name: Aronix M-400, M-408, M- 450, M-305, M-309, M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO- 924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Trade name: KAYARAD D − 10, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR- 9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO- 303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620 R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. product name: Light acrylate PE-4A, DPE-6A, DTMP-4A, etc. can be mentioned.

The blending ratio of the active energy ray-curable compound (F) in the composition is usually in the range of 5 to 80% by mass, preferably 5 to 70% by mass, and more preferably 5 to 50% by mass. If the amount of the active energy ray-curable compound is too small, sufficient coating strength cannot be obtained. Conversely, if it exceeds 80% by mass, the antireflection effect decreases, which is not preferable.
By adding an active energy ray-curable compound to the liquid curable resin composition, the properties of the cured film obtained by curing the liquid curable resin composition, particularly scratch resistance and chemical resistance are more preferable. can do.

  In addition to the components (A) to (F) described above, the liquid curable resin composition has optional coating properties of the liquid curable resin composition and improvement of the physical properties of the thin film after curing, as well as photosensitivity to the coating film. In addition to (G) the photopolymerization initiator, (H) various additives can be added for the purpose of imparting and the like.

(G) Photopolymerization initiator Examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, and xanthone. 4-chlorobenzophenone, 4,4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- ( 4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2, 4,6-trimethylbenzoyldiphenylphosphine oxa 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 3-methylacetophenone, 3 , 3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone 4-benzoyl-4'-methyldiphenyl sulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers.

  Among these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2 -Phenylmethyl) -1-butanone and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl ) -1-butanone, and the like.

  The blending ratio of the (G) photopolymerization initiator in 100% by mass of the total component other than the (E) solvent in the liquid curable resin composition is usually in the range of 0.1 to 10% by mass, preferably 0.1 to 0.1% by mass. It is 5 mass%, More preferably, it is the range of 0.5-3 mass%. When the blending ratio of the photopolymerization initiator is too small, the photopolymerization is not started, and conversely when it exceeds 10% by mass, the catalyst acts as a plasticizer in the cured film, and the transparency is impaired. This is not preferable because sufficient mechanical strength cannot be obtained.

(H) Other additives Examples of additives that can be added to the liquid curable resin composition include, for example, various polymers and monomers having a hydroxyl group, colorants such as pigments and dyes, anti-aging agents, ultraviolet absorbers, and the like. Various additives such as an agent, a photosensitive acid generator, a surfactant, and a polymerization inhibitor can be contained. 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.

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

(ii) 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, and 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.

(iii) 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.

(iv) 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); sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfones represented by the following general formula (9) Imide compounds; (5) Diazomethane compounds represented by the following general formula (10);

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% by mass of the total amount of components other than the solvent (E) in the liquid curable resin composition is preferably 0 to 20% by mass, more preferably 0.1 to 10% by mass. is there. When this ratio is excessive, the strength of the cured film becomes inferior and the transparency is also lowered, which is not preferable.

(v) 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% by mass or less with respect to 100% by mass of the liquid curable resin composition.

(vi) 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% by mass or less with respect to 100% by mass of the liquid curable resin composition.

(vii) Solvents other than the components (C) and (D) A solvent other than the 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 (D) one or more layers in which the metal oxide particles are present at high density and one or less layers in which the (D) 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, the heating is performed at 50 to 180 ° C. for 2 to 120 minutes, more preferably at 80 to 150 ° C. for 2 to 60 minutes.

Moreover, it can harden | cure also by irradiating an active energy ray. Here, the active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. However, ultraviolet rays are preferable from the viewpoint of having a constant energy level, a high curing rate, and a relatively inexpensive and compact irradiation apparatus.
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. Moreover, when making it harden | cure with an ultraviolet-ray, it is preferable to add the radiation (photo) polymerization initiator which can improve a cure rate.
The degree of cure of the cured film can be quantitatively confirmed by measuring the gelation rate using a Soxhlet extractor.

  Since the liquid curable resin composition contains both the (B) thermosetting compound and the (F) active energy ray curable compound, in order to cure more effectively, the above heating and active energy ray It is preferable to use irradiation together. By using heating and irradiation with active energy rays in combination, the scratch resistance and chemical resistance of the cured film can be improved.

