JP6840215B1 - Method for manufacturing active energy ray-curable composition for antiglare hard coat and antiglare hard coat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition for an antiglare hard coat and a method for producing an antiglare hard coat film, which can form an antiglare hard coat layer with almost no glare without deteriorating image quality. .. SOLUTION: In an active energy ray-curable composition for an antiglare hard coat containing a polymerizable unsaturated compound, silica fine particles, and resin particles, an acrylic copolymer having a polyether chain within a specific molecular weight range is used. An active energy ray-curable composition containing a specific amount. [Selection diagram] None

Description

The present invention relates to an active energy ray-curable composition for an antiglare hard coat capable of forming an antiglare hard coat having almost no glare without deteriorating image quality, and a method for producing an antiglare hard coat film using the active energy ray-curable composition.

A display typified by a liquid crystal display such as a television, a personal computer or a smartphone, or an organic EL display may use an antiglare film in order to reduce the reflection of external light.

In recent years, the definition of high-definition displays is accelerating, and when an antiglare protective film is attached to such a high-resolution display in an attempt to suppress reflection of external light, the screen may feel grainy or glare. This is a phenomenon called "glare" (Sparkle) due to the light interference between the coating film of the protective film applied to the display surface and the display pixels, which may promote eye fatigue and cause discomfort. It is a problem.

As a method of imparting antiglare property to an image display body having advanced high definition without deteriorating the image quality, for example, in Patent Document 1, the surface of a transparent plastic film is polyfunctional (meth). ) Hard containing an acrylate-based monomer and / or (meth) acrylate-based prepolymer, an active energy ray-sensitive composition containing silica-based fine particles, spherical organic fine particles, and a dispersant having at least one polar group in the molecule. An antiglare hard coat film having a hard coat layer formed by using a coat layer forming material and having a thickness of the hard coat layer larger than the average particle size of the spherical organic fine particles. It is being developed. In the same document, the external haze value and 60 ° gloss are based on the technical idea that the spherical organic fine particle component is unevenly distributed near the surface of the hard coat layer by adding a dispersant component having at least one polar group in the molecule. When the value is controlled to a desired value, it is said that an antiglare hard coat film having excellent surface hardness can be obtained without lowering the contrast. However, there are still problems in terms of storage stability of the paint and suppression of glare in the obtained hard coat layer.

JP-A-2009-244305

The present invention has been made in view of the above circumstances, and is an active energy ray-curable composition for an antiglare hard coat capable of forming an antiglare hard coat layer with almost no glare without deteriorating image quality. It is intended to provide a method for producing an antiglare hard coat film.

Under such circumstances, as a result of diligent research, the present inventors have found that the active energy ray-curable composition for antiglare hard coat containing polymerizable unsaturated compound, silica fine particles, and resin particles is within a specific molecular weight range. It has been found that the above-mentioned problems can be solved by containing a specific amount of an acrylic copolymer having a polyether chain of the above.

That is, the present invention comprises an acrylic copolymer (A) having a polyether chain having a molecular weight in the range of 200 to 10,000, a polymerizable unsaturated compound (B), silica fine particles (C), resin particles (D), and photopolymerization initiation. The content of the acrylic copolymer (A) containing the agent (E) is within the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the components (B) and (C). It relates to an active energy ray-curable composition for an antiglare hard coat.

According to the present invention, it is possible to form an antiglare hard coat layer with almost no glare without deteriorating the image quality. By applying the present invention, it is possible to reduce "glare" (Sparkle) and screen roughness due to optical interference even in a display having a higher resolution than a conventional display.

The active energy ray-curable composition for antiglare hard coat according to the present invention includes a specific acrylic copolymer (A), a polymerizable unsaturated compound (B), silica fine particles (C), resin particles (D), and light. A composition containing a polymerization initiator (E) and having a content of the specific acrylic copolymer (A) within a specific range.

<Acrylic copolymer (A)>
The active energy ray-curable composition for an antiglare hard coat of the present invention contains an acrylic copolymer (A) having a polyether chain having a molecular weight in the range of 200 to 10,000. The acrylic copolymer (A) having a polyether chain having a molecular weight in the range of 200 to 10000 is a polymerizable unsaturated monomer having a polyether chain having a molecular weight in the range of 200 to 10000 and other copolymerizable products with this monomer. Copolymerization Containing a Monomer It can be obtained by copolymerizing a monomer component.

As the polymerizable unsaturated monomer having a polyether chain, a polyether mono (meth) acrylate (a2) represented by the following formula (1), which is obtained by modifying (meth) acrylate with a polyether macromer, is preferably used. Can be used. In addition, in this specification, "(meth) acrylate" means "acrylate or methacrylate".

(In the formula, R ¹ is H or CH ₃ , R ² is a divalent alkylene group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms and / or aryl. It is a group, and n is a positive integer.)
Examples of the divalent alkylene group having 1 to 6 carbon atoms R ^2, for example, methylene group, ethylene group, n- propylene, isopropylene, n- butylene, n- pentylene, n- hexylene and the like They may be the same or two or more. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferable, and an ethylene group and / or a propylene group is particularly preferable.
R ³ has methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl, hexyl group, heptyl group, octyl group, nonyl group and trimethylpentyl group as alkyl groups having 1 to 15 carbon atoms. Examples thereof include linear or branched alkyl groups having 1 to 15 carbon atoms, and examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a phenanthryl group. These may be optionally substituted with oxygen, halogen, an alkyl group having 1 to 9 carbon atoms, or the like. In particular, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable.

Examples of the polymerizable unsaturated monomer having such a polyether chain include polyethyl ether mono (meth) acrylate, polypropyl ether mono (meth) acrylate, polyethylene-polypropylene block type ether mono (meth) acrylate, and polybutyl ether mono (meth). ) Acrylate and the like can be mentioned, and among them, polyethyl ether mono (meth) acrylate can be preferably used.

In the present invention, in the formula (1) representing the above-mentioned polyether mono (meth) acrylate (a2), the positive integer n means the average number of added moles of the divalent alkylene oxide having 1 to 6 carbon atoms. The molecular weight of the polyether chain is selected to be in the range of 200 to 10000. By setting the molecular weight of the polyether chain within a specific range, it is possible to form an antiglare hard coat layer with almost no glare without deteriorating the image quality. The molecular weight of the polyether chain is preferably in the range of 250 to 3000, more preferably in the range of 300 to 2000.

