KR20210027152A - Active energy ray curing-type antiglare hard coating agent, cured film and laminated film - Google Patents

Abstract

The present invention relates to an active energy ray-curable anti-glare hard coat agent, to a cured film, and to a laminated film. The active energy ray-curable anti-glare hard coat agent comprises: (meth)acrylate (A) having three or more (meth)acryloyl groups; silsesquioxane (B); hydrophilic silica particles (C); and organic particles (D). In addition, the cured film and the laminated film have good anti-glare and scratch resistance.

Description

Active energy ray curing-type antiglare hard coating agent, cured film and laminated film}

The present invention relates to an active energy ray-curable anti-glare hard coat agent, a cured film, and a laminated film.

In the fields of optical components and displays, there is a demand for improving visibility by reducing see-through. In response to such demand, in providing a film having a specific function for an optical component, a display, or the like, a method of improving visibility has been made.

As a specific method for obtaining a film with improved visibility, anti-glare treatment and anti-reflection treatment are exemplified. Anti-glare treatment is a treatment for forming a film with irregularities of about several microns on a surface layer of a display or the like. Incident light is scattered by such irregularities, and the sharpness of an image reflected on the retina is lowered by diffuse reflection, thereby improving visibility. On the other hand, in the antireflection treatment, by forming about 2 to 4 layers of a film having a film thickness of about 100 nm and having optical properties, by using the interference effect of the incident light and the reflected light, the incident light and the reflected light disappear from each other, thereby lowering the reflectance and improving the visibility.

The uneven film subjected to the anti-glare treatment is usually formed on a surface layer of a display or the like. In general, the larger the request to be formed on the film, the better the anti-glare property, but since the unevenness is large, the scratch resistance is often poor. It is believed that rubbing large irregularities with steel wool or the like cuts the convex portion and causes film defects.

Patent Literature 1 discloses an ultraviolet curable hard coat material composition containing dipentaerythritol hexaacyllate and an organosilica sol coated with an organic resin.

Japanese Patent Laid-Open Publication No. Hei 11-092690

However, there is room for improvement in terms of anti-glare properties when using an organosilica sol coated with an organic resin as in Patent Document 1.

The problem to be solved by the present invention is to provide an active energy ray-curable anti-glare hard coat agent, a cured film, and a laminated film having good anti-glare properties and scratch resistance.

As a result of intensive examination by the present inventors, it was found that the above problems were solved by a predetermined active energy ray-curable anti-glare hard coat agent.

In accordance with the present invention, the following items are provided.

(Item 1)

Active energy ray-curable anti-glare hard containing (meth)acrylate (A), silsesquioxane (B), hydrophilic silica particles (C) and organic particles (D) having three or more (meth)acryloyl groups Coat system.

(Item 2)

The cured film of the active energy ray-curable anti-glare hard coat agent according to item 1.

(Item 3)

A laminated film having a substrate and a cured film according to item 2.

(Item 4)

The laminated film according to item 3, wherein the glossiness at an incidence angle of 60 degrees measured according to JIS Z 8741 (1997) is 50% or less.

The cured film and the laminated film provided by the present invention have good anti-glare properties and abrasion resistance.

Throughout the present invention, numerical ranges such as each physical property value and content may be appropriately set (for example, by selecting from the upper and lower limits described in each item below). Specifically, for a numerical value, when the upper limit of the numerical value is exemplified by A1, A2, A3, etc., and the lower limit of the numerical value is exemplified by B1, B2, B3, etc., the range of the numerical value is A1 or less, A2 or less, Examples include A3 or less, B1 or more, B2 or more, B3 or more, A1 to B1, A1 to B2, A1 to B3, A2 to B1, A2 to B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, etc. do. In addition, in the present invention,'~' is used as a meaning including a numerical value described before and after it as a lower limit value and an upper limit value.

<(A) component>

(A) component is (meth)acrylate which has 3 or more (meth)acryloyl groups. In addition, the (meth)acryloyl group is an acryloyl group and/or a methacryloyl group. (Meth)acrylate is an acrylate and/or a methacrylate. The (meth)acryloyl group is represented by the following general formula (1).

<General formula (1)>

[Tue 1]

(In the formula, R ¹ is a hydrogen atom or a methyl group.)

The number of (meth)acryloyl groups of (A) component is 3 or more. The upper limit of the number of (meth)acryloyl groups of the component (A) is exemplified by 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 6, 5, etc. The lower limit is exemplified by 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 6, 5, 4, 3, etc. In one embodiment, the number of (meth)acryloyl groups of the component (A) is preferably about 3 to 20.

The component (A) may further have one or more functional groups or specific bonds other than the (meth)acryloyl group. Examples of functional groups other than (meth)acryloyl groups or specific bonds include urethane bonds and hydroxyl groups.

The compound having a urethane bond and having three or more (meth)acryloyl groups may be a reactant of the following compounds having three or more (meth)acryloyl groups and hydroxyl groups, and various known polyfunctional isocyanates. In the present invention, the polyfunctional isocyanate means having two or more isocyanate groups (N-N=C=O).

(A) As a component, (meth)acrylate having a chain structure and having 3 or more (meth)acryloyl groups, (meth)acrylate having an aliphatic structure and having 3 or more (meth)acryloyl groups, aromatic ring structure And (meth)acrylate having three or more (meth)acryloyl groups are exemplified.

