TWI389963B - A hardened resin composition, a hardened film and a laminate - Google Patents

Description

Curable resin composition, cured film and laminate thereof

The present invention relates to a curable resin composition, a cured film comprising the same, a method for producing the laminate, and a laminate obtained therefrom, and in particular, a coating film can be formed to have a low refractive index layer and a high refractive index layer. A method for producing a laminate of two or more layers of a curable resin composition of a cured film composed of a layer of two or more layers and a coating film of two or more layers.

At present, various display devices (display devices) have been developed as multimedia has developed. Among various display devices, in particular, devices that are mainly used for outdoor use, and gradually pay attention to the improvement of their visibility, even for large display devices, consumers are demanding further sharpness, and this has become a technical issue.

Various display panels, such as a liquid crystal display panel, a cold cathode tube panel, and a plasma display, need to contain hardening which is excellent in low refractive index, scratch resistance, coating property, and durability in order to prevent reflection of external light and improve image quality. An antireflection film of a low refractive index layer composed of a substance. In order to remove the attached fingerprints, dust, and the like, these display panels are often wiped with a gauze impregnated with alcohol or the like, and are required to have scratch resistance. In particular, in the liquid crystal display panel, the antireflection film is placed on the liquid crystal cell in a state in which it is bonded to the polarizing plate. As the substrate, triacetyl cellulose or the like can be used, and in order to increase the adhesion at the time of bonding, the antireflection film using such a substrate usually needs to be saponified with an aqueous alkali solution. Therefore, in the use of a liquid crystal display panel, durability, particularly an alkali-resistant antireflection film, is required.

In the past, one of the methods for improving the visibility of a display device is a method in which an antireflection film composed of a low refractive index material is coated on a substrate of a display device to form an antireflection film, for example, a method of forming a fluorine compound film by vapor deposition has been used. Known. However, in recent years, a liquid crystal display device is mainly required to have a low cost, and even a large-sized display device is required to form an anti-reflection film. However, when the vapor deposition method is used, it is difficult to form a uniform anti-reflection film with high efficiency for a large-area substrate, and a vacuum device is required, so that it is difficult to reduce the cost.

In view of this problem, a method in which a fluorine-based polymer having a relatively low refractive index is dissolved in an organic solvent to prepare a liquid composition, and the composition is applied onto a surface of a substrate to form an antireflection film is reviewed. For example, it is proposed to apply a fluorinated alkyl decane to the surface of a substrate (see, for example, Patent Document 1 and Patent Document 2). Further, a method of applying a fluorine-based polymer having a specific structure is proposed (for example, refer to Patent Document 3).

The material for the low refractive index layer of the antireflection film is, for example, a fluororesin-based coating material containing a fluoropolymer containing a hydroxyl group, and is disclosed in Patent Document 4, Patent Document 5, and Patent Document 6. However, in order to cure the coating film, the fluororesin-based coating material must be heated and crosslinked by a curing agent such as a hydroxyl group-containing fluoropolymer and a melamine resin under an acid catalyst, and the curing time may become excessive due to heating conditions. Long, the type of substrate that can be used is limited. Further, the obtained coating film is excellent in weather resistance, but has a problem of lack of scratch resistance or durability.

Therefore, in order to solve the above problems, Patent Document 7 proposes 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 fluoropolymer, and isocyanate. The coating composition containing the unsaturated group-containing fluorine-containing ethylene polymer obtained by reacting the ratio of the number of bases to the number of hydroxyl groups is from 0.01 to 1.0.

Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

These conventional antireflection films generally form a laminate of a layer having a different refractive index, an antistatic layer, a hard coat layer or the like on a substrate. The conventional manufacturing method is a step of repeatedly applying each layer to a substrate. In other words, in the antireflection film formed by the conventional fluorine-based material, a low refractive index layer made of a fluorine-based material must be formed on the high refractive index layer provided on the substrate, and the coating step of forming these layers must be separately provided. .

Further, the low refractive index layer of the surface layer is insufficient in scratch resistance.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable resin composition which can produce a low refractive index layer and a high refractive index layer with high efficiency and which can be cured by ultraviolet rays. Further, another object of the present invention is to provide a cured film which has high transparency, high adhesion to a substrate, excellent scratch resistance and chemical resistance, and excellent environmental resistance.

The present invention provides a method for producing a laminate in which a coating film obtained by coating a composition can form a layer of 2 or more. Another object of the present invention is to provide a method for producing a laminate having excellent antireflection effect and a laminate obtained by the method. Another object of the present invention is to provide a method for producing a laminate excellent in adhesion to a substrate and having high scratch resistance, and a laminate obtained by the method.

[disclosure of invention]

In order to achieve the above object, the present inventors have carefully examined and found that a composition containing metal oxide particles having two different particle diameters is applied to a fluorine-containing polymer containing an ethylenically unsaturated group which is cured by ultraviolet irradiation. When dried, the layer in which the metal oxide particles are present at a high density and the second layer in which the metal oxide particles are hardly present or present in a low density are separated. Further, the cured film obtained by curing by ultraviolet irradiation is excellent in scratch resistance, chemical resistance, transparency, and weather resistance, and the present invention has been completed.

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

A curable resin composition characterized by comprising (A1) a metal oxide having a number average particle diameter of 1 nm or more and an underlying organic compound (Ab) bonded to a polymerizable unsaturated group of less than 40 nm (A2) metal oxide particles having a number average particle diameter of 40 nm or more and 200 nm or less (hereinafter referred to as "metal oxide particles of (A2)") (hereinafter referred to as "metal oxide particles of (A1)") B) Fluorinated polymer containing an ethylenically unsaturated group (C) (B) One or two or more solvents having a high solubility of a fluorine-containing polymer containing an ethylenically unsaturated group (hereinafter referred to as "(C) (1) a solvent which has high dispersion stability of metal oxide particles of (D) (A1) and (A2) and which has compatibility characteristics with (C) a rapidly volatile solvent (hereinafter referred to as "(D) Slowly evaporating solvent"), and (C) the relative evaporation rate of the rapidly evaporating solvent is greater than (D) the relative evaporation rate of the slowly evaporating solvent.

2. The curable resin composition according to the above item 1, wherein (C) one or two or more solvents having low dispersion stability of the metal oxide particles of the fast-releasing solvent systems (A1) and (A2), (D) The slow-releasing solvent system (B) one or two or more solvents having low solubility of the fluorine-containing polymer containing an ethylenically unsaturated group.

3. The curable resin composition according to Item 1 or 2 above, wherein the metal oxide particles of (A1) are selected from the group consisting of aluminum, zirconium, titanium, zinc, bismuth, indium, tin, antimony and bismuth. An oxide particle of at least one element.

4. The curable resin composition according to any one of the items 1 to 3, wherein the metal oxide particles of (A2) are particles containing cerium oxide as a main component.

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

6. The curable resin composition according to any one of the above items 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. [In the formula, U is NH, O (oxygen atom) or S (sulfur atom), and V is O or S].

7. The curable resin composition according to any one of items 1 to 6, wherein the organic compound (Ab) is a compound having a stanol group in the molecule or a compound which forms a stanol group by hydrolysis.

The curable resin composition according to any one of the above items 1 to 7, wherein the (B) fluoropolymer containing an ethylenically unsaturated group has one isocyanate group and at least one ethylenic unsaturated group. The compound (B-1) is reacted with a hydroxyl group-containing fluoropolymer (B-2).

9. The curable resin composition according to item 8, wherein the hydroxyl group-containing fluoropolymer (B-2) contains the following structural unit (a) 20 to 70 mol%, and (b) 10 to 70 Mohr% and (c) 5 to 70 mol%, and the polystyrene-equivalent number average molecular weight measured by gel permeation chromatography is 5,000 to 500,000, (a) the structural unit represented by the following general formula (1) ( b) the structural unit represented by the following general formula (2) (c) the structural unit represented by the following general formula (3) Wherein R ¹ is a fluorine atom, a fluoroalkyl group or a group represented by -OR ² (R ² is an alkyl group or a fluoroalkyl group)] Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a group represented by —(CH ₂ ) _X —OR ⁵ or —OCOR ⁵ (R ⁵ is an alkyl group or an epoxypropyl group, and x is 0 or 1), carboxyl or alkoxycarbonyl] Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a hydrogen atom or a hydroxyalkyl group, and v is a number of 0 or 1.

10. The curable resin composition according to item 8 or 9, wherein the hydroxyl group-containing fluoropolymer (B-2) further contains the following structural unit derived from the azo group-containing polyoxosiloxane compound (d) ) 0.1 to 10 mol %, (d) the structural unit represented by the following general formula (4) [wherein R ⁸ and R ⁹ may be the same or different hydrogen atom, alkyl group, halogenated alkyl group or aryl group].

11. The curable resin composition according to item 10 above, wherein the hydroxyl group-containing fluoropolymer (B-2) contains the structural unit (d) as a part of the following structural unit (e), (e) The structural unit represented by the following general formula (5) Wherein R ^{1 0} to R ^{1 3} are a hydrogen atom, an alkyl group or a cyano group, R ^{1 4} to R ^{1 7} are a hydrogen atom or an alkyl group, p, q are a number from 1 to 6, and s, t are 0. The number of ~6, y is the number of 1~200].

The curable resin composition according to any one of the items 8 to 11, wherein the hydroxyl group-containing fluoropolymer (B-2) further contains the following structural unit (f) of 0.1 to 5 mol%, (f) The structural unit represented by the following general formula (6) [wherein R ^{1 8} has an emulsification group].

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

The curable resin composition according to any one of the above items 1 to 13, which further comprises a polyfunctional (meth) acrylate compound containing at least two (meth) acrylonitrile groups of component (E). And/or a fluorine-containing (meth) acrylate compound containing at least one or more (meth) acrylonitrile groups.

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

The curable resin composition according to any one of items 1 to 15, which is an ultraviolet curable property.

A cured film obtained by curing the curable resin composition according to any one of the above items 1 to 16 and having a multilayer structure of two or more layers.

18. The cured film according to item 17, wherein the layer containing one or more of the metal oxide particles of (A1) and (A2) and the metal oxide particles of (A1) and (A2) are substantially A layer structure of two or more layers composed of a layer having no or less than one layer.

A method for producing a laminate comprising a substrate and a laminate having a multilayer structure thereon, characterized in that the curable resin composition according to any one of items 1 to 16 is coated. A coating film is formed on the layer formed on the substrate or the substrate, and the coating film of the solvent is evaporated to form a layer of 2 or more.

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

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

The method for producing a laminate according to any one of the items 19 to 21, wherein the layer of the two or more layers is further irradiated with radiation to be cured.

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

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

[Claim 25] The method for producing a laminate according to the above item 21, wherein the laminate is an antireflection film which is laminated on the substrate at least the high refractive index layer and the low refractive index layer from the substrate side in this order, The two layers of the above item 21 are formed of a high refractive index layer and a low refractive index layer.

26. The method for producing a laminate according to the above item 25, wherein the low refractive index layer has a refractive index of 1.20 to 1.55 at 589 nm, and the high refractive index layer has a refractive index of 1.50 to 2.20 at 589 nm, and is lower than the low refractive index layer. The refractive index is high.

[27] The method for producing a laminate according to the above item 21, wherein the laminate is on the substrate, and at least the medium refractive index layer, the high refractive index layer, and the low refractive index layer are laminated in this order from the side closer to the substrate. In the antireflection film, the two layers of the above item 21 are formed of a high refractive index layer and a low refractive index layer.

28. The method for producing a laminate according to the above item 27, wherein the low refractive index layer has a refractive index of 1.20 to 1.55 at 589 nm, and the medium refractive index layer has a refractive index of 1.50 to 1.90 at 589 nm, and is lower than the low refractive index layer. The refractive index is high, and the refractive index of the high refractive index layer at 589 nm is 1.51 to 2.20, and is higher than the refractive index of the medium refractive index layer.

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

A laminate produced by the method for producing a laminate according to any one of the items 19 to 29 above.

The cured film obtained by curing the curable resin composition of the present invention, for example, the coating film obtained by applying the composition, has a low refractive index layer and a high refractive index layer, and has two or more layers. The manufacturing steps of the structured cured film.

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

The cured film of the curable resin composition of the present invention is excellent in scratch resistance, chemical resistance, and transparency. The curable resin composition of the present invention is particularly suitable for forming an antireflection film and a selective transmission film filter. The optical material and the high fluorine content can also be applied to coating materials, weather resistant film materials, coating materials, and other materials for substrates requiring weather resistance. Further, the cured film is excellent in adhesion to a substrate, has high scratch resistance, and can provide a good antireflection effect. Therefore, it is suitably used as an antireflection film, and can be used for various display devices to enhance its visibility. Sex.