As the polyether mono (meth) acrylate, a commercially available product can also be used.
For example, "NK ester M-230G (methoxypolyethylene glycol monomethacrylate, EO (abbreviation of ethylene oxide) average number of moles added = 23)", "NK ester M-450G (methoxypolyethylene glycol monomethacrylate, EO average number of moles added = 23)" 45) ”,“ NK Ester M-90G (methoxypolyethylene glycol monomethacrylate, EO average number of moles added = 9) ”,“ NK ester AM-90G (methoxypolyethylene glycol monoacrylate, EO average number of moles added = 9) ”, "NK ester AM-130G (methoxypolyethylene glycol monoacrylate, EO average number of moles added = 13)" or higher, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name, "Bizomer (registered trademark) MPEG550MA (trade name, manufactured by Cognis), Methoxypolyethylene glycol methacrylate, EO average number of moles added = 12.5) "," Visiomer® MPEG
5005 MAW (trade name, manufactured by Evonic, methoxypolyethylene glycol methacrylate, EO average number of moles added = 113) "," Blemmer (registered trademark) PLE-1300 (trade name, manufactured by Nichiyu Co., Ltd., lauroxypolyethylene glycol methacrylate, Polyethyl ether mono (EO average added moles = 30) "," Blemmer (registered trademark) PSE-1300 (trade name, manufactured by Nichiyu Co., Ltd., stearoxypolyethylene glycol methacrylate, EO average added moles = 30) " Meta) acrylate; "Blemmer (registered trademark) 50POEP-800B (trade name, manufactured by Nichiyu Co., Ltd., Octoxypolyethylene glycol-polypropylene glycol-methacrylate (block type), EO average number of moles added = 8, propylene oxide (PO)) Examples thereof include polyethylene-polypropylene block type ether mono (meth) acrylate such as "average number of added moles = 6, total n = 14".

Examples of other monomers copolymerizable with the polymerizable unsaturated monomer having a polyether chain include carboxyl group-containing unsaturated monomers such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; methyl (meth) acrylate and ethyl. (Meta) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl Acrylate or methacrylic acid such as (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate isostearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name). Alkyl ester with; acrylamide such as (meth) acrylamide, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethyl (meth) acrylamide; polymerizable organic siloxane such as polysiloxane mono (meth) acrylate; styrene, vinyl Examples thereof include toluene, vinyl acetate, acrylonitrile, acrylamide, metaacrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate. These can be used alone or in combination of two or more.

The acrylic copolymer (A) may contain a monomer (a1) having two or more polymerizable unsaturated groups in the molecule as a constituent component of the acrylic copolymer (A), which is a phase of the obtained acrylic copolymer and other components. It is preferable from the viewpoint of solubility. Further, by using the monomer (a1) having two or more polymerizable unsaturated groups in the molecule, a branched structure can be obtained in the acrylic copolymer, and the polyether chain can be efficiently introduced into the acrylic copolymer. preferable. The content of the monomer (a1) having two or more polymerizable unsaturated groups in the molecule is preferably in the range of 0.01 to 10 mol% with respect to the total amount of the copolymerizable monomer components, and more preferably. It is in the range of 0.05 to 8 mol%. Examples of the monomer (a1) having two or more polymerizable unsaturated groups in the molecule include an esterified product of a polyhydric alcohol and (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol. Di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropylene di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butanediol di (meth). ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A Di (meth) acrylate compounds such as ethylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, and isosorbide di (meth) acrylate; glycerintri (meth). Acrylate, glycerin ethylene oxide-modified tri (meth) acrylate, glycerin propylene oxide-modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, trimethylolpropane propylene oxide-modified tri (meth) acrylate Tri (meth) acrylate compounds such as (meth) acrylate, isocyanurate ethylene oxide-modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone-modified tris (acryloxyethyl) isocyanurate; pentaerythritol tetra (meth) ) Acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, pentaerythritol propylene oxide-modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane ethylene oxide-modified tetra (meth) acrylate, ditrimethylolpropane propylene Oxide-modified tetra (meth) acrylate, diglycerin tetra (meth) acrylate, diglycerin ethylene oxide-modified tetra (meth) acrylate Tetra (meth) acrylate compounds such as te, diglycerin propylene oxide-modified tetra (meth) acrylate; other, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; functional groups with (meth) acrylate groups. Examples thereof include acrylated polydimethylsiloxane. The monomer (a1) having two or more polymerizable unsaturated groups in these molecules can be used alone or in combination of two or more.

In the present invention, the content of the acrylic copolymer (A) is a mass ratio [(A) / {(C) + (D)) with respect to the total content of the silica fine particles (C) and the resin particles (D). }], Preferably in the range of 0.10 to 14.00 / 99.90 to 86.00, more preferably in the range of 0.50 to 12.00 / 99.50 to 88.00, and further. It is preferably in the range of 0.80 to 10.00 / 99.20 to 90.00. By setting the content of the acrylic copolymer (A) within a specific range, an active energy ray-curable composition for an antiglare hard coat capable of forming an antiglare hard coat layer having almost no glare is provided.

<Polymerizable unsaturated compound (B)>
The active energy ray-curable composition for an antiglare hard coat of the present invention contains a polymerizable unsaturated compound (B). The polymerizable unsaturated compound (B) is a compound having one or more polymerizable unsaturated groups in the molecule. In the present specification, the polymerizable unsaturated group means an unsaturated group capable of radical polymerization, and specifically, for example, a (meth) acryloyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group, and the like. Examples thereof include a (meth) acrylamide group and a vinyl ether group. In the present specification, "(meth) acryloyl" means acryloyl or methacryloyl, and "(meth) acrylamide" means "acrylamide or methacrylamide". Among these polymerizable unsaturated groups, acryloyl group and methacryloyl group are preferable, and acryloyl group is particularly preferable, from the viewpoint of excellent reactivity.

Further, the polymerizable unsaturated compound (B) may have an ester bond, a urethane bond, a urea bond, a thiourethane bond or the like in the molecule, and particularly from the viewpoint of scratch resistance and curl property. A polymerizable unsaturated compound (b1) having a urethane bond can be preferably used, and examples of the polymerizable unsaturated compound (b1) having a urethane bond include a urethane (meth) acrylate compound.

The urethane (meth) acrylate compound particularly preferably used in the active energy ray-curable composition for antiglare hard coat of the present invention has an unsaturated group equivalent of 110 or more and less than 600, and a weight average molecular weight of 600 to 6,000. It is preferably within the range. The urethane (meth) acrylate is a compound having at least one urethane bond and at least one (meth) acryloyl group in one molecule, and from the viewpoint of excellent reactivity among the (meth) acryloyl groups. , Acryloyl group is particularly preferable.

In the present specification, where the molecular weight of the compound having a polymerizable unsaturated group is M and the number of polymerizable unsaturated groups contained in the molecular weight is σ, the unsaturated group equivalent is a value represented by M / σ. is there.