As a (meth)acrylate having a chain structure and three or more (meth)acryloyl groups, a (meth)acrylate having a chain structure and three (meth)acryloyl groups, and four (meth)acrylates having a chain structure (Meth)acrylate having an acryloyl group, (meth)acrylate having a chain structure and five (meth)acryloyl groups, (meth)acrylate having a chain structure and six (meth)acryloyl groups Is illustrated.

As the (meth)acrylate having a chain structure and three (meth)acryloyl groups, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. Is illustrated.

As (meth)acrylates having a chain structure and four (meth)acryloyl groups, pentaerythritol tetra(meth)acrylate, ditrimethylpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate And the like are exemplified.

Dipentaerythritol penta (meth)acrylate etc. are illustrated as a (meth)acrylate which has a chain structure and has five (meth)acryloyl groups.

Dipentaerythritol hexa (meth)acrylate etc. are illustrated as a (meth)acrylate which has a chain structure and has 6 (meth)acryloyl groups.

It is a (meth)acrylate having a fat structure and having three or more (meth)acryloyl groups, a (meth)acrylate having a fat structure and having three (meth)acryloyl groups, and having a fat structure and having four ( (Meth)acrylate having a meth)acryloyl group, (meth)acrylate having a fat structure and five (meth)acryloyl groups, (meth)acrylate having a fat structure and six (meth)acryloyl groups ) Acrylate, etc. are illustrated.

As a (meth)acrylate having an aromatic ring structure and having three or more (meth)acryloyl groups, a (meth)acrylate having an aromatic structure and having three (meth)acryloyl groups, has an aromatic structure and has four ( (Meth)acrylate having meth)acryloyl group, (meth)acrylate having an aromatic structure and having five (meth)acryloyl groups, (meth) having an aromatic structure and having six (meth)acryloyl groups Acrylate and the like are illustrated.

Other compounds having three (meth)acryloyl groups include ethoxylated isocyanuric acid tri (meth) acrylate, caprolactone-modified tris ((meth)acryloxyethyl) isocyanate, and ethoxylated glycerin tri ( Meth)acrylate, etc. are illustrated.

The thing exemplified by the component (A) and the thing known as the component (A) can be used alone or in combination of two or more.

(A) The upper limit of the number of carbon atoms of the component is 100, 90, 80, 70, 60, 50, 40, 30, 25, 20, 15, 10, 9, 8, 7, 6, etc., and the lower limit is 90, 80 , 70, 60, 50, 40, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, etc. are illustrated. In one embodiment, the number of carbon atoms of the component (A) is preferably 5 or more and 100 or less.

(A) component is preferably a (meth)acrylate having three or more (meth)acryloyl groups and hydroxyl groups, more preferably dipentaerythritol poly (meth)acrylate and/or pentaerythritol poly (meth) ) Acrylate, more preferably dipentaerythritol poly(meth)acrylate.

For 100% by mass of the total amount of the (A) component, (B) component (C) component and (D) component, the upper limit of the content (in terms of solid content) of (A) component is 75, 74, 73, 72, 71, 70 , 65, 60, 55, 50, 45 mass%, etc. are exemplified, and the lower limit is exemplified 73, 72, 71, 70, 65, 60, 55, 50, 45, 40 mass%, etc.

In one embodiment, with respect to 100% by mass of the total amount of the (A) component, (B) component, (C) component, and (D) component, the content (in terms of solid content) of the component (A) is preferably 45 to 75 mass. %, more preferably 45% by mass or more and 75% by mass or less, more preferably 45% by mass or more and 73% by mass or less, and particularly preferably 45% by mass or more and 72% by mass or less.

<(B) component>

(B) The component is silsesquioxane. Examples of silsesquioxane include polymers synthesized by hydrolysis and condensation reaction (sol-gel reaction) of a trifunctional organic alkoxysilane. The component (B) has a structural unit represented by the following general formula 2, for example. Cage type, ladder type, and random type are exemplified as the structure of the polymer. The component (B) of the present invention preferably contains at least one selected from cage type, ladder type and random type, and more preferably includes at least two types selected from cage type, ladder type and random type, and It is more preferable to include a cage type, a ladder type, and a random type. Component (B) of the present invention may have a T structure and may have a Q structure. Examples of the T structure include T6, T7, T8, T9, T10, T11, T12, T13, T14, and the like. Examples of the Q structure include Q6, Q7, Q8, Q9, Q10, Q11, Q12, Q13, Q14, and the like.

<General formula (2)>

[Tue 2]

(In the formula, R ² represents a group which may have an alkylene group having 1 or more and 20 or less carbon atoms)

^{R 2} in the general formula (2) is a group which may have an alkylene group having 1 to 20 carbon atoms, and a hydrophilic group and a hydrophobic group are exemplified. Examples of the hydrophilic group include a hydroxy group, an amino group, a thiol group, and a carboxyl group. Examples of the hydrophobic group include an alkyl group having 1 to 20 carbon atoms, a phenyl group, a functional group having a polymerizable double bond, a functional group having a cyclic ether structure, a nitrile group, and the like. Examples of the functional group having a polymerizable double bond include a (meth)acryloyl group and a vinyl group. Examples of the functional group having a cyclic ether structure include an oxetanyl group and an epoxy group.