In the method for producing a laminate of the present invention, a coating film of 1 obtained from the coating composition can be formed into a layer of 2 or more, so that the production steps of the laminate having a multilayer structure can be simplified. Therefore, the method for producing a laminate of the present invention is particularly suitable for forming an optical material such as an antireflection film or an optical film. Further, the laminate system of the present invention is characterized by a high fluorine content, and is applicable to coatings, weather resistant films, coatings, and the like which are required for weather resistant substrates. Moreover, the laminate system imparts a good antireflection effect by providing a low refractive index layer on the outermost layer (the layer farthest from the substrate). According to the present invention, a laminate excellent in adhesion to a substrate and high in scratch resistance can be obtained. Therefore, the laminate of the present invention is extremely suitable as an antireflection film, and can be used for various display devices to improve its visibility.

[Best form of implementing the invention]

I. Laminate and method for producing the same The present invention relates to a method for producing a laminate having a substrate and a multilayer structure of two or more layers thereon, and a laminate obtained by the method. Specifically, in the production method of the present invention, the following curable resin composition is applied onto a layer formed on a substrate or a substrate, and the solvent is evaporated from the obtained coating film (the solvent is evaporated below). Sometimes referred to as "dry") to form a layer of 2 or more. After drying, the solvent may not be completely solvent-free, and the solvent may remain in the range in which the properties of the cured film can be obtained. Further, in the present invention, two or more layers formed of two or more coating films may be formed.

A specific curable resin composition is applied by a general method, and after drying, it is separated into two or more layers. The layer of 2 or more refers to a layer in which "the layer of the metal oxide particles of (A1) and/or (A2) is present at a high density" and the layer of the metal oxide particles of (A1) and (A2) does not substantially exist. In the case of a layer of 2 or more, or a layer of 2 or more layers composed of only "a layer in which metal oxide particles of (A1) and/or (A2) are present in a high density".

Hereinafter, the layer in which the metal oxide particles of (A1) and/or (A2) are present in a high density in each of the layers of 2 or more layers or the metal oxide particles of (A1) and (A2) are substantially absent. At least one layer of the layer is a layer in which the metal oxide particles of (A1) and/or (A2) are present at a high density. Fig. 1A shows a case where two or more layers are two layers of layers 1 and 1a in which metal oxide particles of (A1) or (A2) are present at a high density. Fig. 1B shows a case where two or more layers of the layer 2, 1a" in which the metal oxide particles of (A1) or (A2) are present at a high density, and "metal oxide particles of (A1) and (A2)" The case of three layers of the layer 3" which does not substantially exist. Fig. 1C is a layer in which two or more layers are "layers 1a and 1a" in which metal oxide particles of (A1) or (A2) are present at a high density, and metal oxide particles of "(A1) and (A2) are substantially absent. The 3rd floor of 3". In Fig. 1D, the layer of 2 or more is "layer 1b" in which the metal oxide particles of (A1) and (A2) are present at a high density and layer 3" of the metal oxide particles of (A1) and (A2) substantially not present. The situation of the 2nd floor.

Since the ultraviolet curable resin composition contains two or more kinds of metal oxide particles, as shown in FIG. 1A, FIG. 1B, and FIG. 1C, "the layer in which the metal oxide particles are present at a high density" can be formed into two or more types.

The "metal oxide particles" of the "layer in which the metal oxide particles are present in a high density" are at least one type, that is, one or two or more kinds of "metal oxide particles". Therefore, the "layer in which the metal oxide particles are present at a high density" is composed of two or more kinds of metal oxide particles (for example, FIG. 1D). Fig. 1D is a layer 1b in which a high density of metal oxide particles is present, and is composed of particles X and Y. Since the particle Y is larger than the thickness of the layer 1b in which the metal oxide particles are present at a high density, it protrudes from the layer 3 in which the metal oxide particles are substantially absent, and the protruding portion is also included in the "high density of the metal oxide particles." In the layer 1b" that exists.

In FIGS. 1A to 1D, the "layer 3 in which metal oxide particles are not substantially present" usually does not contain metal oxide particles, but may contain a small amount within a range that does not impair the effects of the present invention. Further, the "layers 1, 1a, and 1b in which the metal oxide particles are present at a high density" may contain other substances than the metal oxide particles.

A known coating method can be used for the coating method of the curable resin composition, and various methods such as a dipping method, a coating method, and a printing method are used.

Drying is usually carried out at room temperature ~ 100 ° C for about 1 to 60 minutes.

The specific hardening conditions are as follows.

In the present invention, the curable resin composition is applied to various substrates in a solution form, and the resulting coating film is dried/hardened 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 on the outermost layer.

The specific structure of the antireflection film is usually laminated in the order of the substrate and the low refractive index film, or the substrate, the high refractive index film, and the low refractive index film. In addition, other layers may be interposed between the substrate, the high refractive index film, and the low refractive index film, for example, a combination of a hard coat layer, an antistatic layer, a medium refractive index layer, a low refractive index layer, and a high refractive index layer may be provided. The layer of the same.

2 is an antireflection film laminated on the substrate 10 in the order of the high refractive index layer 40 and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a 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 by the coating film of 1.

3 is an antireflection film laminated on the substrate 10 in the order of the hard coat layer 20, the antistatic layer 30, the high refractive index layer 40, and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent.

According to the invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed by a coating film of 1.

4 is an antireflection film laminated on the substrate 10 in the order of the antistatic layer 30, the hard coat layer 20, the high refractive index layer 40, and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a 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 the coating film of 1.

5 is an antireflection film laminated on the substrate 10 in the order of the hard coat layer 20, the antistatic layer 30, the medium refractive index layer 60, the high refractive index layer 40, and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Or the medium refractive index layer 60 and the high refractive index layer 40 correspond to a layer in which the metal oxide particles have a high density, or the medium refractive index layer 60 corresponds to a layer in which the metal oxide particles have a high density, and the high refractive index layer 40 corresponds to A layer that is substantially absent from metal oxide particles.

According to the present invention, the medium refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. It is preferable that the high refractive index layer 40 and the low refractive index layer 50 are formed of a coating film of 1.

6 is an antireflection film laminated on the substrate 10 in the order of the antistatic layer 30, the hard coat layer 20, the medium refractive index layer 60, the high refractive index layer 40, and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Or the medium refractive index layer 60 and the high refractive index layer 40 correspond to a layer in which the metal oxide particles have a high density, or the medium refractive index layer 60 corresponds to a layer in which the metal oxide particles have a high density, and the high refractive index layer 40 corresponds to A layer in which metal oxide particles are substantially absent.

According to the present invention, the medium refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. It is preferable that the high refractive index layer 40 and the low refractive index layer 50 are formed of a coating film of 1.

FIG. 7 is an antireflection film laminated on the substrate 10 in the order of the hard coat layer 20, the high refractive index layer 40, and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a 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 60 and the low refractive index layer 50 can be formed by the coating film of 1.

8 is an antireflection film laminated on the substrate 10 in the order of the hard coat layer 20, the medium refractive index layer 60, the high refractive index layer 40, and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Or the medium refractive index layer 60 and the high refractive index layer 40 correspond to a layer in which the metal oxide particles have a high density, or the medium refractive index layer 60 corresponds to a layer in which the metal oxide particles have a high density, and the high refractive index layer 40 corresponds to A layer in which metal oxide particles are substantially absent.

According to the present invention, the medium refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. It is preferable that the high refractive index layer 40 and the low refractive index layer 50 are formed of a coating film of 1.

FIG. 9 is an antireflection film laminated on the substrate 10 in the order of the antistatic layer 30, the high refractive index layer 40, and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a 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 the coating film of 1.

FIG. 10 is an antireflection film laminated on the substrate 10 in the order of the antistatic layer 30, the medium refractive index layer 60, the high refractive index layer 40, and the low refractive index layer 50.

In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Or the medium refractive index layer 60 and the high refractive index layer 40 correspond to a layer in which the metal oxide particles have a high density, or the medium refractive index layer 60 corresponds to a layer in which the metal oxide particles have a high density, and the high refractive index layer 40 corresponds to A layer in which metal oxide particles are substantially absent.

According to the present invention, the medium refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. It is preferable that the high refractive index layer 40 and the low refractive index layer 50 are formed of a coating film of 1.

When the conductive particles such as tin oxide doped tin oxide (ATO) particles or phosphorus-doped tin oxide (PTO) particles of a metal oxide contained in the curable resin composition to be used are added to the antireflection film, The obtained layer containing a metal oxide at a high density becomes a film of an antistatic layer. Therefore, for example, when the high refractive index layer or the medium refractive index layer is formed of a layer having such a high density of the antistatic metal oxide, the high refractive index layer or the medium refractive index layer can form a film having both antistatic properties. . At this time, the formation of the antistatic film can be omitted.

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

(1) Substrate The type of the substrate for the antireflection film of the present invention is not particularly limited, and specific examples of the substrate include, for example, triethylenesulfonyl cellulose and polyethylene terephthalate resin (Toray) , Lumirror, etc., glass, polycarbonate resin, acrylic resin, styrene-based resin, acryl resin, and borneol-based resin (Arton manufactured by JSR Co., Ltd., Zeonex, manufactured by Zeon, Japan) , various transparent plastic sheets, films, etc., such as methyl methacrylate/styrene copolymer resin and polyolefin resin. Preferred is triethylenesulfonyl cellulose, polyethylene terephthalate resin (Lumirror manufactured by Toray Industries, etc.), and norbornene-based resin (Arton, manufactured by JSR Co., Ltd.).

(2) Low refractive index layer The low refractive index layer means a layer having a refractive index of 1.20 to 1.55 in light having a wavelength of 589 nm.

The material for the low refractive index layer is not particularly limited as long as it has a desired property, and for example, a curable composition containing a fluorine-containing polymer, an acrylic monomer, a fluorine-containing acrylic monomer, an epoxy group-containing compound, or the like A cured product of a fluoroepoxy compound or the like. In order to increase the strength of the low refractive index layer, cerium oxide fine particles or the like may be added.

(3) High refractive index layer The high refractive index layer refers to a layer having a refractive index of light of 589 nm of 1.50 to 2.20.

In order to form a high refractive index layer, inorganic particles having a high refractive index such as metal oxide particles may be added.

Specific examples of the metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, and zinc oxide (ZnO) particles. Antimony-doped zinc oxide (ZnO) particles, aluminum-doped zinc oxide particles, zirconium oxide (ZrO ₂ ) particles, titanium oxide (TiO ₂ ) particles, cerium oxide-coated TiO ₂ particles, and coated Al ₂ O ₃ / ZrO ₂ TiO ₂ particles, cerium oxide (CeO ₂ ) particles, and the like. Preferably, antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, aluminum-doped zinc oxide particles, and coated Al ₂ O ₃ / TiO ₂ particles of ZrO ₂ . These metal oxide particles may be used alone or in combination of two or more.

Further, the high refractive index layer can also function as a hard coat layer or an antistatic layer.

(4) When a medium refractive index layer is combined with a layer having three or more kinds of refractive indices, a refractive index of light having a wavelength of 589 nm is usually 1.50 to 1.90, and has a refractive index higher than that of the low refractive index layer and lower than that of the high refractive index layer. The layers are represented by a medium refractive index layer. The refractive index of the medium refractive index layer is preferably from 1.50 to 1.80, preferably from 1.50 to 1.75.

In order to form the medium refractive index layer, inorganic particles having a high refractive index such as metal oxide particles may be added.

Specific examples of the metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, and zinc oxide (ZnO) particles. Antimony-doped zinc oxide particles, aluminum-doped zinc oxide particles, zirconium oxide (ZrO ₂ ) particles, titanium oxide (TiO ₂ ) particles, cerium oxide-coated TiO ₂ particles, and coated Al ₂ O ₃ /ZrO ₂ TiO ₂ particles, cerium oxide (CeO ₂ ) particles, and the like. Preferably, antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, aluminum-doped zinc oxide particles, zirconium oxide (ZrO ₂ ) particle. These metal oxide particles may be used alone or in combination of two or more.

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

By combining the low refractive index layer and the high refractive index layer, the reflectance can be lowered, and by combining the low refractive index layer, the high refractive index layer, and the medium refractive index layer, the reflectance can be lowered while the color tone can be lowered.

(5) A specific example of the hard coat layer is preferably composed of a material such as SiO ₂ , an epoxy resin, an acrylic resin or a melamine resin. Further, cerium oxide particles may be added to these resins.

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

(6) Antistatic layer Specific examples of antistatic layer include addition of antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, phosphorus-doped tin oxide (PTO) particles, and doped aluminum Conductive metal oxide particles such as zinc oxide (ZnO) particles, or a hardenable film of an organic or inorganic conductive compound, a metal oxide film obtained by vapor deposition or sputtering of a metal oxide, or a conductive organic A film composed of a polymer. Examples of the conductive organic polymer include a polyacetylene-based conductive polymer, a polyaniline-based conductive polymer, a polythiophene-based conductive polymer, a polypyrrole-based conductive polymer, and a polyphenylvinyl-based conductive polymer. . As described above, the metal oxide particles contained in the curable resin composition for use in the present invention, such as ATO particles, ITO particles, phosphorus-doped tin oxide (PTO) particles, antimony-doped zinc oxide ZnO, doped aluminum, are added. In the case of a conductive polymer such as ZnO particles, a layer containing the obtained metal oxide at a high density is a film having antistatic properties. At this time, the formation of the antistatic film in another manner may be omitted.

