JP2021038386A - Active energy ray-curable antiglare hard coat agent, cured film, and laminate film - Google Patents

Abstract

To provide an active energy ray-curable antiglare hard coat agent, a cured film, and a laminate film.SOLUTION: The present disclosure provides an active energy ray-curable antiglare hard coat agent that contains a (meth) acrylate having three or more (meth) acryloyl groups (A), silsesquioxane (B), hydrophilic silica particles (C) and organic particles (D).SELECTED DRAWING: None

Description

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

In the fields of optical components and displays, it is required to reduce glare and improve visibility. In response to such demand, efforts have been made to improve visibility by providing films having specific functions in optical components, displays and the like.

Anti-glare treatment and anti-reflection treatment are exemplified as specific methods for obtaining a film with improved visibility. The antiglare treatment is a treatment for forming a film having irregularities of about several microns on the surface layer of a display or the like. The incident light is scattered by such unevenness, the sharpness of the image reflected on the retina is lowered by the diffused reflection, and the visibility is improved. On the other hand, in the antireflection treatment, about 2 to 4 layers of films having a film thickness of about 100 nm and having optical characteristics are formed, and the incident light and the reflected light are canceled by utilizing the interference effect between the incident light and the reflected light. By reducing the reflectance, the visibility is improved.

A film having an uneven surface that has undergone antiglare treatment is usually provided on the surface layer of a display or the like. In general, the larger the unevenness provided on the film, the better the antiglare property, but the larger the unevenness, the poorer the scratch resistance in many cases. It is considered that this is because the convex portion is scraped off by rubbing the large unevenness with steel wool or the like, and the film is chipped.

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

Japanese Unexamined Patent Publication No. 11-092690

However, when an organosilica sol coated with an organic resin is used as in Patent Document 1, there is room for improvement in terms of antiglare property.

An object to be solved in the present disclosure is to provide an active energy ray-curable antiglare hard coat agent, a cured film, and a laminated film having good antiglare and scratch resistance.

As a result of diligent studies, the present inventor has found that the above-mentioned problems can be solved by a predetermined active energy ray-curable antiglare hard coat agent.

The disclosure provides the following items:
(Item 1)
Active energy ray-curable antiglare containing (meth) acrylate (A), silsesquioxane (B), hydrophilic silica particles (C) and organic particles (D) having three or more (meth) acryloyl groups. Hard coating agent.
(Item 2)
The cured film of the active energy ray-curable antiglare hard coat agent according to item 1.
(Item 3)
A laminated film having a base material and the cured film according to item 2.
(Item 4)
The laminated film according to item 3, wherein the glossiness at an incident angle of 60 degrees is 50% or less, which is measured according to JIS Z 8741 (1997).

The cured film and laminated film provided in the present disclosure have good antiglare and scratch resistance.

Throughout the present disclosure, the range of numerical values such as each physical property value and content can be set as appropriate (for example, by selecting from the upper and lower limit values described in each of the following items). Specifically, for the numerical value α, when the upper limit of the numerical value α is exemplified by A1, A2, A3, etc., and the lower limit of the numerical value α is exemplified by B1, B2, B3, etc., the range of the numerical value α is A1 or less. A2 or less, 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. are exemplified. In addition, in this disclosure, "~" is used in the meaning of including the numerical values described before and after it as the lower limit value and the upper limit value.

<Ingredient (A)>
The component (A) is a (meth) acrylate having three or more (meth) acryloyl groups. The (meth) acryloyl group is an acryloyl group and / or a methacryloyl group. (Meta) acrylate refers to acrylate and / or methacrylate. The (meth) acryloyl group is represented by the following general formula (1).

（式中、
Ｒ^１は水素原子、又はメチル基である。） General formula (1)

(During the ceremony,
R ¹ is a hydrogen atom or a methyl group. )

The number of (meth) acryloyl groups in the component (A) is 3 or more. Examples of the upper limit of the number of (meth) acryloyl groups of the component (A) are 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 6, 5, and the like. , The lower limit is 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 6, 5, 4, 3 and the like. 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 other than the (meth) acryloyl group or a specific bond. Examples of functional groups other than the (meth) acryloyl group and specific bonds include urethane bonds and hydroxyl groups.

