KR100896124B1 - Curable liquid resin composition and method for producing multilayer body using same - Google Patents

Abstract

The present invention

(A) a fluorine-containing polymer having a hydroxyl group in a molecule,

(B) One or two or more metal oxide particles having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more (hereinafter, referred to as "(B) metal oxide particles"),

(C) one or two or more solvents having high solubility in the fluorine-containing polymer having a hydroxyl group in the (A) molecule (hereinafter referred to as "(C) volatile solvent"),

(D) one or two or more solvents having high dispersion stability to the metal oxide particles (B) and compatible with the (C) fast-volatile solvent (hereinafter referred to as "(D) delayed volatile solvent"),

(E) curable compound,

(F) thermal acid generator

And (C) the relative evaporation rate of the fast volatile solvent is greater than the relative evaporation rate of the (D) delayed volatile solvent.

Liquid curable resin composition, hydroxyl-containing fluorine-containing polymer

Description

Liquid curable resin composition and manufacturing method of laminated body using same {CURABLE LIQUID RESIN COMPOSITION AND METHOD FOR PRODUCING MULTILAYER BODY USING SAME}

This invention relates to the liquid curable resin composition and the manufacturing method of the laminated body using the same, and especially relates to the liquid curable resin composition which can form two or more layers from one coating film, and the manufacturing method of the laminated body using the same.

According to the development of multimedia, various developments have been made in various display devices (display devices). In addition, among various display devices, especially those that are used outdoors, especially in portable devices, the improvement of visibility thereof becomes more and more important, and even in large display devices, it is required from the consumer to make it easier to see. The matter became a technical task.

As a means for improving the visibility of a conventional display device, an antireflection film made of a low refractive index material is coated on a substrate of the display device. As a method of forming the antireflection film, for example, a thin film of a fluorine compound is deposited. The method of forming by is known. By the way, the technique which can form an anti-reflective film in low cost and large size display apparatus centering on a liquid crystal display device is calculated | required in recent years. However, in the case of the vapor deposition method, it is difficult to form a uniform antireflection film with high efficiency on a large-area substrate, and it is difficult to lower the cost because a vacuum device is required.

For this reason, a method of forming an antireflection film by dissolving a fluorinated polymer having a low refractive index in an organic solvent to produce a liquid composition and applying it to the surface of a substrate has been studied. For example, it is proposed to apply fluorinated alkylsilane to the surface of a substrate (see Patent Document 1 and Patent Document 2, for example). Moreover, the method of apply | coating the fluoropolymer which has a specific structure was proposed (for example, refer patent document 3).

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

Patent Document 2: Japanese Patent Application Laid-Open No. 6-98703

Patent Document 3: Japanese Unexamined Patent Publication No. 6-115023

Most of these conventional antireflection films are laminates in which different refractive index layers, antistatic layers, hard coating layers and the like are formed on a substrate. In the conventional manufacturing method, the process of apply | coating each layer on the base material was repeated.

This invention is made on the background of the above situation, The objective is to provide the liquid curable resin composition which can efficiently manufacture two or more continuous arbitrary layers, such as a low refractive index layer and a high refractive index layer. .

Another object of the present invention is to provide a cured film having high transparency, large adhesiveness to a substrate, and excellent scratch resistance and dust removal property.

Another object of this invention is to provide the manufacturing method of the laminated body which can form two or more layers from one coating film obtained by apply | coating a composition, and the laminated body obtained by this.

Another object of the present invention is to provide a method for producing a laminate having a good antireflection effect and a laminate obtained thereby.

The other object of this invention is to provide the manufacturing method of the laminated body which is excellent in adhesiveness with respect to a base material, and has high scratch resistance, and the laminated body obtained by this.

<Start of invention>

In order to achieve the above object, the present inventors have made intensive studies to clarify a liquid curable resin composition which provides a cured film having a layer structure of two or more layers from one coating film, and a mechanism that is separated into two or more layers. The fluorine-containing polymer and specific metal oxide particles having at least one selected from the group of solvents divided into two types by the solubility of the fluorine-containing polymer having a hydroxyl group in the molecule, the dispersion stability to the metal oxide particles and the relative evaporation rate By combining the liquid curable resin composition to find that one coating film obtained by applying the liquid curable resin composition is separated into a plurality of layers, and that any kind of metal oxide particles can be separated into a plurality of layers by selecting a kind of solvent and other conditions. The present invention has been completed.

According to this invention, the following liquid curable resin compositions etc. can be provided.

1. (A) a fluorine-containing polymer having a hydroxyl group in a molecule,

(B) One or two or more metal oxide particles having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more (hereinafter, referred to as "(B) metal oxide particles"),

(C) one or two or more solvents having high solubility in the fluorine-containing polymer having a hydroxyl group in the (A) molecule (hereinafter referred to as "(C) volatile solvent"),

(D) one or two or more solvents having high dispersion stability to the metal oxide particles (B) and compatible with the (C) fast-volatile solvent (hereinafter referred to as "(D) delayed volatile solvent"),

(E) curable compound,

(F) thermal acid generator

And (C) the relative evaporation rate of the rapid volatile solvent is greater than the relative evaporation rate of the (D) delayed volatile solvent.

2. (C) The fast volatile solvent is (B) one or two or more solvents having low dispersion stability to the metal oxide particles, and (D) the delayed volatile solvent is (A) for the fluorine-containing polymer having a hydroxyl group in the molecule. It is 1 type or 2 or more types of solvents with low solubility, The liquid curable resin composition of 1 characterized by the above-mentioned.

3. (B) Metal oxide particles include titanium oxide, zirconium oxide, antimony-containing tin oxide, tin-containing indium oxide, aluminum oxide, cerium oxide, zinc oxide, aluminum-containing zinc oxide, tin oxide, antimony-containing zinc oxide and indium-containing oxide The liquid curable resin composition as described in 1 or 2 which is a particle | grain which has 1 type, or 2 or more types of metal oxides chosen from zinc and phosphorus containing tin oxide as a main component.

4. (B) The liquid curable resin composition according to 3, wherein the metal oxide particles are particles containing titanium oxide as a main component.

5. (B) The metal oxide particle is a metal oxide particle which has a multilayered structure, The liquid curable resin composition in any one of 1-4 characterized by the above-mentioned.

6. Cured film obtained by hardening | curing the liquid curable resin composition in any one of 1-5, and having a multilayered structure of two or more layers.

7. Each layer constituting the multilayer structure is a layer in which (B) metal oxide particles are present at a high density, or a layer in which (B) metal oxide particles are substantially not present, and at least one layer is (B) metal oxide particles in a high density. It is a layer which exists with the cured film of 6 characterized by the above-mentioned.

8. It has the process of hardening by heating the liquid curable resin composition in any one of 1-5, or irradiating a radiation, The manufacturing method of the cured film characterized by the above-mentioned.

9. Applying the liquid curable resin composition in any one of 1-5 on the base material or the layer formed on the base material, and form a coating film,

Forming two or more layers by evaporating a solvent from this one coating film, The base material and the manufacturing method of the laminated body which has a multilayered structure on it.

10. Each layer of the two or more layers is a layer in which metal oxide particles are present at high density, or a layer substantially free of metal oxide particles, and at least one layer is a layer in which metal oxide particles are present at high density. The manufacturing method of the laminated body of Claim.

11. Said two or more layers are two layers, The manufacturing method of the laminated body of 10 characterized by the above-mentioned.

12. The method for producing a laminate according to any one of 9 to 11, wherein the two or more layers are further cured by heating.

13. The laminated body is an optical component, The manufacturing method of the laminated body in any one of 9-12 characterized by the above-mentioned.

14. The laminated body is an antireflection film, The manufacturing method of the laminated body in any one of 9-12 characterized by the above-mentioned.

15. The laminate is an antireflection film in which at least a high refractive index layer and a low refractive index layer are laminated in this order on a side close to the base material, and the two layers described in 11 consist of a high refractive index layer and a low refractive index layer. The manufacturing method of the laminated body of 11 to do.

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

The refractive index at 589 nm of a high refractive index layer is 1.50-2.20, and is higher than the refractive index of a low refractive index layer, The manufacturing method of the laminated body of 15 characterized by the above-mentioned.

17. The laminate is an antireflection film in which at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order on a side close to the base material, and the two layers described in 11 are the high refractive index layer and the low refractive index layer. The manufacturing method of the laminated body of 11 characterized by the above-mentioned.

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

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

The refractive index at 589 nm of a high refractive index layer is 1.51-2.20, and is higher than the refractive index of a medium refractive index layer, The manufacturing method of the laminated body of 17 characterized by the above-mentioned.

19. The method for producing a laminate according to any one of 15 to 18, further comprising forming a hard coat layer and / or an antistatic layer on the substrate.

20. The laminated body manufactured by the manufacturing method of the laminated body in any one of 9-19.

Since the liquid curable resin composition of this invention can form the cured film which has multilayered structures, such as a high refractive index layer and a low refractive index layer, from one coating film, the manufacturing process of a cured film can be simplified.

Since the liquid curable resin composition of this invention can form two or more layers from one coating film obtained by apply | coating a composition, the manufacturing process of the laminated body which has a multilayered structure can be simplified.

Moreover, the scratch resistance of a cured film or a laminated body can be improved by localizing metal oxide particle.

The liquid curable resin composition of the present invention can be advantageously used for the formation of optical materials such as antireflection films, selective transmission membrane filters, and the like, and materials for paints and weathering films for substrates requiring weather resistance using a high fluorine content. It can be preferably used as a material for coating, a material for coating, and the like. In addition, the cured film is excellent in adhesion to the substrate, high scratch resistance and can impart a good antireflection effect. Therefore, the cured film or laminated body of this invention is very useful as an antireflection film, and the visibility thereof can be improved by applying to various display apparatuses.

It is a figure for demonstrating "two or more layers formed from one coating film."

1B is a view for explaining "two or more layers formed from one coating film".

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

It is a figure for demonstrating "two or more layers formed from one coating film."

1E is a view for explaining "two or more layers formed from one coating film".

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

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

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

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

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

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

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

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

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

11 is an electron micrograph showing the concept of each state of two-layer separation, unseparation (partial aggregation), and uniform structure.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in detail by dividing it into a liquid curable resin composition, a cured film, and a laminate.

1. Liquid curable resin composition

The liquid curable resin composition of this invention contains the following components (A)-(F).

(A) Fluorine-containing polymer having a hydroxyl group in the molecule

(B) One or two or more metal oxide particles having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more (hereinafter, referred to as "(B) metal oxide particles").

(C) One or two or more solvents having high solubility to the fluorine-containing polymer having a hydroxyl group in the (A) molecule (hereinafter referred to as "(C) fast volatile solvent")

(D) One or two or more solvents having high dispersion stability to the metal oxide particles (B) and compatible with the (C) fast-volatile solvent (hereinafter referred to as "(D) delayed volatile solvent").