The weight average molecular weight of the urethane (meth) acrylate is preferably in the range of 600 to 6,000, preferably in the range of 1,000 to 5,800, from the viewpoint of the appearance of the film, the hardness of the film and the flexibility. Is particularly suitable.

In the present specification, the weight average molecular weight is the retention time (retention capacity) of standard polystyrene having a known molecular weight measured under the same conditions as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). It is a value obtained by converting into the molecular weight of polystyrene. Specifically, "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph device, and "TSKgel G4000HXL", "TSKgel G3000HXL", "TSKgel G2500HXL" and "TSKgel" are used as columns. A total of 4 G2000HXL (trade name, all manufactured by Tosoh Corporation) are used, a differential refractometer is used as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow velocity: 1 mL / min. Can be measured below.

Examples of the urethane (meth) acrylate include
(1) Reacting a polyisocyanate compound with a compound having a hydroxyl group and a (meth) acryloyl group.
(2) An isocyanate group-containing (meth) acrylate monomer is reacted with a polyurethane polyol obtained by reacting a polyisocyanate compound with a polyol.
Examples thereof include reaction products produced by such methods.

Examples of the polyisocyanate compound used for producing urethane (meth) acrylate include an aliphatic diisocyanate compound such as hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, and lysine diisocyanate, and isophorone diisocyanate. , 4,4'-Alicyclic diisocyanate compound such as methylene bis (cyclohexyl isocyanate), tolylene diisocyanate, phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate and other aromatics Examples thereof include diisocyanate compounds and diisocyanate diisocyanates or trimerics (biuret adducts, isocyanurate ring type adducts, etc.).

Examples of the compound having a hydroxyl group and (meth) acryloyl group used in the production of urethane (meth) acrylate include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 2-hydroxyethyl (meth). Acrylate, glycerol di (meth) acrylate, alkylene oxide-modified or lactone-modified compounds obtained by adding ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone, etc. to these, and polyisocyanate to these compounds. Can be mentioned.

Examples of polyols used in the production of urethane (meth) acrylate include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone diol, and polyester. Examples thereof include polyols and polyether polyols.

Examples of the isocyanate group-containing (meth) acrylate monomer include an active hydrogen-containing polymerizable monomer such as isocyanate ethyl (meth) acrylate and isocyanate propyl (meth) acrylate, and a polyisocyanate such as hexamethylene diisocyanate. Examples thereof include unsaturated compounds obtained by adding a compound.

Further, as the urethane (meth) acrylate, a commercially available product can also be used. For example, UV-1700B, UV-6300B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV- of the Shikou (registered trademark) series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 7650B and Negami Kogyo Co., Ltd. Art Resin (registered trademark) series UN-3320HA, UN-3320HC, UN-3320HS, UN-904, UN-906S, UN-901T, UN-905, UN-952, Daicel Ornex EBECRYL (registered trademark) series EBECRYL4666, EBECRYL4680, EBECRYL8210, EBECRYL1290, EBECRYL8254, KRM series KRM8528, KRM8200, KRM8200AE, KRM8904 can be mentioned.
Urethane (meth) acrylate can be used alone or in combination of two or more.

The polymerizable unsaturated compound (b2) other than the polymerizable unsaturated compound (b1) having a urethane bond, which is used as the polymerizable unsaturated compound (B) in the present invention, has a polymerizable unsaturated double bond in its chemical structure. A compound having at least one double bond, the type of which is not particularly limited as long as it does not impair the performance of the active energy ray-curable composition of the present invention, such as antiglare property and glare suppression, and is monofunctional polymerization. Examples include sex-unsaturated compounds and polyfunctional polymerizable unsaturated compounds.

Examples of the monofunctional polymerizable unsaturated compound include an esterified product of a monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl. (Meta) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, N-acryloyloxyethyl hexahydro Examples include phthalimide. Further, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate and the like. Carboxyl group-containing (meth) acrylate; glycidyl group-containing polymerizable unsaturated compound such as glycidyl (meth) acrylate and allyl glycidyl ether; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene; N , N-Dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N-t-butylaminoethyl (meth) acrylate and other nitrogen-containing alkyl (meth) acrylates; acrylamide, methacrylicamide, N- Methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Polymerizable amide compounds such as N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; N- (2-methacryloyloxyethyl) ethylene urea, hydroxyethyl ethylene urea (meth) acrylate Examples thereof include alkoxylated urea (meth) acrylates and the like.

Examples of the polyfunctional polymerizable unsaturated compound include an esterified product of a polyhydric alcohol and (meth) acrylic acid (a polymerizable unsaturated compound having at least two ester bonds in the molecule; polyester (meth) acrylate). There are times) and so on. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth). Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, tricycloden Di (meth) acrylate compounds such as candimethanol di (meth) acrylate, hydride bisphenol A di (meth) acrylate, hydride bisphenol F di (meth) acrylate, hydride hexafluorobisphenol A di (meth) acrylate; (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Trimethylol Propanepropylene Oxide Modified Tri (Meta) Acrylate, Trimethylol Propaneethylene Oxide Modified Tri (Meta) Acrylate, ε-Caprolactone Modified Tris (Acryloxyethyl) Isocyanurate Tri (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; dipentaerythritol hexa (meth) acrylate; Examples thereof include thiourethane (meth) acrylate compounds. These polymerizable unsaturated compounds can be used alone or in combination of two or more.

When the active energy ray-curable composition for antiglare hard coat used in the present invention contains a polymerizable unsaturated compound (b1) having a urethane bond as the polymerizable unsaturated compound (B), the content thereof is determined. When considering curl resistance, adhesion, scratch resistance, glare suppression, weather resistance, etc., the content should be 15% by mass or more with respect to the total cured film-forming component in the active energy ray-curable composition. preferable.

In the present specification, the fully cured film-forming component in the active energy ray-curable composition of the present invention means the total mass of the residue (solid content) excluding solvents such as water and organic solvents from the composition. To do.

<Silica fine particles (C)>
The active energy ray-curable composition for an antiglare hard coat of the present invention contains silica fine particles (C). Examples of the silica fine particles (C) used in the present invention include dry silica, wet silica, silica gel, calcium ion exchange silica fine particles, colloidal silica and the like.

The average primary particle size of the silica fine particles (C) can be used in the range of 1 to 400 nm, but more preferably 2 to 200 nm. From the viewpoint of scratch resistance of the cured film, it is advantageous to use one having a relatively large average primary particle size, but from the viewpoint of achieving both scratch resistance and suppressing glare of the cured film, the range is 5 nm to 150 nm. The inside is particularly preferable.
When the average primary particle size is less than 1 nm, when the silica fine particles (C) are mixed with other organic materials and used, the effect of improving the scratch resistance, glare suppression and antiglare of the film is reduced. There is. If the average primary particle size exceeds 400 nm, the suppression of glare of the material may be impaired.