A compound having a urethane bond and having three or more (meth) acryloyl groups may be a reaction product of the following compounds having three or more (meth) acryloyl groups and hydroxyl groups and various known polyfunctional isocyanates. Good. In the present disclosure, the polyfunctional isocyanate refers to one having two or more isocyanate groups (-N = C = O).

As the component (A), a (meth) acrylate having a chain structure and having three or more (meth) acryloyl groups, and a (meth) acrylate having an alicyclic structure and having three or more (meth) acryloyl groups. , (Meta) acrylate having an aromatic ring structure and having three or more (meth) acryloyl groups, and the like are exemplified.

As a (meth) acrylate having a chain structure and having three or more (meth) acryloyl groups, a (meth) acrylate having a chain structure and three (meth) acryloyl groups has a chain structure. A (meth) acrylate having 4 (meth) acryloyl groups, a chain structure, a (meth) acrylate having 5 (meth) acryloyl groups, a chain structure, and 6 (meth) acryloyl groups. (Meta) acrylate having is exemplified.

Examples of the (meth) acrylate having a chain structure and having three (meth) acryloyl groups include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Will be done.

Examples of the (meth) acrylate having a chain structure and having four (meth) acryloyl groups include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and ethoxylated pentaerythritol tetra (meth) acrylate. Illustrated.

Examples of the (meth) acrylate having a chain structure and having five (meth) acryloyl groups include dipentaerythritol penta (meth) acrylate and the like.

Examples of the (meth) acrylate having a chain structure and having 6 (meth) acryloyl groups include dipentaerythritol hexa (meth) acrylate.

As a (meth) acrylate having an alicyclic structure and having three or more (meth) acryloyl groups, a (meth) acrylate having an alicyclic structure and having three (meth) acryloyl groups, an alicyclic structure A (meth) acrylate having 4 (meth) acryloyl groups, a (meth) acrylate having an alicyclic structure, and a (meth) acrylate having 5 (meth) acryloyl groups, 6 having an alicyclic structure. Examples thereof include (meth) acrylate having a (meth) acryloyl group.

As a (meth) acrylate having an aromatic ring structure and having three or more (meth) acryloyl groups, a (meth) acrylate having an aromatic ring structure and having three (meth) acryloyl groups, an aromatic ring structure A (meth) acrylate having 4 (meth) acryloyl groups, a (meth) acrylate having an aromatic ring structure, and a (meth) acrylate having 5 (meth) acryloyl groups, 6 having an aromatic ring structure. Examples thereof include (meth) acrylate having a (meth) acryloyl group.

Examples of other compounds having three (meth) acryloyl groups include tri (meth) acrylate isocyanuric acid, caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate, and glycerin tri (meth) acrylate ethoxylated. Will be done.

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

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

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

The upper limit of the content (solid content conversion) of the component (A) with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is 75, 74, 73, 72, 71. , 70, 65, 60, 55, 50, 45% by mass and the like, and the lower limit is 73, 72, 71, 70, 65, 60, 55, 50, 45, 40% by mass and the like. In one embodiment, the content (in terms of solid content) of the component (A) with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is preferably 40 to 75. It is about mass%, more preferably 45% by mass or more and 75% by mass or less, further 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.

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

（式中、
Ｒ^２は炭素数１以上２０以下のアルキレン基を有していてもよい基を表す。） General formula (2)

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

Examples of the group which may have an alkylene group having 1 or more and 20 or less carbon atoms ^{of R 2} of the general formula (2) include a hydrophilic group and a hydrophobic group. 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 in the alkylene group ^{R 2} is 20 1 or more carbon atoms which may have the following general formula (2) is 20,19,18,17,16,15,14,13,12,11 10, 9, 8, 7, 6, 5, 4, 3, etc. are exemplified, and the lower limit is 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. are exemplified. In one embodiment, the carbon number 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 preferably about 1 or more and 20 or less.

