JP6260514B2 - Anti-blocking hard coat material - Google Patents

Description

  The present invention relates to a curable composition for hard coat, a hard coat material having antiblocking properties formed using the same, and a film with the hard coat.

  The image display surface of a display (image display device) such as a liquid crystal display (LCD), a cathode ray tube display device (CRT), or a plasma display (PDP), electronic paper, LED, touch panel, tablet PC or the like is not damaged during handling. Thus, scratch resistance and hardness are required. Therefore, by attaching a film with a hard coat in which a hard coat layer is provided on a triacetyl cellulose substrate, and further applying an optical film with an optical function such as antireflection and antiglare properties on the image display surface, the image of the display is displayed. The scratch resistance and hardness of the display surface are improved.

  If the flat hard coat layer serving as the resurface of the image display surface has irregularities, when a hard object comes into contact with the hard coat layer, it may be caught on the convex portions and cause fine damage. Therefore, in order to prevent the hard coat layer surface from being scratched, the hard coat layer surface is preferably smooth in order to improve the scratch resistance.

  A film with a hard coat is stuck on an image display surface of an image display device. Under the present circumstances, the film with a hard coat to be used is normally provided with the shape of the elongate roll by which the continuous strip-shaped film was wound up continuously. The surface of the hard coat layer of the film with the hard coat and the surface of the base film are as in the case of closely attaching the mirror surfaces by winding and superimposing the film with a hard coat with high surface smoothness. A so-called “blocking” phenomenon may occur. When blocking occurs, there is a problem that the film with the hard coat is cut when the film with the hard coat is fed out during the production of the product, making it difficult to manufacture the image display device.

  In order to solve the problem of blocking of the film with hard coat, the hard coat layer contains particles having an average primary particle size of 300 nm or less (smooth particles), and the hard coat layer does not impair the smoothness of the surface. A method for forming a minute protrusion has been proposed (for example, Patent Documents 1 and 2).

  When easy slip particles having a large average primary particle size are contained in the hard coat layer, blocking can be prevented, but there arises a problem that optical properties such as an increase in haze of the hard coat layer and a decrease in total light transmittance are deteriorated.

  Therefore, in order to achieve both hardness, anti-blocking properties and optical properties, the specific particles containing the slippery particles are not formed by forming the surface small protrusions only by the slippery particles having a specific average primary particle size. It has been proposed to form a hard coat layer using a curable resin composition containing secondary particles having a diameter and reactive silica fine particles, a polyfunctional monomer, and a solvent in predetermined amounts (Patent Document 3).

JP 2009-035614 A JP 2009-132880 A International Publication No. WO2012 / 018087 Pamphlet

However, the conventional techniques are satisfactory in anti-blocking properties and optical properties, but are not sufficient in scratch resistance.
An object of the present invention is to provide a hard coat material that is excellent in transparency, anti-blocking property, transparency, adhesion to a substrate, and scratch resistance.
In particular, it is to provide a hard coat material having excellent anti-blocking property and excellent scratch resistance.

According to the present invention, the following curable composition, hard coat material, and film with hard coat are provided.
1. The following components (A) to (D):
(A) Modified inorganic particles having a BET particle diameter of 100 nm or less 88 to 94 parts by weight (B) Unmodified silica particles having a BET particle diameter of 5 to 100 nm 6 to 12 parts by weight (C) Particles having a BET particle diameter of 200 nm to 3 μm Curable composition containing 0.1-3 weight part (D) binder with respect to a total of 100 weight part of component (A) and (B).
2. Furthermore, (E) The curable composition of 1 containing a polymerization initiator.
3. Furthermore, (G) The curable composition of 1 or 2 containing a solvent.
A hard coat material obtained by curing the curable composition according to any one of 4.1 to 3.
The film with a hard coat formed by apply | coating and hardening the curable composition in any one of 5.1-3 to a film-form base material.

  According to the present invention, a hard coat material having excellent anti-blocking properties and excellent scratch resistance can be provided.

I. Curable composition The curable composition of this invention (henceforth the composition of this invention) may contain the following component (A)-(G). Among the following components, (A) to (D) are essential components, and (E) to (G) are optional components to be blended as necessary.
(A) Modified inorganic particles having a BET particle diameter of 5 to 100 nm 88 to 94 parts by weight (B) Unmodified silica particles having a BET particle diameter of 5 to 100 nm 6 to 12 parts by weight (C) BET particle diameter of 200 to 3 μm Particles 0.1 to 3 parts by weight with respect to 100 parts by weight of components (A) and (B) (D) binder (E) polymerization initiator (F) additive (G) solvent

  The composition of this invention mix | blends three types of particle | grains of the said component (A)-(C). By using the modified particles of component (A) and the unmodified particles of component (B) in combination, the surface irregularity of the coating film is improved, and the anti-blocking property is expressed only by adding a small amount of the easy-to-slip particles of component (C). As many surface irregularities as possible can be formed on the coating film. In addition to the development of anti-blocking properties, the cured film obtained can be improved in scratch resistance, transparency and adhesion to the substrate, and various properties can be easily adjusted as compared with the prior art.

  Hereinafter, each component will be described in detail.

(A) Modified inorganic particles having a BET particle diameter of 5 to 100 nm This is a component that improves the hardness of the resulting cured film and facilitates formation of a bond with a binder component by having a polymerizable group on the particle surface. It also has a function of increasing the transparency of the cured film.

  Silica, zirconia, titania, etc. are mentioned as a material of the inorganic particle which comprises a component (A). Moreover, the shape of the inorganic particles may be any of solid, hollow, irregular shape (beads, etc.) and the like.

The silica particles used as the component (A) may be in the form of a powder or a dispersion.
The dispersion medium of silica particles is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.

  As a commercial product of solid spherical particles of silica, for example, colloidal silica, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., trade names: IPA-ST, MEK-ST, MEK-ST-S, MEK-ST-L , MEK-ST-ZL, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50 ST-OL, manufactured by Nissan Chemical Co., Ltd. Product name: MEK-ST, JGC Catalysts & Chemicals colloidal silica sol Product name: OSCAL, and the like. Moreover, as an amorphous particle, Nissan Chemical Industries Ltd. brand name: Snowtex-PS-M, PS-S, PS-SO, UP, OUP, Sakai Chemical Industry Co., Ltd. brand name: PL-1 , PL-2, PL-3, PL-3H and the like.

  Examples of silica hollow particles include those manufactured by Catalytic Chemical Industry Co., Ltd .: JX1008SIV, JX1009SIV, JX1010SIV, JX1011SIV, JS1012SIV, Thruria 22SL-05JX, and the like.

  Examples of the irregularly shaped particles of silica include bead beads manufactured by Nissan Chemical Industries, Ltd. and trade name: MEK-ST-UP.

Examples of the zirconia particles include a product name: UEP-100 manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.
As titania sol, Nagase Corporation trade name: NAT311P and the like can be mentioned.

  In order to disperse the inorganic particles uniformly, a dispersant or a dispersion aid may be used. In the case of zirconia particles, for example, PLAADD ED151 manufactured by Enomoto Kasei Co., Ltd. can be used as a dispersant, and acetylacetone or the like can be used as a dispersion aid.