The average primary particle size of the silica fine particles is the median size (d50) of the volume-based particle size distribution measured by the dynamic light scattering method, and can be measured using, for example, a nanotrack particle size distribution measuring device manufactured by Nikkiso Co., Ltd. it can.

The surface of the silica fine particles (C) may not be modified by an organic substance, but from the viewpoint of balancing glare suppression and scratch resistance, the silica fine particles (C) contain organic modified silica fine particles whose particle surface is modified with an organic substance, among others. Those containing organically modified silica having a polymerizable unsaturated group are preferable. The organic modification of the surface here means that the surface of the silica fine particles is in the form of a complex in which an organic compound or an organic group is physically or chemically (preferably chemically) introduced. Examples of the organic compound or organic group to be introduced include those known in the art, but the silica fine particle content is improved to improve scratch resistance while maintaining the suppression of glare of the film obtained by active energy ray curing. It is preferable to have a polymerizable unsaturated group, and particularly preferably to have a (meth) acryloyl group, from the viewpoint that an excellent film can be obtained.

The hydrolyzable silane having a (meth) acryloyl group in the molecule is not particularly limited as long as it is a compound having a (meth) acryloyloxy group and a hydrolyzable silyl group in the molecule. Specifically, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, At least selected from 3-acryloyloxypropyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, etc. One type of compound is mentioned. These compounds can be used alone or in combination of two or more.

Further, in addition to the above compound, when obtaining reactive particles, an alkoxysilane having an alkyl group having 1 or more carbon atoms may be reacted with the silica fine particles together with the compound, if necessary. By reacting an alkoxysilane having an alkyl group having 1 or more carbon atoms, the water resistance of the coating film obtained by using the obtained reactive particles may be improved. Examples of the alkoxysilane having an alkyl group having 1 or more carbon atoms include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and dodecyltrimethoxy. Examples thereof include silane, and compounds in which the methoxy group in these exemplified compounds is replaced with an ethoxy group (for example, methyltriethoxysilane, etc.) can also be mentioned.

The silica fine particles (C) may be dispersed in a dispersion medium, and the dispersion medium may be, for example, water; an alcohol solvent such as methanol, ethanol, isopropanol, n-propanol, isobutanol, or n-butanol; ethylene. Polyhydric alcohol solvents such as glycol; polyhydric alcohol derivatives such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol can be mentioned.

Commercially available colloidal silica products include methanol silica sol (average primary particle diameter 12.5 nm), MA-ST-M (average primary particle diameter 22.5 nm), IPA-ST (average primary particle diameter 12.5 nm), and IPA- ST-L (average primary particle diameter 45 nm), IPA-ST-ZL (average primary particle diameter 85 nm), MEK-ST-40 (average primary particle diameter 12.5 nm), MEK-ST-L (average primary particle diameter 45 nm) ), MEK-ST-ZL (average primary particle diameter 85 nm), DMAC-ST (average primary particle diameter 12.5 nm), NPC-ST-30 (average primary particle diameter 12.5 nm), PGM-ST (average primary particle diameter) Diameter 12.5 nm), EAC-ST (average primary particle diameter 12.5 nm), IPA-ST-UP (average primary particle diameter 12 nm), ST-UP (average primary particle diameter 70 nm), ST-OUP (average primary particle) Diameter 70 nm), ST-20L (average primary particle diameter 45 nm), ST-30 (average primary particle diameter 12.5 nm), MEK-ST-40 (average primary particle diameter 12.5 nm), ST-O-40 (average) Primary particle size 22.5 nm), ST-N-40 (average primary particle size 22.5 nm), ST-C (average primary particle size 12.5 nm), ST-NS (average primary particle size 9.5 nm), ST -O (average primary particle diameter 12.5 nm), ST-50 (average primary particle diameter 22.5 nm), ST-OL (average primary particle diameter 45 nm), MEK-AC-2140Z (average primary particle diameter 12.5 nm) , PGM-AC-2140Y (average primary particle diameter 12.5 nm), MEK-AC-4130Y (average primary particle diameter 45 nm), MEK-AC-5140Z (average primary particle diameter 85 nm) (all trade names, Nissan Chemical Co., Ltd. (Made by company), etc.

From the viewpoint of scratch resistance, the content of the silica fine particles (C) is preferably more than 10% by mass, more preferably 20 to 20% by mass, based on the total cured film-forming component in the active energy ray-curable composition. It is within the range of 70 mass. The content of the silica fine particles (C) is such that the total content of the silica fine particles (C) and the resin particles (D) is 20% by mass or more with respect to the total cured film-forming component in the active energy ray-curable composition. From the viewpoint of suppressing glare, it is preferable to adjust so as to be.

<Resin particles (D)>
The active energy ray-curable composition for an antiglare hard coat of the present invention contains resin particles (D). Examples of the resin particles (D) include spherical resin particles containing materials such as silicone resin, melamine resin, acrylic resin, polystyrene resin, styrene-acrylic copolymer, urethane resin, polyethylene resin, polycarbonate resin, and benzoguanamine resin. Can be mentioned. Among these, silicone resin particles, acrylic resin particles and the like can be preferably used. These resin particles can be used alone or in combination of two or more.

The average particle size of the resin particles (D) is preferably in the range of 0.5 to 10 μm, more preferably in the range of 0.8 to 8 μm, and more preferably 1 to 5 μm from the viewpoint of suppressing glare. It is more preferable that it is within the range of.
Since the average particle size of the resin particles is low in the present invention, the average value of the particle size measured by the laser diffraction / scattering method (microtrack method) is adopted as the average primary particle size.

The content of the resin particles (D) is preferably in the range of 2 to 40% by mass based on the total cured film forming component in the active energy ray-curable composition from the viewpoint of suppressing glare and antiglare. Yes, more preferably in the range of 3 to 30% by mass, and even more preferably in the range of 4 to 20% by mass. Further, it is preferable to adjust the total content of the silica fine particles (C) and the resin particles (D) to be 20% by mass or more with respect to the total cured film forming component in the active energy ray-curable composition.

<Photopolymerization initiator (E)>
The photopolymerization initiator (E) is a compound that absorbs active energy rays to generate free radicals (also in the form of an intermediate), and may be a mixture of two or more kinds of compounds. The photopolymerization initiator (E) includes a photochemically activating compound (for example, benzoin), a combination of a chromophore and a co-initiator (for example, benzophenone and a tertiary amine), a mixture thereof, and a sensitizer. , coinitiator and (for example thioxanthone and tertiary amine) or chromophore (e.g. thioxanthone and aminoketones) combination, H ₂ O ₂ and iron (II) redox systems such as the combination of the salt, dyes and boric Electron transport pairs such as acid salts and / or amines can be mentioned.