(E) curable compound

(F) thermal acid generator

Hereinafter, these components are demonstrated, respectively.

(A) Fluorine-containing polymer having a hydroxyl group in the molecule

A fluorine-containing polymer is a polymer which has a carbon-fluorine bond in a molecule | numerator, It is preferable that the fluorine content is 30 mass% or more, and it is preferable that the number average molecular weight by polystyrene conversion obtained by gel permeation chromatography is 5000 or more. Here, fluorine content is the value measured by the alizarin complexon method, and a number average molecular weight is the value when tetrahydrofuran was used as a developing solvent.

As an example of the fluorine-containing polymer used by this invention, it is a fluorine-containing polymer (henceforth "hydroxyl group-containing fluorine-containing polymer") which has a hydroxyl group in a molecule | numerator. As a preferable example of a hydroxyl-containing fluorine-containing polymer, what has a polysiloxane segment in the main chain which contains 10 mol%-50 mol% of structural units derived from the monomer containing a hydroxyl group is mentioned. This hydroxyl group containing fluorine-containing polymer is an olefin type polymer which has the polysiloxane segment represented by following General formula (1) in a principal chain, and it is preferable that the ratio of the said polysiloxane segment in a fluorine-containing polymer is 0.1-20 mol% normally.

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

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

The hydroxyl group-containing fluoropolymer includes (a) a fluorine-containing olefin compound (hereinafter referred to as "(a) component") and (b) a monomer compound containing a hydroxyl group copolymerizable with the component (a) (hereinafter, "(b) Components ") and (c) azo group-containing polysiloxane compounds (hereinafter referred to as" (c) component ") and (d) reactive emulsifiers (hereinafter referred to as" (d) component ") as needed, and / or (e) It can obtain by making monomer compounds other than the (b) component copolymerizable with the said (a) component react.

Examples of the fluorine-containing olefin compound as the component (a) include compounds having at least one polymerizable unsaturated double bond and at least one fluorine atom. Specific examples thereof include (1) tetrafluoroethylene and hexafluoro. Fluoroolefins such as propylene and 3,3,3-trifluoropropylene; (2) perfluoro (alkylvinylether) s or perfluoro (alkoxyalkylvinylether) s; (3) Perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether), etc. Perfluoro (alkyl vinyl ether) s; (4) perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether); And the like. These compounds can be used alone or in combination of two or more. Among the above, hexafluoropropylene, perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) is particularly preferable, and a combination thereof is more preferable.

As a monomer compound containing the hydroxyl group which is (b) component, it is (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, for example. Hydroxyl group-containing vinyl ethers such as 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether; (2) hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether; (3) allyl alcohol; (4) hydroxyethyl (meth) acrylic acid ester; And the like. These compounds can be used alone or in combination of two or more. Preferably they are hydroxyl-containing alkyl vinyl ethers.

As the azo group-containing polysiloxane compound as the component (c), a compound containing azo groups readily thermally decomposed as -N = N- and having a polysiloxane segment represented by the above formula (1), for example, It can manufacture by the method of Unexamined-Japanese-Patent No. 6-93100. As a specific example of (c) component, the compound represented by following General formula (2) is mentioned.

In formula, y is 10-500 and z is 1-50.

Preferred combinations of the component (a), the component (b) and the component (c) include, for example, (1) a fluoroolefin / hydroxyl-containing alkyl vinyl ether / polydimethylsiloxane unit, (2) fluorool reffin / perfluoro Furnace (alkylvinylether) / hydroxyl group-containing alkylvinylether / polydimethylsiloxane unit, (3) fluoroolefin / perfluoro (alkoxyalkylvinylether) / hydroxyl group-containing alkylvinylether / polydimethylsiloxane unit, (4) fluoro Low olefin / perfluoro (alkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether / polydimethylsiloxane unit, (5) fluoro olefin / perfluoro (alkoxy alkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether / polydimethylsiloxane unit to be.

In the hydroxyl-containing fluorine-containing polymer, the structural unit derived from the component (a) is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, particularly preferably 30 to 60 mol%. When the ratio of the structural unit derived from (a) component is less than 20 mol%, the fluorine content in the fluorine-containing polymer obtained will become too small, and the hardened | cured material of the obtained liquid curable resin composition does not become low enough in refractive index. On the other hand, when the ratio of the structural unit derived from (a) component exceeds 70 mol%, the solubility to the organic solvent of the fluoropolymer obtained will fall remarkably, and the liquid-curable resin composition obtained will have transparency and adhesiveness to a base material Becomes smaller.

In the hydroxyl-containing fluorine-containing polymer, the structural unit derived from the component (b) is preferably 10 to 50 mol%. More preferably, the lower limit is 13 mol% or more, more preferably 20 mol% or more, 21 mol% or more, still more preferably an upper limit of 45 mol% or less, and still more preferably 35 mol% or less. . By constructing a liquid curable resin composition using a fluorine-containing polymer containing a predetermined amount of such a component (b), good scratch resistance and dust removal property can be realized in the cured product thereof. On the other hand, when the ratio of the structural unit derived from the component (b) is less than 10 mol%, the fluorine-containing polymer has poor solubility in an organic solvent, and when it exceeds 50 mol%, the cured product by the liquid curable resin composition is transparent. And low reflectance optical properties deteriorate.

Although the azo group containing polysiloxane compound which is (c) component is itself a thermal radical generating agent, and acts as a polymerization initiator in the polymerization reaction for obtaining a fluorine-containing polymer, you may use another radical initiator together. The proportion of the structural unit derived from component (c) in the fluorine-containing polymer is preferably 0.1 to 20 mol%, more preferably 0.1 to 15 mol%, particularly preferably 0.1 to the polysiloxane segment represented by the formula (1). To 10 mol%, particularly preferably 0.1 to 5 mol%. When the ratio of the polysiloxane segment represented by General formula (1) exceeds 20 mol%, the hydroxyl-containing fluorine-containing polymer obtained becomes inferior in transparency, and when used as a coating agent, it is easy to produce cratering etc. at the time of application | coating. Lose.

It is preferable to use a reactive emulsifier as a monomer component other than the said (a)-(c) component as (d) component. By using this (d) component, when using a hydroxyl-containing fluorine-containing polymer as a coating agent, favorable applicability | paintability and spreadability can be obtained. Especially as this reactive emulsifier, it is preferable to use a nonionic reactive emulsifier. As a specific example of a nonionic reactive emulsifier, the compound represented by following formula (3) or (4) is mentioned, for example.

In formula, n is 1-20, m and s represent the repeating unit number, m is 0-4, and s is 3-50.

In the formula, m and s are the same as in the general formula (3). R <^3> is an alkyl group which may be linear or branched, Preferably it is a C1-C40 alkyl group.

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

As monomer compounds other than the (b) component copolymerizable with (a) component of (e) component, it is (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, Alkyl such as isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether Vinyl ether or cycloalkyl vinyl ether; (2) carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, and vinyl stearate; (3) methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylic acid esters, such as (meth) acrylate and 2- (n-propoxy) ethyl (meth) acrylate; (4) It is carboxyl group-containing monomer compounds, such as (meth) acrylic acid, crotonic acid, a maleic acid, fumaric acid, and itaconic acid, and the thing which does not contain a hydroxyl group is mentioned. Preferably it is alkyl vinyl ether.

In the hydroxyl-containing fluorine-containing polymer, the proportion of the structural unit derived from the component (e) is preferably 0 to 70 mol%, more preferably 5 to 35 mol%. When this ratio exceeds 70 mol%, since the liquid curable resin composition obtained becomes adhesive, handling becomes difficult, and when used as a coating agent, moisture resistance falls.

Preferable combinations of (a) component, (b) component, (c) component, (d) component and (e) component in the case of containing (d) component are as follows.

(1) Fluoroolefin / hydroxyl group containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (2) Fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group containing vinyl ether / polydimethylsiloxane Unit / nonionic reactive emulsifier / alkylvinylether, (3) fluoroolefin / perfluoro (alkoxyalkylvinylether) / hydroxyl group-containing vinylether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkylvinylether, (4) Fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (5) fluoroolefin / perfluoro (alkoxy alkyl vinyl ether) / Hydroxyl group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether.

As a radical polymerization initiator which can be used together with (c) component, For example, (1) diacyl peroxides, such as acetyl peroxide and benzoyl peroxide; (2) ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; (3) hydroperoxides such as hydrogen peroxide, tert-butylhydroperoxide and cumene hydroperoxide; (4) dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide and dilauroyl peroxide; (5) peroxy esters such as tert-butyl peroxy acetate and tert-butyl peroxy pivalate; (6) azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; (7) persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; And the like.

As a specific example other than the said radical polymerization initiator, For example, perfluoro ethyl iodide, perfluoro propyl iodide, perfluoro butyl iodide, (perfluoro butyl) ethyl iodide, perfluoro Hexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluoro Decyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide Dide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluor Rho-9-methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoroprone iodide, 1H, 1H, 5 H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane And iodine-containing fluorine compounds such as dodecafluoro-1,6-diiodohexane. The iodine-containing fluorine compound may be used alone or in combination with the organic peroxide, azo compound or persulfate.

As a polymerization mode for producing a hydroxyl group-containing fluorine-containing polymer, any of emulsion polymerization, suspension polymerization, block polymerization or solution polymerization using a radical polymerization initiator can be used, and also as a polymerization operation, it may be batchwise, semi-continuous or continuous. A suitable thing can be selected from operation of a formula, etc.

It is preferable to perform the polymerization reaction for obtaining a hydroxyl-containing fluorine-containing polymer in the solvent system using a solvent. Here, as a preferable organic solvent, For example, (1) Ester, such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, a cellosolve; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; (3) cyclic ethers such as tetrahydrofuran and dioxane; (4) amides such as N, N-dimethylformamide and N, N-dimethylacetamide; (5) aromatic hydrocarbons such as toluene and xylene; And the like. Alcohol, aliphatic hydrocarbons, etc. can also be mixed and used as needed.

The hydroxyl group-containing fluorine-containing polymer obtained as described above may sometimes use the reaction solution obtained by the polymerization reaction as it is as the liquid curable resin composition, but it is also possible to perform appropriate post-treatment with respect to the polymerization reaction solution. As this post-treatment, for example, a general reprecipitation treatment typified by a purification method in which the polymerization reaction solution is added dropwise to the insoluble solvent of the hydroxyl group-containing fluorine-containing polymer made of alcohol or the like to solidify the hydroxyl group-containing fluorine-containing polymer can be performed. The solution of the hydroxyl-containing fluorine-containing polymer can be manufactured by dissolving the solid copolymer obtained in the solvent next. Moreover, what removed the residual monomer from the polymerization reaction solution can also be used as it is as a solution of a hydroxyl-containing fluoropolymer.