^{The upper limit of the number of carbon atoms of the alkylene group having 1 or more and 20 or less carbon atoms that R 2} of the general formula (2) may have is 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7 , 6, 5, 4, 3, etc. are illustrated, and the lower limit is 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 Is illustrated. In one embodiment, the number of carbon atoms of the alkylene group having 1 or more and 20 carbon atoms that ^{R 2} of General Formula (2) may have is preferably 1 or more and 20 or less.

(B) As a component, celsesquioxane containing an epoxy group (product name'Glycidyl polysilsesquioxane cage mixture', manufactured by Constru Chemical Co., Ltd.), silsesquioxane containing (meth)acryloyl group (product name'AC-SQ TA-100') 'AC-SQ SI-20''MAC-SQ SI-20''MAC-SQ HDM''MAC-SQ TM-100' made by Dong-A Synthetic Co., Ltd.) (Product name'Mehtacryl polysilsequioxane cave mixture' made by Konsturu Chemical Co., Ltd. ) (Product name'methacryl-POSS' manufactured by Sikhma-Aldrich Japan), silsesquioxane containing oxetanyl group (product name'OX-SQ TX-100''OX-SQ SI-20''OX-SQ HDM' Dong-A Synthesis Co., Ltd. Article), silsesquioxane containing an amino group (product name'Aminopropylisobutyl polysilsequioxane' manufactured by Konsturu Chemical Co., Ltd.) and the like are exemplified.

The thing exemplified by the component (B) and the thing known as the component (B) can be used alone or in combination of two or more.

Component (B) preferably has at least one selected from a functional group having a polymerizable double bond, a functional group having a cyclic ether structure, and a thiol group in consideration of the curability of the active energy ray-curable anti-glare hard coat agent of the present invention. Do. In the present invention, it is more preferable that the component (B) has a functional group having a polymerizable double bond because it is excellent in reactivity with other components. When the functional group having a polymerizable double bond is in the component (B), radical curing can be performed. When the functional group having a cyclic ether structure is in the component (B), cationic curing can be performed. When a thiol group exists in (B) component, N-thiol hardening can be performed. When the component (B) has one or more selected from a functional group having a polymerizable double bond, a functional group having a cyclic ether structure, and a thiol group, the upper limit of the functional group equivalent (g/eq) is 1,000, 900, 800, 700 , 600, 500, 400, 300, 200, 100, etc. are exemplified, and the lower limit is exemplified by 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, etc. In one embodiment, the functional group equivalent (g/eq) is preferably 50 or more and 1,000 or less.

(B) The upper limit of the weight average molecular weight of the component is 20,000, 19,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12,000, 11,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000 And the like are illustrated, and the lower limit is 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12,000, 11,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 500, 100, etc. . In one embodiment, the weight average molecular weight of the component (B) is preferably about 100 or more and 20,000 or less. In the present invention, the weight average molecular weight can be measured in terms of polystyrene by GPC.

The upper limit of the content (in terms of solid content) of the component (B) relative to 100% by mass of the total amount of the (A) component, (B) component, (C) component and (D) component is 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6 mass%, etc. are exemplified, and the lower limit is 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, It is illustrated by 10, 9, 8, 7, 6, 5 mass %. In one embodiment, the content (in terms of solid content) of the component (B) relative to 100% by mass of the total amount of the (A) component, (B) component, (C) component and (D) component is preferably 5 to 50% by weight. It is about, more preferably 10% by mass or more and 45% by mass or less, further preferably 13% by mass or more and 40% by mass or less, and particularly preferably 15% by mass or more and 40% by mass or less. If there is a content (in terms of solid content) of component (B) relative to 100% by mass of the total amount of component A, component (B), component (C) and component (D) within the above range, it is preferable because the haze value is excellent. Do.

The upper limit of the content ratio (mass ratio, solid content conversion, [(A) component/(B) component]) of (A) component and (B) component) is 90/10, 85/15, 80/20, 75/25, 70 It is illustrated as /30, 65/35, and the lower limit is illustrated as 85/15, 80/20, 75/25, 70/30, 65/35, 60/40. In one embodiment, the content ratio (mass ratio, solid content conversion, [(A) component/(B) component]) of (A) component and (B) component is preferably 60/40 to 90/10, more preferably It is preferably 60/40 to 88/12, particularly preferably 62/38 to 84/16.

<(C) component>

(C) component is hydrophilic silica particle. Hydrophilic silica particles mean silica particles having a hydrophilic group. Examples of the hydrophilic group as described above include a hydroxyl group and the like.

(C) The component may be a dispersion or a powder.

The dispersion medium of the dispersion of the component (C) may be various known ones. The dispersion medium of the component (C) is exemplified by water or an organic solvent.

The organic solvent may be various known ones. Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, amide solvents, and the like.

Examples of the ketone solvent include methyl ethyl ketone, acetyl acetone, methyl isobutyl ketone, and cyclohexanone.

Examples of the aromatic solvent include toluene and xylene.

As an alcohol solvent, methanol, ethanol, n-propanol, isopropanol, butalol, etc. are illustrated.

Examples of the glycol-based solvent include ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol.

Examples of the glycol ether solvent include ethylene glycol ethyl ether, ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, etc. are illustrated.