The antistatic layer imparts conductivity to the laminate, and it is possible to prevent electrostatic adhesion of dust and the like.

These layers may form only one layer or form two or more different layers.

Further, the film thicknesses of the low, medium and high refractive index layers are usually 60 to 150 nm, the film thickness of the antistatic layer is usually 0.05 to 3 μm, and the film thickness of the hard coat layer is usually 1 to 20 μm.

In the present invention, any continuous layer of two or more layers of the laminate may be formed by the production method of the present invention, but the method for producing the layer without the method of the present invention may be produced by a known method such as coating, hardening, vapor deposition, sputtering or the like. .

Further, when the layer composed of the curable resin composition of the present invention is cured, in order to form a cured film having excellent optical properties and durability, it is preferable to impart heat history by heating. Of course, when placed at room temperature, the hardening reaction can be formed at the same time as the curing reaction proceeds, but in practice, heat hardening can shorten the required time. Further, the addition of a thermal acid generator as a curing catalyst further promotes the hardening reaction. The curing catalyst is not particularly limited, and various acids or salts thereof which are generally used as a curing agent such as a urea resin or a melamine resin can be used, and in particular, an ammonium salt is preferably used. The heating condition of the hardening reaction can be appropriately selected, but the heating temperature must be below the heat-resistant critical temperature of the substrate to be coated.

According to the present invention, a layer of 2 or more can be formed from the coating film of 1, so that the manufacturing steps of the laminate can be simplified.

Further, the metal oxide particles are unevenly distributed, and the scratch resistance of the laminate can be improved.

The laminate of the present invention can be used for an optical component such as a lens or a selective penetrating film filter in addition to the antireflection film.

II. Curable Resin Composition Next, the curable resin composition and cured product of the present invention will be described.

The curable resin composition of the present invention contains (A1) a metal oxide particle having a number average particle diameter of 1 nm or more and an underlying organic compound (Ab) bonded to a polymerizable unsaturated group of less than 40 nm (hereinafter referred to as " (A1) metal oxide particles (A2) having a number average particle diameter of 40 nm or more and 200 nm or less (hereinafter referred to as "metal oxide particles of (A2)") (B) containing ethylenic unsaturation The fluoropolymer (C) (B) contains one or two or more solvents having high solubility in the fluoropolymer containing an ethylenically unsaturated group (hereinafter referred to as "(C) rapid volatile solvent") (D) (A1) and (A2) a metal oxide particle having high dispersion stability and having one or two or more solvents having compatibility characteristics with (C) a fast-volatile solvent (hereinafter referred to as "(D) slow-volatile solvent) And (C) the relative evaporation rate of the rapidly evaporating solvent is greater than (D) the relative evaporation rate of the slowly evaporating solvent.

1. Each constituent component of the curable resin composition will be specifically described.

Metal Oxide Particles (A1) and (A2) In the present invention, two kinds of metal oxide particles (A1) and (A2) having different particle diameters are used. Among them, the metal oxide particles (A1) must be bonded to the following organic compound (Ab) having a polymerizable unsaturated group. It is preferable that the metal oxide particles (A2) are bonded to the organic compound (Ab) having a polymerizable unsaturated group, but it is not essential.

In the present specification, the metal oxide particles (A1) and (A2) may be collectively referred to as "metal oxide particles (A)". The metal oxide particles of the metal oxide particles (A1) and (A2) which are not bonded to the organic compound (Ab) may be referred to as "metal oxide particles (Aa1)" or "metal oxide particles (Aa2)", respectively. Both are sometimes collectively referred to as "metal oxide particles (Aa)". Further, the metal oxide particles (A1) and (A2) bonded to the organic compound (Ab) may be referred to as "reactive particles (Aab1)" or "reactive particles (Aab2)", respectively. "Reactive particles (Aab)".

The number average particle diameter of the metal oxide particles (A1) and (A2) was measured by an electron microscope, and was 1 nm or more, not more than 40 nm, and 40 nm or more and 200 nm or less. The use of the two types of particles having different particle diameters in this manner can improve the scratch resistance as compared with the cured film obtained only from the curable resin composition using one type of metal oxide particles.

As the metal oxide particles, a plurality of kinds of particles each having a particle diameter within the above range may be used, and three or more kinds of metal oxide particles may be combined. The substances constituting the plurality of metal oxide particles may be the same or different.

The metal oxide particles (A1) and (A2) used in the present invention are preferably selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, bismuth, and indium from the viewpoint of a cured product composed of the obtained curable resin composition. An oxide particle of at least one element of a group of tin, antimony and bismuth.

Particularly preferred metal oxide particles (A1) are oxide particles of at least one element selected from the group consisting of aluminum, zirconium, titanium, zinc, lanthanum, indium, tin, antimony and cerium, of which zirconium oxide is preferred. particle. In order to increase the refractive index of the layer in which the metal oxide particles (A) constituting the cured product are present at a high density, the refractive index of the metal oxide particles (A1) having a wavelength of 589 nm is preferably 1.5 or more. Therefore, particles of cerium oxide (refractive index of 1.45) are not preferable.

The number average particle diameter of the metal oxide particles (A1) is 1 nm or more, and is less than 40 nm, preferably 1 nm or more and 30 nm or less.

The metal oxide particles (A2) are preferably particles having cerium oxide as a main component from the viewpoint of improving the scratch resistance of the cured film.

The number average particle diameter of the metal oxide particles (A2) is 40 nm or more and 200 nm or less, preferably 40 nm or more and 100 nm or less. The particle diameters of the metal oxide particles (A1) and (A2) are the number average particle diameter measured by an electron microscope. The particle size of the rod-shaped particles is called a short diameter.

In order to improve the dispersibility of the metal oxide particles (A1) and (A2), a surfactant or an amine may be added.

Among them, from the viewpoint of high hardness, particles of cerium oxide, aluminum oxide, zirconium oxide and cerium oxide are preferred, and zirconia particles are particularly preferred. A hardened film having a high refractive index can be obtained by using oxide particles such as zirconium or titanium, and conductivity can be imparted to the cured film by using ATO particles, phosphorus-doped tin oxide (PTO) particles, or the like. These may be used alone or in combination of two or more. The metal oxide particles (Aa) are preferably in the form of a powder or a dispersion. The dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Such organic solvents include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate and acetic acid; Esters such as butyl ester, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene An aromatic hydrocarbon such as toluene or xylene; or a guanamine such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. Among them, preferred are methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene.

Commercial products of cerium oxide particles, for example, colloidal cerium oxide is manufactured by Nissan Chemical Industries Co., Ltd. Trade name: methanol cerium oxide 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-0L, etc. Further, the powdered cerium oxide is, for example, manufactured by Japan Aerosil Co., Ltd., trade name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd., trade name: Sildex H31, H32, H51, H52, Product name: E220A, E220, Fuji SYLYSIA (stock), trade name: SYLYSIA 470, Japanese plate glass (stock), trade name: SG Flake, etc.

In addition, the alumina dispersion product is, for example, a product name of Nissan Chemical Industries Co., Ltd.: alumina sol-100, -200, -520; and an isopropyl alcohol dispersion of alumina such as Sumitomo Osaka Cement Co., Ltd. Name: AS-150I; a toluene dispersion of alumina, for example, Sumitomo Osaka Cement Co., Ltd., trade name: AS-150T; zirconium toluene dispersion product, for example, Sumitomo Osaka Cement Co., Ltd., trade name: HXU-110JC; The water-dispersible product of the zinc-zinc powder is, for example, a product of Nissan Chemical Industries Co., Ltd.; Celnax; a powder of alumina, titania, tin oxide, indium oxide, zinc oxide, or the like, and a solvent dispersion product, for example, a CI-formed product. Commercial name; Nanotek; water-dispersed sol of antimony-doped tin oxide, for example, trade name of Ishihara Sangyo Co., Ltd.; SN-100D; ITO powder, for example, a product made by Mitsubishi Materia; Domu Chemical (share) system name: needral and so on.

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 1 or more and 10 or less), a plate shape, a fiber shape, or an indefinite shape. (A1) is preferably a rod shape, and (A2) is preferably a spherical shape.

The use form of these metal oxide particles (A1) and (A2) can be a state in which a powder in a dry state or a water or an organic solvent is used. For example, a dispersion of fine particle-shaped metal oxide particles known in the art can be used as it is. In particular, when a cured product is required to have excellent transparency, it is preferred to use a dispersion of metal oxide particles.

The metal oxide particles (A2) used in the present invention may be directly metal oxide particles (Aa2) having a predetermined number average particle diameter, but are preferably bonded metal oxide particles (Aa2) and having a polymerizable unsaturated group. Particles formed by the organic compound (Ab) (hereinafter sometimes referred to as "reactive particles (Aab2)"). The metal oxide particles (A) are formed by using the reactive particles (Aab2) of the bonded metal oxide particles (Aa2) and the organic compound (Ab) having a polymerizable unsaturated group, thereby improving the composition of the obtained curable resin composition. The scratch resistance of the cured film. Here, the bond refers to a non-covalent bond such as a covalent bond or a physical adsorption.

Organic compound (Ab) having a polymerizable unsaturated group The organic compound (Ab) used in the present invention is a compound having a polymerizable unsaturated group, and preferably an organic group having a group represented by the following general formula (A-1) Compound. Further, at least a group containing [-O-C(=O)-NH-], [-O-C(=S)-NH-], and [-S-C(=O)-NH-] One is preferred. The organic compound (Ab) is preferably a compound having a stanol group in the molecule or a compound which is hydrolyzed to form a stanol group.

[wherein, U is NH, O (oxygen atom) or S (sulfur atom), and V is O or S]

(i) The polymerizable unsaturated group contained in the polymerizable unsaturated organic compound (Ab) is not particularly limited, and preferred examples thereof include an acryl fluorenyl group, a methacryl fluorenyl group, a vinyl group, a propenyl group, a butadienyl group, and the like. Styryl, ethynyl, cinnamyl, maleate, acrylamide.

The polymerizable unsaturated group is a constituent unit of addition polymerization of an active radical species.

(ii) A specific example of the group [-U-C(=V)-NH-] represented by the above formula (A-1) contained in the base organic compound represented by the above formula (A-1) is [-O] -C(=O)-NH-], [-O-C(=S)-NH-], [-S-C(=O)-NH-], [-NH-C(=O)-NH -], 6 kinds of [-NH-C(=S)-NH-] and [-S-C(=S)-NH-]. These groups may be used alone or in combination of two or more. Among them, from the viewpoint of thermal stability, it is preferably [-O-C(=O)-NH-] group and [-O-C(=S)-NH-] group and [-S-C(=O) At least one of -NH-] groups is used in combination.

The group [-U-C(=V)-NH-] represented by the above formula (A-1) imparts a moderate cohesive force by hydrogen bonding between molecules, and when a cured product is formed, excellent mechanical strength is imparted, and The adhesion of the adjacent layer of the substrate or the high refractive index layer and the heat resistance.

(iii) A stanol group or a base organic compound (Ab) which is hydrolyzed to form a stanol group is preferably a compound having a stanol group in the molecule or a compound which is hydrolyzed to form a stanol group. The stanol group-forming compound is, for example, a compound having a ruthenium atom bonded to an alkoxy group, an aryloxy group, an ethoxylated group, an amine group, a halogen atom or the like, preferably an alkoxy group or an aromatic group bonded to a ruthenium atom. A compound of an oxy group, that is, a compound containing an alkoxycarbenyl group or a compound containing an aryloxycarboxyalkyl group.

The stanol group-forming site of the stanol group or the thiol group-forming compound is a constituent unit bonded to the oxide particle (Aa) by a condensation reaction or a condensation reaction after hydrolysis.

(iv) Preferred specific examples of the preferred morphological organic compound (Ab), for example, a compound represented by the following formula (A-2).

Wherein R ^{2 4} and R ^{2 5} may be the same or different hydrogen atoms or alkyl or aryl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, phenyl, Xylyl group and the like. j is an integer from 1 to 3.

The group represented by [(R ^{2 4} O) _j R ^{2 5} _{3 - j} Si-] is, for example, trimethoxymethyl decyl, triethoxy methoxyalkyl, triphenyloxycarbyl, methyl dimethyl Oxymethane alkyl, dimethyl methoxyalkyl, and the like. Of such a group, a trimethoxycarbenyl group or a triethoxycarbenyl group is preferred.

R ^{2 6} is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may have a linear, branched or cyclic structure. Specific examples include methyl group, ethyl group, propyl group, butyl group, hexyl group, hexylene group, phenyl group, xylylene group, and dodecyl group.

R ^{2 7} is a divalent organic group, and is usually selected from a divalent organic group having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a linear polyalkylene group such as a hexyl group, an exo-octyl group, and a dodecyl group; an alicyclic or polycyclic divalent organic group such as a cyclohexyl group or a borneol alkyl group; a divalent aromatic group such as a phenyl group or a polyphenylene group; and these alkyl substituents and aryl substituents. These divalent organic groups may contain an atomic group containing an element other than a carbon atom and a hydrogen atom, and may also contain a polyether bond, a polyester bond, a polyamid bond, or a polycarbonate bond.