The compounding ratio of the (A) hydroxyl-containing fluorine-containing polymer in 100 mass% of solid content of the liquid curable resin composition of this invention is 5-70 mass% normally, Preferably it is 10-50 mass%, and transparency of a cured film becomes favorable.

(B) metal oxide particles

The (B) metal oxide particles used in the present invention are metal oxide particles having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more (wavelength 550 nm). When the number average particle diameter exceeds 100 nm, it may be difficult to uniformly disperse the metal oxide particles. In addition, the metal oxide particles tend to settle, and the storage stability may be insufficient. Moreover, transparency of the cured film obtained may fall, or turbidity (haze value) may rise.

As for a number average particle diameter, 10-80 nm is more preferable, and 20-50 nm is further more preferable.

In addition, "number average particle diameter" is the number average particle diameter measured by the electron microscopy method, and when a metal oxide particle is aggregated, it is a primary particle diameter, and when a metal oxide particle is not spherical (for example, acicular ATO etc.), It is the average of long diameter (length) and short diameter (length). In addition, when particle shape was a rod shape (referring to a shape whose aspect ratio exceeds 1 and 10 or less), the short diameter was made into the particle size.

As the metal oxide particles, preferably titanium oxide, zirconium oxide (zirconia), antimony-containing tin oxide, tin-containing indium oxide, aluminum oxide (alumina), cerium oxide, zinc oxide, aluminum-containing zinc oxide, tin oxide, and antimony-containing oxide Particles composed mainly of one or two or more metal oxides selected from zinc and indium-containing zinc oxide and phosphorus-containing tin oxide can be used.

Here, the metal oxide particle which has a multilayered structure which coat | covered metal oxide particle with the said 1 type, or 2 or more types of metal oxides other than the said metal oxide can also be used. Specific examples of the metal oxide particles having a multilayer structure include silica coated titanium oxide particles, alumina coated titanium oxide particles, zirconia coated titanium oxide particles, alumina and zirconia coated titanium oxide particles. Among these metal oxide particles, particles mainly composed of titanium oxide or alumina and zirconia coated titanium oxide particles are particularly preferable.

By using the metal oxide particle which has a multilayered structure, the photocatalytic activity of titanium oxide can be suppressed and decomposition | disassembly of hardened | cured material can be suppressed. As a result, a cured film with high refractive index and excellent light resistance can be obtained.

In addition, antistatic properties can be imparted to the cured film by using antimony-containing tin oxide particles (ATO) or the like. In this case, as will be described later, since the ATO particles are localized, effective antistatic properties and good transparency can be achieved at a smaller amount of particle addition.

As the particle containing titanium oxide as a main component, known particles can be used, and the shape thereof may also be hollow particles, porous particles, core-shell particles, or the like. Moreover, it is not limited to spherical form, It may be rod-shaped (referring to the aspect ratio exceeding 1 and 10 or less), or an amorphous particle, and rod shape is preferable. It is preferable that the number average particle diameter calculated | required by the electron microscopy exists in the range of 1-100 nm.

In addition, the dispersion medium is preferably water or an organic solvent. As an organic solvent, Alcohol, such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Organic solvents, such as ethers, such as tetrahydrofuran and a 1, 4- dioxane, are mentioned, Among these, alcohol and ketones are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

As a commercial item of the particle which has a titanium oxide as a main component, the product of Teika Co., Ltd. product, CI Kasei Co., etc. is mentioned, for example.

The compounding ratio of (B) metal oxide particle with respect to 100 mass% of solid content of a liquid curable resin composition is 10-90 mass% normally, Preferably it is 20-80 mass%.

(C) fast volatile solvent

The (C) fast volatile solvent contained in the liquid curable resin composition of this invention is a 1 type, or 2 or more types of solvent with high solubility to the said (A) hydroxyl-containing fluorine-containing polymer. Here, the solubility with respect to a hydroxyl-containing fluorine-containing polymer means that (A) hydroxyl-containing fluoropolymer is added to each solvent so that it may become 50 mass%, and when it is stirred at room temperature for 8 hours, it becomes a visually uniform solution. . In addition, the relative evaporation rate of the (C) rapid volatile solvent needs to be larger than the relative evaporation rate of the (D) delayed volatile solvent mentioned later. Here, the "relative evaporation rate" refers to a relative value of the evaporation rate based on the time taken for butyl acetate to evaporate 90 mass%, and more specifically, in the technical literature of ORGANIC SOLVENTS Physical Properties and methods of purification 4th ed. (Interscience Publishers, Inc. 1986 page 62). Moreover, it is preferable that (C) fast volatile solvent is low in dispersion stability with respect to the said (B) metal oxide particle. (C) The fast volatile solvent is a liquid phase of the present invention because the relative evaporation rate is higher than (D), (A) the solubility in the hydroxyl group-containing fluorine-containing polymer, and (B) the dispersion stability to the metal oxide particles is low. In the process of apply | coating curable resin composition to a base material, and evaporating a solvent (C) and (D), (B) metal oxide particle can be localized.

In the present invention, the solvent corresponding to the (C) fast volatile solvent is a solvent having a relative evaporation rate of approximately 1.7 or more, specifically methyl ethyl ketone (MEK; relative evaporation rate 3.8), isopropanol (IPA; 1.7), methyl isobutyl Ketone (MIBK; relative evaporation rate 1.6), methyl amyl ketone (MAK; 0.3), acetone, methyl propyl ketone and the like.

(D) delayed volatile solvent

The (D) delayed volatile solvent contained in the liquid curable resin composition of this invention is a 1 type, or 2 or more types of solvent with high dispersion stability with respect to the said (B) metal oxide particle. Here, (B) high dispersion stability with respect to metal oxide particle means that (B) metal oxide particle dispersion liquid is immersed in glass plate, and (B) metal oxide particle adheres to a glass wall, (B) metal oxide particle adheres When immersed glass plate is immersed in each solvent, it means that (B) metal oxide particle is uniformly disperse | distributed visually in the said solvent. Moreover, it is preferable that (D) delayed volatile solvent is low solubility with respect to the said (A) hydroxyl-containing fluorine-containing polymer.

In the present invention, the solvent corresponding to the (D) delayed volatile solvent is a solvent having a relative evaporation rate of approximately 1.7 or less, specifically methanol (relative evaporation rate 2.1), isopropanol (IPA; 1.7), n-butanol (n-BuOH). 0.5), tert-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl cellosolve, propyl cellosolve, butyl cellosolve and the like.

The (C) fast volatile solvent and / or (D) delayed volatile solvent used by this invention can use the solvent normally used for manufacture of said (A) hydroxyl-containing fluorine-containing polymer normally.

The (C) fast volatile solvent and (D) delayed volatile solvent used in the present invention need to be compatible. Compatibility should just be compatible with the grade which (C) fast volatile solvent and (D) delayed volatile solvent do not separate in the specific structure of the composition of this invention.

Here, whether the selected solvent corresponds to (C) a fast volatile solvent or (D) a delayed volatile solvent used in the present invention is relatively determined among a plurality of selected solvent types. In addition, isopropanol having a relative evaporation rate of 1.7 corresponds to any of (C) fast-volatile solvents and (D) delayed-volatile solvents, but is used only as (D) delayed-volatile solvents in combination with other (C) fast-volatile solvents. .

Moreover, in the liquid curable resin composition of this invention, a solvent can mix | blend solvents other than the said (C) fast-volatile solvent and (D) delayed volatile solvent for the purpose of improving the coating property of a composition, etc. . As a solvent mix | blended for this purpose, ketones, such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester, such as ethyl acetate and butyl acetate, are mentioned. Moreover, in the solution of the liquid curable resin composition of this invention, the solvent which cannot melt | dissolve a fluoropolymer, for example, poor solvents, such as water, alcohol, ether, can be used together in the range which does not precipitate a fluoropolymer. have. Thereby, the solution of the said fluorine-containing polymer may have favorable storage property and preferable applicability | paintability in some cases. As such a poor solvent, ethyl alcohol, isopropyl alcohol, tert- butyl alcohol, ethyl cellosolve, butyl cellosolve, etc. are mentioned.

The total amount of the solvent (C) and the solvent (D) is usually 300 to 5000 parts by mass, preferably 100 parts by mass of the component other than the solvent (including the component (C) and the component (D)) in the liquid curable resin composition. Preferably from 300 to 4000 parts by mass, more preferably from 300 to 3000 parts by mass. The compounding ratio (mass ratio) of a solvent (C) and a solvent (D) can be arbitrarily set in the range of 1: 99-99: 1.

(E) curable compound

(E) A curable compound is a component which superposes | polymerizes by heating etc. and gives curability to this composition.

Examples of the curable compound include various amino compounds, various hydroxyl group-containing compounds such as pentaerythritol, polyphenols, glycols, and the like.

The amino compound used as the curable compound is a compound containing two or more amino groups which can react with hydroxyl groups in the hydroxyl group-containing fluorine-containing polymer, for example, hydroxyalkylamino groups and alkoxyalkylamino groups in total. Specific examples thereof include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples thereof include melamine, alkylated melamine, methylolmelamine, alkoxylated methylmelamine, and the like. It is preferable to have two or more of either or both of the alkoxylated methyl groups in total. Specifically, methylolated melamine, alkoxylated methylmelamine or derivatives thereof obtained by reacting melamine and formaldehyde under basic conditions are preferable, and in particular, in terms of obtaining good storage stability in the liquid curable resin composition, and good reactivity, Preference is given to alkoxylated methylmelamine. There is no restriction | limiting in particular in the methylolation melamine and the alkoxylation methylmelamine used as a curable compound, For example, the various kinds obtained by the method described in the literature [Plastic material course [8] urea melamine resin (Nggan High School new injection)] The use of dendritic materials is also possible.

Examples of the urea compound include polymethylolated urea and derivatives thereof, alkoxylated methyl urea, methylolated ureon having a uron ring, alkoxylated methyluron and the like. Moreover, also about compounds, such as a urea derivative, the use of the various dendritic materials described in the said document is possible.

The compounding ratio of the curable compound contained in 100 mass% of solid content of a liquid curable resin composition is 3 to 70 mass% normally, Preferably it is 3 to 50 mass%, More preferably, it is 5 to 30 mass%. If the amount of the curable compound is too small, the durability of the thin film formed by the resulting liquid curable resin composition may be insufficient. If the amount is out of the range of 3 to 70 mass%, gelation is avoided in the reaction with the fluorine-containing polymer. It is difficult, and hardened | cured material may become weak.

