WO2006051835A1 - Curable resin composition, cured film formed therefrom and multilayer body - Google Patents

Abstract

Disclosed is a method for producing a multilayer body comprising a base (30) and a multilayer structure (40, 50) formed thereon. Specifically disclosed is a method for producing a multilayer body which is characterized in that a coating film is formed by applying a curable resin composition containing metal oxide particles (A1) having a number average particle diameter of not less than 1 nm and less than 40 nm, metal oxide particles (A2) having a number average particle diameter of not less than 40 nm and not more than 200 nm, an ethylenically unsaturated group-containing fluorine polymer (B), a highly volatile solvent (C) and a low volatile solvent (D) to a base (30) or a layer formed on the base, and two or more layers (40, 50) are formed by evaporating the solvents from this single coating film.

Description

 Specification

 Curable resin composition, cured film and laminate comprising the same

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a curable resin composition, a cured film capable of producing the same, a method for producing a laminate, and a laminate obtained thereby, in particular, for example, an arbitrary layer such as a low refractive index layer and a high refractive index layer. The present invention relates to a curable resin composition capable of forming a cured film composed of two or more continuous layers from one coating film, and a method for producing a laminate capable of forming two or more layers from one coating film. .

 Background art

 [0002] Currently, with the development of multimedia, various developments have been seen in various display devices (display devices). And among various types of display devices, especially those used outdoors, mainly for portable use, the improvement of visibility has become increasingly important, and even for large display devices, making it easier to see. This is a technical issue as it is.

 In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, etc., in order to prevent reflection of external light and improve image quality, low refractive index properties, scratch resistance, coating properties, and There is a demand for an antireflection film including a low refractive index layer made of a cured product having excellent durability. In these display panels, in order to remove attached fingerprints, dust, and the like, the surface is often wiped with gauze impregnated with ethanol or the like, and scratch resistance is required. In particular, in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate. In addition, as the base material, for example, triacetyl cellulose is used, but in an antireflection film using such a base material, in order to increase the adhesion when pasted to the polarizing plate, It is necessary to saponify with an alkaline aqueous solution. Therefore, in applications of liquid crystal display panels, there is a demand for an antireflection film excellent in alkali resistance, particularly in durability.

Conventionally, as a means for improving the visibility of a display device, an antireflection film made of a low refractive index material has been coated on the substrate of the display device, and thus antireflection is performed. As a method of forming a film, for example, a method of forming a thin film of a fluorine compound 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 display device having a low cost and a large force, mainly in a liquid crystal display device. However, in the case of the vapor deposition method, it is difficult to form a uniform and high-efficiency antireflection film on a large-area substrate, and a vacuum apparatus is required, which reduces the cost. Is difficult.

 [0005] Under these circumstances, an antireflection film is formed by preparing a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent, and applying this to the surface of the substrate. The law is being considered. 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 fluoropolymer having a specific structure has been proposed (for example, see Patent Document 3).

[0006] As a material for a low refractive index layer of an antireflection film, for example, a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known, which is disclosed in Patent Document 4, Patent Document 5, Patent Document 6, and the like. It is shown. However, in such a fluororesin-based paint, in order to cure the coating film, it is necessary to heat and bridge a hydroxyl group-containing fluoropolymer and a curing agent such as melamine resin under an acid catalyst. Depending on the heating conditions, there are problems that the curing time becomes excessively long and the types of substrates that can be used are limited. In addition, the obtained coating film had a problem that it was excellent in weather resistance but poor in scratch resistance and durability.

 [0007] In order to solve the above problems, Patent Document 7 discloses an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition-polymerizable unsaturated group, and a hydroxyl group-containing compound. Proposal of a coating composition containing an unsaturated group-containing fluorine-containing bull polymer obtained by reacting a fluorine polymer with a ratio of the number of isocyanate groups / number of hydroxyl groups of 0.01 to 1.0. It has been done.

 Patent Document 1: Japanese Patent Application Laid-Open No. 61-40845

 Patent Document 2: Japanese Patent Publication No. 6-98703

Patent Document 3: Japanese Patent Laid-Open No. 6-115023 Patent Document 4: JP-A-57-34107

 Patent Document 5: Japanese Patent Laid-Open No. 59-189108

 Patent Document 6: JP-A-60-67518

 Patent Document 7: Japanese Patent Publication No. 6-35559

[0009] 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, on the substrate

The process of applying each layer was repeated. That is, the conventional antireflective film made of a fluorine-based material needs to form a low-refractive index layer having a fluorine-based material force on a high-refractive index layer provided on a base material. It was necessary to provide a separate coating process.

 Further, the scratch resistance of the low refractive index layer as the surface layer was not sufficient.

 The present invention has been made against the background of the above situation, and its purpose is to provide a curable resin composition that can be cured by ultraviolet rays that can efficiently produce a low refractive index layer and a high refractive index layer. Is to provide. Another object of the present invention is to provide a cured film having excellent scratch resistance and chemical resistance with high adhesion to a substrate with high transparency and excellent environmental resistance. It is in.

[0010] Furthermore, another object of the present invention is to provide a method for producing a laminate capable of forming two or more layers from one coating film obtained by applying the composition, and a laminate obtained thereby. 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, another object of the present invention is to provide a method for producing a laminate having excellent adhesion to a substrate and high scratch resistance, and a laminate obtained thereby.

 Disclosure of the invention

[0011] In order to achieve the above object, the present inventors have conducted intensive research and added two types of metal oxide particles having different particle sizes to an ethylenically unsaturated group-containing fluoropolymer that is cured by irradiation with ultraviolet rays. When the blended composition is applied to a substrate and dried, it is separated into two layers: a layer in which the metal oxide particles are present at a high density and a layer in which the metal oxide is scarcely present or at a low density. I found out. Furthermore, a cured film obtained by curing by irradiating with ultraviolet rays Has found that it has excellent scratch resistance, chemical resistance and transparency, as well as excellent weather resistance, and has completed the present invention.

 According to the present invention, the following curable resin composition, a cured film obtained by curing the composition, a method for producing a laminate, and a laminate obtained thereby can be provided.

 1. The following ingredients:

 (A1) Metal oxide particles having a number average particle diameter of 1 nm or more and less than 40 nm formed by bonding an organic compound (Ab) having a polymerizable unsaturated group (hereinafter referred to as “metal oxide particles of (A1)”)

(A2) Metal oxide particles having a number average particle diameter of 40 nm to 200 nm (hereinafter referred to as “(A2) metal oxide particles”)

 (B) Ethylenically unsaturated group-containing fluoropolymer

 (C) (B) High solubility of fluorine-containing polymer containing ethylenically unsaturated groups, one or more solvents (hereinafter referred to as “(C) fast volatile solvent”)

 (D) One or two or more solvents (hereinafter referred to as “(”) that have high dispersion stability of the metal oxide particles of (A1) and (A2) and are compatible with (C) the fast volatile solvent. D) a slow volatile solvent ”, and (C) the relative evaporation rate of the fast volatile solvent is higher than (D) the relative evaporation rate of the slow volatile solvent.

 2. (C) Fast volatile solvent is one or more solvents with low dispersion stability of metal oxide particles (A1) and (A2). (D) Slow volatile solvent is (B 2. The curable resin composition as described in 1 above, which is one or more solvents having low solubility of the ethylenically unsaturated group-containing fluoropolymer.

 3. The metal oxide particle force of (A1) above is characterized in that it is an oxide particle of at least one element selected from the group consisting of ananolium, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. The curable resin composition according to 1 or 2 above.

 4. The curable resin composition as described in any one of 1 to 3 above, wherein the metal oxide particles (A2) are particles mainly composed of silica.

5. The curable resin composition according to any one of 1 to 4 above, wherein the metal oxide particles (A2) are bonded to the organic compound (Ab) having the polymerizable unsaturated group. object.

 [0013] 6. In addition to the polymerizable unsaturated group, the organic compound (Ab) has a group represented by the following formula (A-1):

 F F

 The curable resin composition according to any one of 1 to 5 above, which has cI I.

 RCFII

 [Chemical 1] 1

—— U— C One N— (A-1)

 II

 V

 [In the formula, U represents NH, O (oxygen atom) or S (ion atom), and V represents ◯ or S.

]

 7. The curable resin composition according to any one of 1 to 6 above, wherein the organic compound (Ab) is a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. .

 8. The (B) ethylenically unsaturated group-containing fluorine-containing polymer comprises a compound (B-1) containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. 8. The curable resin composition according to any one of 1 to 7 above, which is obtained by reacting the polymer (B-2).

 [0014] 9. The hydroxyl group-containing fluoropolymer (B_2) contains the following structural units (a) 20 to 70 mol%, (b) 10 to 70 mol% and (c) 5 to 70 mol%. The curable resin composition according to 8 above, wherein the number average molecular weight in terms of polystyrene measured by gel permeation chromatography is 5,000 to 500,000.

 (a) A structural unit represented by the following general formula (1).

 (b) A structural unit represented by the following general formula (2).

 (c) A structural unit represented by the following general formula (3).

[Chemical 2]

[Wherein R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by OR ² (R ² represents an alkyl group) Or a fluoroalkyl group)]

 [Chemical 3]

Wherein the R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkyl group, _ (CH) _〇_R ⁵ or -

 2

OC_〇_R ⁵ a group represented by (R ⁵ is an alkyl group, or a glycidyl group, X is shows the number 0 or 1), shows a carboxyl group, or alkoxycarbonyl two le radical

[Chemical 4]

HR ⁶

 — C— C—— (3)

H (CH ₂ ) _v OR ⁷

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1]

10. The above 8 or 9, wherein the hydroxyl group-containing fluoropolymer (B-2) further comprises the following structural unit (d) 0.:! To 10 mol% derived from an azo group-containing polysiloxane compound. A curable resin composition.

 (d) A structural unit represented by the following general formula (4).

[Chemical 5]

R ⁸

 — Si-O— (

R ⁹

[Wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]

 11. The hydroxyl group-containing fluoropolymer (B-2) is the structural unit (d) shown below

11. The curable resin composition as described in 10 above, which is contained as part of (e).

(e) A structural unit represented by the following general formula (5). [Chemical 6]

[Wherein R ^{1Q to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyano group, R ^{14 to} R ¹⁷ represent a hydrogen atom or an alkyl group, and p and q are numbers of:! To 6, s, t is a number from 0 to 6, y is a number from:! to 200. ]

 [0016] 12. The curability according to any one of 8 to 11 above, wherein the hydroxyl group-containing fluoropolymer (B-2) further comprises the following structural unit (f) 0.:! To 5 mol%. Resin composition.

 (f) A structural unit represented by the following general formula (6).

 [Chemical 7]

HR ¹⁸

C one C ( ⁶ )

 H H

[Wherein R ¹⁸ represents an emulsifying group]

 13. The curable resin composition according to any one of 8 to 12 above, wherein the compound (B-1) is 2_ (meth) atalylooxychetyl isocyanate.

 14. In addition, it contains component (E) a polyfunctional (meth) attareito to compound containing at least two (meth) attaroyl groups and Z or at least one (meth) attalyloyl group. The curable resin composition according to any one of the above:! To 13, wherein the composition contains a fluorine-containing (meth) acrylate compound.

 15. The curable resin composition according to any one of 1 to 14 above, which further comprises a component (F) a radical polymerization initiator.

 16. The curable resin composition according to any one of the above:! To 15, which is ultraviolet curable.

[0017] 17. A cured film obtained by curing the curable resin composition according to any one of the above:! To 16, and having a multilayer structure of two or more layers. 18. From one or more layers in which (Al) and (A2) metal oxide particles are present in high density and from one or more layers in which (A1) and (A2) metal oxide particles are substantially absent 18. The cured film as described in 17 above, which has a layer structure of two or more layers.

 19. A method of producing a laminate having a base material and a multilayer structure thereon, comprising:

 On the base material or a layer formed on the base material, the curable resin composition according to any one of the above 1 to 16 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.

 20. Each of the two or more layers is a layer in which the metal oxide particles (A1) and / or (A2) are present in high density or the metal oxide particles (A1) and (A2) are substantially present. 20. The method for producing a laminate according to the above 19, wherein at least one layer is a layer in which the metal oxide particles (A1) and / or (A2) are present at a high density.

 21. The method for producing a laminate according to the above 20, wherein the two or more layers are two layers.

 22. The method for producing a laminate according to any one of 19 to 21, further comprising curing the two or more layers by irradiation with radiation.

 23. The method for producing a laminate according to any one of the above 19 to 22, wherein the laminate is an optical component.