As a component (B), an epoxy group-containing silsesquioxane (product name "Glycidol polysilsesquioxane cage mixture", manufactured by Constru Chemical Co., Ltd.), (meth) acryloyl group-containing silsesquioxane (product name "AC-SQ TA") -100, "AC-SQ SI-20", "MAC-SQ SI-20", "MAC-SQ HDM", "MAC-SQ TM-100", manufactured by Toa Synthetic Co., Ltd. , Constru Chemical Co., Ltd.) (Product name "methacryl-POSS" (manufactured by Sigma Aldrich Japan), Oxetanyl group-containing silsesquioxane (Product name "OX-SQ TX-100" "OX-SQ SI-20" "OX-SQ HDM", manufactured by Toa Synthetic Co., Ltd.), amino group-containing silsesquioxane (product name "Aminopropylisobutyl polysilsesquioxane", manufactured by Construchemical Co., Ltd.) and the like are exemplified.

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

The component (B) is 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 antiglare hard coat agent of the present disclosure. It is preferable to have one or more kinds of the above. In the present disclosure, 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. The presence of a functional group having a polymerizable double bond in the component (B) enables radical curing. The presence of a functional group having a cyclic ether structure in the component (B) enables cation curing. The presence of the thiol group in the component (B) makes it possible to carry out en-thiol curing. 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 and the like are exemplified, and the lower limit is 900, 800, 700, 600, 500, 400, 300, 200, 100, 50 and the like. Will be done. In one embodiment, the functional group equivalent (g / eq) is preferably about 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, Examples include 000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, etc., 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 and the like. 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 disclosure, the measurement of the weight average molecular weight is determined in terms of polystyrene by GPC.

The upper limit of the content (solid content conversion) of the component (B) with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is 50, 45, 40, 35, 30. , 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6% by mass, etc., and the lower limit is 40, 35, 30, 25, 20, 15, 14, 13, 12 , 11, 10, 9, 8, 7, 6, 5% by mass and the like. In one embodiment, the content (in terms of solid content) of the component (B) with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is preferably 5 to 50. It is about mass%, 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. When the content of the component (B) (in terms of solid content) is within the above range with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D), the haze value is excellent. Is preferable.

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

<Ingredient (C)>
The component (C) is hydrophilic silica particles. Hydrophilic silica particles are silica particles having a hydrophilic group. Hydroxyl groups and the like are exemplified as such hydrophilic groups.

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

The dispersion medium of the dispersion of the component (C) may be various known ones. Examples of the dispersion medium for the component (C) include water, an organic solvent, and the like.

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

Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclohexanone and the like.

Examples of the aromatic solvent include toluene, xylene and the like.

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, butanol and the like.

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

Examples of the glycol ether solvent include ethylene glycol ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate and the like.

Examples of the petroleum-based solvent include Solbesso # 100 (manufactured by Exxon Co., Ltd.) and Solbesso # 150 (manufactured by Exxon Co., Ltd.).

Chloroform and the like are exemplified as the haloalkane solvent.

Examples of the amide solvent include dimethylformamide and the like.

Those exemplified as the organic solvent and those known as the organic solvent can be used alone or in combination of two or more.

The component (C) may be a commercially available product. As the product, isopropanol-dispersed silica particles (product name "OSCAL1432", manufactured by Nikki Catalyst Kasei Co., Ltd., average particle size 10 to 20 nm), propylene glycol monomethyl ether-dispersed silica particles (product name "Optisol LSG", manufactured by Ranco). , Average particle size 10 to 15 nm) (Product name "PGM-ST", manufactured by Nissan Chemical Co., Ltd., Average particle size 10 nm to 15 nm), Silica particles dispersed in ethylene glycol ethyl ether (Product name "Optisol LSR", manufactured by Ranco) , Average particle size 10 to 15 nm), water-dispersed silica particles (product name "Snowtex ST-CXS", manufactured by Nissan Chemical Co., Ltd., average particle size 5 nm) (product name "Snowtex ST-C", Nissan Chemical Made by Admanano Co., Ltd., average particle size 12 nm), powder silica particles (product name "Admanano 10 nm", manufactured by Admatex Co., Ltd., average particle size 10 nm) (Product name "Admanano 50 nm", manufactured by Admatex Co., Ltd. , Average particle size 50 nm) and the like.