  The BET particle diameter of the inorganic particles of the component (A) is 100 nm or less, preferably in the range of 5 to 100 nm, more preferably in the range of 10 to 100 nm. If the BET particle diameter of the inorganic particles of component (A) exceeds 100 nm, the transparency of the coating film may be impaired.

  Here, the BET particle diameter means an average particle diameter calculated from the specific surface area measured by the BET method, and using a specific surface area measuring apparatus (for example, apparatus name: Tristar II3020, manufacturer: Shimadzu Corporation). The specific surface area of the particles is measured, and is a value calculated from the ratio of volume to surface area assuming that the particles are spherical regardless of whether the particles are spherical or irregular.

The surface of the inorganic particles of component (A) is modified. The modifier is not particularly limited, and for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane and the like having an OH group, bis (2-hydroxyethyl) -3aminotripropylmethoxysilane and the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane and the like having a thiocyanate group 3 As thiocyanate propyltrimethoxysilane and the like having an epoxy group (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like having a thiol group 3 -Mercaptopropyltrimethoxy Sisilane etc. can be mentioned. A preferred compound is 3-mercaptopropyltrimethoxysilane.

The modified inorganic particles of component (A) are preferably those that have been surface-treated with an organic compound containing a polymerizable unsaturated group (hereinafter sometimes referred to as “specific organic compound”).
The specific organic compound is a compound further containing a group represented by the following formula (11) in the molecule, and a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Is preferred.

［式（１１）中、ＸはＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、ＹはＯ又はＳを示す。］

[In the formula (11), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the specific organic compound is not particularly limited. For example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, A cinnamoyl group, a maleate group, and an acrylamide group can be mentioned as preferred examples.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) Group represented by Formula (11) The specific organic compound preferably further includes a group represented by Formula (11) in the molecule. Specific examples of the group [—X—C (═Y) —NH—] represented by the formula (11) include [—O—C (═O) —NH—], [—O—C (═S). ) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [ -S-C (= S) -NH-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH— groups.
The group [—X—C (═Y) —NH—] represented by the formula (11) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.

(Iii) A silanol group or a group that generates a silanol group by hydrolysis The specific organic compound is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or by hydrolysis. A compound that generates a silanol group (hereinafter sometimes referred to as a “silanol group-generating compound”) is preferable. Examples of such a silanol group-forming compound include compounds having an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, etc. on the silicon atom, but an alkoxy group or aryloxy group on the silicon atom. In other words, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iv) Preferred Embodiment Specific examples of the specific organic compound include compounds represented by the following formula (12).

R ¹⁹ and R ²⁰ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and a represents a number of 1, 2 or 3.
Examples of R ¹⁹ and R ²⁰ include methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl groups and the like.

Examples of the group represented by [(R ¹⁹ O) _a R ²⁰ _3-a Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ²¹ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.

R ²² is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. Further, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the formula (11). Can also be included.

R ²³ is a (b + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

  Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferable. Further, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

  For the synthesis of the specific organic compound used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, (i) it can be carried out by an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound. (B) The reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

In order to synthesize the compound represented by the formula (12), (a) is preferably used among these methods. More specifically, for example,
Method (a): First, a mercaptoalkoxysilane and a polyisocyanate compound are reacted to form an intermediate containing an alkoxysilyl group, [—S—C (═O) —NH—] group and an isocyanate group in the molecule. Next, an active hydrogen-containing polymerizable unsaturated compound is reacted with the isocyanate remaining in the intermediate, and this unsaturated compound is bonded via a [—O—C (═O) —NH—] group. How to
Method (b): First, a polyisocyanate compound and an active hydrogen-containing polymerizable unsaturated compound are reacted to form a polymerizable unsaturated group, [—O—C (═O) —NH—] group, and isocyanate in the molecule. Forming an intermediate containing a group, reacting this with a mercaptoalkoxysilane, and bonding the mercaptoalkoxysilane via a [—S—C (═O) —NH—] group,
Etc. Further, among them, the method (a) is preferable in that there is no decrease in polymerizable unsaturated groups due to the Michael addition reaction.

  In the synthesis of the compound represented by the formula (12), examples of the alkoxysilane capable of forming a [—S—C (═O) —NH—] group by reaction with an isocyanate group include an alkoxysilyl group. And compounds having at least one mercapto group in the molecule. Examples of such mercaptoalkoxysilane include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxy silane, mercapto Mention may be made of propyltributoxysilane. Among these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable. Moreover, an addition product of an amino-substituted alkoxysilane and an epoxy group-substituted mercaptan and an addition product of an epoxysilane and an α, ω-dimercapto compound can also be used.

  The polyisocyanate compound used when synthesizing the specific organic compound can be selected from polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons.

  Examples of such polyisocyanate compounds include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4 Xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4, 4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl) Isocyanato), 2,2,4-trimethylhexamethylene diisocyanate, bis (2 Isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3- Bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, and the like can be mentioned. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane and the like are preferable. These can be used alone or in combination of two or more.

  In the synthesis of a specific organic compound, as an example of an active hydrogen-containing polymerizable unsaturated compound that can be bonded to the polyisocyanate compound via an [—O—C (═O) —NH—] group by an addition reaction, Examples of compounds having at least one active hydrogen atom capable of forming a [—O—C (═O) —NH—] group by addition reaction with an isocyanate group and at least one polymerizable unsaturated group Can do.

Examples of these active hydrogen-containing polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythris Litholtri (meth) acrylate, dipentaerythritol penta Meth) acrylate - door, and the like can be given. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are preferable.
These compounds can be used individually by 1 type or in mixture of 2 or more types.

  The surface treatment method of the particles with the specific organic compound is not particularly limited, but it can also be produced by mixing the specific organic compound and particles, heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-forming site of the specific organic compound with the particles. However, when the specific organic compound has a silanol group, there is no need for water. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.

  The reaction amount of the particles and the specific organic compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 1% by weight, with the total of the particles and the specific organic compound being 100% by weight. That's it. If it is less than 0.01% by weight, the dispersibility of the particles in the composition is not sufficient, and the transparency and scratch resistance of the resulting cured product may not be sufficient.

Hereinafter, the surface treatment method will be described in more detail by taking an alkoxysilyl group-containing compound (alkoxysilane compound) as an example of the specific organic compound.
The amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment may be an amount that allows at least one alkoxy group on silicon in one molecule to be hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times. The product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface, and particles composed of such components are not included. In the hardened | cured material of the composition to contain, the effect of expression of high hardness and abrasion resistance is low.

  At the time of surface treatment, after subjecting the alkoxysilane compound to a separate hydrolysis operation, this is mixed with powder particles or solvent dispersion sol of particles, followed by heating and stirring operations; hydrolysis of the alkoxysilane compound; Can be selected in the presence of particles; or a method in which particles are surface-treated in the presence of other components such as a polymerization initiator. In this, the method of hydrolyzing the said alkoxysilane compound in presence of particle | grains is preferable. During the surface treatment, the temperature is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 20 ° C. or higher and 100 ° C. or lower. The processing time is usually in the range of 5 minutes to 24 hours.