R ^{2 8} is an organic group of (k+1) valence, preferably a linear, branched or cyclic saturated hydrocarbon group or an unsaturated hydrocarbon group.

Z is a monovalent organic group having a polymerizable unsaturated group which undergoes an intermolecular crosslinking reaction in the presence of a living radical species. Further, k is preferably an integer of 1 to 20, preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

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

(wherein "Acryl" is a acrylonitrile group and "Me" is a methyl group)

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

The reactive particles (Aab1) and (Aab2) are mixed with an organic compound (Ab) having a stanol group or a group which is hydrolyzed to form a stanol group, and are hydrolyzed to bond the two. The ratio of the organic polymer component in the obtained reaction particles (Aab), that is, the hydrolyzate and the condensate of the hydrolyzable decane, is usually a constant value of % reduction in mass when the dry powder is completely burned in the air, for example, It can be determined by thermal mass analysis in air from room temperature to usually 800 °C.

The amount of bonding of the organic compound (Ab) of the metal oxide particles (Aa) is preferably 100% by mass of the reactive particles (Aab) (the total of the metal oxide particles (Aa) and the organic compound (Ab)). It is 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 bonding of the organic compound (Ab) bonded to the metal oxide particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (Aab) in the composition is insufficient, and the obtained cured product may be transparent. Insufficient sex and scratch resistance. Moreover, the mixing ratio of the metal oxide particles (Aa) in the raw material in the case of producing the reactive particles (Aab) is preferably from 5 to 99% by mass, more preferably from 10 to 98% by mass.

The compounding amount (content) in the curable resin composition of the metal oxide particles (A1) (that is, the reactive particles (Aab1)) is preferably 10 to 90 when the total amount of the composition excluding the organic solvent is 100% by mass. The mass% is more preferably 20 to 80% by mass, and particularly preferably 40 to 80% by mass. When it is less than 10% by mass, the hardness of the cured film is insufficient, or a high refractive index may not be obtained. When it exceeds 90% by mass, the film formability is insufficient. The content of the metal oxide particles (Aa1) constituting the reactive particles (Aab1) at this time is preferably 65 to 95% by mass of the reactive particles (Aab1).

The compounding amount (content) in the curable resin composition of the metal oxide particles (A2) (one of the metal oxide particles (Aa2) and the reactive particles (Aab2)) is 100% of the composition excluding the organic solvent. In the case of % by mass, it is preferably from 1 to 30% by mass, more preferably from 1 to 20% by mass.

(B) Fluorine-containing polymer containing ethylenically unsaturated group The fluorine-containing polymer containing ethylenically unsaturated group used in the invention is a compound having one isocyanate group and at least one ethylenically unsaturated group (B-1) The reaction with the hydroxyl group-containing fluoropolymer (B-2) is preferably carried out by reacting an isocyanate group/hydroxyl molar ratio of 1.1 to 1.9.

(B-1) The compound (B-1) having one isocyanate group and at least one ethylenically unsaturated group is a compound having one isocyanate group and at least one ethylenically unsaturated group in the molecule, that is, There is no special limit. When there are two or more isocyanate groups, it may react with the hydroxyl group-containing fluoropolymer to cause gelation. The ethylenically unsaturated group can make the curable resin composition more easily hardened, and therefore, it is preferably a (meth) acrylonitrile group. Such a compound is, for example, 2-(meth)acryloxyethyl isocyanate, 2-(meth)acryloxypropyl isocyanate, 1,1-bis((meth)acryloxymethyl) Ethyl isocyanate may be used alone or in combination of two or more.

This compound is synthesized by reacting a diisocyanate group with a hydroxyl group-containing (meth) acrylate. At this time, a diisocyanate such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, 1,5-naphthalene diisocyanate, m-benzene Diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbenzene Diisocyanate, 4,4'-biphenyldiisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexa Diisocyanate, bis(2-isocyanateethyl)fumarate, 6-isopropyl-1,3-phenyldiisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenyl Methane diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, tetramethylxylene diisocyanate, 2,5(or 6)-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane A single type or a combination of two or more types. Preferred among them are 2,4-toluene diisocyanate, isophorone diisocyanate, xylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), and 1,3-bis(isocyanate methyl)cyclohexane.

The hydroxyl group-containing (meth) acrylate is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone. (Meth) acrylate, polypropylene glycol (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, trimerization The cyanic acid EO-modified di(meth)acrylate or the like may be used alone or in combination of two or more. Preferred among them are 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate. Commercial products in which a hydroxyl group-containing polyfunctional (meth) acrylate is commercially available, for example, under the trade name HEA of Osaka Organic Chemical Co., Ltd., under the trade name KAYARAD DPHA, PET-30, East Asia Synthetic Co., Ltd. The product names are Aronix M-215, M-233, M-305, M-400, etc.

When it is synthesized from a diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, the amount of the hydroxyl group-containing polyfunctional (meth) acrylate added to the diisocyanate 1 mol is preferably from 1 to 1.2 mol.

The method for synthesizing such a compound is, for example, a method in which a diisocyanate and a hydroxyl group-containing (meth) acrylate are introduced in one step, and a method in which a diisocyanate is dropped into a hydroxyl group-containing (meth) acrylate to carry out a reaction.

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

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

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

In the above general formula (1), the fluoroalkyl group of R ¹ and R ² is, for example, a carbon number such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group or a perfluorocyclohexyl group. ~6 fluoroalkyl. Further, the alkyl group of R ² may have an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a cyclohexyl group.

The structural unit (a) is introduced by using a fluorine-containing vinyl monomer as a polymerization component. The fluorine-containing vinyl monomer is not particularly limited as long as it has at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples of such are fluorine olefins such as tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropene; alkyl perfluorovinyl ether or alkoxyalkyl perfluorovinyl ether; perfluoro(methylethylene) Perfluoro(alkyl vinyl ether)s such as ether), perfluoro(ethyl vinyl ether), (propyl vinyl ether), perfluoro(butyl vinyl ether), perfluoro(isobutyl vinyl ether); A single or a combination of two or more of perfluoro(alkoxyalkylvinyl ether)s such as fluorine (propoxypropyl vinyl ether). Among them, preferred is hexafluoropropylene and perfluoro(alkyl vinyl ether) or perfluoro(alkoxyalkyl vinyl ether), and it is more preferred to use these compounds in combination.

The content of the structural unit (a) is 20 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 rate is less than 20 mol%, the low refractive index of the optical characteristics of the fluorine-containing material desired in the present invention may be less likely to occur, and when the content exceeds 70 mol%, The solubility of the hydroxyl group-containing fluoropolymer (B-2) in an organic solvent, transparency, or adhesion to a substrate may be lowered. Further, for this reason, when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is used, the content of the structural unit (a) is preferably 25 to 65 mol%, more preferably 30 to 60 mol%. %.

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

Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a group represented by —(CH ₂ ) _X —OR ⁵ or —OCOR ⁵ (R ⁵ is an alkyl group or an epoxypropyl group, and x is a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

In the general formula (2), the alkyl group of R ⁴ or R ^{5 is} , for example, an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group or a lauryl group, and an alkoxycarbonyl group such as a group Oxycarbonyl, ethoxycarbonyl and the like.

The vinyl monomer having the above substituent is used as a polymerization component, whereby the structural unit (b) can be introduced. Examples of such a vinyl monomer include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, and positive An alkyl vinyl ether or a cycloalkyl vinyl ether of pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether or the like; Allyl ethers such as ethyl allyl ether and butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, vinyl hexanoate, tertiary carbonic acid ( Versatic acid) vinyl carboxylate such as vinyl ester or vinyl stearate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-(n-propoxy)ethyl (meth) acrylate a (meth) acrylate such as an ester; a single carboxylic acid such as (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid Or a combination of two or more kinds.

The content of the structural unit (b) is 10 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is 100 mol%. For this reason, when the content rate is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer (B-2) in an organic solvent may be lowered, and when the content exceeds 70 mol%, the hydroxyl group is contained. The optical properties such as transparency and low reflectance of the fluoropolymer (B-2) may be lowered. Further, for this reason, when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is used, the content of the structural unit (b) is preferably 20 to 60 mol%, more preferably 30 to 60 mol%. %.

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

Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a hydrogen atom or a hydroxyalkyl group, and v is 0 or 1

In the general formula (3), the hydroxyalkyl group of R ^{7 is} , for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 5-hydroxypentyl. , 6-hydroxyhexyl.

The structural unit (c) is introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. The hydroxyl group-containing vinyl monomer is, for example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether. a hydroxyl group-containing vinyl ether such as 5-hydroxypentyl vinyl ether or 6-hydroxyhexyl vinyl ether; 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether And other hydroxyl-containing allyl ethers; allyl alcohol and the like. Further, in addition to the above, a hydroxyl group-containing vinyl monomer may be, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. Ester, caprolactone (meth) acrylate, polypropylene glycol (meth) acrylate, and the like.

The content of the structural unit (c) is preferably from 5 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is 100 mol%. For this reason, when the amount is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer (B-2) in an organic solvent may be lowered, and when the content exceeds 70 mol%, the hydroxyl group-containing fluorine is contained. The optical properties such as transparency and low reflectance of the polymer (B-2) may be lowered. For this reason, the content of the structural unit (c) is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer (B-2).

Structural unit (d) and structural unit (e) The hydroxyl group-containing fluoropolymer (B-2) may further preferably comprise the following structural unit (d). The construction unit (d) is explained below.

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

Wherein R ⁸ and R ⁹ may be the same or different hydrogen atom, alkyl group, halogenated alkyl group or aryl group]

In the general formula (4), the alkyl group of R ⁸ or R ^{9 is} , for example, an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group; and the halogenated alkyl group is, for example, a trifluoromethyl group or a perfluoroethyl group. A fluoroalkyl group having 1 to 4 carbon atoms such as a perfluoropropyl group or a perfluorobutyl group, and the aryl group is, for example, a phenyl group, a benzyl group or a naphthyl group.

The azo group-containing polyoxyalkylene compound having a polyoxyalkylene segment represented by the above general formula (4) can be used, whereby the structural unit (d) can be introduced. Such an azo-containing polyoxyalkylene compound is, for example, a compound represented by the following general formula (7).

[wherein, R ^{1 0} to R ^{1 3} , R ^{1 4} to R ^{1 7} , p, q, s, t, and y are the same as the above general formula (5), and z is a number from 1 to 20. 〕

When the compound of the general formula (7) is used, the structural unit (d) is a part of the structural unit (e) and is contained in the hydroxyl group-containing fluoropolymer.

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

[wherein, R ^{1 0} to R ^{1 3} represents a hydrogen atom, an alkyl group or a cyano group, and R ^{1 4} to R ^{1 7} represents a hydrogen atom or an alkyl group, and p and q are numbers of 1 to 6, s, t For the number 0~6, y is the number from 1~200]

In the general formula (5), the alkyl group of R ^{1 0} to R ^{1 3 is} , for example, an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group or a cyclohexyl group, and R ^{1 4} to R ^{1 7 .} The alkyl group is, for example, an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group.

In the present invention, the azo-containing polyoxosiloxane compound represented by the above general formula (7) is particularly preferably a compound represented by the following general formula (8).

[wherein, y and z are the same as the above general formula (7). ]

Further, the content ratio of the structural unit (d) is preferably 0.1 to 10 mol% when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is 100 mol%. For this reason, when the content rate is less than 0.1 mol%, the surface smoothness of the coating film after curing may be lowered, and the scratch resistance of the coating film may be lowered, and when the content ratio exceeds 10 mol%, the hydroxyl group-containing content may be contained. The fluoropolymer (B-2) is inferior in transparency, and when used as a coating material, small pits are likely to be formed during coating. For this reason, in the case of the total amount of the hydroxyl group-containing fluoropolymer (B-2), the content of the structural unit (d) is preferably from 0.1 to 5 mol%, more preferably from 0.1 to 3 mol%. For the same reason, the content ratio of the structural unit (d) contained therein is within the above range, and then the content ratio of the structural unit (e) is determined.

Structural unit (f) The hydroxyl group-containing fluoropolymer (B-2) is preferably a structure further containing the following structural unit (f).

The following structural unit (f) will be described.

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

[wherein, R ^{1 8} is a group having an emulsification effect]

In the general formula (6), the emulsification group of R ^{1 8} has, for example, a hydrophobic group and a hydrophilic group, and the hydrophilic group is a polyether structure of polyethylene oxide or polypropylene oxide. good.

The group having such an emulsification action is, for example, a group represented by the following general formula (9).

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

The reactive emulsifier is used as a polymerization component, whereby the structural unit (f) can be introduced. Such a reactive emulsifier is, for example, a compound represented by the following general formula (10).

[wherein, n, m, and u are the same as the above general formula (9)]

Further, the content ratio of the structural unit (f) is preferably 0.1 to 5 mol% when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is 100 mol%. When the content is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer (B-2) in a solvent can be improved, and when the content is 5 mol% or less, the curable resin composition is Adhesiveness is not excessively increased, and handling is easy. Even when used for coating materials, the moisture resistance is not lowered. For this reason, when the total amount of the hydroxyl group-containing fluoropolymer (B-2) is used, the content of the structural unit (f) is preferably 0.1 to 3 mol%, more preferably 0.2 to 3 mol%. %.