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

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

The average particle size is measured by a particle size distribution measurement by a laser diffraction / scattering method using a commercially available measuring machine (product name "Microtrac MT3000II", manufactured by Microtrac BEL Co., Ltd.) in accordance with JIS Z 8828 (2013).

The upper limit of the content (solid content conversion) of the component (C) with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is 20, 15, 10, 5, 3 Mass% and the like are exemplified, and the lower limit is 15, 10, 5, 3, 1 mass% and the like. In one embodiment, the content (in terms of solid content) of the component (C) with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is preferably 1 to 20. It is about mass%, more preferably 3% by mass or more and 20% by mass or less, further 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]) between the component (A) and the component (C) is 98/2, 97/3, 96/4, Examples are 95/5, 94/6, 93/7, 92/8, 91/9, 90/10, 85/15, 82/18, etc., and the lower limit is 97/3, 96/4, 95/5, etc. , 94/6, 93/7, 92/8, 91/9, 90/10, 85/15, 82/18, 80/20 and the like. In one embodiment, the content ratio of the component (A) to the component (C) (mass ratio, solid content conversion, [(A) component / (C) component]) is about 80/20 to 98/2. Is preferable.

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

<Ingredient (D)>
The component (D) is an organic particle. Examples of the component (D) include melamine-based particles, acrylic-based particles, acrylic-styrene-based particles, carbonate-based particles, ethylene-based particles, styrene-based particles, benzoguanamine-based particles, and acrylonitrile-based particles. The above-mentioned "...-based particles" refer to particles containing "..." as a raw material.

The component (D) is preferably acrylic-styrene particles because the refractive index can be easily adjusted by the monomer mixing ratio.

The component (D) may be a commercially available product. As the product, acrylic particles (product name "Eposter MA1004", manufactured by Nippon Catalyst Co., Ltd., average particle size 4 μm) (product name "Eposter MA1006", manufactured by Nippon Catalyst Co., Ltd., average particle size 6 μm) (product name) "Tuftic FH-S005", manufactured by Nippon Exlan Industry Co., Ltd., average particle size 5 μm) (Product name "Chemisnow MR series", manufactured by Soken Kagaku Co., Ltd., average particle size 1-10 μm) (Product name "Techpolymer MBX" -5 ”, Sekisui Kasei Kogyo Co., Ltd., average particle size 5 μm) (Product name“ Techpolymer MBX-8 ”, Sekisui Kasei Kogyo Co., Ltd., average particle size 8 μm), acrylic-styrene particles ( Product name "Eposter MA2003", manufactured by Nippon Catalyst Co., Ltd., average particle size 3 μm) (Product name "Techpolymer MSX", manufactured by Sekisui Kasei Kogyo Co., Ltd., average particle size 5 μm) (Product name "Techpolymer SMX" , Sekisui Kasei Kogyo Co., Ltd., average particle size 5 μm), styrene particles (product name “Techpolymer SBX-4”, Sekisui Kasei Kogyo Co., Ltd., average particle size 4 μm), acrylonitrile particles (product) The name "Tuftic ASF", manufactured by Nippon Exlan Industry Co., Ltd., with an average particle size of 7 μm) is exemplified.

The component (D) may be obtained synthetically. 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. Specific means of the method (1) above include a nozzle vibration method, an SPG film emulsification method, a microchannel method, and a mini-emulsion polymerization method. Specific means of the method (2) above include a soap-free emulsification polymerization method, a dispersion polymerization method, a suspension polymerization method, and a seed emulsification polymerization method.

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

The upper limit of the average particle size of the component (D) is 10, 9, 8, 7, 6, 5, 4, 3, 2 μm, etc., and the lower limit is 9, 8, 7, 6, 5, 4, 3 , 2, 1, 0.5 μm and the like are exemplified. In one embodiment, the average particle size of the component (D) is preferably about 0.5 to 10 μm. When the average particle size of the component (D) is not more than the above upper limit, it is particularly excellent in suppressing glare due to the lens effect. On the other hand, when the average particle size of the component (D) is at least the above lower limit, the cured film or laminated film in the present disclosure can exhibit particularly antiglare properties.