The reaction of the (A) hydroxyl group-containing fluorine-containing polymer with the (E) curable compound includes, for example, adding a curable compound to a solution of an organic solvent in which the hydroxyl group-containing fluorine-containing polymer is dissolved, and reacting the reaction system by appropriate time heating and stirring. It can carry out while making it uniform. The heating temperature for this reaction is preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 120 ° C. When this heating temperature is less than 30 degreeC, reaction progress is very slow and when it exceeds 150 degreeC, the crosslinking reaction by reaction of the methylol group and alkoxylated methyl groups in a curable compound will generate | occur | produce a gel in addition to the target reaction. Because it is not desirable. The progress of the reaction can be quantitatively confirmed by the method of quantifying the methylol group or the alkoxylated methyl group by infrared spectroscopic analysis or the like, or by recovering the dissolved polymer by reprecipitation method and measuring the increase amount thereof.

Moreover, it is preferable to use the same thing as the organic solvent used for manufacture of an organic solvent, for example, a hydroxyl-containing fluorine-containing polymer, for reaction of (A) hydroxyl-containing fluoropolymer and (E) curable compound. In this invention, the reaction solution by the hydroxyl-containing fluoropolymer and curable compound obtained in this way may be used as a solution of a liquid curable resin composition as it is, and may be used after mix | blending various additives as needed.

(F) thermal acid generator

The thermal acid generator which can be mix | blended with the liquid curable resin composition of this invention is a substance which can improve the heating conditions to be milder when the coating film etc. of the said liquid curable resin composition are heated and hardened | cured. As specific examples of the thermal acid generator, for example, various aliphatic carboxylic acids and salts thereof, various aliphatic carboxylic acids such as citric acid, acetic acid and maleic acid, salts thereof, various aromatic carboxylic acids such as benzoic acid and phthalic acid, salts thereof and alkylbenzene sulfonic acid And ammonium salts thereof, various metal salts, and phosphoric acid esters of phosphoric acid and organic acids.

The use ratio of the said thermal acid generator contained in 100 mass% of solid content of a liquid curable resin composition is 0.01-10 mass% normally, Preferably it is 0.1-5 mass%. If this ratio is too large, it is not preferable because the storage stability of the liquid curable resin composition becomes poor.

(G) additive

The liquid curable resin composition of the present invention includes, for example, various polymers, monomers, pigments, dyes, etc. having a hydroxyl group, for the purpose of improving the coating properties of the liquid curable resin composition, the physical properties of the thin film after curing, and providing photosensitivity to a coating film. And various additives such as stabilizers such as colorants, antioxidants, ultraviolet absorbers, photosensitive acid generators, surfactants, and polymerization inhibitors. In particular, it is preferable to add a photoacid generator for the purpose of improving the hardness and durability of the cured film to be formed, and in particular, it is used to select and dissolve uniformly in the solution without lowering the transparency after curing of the liquid curable resin composition. It is preferable.

(1) a polymer having a hydroxyl group

As a polymer which has a hydroxyl group which can be mix | blended with the liquid curable resin composition of this invention, it is known as a polymer obtained by copolymerizing hydroxyl-containing copolymerizable monomers, such as hydroxyethyl (meth) acrylate, a novolak resin, or a resol resin, for example. The resin etc. which have the phenol skeleton which were made are mentioned.

(2) coloring agents such as pigments or dyes

As a coloring agent which can be mix | blended with the liquid curable resin composition of this invention, For example, (1) extender pigments, such as alumina bag, clay, barium carbonate, barium sulfate; (2) inorganic pigments such as zinc oxide, lead white, sulfur lead, briquette, ultramarine blue, royal blue, titanium oxide, zinc chromate, iron group, carbon black and the like; (3) organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue and phthalocyanine green; (4) basic dyes such as magenta and rhodamine; (5) direct dyes such as direct scarlet and direct orange; (6) acid dyes such as loselin and methyl yellow; And the like.

(3) stabilizers such as anti-aging agents and ultraviolet absorbers

A well-known thing can be used as an antioxidant and ultraviolet absorber which can be mix | blended with the liquid curable resin composition of this invention.

Specific examples of the anti-aging agent include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone and n-butyl. Phenol, phenol, hydroquinone monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3- Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole and the like.

Moreover, as a specific example of a ultraviolet absorber, benzophenone type ultraviolet absorbers, such as the salicylic acid type ultraviolet absorber represented by phenyl salicylate, dihydroxy benzophenone, and 2-hydroxy-4- methoxy benzophenone, benzotria, for example. The ultraviolet absorber used as various plastic additives, such as a sol type ultraviolet absorber and a cyanoacrylate type ultraviolet absorber, can be used.

(4) photosensitive acid generator

The photosensitive acid generator which can be blended into the liquid curable resin composition of the present invention imparts photosensitivity to the coating film of the liquid curable resin composition, and makes it possible to photocure the coating film by, for example, irradiating radiation such as light. It is a substance. As this photosensitive acid generator, it is (1) various onium salts, such as an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, a pyridinium salt; (2) sulfone compounds such as β-ketoester and β-sulfonylsulfone and α-diazo compounds thereof; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfonimide compounds represented by the following formula (5); (5) diazomethane compounds represented by the following formula (6); And the like.

In formula, X represents bivalent groups, such as an alkylene group, an arylene group, and an alkoxylene group, and R <^4> represents monovalent groups, such as an alkyl group, an aryl group, a halogen substituted alkyl group, and a halogen substituted aryl group.

In formula, R <^5> and R <^6> may be same or different from each other, and represents monovalent groups, such as an alkyl group, an aryl group, a halogen substituted alkyl group, and a halogen substituted aryl group.

A photosensitive acid generator may be used individually or in combination of 2 or more types, and may be used together with the said thermal acid generator. The use ratio of the photosensitive acid generator in 100 mass parts of solid content of a liquid curable resin composition becomes like this. Preferably it is 0-20 mass parts, More preferably, it is 0.1-10 mass parts. If this ratio is too large, the strength of the cured film is inferior and transparency is also not preferable.

(5) surfactant

Surfactant can be mix | blended with the liquid curable resin composition of this invention for the purpose of improving the applicability | paintability of the said liquid curable resin composition. A well-known thing can be used as this surfactant, For example, various anionic surfactant, cationic surfactant, and nonionic surfactant can be used, but especially a cured film has the outstanding strength, and also the favorable optical characteristic In order to make it have, it is preferable to use a cationic surfactant. Moreover, it is preferable that it is a quaternary ammonium salt, and especially a quaternary polyether ammonium salt is especially preferable at the point which further improves dust removal property. As cationic surfactant which is a quaternary polyether ammonium salt, Adekachol CC-15, CC-36, CC-42, etc. by Asahi Denka Kogyo Co., Ltd. are mentioned. The use ratio of surfactant is preferably 5 mass parts or less with respect to 100 mass parts of solid content of a liquid curable resin composition.

(6) polymerization inhibitor

As a thermal polymerization inhibitor which can be mix | blended with the liquid curable resin composition of this invention, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert- butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyl Oxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane etc. are mentioned. This thermal polymerization inhibitor is preferably used in an amount of 5 parts by mass or less with respect to 100 parts by mass of the solid content of the liquid curable resin composition.

(7) Solvents other than (C) and (D) component

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

2. Cured film

The cured film of this invention is obtained by hardening | curing the liquid curable resin composition of the said invention, and has a multilayer structure of two or more layers, It is characterized by the above-mentioned. In particular, it is preferable to have a two-layer or more layer structure which consists of one or more layers in which the said (B) metal oxide particle exists in high density, and one or less layers in which the said (B) metal oxide particle does not exist substantially.

In addition, since the laminated body mentioned later contains a cured film, description of a cured film is applicable to description of a laminated body, and description of a laminated body is applicable to description of a cured film.

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

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

Moreover, hardening can also be carried out by irradiating a radiation by adding the photo-acid generator mentioned above. In this case, although it can harden | cure under the light irradiation conditions of 0.001-10 J / cm <^2> using an ultraviolet irradiation device (metal halogen lamp, a high pressure mercury lamp, etc.), irradiation conditions are not limited to this, for example. 0.01-5 J / cm <^2> is more preferable, and 0.1-3 J / cm <^2> is further more preferable.

In addition, the hardening degree of a cured film is quantitatively determined by infrared spectroscopic analysis of the quantity of the methylol group or the alkoxylated methyl group of a melamine compound, or the gelation rate using a Soxhlet extractor, for example, when a melamine compound is used as a curable compound. You can check it.

After apply | coating a liquid curable resin composition, (B) metal oxide particle is localized on the application | coating base side (near boundary with an adjacent layer) or the opposite side in the process of evaporating the solvent (C) and solvent (D) in a composition. Therefore, since (B) metal oxide particle exists in high density near one interface of a cured film, and (B) metal oxide particle does not exist substantially in the vicinity of the other interface of a cured film, the low refractive index resin layer is formed. . Therefore, the cured film which has a multilayered structure of two or more layers substantially is obtained by hardening | curing one coating film which consists of liquid curable resin composition. Each layer formed by these separation can be confirmed by observing the cross section of the obtained film | membrane with an electron microscope, for example. (B) A layer in which metal oxide particles are present at a high density is a concept indicating a portion in which metal oxide particles are collected, and is a layer substantially composed of metal oxide particles as a main component. There is a case. On the other hand, the layer in which the metal oxide particles do not substantially exist is a concept indicating a portion in which the metal oxide particles do not exist, but may be included slightly in a range that does not impair the effects of the present invention. This layer is a layer comprised substantially from components other than metal oxide particles, such as hardened | cured material of (A) component and (E) component. In most cases, the cured film of the present invention has a two-layer structure in which a layer in which metal oxide particles are present at a high density and a layer in which the metal oxide particles are not substantially present are each formed of a continuous layer. When a polyethylene terephthalate (PET) resin (including a PET resin having an easy adhesion layer) is used as a substrate, a layer which is usually a substrate, a layer in which metal oxide particles are present at a high density, and a metal oxide particle Are formed adjacent to each other in this order. The layer structure of two or more layers will be described later in more detail.

It is preferable that refractive index changes 0.05-0.8 in the film thickness direction, and, as for the cured film obtained, it is more preferable that it changes 0.1-0.6. It is also desirable that the refractive index change have a major change near the boundary of the substantially two-layer structure.

The change degree of refractive index can be adjusted with content, a kind of (B) metal oxide particle, content, a composition of (A) fluorine-containing polymer, content, a kind, etc. of (E) curable compound.

In addition, the refractive index in the low refractive index part of a cured film is 1.3-1.5, for example, and the refractive index in the high refractive index part is 1.6-2.2.