The hydroxyl group-containing fluoropolymer (B-2) having a hydroxyl group-containing fluoropolymer (B-2) is obtained by gel permeation chromatography (hereinafter referred to as "GPC") and measured by using tetrahydrofuran as a solvent. The number average molecular weight in terms of styrene conversion is preferably 5,000 to 500,000. When the coefficient average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer (B-2) may be lowered, and when the number average molecular weight exceeds 500,000, the viscosity of the curable resin composition may increase, which may be difficult. Film coating was carried out. For this reason, the polystyrene-equivalent number average molecular weight of the hydroxyl group-containing fluoropolymer (B-2) is preferably from 10,000 to 300,000, more preferably from 10,000 to 100,000.

The reaction of the compound (B-1) with the hydroxyl group-containing fluoropolymer (B-2) is more than the ethylenically unsaturated group-containing fluoropolymer (B) used in the present invention as described above, and will contain one The isocyanate group and the at least one ethylenically unsaturated group compound (B-1) and the hydroxyl group-containing fluoropolymer (B-2) are reacted at a ratio of isocyanate group/hydroxyl molar ratio of from 1.1 to 1.9. The result is better. For this reason, when the molar ratio is less than 1.1, the scratch resistance and durability may be lowered. When the molar ratio exceeds 1.9, the alkali aqueous solution of the coating film of the curable resin composition is immersed, and the scratch resistance is improved. It will decrease. Further, for this reason, the isocyanate group/hydroxyl group is preferably from 1.1 to 1.5, more preferably from 1.2 to 1.5.

The content of the (B) ethylenically unsaturated group-containing fluoropolymer in the curable resin composition is 100% by mass based on the total amount of the composition other than the organic solvent, and is usually from 3 to 70% by mass. When the amount of addition 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. When the amount exceeds 70% by mass, the curable resin composition The hardened coating film of the material sometimes does not have scratch resistance. For this reason, the amount of the component (B) to be added is preferably from 10 to 50% by mass, more preferably from 25 to 50% by mass.

(C) (C) The fast-evaporating solvent contained in the composition of the rapid-evaporation solvent-curable resin is one or two or more solvents having higher solubility of the (B) ethylenically unsaturated group-containing fluoropolymer. The higher solubility of the fluoropolymer containing an ethylenically unsaturated group means that (B) the fluoropolymer containing an ethylenically unsaturated group is added to each solvent up to 50% by mass, and stirred at room temperature for 8 hours. The state of becoming a homogeneous solution was visually observed. (C) The relative evaporation rate of the rapidly evaporating solvent must be greater than the relative evaporation rate of the (D) slowly evaporating solvent described later. The "relative evaporation rate" refers to the relative value of the evaporation rate based on the time required for evaporation of 90% by weight of butyl acetate. For details, see "Chemical Technology", Volume 2, "Physical Properties and Purification Methods of Organic Solvents", 4th Edition, 1986 62 pages (TECHNIQUES OF CHEMISTRY VOL.2 ORGANIC SOLVENTS Physical Properties and methods of purification 4th ed. (Interscience Publishers, Inc. 1986 page 62). Further, (C) rapid volatile solvents are the above (A1) and (A2) The metal oxide particles (metal oxide particle component (A)) preferably have a low dispersion stability. (C) The relative evaporation rate of the rapidly evaporating solvent is greater than (D) the slow volatile solvent, and (B) the ethylenicity is not Since the saturated fluoropolymer has high solubility, the curable resin composition is applied to the substrate, and the solvents (C) and (D) are evaporated to oxidize the metals of (A1) and (A2). The localized particles are present in a large amount, and since the metal oxide particles of (A1) and (A2) have low dispersion stability, the metal oxide particles of (A1) and (A2) can be more reliably produced locally. Chemical.

The solvent which can be used as the (C) rapid volatile solvent in the present invention is a solvent having a relative evaporation rate of about 1.7 or more, and specific examples thereof include methyl ethyl ketone (MEK; relative evaporation rate 3.8), isopropyl alcohol (IPA; 1.7), and methyl isobutylene. Ketone (MIBK; 1.6), methyl pentanone (MAK; 0.3), acetone, methyl acetone, and the like.

(D) The (D) slow-releasing solvent contained in the slow-vulcanization solvent-curable resin composition is one or two or more solvents having high dispersion stability of the metal oxide particles of the above (A1) and (A2). The high dispersion stability of the metal oxide particles of (A1) and (A2) means that the glass plate is immersed in the isopropyl alcohol dispersion of the metal oxide particles of (A1) and (A2) to make (A1) and The metal oxide particles of A2) are adhered to the glass wall, and the glass plates of the metal oxide particles (A1) and (A2) are immersed in each solvent to visually detect the metal oxidation of (A1) and (A2). The particles are uniformly dispersed in the solvent. Further, (D) the slow-vulsing solvent is preferably one in which the solubility of the (B) ethylenically unsaturated group-containing fluoropolymer is low.

In the present invention, it can be used as a solvent for (D) a slow-volatile solvent, such as methanol (relative evaporation rate 2.1), isopropanol (IPA: 1.7), n-butanol (n-BuOH: 0.5), and third butanol. , propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl cellosolve, propyl cellosolve, butyl cellosolve, and the like.

In the present invention, (C) a solvent for rapid volatilization and/or a solvent for slowly evaporating (D), a solvent for the production of the above (B) fluoropolymer containing an ethylenically unsaturated group can be usually used as it is.

The (C) fast-evaporating solvent used in the present invention and (D) the slow-evaporating solvent must have compatibility. The compatibility is in a specific configuration of the composition, and it is only required that (C) a solvent which is rapidly volatilized and (D) a solvent which is slowly volatilized does not separate.

The solvent to be selected corresponds to (C) the fast-evaporating solvent used in the present invention or (D) the slow-evaporating solvent is determined by the relative characteristics among the selected solvent types, so that the relative evaporation rate is 1.7. It can also be used as (D) a slow volatile solvent as (C) a rapid volatile solvent.

The total amount of the solvent (C) and the solvent (D) is usually 300 to 5000 parts by mass based on 100 parts by mass of the total amount of the solvent (including the components (C) and (D)) in the curable resin composition. Preferably, it is 300 to 4000 parts by mass, more preferably 300 to 3,000 parts by mass. The mixing ratio of the solvent (C) and the solvent (D) can be arbitrarily selected in the range of 1:99 to 99:1.

(E) a polyfunctional (meth) acrylate compound containing at least two (meth) acrylonitrile groups and/or a fluorine-containing (meth) acrylate containing at least one (meth) acrylonitrile group The polyfunctional (meth) acrylate compound (E-1) having at least two or more (meth) acrylonitrile groups as an ester compound can be used to improve the cured product obtained by hardening the curable resin composition and using the cured product. The scratch resistance of the antireflection film.

The fluorine-containing (meth) acrylate compound (E-2) containing at least one or more (meth) acrylonitrile groups is used to lower the refractive index of the curable resin composition.

The compound (E-1) is not particularly limited as long as it is a compound containing at least two (meth)acryl fluorenyl groups in the molecule. For example, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, Pentaerythritol tetra(meth) acrylate, dipentaerythritol tetra(meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, "U-15HA (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.), a compound represented by the following general formula (11), or a combination of two or more thereof. Preferred among them are neopentyl glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and caprolactone. A dipentaerythritol hexa(meth) acrylate, a compound represented by the following general formula (11).

[In the formula, "Acryl" is an acrylonitrile group].

The compound (E-2) is not particularly limited as long as it is a fluorine-containing (meth) acrylate compound containing at least one (meth) acrylonitrile group. For example, a single one or a combination of two or more of perfluorooctyl (meth) acrylate, octafluoropentyl (meth) acrylate, and trifluoroethyl (meth) acrylate may be used.

The content of the component (E) in the curable resin composition is not particularly limited, but is usually from 3 to 80% by mass based on 100% by mass of the total amount of the composition other than the organic solvent. When the amount of addition is less than 3% by mass, the cured coating film of the curable resin composition may not have scratch resistance, and when the amount is more than 80% by mass, the cured coating of the curable resin composition is refracted. The rate is increased and sometimes the anti-reflection effect is not obtained. For this reason, the amount of the component (E) to be added is preferably from 5 to 70% by mass, more preferably from 5 to 50% by mass.

(F) Photoradical polymerization initiator The curable resin composition may be added with (F) photoradical polymerization initiator (radiation (light) by irradiation with radiation (light) to generate active radical species. ) polymerization initiator).

The radiation (light) polymerization initiator is not particularly limited as long as it is decomposed by light irradiation to generate a radical, and examples thereof include acetophenone, acetophenone ketal, and 1-hydroxycyclohexyl phenyl ketone. , 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, anthrone, benzaldehyde, anthraquinone, anthracene, triphenylamine, carbazole, 3-methyl Ethyl benzene, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether Benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane 1-ketone, thioxanthone, diethylthioxanthone, diisopropylthioxanthone, 2-chlorothioxanthone, 2-methyl 1-[4-(methylthio)phenyl]-2 -morpholinyl-propan-1-one, 2-benzyl-dimethylamino-1-4-(morpholinylphenyl)-butanone-1,4-(2-hydroxyethoxy) Phenyl-(2-hydroxy-2-propyl)ketone, 2,4,6-trimethylphenylnonyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoinyl)-2 ,4,4- Methyl-pentyl phosphine oxide, oligomeric (2-hydroxy - methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

Commercial products of radiation (light) polymerization initiators, for example, those manufactured by CIBA speciality chemicals: IRGACURE 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24 -61, Darocur 1116, 1173, and BASF company name: Lucirin TPO, UCB company name: Ubecuryl P36, Flutetury ranberuty company name: EZacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B, etc. .

In the present invention, the content of the photoradical polymerization initiator (F) to be used is 0.01% by mass or more, preferably 0.1% by mass to 10% by mass based on 100% by mass of the total amount of the composition other than the organic solvent. When the content is less than 0.01% by mass, the hardness of the cured product may be insufficient, and when it exceeds 10% by mass, the cured product may not be cured to the inside (underlayer).

(G) In the other component curable resin composition, a photo-sensitizer, a polymerization inhibitor, a polymerization start aid, a flat agent, and wettability may be appropriately added as needed within a range that does not affect the object or effect of the present invention. A modifier, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, a solvent other than the solvent (C) and (D), and the like.

2. Method for Producing Curable Resin Composition The curable resin composition of the present invention is produced by the following method.

a dispersion of two metal oxide particles (A1) and (A2), an ethylenically unsaturated fluoropolymer (component (B)), and, if necessary, a polyfunctional (meth) acrylate (component E) The radiation (light) polymerization initiator (component (F)) is placed in a reaction vessel equipped with a stirrer, and stirred at 35 to 45 ° C for 2 hours to form a curable resin composition.

When the solvent is replaced with a solvent (β) different from the solvent (α) used in the first reactive particle dispersion, the solvent (β) is added 1.0 times to the mass of the solvent (α) of the reactive particle dispersion. , stirring under the same conditions. Next, this composition liquid was concentrated under reduced pressure using a rotary evaporator to a mass of 50% of a solid content to form a composition.

3. Coating method of curable resin composition The curable resin composition of the present invention is suitable for use as an antireflection film or a covering material, and is a substrate for antireflection or coating, for example, a plastic (polycarbonate). , polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, raw borneol resin, etc.), metal, wood, paper, glass, slate Wait. The shape of the substrate may be a plate shape, a film shape or a ternary shape, and the coating method is a general coating method, for example, a dip coating method, a spray coating method, a flow coating method, a spray coating method, Roll coating method, spin coating method, brush coating method, and the like. The thickness of these applied coating films is dried and hardened. It is usually 0.1 to 400 μm, preferably 1 to 200 μm.

4. Hardening method of curable resin composition The curable resin composition can be hardened by radiation (light). The source of the wire is not particularly limited as long as it can be cured in a short time after coating the composition, for example, a source of infrared rays: a lamp, a resistance heating plate, a laser, etc., a source of visible light: daylight, a lamp, Fluorescent lamps, lasers, etc., ultraviolet light sources: mercury lamps, halogen lamps, lasers, etc., the source of electronic wires: commercially available methods of generating hot electrons using tungsten wires, and applying high voltage pulses to metals. A cathodic method and a secondary electron method of secondary electrons generated by the impact of ionized gas molecules and metal electrodes. line α, γ beta] line and the source line of the line, for example, other nuclear fission substance ^{6 0} Co, γ and vacuum lines may be utilized to accelerate the electrons to the anode an impact and the like. These radiations may be irradiated with one type or two or more types at the same time or at intervals.