  In the process in which the solvent (E-1) and the solvent (E-2) in the composition are evaporated and dried after coating the liquid curable resin composition, (D) the metal oxide particles are coated on the coating base side (adjacent layer). Near the boundary) and the other side. Therefore, (D) metal oxide particles are present at high density near one interface of the cured film, and (D) 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 multilayer 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. (D) 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 cured products of components (A), (B) and (F). In many cases, the cured film of the present invention has a two-layer structure in which a layer in which metal oxide particles are present in 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 the refractive index can be adjusted by the content and type of the metal oxide particles, the content and the composition of the fluoropolymer, and the content and type of the thermosetting compound.
Moreover, the refractive index in the low refractive index part in 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. In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of raw material isocyanate compound disappeared, and new urethane A 1660 Kaiser peak characteristic of the bond and the S (C = O) NH- group and a 1720 Kaiser peak characteristic of the acryloxy group are observed, with an acryloxy group as the polymerizable unsaturated group It was shown that -S (C = O) NH- and an acryloxy group-modified alkoxysilane having both urethane bonds were formed. As described above, 773 parts of a compound having a thiourethane bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group (compound (Ab) represented by the above formulas (7-1) and (7-2)). A composition (A-1) of 220 parts of pentaerythritol tetraacrylate that was not involved in the reaction (hereinafter, this composition may be referred to as “alkoxysilane 1”) was obtained.

Production Example 2
(2) Synthesis of urethane acrylate (compound represented by formula (8)) For a solution comprising 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer, NK manufactured by Shin-Nakamura Chemical Ester A-TMM-3LM-N (participating in the reaction is only pentaerythritol triacrylate having a hydroxyl group) 93 parts dropwise at 10 ° C. for 1 hour, then at 60 ° C. for 6 hours. The reaction solution was stirred under conditions.
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 (compound represented by the above formula (8)) was obtained, and 37 parts of pentaerythritol tetraacrylate not involved in the reaction was mixed (A-2). Got.

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
[Preparation of silica-coated TiO ₂ particle dispersion (S-1)]
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. Time dispersion was performed to remove the glass beads, and 2430 parts by mass of silica-coated titanium oxide particle dispersion (S-1) was obtained. Here, 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 a total solid concentration (ratio of total components other than the solvent in the dispersion). Was 17% by mass. The silica-coated TiO ₂ particle dispersion was weighed in a magnetic crucible, pre-dried on a hot plate at 80 ° C. for 30 minutes, and then baked in a muffle furnace at 750 ° C. for 1 hour. When the inorganic content in the total solid content was determined from the total solid content concentration, it was 82% by mass. As a result of observing this solid matter with an electron microscope, the minor axis average particle size was 15 nm, the major axis average particle size was 46 nm, and the aspect ratio was 3.1.

Production Example 9
[Production of spherical zirconia particle dispersion (S-2)]
300 parts of spherical zirconia fine powder (manufactured by Sumitomo Osaka Cement Co., Ltd., number average primary particle size 0.01 μm) is added to 700 parts of methyl ethyl ketone (MEK), dispersed with glass beads for 168 hours, and crow beads are removed. As a result, 950 parts of methyl ethyl ketone zirconia sol was obtained. 2 g of the dispersed sol was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 30%. As a result of observing this solid matter with an electron microscope, the minor axis average particle size was 15 nm, the major axis average particle size was 20 nm, and the aspect ratio was 1.3.

Production Example 10
[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, 75.4 g of perfluoro (propyl vinyl ether), 34 g of ethyl vinyl ether, 41.6 g of hydroxyethyl vinyl ether, nonionic reactivity 50 g of “Adekaria soap NE-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) as an emulsifier, 7.5 g of “VPS-1001” (manufactured by Wako Pure Chemical Industries, Ltd.) as an azo group-containing polydimethylsiloxane, and lauroyl peroxide After adding 25 g and cooling to −50 ° C. with dry ice-methanol, oxygen in the system was removed again with nitrogen gas.

Next, 99.1 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, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 31%. The obtained polymer solution was poured into a mixed solvent of methanol and water to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a fluoropolymer. About the obtained polymer, it confirmed that the polystyrene conversion number average molecular weight (Mn) by gel permeation chromatography was 37000, and the glass transition temperature (Tg) by DSC was 29.4 degreeC.