The upper limit of the refractive index of the component (D) is 1.70, 1.65, 1.60, 1.55, 1.54, 1.53, 1.52, 1.51, 1.50, 1.45. Etc. are exemplified, and the lower limit is exemplified by 1.65, 1.60, 1.55, 1.54, 1.53, 1.52, 1.51, 1.50, 1.45, 1.40 and the like. Will be done. In one embodiment, the refractive index of the component (D) is preferably about 1.40 to 1.70.

In the present disclosure, the refractive index of component (D) is measured by a method according to JIS K 7142 (1996).

The upper limit of the content (solid content conversion) of the component (D) with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is 30, 25, 20, 15, 10 5, 5% by mass and the like are exemplified, and the lower limit is 25, 20, 15, 10, 5, 3% by mass and the like. In one embodiment, the content (in terms of solid content) of the component (D) with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is preferably 3 to 30. It is about mass%, more preferably 3% by mass or more and 25% by mass or less, further 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]) between the component (A) and the component (D) is 95/5, 90/10, 89/11, 88/12, 87/13, 86/14, 85/15, 80/20, 75/25, 70/30, etc. are exemplified, and the lower limit is 90/10, 89/11, 88/12, 87/13. , 86/14, 85/15, 80/20, 75/25, 70/30, 65/35 and the like. In one embodiment, the content ratio of the component (A) to the component (D) (mass ratio, solid content conversion, [(A) component / (D) component]) is preferably 65/35 to 95 /. It is about 5, more preferably 70/30 to 95/5, even 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]) between the component (B) and the component (D) 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 and the like. In one embodiment, the content ratio of the component (B) to the component (D) (mass ratio, solid content conversion, [(B) component / (D) component]) is preferably 40/60 to 80 /. It is about 20, more preferably 45/55 to 80/20, even 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]) between the component (C) and the component (D) is 45/55, 40/60, 35/65, 34/66, 33/67, 32/68, 31/69, 30/70, etc. are exemplified, and the lower limit is 40/60, 35/65, 34/66, 33/67, 32/68, 31/69. , 30/70, 25/75 and the like. In one embodiment, the content ratio (mass ratio, solid content conversion, [(C) component / (D) component]) of the component (C) to the component (D) is preferably 25/75 to 45 /. It is about 55, more preferably 25/75 to 40/60, even more preferably 30/70 to 40/60, and particularly preferably 30/70 to 35/65.

The presumed mechanism for obtaining a laminated film having a desired effect by using the active energy ray-curable antiglare hard coat agent of the present disclosure is as follows. The hydrophilic component (C) has poor compatibility with the components (A) and (B) and tends to aggregate in the hard coat film. This contributes to the development of internal haze and the appearance of a matte surface. Further, the component (D) imparts unevenness to the surface of the hard coat film, and the component (C) exhibits a matte feeling and antiglare property. Further, the unevenness of the hard coat film is reduced by agglutinating the component (B) around the component (D). From this, it is considered that the laminated film formed by using the active energy ray-curable antiglare hard coat agent of the present disclosure exhibits scratch resistance and antiglare in an optimum balance. As a result, various particles in the active energy ray-curable antiglare hard coat agent of the present disclosure are less likely to fall off than the laminated film, and it is possible to suppress the transparency of the laminated film. On the other hand, although the unevenness of the laminated film is gentle, it exhibits good antiglare properties.

<Other agents that can be blended>
The active energy ray-curable antiglare hard coat agent of the present disclosure further comprises an initiator, a leveling agent, a photosensitizer, a surface conditioner, a surfactant, an ultraviolet absorber, an inorganic filler, and an organic solvent, if necessary. , Defoaming agents, wetting agents, rust preventives, stabilizers and other various additives can also be blended. Examples of the organic solvent that can be blended include the above-mentioned organic solvents. The upper limit of the content of various additives with respect to the total amount of 100% by mass of the component (A), the component (B), the component (C) and the component (D) is 10, 9, 8, 7, 6, 5, 4, 3 , 2, 1% by mass and the like are exemplified, and the lower limit is 9,8,7,6,5,4,3,2,1,0% by mass and the like. In one embodiment, the content of various additives with respect to 100% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D) is preferably about 0 to 10% by mass.