Examples of the ester solvent include ethyl acetate, butyl acetate, methylserosol acetate, and serosol acetate.

Examples of petroleum-based solvents include Sorveso #100 (manufactured by Exxon) and Sorveso #150 (manufactured by Exxon).

As the haloalkane solvent, chloroform and the like are exemplified.

Examples of the amide solvent include dimethylformamide.

Those exemplified as organic solvents and those known as organic solvents may be used alone or in combination of two or more.

Component (C) may be a commercially available product. For this product, isopropanol-dispersed silica particles (product name'OSCAL1432', manufactured by Ilhui Catalyst Chemical Co., Ltd., average particle diameter 10-20nm), propylene glycol monomethyl ether dispersion silica particles (product name'Optisol LSG', Ranco product, average Particle diameter 10~15nm) (product name'PGM-ST', manufactured by Nissan Chemical Co., Ltd., average particle diameter 10nm~15nm), ethylene glycol ethyl ether dispersed silica particles (product name'Optisol LSR', manufactured by Ranco, average particle diameter 10~15nm), number Disperse silica particles (product name'Snotex ST-CXS', manufactured by Nissan Chemical Co., Ltd., average particle diameter 5nm) (product name'Snotex ST-C', manufactured by Nissan Chemical Corporation, average particle diameter 12nm), powdered silica particles (product name'Ah Domanano 10nm', Admatex Co., Ltd., average particle diameter 10nm) (product name'Adomanono 50nm', Admatex Co., Ltd., average particle diameter 50nm) are exemplified.

What is exemplified as the component (C) and what is known as the component (C) can be used alone or in combination of two or more.

The upper limit of the average particle diameter of the component (C) is exemplified by 30, 25, 20, 15, 10 nm, and the like, and the lower limit is 25, 20, 15, 10, 5 nm, and the like. In one embodiment, the average particle diameter of the component (C) is preferably about 5 ~ 30nm.

Measurement of the average particle diameter was carried out by measuring the particle size distribution by laser diffraction and scattering method using a commercially available measuring instrument (product name'Microtrac MT3000II', manufactured by MicrotacBEL Co., Ltd.) in accordance with JIS Z 8828 (2013).

The upper limit of the content (in terms of solid content) of (C) component relative to 100% of the total amount of (A) component, (B) component, (C) component and (D) component is 20, 15, 10, 5, 3% by mass, etc. This is illustrated, and 15, 10, 5, 3, 1 mass %, etc. are illustrated as a lower limit. In one embodiment, the content (in terms of solid content) of the component (C) relative to 100% of the total amount of the (A) component, (B) component, (C) component and (D) component is preferably about 1 to 20% by mass. And more preferably 3% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and particularly preferably 3% by mass or more and 10% by mass or less.

The upper limit of the content ratio (mass ratio, solid content conversion, [(A) component / (C) component]) with the component (A) and the component (C) is 98/2, 97/3, 96/4, 95/5 94 /6, 93/7, 92/8, 91/9, 90/10, 85/15, 82/18, etc. are illustrated, and the lower limit is 97/3, 96/4, 95/5 94/6, 93/ 7, 92/8, 91/9, 90/10, 85/15, 82/18, 80/20, etc. are illustrated. In one embodiment, the content ratio (mass ratio, solid content conversion, [(A) component/(C) component]) of (A) component and (C) component is preferably about 80/20 to 98/2.

The upper limit of the content ratio (mass ratio, solid content conversion, [(B) component / (C) component]) of (B) component and (C) component) is 90/10, 88/12, 85/15, 80/20, 75 /25, 72/28, 70/30, 65/35, etc. are illustrated, and the lower limit is 88/12, 85/15, 80/20, 75/25, 72/28, 70/30, 65/35, 60 /40, etc. are for example. In one embodiment, the content ratio (mass ratio, solid content conversion, [(B) component/(C) component]) of the component (B) and component (C) is preferably about 60/40 to 90/10, more It is preferably 65/35 to 90/10, more preferably 70/30 to 90/10, and particularly preferably 72/28 to 88/12.

<(D) component>

Component (D) is an organic particle. Examples of the component (D) include melamine particles, acrylic particles, acrylic-styrene particles, carbonate particles, ethylene particles, styrene particles, benzoguanamine particles, and acrylonitrile particles. In addition, the'... based particle' means a particle containing'...' in a raw material.

Since the (D) component is easy to adjust the refractive index by the monomer mixing ratio, it is preferably an acrylic-styrene particle.

The component (D) may be a commercially available product. This product includes acrylic particles (product name'Eposter MA1004', made by Nippon Catalyst Co., Ltd., average particle diameter 4μm) (product name'Eposter MA1006', made by Nippon catalyst Co., Ltd., average particle diameter 6μm) (Product name'Tuftic FH-S005' , Japan Exlan Industrial Co., Ltd., average particle diameter 5μm) (Product name'Chemisno MR series', General Research Institute Chemical Co., Ltd., average particle diameter 1~10μm) (Product name'Techpolymer MBX-5', red water chemical industry Co., Ltd., an average particle diameter of 5μm) (Product name'Techpolymer MBX-8', a product made by Hydration Chemical Co., Ltd., an average particle diameter of 8μm), acrylic styrene particles (product name'Eposter MA2003', Japan Catalyst Co., Ltd. , Average particle diameter 3μm) (product name'Techpolymer MSX', manufactured by Jeok Hydration Chemical Industry Co., Ltd., average particle diameter 5μm) (product name'Techpolymer SMX', manufactured by Jeok Hydration Chemical Industry Co., Ltd., average particle diameter 5μm), styrene-based particles ( Examples include the product name'Techpolymer SBX-4', manufactured by Hwasung Chemical Industries, Ltd., an average particle diameter of 4μm), acrylonitrile particles (product name'Tuftic ASF), manufactured by Exlan Industrial Co., Ltd., an average particle diameter of 7μm). do.