In the case of using a powdery powder during the surface treatment, an organic solvent may be added for the purpose of smoothly and uniformly carrying out the reaction with the alkoxysilane compound. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate and Y-butyrolactone. Esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone . Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
The amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.

  When a solvent-dispersed sol is used as the particles, it can be produced by mixing at least a solvent-dispersed sol and a specific organic compound. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring the uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

In addition, an acid, a salt or a base may be added as a catalyst to promote the reaction during the surface treatment.
Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid, and itacone An unsaturated organic acid such as an acid, as a salt, for example, an ammonium salt such as tetramethylammonium hydrochloride or tetrabutylammonium hydrochloride, and as a base, for example, aqueous ammonia, diethylamine, triethylamine, dibutylamine, Primary, secondary or tertiary aliphatic amines such as cyclohexylamine, aromatic amines such as pyridine, quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide Etc.
Among these, preferred examples of the acid include organic acids and unsaturated organic acids, and the base includes tertiary amine or quaternary ammonium hydroxide. The amount of these acids, salts or bases added is preferably 0.001 to 1.0 part by weight, more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the alkoxysilane compound. It is.

In order to accelerate the reaction, it is also preferable to add a dehydrating agent.
As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used. Of these, organic compounds are preferable, and orthoesters such as methyl orthoformate and ethyl orthoformate are more preferable.
The amount of the alkoxysilane compound bonded to the particles is usually a thermogravimetric analysis from 110 ° C. to 800 ° C. in air as a constant value of weight loss% when the dry powder is completely burned in air. It can ask for.

The compounding quantity of a component (A) is 85-95 weight part in a total of 100 weight part of a component (A) and (B), and it is preferable that it is 88-94 weight part. The compounding amount of component (A) includes solids such as a modifier, a dispersant, and a dispersion aid, but does not include a dispersion medium.
If the blending amount of the component (A) is less than 85 parts by weight, the antiblocking property may be insufficient, and if it exceeds 95 parts by weight, the coating film mechanical strength may be impaired.

(B) Unmodified silica particles having a BET particle diameter of 5 to 100 nm The unmodified silica particles of component (B) are components that contribute to the improvement of the hardness of the cured film and the suppression of curing shrinkage of the composition. It also has a function of imparting antiblocking properties to the cured film.

  Examples of the unmodified silica particles used as the component (B) include the silica particles described in the component (A) (solid, hollow, irregular shape (eg beads)).

  The BET particle diameter of the component (B) particles is 5 to 100 nm, preferably 10 to 100 nm, and more preferably 30 to 100 nm. If the BET particle diameter of the component (B) particles is less than 5 nm, the antiblocking property may be insufficient, and if it exceeds 100 nm, the transparency may be impaired.

  The compounding quantity of a component (B) is 6-12 weight part in a total of 100 weight part of a component (A) and (B). When the blending amount of the component (B) is less than 6 parts by weight, anti-blocking properties are hardly exhibited, and when it exceeds 12 parts by weight, mechanical properties are hardly exhibited.

(C) Particles having a particle size of 200 nm to 3 μm The component (C) particles are components that impart antiblocking properties by forming protrusions on the surface of the hard coat layer.

Examples of the material of the particles used as the component (C) include inorganic substances such as silica, and organic substances such as PMMA and urethane, and the shape may be any of solid, hollow, and irregular shapes (such as beads). .
Commercially available products used as component (C) particles include SC1050-KJA manufactured by Admatechs as silica particles, MX80H3wt, MX-150 manufactured by Soken Chemical Co., Ltd. as PMMA particles, J-4PY, J-3PY manufactured by Negami Kogyo, and urethane particles. MM110-SMA manufactured by Negami Kogyo Co., Ltd.

  The BET particle size of the easy-to-slip particles of component (C) is 200 nm to 3 μm, preferably 300 nm to 2 μm, more preferably 300 nm to 1.5 μm. When the particle size of the component (C) particles is less than 200 nm, the anti-blocking property is hardly exhibited, and when it exceeds 3 μm, the mechanical properties of the coating film may be hardly exhibited.

  The amount of component (C) is 0.1 to 3.0 parts by weight, preferably 0.5 to 3.0 parts by weight, based on a total of 100 parts by weight of components (A) and (B). More preferably, it is 0.5 to 2.0 parts by weight. If the amount of component (C) is less than 0.1 parts by weight, anti-blocking properties may not be exhibited, and if it exceeds 3.0 parts by weight, haze may deteriorate and transparency may be impaired.

(D) Binder The component (D) is a component that forms a matrix of a cured film, and adheres the cured film to a substrate to improve scratch resistance.

Component (D) binders include cationic monomers such as polymerizable monomers, polymer / radical polymerizable compounds, ethylenically unsaturated group-containing compounds, polymers, epoxy group-containing compounds and oxetane group-containing compounds. And those used in.
The component (D) may be monofunctional or polyfunctional, and one having a high refractive index or one having a low refractive index can be appropriately selected and used depending on the use of the resulting cured film. .

  KAYARAD DPHA made by Nippon Kayaku as a commercially available polymerizable monomer, Art Resin H-34, Art Resin UN-904M, U6HA made by Shin-Nakamura Chemical as urethane acrylate compounds, Tricyclodecane dimethanol diacrylate made by Shin-Nakamura Chemical, Osaka Organic Chemical 2-hydroxyethyl acrylate, RA311M manufactured by Negami Kogyo as a polymer / radical polymerizable compound, Daicel Cytec Celoxide 2021P as a cationic polymerizable compound, DIC EXA830CRP, OXPT manufactured by Ube Industries, Shin-Nakamura Chemical A- as a high refractive index monomer BPEF, Osaka Gas Chemicals Ogsol EA0200, and low refractive index monomers include Solvay Solexis AD1700 and Kyoeisha LIC3A.

  RA311M (manufactured by Negami Industrial Co., Ltd., polymer side chain acrylate branch) can be mentioned as a binder that can reduce curing shrinkage.

  In order to form a hard coat having a relatively high refractive index, a binder having a high refractive index may be used. Examples of commercially available high refractive index binders include A-BPEF (manufactured by Shin-Nakamura Chemical, fluorene), Ogsol EA0200, Ogsol EA5510 (manufactured by Osaka Gas, fluorene), and the like.

  In order to form a hard coat having a relatively low refractive index, a low refractive index binder such as a fluoropolymer may be used. As the fluoropolymer, the following ethylenically unsaturated group-containing fluoropolymer is preferable.

The ethylenically unsaturated group-containing fluoropolymer is a polymer of a fluoroolefin.
The fluorine-containing polymer containing an ethylenically unsaturated group is preferably modified with a (meth) acrylic compound having a side chain hydroxyl group having an isocyanate group, an acid chloride group or a carboxylic acid group. Such modification allows co-crosslinking with the radically polymerizable (meth) acrylic compound and improves the scratch resistance.

  The ethylenically unsaturated group-containing fluorine-containing polymer is obtained by reacting a compound containing at least one ethylenically unsaturated group and a group capable of reacting with a hydroxyl group with a hydroxyl group-containing fluoropolymer.