Specifically, as the photopolymerization initiator (E), for example, α-diketone compounds such as benzyl and diacetyl; acyloin compounds such as benzoin; acyloin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone. , 2,4-Diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid and other thioxanthone compounds; benzophenone, o-methylbenzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis (dimethyl) Benzophenone compounds such as amino) benzophenone, 4,4'-bis (diethylamino) benzophenone; Michler ketone compound; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α'- Dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino- Acetphenone compounds such as 1- (4-morpholinophenyl) -butane-1-one, α-isohydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone; 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, acylphosphine oxide compounds such as bis (acyl) phosphine oxide; quinone such as anthraquinone and 1,4-naphthoquinone; ) -S-Halogen compounds such as triazine; peroxides such as di-t-butyl peroxide and the like can be mentioned.

Commercially available products of the photopolymerization initiator (E) include, for example, IRGACURE-127, Irgacure-184, Irgacure-261, Irgacure-369, Irgacure-500, Irgacure-651, Irgacure-754, Irgacure-819, Irgacure-907, Irgacure-CGI-1700, Irgacure-2959, Irgacure-TPO, Darocur-1173 (above, BASF, trade name); KAYACURE-MBP, Kayacure-DETX-S, Kayacure- DMBI, KayaCure-EPA, KayaCure-OA (above, Nippon Kayaku Co., Ltd., trade name); VICURE-10, Vicure-55 (above, STAUFFER Co., LTD., Product name) Trigonal P1 (manufactured by AKZO Co., LTD., Product name); Sandolay 1000 (manufactured by SANDOZ Co., LTD., Product name); Deep (DEAP) ( Apjon (APJOHN Co., LTD., Product name); CantaCure (QUANTACURE) -PDO, CantaCure-ITX, CantaCure-EPD (above, Ward BLEKINSOP Co., LTD.), Product Name), ESACURE KIP 150, ESACURE ONE (manufactured by LAMBERTI, trade name) and the like.
The photopolymerization initiator (E) can be used alone or in combination of two or more.

Further, the solid content of the photopolymerization initiator (E) in the active energy ray-curable composition used in the present invention is the silica particles (C) and the polymerizable unsaturated compound (B) from the viewpoint of curability and film hardness. ) Is preferably in the range of 0.01 to 30 parts by mass, and more preferably in the range of 1 to 15 parts by mass with respect to 100 parts by mass of the total solid content.
When the cumulative irradiation amount of the active energy rays is 200 mJ / cm ² or less, the solid content of the photopolymerization initiator (E) is the total of the silica particles (C) and the polymerizable unsaturated compound (B). The solid content is preferably in the range of 5 to 30 parts by mass with respect to 100 parts by mass.

<Other ingredients>
The active energy ray-curable composition used in the present invention may be further blended with various additives as required, or may be diluted with a solvent if desired. Examples of the additive include an ultraviolet absorber, a light stabilizer, an antioxidant, a rheology control agent, and a surface conditioner (silicone type surface conditioner, acrylic type surface conditioner, fluorine type surface conditioner, vinyl type surface conditioner). Etc.), surfactants, resin particles, lubricants, defoamers, mold release agents, silane coupling agents, antistatic agents, antifogging agents, colorants and the like can be used. The active energy ray-curable composition of the present invention may further contain an ultraviolet absorber and / or a light stabilizer for applications requiring light resistance.

Ultraviolet absorbers As the ultraviolet absorbers, conventionally known organic ultraviolet absorbers and inorganic ultraviolet absorbers can be used. For example, benzotriazole-based absorbers, triazine-based absorbers, salicylic acid derivative-based absorbers, and benzophenone-based agents can be used. Examples thereof include absorbents and other compounds (hydroxyphenyltriazine-based, oxalic acid anilide, cyanoacrylate, etc.). Examples of the inorganic ultraviolet absorber include fine particle titanium oxide, fine particle zinc oxide, fine particle iron oxide and the like. Further, the ultraviolet absorber may have a polymerizable unsaturated group. When the ultraviolet absorber is contained, the content of the ultraviolet absorber is in the range of 0.01 to 10% by mass, preferably 0.05 to 9% by mass, based on the total cured film-forming component. Is preferable.

Light Stabilizer The light stabilizer is not particularly limited, and conventionally known ones can be widely used, and a hindered piperidine compound is preferable. A hindered piperidine compound is a compound having at least one hindered piperidine group in one molecule.
Examples of the hindered piperidine compound include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-. Benzoyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4 -Hydroxyphenyl] methyl} butylmalonate and other monomer types; poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] Orphan type such as [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol]} Examples thereof include polyester-bonded types such as a polyester compound of hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid, but the present invention is not limited thereto. As the light stabilizer, a known polymerizable light stabilizer can also be used.

Examples of commercially available light stabilizers include TINUVIN123, TINUVIN 152, TINUVIN292 (trade name, manufactured by BASF), HOSTAVIN3050, HOSTAVIN3052, HOSTAVIN3058 (trade name, manufactured by Clariant), and ADEKA STAB LA-82 (trade name, stock). (Made by company ADEKA) and the like.
These can be used alone or in combination of two or more.
When the light stabilizer is contained, the content thereof is preferably in the range of 0.01 to 10% by mass, preferably 0.05 to 9% by mass, based on the total cured film-forming component. Is.

The solvent is preferably selected as appropriate because the solution viscosity of the active energy ray-curable composition of the present invention can be appropriately adjusted, and the film thickness can be adjusted particularly when thin film coating is performed. The organic solvent that can be used here is not particularly limited as long as it can dissolve or disperse the active energy ray-curable composition of the present invention, but for example, aromatic hydrocarbons such as toluene and xylene; methanol and ethanol. , Alcohols such as isopropanol and t-butanol; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. These solvents may be used alone or in combination of two or more.

<Preparation method of active energy ray-curable composition for antiglare hard coat>
The active energy ray-curable composition for antiglare hard coat of the present invention comprises the acrylic copolymer (A), the polymerizable unsaturated compound (B), the silica fine particles (C), the resin particles (D) and the resin particles (D) described above. The photopolymerization initiator (E) is contained as a main component as an essential component, and if necessary, an additive component used can be mixed, dissolved or dispersed in a solvent.