(D) component can be obtained by synthesis. Examples of the method for synthesizing the component (D) include (1) a method of uniformly controlling and polymerizing monomer droplets, and (2) a method of growing and granulating the nuclei of the polymer produced by the reaction. As specific means of the method (1), a nozzle vibration method, an SPG film emulsification method, a microchannel method, and a mini emulsion polymerization method are exemplified. As a specific means of the method (2), a soap-free emulsion polymerization method, a dispersion polymerization method, a suspension polymerization method, and a seed emulsion polymerization method are exemplified.

What is exemplified as the component (D) and what is known as the component (D) can be used alone or in combination of two or more.

(D) The upper limit of the average particle size of the component is 10, 9, 8, 7, 6, 5, 4, 3, 2 μm, etc. are illustrated, and the lower limit is 9, 8, 7, 6, 5, 4, 3, 2, 1 , 0.5 μm, etc. are illustrated. In one embodiment, the average particle diameter of the component (D) is preferably about 0.5 to 10 μm.

When the average particle diameter of the component (D) is less than or equal to the above upper limit, it can be particularly excellent in suppressing the lifting due to the lens effect. On the other hand, when the average particle diameter of the component (D) is equal to or greater than the above lower limit, the cured film or laminated film of the present invention can exhibit particularly anti-glare properties.

(D) The upper limit of the refractive index of the component is 1.70, 1.65, 1.60, 1.55, 1.53, 1.51, 1.51, 1.51, 1.50, 1.45, etc., and the lower limit is 1.65, 1.60, 1.55, 1.53, 1.51, 1.51, 1.51, 1.50, 1.45 , 1.40, etc. are illustrated. In one embodiment, the refractive index of the component (D) is preferably about 1.40 to 1.70.

In the present invention, the measurement of the refractive index of the component (D) was performed by a method in accordance with JIS K 7142 (1996).

The upper limit of the content (in terms of solid content) of (D) component relative to 100% by mass of the total amount of (A) component, (B) component, (C) component and (D) component is 30, 25, 20, 15, 10, 5 mass% etc. are illustrated, and 25, 20, 15, 10, 5, 3 mass% etc. are illustrated as a lower limit. In one embodiment, the content (in terms of solid content) of the component (D) relative to 100% by mass of the total amount of the (A) component, (B) component, (C) component, and (D) component is preferably about 3 to 30% by mass. And more preferably 3% by mass or more and 25% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and particularly preferably 5% by mass or more and 20% by mass or less.

The upper limit of the content ratio (mass ratio, solid content conversion, [(A) component / (D) component]) of (A) component and (D) component) is 95/5, 90/10, 89/11, 88/12, 87 /13, 86/14, 85/15, 80/20, 75/25, 70/30, etc. are illustrated, and the lower limit is 90/10, 89/11, 88/12, 87/13, 86/15, 80 /20, 75/25, 70/30, 65/35, etc. are illustrated. In one embodiment, the content ratio (mass ratio, solid content conversion, [(A) component/(D) component]) of (A) component and (D) component is preferably about 65/35 to 95/5, more preferably It is preferably 70/30 to 95/5, more preferably 70/30 to 90/10, and particularly preferably 75/25 to 90/10.

The upper limit of the content ratio (mass ratio, solid content conversion, [(B) component / (D) component]) of (B) component and (D) component) is 80/20, 78/22, 75/25, 70/30, 65 /35, 60/40, 58/42, 55/45, 50/50, 45/55, etc. are exemplified, and the lower limit is

78/22, 75/25, 70/30, 65/35, 60/40, 58/42, 55/45, 50/50, 45/55, 40/60, etc. are illustrated. In one embodiment, the content ratio (mass ratio, solid content conversion, [(B) component/(D) component]) of (B) component and (D) component is preferably about 40/60 to 80/20, more preferably It is preferably 45/55 to 80/20, more preferably 50/50 to 80/20, and particularly preferably 58/42 to 78/22.

The upper limit of the content ratio (mass ratio, solid content conversion, [(C) component / (D) component]) of (C) component and (D) component) is 45/55, 40/60, 35/65, 34/66, 33 /67, 32/68, 31/69, 30/70, etc. are illustrated, and the lower limit is 40/60, 35/65, 34/66, 33/67, 32/68, 31/69, 30/70, 25 /75, etc. are illustrated. In one embodiment, the content ratio (mass ratio, solid content conversion, [(C) component/(D) component]) of the (C) component and (D) component is preferably about 25/75 to 45/55, more It is preferably 25/75 to 40/60, more preferably 30/70 to 40/60, and particularly preferably 30/70 to 35/65.