(1) A compound containing at least one ethylenically unsaturated group and a group capable of reacting with a hydroxyl group. Such a compound is a compound containing at least one ethylenically unsaturated group in the molecule. Any functional group capable of reacting with the hydroxyl group of the fluoropolymer is not particularly limited.
Moreover, as said ethylenically unsaturated group, since the curable resin composition mentioned later can be hardened more easily, the compound which has a (meth) acryloyl group is more preferable.
Such compounds include (meth) acrylic acid, (meth) acryloyl chloride, anhydrous (meth) acrylic acid, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1- One kind of (bisacryloyloxymethyl) ethyl isocyanate or a combination of two or more kinds may be mentioned.
In addition, as a commercial item of the (meth) acrylate which has an isocyanate group, Showa Denko Co., Ltd. brand name Karenz MOI, AOI, and BEI are mentioned, for example.

Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
As examples of diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferred.

As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable.
In addition, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, for example, Osaka Organic Chemical Co., Ltd. product name HEA, Nippon Kayaku Co., Ltd. product name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. Product name Aronix M-215, M-233, M-305, M-400 and the like can be obtained.

(2) Hydroxyl group-containing fluoropolymer The hydroxyl group-containing fluoropolymer preferably contains the following structural unit (a), (b-1) and / or (b-2), and (c). Become.
(A) A structural unit represented by the following formula (1).
(B-1) A structural unit represented by the following formula (2-1).
(B-2) A structural unit represented by the following formula (2-2).
(C) A structural unit represented by the following formula (3).

［式（１）中、Ｒ¹はフッ素原子、フルオロアルキル基又は−ＯＲ²で表される基（Ｒ²
はアルキル基又はフルオロアルキル基を示す）を示す］

[In the formula (1), R ¹ is a fluorine atom, a fluoroalkyl group or a group represented by —OR ² (R ²
Represents an alkyl group or a fluoroalkyl group)]

［式（２−１）中、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_ｄ−
ＯＲ⁵若しくは−ＯＣＯＲ⁵で表される基（Ｒ⁵はアルキル基又はグリシジル基を、ｄは０又は１の数を示す）、カルボキシル基又はアルコキシカルボニル基を示す］

[In Formula (2-1), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, — (CH ₂ ) _d —
A group represented by OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group, d represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

［式（２−２）中、Ｒ^３は式（２−１）で定義した通りであり、Ｒ^２４はフルオロアルキル基を示し、ｘは０〜２の数を示す］

[In Formula (2-2), R ³ is as defined in Formula (2-1), R ²⁴ represents a fluoroalkyl group, and x represents a number from 0 to 2.]

［式（３）中、Ｒ⁶は水素原子又はメチル基を、Ｒ⁷は水素原子又はヒドロキシアルキル基を、ｖは０又は１の数を示す］

[In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

(I) Structural unit (a)
In the above formula (1), examples of the fluoroalkyl group represented by R ¹ and R ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorocyclohexyl group, and the like. A C1-C6 fluoroalkyl group is mentioned. Examples of the alkyl group for R ² include a methyl group, an ethyl group, a propyl group,
C1-C6 alkyl groups, such as a butyl group, a hexyl group, a cyclohexyl group, are mentioned.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluororefines such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); Perfluoro (alkoxyalkyl vinyl ether) s such as perfluoro (propoxypropyl vinyl ether) These may be used alone or in combination of two or more.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and it is more preferable to use these in combination.

The content of the structural unit (a) is 30 when the total of the structural unit (a), (b-1) and / or (b-2), and (c) is 100 mol%. -65 mol%. The reason for this is that when the content is less than 30 mol%, it is difficult to develop a low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present invention, whereas This is because when the ratio exceeds 65 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
Moreover, for such reasons, the content of the structural unit (a) is set to 100 mol% of the total of the structural unit (a), (b-1) and / or (b-2), and (c). When it is, it is more preferable to set it as 35-60 mol%, and it is more preferable to set it as 40-55 mol%.

(Ii) Structural unit (b-1)
In formula (2-1), examples of the alkyl group represented by R ⁴ or R ⁵ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The structural unit (b-1) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n -Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid vinyl, vinyl caproate, vinyl vinyl versatate, vinyl stearate Tellurium; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- ( (Meth) acrylic acid esters such as n-propoxy) ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc. The combination of is mentioned.

(Iii) Structural unit (b-2)
In the copolymer of the present invention, the structural unit (b-2) can be used together with the structural unit (b-1) or in place of the structural unit (b-1). The structural unit (b-2) can be introduced by using a vinyl monomer represented by the formula (2-2) as a polymerization component. Specific examples of such vinyl monomers include those having the following structural formula.

（式中、Ｒ^３は水素原子又はメチル基であり、ｘは０〜２の数を表す。また、上記式中、芳香環の中にFと記した基は、５つの水素の全てがフッ素原子で置換されていることを示
す。）

(In the formula, R ³ represents a hydrogen atom or a methyl group, and x represents a number from 0 to 2. In the above formula, the group marked F in the aromatic ring is all five hydrogens are fluorine. Indicates that the atom is substituted.)

The content of the structural unit (b-1) and / or (b-2) is the sum of the structural unit (a), (b-1) and / or (b-2), and (c). When the content is 100 mol%, it is 1 to 50 mol%. The reason for this is that when the content rate is less than 1 mol%, the solubility of the hydroxyl group-containing fluorine-containing copolymer in the organic solvent may be reduced. On the other hand, when the content rate exceeds 50 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluorine-containing copolymer may deteriorate.
For these reasons, the content of the structural units (b-1) and / or (b-2) is changed to the structural units (a), (b-1) and (b-2), and (c )) Is more preferably from 1 to 45 mol%. Moreover, the content rate of (b-1) and / or (b-2) shown above is the structural unit when the structural unit (b-1) or (b-2) is used alone. It means the content of either (b-1) or (b-2), and when the structural units (b-1) and (b-2) are used together, it means the total content of both. .

(Iv) Structural unit (c)
In the formula (3), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group , 6-hydroxyhexyl group.

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, Examples include hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like.
Moreover, as a hydroxyl-containing vinyl monomer, in addition to the above, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polypropylene Glycol (meth) acrylate or the like can be used.

The content of the structural unit (c) is 5 when the total of the structural units (a), (b-1) and / or (b-2), and (c) is 100 mol%. It is preferable to set it as -60 mol%. The reason for this is that when the content is less than 5 mol%, the hydroxyl group content of the fluoropolymer is lowered, and sufficient hardness of the cured coating film may not be obtained. On the other hand, the content is 60 mol. This is because if it exceeds%, optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
For these reasons, the content of the structural unit (c) is set to 100 mol% of the total of the structural units (a), (b-1) and / or (b-2), and (c). When it is, it is more preferable to set it as 5-55 mol%, and it is more preferable to set it as 10-50 mol%.

(Iv) Structural unit (d) and structural unit (e)
The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).

［式（４）中、Ｒ⁸及びＲ⁹は、同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン化アルキル基又はアリール基を示す］ (D) A structural unit represented by the following formula (4).