3. Laminate

In the manufacturing method of the laminated body of this invention, when a solvent is evaporated from one coating film obtained by apply | coating the said liquid curable resin composition on the base material or the layer formed on the base material (Hereinafter, evaporating a solvent is called "drying." Also forms two or more layers). In addition, after drying, the solvent may not be completely eliminated, and a solvent may remain in the range from which the characteristic as a cured film is obtained. In addition, in this invention, formation of two or more layers from one coating film can be performed twice or more.

The specific liquid curable resin composition is applied in a conventional manner, and then dried to separate into two or more layers. Here, two or more layers may be two or more layers containing both "a layer in which a metal oxide particle exists in high density", and a "layer in which a metal oxide particle does not exist substantially", and "the metal oxide particle exists in high density. It may be two or more layers which consist only of "layer to say."

Hereinafter, referring to the drawings, "each layer of two or more layers is a layer in which metal oxide particles are present at high density, or a layer in which metal oxide particles are substantially not present, and at least one layer is a layer in which metal oxide particles are present at high density." It demonstrates. FIG. 1A shows the case where two or more layers are two layers of "layer (1) in which metal oxide particles are present at high density" and "layer (3) in which metal oxide particles do not substantially exist". 1B shows the case where two or more layers are two layers of "layers (1) and (1a) in which metal oxide particles are present at high density". FIG. 1C shows the case where two or more layers are three layers of "layers (1) and (1a) in which metal oxide particles are present at high density" and "layer (3) in which metal oxide particles are substantially absent." FIG. 1D shows a case where two or more layers are three layers of "layers (1) and (1a) in which metal oxide particles are present at high density" and "layer (3) in which metal oxide particles are substantially absent." FIG. 1E shows the case where two or more layers are two layers of "layer (1b) in which metal oxide particles are present at high density" and "layer (3) in which metal oxide particles do not substantially exist".

When the liquid curable resin composition contains two or more kinds of metal oxide particles, two or more kinds of "layers in which metal oxide particles exist at high density" may be formed as shown in FIGS. 1B, 1C, and 1D.

In addition, the "metal oxide particle" of the "layer in which metal oxide particle exists in high density" means 1 or more types, ie, 1 or 2 or more types of "metal oxide particle." When the liquid curable resin composition contains two or more kinds of metal oxide particles, the "layer in which the metal oxide particles are present at high density" may be composed of two or more kinds of metal oxide particles (for example, FIG. 1E). In FIG. 1E, the "layer (1b) in which metal oxide particles exist at high density" 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 into the "layer (3) in which the metal oxide particles do not substantially exist," but this protruding portion is also "metal oxide." Layer (1b) in which particles are present at high density ”.

In addition, in FIG. 1A-1E, although the metal oxide particle does not exist normally in the "layer (3) which a metal oxide particle does not exist substantially", it may be included in the range which does not impair the effect of this invention. In addition, "layers (1), (1a), and (1b) in which metal oxide particles are present at high density" may also contain other materials other than metal oxide particles.

As a coating method of a liquid curable resin composition, a well-known coating method can be used, In particular, various methods, such as an immersion method, a coating method, and a printing method, can be applied.

Drying is normally performed for about 1 to 60 minutes by heating at about 100 degreeC from room temperature.

Preferably these two or more layers are cured by heating. Specific curing conditions will be described later.

In this invention, a liquid curable resin composition is apply | coated to various base materials in solution form, and the obtained coating film can be dried / cured, and a laminated body can be obtained. For example, when the substrate is a transparent substrate, an excellent antireflection film is formed by providing a low refractive index layer on the outermost layer.

The specific structure of the anti-reflection film is a laminate of a substrate and a low refractive index film, or a substrate, a high refractive index film, and a low refractive film in this order. In addition, another layer may be interposed between the substrate, the high refractive film, and the low refractive film. For example, layers, such as a combination of a hard coating layer, an antistatic layer, a medium refractive index layer, a low refractive index layer, and a high refractive index layer, can be provided.

2 shows an antireflection film in which a high refractive index layer 40 and a low refractive index layer 50 are laminated in this order on the substrate 10.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles.

According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

FIG. 3 shows an antireflection film in which a hard coating layer 20, an antistatic layer 30, a high refractive index layer 40 and a low refractive index layer 50 are laminated on this substrate 10 in this order.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles.

According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

4 shows an antireflection film in which an antistatic layer 30, a hard coating layer 20, a high refractive index layer 40 and a low refractive index layer 50 are laminated on the substrate 10 in this order.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles.

According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

5 shows an antireflection film in which a hard coating layer 20, an antistatic layer 30, a medium refractive index layer 60, a high refractive index layer 40 and a low refractive index layer 50 are laminated in this order on a substrate 10. Indicates.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to layers in which metal oxide particles are present at a high density, or the medium refractive index layer 60 is formed in a layer where the metal oxide particles are present at a high density. The refractive index layer 40 corresponds to a layer substantially free of 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 from one coating film. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.

6 shows an antireflection in which an antistatic layer 30, a hard coating layer 20, a medium refractive index layer 60, a high refractive index layer 40 and a low refractive index layer 50 are laminated in this order on the substrate 10. It represents a film.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to layers in which metal oxide particles are present at a high density, or the medium refractive index layer 60 is formed in a layer where the metal oxide particles are present at a high density. The refractive index layer 40 corresponds to a layer substantially free of 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 from one coating film. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.

FIG. 7 shows an antireflection film in which a hard coating layer 20, a high refractive index layer 40 and a low refractive index layer 50 are laminated in this order on the substrate 10. As shown in FIG.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles.

According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

FIG. 8 shows an antireflection film in which a hard coating layer 20, a medium refractive index layer 60, a high refractive index layer 40 and a low refractive index layer 50 are laminated in this order on the substrate 10. As shown in FIG.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to layers in which metal oxide particles are present at a high density, or the medium refractive index layer 60 is formed in a layer where the metal oxide particles are present at a high density. The refractive index layer 40 corresponds to a layer substantially free of 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 from one coating film. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.

9 shows an antireflection film in which an antistatic layer 30, a high refractive index layer 40 and a low refractive index layer 50 are laminated in this order on the substrate 10. As shown in FIG.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles.

According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from one coating film.

FIG. 10 shows an antireflection film in which an antistatic layer 30, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on the substrate 10. As shown in FIG.

In this anti-reflection film, the high refractive index layer 40 corresponds to a layer having high density of metal oxide particles, and the low refractive index layer 50 corresponds to a layer substantially free of metal oxide particles. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to layers in which metal oxide particles are present at a high density, or the medium refractive index layer 60 is formed in a layer where the metal oxide particles are present at a high density. The refractive index layer 40 corresponds to a layer substantially free of 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 from one coating film. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from one coating film.

Moreover, when electroconductive particle, such as antimony containing tin oxide (ATO) particle | grains, is added as a metal oxide contained in the liquid curable resin composition used for the said antireflection film, the layer containing a high density of the metal oxide obtained will be antistatic property. It has a film. Therefore, for example, when a high refractive index layer or a medium refractive index layer is formed as a layer containing such an antistatic metal oxide at a high density, the high refractive index layer or the medium refractive index layer can be an antistatic film. . In this case, the formation of the antistatic film can be omitted.

Although the film thickness of the cured film of this invention in an antireflection film is 0.05 micrometer-50 micrometers, for example, it is not limited to this.

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

(1) mention

Although the kind of base material used for the antireflection film of this invention is not restrict | limited, As a specific example of a base material, For example, triacetyl cellulose, polyethylene terephthalate resin (Rumiler made by Toray Co., Ltd.), glass, polycarbonate Resins, acrylic resins, styryl resins, acrylate resins, norbornene-based resins (Aton manufactured by JSR Corporation, Zeonex manufactured by Nippon Xeon Corporation, etc.), methyl methacrylate / styrene copolymer resins, polyolefin resins, and the like. Various transparent plastic plates, films, etc. are mentioned. Preferably, they are triacetyl cellulose, polyethylene terephthalate resin (Rumiler made by Toray Corporation etc.), and norbornene-type resin (Aton made by JSR Corporation etc.).

(2) low refractive index layer

The low refractive index layer refers to a layer having a refractive index of 1.20 to 1.55 at a wavelength of 589 nm.

Although the material used for a low refractive index layer will not be specifically limited if the target characteristic is acquired, For example, the curable composition containing a fluorine-containing polymer, an acrylic monomer, a fluorine-containing acrylic monomer, an epoxy-group-containing compound, a fluorine-containing epoxy group-containing compound Hardened | cured material, such as these, can be mentioned. Moreover, in order to raise the intensity | strength of a low refractive index layer, you may mix | blend a silica fine particle etc ..

(3) high refractive index layer

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

In order to form a high refractive index layer, high refractive index inorganic particles, for example, metal oxide particles can be blended.

Specific examples of the metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, zinc oxide (ZnO) particles, antimony-containing zinc oxide, aluminum-containing zinc oxide particles, zirconia (ZrO ₂ ) particles, Titanium oxide (TiO ₂ ) particles, silica coated titanium oxide particles, Al ₂ O ₃ / ZrO ₂ coated TiO ₂ Particles, ceria (CeO ₂ ) particles, phosphorus-containing tin oxide (PTO) particles, and the like. Preferably, they are antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide particles, aluminum-containing zinc oxide particles, and Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles. These metal oxide particles can be used individually by 1 type or in combination of 2 or more types.

In addition, the high refractive index layer may have a function of a hard coating layer or an antistatic layer.

(4) medium refractive index layer

When combining layers having three or more refractive indices, a refractive index at a wavelength of 589 nm is 1.50 to 1.90, and a layer having a refractive index higher than the low refractive index layer and lower than the high refractive index layer is referred to as a medium refractive index layer. The refractive index of the medium refractive index layer is preferably 1.50 to 1.80, more preferably 1.50 to 1.75.

In order to form a medium refractive index layer, high refractive index inorganic particles, for example, metal oxide particles can be blended.

Specific examples of the metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, zinc oxide particles, antimony-containing zinc oxide, aluminum-containing zinc oxide particles, zirconia (ZrO ₂ ) particles, and titanium oxide particles. , Silica coated titanium oxide particles, Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles, ceria (CeO ₂ ) particles, and the like. Preferably, they are antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, aluminum-containing zinc oxide particles, zirconia (ZrO ₂ ) particles, and phosphorus-containing tin oxide (PTO) particles. These metal oxide particles can be used individually by 1 type or in combination of 2 or more types.

The medium refractive index layer may also have a function of a hard coating layer and an antistatic layer.

The combination of the low refractive index layer and the high refractive index layer can lower the reflectance, and the combination of the low refractive index layer, the high refractive index layer, and the medium refractive index layer can lower the reflectance and reduce the glare and blue tone (color). Can be.

(5) hard coating layer

It is composed of a hard coat layer such as a concrete example of SiO _2, an epoxy resin, an acrylic resin, a melamine-based resin material is preferable. Moreover, silica particle can also be mix | blended with these resin.