Production Example 11
[Production of Reactive Silica-Coated TiO ₂ Particle Sol (Compound (Z-1)) Combined with Organic Compound Having Polymerizable Unsaturation Group]
556 parts of silica-coated TiO ₂ particle dispersion (S-1) produced in Production Example 8 (total solid concentration 17%, particle concentration 15%), 2.2 parts of alkoxysilane 1 solution produced in Production Example 1, Distilled water 0.23 part and p-hydroquinone monomethyl ether 0.04 part were mixed and heated and stirred at 65 ° C. Four hours later, 2.5 parts of orthoformate methyl ester was added and further heated for 1 hour to obtain a reactive silica-coated TiO ₂ particle sol (compound (Z-1)) having a solid content of 18%.

Production Example 12
[Production of reactive alumina, zirconia-coated TiO ₂ particle sol (compound (Z-2)) bonded with an organic compound having a polymerizable unsaturated group]
394 parts of alumina, zirconia-coated TiO ₂ particle dispersion (Taca Co., Ltd., total solid content concentration 28%, particle concentration 24%), 2.2 parts of alkoxysilane 1 solution prepared in Production Example 1, and distilled water 0.23 Part and 0.04 part of p-hydroquinone monomethyl ether were mixed and heated and stirred at 65 ° C. Four hours later, 2.5 parts of orthoformate methyl ester was added, and further heated for 1 hour to obtain a reactive alumina having a solid content of 25% and a zirconia-coated TiO ₂ particle sol (compound (Z-2)).

Production Example 13
[Reactive zirconia particle sol to which an organic compound having a polymerizable unsaturated group is bonded (compound (Z
-3)) Production]
315 parts of spherical zirconia particle dispersion (S-2) (particle concentration 30%) produced in Production Example 9, 2.2 parts of solution of alkoxysilane 1 produced in Production Example 1, 0.23 parts of distilled water, p- Hydroquinone monomethyl ether (0.04 part) was mixed and heated and stirred at 65 ° C. After 4 hours, 2.5 parts of orthoformate methyl ester was added, and the mixture was further heated for 1 hour to obtain a reactive zirconia particle sol (compound (Z-3)) having a solid content of 31%.

Production Example 14
[Production of Reactive Alumina, Zirconia-Coated TiO ₂ Particle Sol (Compound (Z-4)) Combined with Organic Compound Having Polymerizable Unsaturation Group]
333.7 parts of alumina, zirconia-coated TiO ₂ particle dispersion (manufactured by Teika Co., Ltd., total solid concentration 28%, particle concentration 24%), 5.4 parts of alkoxysilane 1 solution prepared in Production Example 1, distilled water 0 20 parts and 0.03 part of p-hydroquinone monomethyl ether were mixed and heated and stirred at 65 ° C. Four hours later, 2.2 parts of orthoformate methyl ester was added, and the mixture was further heated for 1 hour to obtain a reactive alumina having a solid content of 32% and a zirconia-coated TiO ₂ particle sol (compound (Z-4)).

Production Example 15
[Preparation of Liquid Curable Resin Composition 1]
Reactive silica-coated TiO ₂ particle sol obtained in Production Example 11 (compound (Z-1), 50.6 g as reactive particles) 280.9 g, fluorinated polymer obtained in Production Example 10 23.1 g , 14.3 g of a thermosetting compound methoxylated methylmelamine “Cymel 303” (Mitsui Cytec Co., Ltd.) and “Catalyst 4050” (Mitsui Cytec Co., Ltd., an aromatic sulfonic acid compound active ingredient) which is a curing catalyst (Concentration 32%) 11.9 g, active energy ray-curable compound 2.0 g produced in Production Example 2 represented by the above formula (8), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd. : KAYARAD DPHA-2C) 5.3 g as a photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-o (Irgacure 907, Ciba Specialty Ltd. Chemicals) Methyl ethyl ketone 300g of solvent 1.0 g, methyl isobutyl ketone 320 g, by dissolving in tertiary butanol 213 g, to obtain a curable liquid resin composition 1. When the total solid content concentration in this liquid curable resin composition (the ratio of the total amount of components other than the solvent in the liquid curable resin composition) was measured in the same manner as in Production Example 8, it was 8.5% by mass.