<Cured film>
The present disclosure also provides a cured film obtained by irradiating an active energy ray-curable antiglare hard coat agent with active energy rays.

As a method of curing by irradiation with active energy rays, high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs, etc. that emit light in the 150 nm wavelength range or more and 450 nm wavelength range or less. using, 10 mJ / cm ² or more 10,000 / cm ² method of degree radiation below are exemplified. Conditions such as the amount of light, the light source, and the transport speed may be appropriately adjusted. For example, when a high-pressure mercury lamp is used, the amount of light is usually ^{about 0.1 to 160 W / cm 2} , and the transport speed is usually about 5 to 50 m / min. is there. Before irradiation with active energy rays, heating may be performed to dry the cells, if necessary. After irradiation with active energy rays, heating may be performed if necessary to completely cure the cells.

<Laminated film>
The present disclosure also provides a laminated film containing a base material and the cured film.

The surface of the base material is subjected to various surface treatments such as corona treatment, plasma treatment, primer coating, degreasing treatment, and surface roughening treatment for the purpose of improving the adhesiveness and adhesion between the base material and the cured film. You may. Further, another layer (for example, an easy-adhesive layer, an adhesive layer, etc.) may be arranged between the base material and the cured film for the purpose of improving the adhesiveness and adhesion between the base material and the cured film. ..

As a specific example of the laminated film of the present invention, a laminated film having various layers in the following order is exemplified.
(1) Hardened film / base material,
(2) Hardened film / easy-adhesive layer or adhesive layer / base material,

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

Examples of the base material to which the active energy ray-curable antiglare hard coating agent of the present disclosure is applied include wood, paper, slate, metal, plastic, glass and other resins. Examples of the metal include iron, aluminum, aluminum-plated steel sheet, tin-free steel sheet (TFS), stainless steel sheet, zinc phosphate-treated steel sheet, and zinc-zinc alloy plated steel sheet (bonded steel sheet). Examples of the plastic include a thermoplastic plastic base material and a thermosetting plastic base material. Examples of the thermoplastic plastic base material include general-purpose plastic base materials and engineering plastic base materials. Examples of the general-purpose plastic base material include olefin-based, polyester-based, acrylic-based, vinyl-based, and polystyrene-based. Examples of the olefin-based resin include polyethylene, polypropylene, alicyclic olefin-based resin (norbornene, etc.) and the like. Examples of polyesters include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of acrylics include polymethylmethacrylate (PMMA) and the like. Examples of the vinyl type include polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol and the like. Examples of polystyrene-based resins include polystyrene (PS) resin, styrene-acrylonitrile (AS) resin, and styrene-butadiene-acrylonitrile (ABS) resin. Examples of engineering plastic base materials include general-purpose engineering plastics and super engineering plastics. Examples of general-purpose engineering plastics include polycarbonate, polyamide (nylon), and the like. Examples of super engineering plastics include polyetheretherketone (PEEK) and the like. Examples of the thermosetting plastic base material include polyimide, epoxy resin, and melamine resin. Examples of other plastic substrates include triacetyl cellulose resin and the like. Among these, one selected from the group consisting of polyester-based, triacetyl cellulose resin, polycarbonate, acrylic resin and alicyclic olefin-based resin is preferable from the viewpoint of transparency and adhesion to the laminated film. The average thickness of the base film is not particularly limited, but the upper limit of the average thickness of the base film is exemplified by 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 50 μm and the like. The lower limit is exemplified by 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 30 μm and the like. 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 disclosure has a fine uneven structure. Therefore, it is possible to suppress the reflection of the external scene due to the surface reflection, and it is possible to enhance the antiglare property. The antiglare property is related to the glossiness, and the glossiness of the laminated film of the present disclosure is as follows. The upper limit of the glossiness of the laminated film of the present disclosure at an incident angle of 60 degrees is 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18 , 16, 14%, etc., 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 exemplified. In one embodiment, the glossiness of the laminated film of the present disclosure at an incident angle of 60 degrees may be 50% or less, preferably about 10 to 50%. Further, the upper limit of the glossiness of the laminated film of the present disclosure at an incident angle of 20 degrees is exemplified by 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2% and the like. The lower limit is 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1% and the like. In one embodiment, the glossiness of the laminated film of the present disclosure at an incident angle of 20 degrees is preferably about 1 to 15%. When the glossiness is at least the above lower limit, blurring of the displayed image is reduced and it becomes easier to see. Further, when the glossiness is not more than the above upper limit, the antiglare property is excellent. The glossiness of the antiglare hard coat layer of the laminated film of the present disclosure at an incident angle of 60 degrees and the glossiness at an incident angle of 20 degrees are measured by the method described in JIS Z 8741 (1997).