Although it is not always clear why the active energy ray-curable composition for antiglare hard coat of the present invention can form an antiglare hard coat layer with almost no glare without deteriorating image quality, silica fine particles, By using an acrylic copolymer having a specific molecular weight polyether chain in combination with the resin particles, the silica fine particles and the small particle size resin particles are appropriately filled in the coating film, and a finer uneven shape than before is applied. It is presumed that it is formed on the film surface.

The form of the product in which the film is formed by the active energy ray-curable composition for antiglare hard coat of the present invention is not particularly limited, but the hard coat film in which the film is formed on a film base material such as a transparent plastic film. It is particularly suitable to use as.

<Manufacturing method of hard coat film>
An antiglare hard coat film can be obtained by coating the active energy ray-curable composition for an antiglare hard coat of the present invention on a film substrate to form a film. The film base material is not particularly limited, and can be appropriately selected and used as a film for hard coating from conventionally known film base materials.
Examples of the film base material include films such as polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyethylene terephthalate, polyethylene naphthalate, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, and norbornene-based resin. Can be mentioned. The thickness of these film substrates is 23 to 250 μm, preferably 38 to 188 μm, and these film substrates may be appropriately surface-treated. Among these film substrates, polyethylene terephthalate is preferable from the viewpoint of adhesiveness.

Coating Step The method for coating the active energy ray-curable composition for antiglare hard coat of the present invention is not particularly limited. For example, spray, rotary atomization coating machine, immersion coating, die coat, micro gravure coat, gravure coat, roll coat, comma coat, air knife coat, kiss coat, spray coat, overcoat, dip coat, spinner coat, wheeler coat, brush. It can be painted, solid coat with silk screen, wire bar coat, flow coat, etc. At the time of painting, electrostatic application may be performed.

Coating film thickness The coating film thickness can be usually in the range of 1 to 100 μm, preferably 1 to 10 μm, and more preferably 1.5 to 5 μm in terms of cured film thickness. The active energy ray-curable composition for an antiglare hard coat of the present invention can form a cured film having excellent glare suppression and scratch resistance, particularly in a thin film of 10 μm or less.

In the coating film forming method according to the present invention, the active energy ray-curable composition may be coated on a substrate, set and / or preheated, and then irradiated with active energy rays. This step of setting and / or preheating is performed to reduce the volatile matter in the coating film immediately after painting or to remove the volatile matter, and can be performed in an air blow, an IR furnace, or the like. The setting can usually be performed by leaving the painted object to be coated in a dust-free atmosphere at room temperature for 30 to 600 seconds. Preheating can be usually carried out by heating the coated object to be coated in a drying oven at a temperature of 40 to 110 ° C., preferably 50 to 100 ° C. for 30 seconds to 30 minutes. Further, when the air blow is performed, it can be usually performed by blowing air heated to room temperature or a temperature of 25 ° C. to 80 ° C. on the coated surface of the object to be coated. The preheating time is preferably 30 seconds to 600 seconds. Further, when heating and irradiation with active energy rays, which will be described later, are performed in combination, heat from an irradiation source of light rays (for example, heat generated by a lamp) may be used as a heat source. Further, when light irradiation is performed after heating, light irradiation may be performed while the object to be coated is heated (with residual heat).

Irradiation with active energy rays The coating film applied to the base material can be polymerized by irradiating with active energy rays to form a cured film. As the activated energy ray to be irradiated, a known one can be used. Specific examples thereof include ultraviolet rays, visible light, laser light (near infrared laser, visible light laser, ultraviolet laser, etc.), microwaves, electron beams, electromagnetic waves, and the like. Of these active energy rays, ultraviolet rays can be preferably used from the viewpoint of economy.

As the irradiation source of the active energy ray, a known source can be used. Specifically, for example, ultra-high pressure, high-pressure, medium-pressure, low-pressure mercury lamps, electrodeless lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, LEDs (Light Emitting Diodes, light emitting diodes). ), Sunlight, etc. can be used. Further, a pulse emitting type active energy ray irradiation device can also be used.
Further, the irradiation of the active energy rays may be performed over the entire region and / or a part thereof, for example, through a mask or by using a laser beam. It is also possible to cure the coating film only in a specific region by such means. The irradiation amount of the active energy ray varies depending on the irradiation source, but it may be within the range where the polymerization of the active energy ray-curable composition can be performed. For example, when a high-pressure mercury lamp is used, the integrated irradiation amount is 100 to 500 mJ. It is preferably in the range of / cm ² , particularly 200 to 500 mJ / cm ^2.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. However,
The present invention is not limited thereto. In each example, "parts" and "%" are based on mass unless otherwise specified. The film thickness of the coating film is based on the cured coating film.

(Manufacturing Example 1)
Colloidal silica fine particles (dispersion medium; isopropanol, silica concentration; 30% by mass, average primary particle size; 12.5 nm, trade name; IPA-ST, Nissan Chemical) in a separable flask equipped with a reflux condenser, a thermometer and a stirrer. (Manufactured by Co., Ltd.) 333 parts (100 parts of silica fine particles), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.20 parts of p-methoxyphenol and 233 parts of isopropanol were mixed, and then the temperature was raised while stirring. When the reflux of the volatile component started, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, a dehydration condensation reaction was carried out with stirring at 95 ° C. for 2 hours, then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the reaction was carried out with stirring for another 1 hour. After completion of the reaction, the volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added and azeotropically distilled off. The solvent was replaced by adding propylene glycol monomethyl ether and azeotropically distilling several times to obtain a 30% non-volatile dispersion (P1) of the reactive particles.

(Example 1)
Acrylic copolymer No. Reactivity with an average primary particle diameter of 12 nm obtained in Production Example 1 using 1 as 0.3 parts (solid content: 0.3 part), polymerizable unsaturated compound B-1 as 30 parts (solid content), and silica fine particles. 70 parts (21 parts of solid content) of dispersion liquid (P1) of particles (C-1), 8 parts (solid content) of resin fine particles D-1 (solid content), 0.6 part of DAIDO # 174 as a photopolymerization initiator (Solid content), 0.6 parts (solid content) of Photocure 50, and 1.0 part (solid content) of BYK-333 as a surface conditioner, diluted with ethyl acetate to a solid content content of 40%, and stirred. The active energy ray-curable composition No. 1 for antiglare hard coat was produced. Table 1 shows the blending amount of each component in terms of solid content mass ratio.

(Examples 2 to 17 and Comparative Examples 1 to 4)
In Example 1, the solid content content of Examples 2 to 17 and Comparative Examples 1 to 4 was 40% in the same manner as in Example 1 except that the composition of each component was shown in Tables 1 to 3. Active energy ray-curable composition No. for antiglare hard coat. 2 to 21 were obtained. The composition of each composition shown in Tables 1 to 3 is the solid content mass ratio of each component.

