TWI711661B - Active energy ray curable resin composition, paint, coating film, and film - Google Patents

Abstract

The present invention provides an active energy ray curable resin composition having excellent compatibility with various resin materials and excellent hardness or smoothness of the cured product, and excellent adhesion resistance; a coating containing the resin composition; A coating film composed of paint; and a laminated film having a layer containing the coating film. The active energy ray curable resin composition is characterized by containing inorganic fine particles (A) and matrix resin (B) with an average particle diameter in the range of 80 to 250 nm, and the mass of the inorganic fine particles (A) and the matrix resin (B) The ratio [(A)/(B)] is in the range of 30/70 to 70/30, and the aforementioned matrix resin (B) contains a dendrimer type poly(meth)acrylate compound (B1) as an essential component.

Description

Active energy ray curable resin composition, paint, coating film, and film

The present invention relates to an active energy ray-curable resin composition having excellent compatibility with various resin materials and excellent hardness or smoothness of the cured product, and excellent adhesion resistance; a coating containing the resin composition; A coating film composed of the paint; and a film with the coating film layer.

Compared with resin materials composed of only organic materials, inorganic fine particles dispersed resin materials obtained by dispersing inorganic fine particles in a resin component have been used in recent years to increase the hardness of the cured coating film, adjust the refractive index, and impart adhesion resistance. And other novel materials that achieve high performance or impart new functions are attracting attention. The inorganic fine particle dispersion type resin material has various uses, but it is widely used as a hard coat agent for protecting the surface of molded articles or displays, and various film materials from scratches, for example. In order to increase the performance achieved by the addition of inorganic fine particles, the development of resin materials containing more inorganic fine particles is expected. However, resin materials containing a large number of inorganic fine particles are prone to precipitation of inorganic fine particles over time and storage stability. In addition to the poor, there are disadvantages such as low compatibility with organic resin materials, and reduced transparency or smoothness of the coating film.

As an inorganic fine particle dispersion type resin material, a polymer containing an acrylic polymer obtained by adding acrylic acid to glycidyl methacrylate, trimethylolpropane triacrylate, and polyfunctional urethane is known. A resin composition for an anti-glare film of acrylate and silica particles with an average particle diameter in the range of 297 to 540 nm (see Patent Document 1). Compared with the hard coat agent composed only of organic system, this dispersion can obtain a high-hardness coating film, but only about 17% of the non-volatile matter of the resin composition contains silica particles, so it cannot Reach the market requirement level that has required higher surface hardness in recent years. In addition, because it is a resin composition for anti-glare film, the particle size of the silicon dioxide particles contained is very large, and a cured coating film with high transparency cannot be realized. In addition, there is known an acrylic polymer containing an acrylic acid equivalent of 214 g/eq, a hydroxyl value of 262 mgKOH/g, a weight average molecular weight of 40,000, and alumina particles or zirconia particles with an average particle diameter in the range of 55 to 90 nm. The reactive dispersion (refer to Patent Document 2). Compared with the hard coat agent composed of only organic system, this dispersion can obtain a high-hardness coating film, but due to the small average particle size of the inorganic fine particles in the dispersion, it is in contrast to the recent increasing demand for coating film hardness For the grade, it is impossible to obtain sufficient coating film hardness.

Prior art literature Patent literature

Patent Document 1 JP 2008-62539 A

Patent Document 2 JP 2007-289943 A

The problem to be solved by the present invention is to provide an active energy ray curable resin composition that has excellent compatibility with various resin materials and excellent hardness, smoothness, and adhesion resistance of the cured product; a resin composition containing the resin composition The paint; a coating film composed of the paint; and a film with the coating film layer.

The inventors of the present invention devoted themselves to research to solve the above-mentioned problems. As a result, they found that by making the size of the inorganic fine particles in the active energy ray-curable resin composition into an average particle size range of 80 to 250 nm and the dendrimer type Poly(meth)acrylate is used as a matrix resin to make an active energy ray curable resin composition that has excellent compatibility with various resin materials and excellent hardness, smoothness, and adhesion resistance of the cured product. Complete the present invention.