 24. The method for producing a laminate according to any one of the above 19 to 22, wherein the laminate is an antireflection film.

25. The laminate 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 substrate on the substrate, and the two layers according to 21 above Is a high refractive index layer and

 Consists of low refractive index layer

22. The method for producing a laminate as described in 21 above, wherein

26. The refractive index of the low refractive index layer at 589 nm is 1.20 to: 1.55,

26. The method for producing a laminate as described in 25 above, wherein the refractive index at 589 nm of the high refractive index layer is 1.50-2.20, which is higher than the refractive index of the low refractive index layer. 27. 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 substrate on the substrate, The two layers described in

 High refractive index layer and

 Consists of low refractive index layer

 22. The method for producing a laminate as described in 21 above, wherein

 28. The refractive index of the low refractive index layer at 589 nm is 1.20 to: 1.55,

 The refractive index of the middle refractive index layer at 589 nm is 1.50 to: 1.90, which is higher than the refractive index of the low refractive index layer.

 28. The method for producing a laminate as described in 27 above, 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.

 29. The method for producing a laminate according to any one of 25 to 28, further comprising forming a hard coat layer and Z or an antistatic layer on a substrate.

 30. A laminate produced by the method for producing a laminate described in any one of 19 to 29 above.

 [0019] The cured film obtained by curing the curable resin composition of the present invention is, for example, a low refractive index layer, a high refractive index layer, or the like from one coating film obtained by applying the present composition. Since any two or more layers can be formed, the manufacturing process of a cured film having a multilayer structure can be simplified.

 Since the curable resin composition of the present invention does not undergo a curing reaction due to heat involving hydrolysis, it can provide a cured film excellent in environmental resistance (such as resistance to moist heat).

[0020] A cured film obtained by curing the curable resin composition of the present invention is excellent in scratch resistance, chemical resistance, and transparency, and the curable resin composition of the present invention is particularly an antireflection film. It can be used advantageously in the formation of optical materials such as permeable membrane filters, and by utilizing the high fluorine content, it can be used for coating materials, weather resistant film materials, It can be suitably used as a material for coating. In addition, since the cured film has excellent adhesion to the substrate and provides a good antireflection effect with high scratch resistance, it is extremely useful as an antireflection film and can be applied to various display devices. By The visibility can be improved.

 [0021] The method for producing a laminate of the present invention can form two or more layers from one coating film obtained by applying the composition, thus simplifying the production process of a laminate having a multilayer structure. Can be used. 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 and optical filters. Further, the laminate of the present invention can be suitably used as a paint, weather resistant film, coating, etc. for a substrate requiring weather resistance by utilizing the high fluorine content. In addition, the laminated body provides a good antireflection effect by providing a low refractive index layer in the outermost layer (the layer farthest in base material strength). Moreover, according to the present invention, a laminate having excellent adhesion to a substrate and high scratch resistance can be obtained. Because of these forces, the laminate of the present invention is extremely useful as an antireflection film, and its visibility can be improved by applying it to various types of display devices.

 Brief Description of Drawings

 FIG. 1A is a diagram for explaining “two or more layers formed from one coating film”.

 FIG. 1B is a diagram for explaining “two or more layers formed from one coating film”.

 FIG. 1C is a diagram for explaining “two or more layers formed from one coating film”.

 FIG. 1D is a diagram for explaining “two or more layers formed from one coating film”.

 FIG. 2 is a cross-sectional view of an antireflection film according to an embodiment of the present invention.

 FIG. 3 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.

 FIG. 4 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.

 FIG. 5 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.

 FIG. 6 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.

 FIG. 7 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.

 FIG. 8 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.

 FIG. 9 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.

 FIG. 10 is a cross-sectional view of an antireflection film according to another embodiment of the present invention.

 FIG. 11 is an electron micrograph showing the concept of each state of two-layer separation, no separation (partial aggregation), and uniform structure.

BEST MODE FOR CARRYING OUT THE INVENTION [0023] I. Laminate and production method thereof

 The present invention relates to 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, the coating force of 1 obtained by applying a predetermined curable resin composition to be described later on a substrate or a layer formed on the substrate also has a solvent. Two or more layers are formed by evaporating (hereinafter, evaporating the solvent is sometimes referred to as “drying”). It should be noted that the solvent may not remain completely after drying, and the solvent may remain as long as the cured film can be obtained. In the present invention, two or more layers can be formed twice or more from one coating film.

 [0024] When a specific 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 are “a layer in which the metal oxide particles (A1) and / or (A2) are present in high density” and “the metal oxide particles (A1) and (A2) are substantially In some cases, it may be two or more layers including both “layers that are not present at all” and only “layers in which the metal oxide particles (A1) and / or (A2) are present at high density” 2 In some cases, these layers are used. Hereinafter, using the drawings, “each of two or more layers is a layer in which (A1) and / or (A2) metal oxide particles are present in a high density or (A1) and (A2) metal oxide particles. A layer that does not substantially exist and at least one layer is a layer in which the metal oxide particles (A1) and / or (A2) are present in high density will be described. FIG. 1A shows a case where two or more layers are “layer 1, la in which metal oxide particles (A1) or (A2) are present at high density”. Figure 1B shows that two or more layers are “layers 1, 1 aj in which metal oxide particles (A1) or (A2) are present in high density, and metal oxide particles (A1) and (A2) The case where there are three layers of “layer 3” which does not substantially exist is shown. FIG. 1C shows that two or more layers are “layer 1, la in which metal oxide particles (A1) or (A2) are present in high density” and “metal oxide particles (A1) and (A2) are The case where there are three layers of “layer 3” which does not substantially exist is shown. Fig. 1D shows that two or more layers are "layer lb in which metal oxide particles (A1) and (A2) exist in high density" and "metal oxide particles (A1) and (A2) are actual. This shows the case where there are two layers of layer 3 ”that do not exist.

Since the ultraviolet curable resin composition contains two or more kinds of metal oxide particles, as shown in FIGS. 1A, IB, and 1C, there are two or more types of “layers in which the metal oxide particles exist at high density”. Can be formed.

 The “metal oxide particles” in the “layer in which metal oxide particles are present in high density” means at least one, ie, one or more “metal oxide particles”. Therefore, the “layer in which metal oxide particles are present in high density” may be composed of two or more kinds of metal oxide particles (for example, FIG. 1D). In Figure ID, “Layer lb with high density of metal oxide particles” consists of particles X and Y. Since the particle Y is thicker than the “layer lb where the metal oxide particles are present at high density”, the force that protrudes into the “layer 3 where the metal oxide particles are substantially absent” It is included in the layer “lb” in which the particles are present in high density.

 [0026] In FIGS. 1A to 1D, 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. It may be. Similarly, “layer 1, la, lb in which metal oxide particles are present at high density” may also contain other substances other than metal oxide particles.

 [0027] As a coating method of the 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. Specific curing conditions will be described later.

 [0028] In the present invention, the curable resin composition can be applied to various substrates in the form of a solution, and the resulting coating film can be dried / cured to obtain a laminate. For example, when the substrate is a transparent substrate, an excellent antireflection film can be 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 film, 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 in 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 in 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 in 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 structure 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 base material 10. The membrane is shown.

 In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. In other words, the medium refractive index layer 60 and the high refractive index layer 40 each have a force equivalent to a layer in which metal oxide particles are present in a high density. In the present invention, the high refractive index layer 40 corresponds to a layer having substantially no metal oxide particles, and the medium refractive index layer 60 and the high refractive index layer 40, Alternatively, 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.

 [0033] FIG. 6 shows an antireflection structure 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. The membrane is shown.

In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. On the other hand, the medium refractive index layer 60 and the high refractive index layer 40 both have a force equivalent to a layer in which metal oxide particles are present at a high density, or the medium refractive index layer 60 has metal oxide particles. High density In the present invention, the high refractive index layer 40 corresponds to a layer having substantially no metal oxide particles. According to the present invention, the intermediate refractive index layer 60 and the high refractive index layer 40 or the high refractive index layer 40 is used. The 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 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 in 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 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 in high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. In other words, the medium refractive index layer 60 and the high refractive index layer 40 each have a force equivalent to a layer in which metal oxide particles are present in a high density. In the present invention, the high refractive index layer 40 corresponds to a layer having substantially no metal oxide particles, and the medium refractive index layer 60 and the high refractive index layer 40, Alternatively, 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 in 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 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 in high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. On the other hand, the medium refractive index layer 60 and the high refractive index layer 40 both have a force equivalent to a layer in which metal oxide particles are present at a high density, or the medium refractive index layer 60 has metal oxide particles. According to the present invention, the high refractive index layer 40 corresponds to a layer in which the metal oxide particles are not substantially present in the high density layer. According to the present invention, the medium refractive index layer 60 and the high refractive index layer 40, Alternatively, 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.

 [0038] In the antireflection film, conductive particles such as antimony-doped tin oxide (ATO) particles and phosphorus-doped tin oxide (PTO) particles are used as metal oxides contained in the curable resin composition to be used. Is added, a layer containing the resulting metal oxide at a high density becomes a film having antistatic properties. Therefore, for example, if a high refractive index layer or a medium 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 medium refractive index layer is charged. It can be set as the film | membrane which served as prevention property. In this case, the formation of the antistatic film can be omitted.

Next, each layer of the antireflection film will be described.

 (1) Base material

 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

(Toray Co., Ltd. Lumirror, etc.), glass, polycarbonate resin, acrylic resin, styryl resin, arylate resin, norbornene resin (JSR Co., Ltd. Arton, Nippon Zeon Co., Ltd. Zenex, etc.), Methyl Metal Examples include various transparent plastic plates and films such as rate / styrene copolymer resins and polyolefin resins. Preferred examples include triacetyl cellulose, polyethylene terephthalate resin (Lumirror, etc. manufactured by Toray Industries, Inc.), norbornene-based resin CFSR, Arton, etc., and the like.

[0040] (2) Low refractive index layer

The low refractive index layer refers to a layer having a refractive index of 1.20-1.55 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 fluoropolymer, 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. In order to increase the strength of the low refractive index layer, silica fine particles and the like can be blended.

[0041] (3) High refractive index layer

 The high refractive index layer refers to a layer having a refractive index of 1.50-2.20 for light having a wavelength of 589 nm and a higher refractive index than the low refractive index layer.

 In order to form a high refractive index layer, it is possible to combine inorganic particles with high refractive index, for example, metal oxide particles.

 Specific examples of metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, Zn ○ particles, antimony-doped ZnO, and A1-doped Zn ○ particles. , ZrO particles, TiO particles, silica-coated TiO particles, A1

 2 2 2

 O / ZrO-coated TiO particles, CeO particles, and the like. Preferably, antimo

2 3 2 2 2

 N-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, A1-doped ZnO particles, Al 2 O 3 / ZrO-coated TiO particles. These gold

 2 3 2 2

 The metal oxide particles are a single type.

 It can be used alone 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.

 [0042] (4) Medium refractive index layer

 When combining layers with 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 lower than the high refractive index layer. This layer is referred to as a medium 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 a medium refractive index layer, it is possible to combine inorganic particles having a high refractive index, for example, metal oxide particles.

Specific examples of metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, ZnO particles, antimony Doped ZnO, A1-doped ZnO particles, ZrO particles, TiO particles, silica-coated TiO particles, A1

 2 2 2

 O / ZrO

 2 3 2

 Coated TiO particles, CeO particles, and the like. Preferably, antimony doped acid

 twenty two

 Tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (ΡΤΟ) particles, A1-doped ΖηΟ particles, and ZrO particles. These metal oxide particles may be used alone or in combination.

 2

 Can be used in combinations of two or more.

 Further, the medium refractive index layer can have a function of a hard coat layer or an antistatic layer.

[0043] The reflectance can be lowered by combining the low refractive index layer and the high refractive index layer, and the reflectance can be reduced by combining the low refractive index layer, the high refractive index layer, and the middle refractive index layer. Can be lowered and the color can be reduced.

[0044] (5) Hard coat layer

Specific examples of the hard coat layer include _Si0 , epoxy resin, acrylic resin, and melamine.

 2

 It is also preferable that the material strength of the system resin or the like is also configured. Silica particles may be blended with these resins.

 The hard coat layer has the effect of increasing the mechanical strength of the laminate.