[In formula (4), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]

In the formula (4), the alkyl group of R ⁸ or R ^{9 is} an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, and the halogenated alkyl group is a trifluoromethyl group or perfluoro group. C1-C4 fluoroalkyl groups, such as an ethyl group, a perfluoropropyl group, a perfluorobutyl group, etc., A phenyl group, a benzyl group, a naphthyl group etc. are each mentioned as an aryl group.

  The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (4). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following formula (5).

［式（５）中、Ｒ¹⁰〜Ｒ¹³は、同一でも異なっていてもよく、水素原子、アルキル基又はシアノ基を示し、Ｒ¹⁴〜Ｒ¹⁷は、同一でも異なっていてもよく、水素原子又はアルキル基を示し、ｐ、ｑは１〜６の数、ｓ、ｔは０〜６の数、ｙは１〜２００の数、ｚは１〜２０の数を示す。］

[In the formula (5), R ^{10 to} R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ^{14 to} R ¹⁷ may be the same or different and represent a hydrogen atom. Alternatively, it represents an alkyl group, p and q are numbers 1 to 6, s and t are numbers 0 to 6, y is a number 1 to 200, and z is a number 1 to 20. ]

  When the compound represented by the formula (5) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).

［式（６）中、Ｒ¹⁰〜Ｒ¹³、Ｒ¹⁴〜Ｒ¹⁷、ｐ、ｑ、ｓ、ｔ及びｙは、上記式（５）と同じである。］ (E) A structural unit represented by the following formula (6).

[In the formula (6), R ^{10 to} R ¹³ , R ^{14 to} R ¹⁷ , p, q, s, t, and y are the same as in the above formula (5). ]

In the formulas (5) and (6), examples of the alkyl group represented by R ^{10 to} R ¹³ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. Examples of the alkyl group of ^{14 to} R ¹⁷ include alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

  In the present invention, the azo group-containing polysiloxane compound represented by the above formula (5) is particularly preferably a compound represented by the following formula (7).

［式（７）中、ｙ及びｚは、上記式（５）と同じである。］

[In Formula (7), y and z are the same as the said Formula (5). ]

In addition, the content rate of the structural unit (d) is 0.1 to the total 100 mol parts of the structural unit (a), (b-1) and / or (b-2), and (c). It is preferable to set it as 10 mol part. The reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing is decreased, and the scratch resistance of the coated film may be decreased. If the amount exceeds 10 parts by mole, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling and the like are likely to occur during coating.
Moreover, for such reasons, the content of the structural unit (d) is adjusted to 100 mol parts in total of the structural unit (a), (b-1) and / or (b-2), and (c). On the other hand, it is more preferable to set it as 0.1-5 mol part, and it is further more preferable to set it as 0.1-3 mol part. For the same reason, the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.

(V) Structural unit (f)
It is also preferred that the hydroxyl group-containing fluoropolymer further comprises the following structural unit (f).

［式（８）中、Ｒ¹⁸は乳化作用を有する基を示す］ (F) A structural unit represented by the following formula (8).

[In formula (8), R ¹⁸ represents a group having an emulsifying action]

In the formula (8), the group having an emulsifying action of R ¹⁸ includes a group having both a hydrophobic group and a hydrophilic group, and the hydrophilic group having a polyether structure such as polyethylene oxide and polypropylene oxide. preferable.

［式（９−１）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］

［式（９−２）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］ Examples of the group having such an emulsifying action include groups represented by the following formula (9-1) or (9-2).

[In Formula (9-1), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]

[In Formula (9-2), n, m, and u are the same as in Formula (9-1) above]

  The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such a reactive emulsifier include compounds represented by the following formula (10-1) or (10-2).

［式（１０−１）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］

［式（１０−２）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］

[In Formula (10-1), n, m, and u are the same as in Formula (9-1) above]

[In Formula (10-2), n, m, and u are the same as in Formula (9-1) above]

In addition, the content rate of the structural unit (f) is 0.1 to the total 100 mol parts of the structural unit (a), (b-1) and / or (b-2), and (c). It is preferable to set it as -5 mol part. The reason for this is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol parts, the curable resin composition This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
For such reasons, the content of the structural unit (f) is adjusted to 100 mol parts in total of the structural unit (a), (b-1) and / or (b-2), and (c). On the other hand, it is more preferable to set it as 0.1-3 mol part, and it is further more preferable to set it as 0.2-3 mol part.

(Vi) Molecular Weight The hydroxyl group-containing fluoropolymer preferably has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000 measured by gel permeation chromatography using tetrahydrofuran as a solvent. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult.
For these reasons, the number average molecular weight in terms of polystyrene of the hydroxyl group-containing fluoropolymer is more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000.

  The amount of the component (D) binder is preferably 30 to 200 parts by weight, more preferably 80 to 120 parts by weight, based on 100 parts by weight of the total of components (A) and (B).

(E) Polymerization initiator A polymerization initiator may be added to the composition of the present invention. The reaction is promoted by adding a polymerization initiator.
Examples of the polymerization initiator include a compound that generates active species by irradiation with active energy rays and / or heat, an acidic compound and / or a compound that generates acid by heating, a TCI reagent, and the like.

(1) Compounds that generate active species upon irradiation with active energy rays Compounds that generate active species upon irradiation with active energy rays (hereinafter referred to as “photopolymerization initiators”) include light that generates radicals as active species. A radical generator etc. are mentioned.
The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet light because it has a certain energy level, has a high curing speed, is relatively inexpensive, and is compact.

(I) Kind Examples of the photo radical generator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4- Chlorobenzophenone, 4,4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-dodecyl) Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 3-methylacetophenone, 3, 3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 4 Examples thereof include -benzoyl-4'-methyldiphenyl sulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers.

  Among these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2 -Phenylmethyl) -1-butanone and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl ) -1-butanone, and the like.

Examples of commercially available photopolymerization initiators include Irgacure 127 (manufactured by BASF), Irg OXE02 (manufactured by BASF), Irgacure 369 (manufactured by Ciba Specialty Chemicals, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1) and Irgacure 907 (manufactured by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one) are preferred.
Etc.
Examples of long-wavelength absorption include Irg OXE02, nifedipine (TCI reagent), 2,4-diethylthioxanthen-9-one (TCI reagent), and the like.

(2) Compound that generates active species by heat As a compound that generates active species by heat (hereinafter referred to as “thermal radical polymerization initiator”), a thermal radical generator that generates radicals can be used as the active species. .

(I) Type Examples of thermal radical generators include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert -One kind of butyl peroxide, tert-butyl hydroperoxide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. Single or 2 or more types of combinations can be mentioned.

(3) Compound that generates acid upon irradiation with light The compound that generates acid upon irradiation with light used in the present invention functions as a curing catalyst. A compound that generates an acid upon irradiation with light is generally referred to as a “photoacid generator”, and is a variety of photocationic polymerization initiators, and decomposes into an acidic compound upon irradiation with light.
Examples of commercially available photoacid generators include CPI-100P (manufactured by San Apro Co., Ltd.).