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

(6) antistatic layer

Specific examples of the antistatic layer include metal oxide particles having conductivity such as antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, aluminum-containing zinc oxide particles, phosphorus-containing tin oxide particles, or organic or inorganic conductive compounds. The film containing the curable film which added this, the metal oxide film obtained by depositing or sputtering the said metal oxide, and a conductive organic polymer is mentioned. Examples of the conductive organic polymer include polyacetylene-based conductive polymers, polyaniline-based conductive polymers, polythiophene-based conductive polymers, polypyrrole-based conductive polymers, and polyphenylenevinylene-based conductive polymers. As described above, as the metal oxide included in the liquid curable resin composition used in the present invention, conductive particles such as ATO particles, ITO particles, antimony-containing zinc oxide particles, aluminum-containing zinc oxide particles, and phosphorus-containing tin oxide particles When added, the layer containing the metal oxide obtained at high density becomes a film which has antistatic property. In this case, formation of another antistatic film can be omitted.

The antistatic layer prevents adhesion of dust and the like due to electrification by imparting conductivity to the laminate.

These layers may form only one layer, and may also form two or more other layers.

In addition, the film thickness of the low, medium and high refractive index layers is usually 60 to 150 nm, the film thickness of the antistatic layer is usually 0.05 to 3 µm, and the film thickness of the hard coating layer is usually 1 to 20 µm.

In the present invention, any two or more successive layers of the laminate can be formed by the production method of the present invention, but the production method of the layer not in accordance with the production method of the present invention is a method such as known coating and curing, vapor deposition, sputtering, and the like. It can manufacture by.

Moreover, in order to harden | cure the layer which consists of liquid curable resin composition by this invention to form the cured film which has the outstanding optical characteristic and durability, it is preferable to provide the heat history by heating especially. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time to form a target cured film, but in practice, heating and curing are effective for shortening the required time. In addition, the curing reaction can be further promoted by adding a thermal acid generator as a curing catalyst. There is no restriction | limiting in particular as this hardening catalyst, Various acids and its salts used as hardening | curing agent for general urea resin, melamine resin, etc. can be used, Especially an ammonium salt can be used preferably. Although the heating conditions for hardening reaction can be selected suitably, heating temperature needs to be below the heat-resistant limit temperature of the base material of application | coating.

According to this invention, since two or more layers can be formed from one coating film, the manufacturing process of a laminated body can be simplified.

In addition, scratch resistance of the laminate can be improved by localizing the metal oxide particles.

The laminated body of this invention can be used for optical components, such as a lens and a selective permeable membrane filter, in addition to an antireflection film.

In the following description, "part" or "%" shows a "mass part" or the "mass%" unless there is particular notice.

Preparation Example 1

(1) Synthesis of Organic Compound Having Polymeric Unsaturation

222 parts of isophorone diisocyanate were dripped at 50 degreeC over 1 hour in dry air over the mixed solution of 221 parts of mercaptopropyl trimethoxysilane and 1 part of dibutyltin dilaurates in the container with a stirrer, and also 70 degreeC Stirred for 3 hours.

Subsequently, it consists of NK ester A-TMM-3 LM-N (60 mass% of pentaerythritol triacrylates and 40 mass% of pentaerythritol tetraacrylates) by the Shin-Nakamura Chemical Corporation in this reaction solution. 549 parts of pentaerythritol triacrylate having a hydroxyl group were added dropwise at 30 ° C. over 1 hour, followed by stirring at 60 ° C. for 10 hours to obtain a reaction solution.

As a result of measuring the amount of remaining isocyanate in the product in this reaction liquid, ie, the organic compound which has a polymerizable unsaturated group, by FT-IR, it was 0.1 mass% or less, and it confirmed that each reaction was performed almost quantitatively. From the above, 773 parts of compounds which have a thiourethane bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group, and the composition (A-1) of 220 parts of pentaerythritol tetraacrylate which were not involved in reaction were obtained.

Preparation Example 2

(2) Synthesis of Urethane Acrylate

NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. in a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container with a stirrer After only 93 parts of triacrylates were dripped on the conditions of 10 degreeC and 1 hour, it stirred on the conditions of 60 degreeC and 6 hours, and set it as the reaction liquid.

As a result of measuring the amount of remaining isocyanate in FT-IR in the same manner as in Production Example 1, that is, Production Example 1, the reaction was confirmed to be 0.1 mass% or less, and the reaction was almost quantitatively performed. In addition, it was confirmed that the molecule contains a urethane bond and acryloyl group (polymerizable unsaturated group).

75 parts of urethane hexaacrylate compounds were obtained from the above, and the composition (A-2) which mixed 37 parts of pentaerythritol tetraacrylates which did not participate in reaction was obtained.

Preparation Example 3

[Production of Composition for Silica Particle-containing Hard Coating Layer]

2.32 parts of compositions (A-1) containing a polymerizable unsaturated group prepared in Production Example 1, silica particle sol (methyl ethyl ketone silica sol, manufactured by Nissan Chemical Industries, Ltd. MEK-ST, number average particle diameter 0.022 µm, silica Concentration 30%) After stirring a mixture liquid of 91.3 parts (27 parts as silica particles), 0.12 parts of ion-exchanged water, and 0.01 parts of p-hydroxyphenyl monomethyl ether at 60 degreeC for 4 hours, 1.36 parts of ortho formic acid methyl esters are added, and Reactive particles (dispersion liquid (A-3)) were obtained by heating and stirring at the temperature for 1 hour. After weighing 2g of this dispersion liquid (A-3) to the aluminum dish, it dried for 1 hour and weighed on the hot plate of 175 degreeC, and calculated | required solid content, and it was 30.7%. Furthermore, after weighing 2 g of the dispersion liquid (A-3) in a magnetic crucible, preliminarily drying for 30 minutes on a hot plate at 80 ° C., and in solid content from the inorganic residue after firing for 1 hour in a muffle furnace at 750 ° C. It was 90% when the inorganic content was calculated | required.

98.6 g of this dispersion (A-3), 3.4 g of composition (A-2), 2.1 g of 1-hydroxycyclohexylphenyl ketone, IRGACURE 907 (2-methyl-1- [4- (methylthio) phenyl] -2 Morpholino propane-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd., 1.2 g, dipentaerythritol hexaacrylate (DPHA) 33 g, and cyclohexanone 7 g were mixed and stirred to prepare a composition for a silica particle-containing hard coating layer. 145g of (solid content concentration 50%) was obtained.

Preparation Example 4

[Production of Zirconia Particle-Containing Composition]

300 parts of Daiichi Kigenso Kagaku Kogyo Co., Ltd. make and 100 parts of UEP-100 (primary particle diameters 10-30 nm) are added to 700 parts of methyl ethyl ketone (MEK), dispersion | distribution is carried out with glass beads for 168 hours, and glass beads are removed. 950 parts of zirconia dispersion sol was obtained. After weighing 2 g of zirconia dispersion sol in an aluminum dish, it was dried for 1 hour and weighed on a 120 degreeC hotplate, and solid content was calculated | required and it was 30%. A mixed solution of 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, in 100 g of this zirconia dispersion sol. After stirring at 60 degreeC for 3 hours, 0.332 g of ortho formic acid methyl esters were added, and it stirred for further 1 hour at the same temperature, and obtained 116g of dispersion liquids of surface modified zirconia particle. 116 g of this dispersion, 1.34 g of composition (A-2), 1.26 g of 1-hydroxycyclohexylphenyl ketone, IRGACURE 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane 0.76 g of 1-one, Ciba Specialty Chemicals Co., Ltd., and MEK 2846 g were mixed and stirred to obtain 2964 g of a zirconia particle-containing composition (solid content concentration of 4%).

Preparation Example 5

[Production of Tin-Containing Indium Oxide (ITO) Particle-Containing Composition]

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

Preparation Example 6

[Preparation of antimony-containing tin oxide (ATO) particle-containing composition]

ATO particle (Ishihara Techno Co., Ltd. make, SN-100P, primary particle diameter 10-30 nm), a dispersing agent (Asahi Denka Kogyo Co., Ltd. make, Adeka Pluronic TR-701) and methanol 90 / 2.78 / 211 ( Weight ratio) (31% total solids content, 29.6% total inorganic content). Into a 50 ml poly bottle of a paint shaker, 40 g of glass beads (BZ-01, manufactured by TOSHINRIKO, bead diameter 0.1 mm) (about 16 ml in volume) and the mixed solution (30 g) were added and dispersed for 3 hours, followed by median diameter of 80 nm. A dispersion sol was obtained. After stirring the mixture liquid of composition (A-1) 5.7g, p-methoxyphenol 0.01g, and 0.12g of ion-exchange water at 60 degreeC for 3 hours, 304 g of this sol, 1.3 g of ortho formic-acid methyl ester are added, and it is the same temperature 311g of dispersion liquid of surface-modified ATO particle | grains was obtained by further heating and stirring for 1 hour. 278.3 g of this dispersion, 1.7 g of composition (A-2), 8.59 g of pentaerythritol triacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 0.88 g, 33 g of methanol, and 1675 g of propylene glycol monomethyl ether were mixed and stirred to obtain 2000 g of an ATO particle-containing composition (solid content concentration of 5%).

Preparation Example 7

[Preparation of aluminum-containing zinc oxide (Al-doped ZnO) particle-containing composition]

Zinc oxide particles (Al-doped ZnO particles manufactured by Kakaku Chemical Co., Ltd., primary particle diameter 10 to 20 nm), dispersant (made by Kusumoto Kasei Co., Ltd., High Flat ED151) and propylene glycol monomethyl ether 27.6 / 4.8 / 67.6 ( Weight ratio) (total weight content 30%, total inorganic content 27.6%). In a 50 ml poly bottle of a paint shaker, 40 g of zirconia beads (0.1 mm of bead diameter) and the mixed solution (30 g) were added and dispersed for 8 hours to obtain a dispersion sol having a center diameter of 40 nm. To 290 g of this sol, 10 g of pentaerythritol triacrylate, 0.5 g of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, and 2138 g of propylene glycol monomethyl ether Was added and mixed and stirred to give 2438 g of a zinc oxide particle-containing composition (solid content concentration 4%).