[0045] (6) Antistatic layer

Specific examples of the antistatic layer include conductive oxides such as antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, and A1-doped ZnO particles. Curable films to which organic particles or organic or inorganic conductive compounds are added, metal oxide films obtained by vapor deposition or sputtering of the metal oxides, and films made of conductive organic polymers. it can. Examples of the conductive organic polymer include polyacetylene conductive polymer, polyaniline conductive polymer, polythiophene conductive polymer, polypyrrole conductive polymer, and polyphenylene vinylene conductive polymer. It can be illustrated. As described above, as the metal oxide contained in the curable resin composition used in the present invention, AT o particles, IT o particles, phosphorus-doped tin oxide (（o) particles, antimony-doped Zn o, A1 dope ΖηΟ When conductive particles such as particles are added, 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 electrical conductivity to the laminate and prevents dust from adhering due to static electricity.

 [0046] These layers may be formed in only one layer, 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 _β m, and the film thickness of the hard coat layer is usually 1 to 20 μm. It is.

 [0047] 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 a known application and curing, It can be manufactured by methods such as vapor deposition and sputtering.

 [0048] In addition, the layer made of the curable resin composition according to the present invention is preferably imparted with a heat history by heating in order to be cured 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, heating and curing are 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 thereof used as curing agents for general urea resins and melamine resins can be used. In particular, ammonium salts are preferably used. it can. 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.

 [0049] According to the present invention, since two or more layers can be formed from one coating film, the production process of the laminate can be simplified.

 Further, by making the metal oxide particles unevenly distributed, it is possible to improve the scratch resistance of the laminate.

 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.

[0050] II. Curable resin composition

 Next, the curable resin composition of the present invention will be described.

 The curable resin composition of the present invention is

(A1) Number average particle diameter formed by bonding an organic compound (Ab) having a polymerizable unsaturated group 1 Metal oxide particles with a diameter of at least nm and less than 40 nm (hereinafter referred to as “(A1) metal oxide particles”)

(A2) Metal oxide particles having a number average particle diameter of 40 nm to 200 nm (hereinafter referred to as “(A2) metal oxide particles”)

 (B) Ethylenically unsaturated group-containing fluoropolymer

 (C) (B) High solubility of fluorine-containing polymer containing ethylenically unsaturated groups, one or more solvents (hereinafter referred to as “(C) fast volatile solvent”)

 (D) One or two or more solvents (hereinafter referred to as “(”) that have high dispersion stability of the metal oxide particles of (A1) and (A2) and are compatible with (C) the fast volatile solvent. D) slow volatile solvent ”).

 [0051] 1. Each component of the curable resin composition will be specifically described.

 Metal oxide particles (A1) and (A2)

 In the present invention, two types of metal oxide particles (A1) and (A2) having different particle diameters are used. Among these, the metal oxide particles (A1) need to be bonded to an organic compound (Ab) having a polymerizable unsaturated group described later. The metal oxide particles (A2) are preferably bonded to the organic compound (Ab) having a polymerizable unsaturated group, but are not essential.

 In the present specification, the metal oxide particles (A1) and (A2) may be collectively referred to as “metal oxide particle component (A)”. In the metal oxide particles (Al) and (A2), the metal oxide particles not bonded to the organic compound b) are referred to as “metal oxide particles (Aal)” and “metal oxide particles (Aa2)”, respectively. Sometimes they are collectively referred to as “metal oxide particles (Aa)”. In addition, the metal oxide particles (Al) and (A2) bonded to the organic compound (Ab) are sometimes referred to as “reactive particles (Aabl)” and “reactive particles (Aab2)”, respectively. Sometimes, both are collectively referred to as “reactive particles (Aab)”.

[0052] The number average particle sizes of the metal oxide particles (A1) and (A2) are in the range of 1 nm to less than 40 nm and in the range of 40 nm to 200 nm, respectively, as measured by electron microscopy. By using two types of particles having different particle diameters in this way, the scratch resistance is improved compared to a cured film obtained from a curable resin composition containing one type of metal oxide particles. The two types of metal oxide particles may be a combination of three or more types of metal oxide particles as long as each particle size is within the above range. Further, the substances constituting the plurality of types of metal oxide particles may be the same or different.

 [0053] The metal oxide particles (A1) and (A2) used in the present invention are obtained from the viewpoint of hardness and colorlessness of the cured film, which is a curable resin composition, and can be obtained by using silicon, aluminum, dinoleconium, titanium, Metal oxide particles of at least one element selected from the group consisting of zinc, germanium, indium, tin, antimony and cerium are preferred.

 [0054] In particular, the metal oxide particles (A1) are preferably oxide particles of at least one element selected from the group consisting of anoleminium, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Among these, zirconium oxide particles are particularly preferable. For the purpose of increasing the refractive index of the layer in which the metal oxide particle component (A) constituting the cured film is present at a high density, the refractive index of the metal oxide particle (A1) at a wavelength of 589 nm is 1. It is preferably 5 or more. For this purpose, siri force (refractive index of about 1.45) particles are not preferred.

 The metal oxide particles (A1) have a number average particle size in the range of 1 nm to less than 40 nm, preferably in the range of 1 nm to 30 nm.

 [0055] The metal oxide particles (A2) are preferably particles mainly composed of silica from the viewpoint of improving the scratch resistance of the cured film.

 The metal oxide particles (A2) have a number average particle size in the range of 40 nm to 200 nm, preferably in the range of 40 nm to lOOnm. Here, the particle diameters of the metal oxide particles (A1) and (A2) are number average particle diameters measured by electron microscopy. Moreover, the particle diameter in the case of a rod-shaped particle means a short axis.

 Various surfactants and amines may be added to improve the dispersibility of the metal oxide particles (A1) and (A2).

[0056] Among them, from the viewpoint of high hardness, particles of silica, anoremina, zircoua and antimony oxide are preferred, and zircoua particles are particularly preferred. Moreover, it is possible to obtain a cured film having a high refractive index by using oxide particles such as zirconium and titanium, and by using AT particles, phosphorus-doped tin oxide (PTO) particles, etc., a cured film can be obtained. Add conductivity You can also. These can be used alone or in combination of two or more. Furthermore, the metal oxide particles (Aa) are preferably in the form of powder or dispersion. In the case of a dispersion, an organic solvent is preferred as the dispersion medium from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, and lactate. Estenoles such as chinole, ブ -butyla ratatone, propylene glycolenomonomethinoreethenoreacetate, propyleneglycolenomonoethylenoatenoreacetate; ethers such as ethyleneglycolenomonomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

 [0057] Commercially available silica particles include, for example, colloidal silica manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-0, ST-50, ST-0. In addition, as the silica powder, Nippon Aerosil Co., Ltd. trade names: Aerosil 130, Aerosil 300, Aerogenore 380, Aerosil Nore TT600, Aerosilore 0X50, Asahi Glass Co., Ltd. Trade names: Sildex Η31, Η32, Η51 , Η52, Η121, Η122, manufactured by Enomoto Silica Industry Co., Ltd. Product name: Ε220Α, Ε220, manufactured by Fuji Silysia Co., Ltd. Product name: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd. Product name: SG Flakes .

 [0058] As an aqueous dispersion of alumina, product name: Alumina sol manufactured by Nissan Chemical Industries, Ltd.

100, 200, 520; Asalumina isopropanol dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: AS—150I; As alumina tonolene dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: AS— 150T; Ginolecoyu's tonoleene dispersion is manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: HXU_ 110JC; Zinc antimonate powder is dispersed in water by Nissan Chemical Industries, Ltd. Product name: Cellnax; Alumina , Titanium oxide, tin oxide, oxide For powder and solvent dispersions such as zinc and zinc oxide, manufactured by CIA Kasei Co., Ltd. Product name: Nanotech; for antimony-doped tin oxide aqueous dispersion sol, manufactured by Ishihara Sangyo Co., Ltd. Product name: SN-100D; IT 〇 As powder, product made by Mitsubishi Materials Co., Ltd .; As cerium oxide aqueous dispersion, Taki Chemical Co., Ltd. trade name: Niedral etc.

[0059] The metal oxide particles (A1) and (A2) have a spherical shape, a hollow shape, a porous shape, a rod shape (a shape having an aspect ratio of more than 1 and 10 or less), a plate shape. , Fibrous or indefinite shape, preferably (A1) is rod-shaped and (A2) is spherical.

 These metal oxide particles (A1) and (A2) can be used in a state of being dispersed in a dry powder, water or an organic solvent. For example, a dispersion of fine metal oxide particles known in the art as the dispersion can be used directly. In particular, it is preferable to use a dispersion of metal oxide particles in applications that require excellent transparency in the cured product.

 [0060] The metal oxide particles (A2) used in the present invention may be the metal oxide particles (Aa2) having a predetermined number average particle diameter as they are, but they are polymerized with the metal oxide particles (Aa2). It is preferably a particle formed by binding an organic compound (Ab) containing a reactive unsaturated group (hereinafter sometimes referred to as “reactive particle (Aab2)”). As the metal oxide particle component (A), a cured product obtained by using reactive particles (Aab2) in which metal oxide particles (Aa2) are combined with an organic compound (Ab) having a polymerizable unsaturated group. The scratch resistance of the cured film made of the conductive resin composition is further improved. Here, the bond may be a covalent bond or a non-covalent bond such as physical adsorption.

 [0061] Organic compound having a polymerizable unsaturated group (Ab)

The organic compound (Ab) used in the present invention is a compound having a polymerizable unsaturated group, and is preferably an organic compound containing a group represented by the following formula (A-1). In addition, it includes a [−0_C (= 〇) _NH_] group, and further includes at least one of a [_〇_C (= S) _NH_] group and a [_S_C (= 0) _NH_] group. I like it. In addition, 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. [0062] [Chemical 8]

― U— C— N— (A-l)

 II

 V

 [In the formula, U represents NH, ◯ (oxygen atom) or S (Y atom), and V represents ◯ or S.

]

 [0063] (i) polymerizable unsaturated group

 The polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited. Group and acrylamide group can be cited as preferred examples.

 This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

[0064] (ii) a group represented by the formula (A-1)

 The group [—U—C (= V) —NH] represented by the above formula (A-1) contained in the organic compound is specifically represented by [—0—C (= 〇) one NH—], [ 0—C (= S) —NH—], [-SC (= 0) One NH], [One NH—C (= 〇) One NH], [One NH—C (= S) —NH], and [One SC (= S) -NH]. These groups can be used alone or in combination of two or more. In particular, from the viewpoint of thermal stability, the [_0_C (= 0) _NH_] group and at least one of the [_0_C (= S) _NH_] group and the [_ S_C (= 〇) _NH_] group may be used in combination. preferable.

 The group [_U_C (= V) _NH_] shown in the above formula (A_1) is excellent when it is made into a cured product by generating moderate cohesive force due to hydrogen bonding between molecules. It is considered that the mechanical strength, the substrate, and the properties such as adhesion to adjacent layers such as a high refractive index layer and heat resistance are imparted.

 (Iii) a silanol group or a 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 an alkoxy group or an aryloxy 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 is bonded to the oxide particles (Aa) by a condensation reaction or a condensation reaction that occurs after hydrolysis.

 [0066] (iv) Preferred embodiment

 As a preferred example of the organic compound (Ab), a specific example thereof includes a compound represented by the following formula (A_2).

[0067] [Chemical 9]

(A-2)

[0068] In the formula, R ²⁴ and R ²⁵ may be the same or different and each represents a hydrogen atom or an alkyl group or an aryl group having from 8 to 8 carbon atoms, such as methinole, ethyl, propyl, butyl, Examples include octanol, phenyl, xylyl groups and the like. Where j is an integer between:!

[0069] Examples of the group represented by [(R ²⁴ 0) R ²⁵ Si—] include, for example, a trimethoxysilyl group, a triethoxy group, and the like.

 j 3-j

 Examples thereof include a silyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ²⁶ 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, and dodecamethylene.

R ²⁷ 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 chain polyalkylene groups such as hexamethylene, otatamethylene and dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; phenylene, naphthylene and biphenyl. Divalent aromatic groups such as len and polyphenylene; and alkyl and substituted aryl groups thereof. That power S. In addition, these divalent organic groups may contain a polyether bond, a polyester bond, a polyamide bond, or a polycarbonate bond, which may contain an atomic group containing an element other than carbon and hydrogen atoms.

R ²⁸ is a (k + 1) -valent organic group, 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:! To 20, more preferably an integer of 1 to 10, and particularly preferably an integer of:! To 5.

[0070] Specific examples of the compound represented by the formula (A-2) include compounds represented by the following formulas (A-4) and (A-5).

[0071] [Chemical 10]

 [In the formula, “Acryl” represents an taliloyl group. “Me” represents a methyl group. "

[0072] 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 tritalylate is added, and further 60 to 70 It is produced by reacting for several hours at ° C.