When the active energy ray is used, the exposure amount is preferably a value in the range of 0.01 to 10 J/cm ² . The reason is that when the exposure amount reaches 0.01 J/cm ² at the end, the curing may be poor, and when the exposure amount exceeds 10 J/cm ² , the curing time is too long. For this reason, the exposure amount is desirably a value in the range of 0.1 to 5 J/cm ² , more preferably a value in the range of 0.3 to 3 J/cm ² .

The hardening reaction of the curable resin composition must be carried out under anaerobic conditions such as nitrogen. The reason is that when oxygen is present, radical polymerization is inhibited, and thus the hardening reaction is insufficient.

III. Cured Film The cured film of the present invention is obtained by applying the above curable resin composition to various substrates, for example, a plastic substrate, and curing. Specifically, after the composition is applied, it is preferred to dry the volatile component at 0 to 200 ° C and then to cure the coating by the above-described radiation curing treatment. It is preferred to use ultraviolet rays or electron wires for the radiation hardening treatment. The ultraviolet irradiation amount at this time is preferably from 0.01 to 10 J/cm ² , more preferably from 0.1 to ² J/cm ² . The preferred electron beam irradiation conditions are a pressing 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 1 to 10 Mrad.

After the curable resin composition is applied, the metal oxide particles (metal oxide particle component (A)) of (A1) and (A2) are partially evaporated during the evaporation of the solvent (C) and the solvent (D) in the composition. A large amount is present on the coated underlayer side (near the interface with the adjacent layer) or on the opposite side thereof. Therefore, in the vicinity of the interface of one of the cured films, the metal oxide particle component (A) exists at a high density, and in the vicinity of the other interface of the cured film, the metal oxide particle component (A) does not substantially exist, so that it is formed. A low refractive index resin layer. Therefore, a layer coating film composed of a curable resin composition is cured, whereby a cured film having a layer structure of substantially two or more layers can be obtained. Each of these layers formed after separation is confirmed, for example, by a cross section of the film obtained by electron microscopic observation. The layer in which the metal oxide particle component (A) is present at a high density means a concept in which the metal oxide particle component (A) is concentrated, and the metal oxide particle component (A) is a layer mainly composed of a metal oxide particle component (A). The case where the inside of the time layer contains the component (B) at the same time. Further, the layer in which the metal oxide particle component (A) does not substantially exist means a concept in which the metal oxide particle component (A) does not exist, but may contain some metal oxidation insofar as the effect of the present invention is not impaired. Particle component (A). This layer is substantially a layer composed of components other than the metal oxide particle component (A) such as the cured product of the component (B) and the component (E). Most of the cured film has a two-layer structure in which a layer in which the metal oxide particle component (A) is present in a high density and a layer in which the metal oxide particle component (A) does not substantially exist is formed. When a polyethylene terephthalate (PET) resin (including a PET resin having an easy-adhesion layer) is used as the substrate, it is usually a layer having a high density in the layer of the substrate or the metal oxide particle component (A). The metal oxide particle component (A) is formed by abutting the layers in which the layers are substantially absent.

The layer structure of two or more layers refers to a layer containing "a layer of metal oxide particles of (A1) and (A2) at a high density" and a layer of "metal oxide particles of (A1) and (A2) substantially absent" In the case where two or more layers are formed, or only two or more layers of "(A1) or (A2) metal oxide particles are present in a high density".

When two or more kinds of metal oxide particles containing a curable resin composition are combined, two or more layers of "a metal oxide particle having a high density" may be formed. The "metal oxide particles" of the "layer in which the metal oxide particles are present in a high density" means at least one type, in other words, one or two or more types of "metal oxide particles". The "layer in which the metal oxide particles are present at a high density" in one layer may be composed of two or more kinds of metal oxide particles.

In the curable resin composition, (B) a fluorine-containing polymer containing an ethylenically unsaturated group has a refractive index lower than that of a thermosetting resin (for example, a melamine compound), and is an ideal optical material having a low refractive index layer of an antireflection film. The constituent material of the metal oxide particle component (A) can form a more excellent antireflection film by using the metal oxide particles (Aa) having a high refractive index.

The curable resin composition of the present invention is applied onto a substrate, and the cured film of the present invention which is UV-cured is excellent in transparency, high in hardness, and has scratch resistance and substrate and substrate or low. A coating film (film) having excellent adhesion to an adjacent layer such as a refractive index layer. Since the hardening reaction does not use heat, it does not accompany the hydrolysis reaction by the thermosetting reaction, and the obtained cured film is excellent in moist heat resistance. Therefore, the cured film is suitable for a film type liquid crystal element, a touch panel, a plastic optical part, or the like.

[Examples]

The invention is illustrated in more detail below by means of examples, but the scope of the invention is not limited to the examples. In the examples, the amount of each component used is not particularly indicated, and "part" means mass parts, or "%" means mass%.

Manufacturing example 1

(1) Synthesis of Organic Compound (Ab) Having Polymerizable Unsaturated Group In a mixed solution of 221 parts by mass of mercaptopropyltrimethoxydecane and 1 part by mass of dibutyltin dilaurate in a container to which a stirrer is attached, After 222 parts by mass of isophorone diisocyanate was added dropwise at 50 ° C for 1 hour in dry air, the mixture was further stirred at 70 ° C for 3 hours.

Next, in the reaction solution, NK ester A-TMM-3LM-N (manufactured by Xinzhongcun Chemical Co., Ltd. 60% by mass and pentaerythritol tetraacrylate 40% by mass) was added dropwise at 30 ° C for 1 hour. After only 549 parts by mass of the pentaerythritol triacrylate having a hydroxyl group was involved in the reaction, the mixture was stirred at 60 ° C for 10 hours to obtain a reaction liquid.

When the amount of the isocyanate remaining in the organic compound having a polymerizable unsaturated group was measured by the FT-IR, the amount of the isocyanate remaining in the polymerizable unsaturated group was 0.1% by mass or less, and it was confirmed that each reaction was carried out substantially quantitatively. The absorption spectrum of the 2550-locked thiol characteristic of the fluorenyl group in the raw material of the product and the absorption peak of the 2260-locked characteristic of the raw isocyanate compound disappeared, and the urethane bond and -S (C=O) were newly observed. The peak of the 1660 latch of the NH-based feature and the peak of the 1720 latch of the propyleneoxy characteristic indicate that a propyleneoxy group having a polymerizable unsaturated group and a -S(C=O)NH- group, an amine group are formed. The propyleneoxy group of the formate linkage modifies the alkoxy decane. By the above, a compound having a thiocarbamate bond, a urethane bond, an alkoxycarbenyl group, or a polymerizable unsaturated group is obtained (the above formulas (A-4) and (A-5) 773 parts by mass of the compound (Ab) shown and 220 parts by mass of pentaerythritol tetraacrylate which is not involved in the reaction (hereinafter, this composition is sometimes referred to as "alkoxydecane (1)") (A#1) ).

Manufacturing Example 2

(2) Synthesis of urethane acrylate (compound represented by formula (11)): 18.8 parts by mass of isophorone diisocyanate and 0.2 parts by mass of dibutyltin dilaurate in a container to which a stirrer is attached In the solution, 93 parts by mass of NK ester A-TMM-3LM-N (participating only the hydroxyl group pentaerythritol triacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. was added dropwise at 10 ° C for 1 hour, at 60 ° C. After stirring for 6 hours, a reaction liquid was obtained.

The amount of the isocyanate remaining in the same manner as in Production Example 1 was measured by FT-IR. The amount of the isocyanate remaining in the same manner as in Production Example 1 was 0.1% by mass or less, and it was confirmed that the reaction was carried out substantially quantitatively. Further, it was confirmed that a urethane bond and an acrylonitrile group (polymerizable unsaturated group) were contained in the molecule.

By the above, 75 parts by mass of the urethane hexaacrylate (the compound represented by the above formula (11)) and 37 parts by mass of the pentaerythritol tetraacrylate which is not involved in the reaction are obtained (A#2).

Manufacturing Example 3 [Preparation of a composition for a hard coat layer containing cerium oxide particles]

2.32 parts by mass of the polymerizable unsaturated composition (A#1) obtained in Production Example 1, cerium oxide particle sol (methyl ethyl ketone cerium oxide sol, MEK-ST manufactured by Nissan Chemical Industries Co., Ltd., number average a particle size of 0.022 μm, a cerium oxide concentration of 30%), 91.3 parts by mass (27 parts by mass of cerium oxide particles), 0.12 parts by mass of ion-exchanged water, and 0.01 parts by mass of p-hydroxyphenyl monomethyl ether, at 60 After stirring at ° C for 4 hours, 1.36 parts by mass of methyl orthoformate was added, and the mixture was heated and stirred at the same temperature for 1 hour to obtain reactive particles (dispersion A #3)). After 2 g of this dispersion (dispersion A #3) was weighed in an aluminum pan, it was dried on a hot plate at 175 ° C for 1 hour, and the solid content was determined to be 30.7%. Further, 2 g of the dispersion (A #3) was weighed by a magnetic crucible, and then preliminarily dried on a hot plate at 80 ° C for 30 minutes, and fired in an 750 ° C muffle furnace for 1 hour to obtain an inorganic residue. The inorganic content of the fraction is 90%.

98.6 g of this dispersion (A #3), 3.4 g of composition (A #2), 2.1 g of 1-hydroxycyclohexyl phenyl ketone, and IRGACURE 907 (2-methyl-1-[4-(methylthio)) 1.2 g of phenyl]-2-morpholinopropan-1-one (manufactured by Ciba. Specialty. Chemicals), 33.2 g of dipentaerythritol hexaacrylate (DPHA), and 7 g of cyclohexanone were mixed and stirred to obtain cerium oxide-containing particles. The composition for a hard coat layer (solid content concentration: 50%) was 145 g.

Manufacturing Example 4 [Preparation of composition containing zirconia particles]

300 parts by mass of UEP-100 (primary particle size 10 to 30 nm) manufactured by the first rare element chemical industry (stock) was added to 700 parts by mass of methyl ethyl ketone (MEK), dispersed with glass beads for 168 hours, and glass beads were removed to obtain zirconia. 950 parts by mass of the dispersed sol. After 2 g of the zirconia dispersion sol was weighed on an aluminum pan, it was dried on a hot plate at 120 ° C for 1 hour, and the solid content was determined to be 30%. 100 g of the zirconia dispersion sol, 0.86 g of the composition (A #1) synthesized in Production Example 1, 13.4 g of dipentaerythritol hexaacrylate (DPHA), 0.016 g of p-methoxyphenol, and 0.033 g of ion-exchanged water. After stirring at 60 ° C for 3 hours, 0.332 g of methyl orthoformate was added, and the mixture was heated and stirred at the same temperature for 1 hour to obtain 116 g of a dispersion of surface-modified zirconia particles. 116 g of this dispersion, 1.34 g of composition (A # 2), 1.26 g of 1-hydroxycyclohexyl phenyl ketone, and IRGACURE 907 (2-methyl-1-[4-(methylthio)phenyl]-2- 0.76 g of morpholinopropan-1-one, manufactured by Ciba. Specialty. Chemicals, and 2846 g of MEK were stirred and mixed to obtain 2964 g of a composition containing zirconium oxide particles (solid content: 4%).

Manufacturing Example 5 [Preparation of composition containing tin-doped indium oxide (ITO) particles]

ITO sol (10 wt% IPA sol) made of Fuji Chemical Co., Ltd. 700 g, DPHA 29.5 g, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one 1 g and 1769.5 g of isopropyl alcohol (IPA) were mixed to obtain a composition containing ITO particles having a solid content of 4%.

Manufacturing Example 6 [Preparation of composition containing antimony-doped tin oxide (ATO) particles]

ATO particles (made by Ishihara Techno Co., Ltd., SN-100P, primary particle size 10 to 30 nm), dispersant (made by Asahi Kasei Co., Ltd., Adecapurunix TR-701), and methanol at 90/2.78/211 (weight ratio) The amount of the mixture was mixed (the total solid content was 31%, and the total inorganic content was 29.6%). Into a 50 ml plastic bottle of a paint shaker, 40 g of glass beads (manufactured by TOSHINRIKO, BZ-01) (bead diameter: 0.1 mm) (volume: about 16 ml) and 30 g of the above mixed solution were added and dispersed for 3 hours to obtain a median diameter of 80 nm. Dispersing the sol. 304 g of the dispersion sol, a mixture of 5.7 g of a composition (A #1), 0.01 g of p-methoxyphenol, and 0.12 g of ion-exchanged water were stirred at 60 ° C for 3 hours, and then 1.3 g of methyl orthoformate was added thereto. The mixture was heated and stirred at the same temperature for 1 hour to obtain 311 g of a dispersion of surface-modified ATO particles. 278.3 g of this dispersion, 1.7 g of composition (A #2), 8.59 g of pentaerythritol triacrylate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 0.88 g of 1-ketone, 33 g of methanol, and 1675 g of propylene glycol monomethyl ether were mixed and stirred to obtain 2000 g of a composition containing ATO particles (solid content: 5%).