The mechanism presumed to be capable of obtaining a laminated film producing a desired effect by using the active energy ray-curable anti-glare hard coat agent of the present invention is as follows.

The hydrophilic component (C) has poor compatibility with the component (A) and the component (B), and tends to aggregate in the hard coat film. This contributes to the expression of internal haze and the expression of a matte feeling on the surface. Further, the surface of the hard coat film is uneven by the component (D), and a matte feeling and anti-glare property are expressed together with the component (C). Further, the unevenness of the hard coat film is reduced by agglomeration of the component (B) around the component (D). Accordingly, it is considered that the laminated film formed using the active energy ray-curable anti-glare hard coat agent of the present disclosure exhibited an optimum balance of scratch resistance and anti-glare property. As a result, various particles in the active energy ray-curable anti-glare hard coat agent of the present invention are more difficult to fall off than the laminated film, and it becomes possible to suppress the transparency of the laminated film. On the other hand, although the irregularities of the laminated film are gentle, good anti-glare properties are expressed.

<Other formulations available>

Active energy ray-curable anti-glare hard coat agent of the present invention, if necessary, initiator, leveling agent, photosensitizer, surface modifier, surfactant, ultraviolet absorber, inorganic filler, organic solvent, antifoaming agent, wetting agent, rust inhibitor and stabilizer, etc. Various additives can be blended. The organic solvent described above is exemplified as the organic solvent that can be blended. The upper limit of the content of various additives with respect to 100% by mass of the total amount of (A) component, (B) component, (C) component and (D) component is 10, 9, 8, 7, 6, 5, 3, 2, 1 Mass% etc. are illustrated, and 9, 8, 7, 6, 5, 4, 3, 1, 0 mass% etc. are illustrated as a lower limit. In one embodiment, the content of various additives relative to 100% by mass of the total amount of the (A) component, (B) component, (C) component and (D) component is preferably about 0 to 10% by mass.

<cured film>

The present invention provides a cured film obtained by irradiating an active energy ray-curable anti-glare hard coat agent with an active energy ray.

As a method of curing by irradiation with active energy rays, a high-pressure mercury lamp, ultra-high-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp or the method of irradiating the degree 10mJ / cm ² or more 10,000mJ / cm ² or less by using a LED and the like. Conditions such as the amount of light, light source, and conveying speed can be appropriately adjusted, and when a high-pressure mercury lamp is used, the amount of light is usually about 0.1 to 160 W/cm ² , and the conveying speed is usually about 5 to 50 m/min. Before irradiation with active energy rays, it may be heated and dried as necessary. After irradiation with active energy rays, it may be heated and completely cured as necessary.

<Laminated film>

The present invention provides a laminated film including a substrate and the cured film.

The surface of the substrate may be subjected to various surface treatments such as corona treatment, plasma treatment, primer coating, degreasing treatment, and surface roughening treatment in order to improve the adhesion or adhesion of the substrate and the cured film. Further, in order to improve the adhesiveness or adhesion of the substrate and the cured film, another layer (eg, an adhesive layer, an adhesive layer, etc.) may be disposed between the substrate and the cured film.

As a specific example of the laminated film in the present invention, a laminated film having various layers in the following order is illustrated.

(1) cured film/substrate,

(2) cured film/reverse adhesive layer or adhesive layer/substrate,

As a method of coating the active energy ray-curable anti-glare hard coat agent of the present invention on a substrate, bar coater coating, Mayer burr coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexo printing, screen printing method And the like are exemplified. In addition, the coating amount is not particularly limited, but is usually ^{in the range of 0.05 to 30 g/m 2} after drying, and preferably 0.1 to 20 g/m ² . In addition, the film thickness of the cured film of the active energy ray-curable anti-glare hard coat agent of the present invention is usually about 1 to 10 μm, preferably about 2 to 6 μm.

Examples of the substrate to which the active energy ray-curable anti-glare hard coat agent of the present invention is applied include wood, paper, slate, metal, plastic, organic or other resin. Examples of the metal include iron, aluminum, aluminum-plated steel, tin-free steel (TFS), stainless steel, zinc phosphate-treated steel, zinc-galvanized steel (bonded steel), and the like. Examples of plastics include thermoplastic plastic substrates and thermosetting plastic substrates. Examples of the thermoplastic plastic substrate include general-purpose plastic substrates and engineering plastic substrates. Examples of general-purpose plastic substrates include olefin-based, polyester-based, acrylic-based, vinyl-based, and polystyrene-based. Polyethylene, polypropylene, alicyclic olefin resin (norbornene, etc.) etc. are illustrated as an olefin system. Examples of the polyester system include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of the acrylic type include polymethyl methacrylate (PMMA). Examples of the vinyl system include polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol. Examples of the polystyrene-based resin include polystyrene (PS) resin, styrene acrylonitrile (AS) resin, and styrene butadiene acrylonitrile (ABS) resin. Examples of engineering plastic substrates include general-purpose engineering plastics and super engineering plastics. Examples of general-purpose engineering plastics include polycarbonate and polyamide (nylon). Polyether ether ketone (PEEK) and the like are exemplified as super temperamental plastics. Examples of the thermosetting plastic substrate include polyimide, epoxy resin, and melamine resin. Examples of other plastic substrates include triacetyl cellulose resin. Among these, from the viewpoint of transparency and adhesion to the laminated film, one selected from the group consisting of polyester, triacetylcellulose resin, polycarbonate, acrylic resin, and alicyclic olefin resin is preferable.