(4) Acidic compound and / or compound that generates acid by heating The acidic compound used in the present invention and / or the compound that generates acid by heating functions as a curing catalyst. Acidic compounds are various acids. A compound that generates an acid by heating is generally called a “thermal acid generator”, and is a salt or ester compound of various acids, which decomposes to become an acidic compound by heating.
The thermal acid generator is a substance that can accelerate the curing reaction when the coating film of the curable composition is heated and cured, and the heating condition is improved to be milder. It is a substance that can do. There is no restriction | limiting in particular as this thermal acid generator, The various acids currently used as a hardening | curing agent for general urea resin, melamine resin, etc. and its salt can be utilized. Specific examples of acidic compounds and thermal acid generators include, for example, various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid, and maleic acid, and various types such as benzoic acid and phthalic acid. Examples thereof include aromatic carboxylic acids and salts thereof, various alkylbenzene sulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid and ammonium salts thereof, various metal salts, phosphoric acid and organic acid phosphates, and the like.

  When the binder of component (D) to be used is a radical polymerizable compound, the polymerization initiator is preferably a radical polymerization initiator (light and / or thermal radical polymerization initiator), and is preferably a cationic polymerizable compound (for example, , Epoxy-based and oxetane-based resins), it is preferable to use a photoacid generator.

  The blending amount of the polymerization initiator of component (E) is preferably 2 to 20 parts by weight and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the binder of component (D).

(F) Additives Various additives can be blended in the composition of the present invention as long as the effects of the present invention are not impaired. Examples of such additives include adhesion assistants, slip agents, sensitizers, chain transfer agents, antifoaming agents, antioxidants, ion scavengers, water absorbing agents, and leveling agents.

Examples of the adhesion assistant include SZ6030 and SZ6020 (manufactured by Toray Dow Co., Ltd.).
Examples of the slip agent include Silaplane FM0725 (manufactured by JNC Corporation).
As an antifoamer, AC901 (made by Kyoeisha) etc. are mentioned, for example.
Examples of the antioxidant include Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd., phenolic antioxidant).
Examples of the chain transfer agent include Karenz MT PE1 (manufactured by Showa Denko KK, polyfunctional thiol).

  0.5-10 weight part is preferable with respect to 100 weight part of binders of a component (D), and, as for the total compounding quantity of the various additive of a component (F), 1-6 weight part is more preferable.

(G) Solvent The solvent to be used is not particularly limited and may be appropriately selected. Preferred solvents include methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, ethyl lactate, n-methylpyrrolidone (NMP), propylene glycol monomethyl ether (PGME), isopropyl alcohol (IPA), butyl acetate and the like.

  What is necessary is just to determine suitably the compounding quantity of the solvent of a component (G) so that it may become the total solid content (Total Solid Content; weight%) in a desired composition, or a desired particle component content (weight%).

The total solid content (TSC; wt%) indicates the ratio of the weight of the remaining components after heating the composition at 175 ° C. for 1 hour to the initial weight of the composition.
The total solid content is preferably 5 to 70% by weight, and more preferably 10 to 50% by weight.

The particle component content (% by weight) represents the total proportion of the particle components (A) to (C) in the total solid content in the composition.
The particle component content is preferably 50 to 70% by weight, and more preferably 50 to 60% by weight.

  The curable composition concerning this Embodiment can be prepared by adding each component and mixing under room temperature or heating conditions. Specifically, it can prepare using mixers, such as a mixer, a kneader, a ball mill, and a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition temperature of the thermal polymerization initiator.

II. Hard coat material and film with hard coat The hard coat material of the present invention means a hard coat layer obtained by applying and curing the composition of the present invention on a substrate, and the film with a hard coat of the present invention is a film. As a base material, it means a member obtained by applying and curing the composition of the present invention.

  The method for coating the composition on the substrate is not particularly limited, and examples thereof include a roll coating method, a gravure coating method, a spin coating method, and a method using a doctor blade.

  The composition can be formed by applying the composition onto a substrate and forming the coating film by removing the organic solvent by a drying process, and then curing the coating film by irradiating or heating active energy rays. preferable.

  The film substrate is not particularly limited and may be selected from those used in the art. Commercially available film base materials include PET (Toyobo Cosmo Shine A4300), TAC film (Fuji Film, Fujitac TDY80ULM), ARTON (JSR, GX5000), acrylic film (Mitsubishi Rayon, Acrylite L), etc. Is mentioned.

  The film thickness of the hard coat material is preferably 0.1 μm to 10 μm, more preferably 0.5 μm to 5 μm. By being in the said range, the coating film which is excellent in transparency, coating-film intensity | strength, and antiblocking property is obtained.

  The hard coat material obtained by curing the curable composition of the present invention has low haze, high total light transmittance, and excellent steel wool resistance, adhesion to a substrate, and antiblocking property.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.

分散助剤：アセチルアセトン
多官能（メタ）アクリレートモノマー：日本化薬（株）製、商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートとの重量比６０対４０の混合物
分散媒：メチルエチルケトン、２−ブタノール Production Example 1: Production of modified zirconia sol (material)
Zirconia particles: UEP-100 (primary particle size: 10 nm), manufactured by Daiichi Rare Element Chemical Co., Ltd.
Dispersant: PLAADD ED151 manufactured by Enomoto Kasei Co., Ltd. (in the following formula (1), m = about 9, n = about 13)

Dispersing aid: Acetylacetone Polyfunctional (meth) acrylate monomer: Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate in a weight ratio of 60:40) Dispersion medium: Methyl ethyl ketone, 2-butanol

A dispersant 3.4 parts by weight, a dispersion aid 1.5 parts by weight, a binder resin (polyfunctional (meth) acrylate monomer) 4.0 parts by weight, methyl ethyl ketone 54 parts by weight and 2-butanol 4.2 parts by weight are mixed. While stirring with a homogenizer, 28.8 parts by weight of zirconia particles were added over about 10 minutes. Stir for about 15 minutes after adding the particles. The obtained slurry was dispersed using an SC mill manufactured by Mitsui Mining Co., Ltd. under the following conditions.
Equipment: SC mill manufactured by Mitsui Mining Co., Ltd. Frequency: 60 Hz (equivalent to 3600 rpm)
Casing capacity: 59 mL
Slurry amount: 500g
Dispersed bead filling amount: Glass beads (manufactured by TOSHINRIKO, BZ-01)
(Bead diameter 0.1mm) 46g Volume filling rate 31%
Dispersion time: The particle size was measured over time, and the point at which no decrease in particle size was observed was taken as the end point of dispersion. The dispersion time was 6 hours.

Production Example 2: Production of Organic Compound S 1 hour at 50 ° C. with stirring 20.6 parts of isophorone diisocyanate in a solution consisting of 7.8 parts of mercaptopropyltrimethoxysilane and 0.2 parts of dibutyltin dilaurate in dry air After dropping, the mixture was stirred at 60 ° C. for 3 hours. To this, 71.4 parts of pentaerythritol triacrylate was added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 3 hours to obtain an organic compound S. In the infrared absorption spectrum of the product, the absorption peak of 2550 cm ⁻¹ characteristic of the mercapto group in the raw material and the absorption peak of 2260 cm ⁻¹ characteristic of the isocyanate group disappeared. -O-C (= O) -NH- ] group and [-S-C (= O) -NH-] of the characteristic 1660 cm ^-1 based on peak - to click and acryloyl groups characteristic 1720 cm ^-1 A peak is observed, and an organic group having both an acryloyl group as a polymerizable unsaturated group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group. It was shown that the compound was produced.