[0073] Reactive particles (Aabl) and (Aab2)

Organic compounds having silanol groups or groups that generate silanol groups by hydrolysis The product (Ab) is mixed with the metal oxide particles (Aa), hydrolyzed, and bonded together. The ratio of the organic polymer component, that is, hydrolyzable silane hydrolyzate and condensate in the resulting reactive particles (Aab) is usually reduced by mass when the dry powder is completely burned in air. As a constant value of%, it can be obtained, for example, by thermal mass spectrometry in air from room temperature to usually 800 ° C.

[0074] The amount of organic compound (Ab) bound to metal oxide particles (Aa) is 100% by mass of reactive particles (Aab) (total of metal oxide particles (Aa) and organic compounds (Ab)). Is preferably 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 particle (Aa) is less than 0.01% by mass, the curing can be obtained with sufficient dispersibility of the reactive particle (Aab) in the composition. The transparency and scratch resistance of the object may not be sufficient. The mixing ratio of the reactive particles (Aab) metal oxide particles in the raw material during manufacture (Aa) is preferably a 5 to 99 weight _^0/0, more preferably, 10 to 98 weight _^0/0 It is.

 [0075] The amount of the metal oxide particles (A1) (that is, the reactive particles (Aabl)) in the curable resin composition is 100% by mass based on the total amount of the composition excluding the organic solvent. A range of 10 to 90% by mass is preferable, and a range of 20 to 80% by mass is more preferable, and a range of 40 to 80% by mass is particularly preferable. If it is less than 10% by mass, a cured film with insufficient hardness or a high refractive index may not be obtained. If it exceeds 90% by mass, film formability may be insufficient. In this case, the content of the metal oxide particles (Aal) constituting the reactive particles (Aabl) is preferably 65 to 95% by mass of the reactive particles (Aabl).

 [0076] The amount (inclusive) of the metal oxide particles (A2) (even if the metal oxide particles (Aa2) and reactive particles (Aab2) are misaligned) in the curable resin composition is Excluding the organic solvent, the total amount of the composition is preferably 100% by mass, and preferably in the range of 1 to 30% by mass: more preferably in the range of 20 to 20% by mass.

 [0077] (B) Ethylenically unsaturated group-containing fluoropolymer

The ethylenically unsaturated group-containing fluoropolymer used in the present invention comprises a compound (B-1) containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing polymer. It is preferably obtained by reacting the fluorinated polymer (B-2) with an isocyanate group / hydroxyl molar ratio of 1.1 to 1.9.

[0078] (B-1) Compound containing one isocyanate group and at least one ethylenically unsaturated group

 The compound (B-1) is not particularly limited as long as the compound contains one isocyanate group and at least one ethylenically unsaturated group in the molecule. If two or more isocyanate groups are contained, gelling may occur when reacting with a hydroxyl group-containing fluoropolymer. In addition, as the ethylenically unsaturated group, a (meth) atalyloyl group is more preferable because the curable resin composition can be cured more easily. Examples of such compounds include 2- (meth) ataloyloxychetyl isocyanate, 2— (meth) atallyloyloxypropyl isocyanate, 1,1-bis [(meth) atalylooxymethyl] ethyl One type of isocyanate or a combination of two or more types may be mentioned.

[0079] Incidentally, such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate. In this case, examples of diisocyanates include 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3-xylylene diisocyanate, 1 isocyanate, p-phenylene diisocyanate, 3,3 ′ Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-Dimethylphenylene diisocyanate, 4,4'-biphenyldiisocyanate, 1, 6-hexanediisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), 2,2,4_trimethylhexamethylenediisocyanate, bis (2-isocyanate ethanolate) fumarate, 6_ Isopropinole _ 1,3 _Pheninoresiocyanate, 4-Diphenol propane diisocyanate, lysine diiso Hydrogenate, hydrogenated diphenylmethane diisocyanate, 1,3_bis (isocyanatemethyl) cyclohexane, tetramethylxylylene diisocyanate, 2, 5 (or 6) _bis (iso Cyanatemethyl) monobicyclo [2.2.1] heptane, etc., may be used singly or in combination of two or more. Among these, 2,4_tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methyl Bis (4-cyclohexylisocyanate) and 1,3-bis (isocyanatemethyl) cyclohexane are particularly preferred.

 [0080] Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, force Prolatataton (meth) acrylate, polypropylene glycol (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol nortri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid E〇 Modified Examples include one kind alone or a combination of two or more kinds such as di (meth) acrylate. Of these, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferred. In addition, as a commercial item of a hydroxyl group-containing polyfunctional (meth) atalylate, for example, Osaka Organic Chemical Co.

 Product Name HEA, Nippon Kayaku Co., Ltd. Product Name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. Product Name ALONIX M-215, M-233, M-305, M-40

It can be obtained as 0.

[0081] When synthesizing from diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, the addition amount of the hydroxyl group-containing polyfunctional (meth) acrylate is 1 to 1 with respect to 1 mol of diisocyanate.

2 mol is preferred.

[0082] As a method for synthesizing such a compound, a method in which diisocyanate and a hydroxyl group-containing (meth) acrylate are charged together and reacted, a method in which diisocyanate is dropped and reacted in a hydroxyl group-containing (meth) acrylate Etc.

[0083] (B-2) Hydrofluoric polymer containing hydroxyl group

 The hydroxyl group-containing fluoropolymer (B-2) is preferably composed of the following structural units (a), (b), and (c). Furthermore, the structural units (d), (e), (f ) Is more preferable.

[0084] Structural unit (a)

 The structural unit (a) is represented by the following general formula (1).

[Chemical 11]

[Wherein R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

In the above general formula (1), the fluoroalkyl group of R ¹ and R ² includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoro mouth Examples thereof include fluorinated alkyl groups having 1 to 6 carbon atoms such as xyl group and perfluorocyclohexyl group. Examples of the alkyl group for R ² include alkyl groups having 1 to 6 carbon atoms such as a methinole group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group.

 [0086] The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples of this include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers. Perfluoro (alkyl vinyl ether), such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether), etc .; perfluoro (propoxypropyl) One perfluoro (alkoxyalkyl biether) or a combination of two or more perfluoro (bialkylene). Of these, hexafluoropropylene and perfluoro (alkyl butyl ethereol) or perfluoro (alkoxyalkyl biether) are more preferred, and it is even more preferable to use these in combination.

[0087] The content of the structural unit (a), the total amount of the hydroxyl group-containing fluoropolymer (B- 2) is taken as 10 0 Monore _^0/0, is 20 to 70 Monore _^0/0 . This is because if the content is less than 20 mole _^0/0, which is the optical characteristics of the fluorine-containing materials where the application is intended, the low refractive index On the other hand, when the content exceeds 70 mol%, the solubility of the hydroxyl group-containing fluoropolymer (B-2) in an organic solvent, transparency, or group This is because the adhesion to the material may decrease. For this reason, it is more preferable that the content of the structural unit (a) is 25 to 65 mol% with respect to the total amount of the hydroxyl group-containing fluoropolymer (B_2). More preferably, it is 60 mol%.

[0088] Structural unit (b)

 The structural unit (b) is represented by the following general formula (2).

 [Chemical 12]

HR ³

 — C— C (2)

HR ⁴

[Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, _ (CH 2) 2 -OR ⁵

 2 x

Or a group represented by OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group, or an alkoxycarbonyl group]

In the general formula (2), the alkyl group represented by R ⁴ or R ⁵ is a carbon number such as a methyl group, an ethyl group, a propynole group, a hexyl group, a cyclohexyl group, or a lauryl group. Examples of the alkylcarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

[0090] The structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component. Examples of such Biel monomers include methyl vinyl ethere, ethino levinino le ethere, _n- propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl butyl ether, tert butyl butyl etherenore, n-pentinolevinoreethenore, n_hexinorevininoreethenore, _n- octinorevininoreethenore, _n- dodecinorevininoreethenore, 2-ethinorehexinorevininoreate nore Alkyl butyl etherols such as cyclohexyl butyl ether or cycloalkyl butyl ethers; aralkyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, butyl propionate, vinyl butyrate, butyl valerate, Power Pro Acid Bull, Versatic Acid Carboxylic acid bull esthetics such as bull and stearic acid bull Methyl (meth) acrylate, ethyl (meth) acrylate, _n -butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxy ethyl (meth) acrylate (Meth) acrylic acid esters such as 2- (n-propoxy) ethyl (meth) acrylate; unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid Or a combination of two or more.

[0091] The content of the structural unit (b), the total amount of the hydroxyl group-containing fluoropolymer (B- 2) is taken as 10 0 Monore _^0/0, is 10 to 70 mole _^0/0 . This is because if the content is less than 10 mole _^0/0, is because there are cases in which the hydroxyl group-containing fluoropolymer solubility in organic solvents (B- 2) is decreased, whereas, the content of This is because if it exceeds 70 mol%, the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer (B-2) may deteriorate. Moreover, such a reason, the content of the structural units (b), with respect to the total weight of the hydroxyl group-containing fluoropolymer (B- 2), preferably from force of 20 to 60 Monore _^0/0, More preferably, it is 30-60 monole%.

 [0092] Structural unit (c)

 The structural unit (c) is represented by the following general formula (3).

 [Chemical 13]

HR ⁶

 — C— C—— (3)

H (CH ₂ ) _v OR ⁷

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1]

[0093] In the general formula (3), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, Examples include 5-hydroxypentyl group and 6-hydroxyhexyl group.

[0094] The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl-containing bur monomers include 2-hydroxyethylenovininoleetenore, 3-hydroxypropinorevininoleetenore, 2-hydroxypropinorevininoleetenore, 4-hydroxybutinolebi Ninoreetenore, 3-hydroxybutinorebininore Hydroxyl-containing vinyl ethers such as ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, hydroxyl-containing vinyl ethers such as 2-hydroxyethyl aryl ether, 4-hydroxybutyl aryl ether, glycerol monoallyl ether, And aryl alcohol. In addition to the above, the hydroxyl group-containing butyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and force prolatatone. (Meth) acrylate, polypropylene glycol (meth) acrylate, etc. can be used.

[0095] The content of the structural unit (c) is preferably 5 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is 100 mol%. ,. The reason for this is that when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer (B-2) in an organic solvent may decrease, while the content is 70%. This is because if it exceeds mol%, the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer (B-2) may deteriorate. Moreover, this reason, the content of the structural unit (c), relative to the total weight of the hydroxyl group-containing fluoropolymer (B- 2), preferably from the force S 5 to 40 mole _^0/0 , further preferably set to 5 to 3 0 mol ^_0/0.

 [0096] Structural unit (d) and structural unit (e)

 The hydroxyl group-containing fluoropolymer (B-2) preferably further comprises the following structural unit (d). Hereinafter, the structural unit (d) will be described.

 The structural unit (d) is represented by the following general formula (4).

 [Chemical 14]

R ⁸

— Si— 0— ( ⁴ )

R ⁹

[Wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]

[0097] In the general formula (4), the alkyl group represented by R ⁸ or R ^{9 is} an alkyl group having 1 to 3 carbon atoms, such as a methinore group, an ethyl group, or a propyl group. Is trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group Examples of C1-4 fluoroalkyl group isotopes S and aryl groups include phenyl group, benzyl group, naphthyl group and the like.

The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the general formula (4). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following general formula (7).

[0099] [Chemical 15]

 (7)

[Wherein, R ^{1Q to} R ¹³ , R ″ to R ¹⁷ , p, q, s, t, and y are the same as those in the general formula (5), and z is a number of! ]

 [0100] When the compound represented by the general formula (7) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the following structural unit (e).

 The structural unit (e) is represented by the following general formula (5).

 [Chemical 16]

{ ₅₎

[Wherein R ^{1Q to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyano group, R ^{14 to} R ¹⁷ represent a hydrogen atom or an alkyl group, and P and q are the numbers:! To 6, s, t Is a number from 0 to 6, y is 1 to 20

Indicates the number 0. ]

[0101] In general formula (5), the alkyl groups represented by R ^{1 () to} R ^{13 have} 1 carbon atom such as a methinole group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. And alkyl groups of RM to R ¹⁷ include alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

[0102] In the present invention, the azo group-containing polysiloxane compound represented by the general formula (7) is used. In particular, a compound represented by the following general formula (8) is particularly preferred.