Preparation Example 8

[Production of hydroxyl-containing fluorine-containing polymer]

After fully replacing the autoclave made of stainless steel with an internal volume 1.5 L stirrer with nitrogen gas, 500 g of ethyl acetate, 43.2 g of perfluoro (propyl vinyl ether), 41.2 g of ethyl vinyl ether, and hydroxyethyl vinyl ether As 21.5 g, nonionic reactive emulsifier, "Adeka Riaso NE-30" (made by Asahi Denka Kogyo Co., Ltd.) 40.5 g, azo-group containing polydimethylsiloxane "VPS-1001" (made by Wako Pure Chemical Industries, Ltd.) 6.0 g and lauroyl peroxide 1.25 g were added, cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

Then, 97.4 g of hexafluoropropylene was added to start the temperature increase. The pressure when the temperature in autoclave reached 60 degreeC showed 5.3x10 <^5> Pa. Thereafter, the reaction was continued under stirring at 70 ° C. for 20 hours, and the autoclave was water-cooled to stop the reaction when the pressure was lowered to 1.7 × 10 ⁵ Pa. After reaching room temperature, the unreacted monomer was released and the autocrab was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was thrown into methanol, and the polymer was deposited, washed with methanol, and vacuum dried at 50 deg. C to obtain 220 g of a fluorine-containing polymer.

With respect to the obtained polymer, it was confirmed that the polystyrene reduced number average molecular weight (Mn) by gel permeation chromatography was 48000, the glass transition temperature (Tg) by DSC was 26.8 ° C, and the fluorine content by the alizarin complexon method was 50.3%. .

Preparation Example 9

[Silica Coated TiO ₂ Particle Dispersion]

350 parts by mass of fine silica oxide powder coated with silica, 80 parts by mass of ethylene oxide-propylene oxide copolymer (average degree of polymerization: about 20), 1000 parts by mass of isopropyl alcohol, 1000 parts by mass of butyl cellosolve were added to the glass beads. It disperse | distributed for 10 hours, the glass bead was removed, and 2430 mass parts of silica coated titanium oxide particle dispersions were obtained. The silica-coated TiO ₂ particle dispersion thus obtained was weighed on an aluminum plate, dried on a hot plate at 120 ° C. for 1 hour, and the total solid concentration was 17 mass%. Further, the silica-coated TiO ₂ particle dispersion-1 was weighed in a magnetic crucible and preliminarily dried on a hot plate at 80 ° C. for 30 minutes, followed by firing for 1 hour in a muffle furnace at 750 ° C., and the total solid content. It was 82 mass% when the inorganic content in all solid content was calculated | required from concentration.

As a result of electron microscopic observation of this solid, the uniaxial average particle diameter was 15 nm, the long axis average particle diameter was 46 nm, the aspect ratio 3.1, and the number average particle diameter was 15 nm.

Example 1, Comparative Example 1

[Production of Liquid Curable Composition]

(1) Preparation of Liquid Curable Resin Composition (Compositions 1 to 5)

24 g of silica-coated titanium oxide dispersion liquid obtained in Production Example 9 (solid content 4.08 g), 2 g of hydroxyl group-containing fluorine-containing polymer obtained in Production Example 8, and methoxylated methyl melamine `` cymel 303 '' of a crosslinkable compound (Mitsui Cytec Co., Ltd.) Composition) by dissolving 1.2 g of the catalyst and 0.68 g of Catalyst 4050 (manufactured by Mitsui Cytec Co., Ltd., aromatic sulfonic acid compound) as a curing catalyst in 32 g of methyl ethyl ketone, 24 g of methyl isobutyl ketone, and 16 g of tert-butanol. 1 was obtained. It was 7.5 mass% when the total solid content concentration in this liquid curable resin composition was measured similarly to Production Example 9.

In the same manner, each component was blended to obtain a blending ratio shown in Table 1 below to obtain compositions 2 to 5. In addition, in Compositions 2 to 5, alumina and zirconia-coated TiO ₂ particle dispersions (manufactured by Teika Co., Ltd.) were used instead of silica-coated titanium oxide dispersions, and normal butanol (n-BuOH) was used instead of tertiary butanol. The composition of the solvent was methyl ethyl ketone (MEK) / isopropanol (IPA) / methyl isobutyl ketone (MIBK) / normal butanol (n-BuOH) = 40/20/30/10.

As a result of measuring the particle size in the same manner as in Production Example 9, the number average particle diameter (shortened average particle diameter) was 20 nm.

(2) Preparation of Liquid Curable Resin Composition (Composition 6)

Instead of the hydroxyl group-containing fluorine-containing polymer obtained in Production Example 8, manufactured by Kynar ADS (Elves, Atochem, Japan Co., Ltd. Copolymer of propylene hexafluoride, ethylene tetrafluoride and difluoroethylene, having no hydroxyl group and polymerizable unsaturated group) ) Was used in the same manner as in the preparation of the liquid curable resin composition (composition 1) to obtain a liquid curable resin composition (composition 6).

Example 2, Comparative Example 2

[Production of Cured Film]

Silica particle sol (methyl ethyl ketone silica sol, manufactured by Nissan Chemical Industries, Ltd. MEK-ST, number average particle diameter 0.022 µm, silica concentration 30%) 98.6 g, 1-hydroxycyclohexylphenyl ketone 2.1 g, IRGACURE 907 ( 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, manufactured by Ciba Specialty Chemicals) 1.2 g, dipentaerythritol hexaacrylate (DPHA) 33.2 g And 7 g of cyclohexanone were mixed and stirred to obtain a composition for a silica particle-containing hard coating layer. This silica particle-containing hard coating layer was coated on a triacetyl cellulose film (LOFO, film thickness of 80 μm) using a wire bar coater (# 12), and then dried at 80 ° C. in an oven for 1 minute. Subsequently, a hard coat layer was formed by irradiating ultraviolet rays under light irradiation conditions of 0.6 J / cm ² using a high pressure mercury lamp under air. It was 5 micrometers when the film thickness of the hard coat layer was measured with the stylus type film thickness meter.

After coating the composition 1-6 obtained in Example 1 and the comparative example 1 using the wire bar coater (# 3) on the obtained hard coat layer, the cured film layer whose film thickness is 0.2 micrometer by heating for 10 minutes at 120 degreeC in oven. Formed.

Evaluation example 1

[Evaluation of Curing Film]

The cross section of the cured film obtained in Example 2 and the comparative example 2 was observed under the microscope, and it evaluated whether it isolate | separated into two layers. Evaluation criteria are as follows. 11 shows a typical example of each state.

<Evaluation Criteria>

2-layer separation

Not separated (some coagulation)

Uniform structure

Haze (%) measured haze (haze value) in the obtained laminated body using the haze meter, and evaluated it based on the following references | standards.

○: The haze value is 1% or less.

(Triangle | delta): A haze value is 5% or less.

X: Haze value exceeds 5%.

The results are shown in Table 1 below.

The symbol in Table 1 shows the following.

(A) Fluorine-containing polymer: It is a fluorine-containing polymer manufactured by the said manufacture example 1.

Kynar ADS: Elf Atochem Japan Co., Ltd .; Copolymers of propylene hexafluoride, ethylene tetrafluoride and ethylene difluoride. It does not have a hydroxyl group and a polymerizable unsaturated group.

(B) metal oxide particles

Alumina, zirconia-coated TiO ₂ particle dispersion: produced by Teika Co., Ltd. 28% total solids concentration, 24% particle concentration, 20 nm average particle diameter

Silica Coated TiO ₂ Particle Dispersion: Prepared in Preparation Example 2.

(E) Cymel 303: Methylated methylmelamine, manufactured by Mitsui Cytec Co., Ltd.

(F) Catalyst 4050: Mitsui Scitech Co., Ltd. makes. Aromatic sulfonic acid compounds

From the results of Table 1, it was found that even if the (E) curable compound and the (F) thermal acid generator were not blended, two-layer separation occurred (compositions 2 and 5).

(A) When no hydroxyl-containing fluorine-containing polymer was present, it was found that two-layer separation did not occur (compositions 4 and 6).

Example 3, Comparative Example 3

[Production of Liquid Curable Resin Composition and Cured Film]

In the liquid curable resin composition of the solid content mix ratio of the composition 3 in Example 1, the solvent used was changed as shown in Table 2, and the liquid curable resin composition of compositions 7-10 was obtained.

Using the liquid curable resin composition of the composition 3 and 7-10, it carried out similarly to Example 2, and manufactured the cured film on the same conditions.

(A) The solubility of the hydroxyl-containing fluorine-containing polymer is added to each solvent so that the (A) hydroxyl-containing fluorine-containing polymer is 50 mass%, and is determined by whether or not it is a uniform solution visually when stirred at room temperature for a certain time. Evaluation was made based on the following criteria. The results are shown in Table 2.

<Evaluation Criteria>

(Circle): It is a uniform solution after stirring for 2 hours.

(Triangle | delta): It is a uniform solution after stirring for 8 hours.

X: It is not a uniform solution after stirring for 8 hours.

(B) The dispersion stability of the TiO ₂ particles is immersed in the glass plate in the (B) metal oxide particle dispersion (B) to adhere the metal oxide particles to the glass wall, and (B) the glass plate with the metal oxide particles attached to each solvent In the case of immersion, it was determined by (B) whether the metal oxide particles were uniformly dispersed in the solvent with the naked eye, and evaluated based on the following criteria. The results are shown in Table 2.

<Evaluation Criteria>

○: uniformly dispersed.

X: It is not uniformly distributed.

In Table 2, solvents are listed in order of decreasing the relative evaporation rate of a solvent from the left side to the right side.

The symbol of a solvent represents the following, respectively.

MEK: methyl ethyl ketone

MeOH: Methanol

IPA: Isopropanol

MIBK: methyl isobutyl ketone

n-BuOH: n-butanol

MAK: methyl amyl ketone

Evaluation example 2

[Evaluation of Curing Film]

The cured films obtained in Example 3 and Comparative Example 3 were prepared in the same manner as in Evaluation Example 1 to evaluate layer separation properties and haze. The results are shown in Table 2.

From the result of Table 2, in order to generate two-layer separation, it is preferable to mix | blend 2 or more types of solvents, 1 or more types are (C) (A) high solubility with respect to a fluoropolymer, and the other 1 or more types are (D (B) It is necessary to select a thing with high dispersion stability with respect to a metal oxide particle, and it turns out that it is necessary that the relative evaporation rate of a solvent (C) is larger than the relative evaporation rate of a solvent (D).

Example 4, Comparative Example 4

[Production of Laminate]

(1) Preparation of Hard Coating Layer

Silica particle-containing hard coating layer composition (solid content concentration 50%) prepared in Production Example 3 was coated on a triacetylcellulose film (LOFO manufactured, film thickness of 80 μm) using a wire bar coater (# 12), and then in an oven. It dried at 80 degreeC for 1 minute. Subsequently, the cured film layer was formed by irradiating ultraviolet-ray on the light irradiation conditions of 0.6 J / cm <^2> using the high pressure mercury lamp under air. It was 5 micrometers when the film thickness of the cured film layer was measured with the stylus type film thickness meter.