  Under a nitrogen stream, the organic compound S synthesized as described above and the particle component serving as the component (A) were mixed, heated and stirred to obtain a dispersion of modified particles.

Production Example 3: Production of fluorinated polymer (1) Synthesis of hydroxyl-containing fluorinated polymer A 2.0-liter stainless steel autoclave with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 11544 g of ethyl acetate, perfluoro (propyl (Vinyl ether) 3464 g, ethyl vinyl ether 938 g, hydroxyethyl vinyl ether 1145 g, lauroyl peroxide 37.5 g, azo group-containing polydimethylsiloxane represented by the above formula (7) (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) ) 225 g and nonionic reactive emulsifier (ER-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd. in a solid composition obtained by distilling off all the solvents in advance) 1125 g, and dry ice-methanol at −50 ° C. Then, the oxygen in the system was removed again with nitrogen gas.

Next, 1953 g of hexafluoropropylene was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Then 70
The reaction was continued with stirring at 20 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain about 5 kg of a hydroxyl group-containing fluoropolymer. This is referred to as a hydroxyl group-containing fluoropolymer. Table 1 shows the monomers and solvents used.

It attached to the obtained hydroxyl-containing fluoropolymer, and measured the polystyrene conversion number average molecular weight and fluorine content by gel permeation chromatography, respectively. ^{Further, 1 H-NMR, 13 C} -NMR both results of NMR analysis, elemental analysis and fluorine content to determine the percentage of each monomer component constituting the hydroxyl group-containing fluoropolymer. The results are shown in Table 2.

VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (7) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000. ER-30 is a nonionic reactive emulsifier wherein n is 10 to 14, m is 1 and u is 14 to 45 in the above formula (10-2).
Furthermore, in Table 2, the correspondence between the monomer and the structural unit is as follows.
Monomer Structural unit Hexafluoropropylene (a)
Perfluoro (propyl vinyl ether) (a)
Ethyl vinyl ether (b-1)
Hydroxyethyl vinyl ether (c)
ER-30 (f)
Polydimethylsiloxane skeleton (d)

(2) Synthesis of ethylenically unsaturated group-containing fluoropolymer A (methacryl-modified fluoropolymer) To a 1 liter separable flask equipped with an electromagnetic stirrer, a glass condenser and a thermometer, 120 g of the obtained hydroxyl group-containing fluoropolymer, 0.02 g of 2,6-di-t-butylmethylphenol and 862 g of methyl isobutyl ketone (MIBK) were charged as a polymerization inhibitor, and the hydroxyl group-containing fluoropolymer at 20 ° C. Was dissolved in MIBK and stirred until the solution became clear and uniform.
Next, to this system, 32.1 g of 2-methacryloyloxyethyl isocyanate was added and stirred until the solution became homogeneous, then 0.3 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. A MIBK solution of the ethylenically unsaturated group-containing fluoropolymer A was obtained by maintaining the temperature at 65 ° C. and continuing stirring for 5 hours.
2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0% by weight. The compounds used, solvent and solid content are shown in Table 3.

Example 1
(1) Production of curable composition In a container shielded from ultraviolet rays, MEK-ST (manufactured by Nissan Chemical Industries, silica particles, dispersion medium: methyl ethyl ketone) modified with organic compound S synthesized in Production Example 2 is converted into solid content. 91 parts by weight, MEK-ST-ZL (manufactured by Nissan Chemical Co., Ltd., methyl ethyl ketone sol) 9 parts by weight in terms of solid content, and MX-80H3 wt (manufactured by Soken Chemical Co., Ltd.) in terms of solids content 2 Parts by weight, KAYARAD DPHA (manufactured by Nippon Kayaku) as a binder is 100 parts by weight in terms of solids, Irg127 (manufactured by BASF) is 8 parts by weight in terms of solids, and 30 parts by weight of methyl ethyl ketone as a solvent A uniform curable composition was obtained by adding 70 parts by weight of ketone and stirring at room temperature for 2 hours.

(2) Production of film with hard coat The curable composition obtained by the production of the curable composition is cured on a PET film (Toyobo Cosmo Shine A4300) using a bar coater to give a cured film thickness of 1.5 μm. After being coated at 80 ° C. for 2 minutes, it was cured using a high-pressure mercury lamp (300 mJ / cm ² ) under a nitrogen flow to obtain an antireflection laminate.

(3) Characteristic evaluation of film with hard coat About film with hard coat obtained in the above (2), haze, total light transmittance (Tt;%), anti-blocking property, steel wool resistance and cross-cut peeling, The following measurement method or evaluation method evaluated. The results are shown in Table 4-1.

Haze (%): Measured using a color haze meter in accordance with JIS-K-7105.

Total light transmittance (Tt;%): Measured using a color haze meter in accordance with JIS-K-7105.

Anti-blocking property:
The coated surfaces of the two cured films obtained were rubbed together and evaluated by the degree of blocking.
The anti-blocking property was evaluated according to the following evaluation criteria.
5: Blocking does not occur even when rubbing both sides with strong force 4: Blocking does not occur even when rubbing with force 3: Blocking does not occur even when rubbing 2: Blocking even with rubbing with weak force Does not occur 1: Blocking occurs even when rubbing with a weak force

Steel wool resistance:
Steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is subjected to a load of 100 g. By rubbing repeatedly 10 times, the presence or absence of scratches on the surface of the cured film was visually confirmed and evaluated according to the following criteria.
Steel wool resistance was evaluated according to the following evaluation criteria.
○: Scratch is not recognized ×: Scratch is observed

Cross-cut peeling:
Evaluation was performed in accordance with JIS-K-5400-8.5.

Examples 2-7 and Comparative Examples 1-6
A curable composition was produced in the same manner as in Example 1 except that each component was as described in Tables 4-1 and 4-2, and applied to the substrates described in Tables 4-1 and 4-2. A film with a hard coat was produced by curing.
About the obtained film with a hard coat, the result evaluated similarly to Example 1 is shown to Table 4-1 and 4-2.

From the comparison between Table 4-1 (Examples 1 to 7) and Table 4-2 (Comparative Examples 1 to 6), from a curable composition containing a predetermined particle component at a predetermined ratio and containing a binder component. It can be seen that the formed hard-coated film is excellent in transparency, anti-blocking property and scratch resistance. In particular, it can be seen that the anti-blocking property is maintained and the scratch resistance is also excellent.
In all of Examples 1 to 7 and Comparative Examples 1 to 6, it was confirmed that the adhesion was good when a PET film was used as a base material. Moreover, about Example 1, 5 and 7, it was confirmed that adhesiveness is also favorable when each of TAC, ARTON, and an acrylic film is used as a base material.