[0103] [Chemical 17]

 (8)

 [Wherein y and z are the same as those in the general formula (7). ]

 [0104] The content of the structural unit (d) may be 0.1 to 10 mol% when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is 100 mol%. I like it. The reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the cured coating film is lowered, and the scratch resistance of the coating film may be lowered. When the amount exceeds 10 mol%, the transparency of the hydroxyl group-containing fluoropolymer (B — 2) is inferior, and when used as a coating material, repelling and the like are likely to occur during coating. For this reason, the content of the structural unit (d) is more preferably set to 0.:! To 5 mol% with respect to the total amount of the hydroxyl group-containing fluoropolymer (B-2). Desirable 0: More preferably, it is set to 3 to 3 mol%. For the same reason, it is desirable that the content of the structural unit (e) is determined so that the content of the structural unit (d) contained therein falls within the above range.

 [0105] Structural unit (f)

 The hydroxyl group-containing fluoropolymer (B-2) preferably further comprises the above structural unit (f). Hereinafter, the structural unit (f) will be described.

 [0106] The structural unit (f) is represented by the following general formula (6).

 [Chemical 18]

[Wherein R ¹⁸ represents an emulsifying group]

[0107] In the general formula (6), the group having an emulsifying action for R ¹⁸ has both a hydrophobic group and a hydrophilic group, and the hydrophilic group is polyethylene oxide, polypropylene oxide, or the like. A group having a polyether structure is preferred.

 [0108] Examples of the group having an emulsifying action include a group represented by the following general formula (9).

[0109] [Chemical 19]

< ⁹⁾

 [Where n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]

[0110] The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following general formula (10).

[0111] [Chemical 20]

 [Wherein, n, m, and u are the same as those in the general formula (9)]

[0112] Incidentally, the content of the structural unit (f), the entire amount of the hydroxyl group-containing fluoropolymer (B- 2) is 100 mol%, and 0.:!～ 5 mole _^0/0 It is preferable. The reason for this is that when the content rate is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer (B-2) in the solvent is improved, while if the content rate is within mol%, This is because the adhesiveness of the curable resin composition does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material. For these reasons, the content of the structural unit (f) is more preferably 0.:! To 3 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer (B-2). More preferably, it is 0.2 to 3 mol%.

 [0113] Molecular weight of hydroxyl-containing fluoropolymer (B-2)

The hydroxyl group-containing fluoropolymer (B_2) has a polystyrene-reduced number average molecular weight of 5 as measured by gel permeation chromatography (hereinafter referred to as “GPC”) using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent. , 000 to 500,000. This reason The reason is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer (B-2) may decrease, while the number average molecular weight exceeds 500,000. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult. For these reasons, the hydroxyl-containing fluoropolymer (B-2) has a polystyrene equivalent number average molecular weight of preferably 10,000 to 300,000, more preferably 10,000 to 100,000. Power S More preferred.

[0114] Reaction molar ratio of compound (B-1) to hydroxyl group-containing fluoropolymer (B-2)

 The ethylenically unsaturated group-containing fluoropolymer (B) used in the present invention comprises the above-described compound (B_ 1) containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group. It is preferably obtained by reacting the fluorine-containing polymer (B-2) with a molar ratio of isocyanate group Z hydroxyl group of 1.:! To 1.9. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be lowered. On the other hand, if the molar ratio exceeds 1.9, the coating film of the curable resin composition may be deteriorated. This is because the scratch resistance after immersion in an alkaline aqueous solution may be reduced. For this reason, it is more preferable to set the molar ratio of isocyanate group / hydroxyl group to 1.1 to L5, more preferably 1.2 to 1.5.

 [0115] The content of (i) the ethylenically unsaturated group-containing fluoropolymer in the curable resin composition is usually 3 to 70% by mass with respect to 100% by mass of the total composition excluding the organic solvent. is there . The reason for this is that when the content is less than 3% by mass, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained. This is because if the added amount exceeds 70% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained. In addition, it is more preferable to set the addition amount of the component (ii) to 10 to 50% by mass, and more preferably to a value within the range of 25 to 50% by mass.

[0116] (C) Fast volatile solvent

The (C) fast volatile solvent contained in the curable resin composition is one or two or more kinds of solvents which have high solubility of the above-mentioned (ii) ethylenically unsaturated group-containing fluoropolymer. Here, the high solubility of the ethylenically unsaturated group-containing fluoropolymer means that (i) the ethylenically unsaturated group-containing fluoropolymer is When a fluoropolymer is added to each solvent so as to be 50% by mass and stirred at room temperature for 8 hours, it means that the solution becomes visually uniform. The relative evaporation rate of the (C) fast volatile solvent needs to be larger than the relative evaporation rate of the later-described (D) slow volatile solvent. Here, the “relative evaporation rate” is the relative value of the evaporation rate based on the time required for 90% by weight of butyl acetate to evaporate. For details, see TECHNIQUES OF CHEMISTRY VOL.2 ORG ANIC. SOLVENTS Physical Properties and methods of purification 4th ed. (Interscience Publishers, Inc. 1986 page 62). The (C) fast volatile solvent preferably has low dispersion stability of the metal oxide particles (metal oxide particle component (A)) of (A1) and (A2). (C) The fast volatile solvent has a relative evaporation rate higher than that of (D), and (B) the high solubility of the fluorine-containing polymer containing ethylenically unsaturated groups allows the curable resin composition to be used as a base material. In the process of applying and evaporating the solvents (C) and (D), (A

The metal oxide particles 1) and (A2) can be unevenly distributed. In addition, (A1) and (A

Due to the low dispersion stability of the metal oxide particles of 2), the uneven distribution of the metal oxide particles of (A1) and (A2) can be made more reliable.

 [0117] The solvent that can be used as the (C) fast volatile solvent in the present invention is a solvent having a relative evaporation rate of about 1.7 or more, specifically, methyl ethyl ketone (MEK; relative evaporation rate). 3.8), isopropanol (IPA; 1.7), methylisoptyl ketone (MIBK; relative evaporation rate 1.6), methyl amyl ketone (ΜΑΚ; 0 · 3), acetone, methyl propyl ketone, etc. .

 [0118] (D) Slow volatile solvent

The (D) slow volatile solvent contained in the curable resin composition is one or two or more kinds of solvents that have high dispersion stability of the metal oxide particles (A1) and (Α2). Here, the high dispersion stability of the metal oxide particles (A1) and (Α2) means that the glass plate is immersed in an isopropanol dispersion of the metal oxide particles (A1) and (Α2) (A1) When (A1) and (粒子 2) are attached to the glass wall, and the glass plate to which the metal oxide particles (A1) and (Α2) are attached is immersed in each solvent. ) Is uniformly dispersed visually in the solvent. In addition, (D) the slow volatile solvent preferably has the low solubility of the above (ii) ethylenically unsaturated group-containing fluoropolymer. [0119] The solvent that can be used as the (D) slow volatile solvent in the present invention includes methanol (relative evaporation rate 2 · 1), isopropanol (ΙΡΑ; 1 · 7), η-butanol (n-BuOH; 0.5), tert-butanol, propylene glycol monomethyl ether, propylene glycol monoethylenoateolene, propyleneglycolmonopropinoleethenole, ethinorescerosolev, propylcellosolve, butylcetosolve and the like.

 [0120] As the (C) fast volatile solvent and Z or (D) slow volatile solvent used in the present invention, the solvent used in the production of the (B) ethylenically unsaturated group-containing fluoropolymer is usually used as it is. be able to.

 The (C) fast volatile solvent and (D) slow volatile solvent used in the present invention must be compatible. The compatibility is sufficient if the specific composition of the composition has such a degree of compatibility that (C) fast volatile solvent and (D) slow volatile solvent do not separate.

 [0121] Here, whether the selected solvent corresponds to (C) fast volatile solvent or (D) slow volatile solvent used in the present invention is relatively determined among a plurality of selected solvent types. Therefore, isopropanol with a relative evaporation rate of 1.7 may be used as either (C) a fast volatile solvent or (D) a slow volatile solvent.

 [0122] The total amount of the solvent (C) and the solvent (D) is usually 300 parts by mass with respect to 100 parts by mass of the components other than the solvent (including the components (C) and (D)) in the curable resin composition. To 5000 parts by mass, preferably 300 to 4000 parts by mass, more preferably 300 to 3000 parts by mass. The mixing ratio of the solvent (C) and the solvent (D) can be arbitrarily selected within the range of 1:99 to 99: 1.

 [0123] (E) a polyfunctional (meth) ateryl toy compound containing at least two or more (meth) attalyloyl groups, and / or a fluorine-containing product containing at least one or more (meth) attalyloyl groups (Metal) Atre relay toy compound

 A polyfunctional (meth) attareito toy compound (E-1) containing at least two (meth) attaroyl groups is a cured product obtained by curing a curable resin composition and a reflection using the same. It can be used to increase the scratch resistance of the protective film.

 The fluorine-containing (meth) ataretoy compound (E_2) containing at least one (meth) ataryloyl group is used to lower the refractive index of the curable resin composition.

[0124] With regard to compound (E-1), at least two (meth) atalyloyl groups are present in the molecule. If it is a compound to contain, it will not restrict | limit in particular. Examples include neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, penta erythritol tetra (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, force prolatatatone modified dipenta erythritol hex (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, “U_ 15HA” ( Name, manufactured by Shin-Nakamura Chemical Co., Ltd.) Other include alone or in combinations of two or more such compounds represented by the following formula (11). Of these, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and force prolatathone modification Dipentaerythritol hexa (meth) acrylate, a compound represented by the following formula (11) is particularly preferred.

 [Chemical 21]

[In the formula, “Acryl” is an taliloyl group. ]

[0125] The compound (E-2) is not particularly limited as long as it is a fluorine-containing (meth) ataretoy compound containing at least one (meth) ataryloyl group. Examples thereof include perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like alone or in combination. The combination of the above is mentioned.

[0126] The content of component (E) in the curable resin composition is not particularly limited, but is usually 3 to 80% by mass with respect to 100% by mass of the total composition excluding the organic solvent. is there. The reason for this is that if the addition amount is less than 3% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained, while if the addition amount exceeds 80% by mass, This is because the refractive index of the cured coating film of the curable resin composition becomes high and a sufficient antireflection effect may not be obtained. For this reason, it is more preferable to set the added amount of component (E) to a value in the range of 5 to 50% by mass, more preferably 5 to 70% by mass.

[0127] (F) Photoradical polymerization initiator

 In the curable resin composition, if necessary, it is possible to add (F) a radical photopolymerization initiator (radiation (photo) polymerization initiator) that generates active radical species by radiation (light) irradiation. .

 [0128] The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzil ketal, 1-hydroxycyclohexyl. Phenyl ketone, 2,2-dimethoxy-1,1,2-diphenylethane 1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4, 4'-dimethoxybenzophenone, 4, 4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) 1 2-hydroxy 1 2 —Methylpropane-1-one, 2-hydroxy-2-methyl 1- (4- (methylthio) phenyl) -2-morpholinopropane 1 1—Tiluone 1-phenylpropane 1-one, thixanthone, dimethylthioxanthone, 2-isopropylthixanthone, 2-chlorothixanthone, 2 —methylolone ON, 2—Benzyl 2-dimethylamino 1 1 (4-morpholinophenyl) 1 Butanone 1 1, 4 — (2 Hydroxyethoxy) phenyl 1 (2 hydroxy 1 2 propyl) ketone, 2, 4, 6 Trimethyl Benzyldiphenylphosphine oxide, bis _ (2, 6-dimethoxybenzoinole) -1, 2, 4, 4 Trimethylpentylphosphine oxide, oligo (2 hydroxy-1- 2-methyl-1- 1 _ (4— (1 _Methylbule) phenyl) propanone)

[0129] Commercially available radiation (photo) polymerization initiators include, for example, Ciba 'Specialty' Chemicals Co., Ltd. trade names: Inoregacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur 1116, 1173, manufactured by BAS F Product name: Lucirin TPO, manufactured by UCB Product name: Nubekril P36, Fratelli 'manufactured by Lamberti Company Name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, ΚΤ046, ΚΙΡ75 / Β etc.

 [0130] The amount of the radical photopolymerization initiator (F) used as necessary in the present invention may be 0.01 to 10% by mass, with the total amount of the composition excluding the organic solvent being 100% by mass. Preferred 0.1 to 10% by mass is more preferred. If the content is less than 0.01% by mass, the hardness of the cured product may be insufficient, and if it exceeds 10% by mass, the cured product may not be cured to the inside (lower layer).

 [0131] (G) Other ingredients

 In the curable composition, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, a plasticizer are used as necessary. An agent, an absorbent, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, a solvent other than the solvents (C) and (D), and the like can be appropriately blended.

 [0132] 2. Method for producing curable resin composition

 The curable resin composition of the present invention is produced as follows.