In addition, the average thickness of the base film is not particularly limited, but the upper limit of the average thickness of the base film is 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 50 μm, etc., and the lower limit is 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 30 μm, etc. are illustrated. In one embodiment, the average thickness of the base film is preferably about 30 to 1,000 μm, more preferably 30 to 200 μm, and even more preferably 50 to 100 μm.

The laminated film of the present invention has a fine uneven structure. Accordingly, it is possible to suppress the reflection of the outer diameter by the surface reflection, and the anti-glare property can be improved. The anti-glare property is related to the glossiness, and the glossiness of the laminated film of the present invention is as follows. The upper limit of gloss at an incident angle of 60 degrees of the laminated film of the present invention is 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18, 16 , 14%, etc. are illustrated, and the lower limit is 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, 10% And the like are illustrated. In one embodiment, the glossiness at an incidence angle of 60 degrees of the laminated film of the present invention may be 50% or less, preferably about 10 to 50%. In addition, the upper limit of the glossiness of the particles of the laminated film of the present invention at 20 degrees is 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2%, etc. 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1%, etc. are illustrated as a lower limit. In one embodiment, the glossiness at an incident angle of 20 degrees of the laminated film of the present invention is preferably about 1 to 15%. When the gloss is more than the lower limit, the phenomenon of blurring of the displayed image is reduced and the viewing becomes easier. Moreover, when the glossiness is less than or equal to the above upper limit, the anti-glare property is excellent. In addition, the glossiness at an incidence angle of 60 degrees and the glossiness at an incidence angle of 20 degrees of the anti-glare hard coating layer of the laminated film of the present invention are measured by the method described in JIS Z 8741 (1997).

Specific examples of the present invention will be described below through examples, but the present invention is not limited to the following examples. In addition, in the examples, parts and% are all based on solid content unless otherwise specified.

<Example 1: Preparation of active energy ray-curable anti-glare hard coat agent (1)>

(A) 65.5 parts by mass of dipentaerythritol (meth)acrylate (product name'Allonics M-402', manufactured by Dong-A Synthetic Co., Ltd.), (B) component is silsesquioxane (product name'MAC-SQ) TM-100', manufactured by Dong-A Synthetic Co., Ltd.) is 20.0 parts by mass, and (C) is 5.0 parts by mass of propylene glycol monomethyl ether dispersion silica particles (product name'PGM-ST', manufactured by Nissan Chemical), (D) Ingredients include 9.5 parts by weight of organic particles (product name'Techpolymer SSX series customized product', manufactured by Sustainable Chemical Industry Co., Ltd., average particle diameter: 4 μm refractive index: 1.535), 1-[4-(2-hydroxyethoxyl) as an initiator. )-Phenyl]-2-hydroxy-methylpropanone 2.0 parts by mass and 2-hydroxy-1-(4-(2-methylpropionyl)benzyl)-phenyl)-2-methylpropan-1-one 2.0 parts by mass, 0.2 parts by mass of the product name'BYK-350' (manufactured by BYK Additives & Instruments) as a leveling agent was mixed and diluted with propylene glycol methyl ether to prepare an active energy ray-curable anti-glare developer having a solid content of 30% by weight. .

<Examples 2 to 5 and Comparative Examples 1 to 5: Preparation of active energy ray-curable anti-glare hard coat agents (2) to (5) and (C1) to (C5)>

Examples 2 to 5 and Comparative Examples 1 to 5 were carried out in the same manner as in Example 1, except that the composition was changed to the composition shown in Table 1, and the active energy ray-curable anti-glare hard coat agents (2) to (5) and (C1) to (C5) were prepared.

<Evaluation Example 1: Preparation of laminated film (1)>

The active energy ray-curable anti-glare hard coat agent (1) was dried using Mayer No.9 on a triacetyl cellulose film (product name'FTTD80ULM', manufactured by Fujifilm Co., Ltd., film thickness of 80μm) so that the thickness of the film after drying became 3.6μm. After coating and drying at 80° C. for 1 minute, an active energy ray was irradiated under a nitrogen atmosphere (ultraviolet irradiation: 550 mW/cm ² , 300 mJ/cm ² ) to obtain a laminated film (1).

<Evaluation Examples 2 to 5 and Comparative Evaluation Examples 1 to 5: Preparation of Laminated Films (2) to (5) and (C1) to (C5)>

In the evaluation examples 2 to 5 and comparative evaluation examples 1 to 5, the active energy ray-curable anti-glare hard coat agent (1) was used as an active energy ray-curable anti-glare hard coat agent (2) to (5) or (C1) to (C5), respectively. ), except that it was changed to, and was carried out in the same manner as in Evaluation Example 1, and laminated films (2) to (5) and (C1) to (C5) were obtained.

<Performance evaluation (1): τT (total transmittance)>

In accordance with the standard of JIS K 7361-1 (1997), the laminated films (1) to (5) and (C1) to (C5) are The total light transmittance was measured.

<Performance evaluation (2): Haze value>

Haze values of laminated films (1) to (5) and (C1) to (C5) using a hezmeter (product name'HZ-V3, manufactured by Suga Testing Machine Co., Ltd.) in accordance with the standard of JIS K 7136 (2000) Was measured.