Production Examples 16-22
[Preparation of liquid curable resin compositions 2 to 8]
Liquid curable resin compositions 2 to 8 were prepared in the same manner as in Production Example 15 except that the blending ratio of each component of the composition was changed as shown in Table 1 below.
The solid content compositions of the liquid curable resin compositions 1 to 8 are shown in Table 1 below.

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), the liquid curable resin compositions 1 to 8 obtained in Production Examples 15 to 22, respectively (2) After being coated on the medium refractive index layer prepared in Step 1, it was dried in an oven at 140 ° C. for 2 minutes and irradiated with 0.6 J / cm ² of ultraviolet light in the air using a conveyor type mercury lamp manufactured by Oak Manufacturing Co., Ltd. A cured film layer having a thickness of 0.2 μm was formed.
In addition, the liquid curable resin compositions 1 to 8 obtained in Production Examples 15 to 22 were respectively coated on the medium refractive index layer prepared in (2) using a wire bar coater (# 3). Then, the cured film layer with a film thickness of 0.2 micrometer was formed by heating at 120 degreeC for 10 minute (s) in oven.

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), the liquid curable resin compositions 1 to 8 obtained in Production Examples 15 to 22, respectively (3) After being coated on the medium refractive index layer prepared in Step 1, it was dried in an oven at 140 ° C. for 2 minutes and irradiated with 0.6 J / cm ² of ultraviolet light in the air using a conveyor type mercury lamp manufactured by Oak Manufacturing Co., Ltd. A cured film layer having a thickness of 0.2 μm was formed.
In addition, the liquid curable resin compositions 1 to 8 obtained in Production Examples 15 to 22 were respectively coated on the medium refractive index layer prepared in (3) using a wire bar coater (# 3). Then, the cured film layer with a film thickness of 0.2 micrometer was formed by heating at 120 degreeC for 10 minute (s) in oven.

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), the liquid curable resin compositions 1 to 8 obtained in Production Examples 15 to 22, respectively (3) After being coated on the medium refractive index layer prepared in Step 1, it was dried in an oven at 140 ° C. for 2 minutes and irradiated with 0.6 J / cm ² of ultraviolet light in the air using a conveyor type mercury lamp manufactured by Oak Manufacturing Co., Ltd. A cured film layer having a thickness of 0.2 μm was formed.
In addition, the liquid curable resin compositions 1 to 8 obtained in Production Examples 15 to 22 were respectively coated on the medium refractive index layer prepared in (3) using a wire bar coater (# 3). Then, the cured film layer with a film thickness of 0.2 micrometer was formed by heating at 120 degreeC for 10 minute (s) in oven.

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), the liquid curable resin compositions 1 to 8 obtained in Production Examples 15 to 22, respectively (1) After being coated on the hard coat layer prepared in Step ² , the coating is dried in an oven at 140 ° C. for 2 minutes, and irradiated with 0.6 J / cm ² of ultraviolet light in the atmosphere using an Oak Manufacturing conveyor type mercury lamp. A cured film layer having a thickness of 0.2 μm was formed.
Moreover, after apply | coating the liquid curable resin compositions 1-8 obtained by manufacture examples 15-22 on the hard-coat layer produced in (1), respectively using a wire bar coater (# 3). Then, a cured film layer having a film 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 were observed with a transmission electron microscope, the low refractive index layer and the high refractive index layer were separated into two layers in any laminate. Was confirmed. 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.
FIG. 11 is an electron micrograph showing the concept of each state of two-layer separation, no separation (partial aggregation), and uniform structure.
The antireflection property of the obtained antireflection laminate 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, manufactured by Hitachi, 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.