 Dispersion of two types of metal oxide particles (A1) and (Α2) and ethylenically unsaturated group-containing fluoropolymer (component (B)), if necessary, polyfunctional (meth) acrylate ((E) Component), radiation (light) polymerization initiator (component (F)), etc. are placed in a reaction vessel equipped with a stirrer and stirred at 35 ° C. to 45 ° C. for 2 hours to obtain a curable resin composition.

 When replacing the solvent with a different type of solvent (β) from the solvent (a) used in the first reactive particle dispersion, it is 1.0 times the mass of the solvent (a) in the reactive particle dispersion. Add solvent (β) and stir under the same conditions. Next, this composition solution is concentrated under reduced pressure to a mass of 50% solid content using a rotary evaporator to obtain a composition.

[0133] 3. Method of applying (coating) curable resin composition

The curable resin composition of the present invention is suitable for use as an antireflection film or a coating material. Examples of the base material to be antireflection or coated include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin). , Epoxy, melamine, triaceti Cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, and slate. These base materials may be plate-like, film-like or three-dimensionally formed by a usual coating method such as date coating, spray coating, flow coating, shower coating, ronore coating, spin coating, brush. The ability to raise paints etc. The thickness of the coating film by these coatings is usually from 0.:! To 400 xm after drying and curing, and preferably from :! to 200 μπι.

 [0134] 4. Curing method of curable resin composition

The curable resin composition of the present invention can be cured by radiation (light). The radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, a laser, etc. Commercially available as sources of visible light, such as sunlight, lamps, fluorescent lamps, and lasers, as sources of ultraviolet rays, mercury lamps, lamps, laser lamps, lasers, etc., and as sources of electron beams A method using thermal electrons generated from tungsten filaments, a cold cathode method that generates high-voltage pulses in metals, and a secondary electron method that uses secondary electrons generated by collisions between ionized gaseous molecules and metal electrodes. Can be mentioned. In addition, as a source of alpha rays, beta rays, and gamma rays, for example, a fission material such as ⁶ ° Co can be cited, and a gamma ray or a vacuum tube that collides accelerated electrons with the anode should be used. Can do. These radiations can be used alone or in combination of two or more simultaneously or at regular intervals. The curable resin composition of the present invention is preferably ultraviolet curable.

[0135] When using the active energy ray, preferably a value within the range of exposure amount of 0. 01~10j / cm ^2. This is because when the exposure dose is less than 0.01 j / cm ² , a curing failure may occur. On the other hand, when the exposure dose exceeds lOjZcm ² , the curing time may become excessively long. Because there is. For these reasons, it is more preferable to set the exposure value within the range of 0.:! To 5j / cm ^{2. It} is more preferable to set the exposure value within the range of 0.3 to 3jZcm ² . preferable.

[0136] The curing reaction of the curable resin composition must be performed under anaerobic conditions such as nitrogen. The reason is that in the presence of oxygen, radical polymerization is inhibited, so that the curing reaction is not sufficient. Because it becomes minutes.

[0137] III. Cured film

The cured film of the present invention can be obtained by coating the curable resin composition on various substrates, for example, a plastic substrate and curing it. Specifically, it is possible to obtain a coated molded body by coating the composition, and preferably drying the volatile component at 0 to 200 ° C. and then performing the above-described curing treatment with radiation. For the curing treatment with radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 j / cm ² , and more preferably is 0.:! To ² j / cm ² . Moreover, preferable electron beam irradiation conditions are a pressurization voltage of 10 to 300 KV, an electron density of 0.02 to 0.30 mA / cm ² , and an electron beam irradiation amount of:! To 1 OMrad.

[0138] After applying the curable resin composition, in the process of evaporating the solvent (C) and solvent (D) in the composition, the metal oxide particles (A1) and (A2) (metal oxide The substance particle component (A)) is unevenly distributed on the coated base side (near the boundary with the adjacent layer) or on the opposite side. Therefore, the metal oxide particle component (A) is present in high density near one interface of the cured film, and the metal oxide particle component (A) is substantially absent near the other interface of the cured film. A resin layer having a low refractive index is formed. Therefore, a cured film having a layer structure of two or more layers can be obtained by curing one coating film made of the 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. The layer in which the metal oxide particle component (A) is present at a high density is a concept indicating a portion where the metal oxide particle component (A) is aggregated. Although the layer is configured as the main component, component (B) may coexist in the layer. On the other hand, (the layer in which the metal oxide particle component (A) does not substantially exist is a concept indicating a portion in which the metal oxide particle component (A) does not exist, but does not impair the effects of the present invention. The layer may contain a slight amount of the metal oxide particle component (A), and this layer is substantially a component other than the metal oxide particle component (A) such as a cured product of the components (B) and (E). In many cases, the cured film includes a layer in which the metal oxide particle component (A) is present at a high density and a layer in which the metal oxide particle component (A) is substantially absent. Each has a two-layer structure with a continuous layer of PET resin (PET resin with an easy-adhesion layer) In general, a layer that is a base material, a layer in which the metal oxide particle component (A) is present at a high density, and a layer in which the metal oxide particle component (A) is not substantially present They are formed adjacent to each other in this order.

 Here, the layer structure of two or more layers means “a layer in which metal oxide particles (A1) and (A2) are present at high density” and “metal oxide (A1) and (A2)”. It may consist of two or more layers including both of the particles and layers that are substantially free of particles, and two or more “(A1) or (A2) metal oxide particles exist in high density. In some cases, it consists only of “layers”.

 Depending on the combination of two or more kinds of metal oxide particles contained in the curable resin composition, two or more “layers in which the metal oxide particles exist at high density” may be formed. Furthermore, the “metal oxide particles” in the “layer in which metal oxide particles are present at high density” means at least one, that is, one or more “metal oxide particles”. In addition, one “layer in which metal oxide particles exist at high density” may be composed of two or more kinds of metal oxide particles.

 [0140] The (B) ethylenically unsaturated group-containing fluorine-containing polymer in the curable resin composition has a lower refractive index than that of a thermosetting resin (for example, a melamine compound). The layer has preferable optical characteristics. Further, by using metal oxide particles (Aa) having a high refractive index as a constituent material of the metal oxide particle component (A), a further excellent antireflection film can be formed.

 [0141] The cured film of the present invention obtained by coating the curable resin composition of the present invention on a substrate and UV-curing the same is excellent in transparency, high hardness, scratch resistance, substrate, and The base material has a feature capable of forming a coating film (coating film) excellent in adhesion to an adjacent layer such as a low refractive index layer. In addition, since no heat is used for the curing reaction, it does not involve a hydrolysis reaction caused by the thermosetting reaction, and thus the resulting cured film has excellent heat and heat resistance. Accordingly, the cured film is particularly suitably used for an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components and the like.

 [Example]

[0142] Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to the description of these examples. In the examples, the amount of each component is Unless otherwise indicated, “part” means mass part and “%” means mass%.

 [0143] Production Example 1

 (1) Synthesis of organic compound (Ab) having polymerizable unsaturated group

 To a mixed solution of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyl suddilaurate in a vessel equipped with a stirrer, 222 parts of isophorone diisocyanate was added dropwise in dry air at 50 ° C over 1 hour. The mixture was stirred at 70 ° C for 3 hours.

Subsequently, consisting Shin Nakamura I匕学Ltd. NK Ester A _TMM_ 3LM_N (pentaerythritol tri Atari rate 60 mass _^0/0 and pentaerythritol Atari rate 40% by weight in the reaction solution. Of these, participating in the reaction (Only pentaerythritol triatallylate 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 it was 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 the mercapto group in the raw material, and the absorption peak of 2260 Kaiser, characteristic of the raw isocyanate compound, disappeared. A 1660-membered peak characteristic of urethane bonds and S (C = 〇) NH-groups and a 1720-force peak characteristic of attaryloxy groups were observed as polymerizable unsaturated groups. It was shown that attaxyloxy group-modified alkoxysilanes that have both an talyloxy group, 1 S (C = 〇) NH—, and a urethane bond 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 (compounds represented by the above formulas (A-4) and (A-5) (Ab)) A composition of 220 parts of pentaerythritol tetratalylate that was not involved in the reaction (hereinafter, this composition may be referred to as “alkoxysilane (1)”) (A # l) was obtained.

 [0144] Production Example 2

 (2) Synthesis of urethane acrylate (compound represented by formula (11))

NK ester A—TMM—3LM—N made by Shin-Nakamura Chemical Co., Ltd. for a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer (Only the pentaerythritol triatalylate having a hydroxyl group is involved in the reaction.) 93 parts were added dropwise at 10 ° C for 1 hour, and then stirred at 60 ° C for 6 hours. The reaction solution was used.

 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. I confirmed. In addition, it was confirmed that the molecule contains a urethane bond and an taliloyl group (polymerizable unsaturated group).

 As a result, 75 parts of urethane hexatatereitohi compound (compound represented by the above formula (11)) was obtained, as well as 37 parts of pentaerythritol tetraatalylate that was not involved in the reaction. I got a composition (A # 2).

 [0145] Production Example 3

 [Preparation of composition for silica particle-containing hard coat layer]

 Composition containing polymerizable unsaturated groups produced in Production Example 1 (A # 1) 2. 32 parts, silica particle sol (methylethylketone silica sol, MEK-ST, Nissan Chemical Industries, Ltd., number average particle) (Diameter 0.022 μ 0η, silica concentration 30%) 91. 3 parts (27 parts as silica particles), 0 · 1 2 parts of ion-exchanged water, and 0.01 part of ρ-hydroxyphenyl monomethyl ether After stirring at 60 ° C for 4 hours, 1.36 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain reactive particles (dispersion liquid (A # 3)). 2 g of this dispersion (A # 3) was weighed on an aluminum pan, dried on a hot plate at 175 ° C for 1 hour and weighed to obtain a solid content of 30.7%. Also, weigh 2g of the dispersion (A # 3) in a magnetic crucible, pre-dry on a hot plate at 80 ° C for 30 minutes, and calcinate in a 750 ° C pine furnace for 1 hour. The inorganic content in the minute was determined to be 90%.

 [0146] This dispersion (A # 3) 98.6 g, composition (A # 2) 3.4 g, 1-hydroxy cyclohexyl phenyl ketone 2. lg, 11 ^^ 80 111 £ 907 (2 _methyl_ 1 _ [4_ (Methylthio) phenyl] —2-morpholinopropane 1-one, manufactured by Chinoku Specialty Chemicals) 1.2 g, dipentaerythritol hexatatalylate (DPHA) 33.2 g, cyclohexanone 7 g Mixing and stirring were carried out to obtain 145 g of a silica particle-containing composition for hard coat layer (solid content concentration: 50%).

[0147] Production Example 4 [Preparation of a composition containing zirconia particles]

 Made by Daiichi Elemental Chemical Co., Ltd., 300 parts of UEP-100 (—next particle size 10-30 nm) is added to 700 parts of methyl ethyl ketone (MEK), and dispersed for 168 hours with glass beads. The beads were removed to obtain 950 parts of a zircouore dispersed sol. After weighing 2g of the zircoyu dispersed sol in an aluminum dish, drying on a hot plate at 120 ° C for 1 hour and weighing, the solid content was determined to be 30%. To 100 g of this zircouore dispersed sol, the composition synthesized in Production Example 1 (A # 1) 0.86 g, dipentaerythritol hexahexarate (DPHA) 13.4 g, p methoxy sifenore 0.016 g, Exchange water 0.03g? Kunming f After stirring at 60 ° C for 3 days, add 0.332 g of methyl noreformic acid methyl ester and heat and stir at the same temperature for 1 hour to obtain 116 g of a dispersion of surface-modified dinoleconia particles. It was. 116 g of this dispersion, composition (A # 2) 1.34 g, 1-hydroxycyclohexenolephenoloketone 1.26 g, IRGACURE907 (2-methyl-1- [4- (methylthio) phenyl] _ 2_morpholino Propane 1_one, Ciba Specialty Chemicals) 0 · 76 g and MEK2846 g were mixed and stirred to obtain 2964 g of a zirconia particle-containing composition (solid content concentration 4%).

 [0148] Production Example 5

 [Preparation of composition containing tin-doped indium oxide (ITO) particles]

 ITO sol (10wt% IPA sol) made by Fuji Chemical Co., Ltd. 700g, DPHA 29.5g, 2 methyl 1 [4 (methylthio) phenyl] 2-morpholinopropane 1on lg, isopropyl alcohol (IP A) 1769. 5g An ITO particle-containing composition having a solid content concentration of 4% was obtained.