Manufacturing Example 7 [Modulation of composition containing ZnO particles doped with aluminum]

Zinc oxide particles (ZnO particles doped with A1, primary particle size 10-20 nm), dispersant (manufactured by Nanben Chemical Co., Ltd., Hybulad 151) and propylene glycol monomethyl ether at 27.6/4.8/67.6 (weight ratio) The amount of the mixture is mixed (the total solid content is 30%, and the total inorganic content is 27.6%). Into a 50 ml plastic bottle of a paint shaker, 40 g of zirconia beads (bead diameter: 0.1 mm) and 30 g of the above mixture were placed, and dispersed for 8 hours to obtain a dispersion sol having a median diameter of 40 nm. 10 g of pentaerythritol triacrylate, 0.5 g of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2138 g of propylene glycol monomethyl ether were added to 290 g of the sol. 2,438 g of a composition containing zinc oxide particles (solid content concentration: 4%) was obtained.

Manufacturing Example 8 [Manufacture of coated reactive alumina with a polymerizable unsaturated organic compound (Ab) and TiO ₂ particle sol (A1-1) of zirconia]

333.7 parts by mass of a dispersion of TiO ₂ particles coated with alumina and zirconia (a total solid concentration of 28% by Tika Co., Ltd., particle concentration: 24%), and a solution of alkoxy decane (1) obtained in Production Example 1. The mass fraction, 0.20 parts by mass of distilled water, and 0.03 parts by mass of hydroquinone monomethyl ether were heated and stirred at 65 °C. After 4 hours, 2.2 parts by mass of methyl orthoformate was added, and the mixture was further heated for 1 hour to obtain a solid fraction of 31.6% of the coated reactive alumina and zirconia TiO ₂ particle sol (A1-1).

The number average particle diameter of this TiO ₂ particle was 20 nm. The average particle size was measured by a transmission electron microscope.

Manufacturing Example 9 [Manufacture of hydroxyl group-containing fluoropolymer (B-2)]

After replacing 1.5 L of the inner pressure stainless steel pressure cooker with a magnetic stirrer with nitrogen, 500 g of ethyl acetate, 43.2 g of perfluoro(propyl vinyl ether), 41.2 g of ethyl vinyl ether, and 21.5 of hydroxyethyl vinyl ether were added. g, "Adekariasope NE-30" (made by Asahi Kasei Kogyo Co., Ltd.), 40.5 g of non-ionic reactive emulsifier, "VPS-1001" of azo-containing polydimethyloxane (Wako Pure Chemical Industries Co., Ltd.) The company made 6.0 g and 1.25 g of lauryl peroxide, and after cooling to -50 ° C with dry ice-methanol, the oxygen in the system was again removed by nitrogen.

Next, 97.4 g of hexafluoropropylene was added, and the temperature was raised. The pressure in the autoclave at a temperature of 60 ° C was 5.3 × 10 ⁵ pa. Thereafter, the reaction was continued by stirring at 70 ° C for 20 hours, and when the pressure was lowered to 1.7 × 10 ⁵ Pa, the autoclave was water-cooled to stop the reaction. After reaching room temperature, unreacted monomers were released, and the autoclave was opened to obtain a polymer solution having a solid concentration of 26.4%. The obtained polymer solution was poured into methanol to precipitate a polymer, and then washed with methanol, and vacuum-dried at 50 ° C to obtain 220 g of a fluoropolymer (B-2).

Manufacturing Example 10 [Manufacture of fluoropolymer (B1) containing ethylenically unsaturated group]

50.0 g of a hydroxyl group-containing fluoropolymer (B-2) obtained in Production Example 9 and a polymerization inhibitor of 2,6-di-t-butylmethylphenol 0.01 g and methyl isobutyl ketone (MIBK) 374 g The separable flask containing a magnetic stirrer, a glass cooling tube, and a thermometer in a volume of 1 liter was placed, and the hydroxyl group-containing fluoropolymer (B-2) was dissolved in MIBK at 20 ° C, and stirred until the solution became transparent and uniform. until. Next, 16.0 g of 2-propenylmethoxyethyl isocyanate was added to the system, and the mixture was stirred until the solution became homogeneous. Then, 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was maintained at 55 to 65 ° C, and stirring was continued. A MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (B1) was obtained in 5 hours. After taking 2 g of this solution on an aluminum pan, it was dried on a hot plate at 150 ° C for 5 minutes, and the solid content was 15.0%.

Manufacturing Example 11 [Manufacture of particles (A2-1) having a polymerized unsaturated ruthenium oxide as a main component]

In the same manner as in Production Example 8, 1.1 parts by mass of alkoxydecane (1) and methyl ethyl ketone cerium oxide sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST-L (number average particle diameter: 0.050 μm, cerium oxide) concentration of 30%) 91.3 parts by mass (27.4 parts by mass of the solid parts), ion-exchanged water, 0.1 parts by mass, 1.4 parts by mass of methyl orthoformate to give a particle dispersion (A2-1). this TiO ₂ particles of average particle diameter 20 μm. The solid content of the particle dispersion (A2-1) was 36% by mass.

The cerium oxide particles had an average particle diameter of 50 nm. The average particle size was measured by a transmission electron microscope.

Manufacturing Example 12 [Manufacture of particles (A1-2) having a polymerized unsaturated ruthenium oxide as a main component]

In the same manner as in Production Example 11, 1.1 parts by mass of alkoxydecane (1) and methyl ethyl ketone cerium oxide sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST (number average particle diameter: 0.020 μm, cerium oxide concentration 30) were used. %) 91.3 parts by mass (solid content: 27.4 parts by mass), 0.1 parts by mass of ion-exchanged water, and 1.4 parts by mass of methyl orthoformate to obtain a particle dispersion liquid (A1-2). The number average particle diameter of the TiO ₂ particles is 20 μm. The solid content of the particle dispersion (A1-2) was 36% by mass.

The cerium oxide particles had an average particle diameter of 20 nm. The average particle size was measured by a transmission electron microscope.

Example 1 [Preparation of Curable Resin Composition 1]

110 g of the TiO ₂ particle sol (A) coated with the cerium oxide and the zirconia obtained in Production Example 8 (reactive particles 34.8 g), and the fluoropolymer containing the ethylenically unsaturated group obtained in Production Example 10 (B1) 285g (42.7g of fluoropolymer containing ethylenically unsaturated group), 15.4g of dipentaerythritol pentaacrylate (DPPA), 2-benzyl-2-dimethylamino-1-(4-morpholinium) 3.9 g of 1-butanone (IRGACURE 369, CIBA. speciality. chemicals, photoradical polymerization initiator), 3.2 g of the compound represented by the formula (11) obtained in Production Example 2, and 530 g of methyl ethyl ketone 150 g of methyl isobutyl ketone and 100 g of n-butanol were stirred. The solid content of the obtained curable resin composition was 8.4%.

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

The curable resin compositions 2 to 5 were obtained in the same manner as in Example 1 except that the combination of the metal oxide particles to be used was changed to that shown in Table 1, and the mixing ratio of each component was changed as shown in Table 1.

A cured film was produced using the curable resin compositions 1 to 5 produced in the above Examples 1 to 3 and Comparative Examples 1 and 2, and the properties of the cured film were evaluated. The method for producing the cured film is as follows.

A cerium oxide particle sol (methyl ethyl ketone cerium oxide sol, MEK-ST manufactured by Nissan Chemical Industries Co., Ltd., number average particle diameter 0.022 μm, cerium oxide concentration 30%) 98.6 g, 1-hydroxycyclohexyl phenyl ketone 2.1 g, IRGACURE 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, manufactured by Ciba. Specialty. Chemicals) 1.2 g, dipentaerythritol hexaacrylate ( 33.2 g of DPHA) and 7 g of cyclohexanone were mixed and stirred to obtain a composition for a hard coat layer containing cerium oxide particles. The composition of the hard coat layer containing the cerium oxide particles was applied to a triethylenesulfonated cellulose film (manufactured by LOFO, film thickness: 80 μm) using a wire bar coater (#12), and then 80 in an oven. Dry at °C for 1 minute. Next, ultraviolet rays were irradiated under high light with a high-pressure mercury lamp under a light irradiation condition of 0.6 J/cm ^{2 to} form a hard coat layer. The film thickness of the hard coat layer was measured by a stylus type film thickness meter to be 5 μm.

The curable resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were applied onto the obtained hard coat layer using a wire bar coater (#3), and then heated at 80 ° C in an oven. 1 minute. Subsequently, ultraviolet rays were irradiated under a nitrogen atmosphere using a high-pressure mercury lamp under a light irradiation condition of 0.9 J/cm ^{2 to} form a cured film layer having a film thickness of 0.2 μm.

<Evaluation of hardened film>

(1) Resistance to steel wool The steel wool resistance test of the cured film was carried out in the following manner. In other words, steel wool (Bonster No. 0000, manufactured by Japan Steel Wire Co., Ltd.) was attached to a vibration-type friction fastness tester (AB-301, manufactured by Tester Industries Co., Ltd.), and was repeatedly wiped under the condition of a load of 1 kg. After 10 times on the surface of the dura mater, the surface of the cured film was visually observed for scratching and confirmed on the following basis.

○: The cured film was almost free from peeling and scratching.

△: The cured film has a small scratch.

×: The cured film was partially peeled off, or the surface of the cured film was scratched.

(2) Turbidity (%) The haze (Haze value) of the obtained laminate was measured by a Haze meter and evaluated on the following basis.

○: The Haze value is 1% or less.

△: The Haze value is 3% or less.

×: The Haze value exceeds 3%.

(3) Ethanol resistance The ethanol resistance of the cured film was carried out by the following method. In other words, a non-woven fabric (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) impregnated with ethanol was attached to a vibration-type friction fastness tester (AB-301, manufactured by Tester Industries Co., Ltd.), and was repeatedly rubbed with a load of 500 g. After 20 times on the surface of the film, the surface of the cured film was visually observed for scratching and confirmed on the following basis.

○: The cured film was almost free from peeling and scratching.

△: The cured film has a small scratch.

×: The cured film was partially peeled off, or the surface of the cured film was scratched.

(4) Layer separation The cross section of the obtained cured film was observed under a microscope to evaluate whether or not the two layers were separated. The evaluation criteria are as follows. An electron micrograph of a typical example of each state is shown in FIG.

○: Separation of the second layer.

△: not separated (partially agglomerated) ×: uniform structure

<Evaluation Benchmark>

○: Separation of the second layer.

△: not separated (partially agglomerated) ×: uniform structure

The abbreviations in the table are as follows.

DPPA: dipentaerythritol pentaacrylate; UV curable crosslinker (5-functional) IRGACURE 369: 2-benzyl-2-dimethylamino-1-(4-morpholinyl)-1-butanone; CIBA Specialty chemicals, photopolymerization initiator

From the results of Table 1, it was found that Examples 1 to 3 containing both of the metal oxide particles (A1) and (A2) have good layer separation properties and are excellent in scratch resistance, haze and chemical resistance.

On the other hand, in Comparative Example 1 containing only the metal oxide particles (A1), the scratch resistance and chemical resistance were lowered. Further, in Comparative Example 2 containing two kinds of particles corresponding to the metal oxide particles (A1), the layer separation property was lowered, and the scratch resistance and the transparency were inferior.

Example 4 [Production of laminate]

(1) Preparation of hard coat layer The composition of the hard coat layer containing the cerium oxide particles prepared in Production Example 3 (solid content concentration: 50%) was applied to triethylene oxime using a metal bar coater (#12). The venetian film (manufactured by LOFO, film thickness: 80 μm) was dried in an oven at 80 ° C for 1 minute. Next, ultraviolet rays were irradiated under high light with a high-pressure mercury lamp under a light irradiation condition of 0.6 J/cm ^{2 to} form a cured film layer. The film thickness of the cured film layer was measured by a stylus type film thickness meter to be 5 μm.

(2) Preparation of Medium Refractive Index Layer The composition containing zirconia particles prepared in Production Example 4 (solid content concentration: 4%) was applied to (1) hard coat produced by using a metal bar coater (#3). The layers were then dried in an oven at 80 ° C for 1 minute. Next, ultraviolet rays were irradiated under a nitrogen atmosphere using a high-pressure mercury lamp under a light irradiation condition of 0.6 J/cm ^{2 to} form a cured film layer. The film thickness of the cured film layer was calculated by reflection spectrometry to be 65 nm.

(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 applied to (2) by using a metal bar coater (#3), respectively. The middle refractive index layer was then dried in an oven at 140 ° C for 2 minutes. Next, under a vacuum, a transfer type mercury lamp manufactured by OAK Co., Ltd. was irradiated with ultraviolet rays at 0.6 J/cm ^{2 to} form a cured film layer having a film thickness of 0.2 μm.

Example 5 [Production of laminate]

(1) The production of the hard coat layer was produced in the same manner as in Example 4 (1).

(2) Preparation of an antistatic layer The composition containing the ITO particles prepared in Production Example 5 (solid content concentration: 4%) was applied onto the hard coat layer prepared in (1) using a metal bar coater (#3). Then, it was dried at 80 ° C for 1 minute in an oven. Next, ultraviolet rays were irradiated under a nitrogen atmosphere using a high-pressure mercury lamp under a light irradiation condition of 0.6 J/cm ^{2 to} form a cured film layer. The film thickness of the cured film layer was calculated by reflection spectrometry to be 65 nm.