Specific examples of the present disclosure will be described below with reference to examples, but the present disclosure is not limited to these examples. In the examples, parts and% are all based on solid content mass unless otherwise specified.

<Example 1: Preparation of active energy ray-curable antiglare hard coat agent (1)>
65.5 parts by mass of dipentaerythritol poly (meth) acrylate (product name "Aronix M-402", manufactured by Toa Synthetic Co., Ltd.) as the component (A), and silsesquioxane (product name "product name") as the component (B). MAC-SQ TM-100 ”, manufactured by Toa Synthetic Co., Ltd., 20.0 parts by mass, and silica particles dispersed in propylene glycol monomethyl ether (product name“ PGM-ST ”, manufactured by Nissan Chemical Co., Ltd.) as component (C) 5 .0 parts by mass, (D) organic particles (product name "Techpolymer SSX series customized product", manufactured by Sekisui Kasei Kogyo Co., Ltd., average particle diameter: 4 μm, refractive index: 1.535) 9.5 By mass, 2.0 parts by mass of 1- [4- (2-hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanol as an initiator and 2-hydroxy-1- (4- (4- (2- (2-) 2-) Methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one was mixed in an amount of 2.0 parts by mass, and the product name "BYK-350" (manufactured by BYK Adaptives & Instruments) was mixed as a leveling agent by 0.2 parts by mass. Diluted with propylene glycol monomethyl ether to prepare an active energy ray-curable antiglare hard coat agent having a solid content of 30% by mass.

<Examples 2 to 5 and Comparative Examples 1 to 5: Preparation of active energy ray-curable antiglare 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 compositions shown in Table 1 were changed, and the active energy ray-curable antiglare hard coat agent (2). -(5) and (C1)-(C5) were obtained.

<Evaluation Example 1: Preparation of Laminated Film (1)>
Triacetyl cellulose film (product name "FT TD80ULM", manufactured by Fuji Film Co., Ltd., film thickness so that the film thickness after drying of the active energy ray-curable antiglare hard coat agent (1) is 3.6 μm. : 80 μm) using Mayer Bar No. 9, dried at 80 ° C. for 1 minute, then irradiated with active energy rays in a nitrogen atmosphere (ultraviolet irradiation: 550 mW / cm ² , 300 mJ / cm ² ), laminated film. (1) was obtained.

<Evaluation Examples 2 to 5 and Comparative Evaluation Examples 1 to 5: Preparation of Laminated Films (2) to (5) and (C1) to (C5)>
In Evaluation Examples 2 to 5 and Comparative Evaluation Examples 1 to 5, the active energy ray-curable antiglare hard coat agent (1) was used as the active energy ray curable antiglare hard coat agent (2) to (5) or ( Laminated films (2) to (5) and (C1) to (C5) were obtained by the same method as in Evaluation Example 1 except that the changes were changed to C1) to (C5).

<Performance evaluation (1): τT (total light transmittance)>
Laminated films (1) to (5) and (C1) using a haze meter (product name "HZ-V3", manufactured by Suga Test Instruments Co., Ltd.) in accordance with the JIS K 7361-1 (1997) standard. The total light transmittance of ~ (C5) was measured.