<Performance evaluation (3): gloss at an incident angle of 20 degrees>

Incident angle of laminated films (1) to (5) and (C1) to (C5) 20 degrees using a gloss meter (product name'VG-7000, manufactured by Nippon Electric Co., Ltd.) in accordance with the standard of JIS K 8741 (1997). The gloss at was measured.

<Performance evaluation (4): Glossiness at an incidence angle of 60 degrees>

In accordance with the standard of JIS K 8741 (1997), the incident angle of the laminated films (1) to (5) and (C1) to (C5) is 60 degrees using a gloss meter (product name'VG-7000, manufactured by Nippon Electric Co., Ltd.). The gloss at was measured.

<Performance evaluation (5): scratch resistance>

Install the steel wool tester so that the anti-glare hard coat layer of the laminated films (1) to (5) and (C1) to (C5) faces upward, and with a load of ^{500 g/cm 2 using # 0000 steel wool.} The test was conducted by rubbing 10 reciprocations with a sliding distance of 4 cm. The change in appearance (transparency) of the anticorrosive hard coat layer was visually checked, and evaluated according to the following criteria.

○: Transparency does not occur.

△: Slightly transparent.

X: Completely transparent.

Example Comparative example One 2 3 4 5 One 2 3 4 5 (A) DPPA 65.5 55.5 71.5 49.6 73.5 69.0 85.5 67.5 67.0 78.5 (B) SQ 20.0 30.0 14.0 26.8 12.0 16.5 - 23.0 28.0 - (C) Hydrophilic
Silica 5.0 5.0 5.0 7.2 5.0 - 5.0 - 5.0 12.0 Hydrophobic
Silica - - - - - 5.0 - - - - (D) Organic particles 9.5 9.5 9.5 16.4 9.5 9.5 9.5 9.5 - 9.5 τT (%) 90.5 90.8 90.6 92.0 90.6 91.5 91.0 91.6 92.2 89.9 Haze value 16.5 19.1 10.2 33.5 8.3 4.9 4.1 5.4 0.2 16.4 Glossiness (20 degrees)(%) 8.8 6.7 9.9 3.3 11.2 34.2 18.4 37.9 92.2 9.2 Glossiness (60 degrees)(%) 40.1 33.8 45.0 24.9 46.6 88.5 61.9 78.7 93.8 33.8 Scratch resistance ○ ○ ○ ○ ○ ○ △ ○ ○ ×

The meaning of terms in Table 1 is as follows.

DPPA: Dipentaerythritol polyacrylate (product name'Allonics M-402, manufactured by Dong-A Synthetic Co., Ltd.)

SQ: Silsesquioxane (product name "MAC-SQTM-100", manufactured by Dong-A Synthetic Co., Ltd.)

Hydrophilic silica: Propylene glycol monomethyl ether dispersion silica particles (product name'PGM-ST, manufactured by Nissan Chemical Co., Ltd., average particle diameter of 12 nm)

Hydrophobic silica: silica particles surface-treated with a silane coupling agent containing a urethane (meth)acrylate structure obtained through Preparation Examples 1 and 2 below

Organic particles: Polymethyl methacrylate and styrene copolymer

<Production Example 1: Preparation of a silane coupling agent containing a urethane (meth)acrylate structure>

20 parts by mass of isophorone diisocyanate, 72 parts by mass of pentaerythritol triacrylate and pentaerythritol tetraacrylate compound (product name''KAYARADPET-30) in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and air inlet ', Nippon Chemical Co., Ltd.), 8 parts by mass of (3-mercaptopropyl) trimethoxysilane, 0.02 parts by mass of 2, 6-di-tert-butyl-4-methylphenol as a polymerization inhibitor, and dioctyl tin di as a catalyst. 0.2 parts by mass of laurate were mixed, and the reaction was carried out at 70° C. for 5 hours. After the kind of reaction, a mixture containing a urethane (meth) acrylate structure-containing trimethoxy silane, urethane (meth) acrylate, and pentaerythritol tetra markrylate in an amount of 1/3% by mass was obtained. The mixture was used as a silane coupling agent containing a urethane (meth)acrylate structure.

<Production Example 2: Silica particles surface-treated with a silane coupling agent containing a urethane (meth)acrylate structure>

In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and air inlet, 9.4% by mass of silica dispersion (solid content: 30%, solution: methyl ethyl ketone (hereinafter referred to as'MEK')) and A silane coupling agent containing 1.3% by mass of a urethane (meth)acrylate structure was mixed and reacted at 60° C. for 4 hours to prepare surface-treated silica particles, having an average particle diameter of 10 nm. Is a numerical value including the urethane (meth)acrylate and pentaerythritol tetraacrylate in addition to the surface-treated silica particles.

Claims (4)

Active energy ray-curable anti-glare hard containing (meth)acrylate (A), silsesquioxane (B), hydrophilic silica particles (C) and organic particles (D) having three or more (meth)acryloyl groups Coat system.
The cured film of the active energy ray-curable anti-glare hard coat agent according to claim 1.
A laminated film having a substrate and the cured film of claim 2.
The method of claim 3,
A laminated film having a glossiness of 50% or less at an incidence angle of 60 degrees measured in accordance with JIS Z 8741 (1997).