 [0149] Production Example 6

 [Preparation of antimony-doped tin oxide (AT〇) particle-containing composition]

ATO particles (Ishihara Techno Co., Ltd., SN-100P, primary particle size 10-30nm), dispersant (Asahi Denka Kogyo Co., Ltd., Adekapulu Knick TR-701), and methanol were mixed in 90/2. 78/21 1 (weight ratio) was mixed (total solid content 31%, total inorganic content 29.6%). In a 50ml plastic bottle of Pain Tossier, put 40g of glass beads (manufactured by T ○ SHINRIK〇, BZ-01) (bead diameter: 0.1mm) (volume: about 16ml) and the above mixture (30g) for 3 hours. Dispersion and a dispersion sol having a median diameter of 80 nm were obtained. 304 g of this sol has a composition (A # l) 5.7 g, p-methoxyphenol After stirring a mixed solution of 0.1 g of diol and 0.12 g of ion-exchanged water at 60 ° C for 3 hours, add 1.3 g of orthoformate methyl ester and heat and stir at the same temperature for 1 hour. 311 g of ATO particle dispersion was obtained. 278.3 g of this dispersion, 1.7 g of composition (A # 2), 1.7 g of pentaerythritol retriate acrylate, 2_methyl _ 1 _ [4_ (methylthio) phenyl] — 2 morpholinopropane 1 1— 0.88 g of ON, 33 g of methanol, and 1675 of propylene glycolanol monomethyl ether were mixed and stirred to obtain 2000 g of an ATO particle-containing composition (solid content concentration 5%).

 [0150] Production Example 7

 [Preparation of composition containing A1-doped ZnO particles]

 Zinc oxide particles (A1-doped ZnO particles manufactured by Sakai Chemical, primary particle size 10-20 nm), dispersant (manufactured by Takamoto Kasei Co., Ltd., High Blood ED151) and propylene glycol monomethyl ether, 27.6 / 4.8 / 67.6 (weight ratio) was mixed (total solid content 30%, total inorganic content 27.6%). Zirconia beads 40 g (bead diameter 0.1 mm) and the above mixed solution (30 g) were placed in a 50 ml plastic bottle of paint cheer, and dispersed for 8 hours to obtain a dispersion zone with a median diameter of 40 nm. Add 290 g of this Zonole to 10 g of Pentaerythritol Retriate Talilate, 2-Methylenole 1 [4- (Methylthio) phenyl] — 2-morpholinopropane 1-one 0.5 g, and 2138 g of propylene glycol monomethyl ether. After mixing and stirring, 2438 g of a zinc oxide particle-containing composition (solid content concentration 4%) was obtained.

 [0151] Production Example 8

 [Production of reactive alumina and zirconia-coated TiO particle sol (A1-1) bonded with organic compound (Ab) having polymerizable unsaturated groups]

 2

 Alumina, Ginoleconia-coated TiO particle dispersion (Tika Co., Ltd., total solids concentration 28

 2

 33, 7 parts, solution of alkoxysilane (1) produced in Production Example 1 5.4 製造 ^ Distilled water 0.20 咅 ^ p Hydroquinone monomethylenoateolate 0.03 ？? Keen and stirred at 65 ° C. After 4 hours, add 2.2 parts of orthoformate methyl ester and heat for another 1 hour. Reactive alumina with a solid content of 31.6%, zirconia-coated TiO particle sol (Al _

 2

 1) was obtained.

The number average particle diameter of the TiO particles was 20 nm. Here, the average particle size is transmission type Measured with an electron microscope.

 [0152] Production Example 9

 [Production of hydroxyl-containing fluoropolymer (B-2)]

 After replacing the stainless steel autoclave with a 1.5 L magnetic stirrer with nitrogen gas sufficiently, 500 g of ethynole acetate, 43.2 g of perfluoro (propyl butyl ether), 41.2 g of ethyl vinylenoleethenole, 21% hydroxyethyl vinyl ether 21 .5g, "Adekaria soap NE_ 30" (made by Asahi Denka Kogyo Co., Ltd.) as nonionic reactive emulsifier 40.5g, "VPS-1001" (made by Wako Pure Chemical Industries, Ltd.) as polydimethylsiloxane containing azo group 6. Og and lauroyl peroxide 1. 25 g was calorie, cooled to _50 ° C with dry ice and methanol, and then the oxygen in the system was removed again with nitrogen gas.

Next, 97.4 g of hexafluoropropylene was added and the temperature was raised. The pressure when the temperature in the autoclave reached 60 ° C was 5.3 X 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours, and 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 released to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a fluoropolymer (B-2).

[0153] Production Example 10

 [Production of ethylenically unsaturated group-containing fluoropolymer (B1)]

A separable flask with a capacity of 1 liter equipped with a magnetic stirrer, a glass cooling tube and a thermometer, 50.0 g of the hydroxyl group-containing fluoropolymer (B-2) obtained in Production Example 9 was used as a polymerization inhibitor. — Di_t_butylmethylphenol 0. Olg and MIBK374g were charged, and the mixture was stirred until the hydroxyl group-containing fluoropolymer (B-2) was dissolved in MIBK at 20 ° C until the solution became clear and uniform. Next, 2-atallyloyloxetyl isocyanate (B-1) 16. Og was added to this system, and the mixture was stirred until the solution became homogeneous, and then dibutyltin dilaurate 0. lg Was added to start the reaction, and the system temperature was maintained at 55 to 65 ° C. and stirring was continued for 5 hours to obtain a MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (B1). Weigh 2g of this solution in an aluminum dish, dry on a hot plate at 150 ° C for 5 minutes, and weigh. The solid content was determined to be 15.0%.

[0154] Production Example 11

 [Production of silica-based particles (A2-1) bonded with a compound having a polymerizable unsaturated group]

 As in Production Example 8, 1. 1 part of alkoxysilane (1), methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK—ST—L (number average particle size of 0.050 xm, Silica concentration 30./.) 91. 3 parts (solid content 27.4 parts), ion-exchanged water 0.1 parts, orthoformate methyl ester 1. 4 parts were added to the particle dispersion (A2-1). The solid content of the particle dispersion (A2-1) was determined to be 36% by mass.

 The average particle diameter of the silica-based particles was 50 nm. Here, the average particle diameter was measured with a transmission electron microscope.

[0155] Production Example 12

 [Manufacture of silica-based particles (A1-2) bonded with a compound having a polymerizable unsaturated group]

 Alkoxysilane (1) 1 part 1 as in Production Example 11, Methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST (number average particle size 0.020 / m, silica concentration) 30%) 91.3 parts (solid content 27.4 parts), ion-exchanged water 0.1 parts, orthoformate methyl ester 1.4 parts were used to obtain a particle dispersion (A2-2). The solid content of the dispersion (A1-2) was determined to be 36% by mass.

 The average particle diameter of the silica-based particles was 20 nm. Here, the average particle diameter was measured with a transmission electron microscope.

[0156] Example 1

 [Preparation of Curable Resin Composition 1]

 Alumina, Zircoure coated TiO particle sol obtained in Production Example 8 (A) 110 g (reactive particles

 2

34.8 g) as a polymer, 285 g of an ethylenically unsaturated group-containing fluoropolymer (Bl) obtained in Production Example 10 (42.7 g as an ethylenically unsaturated group-containing fluoropolymer), dipentaerythritol Rupentatalylate (DPPA) 15. 4 g, 2_benzyl _ 2 -dimethylamino _ 1 _ (4 —morpholinophenyl) 1 1-butanone (Irgacure 369, Chinoku 'Specialty' Chemi 3.9 g, a compound represented by the formula (11) obtained in Production Example 2 3.2 g, methylol ethyl ketone 530 g, methyl isobutyl ketone 150 g, and normal butanol 100 g. Stirring. The resulting curable resin composition had a solid content concentration of 8.4%.

 [0157] Examples 2 and 3 and Comparative Examples 1 and 2 [Preparation of Curable Resin Compositions 2 and 3]

 The combinations of the metal oxide particle components used were changed as shown in Table 1, and curable resin compositions 2 to 5 were obtained in the same manner as in Example 1 except that the respective components were blended in the proportions shown in Table 1. It was.

 [0158] Further, cured films were prepared using the curable resin compositions:! To 5 produced in the above Examples:! To 3 and Comparative Examples 1 and 2, and properties of the cured films were evaluated. The method for producing the cured film is as follows.

Silica particle sol (Methyl ethyl ketone silica sol, MEK_ST, Nissan Chemical Industries, Ltd., number average particle size 0.022 μΐη, silica concentration 30 ^ο / _ο ) 98.6 g, 1-hydroxycyclohexenoyl phenyl ketone 2 · Lg, IRGACURE907 (2—Methyl— 1— [4— (Methylthio) phenol 2-NO] — 2-morpholinopropane 1-one, manufactured by Chinoku “Specialty Chemicals” 1 • 2 g, Dipentaerythritol Hexaatalylate (DPHA) 3 · 2 g and cyclohexanone 7 g were mixed and stirred to obtain a silica particle-containing composition for hard coat layer. This silica particle-containing hard coat layer composition was applied to a triacetyl cellulose film (LOFO, film thickness 80 _β m) using a wire bar coater (# 12), and then heated in an oven at 80 ° C. Dried for a minute. Subsequently, a hard coat layer was formed by irradiating with ultraviolet rays under a light irradiation condition of 0.6 j / cm ² using a high-pressure mercury lamp in air. When the film thickness of the hard coat layer was measured with a stylus type film thickness meter, it was 5 am.

On the obtained hard coat layer, using a wire bar coater (# 3), the curable resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were applied, and then in an oven. Dry at 80 ° C for 1 minute. Subsequently, a cured film layer having a thickness of 0.2 zm was formed by irradiating ultraviolet rays under a light irradiation condition of 0.9 j / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere.

[0159] Evaluation of cured films> (1) Steel wool resistance

 The steel wool resistance test of the cured film was performed by the following method. In other words, steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB_ 301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded to 1 kg. Under these conditions, rubbing was repeated 10 times, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria.

 ◯: The cured film is almost free from peeling and scratches.

 (Triangle | delta): A thin crack is recognized by the cured film.

 X: Peeling occurred on a part of the cured film, or streak scratches occurred on the surface of the cured film.

[0160] (2) Haze (%)

 Turbidity (Haze value) in the obtained laminate was measured using a Haze meter and evaluated according to the following criteria.

 ○: Haze value is 1% or less.

 Δ: Haze value is 3% or less.

 X: Haze value exceeds 3%.

[0161] (3) Ethanol tolerance

 The ethanol resistance test of the cured film was performed by the following method. That is, a non-woven fabric soaked with ethanol (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film Was repeatedly rubbed 20 times under the condition of a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria.

 ◯: The cured film is almost free from peeling and scratches.

 (Triangle | delta): A thin crack is recognized by the cured film.

 X: Peeling occurred on a part of the cured film, or streak scratches occurred on the surface of the cured film.

[0162] (4) Layer separation

The cross section of the obtained cured film was observed with a microscope, and the ability to separate into two layers was evaluated. The evaluation criteria are as follows. Fig. 2 shows an electron micrograph showing typical examples of each state as a concept.

《¥ 《Appendix》 DPPA: Dipentaerythritol pentaatarylate; UV curable crosslinking agent (pentafunctional) Inoregacure 369: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenol) 1-butanone; Ciba Specialty Chemicals photopolymerization initiator

[0165] From the results in Table 1, Examples in which both metal oxide particles (A1) and (A2) were blended:! To 3 had good layer separation and scratch resistance, haze and chemical resistance. It can be seen that it has excellent properties.

 In contrast, in Comparative Example 1 in which only one type of metal oxide particles (A1) was blended, the scratch resistance and chemical resistance were lowered. Further, in Comparative Example 2 in which two types of particles corresponding to the metal oxide particles (A1) were blended, the layer separability was lowered, and the scratch resistance and transparency were inferior.

[0166] Example 4

 [Production of laminate]

 (1) Preparation of hard coat layer

Using a wire bar coater (# 12), the silica particle-containing hard coat layer composition prepared in Production Example 3 is applied to a triacetyl cellulose film (LOFO, film thickness 80 / m). 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 the air. When the film thickness of the cured film layer was measured with a stylus type film thickness meter, it was 5 / m.

 [0167] (2) Preparation of medium refractive index layer

After coating the zirconia particle-containing composition prepared in Production Example 4 (solid content concentration 4%) on the hard coat layer prepared in (1) using a wire bar coater (# 3), in the oven 80 ° Dry at 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. The thickness of the cured film layer was calculated with a reflection spectrometer to be 65 nm.