  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 (20)

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, the following components (A), (B), (C), (D), (E-1), (E-2) and (F) A liquid curable resin composition containing 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) fluorinated polymer (B) thermosetting compound (C) thermal acid generator (D) metal oxide particles having a number average particle diameter of 100 nm or less (hereinafter referred to as “(D) metal oxide particles” )
(E-1) One type or two or more types of solvents (hereinafter referred to as “( E-1 ) fast volatile solvent”) having high solubility of the (A) fluoropolymer.
(E-2) (D) One or two or more solvents (hereinafter referred to as “(E-)” which have high dispersion stability of metal oxide particles and are compatible with (E-1) fast volatile solvents. 2) Slow volatile solvent ")
(F) The active energy ray-curable compound and (E-1) the relative evaporation rate of the fast volatile solvent is larger than (E-2) the relative evaporation rate of the 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, it hardens | cures by heating the said 2 or more layer and / or irradiating a radiation, 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. In 100 mass% of the total amount of components other than (E-1) fast volatile solvent and (E-2) slow volatile solvent (hereinafter referred to as “(E) solvent”) in the liquid curable resin composition. ,
(C) 0.1-20 mass% of component
The manufacturing method of the laminated body as described in any one of Claims 1-11 characterized by the above-mentioned.   The component (B) 5 to 80% by mass is contained in 100% by mass of the total component other than the solvent (E) in the liquid curable resin composition, according to any one of claims 1 to 12. The manufacturing method of the laminated body of description.   (D) The metal oxide particles of the liquid curable resin composition contain titanium oxide, zirconium oxide, antimony-containing tin oxide, tin oxide-containing indium, silicon dioxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide, and antimony. It is a particle | grain which has as a main component the 1 or 2 or more metal oxide selected from a zinc oxide and an indium containing zinc oxide, The manufacturing method of the laminated body as described in any one of Claims 1-13 characterized by the above-mentioned. .   The method for producing a laminate according to any one of claims 1 to 14, wherein (D) the metal oxide particles of the liquid curable resin composition are metal oxide particles having a multilayer structure. .   The (D) metal oxide particle of the said liquid curable resin composition is couple | bonded with the organic compound which has a polymerizable unsaturated group, The lamination | stacking as described in any one of Claims 1-15 characterized by the above-mentioned. Body manufacturing method.   The laminated body manufactured by the manufacturing method of the laminated body as described in any one of Claims 1-16. Two layers obtained by curing a liquid curable resin composition containing the following components (A), (B), (C), (D), (E-1), (E-2) and (F) A cured film having the multilayer structure described above.
[Liquid curable resin composition]
(A) Fluoropolymer
(B) Thermosetting compound
(C) Thermal acid generator
(D) Metal oxide particles having a number average particle diameter of 100 nm or less (hereinafter referred to as “(D) metal oxide particles”)
(E-1) (A) One type or two or more types of solvents having high solubility of the fluoropolymer (hereinafter referred to as “(E-1) fast volatile solvent”)
(E-2) (D) One or two or more solvents (hereinafter referred to as “(E-)” which have high dispersion stability of metal oxide particles and are compatible with (E-1) fast volatile solvents. 2) Slow volatile solvent ")
(F) Active energy ray-curable compound
And (E-1) the relative evaporation rate of the fast volatile solvent is greater than the (E-2) relative evaporation rate of the slow volatile solvent. The cured film has a layer structure of two or more layers including one or more layers in which the component (D) is present at high density and one or less layers in which the component (D) is not substantially present. The cured film as described in 2. By heating a liquid curable resin composition containing the following components (A), (B), (C), (D), (E-1), (E-2) and (F) and / or radiation The manufacturing method of the cured film which has the process hardened | cured by irradiating.
[Liquid curable resin composition]
(A) Fluoropolymer (B) Thermosetting Compound (C) Thermal Acid Generator (D) Metal Oxide Particles with Number Average Particle Diameter of 100 nm or Less (hereinafter referred to as “(D) Metal Oxide Particles” )
(E-1) (A) One type or two or more types of solvents having high solubility of the fluoropolymer (hereinafter referred to as “(E-1) fast volatile solvent”)
(E-2) (D) One or two or more solvents (hereinafter referred to as “(E-)” which have high dispersion stability of metal oxide particles and are compatible with (E-1) fast volatile solvents. 2) Slow volatile solvent ")
(F) The active energy ray-curable compound and (E-1) the relative evaporation rate of the fast volatile solvent is larger than (E-2) the relative evaporation rate of the slow volatile solvent.