The components described in Tables 4-1 and 4-2 are as follows.
The “BET particle size” of each particle is determined by measuring the specific surface area of the particle using a specific surface area measuring device (device name: Tristar II 3020, manufacturer: Shimadzu Corporation), and assuming that the particle is a sphere. And the particle diameter (dispersed particle diameter) calculated from the ratio of the surface area.
The numerical values of the blending amounts of the components (A) to (F) are indicated by “parts by weight”.
The numerical value of the compounding amount of the component (G) solvent is a ratio between the solvent types, and indicates the ratio of each compound in a total of 100% by weight of the solvent types. What are the compounding amounts of the components (A) to (F)? Different. The proportion of the component (G) solvent in the composition can be determined from the total solid content (% by weight).

Components (A) and (B):
In addition, the modified | denatured inorganic particle of a component (A) is the particle | grains which modified | denatured the zirconia sol manufactured by the following commercial item or manufacture example 1 with the organic compound S manufactured by manufacture example 2.
MEK-ST: Nissan Chemical Co., silica particles, dispersion medium: methyl ethyl ketone MEK-ST-L: Nissan Chemical Co., silica particles, dispersion medium: methyl ethyl ketone MEK-ST-ZL: Nissan Chemical Co., silica particles, dispersion medium : Methyl ethyl ketone MEK-ST-UP: manufactured by Nissan Chemical Co., Ltd., beaded silica particles, dispersion medium: methyl ethyl ketone NAT311P: manufactured by Nagase; titania sol; dispersion medium: propylene glycol monomethyl ether JS1012 SIV: manufactured by Catalysts &Chemicals; hollow silica particles; : Methyl isobutyl ketone Thruria 22SL-05JX: manufactured by Catalyst Kasei Co., Ltd .; hollow silica particles: dispersion medium: methyl isobutyl ketone

Component (C):
MX-80H3wT: manufactured by Soken Chemical Co., Ltd .; 0.7 μm polymethyl methacrylate (PMMA) particles, solvent-free MX-150: manufactured by Soken Chemical Co., Ltd .; PMMA particles having a particle diameter of 1.5 μm, solvent-free J-4PY: Soken PMMA particles with a particle size of 2.1 μm, solvent-free J-3PY: manufactured by Soken Kagaku; PMMA particles with a particle size of 1.0 μm, solventless SC1050-KJA: manufactured by Admatechs; silica particles with a particle size of 300 nm :
MM110-SMA: manufactured by Negami Kogyo; urethane particles having a particle size of 1.0 μm, no solvent

Component (D):
DPHA: Nippon Kayaku Co., Ltd .; Dipentaerythritol hexaacrylate Art Resin H-34: Negami Kogyo Co., Ltd .; Urethane acrylate Art Resin UN904M: Negami Kogyo Co., Ltd .; Urethane acrylate U6HA: Shin Nakamura Chemical Co .; Urethane acrylate tricyclode Candimethanol diacrylate RA311M: manufactured by Negami Kogyo; polymer side chain acrylate branch HEA: manufactured by Osaka Organic Industry Co., Ltd .; 2-hydroxyethyl acrylate Celoxide 2021P: manufactured by Daicel Cytec; alicyclic epoxy EXA830CRP: manufactured by DIC; bisphenol A type epoxy OXPT: Ube Industries, Ltd .; Oxetane

Ingredient (E):
Irg127: manufactured by BASF; photo radical polymerization initiator Irg OXE02: manufactured by BASF; photo radical polymerization initiator Nifedipine :: manufactured by Tokyo Chemical Industry Co., Ltd .; photo radical polymerization initiator (TCI reagent)
2,4-diethylthioxanthen-9-one: manufactured by TCI; photo radical polymerization initiator, TCI reagent, thioxanthone series CPI-100P: manufactured by San Apro; photo acid generator BPO special: manufactured by Kawaguchi Pharmaceutical Co., Ltd .; thermal radical Polymerization initiator

Ingredient (F):
SZ6030: manufactured by Toray Dow Co .; adhesion assistant SZ6020: manufactured by Toray Dow Corporation; adhesion assistant Sailor Plane FM0725: manufactured by JNC; slip agent

Ingredient (G):
NMP: n-methylpyrrolidone PGME: Propylene glycol monomethyl ether IPA: Isopropanol

Base material:
PET: manufactured by Toyobo; polyethylene terephthalate film TAC: manufactured by Fuji Film; triacetyl cellulose film ARTON: manufactured by JSR; transparent film acrylic film: manufactured by Mitsubishi Rayon

(High refractive index hard coat material)
Examples 8-10
A curable composition was produced in the same manner as in Example 1 except that each component was as described in Table 5, and applied to a substrate described in Table 5 and cured to produce a film with a hard coat.
About the obtained film with a hard coat, the result evaluated in the same manner as Example 1 is shown in Table 5.

  From the results of Table 5, the film with a hard coat formed from a curable composition containing a predetermined particle component and a binder component having a high refractive index is transparent, anti-blocking, scratch-resistant and adhesive. It turns out that it is excellent in.

The components described in Table 5 are as follows.
Component (D):
A-BPEF: Shin-Nakamura Chemical; Fluorene Ogsol EA0200: Osaka Gas; Fluorene component (F):
AC901: manufactured by Kyoeisha; defoaming agent Sumilizer GA80: manufactured by Sumitomo Chemical; antioxidant

(Low refractive index hard coat material)
Examples 11-14
A curable composition was produced in the same manner as in Example 1 except that each component was as described in Table 6, and applied to a substrate described in Table 6 and cured to produce a film with a hard coat.
Table 6 shows the results of evaluating the obtained film with hard coat in the same manner as in Example 1.

  From the results in Table 6, a film with a hard coat formed from a curable composition containing a predetermined particle component and a binder component having a low refractive index is transparent, anti-blocking, scratch-resistant and adhesive. It turns out that it is excellent in.

The components described in Table 6 are as follows.
Component (D):
AD1700: manufactured by Solvay; perfluoropolyether (PFPE) acrylate LIC3A: manufactured by Kyoeisha; fluorine acrylate component (F):
Karenz MT PE1: Showa Denko KK; polyfunctional thiol, chain transfer agent

  The hard coating material excellent in antiblocking property and scratch resistance of the present invention is a liquid crystal display (LCD), a cathode ray tube display (CRT), or a plasma display (PDP), electronic paper, LED, touch panel, tablet PC, etc. It is installed in front of displays (image display devices) and is useful as a hard coat material for protecting the display surfaces of these displays.

Claims (5)

The following components (A) to (D):
(A) Modified inorganic particles having a BET particle diameter of 100 nm or less 88 to 94 parts by weight (B) Unmodified silica particles having a BET particle diameter of 5 to 100 nm 6 to 12 parts by weight (C) Particles having a BET particle diameter of 200 nm to 3 μm Curable composition containing 0.1-3 weight part (D) binder with respect to a total of 100 weight part of component (A) and (B).   Furthermore, (E) The curable composition of Claim 1 containing a polymerization initiator.   Furthermore, (G) The curable composition of Claim 1 or 2 containing a solvent.   A hard coat material obtained by curing the curable composition according to claim 1.   The film with a hard coat formed by apply | coating and hardening the curable composition in any one of Claims 1-3 to a film-form base material.