(2) Preparation of the medium refractive index layer

The zirconia particle-containing composition (solid content concentration 4%) prepared in Production Example 4 was coated on the hard coating layer prepared in (1) using a wire bar coater (# 3), and then dried at 80 ° C. in an oven for 1 minute. . Then, the cured film layer was formed by irradiating an ultraviolet-ray on the light irradiation conditions of 0.6 J / cm <^2> using the high pressure mercury lamp in nitrogen atmosphere. It was 65 nm as a result of calculating the film thickness of the cured film layer with the reflection spectrometer.

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

After coating the liquid curable resin compositions of the compositions 1 to 6 obtained in Example 1 and Comparative Example 1 onto the medium refractive index layer prepared in (2) using a wire bar coater (# 3), respectively, at 120 ° C. in an oven. By heating for 10 minutes, the cured film layer whose film thickness is 0.2 micrometer was formed.

Example 5, Comparative Example 5

[Production of Laminate]

(1) Preparation of Hard Coating Layer

It manufactured like Example 4 (1).

(2) Preparation of antistatic layer

The ITO particle-containing composition (solid content concentration 4%) prepared in Production Example 5 was coated on the hard coat layer prepared in (1) using a wire bar coater (# 3), and then dried at 80 ° C. in an oven for 1 minute. . Then, the cured film layer was formed by irradiating an ultraviolet-ray on the light irradiation conditions of 0.6 J / cm <^2> using the high pressure mercury lamp in nitrogen atmosphere. It was 65 nm as a result of calculating the film thickness of the cured film layer with the reflection spectrometer.

(3) Preparation of the medium refractive index layer

It manufactured like Example 4 (2).

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

The liquid curable resin compositions of the compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were respectively coated on the medium refractive index layer prepared in (3) using a wire bar coater (# 3), and then at 120 ° C. in an oven. By heating for 10 minutes, the cured film layer whose film thickness is 0.2 micrometer was formed.

Examples 6, 7, Comparative Examples 6 and 7

[Production of Laminate]

(1) Preparation of antistatic layer

Instead of the ITO particles prepared in Production Example 5, the ATO particle-containing composition (solid content 5%) or Al-doped ZnO particle-containing composition (solid content 4%) prepared in Production Example 6 or 7 was replaced with a wire bar coater (# 3). After coating on the triacetyl cellulose film (LOFO, film thickness 80㎛), and dried for 1 minute at 80 ℃ in an oven. Then, the cured film layer was formed by irradiating an ultraviolet-ray on the light irradiation conditions of 0.6 J / cm <^2> using the high pressure mercury lamp in nitrogen atmosphere. It was 65 nm as a result of measuring the film thickness of the cured film layer with a tactile film thickness meter.

(2) Preparation of Hard Coating Layer

The composition for the silica particle-containing hard coating layer (solid content concentration 50%) prepared in Production Example 3 was coated using a wire bar coater (# 12), and then dried at 80 ° C. in an oven for 1 minute. Subsequently, the cured film layer was formed by irradiating ultraviolet-ray on the light irradiation conditions of 0.6 J / cm <^2> using the high pressure mercury lamp under air.

(3) Preparation of the medium refractive index layer

It manufactured like Example 4 (2).

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

The liquid curable resin compositions of the compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were respectively coated on the medium refractive index layer prepared in (3) using a wire bar coater (# 3), and then at 120 ° C. in an oven. By heating for 10 minutes, the cured film layer whose film thickness is 0.2 micrometer was formed.

Example 8, Comparative Example 8

[Production of Laminate]

(1) Preparation of Hard Coating Layer

It manufactured like Example 4 (1).

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

The liquid curable resin compositions of the compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were respectively coated on the hard coating layer prepared in (1) by using a wire bar coater (# 3), followed by 10 at 120 ° C. in an oven. By heating for a minute, the cured film layer whose film thickness was 0.2 micrometer was formed.

Evaluation Example 3

[Evaluation of Laminate]

As a result of observing the cross section of the laminate obtained in Examples 4 to 8 and Comparative Examples 4 to 8 with a transmission electron microscope, in the laminate using the compositions 1, 2, 3, and 5, the low refractive index layer and the high refractive index layer were two layers. It was confirmed that the layers were separated. At this time, the low refractive index layer was a layer substantially free of metal oxide particles, and the high refractive index layer was a layer having high density of metal oxide particles. In the laminate using the composition 4, the high refractive index layer and the low refractive index layer had a uniform structure and were not separated from each other. In the laminate using the composition 6, the high refractive index layer and the low refractive index layer were partially aggregated and did not separate into layers.

Spectroscopic reflectance measuring device (magnetic spectrophotometer U-3410 incorporating large sample chamber integrating sphere accessory 150-09090, Hitachi Seisakusho (Note) (Reflection) and the reflectance of wavelength 550 nm were measured and evaluated. Specifically, the reflectance of the antireflection laminate (antireflection film) was measured based on the reflectance in the aluminum vapor deposition film (100%). As a result, the reflectance in wavelength 55Onm of all the laminated bodies was 1% or less.

Since the cured film obtained by hardening | curing the liquid curable resin composition of this invention can form the cured film which has a continuous multilayer structure, such as a low refractive index layer and a high refractive index layer, from one coating film, the manufacturing process of the cured film which has a multilayered structure is simplified. can do. That is, using the liquid curable resin composition of this invention, the manufacturing process of the laminated body which has a multilayered structure of two or more layers can be simplified. Therefore, especially the liquid curable resin composition of this invention can be used advantageously for formation of optical materials, such as an antireflection film, a lens, and a selective permeable film filter. Moreover, the obtained cured film or laminated body can be used suitably as a coating material, a weathering film, a coating, etc. with respect to the base material where weather resistance is calculated | required using what may contain a layer with a high fluorine content. Moreover, since the said cured film or laminated body is excellent in adhesiveness with respect to a base material, high scratch resistance, and gives a favorable anti-reflective effect, it is very useful as an anti-reflective film, and can apply it to various display apparatuses, and its visibility can be improved. have.

Claims (20)

(A) Fluorine-containing polymer having a hydroxyl group in the molecule (B) One or two or more metal oxide particles having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more (hereinafter, referred to as "(B) metal oxide particles"). (C) One or two or more solvents having high solubility to the fluorine-containing polymer having a hydroxyl group in the (A) molecule (hereinafter referred to as "(C) fast volatile solvent") (D) One or two or more solvents having high dispersion stability to the metal oxide particles (B) and compatible with the (C) fast-volatile solvent (hereinafter referred to as "(D) delayed volatile solvent"). (E) a compound containing at least two of any one or both of a hydroxyalkylamino group and an alkoxyalkylamino group, and (F) thermal acid generator The content of (A), (B), (E) and (F) is 5 to 70% by mass, 10 to 90% by mass, 3 to 70% by mass, and 0.01 to 100% by mass of solids, respectively. 10 mass%, the total amount of the component (C) and the component (D) is 300 to 5000 parts by mass, relative to 100 parts by mass of the total component other than the solvent, (C) The relative evaporation rate of the rapid volatile solvent is greater than the relative evaporation rate of the (D) delayed volatile solvent. The volatile solvent according to claim 1, wherein (C) the fast-volatile solvent is (B) one or two or more solvents having low dispersion stability to the metal oxide particles, and (D) the delayed-volatile solvent is (A) a fluorine having a hydroxyl group in the molecule. It is 1 type (s) or 2 or more types of solvents with low solubility to a containing polymer, The liquid curable resin composition characterized by the above-mentioned. The metal oxide particles according to claim 1, wherein the metal oxide particles are titanium oxide, zirconium oxide, antimony-containing tin oxide, tin-containing indium oxide, aluminum oxide, cerium oxide, zinc oxide, aluminum-containing zinc oxide, tin oxide, and antimony-containing zinc oxide. And particles having, as a main component, one or two or more metal oxides selected from indium-containing zinc oxide and phosphorus-containing tin oxide. The liquid curable resin composition according to claim 3, wherein the metal oxide particles (B) are particles containing titanium oxide as a main component. The liquid curable resin composition according to claim 1, wherein the metal oxide particles (B) are metal oxide particles having a multilayer structure. It is obtained by hardening | curing the liquid curable resin composition of Claim 1, and has a multilayered structure of two or more layers, The cured film characterized by the above-mentioned. The layer constituting the multilayer structure according to claim 6, wherein each layer constituting the multilayer structure is a layer in which (B) metal oxide particles are present at a high density, or a layer substantially free of (B) metal oxide particles, and at least one layer is a (B) metal oxide. The cured film characterized by being a layer in which particle | grains exist in high density. It has the process of hardening by heating the liquid curable resin composition of Claim 1, or irradiating a radiation, The manufacturing method of the cured film characterized by the above-mentioned. A coating film is formed by apply | coating the liquid curable resin composition of Claim 1 on the base material or the layer formed on the base material, Forming two or more layers by evaporating a solvent from this one coating film, The base material and the manufacturing method of the laminated body which has a multilayered structure on it. 10. The method of claim 9, wherein each layer of the two or more layers is a layer in which metal oxide particles are present at a high density, or a layer substantially free of metal oxide particles, and at least one layer is a layer in which metal oxide particles are present at a high density. The manufacturing method of the laminated body made into. The manufacturing method of the laminated body of Claim 10 whose two or more layers are two layers. The method for producing a laminate according to claim 9, wherein at least two layers are further cured by heating. The manufacturing method of the laminated body of Claim 9 whose laminated body is an optical component. The manufacturing method of the laminated body of Claim 9 whose laminated body is an anti-reflective film. The antireflection film according to claim 11, wherein the laminate is an antireflection film in which at least a high refractive index layer and a low refractive index layer are laminated in this order on a side close to the base material, and the two layers according to claim 11 are a high refractive index layer and a low refractive index. It consists of layers, The manufacturing method of the laminated body characterized by the above-mentioned. The refractive index of the low refractive index layer at 589 nm is 1.20 to 1.55, The refractive index at 589 nm of a high refractive index layer is 1.50-2.20, and is higher than the refractive index of a low refractive index layer, The manufacturing method of the laminated body characterized by the above-mentioned. 12. The laminated body is an antireflection film in which at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order on a side close to the base material, and the two layers according to claim 11 are high refractive index. The manufacturing method of the laminated body which consists of a layer and a low refractive index layer. The refractive index of the low refractive index layer at 589 nm is 1.20 to 1.55, The refractive index at 589 nm of the medium refractive index layer is 1.50 to 1.90, which is higher than the refractive index of the low refractive index layer, The refractive index at 589 nm of a high refractive index layer is 1.51-2.20, and is higher than the refractive index of a medium refractive index layer, The manufacturing method of the laminated body characterized by the above-mentioned. The manufacturing method of the laminated body of Claim 15 or 17 which further forms a hard-coat layer and / or an antistatic layer on a base material. The laminated body manufactured by the manufacturing method of the laminated body of Claim 9.

Images