<Performance evaluation (2): Haze value>
In accordance with the JIS K 7136 (2000) standard, using a haze meter (product name "HZ-V3", manufactured by Suga Test Instruments Co., Ltd.), laminated films (1) to (5) and (C1) to ( The haze value of C5) was measured.

<Performance evaluation (3): Gloss at an incident angle of 20 degrees>
Laminated films (1) to (5) and (C1) to using a gloss meter (product name "VG-7000", manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with the JIS Z 8741 (1997) standard. The glossiness at an incident angle of 20 degrees in (C5) was measured.

<Performance evaluation (4): Gloss at an incident angle of 60 degrees>
Laminated films (1) to (5) and (C1) to using a gloss meter (product name "VG-7000", manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with the JIS Z 8741 (1997) standard. The glossiness at an incident angle of 60 degrees in (C5) was measured.

<Performance evaluation (5): Scratch resistance>
The laminated films (1) to (5) and (C1) to (C5) were installed in a steel wool testing machine with the antiglare hard coat layers facing upward, and 500 g / g using # 0000 steel wool. The test was carried out by rubbing 10 reciprocations with a load of ^{cm 2 at a sliding distance of 4 cm.} The appearance change (transparency) in the antiglare hard coat layer was visually confirmed and evaluated according to the following criteria.
◯: Transparency does not occur.
Δ: Slightly transparent.
X: Completely transparent.

The meanings of the terms in Table 1 are as follows.
DPPA: Dipentaerythritol polyacrylate (product name "Aronix M-402", manufactured by Toagosei Co., Ltd.)
SQ: Silsesquioxane (product name "MAC-SQ TM-100", manufactured by Toagosei Co., Ltd.)
Hydrophilic silica: Silica particles dispersed in propylene glycol monomethyl ether (product name "PGM-ST", manufactured by Nissan Chemical Co., Ltd., average particle size 12 nm)
Hydrophobic silica: Silica particles surface-treated with a urethane (meth) acrylate structure-containing silane coupling agent obtained through Production Examples 1 and 2 below Organic particles: Copolymer of polymethyl methacrylate and styrene (product name "Product name" Techpolymer SSX Series Customized Product ", manufactured by Sekisui Kasei Kogyo Co., Ltd., average particle size: 4 μm, refractive index: 1.535)

<Production Example 1: Preparation of Urethane (Meta) Acrylate Structure-Containing Silane Coupling Agent>
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and an air inlet, 20 parts by mass of isophorone diisocyanate, 72 parts by mass of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name "KAYARAD PET-30"). , Nippon Kayaku Co., Ltd.), (3-mercaptopropyl) trimethoxysilane 8 parts by mass, 2,6-di-tert-butyl-4-methylphenol 0.02 parts by mass as a polymerization inhibitor, and as a catalyst 0.2 parts by mass of dioctyltin dilaurate was mixed, and the reaction was carried out under the condition of 70 ° C. for 5 hours. After completion of the reaction, a mixture containing urethane (meth) acrylate structure-containing trimethoxysilane, urethane (meth) acrylate and pentaerythritol tetraacrylate in an amount of 1/3 by mass was obtained. The mixture was used as a urethane (meth) acrylate structure-containing silane coupling agent.

<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) and 1.3% by mass in terms of solid content. A silane coupling agent containing% urethane (meth) acrylate structure was mixed and reacted at 60 ° C. for 4 hours to produce surface-treated silica particles. The average particle size was 10 nm. The values of hydrophobic silica in Table 1 include the urethane (meth) acrylate and pentaerythritol tetraacrylate in addition to the surface-treated silica particles.

Claims (4)

Active energy ray-curable antiglare containing (meth) acrylate (A), silsesquioxane (B), hydrophilic silica particles (C) and organic particles (D) having three or more (meth) acryloyl groups. Hard coating agent. A cured film of the active energy ray-curable antiglare hard coat agent according to claim 1. A laminated film having a base material and the cured film according to claim 2. The laminated film according to claim 3, wherein the glossiness at an incident angle of 60 degrees is 50% or less, which is measured according to JIS Z 8741 (1997).