The symbols and (* 1) to (* 3) in Example 1 and Tables 1 to 3 mean the following.

Acrylic copolymer No. 1: As a copolymerization component, Visiomer (registered trademark) 5005 MA W (product name, manufactured by Ebonic Deguza, polyethyl ether monomethacrylate, methoxypolyethylene glycol monomethacrylate having a number average molecular weight / 5000 mol, polyether chain- (O) -C ₂ H ₄ ) n-n = 113, molecular weight of polyether chain 5000) is 27 mol%, 1,6-hexanediol diacrylate is 0.3 mol%, and other acrylates (2-ethylhexyl acrylate). Acrylate copolymer having a randomly branched structure having a polyether chain having a molecular weight of 5000, containing 72.7 mol% of solid content, 100% by mass,

Acrylic copolymer No. 2: As a copolymerization component, Bisomer (registered trademark) MPEG550 (product name, manufactured by Cognis, polyethyl ether monomethacrylate, methoxypolyethylene glycol monomethacrylate having a number average molecular weight of 628 / mol, polyether chain- (OC ₂ H). ₄ ) n-n = 12 to 13, polyether chain molecular weight 550) 27 mol%, tripropylene glycol diacrylate 0.3 mol%, other acrylates (including 2-ethylhexyl acrylate) 72 .Acrylic copolymer having a randomly branched structure having a polyether chain having a molecular weight of 5000, containing 7 mol%, solid content 100% by mass,

Acrylic copolymer No. 3: As a copolymerization component, Bisomer (registered trademark) MPEG550 (product name, manufactured by Cognis, polyethyl ether monomethacrylate, methoxypolyethylene glycol monomethacrylate having a number average molecular weight of 628 / mol, polyether chain- (OC ₂ H). ₄ ) n-n = 12 to 13, polyether chain molecular weight 550) in 17 mol%, Silaprane FM0721 monomer (trade name, Chisso Corp. polysiloxane monomethacrylate, weight average molecular weight 5000). ) Containing 10 mol% and other acrylates (including 2-ethylhexyl acrylate) 73 mol%, a linear acrylic copolymer having a polyether chain having a molecular weight of 550, solid content 100% by mass,

Acrylic copolymer No. 4 As copolymerization components, methoxypolypropylene glycol monomethacrylate, n = 4 of polyether chain- (O-C3H6) n-, molecular weight 232) of the polyether chain) is 27 mol%, and tripropylene glycol diacrylate is 0.3 mol. Acrylic copolymer having a randomly branched structure having a polyether chain having a molecular weight of 232, containing 72.7 mol% of other acrylates (including 2-ethylhexyl acrylate), 100% by mass of solid content,

Acrylic copolymer No. 5: As a copolymerization component, Visiomer (registered trademark) BDGMA (product name, polyethyl ether monomethacrylate, manufactured by Evonic, methoxypolyethylene glycol monomethacrylate having a number average molecular weight / 230.3 mol, polyether chain- (OC). ₂ H ₄₎ n-n = 2, the molecular weight 88) of 27 mol% of the polyether chains, tripropylene glycol diacrylate 0.3 mol%, and other acrylates (including 2-ethylhexyl acrylate) 72 .Acrylic copolymer having a randomly branched structure having a polyether chain having a molecular weight of less than 200, containing 7 mol%, solid content 100% by mass,

Acrylic copolymer No. 6: As a copolymerization component, 27 mol% of polyethyl ether monomethacrylate having a molecular weight of 11000 of n = 250 polyether chain of polyether chain- (OC ₂ H _{4) n- and 0.3 of tripropylene glycol diacrylate.} A randomly branched acrylic copolymer having a 11000 molecular weight polyether chain containing 72.7 mol% of mol% and other acrylates (including 2-ethylhexyl acrylate), solid content 100% by mass. ..

Polymerizable unsaturated compound B-1: Urethane acrylate having an unsaturated group equivalent of 200 and a weight average molecular weight of 2,000 Polymerizable unsaturated compound B-2: Urethane acrylate having an unsaturated group equivalent of 490 and a weight average molecular weight of 4,900 Unsaturated compound B-3: Urethane acrylate having an unsaturated group equivalent of 667 and a weight average molecular weight of 2,000.

Silica fine particles C-1: dispersion liquid P1 obtained in Production Example 1, average primary particle diameter 12 nm, solid content 30% by mass,
Silica fine particles C-2: MEK-AC-4130Y, trade name, manufactured by Nissan Chemical Co., Ltd., organic solvent-dispersed colloidal silica, average primary particle diameter 45 nm, dispersion liquid; methyl ethyl ketone, solid content 30% by mass, silica and 3-methacryloyloxy Reaction product with propyltrimethoxysilane,
Silica fine particles C-3: MEK-AC-5140Z, trade name, manufactured by Nissan Chemical Co., Ltd., average primary particle size 85 nm, dispersion: methyl ethyl ketone, solid content 40% by mass, silica and 3-methacryloyloxypropyltrimethoxysilane Reaction product,
Silica fine particles C-4: MEK-ST-40, trade name, manufactured by Nissan Chemical Co., Ltd., organic solvent-dispersed colloidal silica, average primary particle size 15 nm, dispersion liquid; methyl ethyl ketone, solid content 40% by mass.

Resin particles D-1: SSX-102, trade name, manufactured by Sekisui Kasei Kogyo Co., Ltd., crosslinked acrylic resin monodisperse particles, average primary particle size 2 μm, spherical organic fine particles, solid content 100% by mass,
Resin particles D-2: MX-150, trade name, manufactured by Soken Kagaku Co., Ltd., crosslinked acrylic resin monodisperse particles, average primary particle diameter 1.5 μm, spherical organic fine particles, solid content 100% by mass,
Resin particles D-3: J-7PY, trade name, manufactured by Negami Kogyo Co., Ltd., crosslinked acrylic resin monodisperse particles, average primary particle diameter 5.8 μm, spherical organic fine particles, solid content 100% by mass,
Resin particles D-4: Artpearl C-1000, trade name, manufactured by Negami Kogyo Co., Ltd., crosslinked urethane resin particles, average primary particle diameter 3 μm, spherical organic fine particles, solid content 100% by mass,
Resin particles D-5: Tospearl (registered trademark) 120, trade name, manufactured by Momentive Performance Materials Japan GK, spherical silicone resin fine particles, average primary particle diameter 2 μm, solid content 100% by mass.

DAIDO UV-CURE # 174, trade name (described as DAIDO # 174 in the example table), manufactured by Daido Kasei Kogyo Co., Ltd., photopolymerization initiator, alkylphenone-based photopolymerization initiator, solid content 100%,
Photocure 50, trade name, manufactured by Daido Kasei Kogyo Co., Ltd., photopolymerization initiator, alkylphenone-based photopolymerization initiator, solid content 100%,

BYK-333, trade name, manufactured by Big Chemie Japan, silicone-based surface conditioner, solid content 100% by mass.