(3) The middle refractive index layer was produced in the same manner as in Example 4 (2).

(4) 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 applied to (3) by using a metal bar coater (#3), respectively. The middle refractive index layer was then dried in an oven at 140 ° C for 2 minutes. Next, ultraviolet rays of 0.6 J/cm ^{2 were} irradiated with a transport type mercury lamp manufactured by OAK Co., Ltd. under the atmosphere to form a cured film layer having a film thickness of 0.2 μm.

Example 6, 7 [Production of laminate]

(1) Preparation of Antistatic Layer A composition containing ATO particles prepared in Production Example 6 or 7 (solid content concentration: 5%) or a composition containing ZnO particles doped with Al (solid content concentration: 4%) was used instead of the production example. The ITO particles prepared in 5 were applied to a triethylenesulfonated cellulose film (manufactured by LOFO, film thickness: 80 μm) using a wire bar coater (#3), and then dried in an oven at 80 ° C for 1 minute. Next, the cured film layer was formed by irradiating ultraviolet rays with a high-pressure mercury lamp under a nitrogen atmosphere at a light irradiation condition of 0.6 J/cm ² . The film thickness of the cured film layer was calculated by reflection spectrometry to be 65 nm.

(2) Preparation of hard coat layer A composition for a hard coat layer containing cerium oxide particles prepared in Production Example 3 (solid content concentration: 50%) was applied using a metal bar coater (#12) in an oven. Dry at 80 ° C for 1 minute. Next, ultraviolet rays were irradiated under high light with a high-pressure mercury lamp under a light irradiation condition of 0.6 J/cm ^{2 to} form a cured film layer.

(3) The middle refractive index layer was produced in the same manner as in Example 4 (2).

(4) 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 applied to (3) by using a metal bar coater (#3), respectively. The middle refractive index layer was dried in an oven at 140 ° C for 2 minutes, and irradiated with ultraviolet rays of 0.6 J/cm ² under a vacuum using a transport-type mercury lamp manufactured by OAK Co., Ltd. to form a cured film layer having a film thickness of 0.2 μm.

Example 8 [Production of laminate]

(1) The production of the hard coat layer was produced in the same manner as in Example 4 (1).

(2) 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 applied to (1) by using a metal bar coater (#3), respectively. The hard coat layer was then dried at 140 ° C for 2 minutes in an oven, and irradiated with ultraviolet rays of 0.6 J/cm ² by a transfer type mercury lamp manufactured by OAK Co., Ltd. under the atmosphere to form a cured film layer having a film thickness of 0.2 μm.

Evaluation Example 1 [Evaluation of laminates]

The cross sections of the laminates obtained in Examples 4 to 8 were observed by a transmission electron microscope, and it was confirmed that the low refractive index layer and the high refractive index layer in either of the laminates were separated into two layers. In this case, the low refractive index is a layer in which the metal oxide particles are substantially absent, and the high refractive index layer is a layer in which the metal oxide particles are present in a high density.

Figure 11 is a conceptual diagram showing states of two layers separated, unseparated (partially agglomerated), and uniformly structured.

The reflectance at a wavelength of 550 nm was measured by a spectroscopic reflectance measuring device (combined with a large-scale sample integrating sphere attachment 150-09090 self-recording spectrophotometer U-3410, manufactured by Hitachi, Ltd.) to evaluate the obtained anti-reflection. The antireflection properties of the laminate are used. Specifically, the reflectance of the antireflection laminate (antireflection film) was measured based on the reflectance of the aluminum vapor deposited film (100%). As a result, the reflectance at a wavelength of 550 nm of any of the laminates was 1% or less.

[industrial use]

The curable resin composition of the present invention can form a cured film composed of two or more layers from the coating film of one, and the manufacturing steps can be simplified.

The curable resin composition and cured product of the present invention can be used for, for example, plastic optical parts, touch panels, film type liquid crystal elements, plastic containers, floor boards for building interior materials, wall materials, artificial marble, etc. to prevent scratches (scratches). Or anti-pollution protective coating material; anti-reflection film for film type liquid crystal element, touch panel, plastic optical parts, etc.; adhesive for various substrates, sealant: bonding agent for printing ink, etc., especially suitable for anti-reflection film .

The method for producing a laminate of the present invention can form a layer of 2 or more from the coating film of 1, and can simplify the production steps of the laminate having a multilayer structure of two or more layers. Therefore, the method for producing a laminate of the present invention is particularly suitable for forming an optical material such as an antireflection film, a lens, or a selective transmission film filter. Further, the obtained laminate system can be applied to a coating material, a weather-resistant film, a coating, and the like for a substrate requiring weather resistance by using a layer having a high fluorine content. Further, the laminate is excellent in adhesion to a substrate, has high scratch resistance, imparts a good antireflection effect, and is extremely suitable for an antireflection film, and can be applied to various display devices to improve the visibility.

10. . . Substrate

20. . . Hard coating

30. . . Antistatic layer

40. . . High refractive index layer

50. . . Low refractive index layer

60. . . Medium refractive index layer

1, 1a, 1b. . . Floor

3. . . Floor

Fig. 1A is an explanatory view of "a layer of 2 or more formed of a coating film of 1".

Fig. 1B is an explanatory view of "a layer of 2 or more formed of a coating film of 1".

Fig. 1C is an explanatory view of "a layer of 2 or more formed of a coating film of 1".

Fig. 1D is an explanatory view of "a layer of 2 or more formed of a coating film of 1".

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

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

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

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

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

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

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

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

Fig. 10 is a cross-sectional view showing 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, non-separation (partial aggregation), and uniform structure.

10. . . Substrate

40. . . High refractive index layer

50. . . Low refractive index layer

Claims (29)

A curable resin composition characterized by comprising: (A1) a metal oxide particle having an average number of particles of 1 nm or more and less than 40 nm formed by 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 or more and 200 nm or less (hereinafter referred to as "metal oxide particles of (A2)") (B) Fluorine-containing polymer (C) containing an ethylenically unsaturated group (B) One or two or more solvents having high solubility in a fluorine-containing polymer containing an ethylenically unsaturated group (hereinafter referred to as "(C) rapid volatilization Solvent") (D) (A1) and (A2) A metal oxide particle having high dispersion stability and having one or two or more solvents having compatibility characteristics with (C) a fast-volatile solvent (hereinafter referred to as "( D) Slowly evaporating the solvent"), and (C) the relative evaporation rate of the rapidly evaporating solvent is greater than (D) the relative evaporation rate of the slowly evaporating solvent. The curable resin composition of the first aspect of the invention, wherein (C) one or two or more solvents having low dispersion stability of the metal oxide particles of the rapid volatile solvent systems (A1) and (A2), (D) The slow-releasing solvent system (B) one or two or more solvents having low solubility of the fluorine-containing polymer containing an ethylenically unsaturated group. Such as the curable resin composition of claim 1 of the patent scope, The metal oxide particles of (A1) are oxide particles of at least one element selected from the group consisting of aluminum, zirconium, titanium, zinc, antimony, indium, tin, antimony and antimony. The curable resin composition according to claim 1, wherein the metal oxide particles of (A2) are particles containing cerium oxide as a main component. The curable resin composition of claim 1, wherein the metal oxide particles of (A2) are bonded to the organic compound (Ab) having a polymerizable unsaturated group. The curable resin composition of claim 1, wherein the organic compound (Ab) has a group represented by the following formula (A-1) in addition to the polymerizable unsaturated group. [In the formula, U is NH, O (oxygen atom) or S (sulfur atom), and V is O or S]. The curable resin composition of claim 1, wherein the organic compound (Ab) is a compound having a stanol group in the molecule or a compound which is hydrolyzed to form a stanol group. The sclerosing resin composition of claim 1, wherein the (B) fluoropolymer containing an ethylenically unsaturated group is a compound having one isocyanate group and at least one ethylenically unsaturated group (B- 1) The reaction with a hydroxyl group-containing fluoropolymer (B-2). The curable resin composition of claim 8, wherein the hydroxyl group-containing fluoropolymer (B-2) contains the following structural unit (a) 20 to 70 mol%, and (b) 10 to 70 Mohr% and (c) 5 to 70 mol%, and the polystyrene-equivalent number average molecular weight measured by gel permeation chromatography is 5,000 to 500,000, (a) the structural unit represented by the following general formula (1) ( b) the structural unit represented by the following general formula (2) (c) the structural unit represented by the following general formula (3) Wherein R ¹ is a fluorine atom, a fluoroalkyl group or a group represented by -OR ² (R ² is an alkyl group or a fluoroalkyl group)] Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a group represented by —(CH ₂ )x-OR ⁵ or —OCOR ⁵ (R ⁵ is an alkyl group or an epoxypropyl group, and x is 0 or 1), carboxyl or alkoxycarbonyl] Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a hydrogen atom or a hydroxyalkyl group, and v is a number of 0 or 1. The sclerosing resin composition of claim 8, wherein the hydroxyl group-containing fluoropolymer (B-2) further contains the following structural unit (d) 0.1 from the azo group-containing polyoxy siloxane compound; ~10 mol%, (d) the structural unit represented by the following general formula (4) [wherein R ⁸ and R ⁹ may be the same or different hydrogen atom, alkyl group, halogenated alkyl group or aryl group]. The sclerosing resin composition of claim 10, wherein the hydroxyl group-containing fluoropolymer (B-2) contains the structural unit (d) as a part of the following structural unit (e), (e) The structural unit represented by the following general formula (5) Wherein R ¹⁰ to R ¹³ are a hydrogen atom, an alkyl group or a cyano group, R ¹⁴ to R ¹⁷ are a hydrogen atom or an alkyl group, p and q are numbers 1 to 6, and s and t are 0 to 6 , y is the number from 1 to 200]. The curable resin composition of claim 8, wherein the hydroxyl group-containing fluoropolymer (B-2) further contains the following structural unit (f) of 0.1 to 5 mol%, (f) the following general Structural unit represented by formula (6) [wherein R ¹⁸ has an emulsification group]. The curable resin composition of claim 8, wherein the compound (B-1) is 2-(meth)acryloxyethyl isocyanate. The curable resin composition of claim 1, which further comprises a polyfunctional (meth) acrylate compound containing at least two (meth) acryl fluorenyl groups of component (E) and/or at least 1 Fluorine (meth) acrylate combination of more than one (meth) acrylonitrile group Things. The curable resin composition of claim 1, wherein the component (F) radical polymerization initiator is further contained. The curable resin composition of the first aspect of the patent application is ultraviolet curable. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 16 and having a multilayer structure of two or more layers. The cured film of claim 17, which comprises a layer having a high density of metal oxide particles of (A1) and (A2) and a metal oxide particle of (A1) and (A2) substantially A layer structure of two or more layers composed of a layer having no or less than one layer. A method for producing a laminate comprising a substrate and a laminate having a multilayer structure thereon, characterized in that the curable resin composition according to any one of claims 1 to 16 is coated. A coating film is formed on the layer formed on the substrate or the substrate, and the coating film of the solvent is evaporated to form a layer of 2 or more. The method for producing a laminate according to claim 19, wherein each of the two or more layers is a layer having a high density of metal oxide particles of (A1) and/or (A2) or (A1) and (A2) At least one of the layers in which the metal oxide particles are substantially absent is a layer in which the metal oxide particles of (A1) and/or (A2) are present at a high density. The method for producing a laminate according to claim 20, wherein the two or more layers are two layers. The method for producing a laminate according to claim 19, wherein the two or more layers are further irradiated with radiation to cause hardening. The method for producing a laminate according to claim 19, wherein the laminate is an optical component. The method for producing a laminate according to claim 19, wherein the laminate is an antireflection film. The method for producing a laminate according to claim 21, wherein the laminate is an antireflection film which is laminated on the substrate at least the high refractive index layer and the low refractive index layer from the substrate side in this order, The two layers of claim 21 of the patent application are formed of a high refractive index layer and a low refractive index layer. The method for manufacturing a laminate according to claim 25, wherein the low refractive index layer has a refractive index of 1.20 to 1.55 at 589 nm, and the high refractive index layer has a refractive index of 1.50 to 2.20 at 589 nm, and is lower than the low refractive index layer. The refractive index is high. The method for producing a laminate according to claim 21, wherein the laminate is on the substrate, and at least the medium refractive index layer, the high refractive index layer and the low refractive index layer are laminated in this order from the side closer to the substrate. The antireflection film is formed of a high refractive index layer and a low refractive index layer in the second layer of claim 21 of the patent application. The method for manufacturing a laminate according to claim 27, wherein the low refractive index layer has a refractive index of 1.20 to 1.55 at 589 nm, and the medium refractive index layer has a refractive index of 1.50 to 1.90 at 589 nm, and is lower than the low refractive index layer. High refractive index, The high refractive index layer has a refractive index of 591 nm of 1.51 to 2.20 and a higher refractive index than the medium refractive index layer. The method for producing a laminate layer according to claim 25, further comprising forming a hard coat layer and/or an antistatic layer on the substrate.