 [0168] (3) Preparation of high refractive index layer and low refractive index layer

The curable resin compositions 1 to 3 obtained in Examples 1 to 3 were each coated on the medium refractive index layer prepared in (2) using a wire bar coater (# 3), and then the oven. Medium Dry for 2 minutes at 140 ° C, use a conveyor-type mercury lamp manufactured by Oak Manufacturing Co., Ltd., 0.6j / cm ² By irradiating with ultraviolet rays, a cured film layer having a film thickness of 0.2 μΐη was formed.

[0169] Example 5

 [Production of laminate]

 (1) Preparation of hard coat layer

 It was produced in the same manner as in Example 4 (1).

 (2) Preparation of antistatic layer

 After coating the soot particle-containing composition (solid content concentration 4%) prepared in Production Example 5 on the hard coat layer prepared in (1) using a wire bar coater (# 3), Dry 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. The thickness of the cured film layer was calculated with a reflection spectrometer to be 65 nm.

 (3) Preparation of medium refractive index layer

 Example 4 It was produced in the same manner as (2).

 (4) Preparation of high refractive index layer and low refractive index layer

After coating the curable resin compositions 1 to 3 obtained in Examples 1 to 3 on the medium refractive index layer prepared in (3) using a wire bar coater (# 3), respectively, Medium Dry at 140 ° C for 2 minutes, use a conveyor type mercury lamp manufactured by Oak Manufacturing Co., Ltd. in the air, and cure the film with a thickness of 0.2 μΐη by irradiating with 0.6 j / cm ² of ultraviolet light. A layer was formed.

[0170] Examples 6, 7

 [Production of laminate]

 (1) Preparation of antistatic layer

Instead of the soot particles prepared in Production Example 5, the soot particle-containing composition (solid content concentration 5%) or A1-doped ΖηΟ particle-containing composition (solid content concentration 4%) prepared in Production Example 6 or 7 is used. Using a wire bar coater (# 3), it was coated on a triacetyl cellulose film (LOFO, film thickness 80 zm), 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 jZcm ² using a high-pressure mercury lamp in a nitrogen atmosphere. When the thickness of the cured film layer was calculated with a reflection spectrometer, it was 7 at 65 nm. (2) Preparation of hard coat layer

The silica particle-containing hard coat layer composition (solid content concentration 50%) prepared in Production Example 3 was applied using a wire bar coater (# 12) and then dried in an oven at 80 ° C for 1 minute. . Subsequently, a cured film layer was formed by irradiating with ultraviolet rays under a light irradiation condition of 0.6 j / cm ² using a high-pressure mercury lamp in air.

 (3) Preparation of medium refractive index layer

 Example 4 It was produced in the same manner as (2).

 (4) Preparation of high refractive index layer and low refractive index layer

After coating the curable resin compositions 1 to 3 obtained in Examples 1 to 3 on the medium refractive index layer prepared in (3) using a wire bar coater (# 3), respectively, Medium Dry at 140 ° C for 2 minutes, use a conveyor-type mercury lamp manufactured by Oak Manufacturing Co., Ltd., and irradiate with 0.6j / cm ² of ultraviolet rays to form a cured film layer with a thickness of 0.2m Formed.

[0171] Example 8

 [Production of laminate]

 (1) Preparation of hard coat layer

 It was produced in the same manner as in Example 4 (1).

 (2) Preparation of high refractive index layer and low refractive index layer

 After coating the curable resin compositions 1 to 3 obtained in Examples 1 to 3 on the hard coat layer prepared in (1) using a wire bar coater (# 3), respectively, Dry for 2 minutes at 140 ° C, and use a conveyor type mercury lamp manufactured by Oak Manufacturing Co., Ltd. Formed.

[0172] Evaluation Example 1

 [Evaluation of laminate]

 When the cross sections of the laminates obtained in Examples 4 to 8 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. It 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.

Figure 11 shows the concept of two-layer separation, no separation (partially agglomerated) and uniform structure. The anti-reflection properties of the resulting anti-reflection laminate were measured using a spectral reflectance measurement device (self-recording spectrophotometer U— 3410 incorporating Hitachi Integrating Sphere 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.

 Industrial applicability

[0173] The curable resin composition of the present invention can form a cured film composed of two or more layers on a substrate from one coating film, and can simplify the manufacturing process. .

 The curable resin composition of the present invention and the cured film thereof are scratched (scratched) such as plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, and artificial marble. ) Protective coating materials for prevention and contamination prevention; antireflection films for film-type liquid crystal elements, touch panels, plastic optical parts, etc .; adhesives for various substrates, sealing materials; It can be suitably used as a prevention film.

 [0174] Since the method for producing a laminate of the present invention can form two or more layers from one coating film, the production process of a laminate having a multilayer structure of two or more layers can be simplified. 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. Further, the obtained laminate can be suitably used as a paint, weather resistant film, coating, etc. for a substrate requiring weather resistance by utilizing the fact that a layer having a high fluorine content can be included. In addition, the laminate is excellent in adhesion to the base material and imparts a good antireflection effect with high scratch resistance. Therefore, the laminate is extremely useful as an antireflection film and is applied to various display devices. Therefore, the visibility can be improved.

Claims

Claims [1] The following ingredients:  (A1) Metal oxide particles having a number average particle diameter of 1 nm or more and less than 40 nm formed by bonding an organic compound (Ab) having a polymerizable unsaturated group (hereinafter referred to as “metal oxide particles of (A1)”) (A2) Metal oxide particles having a number average particle diameter of 40 nm to 200 nm (hereinafter referred to as “(A2) metal oxide particles”)  (B) Ethylenically unsaturated group-containing fluoropolymer  (C) (B) One or more solvents with high solubility of the ethylenically unsaturated group-containing fluoropolymer (hereinafter referred to as “(C) fast volatile solvent”)  (D) One or two or more solvents (hereinafter referred to as “(”) that have high dispersion stability of the metal oxide particles of (A1) and (A2) and are compatible with (C) the fast volatile solvent. D) a slow volatile solvent ”, and (C) the relative evaporation rate of the fast volatile solvent is higher than (D) the relative evaporation rate of the slow volatile solvent. [2] (C) The fast volatile solvent is one or more solvents having low dispersion stability of the metal oxide particles (A1) and (A2), and (D) the slow volatile solvent is ( 2. The curable resin composition according to claim 1, wherein the curable resin composition is one or more solvents having low solubility of the ethylenically unsaturated group-containing fluoropolymer. [3] The metal oxide particles of (A1) are oxide particles of at least one element selected from the group force consisting of aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. The curable resin composition according to claim 1, wherein the curable resin composition is provided.  [4] The curable resin composition according to any one of claims 1 to 3, wherein the metal oxide particles (A2) are particles mainly composed of silica. [5] The force of any one of [1] to [4], wherein the metal oxide particles (A2) are bonded to the organic compound (Ab) having the polymerizable unsaturated group. Curable resin composition. [6] The force of any one of claims 1 to 5, wherein the organic compound (Ab) has a group represented by the following formula (A-1) in addition to the polymerizable unsaturated group: Curable resin composition. [Chemical 22]  | _ |  —— U— C— N— (A— 1)  li  V  [In the formula, U represents NH, ◯ (oxygen atom) or S (Y atom), and V represents ◯ or S. ]  7. The organic compound (Ab) force S, a compound having a silanol group in the molecule, or a compound that generates a silanol group by hydrolysis, according to any one of claims 1 to 6, Curable resin composition.  [8] The (B) ethylenically unsaturated group-containing fluoropolymer comprises a compound (B-1) containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group. 8. The curable resin composition according to claim 1, which is obtained by reacting the containing fluorine-containing polymer (B-2).  [9] Hydroxyl-containing fluorine-containing polymer (B-2) force comprising the following structural units (a) 20 to 70 mol%, (b) 10 to 70 monole% and ((:) 5 to 70 monole% The curable resin composition according to claim 8, wherein the number average molecular weight in terms of polystyrene measured by gel permeation chromatography is 5,000 to 500,000.  (a) A structural unit represented by the following general formula (1).  (b) A structural unit represented by the following general formula (2).  (c) A structural unit represented by the following general formula (3).  [Chemical 23]

[Wherein R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)] [Chemical 24] HR ³  — C-C― (2) HR ⁴ [Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, — (CH 3) OR ⁵ or  2 A group represented by OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group, or an alkoxycarbonyl group]  [Chemical 25] HR ⁶ — C— C ( ³ ) H (CH ₂ ) _v OR ⁷ [Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1] [10] The hydroxyl group-containing fluoropolymer (B-2) further comprises the following structural unit (d) derived from an azo group-containing polysiloxane compound: 0.:! To 10 mol%. The curable resin composition according to 8 or 9.  (d) A structural unit represented by the following general formula (4).  [Chemical 26]

[Wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group] [11] The curable resin according to claim 10, comprising the hydroxyl group-containing fluoropolymer (B-2) force S and the structural unit (d) as a part of the following structural unit (e). Composition.  (e) A structural unit represented by the following general formula (5). [Chemical 27] HCHII

 RCHII [Wherein R ^{1Q to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyano group, R ^{14 to} R ¹⁷ represent a hydrogen atom or an alkyl group, and p and q are numbers of:! To 6, s, t is a number from 0 to 6, y is a number from:! to 200. ]  [12] Furthermore, the hydroxyl group-containing fluoropolymer (B-2) contains the following structural unit (f) 0.:! To 5 mol%, any one of claims 8 to 11: Curable resin composition.  (f) A structural unit represented by the following general formula (6). [Chemical 28]

[Wherein R ^1S represents an emulsifying group] [13] The curable resin composition according to any one of Claims 8 to 12, wherein the compound (B-1) is 2- (meth) atalylooxychetyl isocyanate. [14] In addition, the component (E) contains at least two (meth) atalyloyl groups, and / or contains at least one (meth) atalyloyl group. 14. The curable resin composition according to any one of claims 1 to 13, wherein the curable resin composition comprises a fluorine (meth) attale toy compound. [15] The curable resin composition according to any one of [1] to [14], further comprising a component (F) a radical polymerization initiator. [16] The curable resin composition according to any one of [15] to [15], which is ultraviolet curable.  [17] Claims: A cured film obtained by curing the curable resin composition according to any one of! To 16, and having a multilayer structure of two or more layers. [18] One or more layers in which the metal oxide particles of (A1) and (A2) are present at high density, and (A1) and 18. The cured film according to claim 17, having a layer structure of two or more layers composed of one or less layers substantially free of metal oxide particles (A2). [19] A method for producing a substrate and a laminate having a multilayer structure thereon,  A coating film is formed by applying the curable resin composition according to any one of claims 1 to 16 on the substrate or a layer formed on the substrate,  A method for producing a laminate, wherein two or more layers are formed by evaporating a solvent from the coating film of 1.  [20] Each of the two or more layers is substantially composed of a layer in which the metal oxide particles (A1) and / or (A2) are present in high density or the metal oxide particles (A1) and (A2). 20. The laminate according to claim 19, wherein at least one layer is a layer in which the metal oxide particles (A1) and / or (A2) are present at a high density. Manufacturing method.  21. The method for manufacturing a laminate according to claim 20, wherein the two or more layers are two layers.  [22] The method for producing a laminate according to any one of claims 19 to 21, wherein the two or more layers are cured by irradiation with radiation. [23] The method for producing a laminate according to any one of [19] to [22], wherein the laminate is an optical component.  [24] The method for producing a laminate according to any one of [19] to [22], wherein the laminate is an antireflection film.  [25] The antireflection film according to claim 21, wherein the laminate 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 substrate. The two layers are a high refractive index layer and  Consists of low refractive index layer  The method for producing a laminate according to claim 21, wherein [26] The refractive index of the low refractive index layer at 589 nm is 1.20 to: 1.55,  26. The method for producing a laminate according to claim 25, wherein the refractive index at 589 nm of the high refractive index layer is 1.50-2.20, which is higher than the refractive index of the low refractive index layer. [27] The laminate is at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer on a substrate. The antireflection film is laminated in this order from the side close to the force base material, and the two layers according to claim 21  High refractive index layer and  Consists of low refractive index layer  The method for producing a laminate according to claim 21, wherein [28] The refractive index of the low refractive index layer at 589 nm is 1.20 to: 1.55,  The refractive index of the middle refractive index layer at 589 nm is 1.50 to: 1.90, which is higher than the refractive index of the low refractive index layer.  28. The method for producing a laminate according to claim 27, 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.  [29] The method for producing a laminate according to any one of [25] to [28], further comprising forming a hard coat layer and Z or an antistatic layer on a substrate.  [30] A laminate produced by the laminate production method according to any one of [19] to [29].