* 1) Content and unit of the polymerizable unsaturated compound (B) component and the silica fine particle (C) component with respect to a total of 100 parts by mass [parts by mass]
* 2) Content, unit [mass%] of the total cured film-forming component in the active energy ray-curable composition.
* 3) Ratio of acrylic copolymer (A) used to the content of silica fine particles (C) and the resin particles (D) [mass ratio]

<Manufacturing method of anti-glare hard coat film>
Each active energy ray-curable composition is coated on a 100 μm-thick PET film substrate that has been easily bonded with a bar coater under the condition that the film thickness after curing is 4 μm, and preheated at 100 ° C. for 30 seconds to prepare a solvent. After removing the above, irradiate with an ultraviolet irradiation device with ultraviolet rays (peak top wavelength 365 nm) under the condition that the illuminance is 150 mW / cm ² and the integrated irradiation amount is 500 mJ / cm ^2, and the coating film is cured to form an antiglare hard coat film. Made. The obtained coating film was used as a test plate and subjected to each performance test according to the following test method. The results are shown in Tables 1 to 3.

(Test items)
Test item 1: Storage stability Changes in the appearance of the paint were observed after each active energy ray-curable composition for antiglare hard coat was stored at 40 ° C. for 5 days in a closed container.
◯: There is no change in appearance or slight yellowing is observed, but there is no problem in use.
X: Yellowing, sedimentation, etc. are observed to some extent that there is a problem in use.

Test item 2: According to Haze JIS K7136 (2000), the haze value of a hard coat film having a cured film layer with each active energy ray-curable composition for antiglare hard coat was measured from the film layer side. From the viewpoint of antiglare, the haze value is preferably in the range of 3 to 45, more preferably in the range of 5 to 35.

Test item 3: Anti-glare Anti-glare hard coat A black acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., thickness 2.0 mm) is attached to the surface of the anti-glare hard coat film where the anti-glare hard coat layer is not formed. Generally, in an office environment where a display is used (about 1000 Lx), the sample prepared above was placed directly under the fluorescent lamp, and the antiglare property was visually judged according to the following criteria.
〇: Fluorescent lamp is reflected, but the outline looks blurry 〇-: The outline of the fluorescent lamp is visible, which is a little worrisome, but there is no problem when it is made into a product △: The outline of the fluorescent lamp is Visible and a little worrisome ×: The outline of the fluorescent lamp is clearly reflected, and it is quite worrisome.

Test item 4: Glitter evaluation The obtained anti-glare hard coat film is placed on a smartphone (Apple's "iPhone (registered trademark) 7") having a liquid crystal display with a resolution of 326 ppi, and the following is visually observed. Glitter was evaluated according to the criteria.
⊚: No glare ○: Almost no glare ○ −: Slight glare but no problem when made into a product ×: Glitter is felt.

Test item 5: Pencil hardness The pencil hardness of the coated surface of each test coating plate obtained above was measured in accordance with JIS K5600-5-4 (1999) "Scratch hardness (pencil method)". When the pencil hardness is more preferably H or more than F or more, the hardness is good.

Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments, and various modifications based on the technical idea of the present invention are possible.

Claims (13)

Acrylic copolymer (A) having a polyether chain having a molecular weight in the range of 200 to 10,000, a polymerizable unsaturated compound (B), silica fine particles (C), resin particles (D), and a photopolymerization initiator (E). Including and
The content of the acrylic copolymer (A) is in the range of 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the components (B) and (C).
An active energy ray-curable composition for an antiglare hard coat. The active energy ray-curable composition for an antiglare hard coat according to claim 1, wherein the acrylic copolymer (A) contains a methoxypolyethylene glycol ester bond. The active energy ray-curable composition for an antiglare hard coat according to claim 1 or 2, wherein the acrylic copolymer (A) contains a branched structure in at least a part of the molecule. The copolymerization monomer component constituting the acrylic copolymer (A) contains a monomer (a1) having two or more polymerizable unsaturated groups in the molecule, 0.01 to 10 with respect to the total amount of the copolymerization monomer component. The active energy ray-curable composition for an antiglare hard coat according to any one of claims 1 to 3, which contains a molar%. Claims 1 to 4 in which the copolymerization monomer component constituting the acrylic copolymer (A) contains 5 mol% or more of the polyether mono (meth) acrylate (a2) with respect to the total amount of the copolymerization monomer component. The active energy ray-curable composition for an antiglare hard coat according to any one of the above items. The polymerizable unsaturated compound (B) contains a urethane meta (acrylate) compound, the unsaturated group equivalent of the urethane meta (acrylate) compound is 110 or more and less than 600, and the weight average molecular weight is 600 to 6,000. The active energy ray-curable composition for an antiglare hard coat according to any one of claims 1 to 5, which is within the range of. The antiglare hard according to any one of claims 1 to 6, wherein the silica fine particles (C) are reactive particles obtained by reacting with a hydrolyzable silane having a (meth) acryloyl group in the molecule. Active energy ray-curable composition for coating. Claims 1 to 7, wherein the total content of the silica fine particles (C) and the resin particles (D) is 20% by mass or more with respect to the total cured film forming component in the active energy ray-curable composition. The active energy ray-curable composition for an antiglare hard coat according to any one item. The ratio of the acrylic copolymer (A) used to the total content of the silica fine particles (C) and the resin particles (D) is 0. The active energy ray-curable composition for an antiglare hard coat according to any one of claims 1 to 8, which is 10 to 14.00 / 99.90 to 86.00. The active energy ray-curable composition for an antiglare hard coat according to any one of claims 1 to 9, wherein the average primary particle diameter of the silica fine particles (C) is in the range of 1 to 200 nm. The active energy ray-curable composition for an antiglare hard coat according to any one of claims 1 to 10, wherein the average particle diameter of the resin particles (D) is in the range of 0.5 to 10 μm. At least one material in which the resin particles (D) are selected from the group consisting of silicone resin, melamine resin, acrylic resin, polystyrene resin, styrene-acrylic copolymer, urethane resin, polyethylene resin, polycarbonate resin and benzoguanamine resin. The active energy ray-curable composition for an antiglare hard coat according to any one of claims 1 to 11, which is a spherical resin particle containing. An antiglare hard coat film comprising a step of coating an active energy ray-curable composition for an antiglare hard coat according to any one of claims 1 to 12 on a film substrate and irradiating the film base material with active energy rays. Manufacturing method.