That is, the present invention relates to an active energy ray-curable resin composition characterized by containing inorganic fine particles (A) and matrix resin (B) having an average particle diameter in the range of 80 to 250 nm, the aforementioned inorganic fine particles (A) and The mass ratio [(A)/(B)] of the aforementioned matrix resin (B) is in the range of 30/70 to 70/30, and the aforementioned matrix resin (B) is a dendrimer type poly(meth)acrylate compound (B1) is an essential ingredient.

The present invention further relates to a coating containing the aforementioned resin composition.

The present invention further relates to a coating film containing the aforementioned paint.

The present invention further relates to a laminated film having one or more layers including the aforementioned coating film.

According to the present invention, it is possible to provide an active energy ray curable resin composition having excellent compatibility with various resin materials and excellent hardness, smoothness, and adhesion resistance of the cured product; a resin composition containing the resin composition Paint; a coating film composed of the paint; and a laminated film having a layer containing the coating film.

1‧‧‧Shell of shaft sealing device

2‧‧‧Separator

3‧‧‧Rotating ring

4‧‧‧Fixed ring

5‧‧‧External sealing liquid supply port

6‧‧‧External sealing liquid outlet

7‧‧‧External sealing liquid tank

8‧‧‧Pump

9‧‧‧Gap

10‧‧‧Spring

11‧‧‧Liquid Seal Space

p1‧‧‧Container

q1‧‧‧Rotating bearing

r1‧‧‧Mixing blade

s1‧‧‧Supply port

t1‧‧‧Exhaust outlet

u1‧‧‧Shaft seal device

R‧‧‧External sealing liquid

Fig. 1 is a longitudinal sectional view of a wet ball mill that can be used when manufacturing the resin composition of the present invention.

Fig. 2 is a longitudinal sectional view of a shaft sealing device of a wet ball mill that can be used when manufacturing the resin composition of the present invention.

[The form of implementing the invention]

The active energy ray-curable resin composition of the present invention is characterized by containing inorganic fine particles (A) and matrix resin (B) having an average particle diameter in the range of 80 to 250 nm, the aforementioned inorganic fine particles (A) and the aforementioned matrix resin (B) The mass ratio [(A)/(B)] is in the range of 30/70 to 70/30, and the aforementioned matrix resin (B) is required to be dendritic polymer poly(meth)acrylate compound (B1) ingredient.

The active energy ray-curable resin composition of the present invention contains the aforementioned inorganic fine particles (A) with an average particle diameter in the range of 80 to 250 nm to achieve various properties such as hardness, smoothness, and adhesion resistance of the cured product. Outstanding ones. If the average particle diameter of the aforementioned inorganic fine particles (A) is less than 80 nm, the surface hardness of the obtained coating film will decrease, and if it exceeds 250 nm, the smoothness of the obtained coating film will decrease. Furthermore, in terms of the hardness, smoothness, and adhesion resistance of the cured product, the average particle size of the aforementioned inorganic fine particles (A) is more preferably in the range of 90 to 180 nm, particularly preferably in the range of 100 to 150 nm. .

In the present invention, the average particle diameter of the aforementioned inorganic fine particles (A) is a value obtained by measuring the particle diameter in the active energy ray-curable resin composition under the following conditions.

Particle size measuring device: "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.

Sample for particle size measurement: A 1% by mass solution of non-volatile matter in methyl isobutyl ketone from the active energy ray-curable resin composition.

The aforementioned inorganic fine particles (A) contained in the active energy ray-curable resin composition of the present invention are obtained by dispersing inorganic particles (a) as a raw material in a matrix resin (B), or a matrix resin (B) and an organic solvent. Obtained in a blend. Examples of the aforementioned inorganic particle (a) system include fine particles such as silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These systems may be used alone, or two or more of them may be used in combination.

Among these inorganic particles (a), silicon dioxide particles are preferred in terms of easy availability and simple operation. The silica particles include, for example, fumed silica, or precipitation silica, gel silica, sol-gel silica, etc. Various silica particles called wet silica , You can use either.

The aforementioned inorganic particles (a) can be those that use various silane coupling agents to introduce functional groups on the surface of the fine particles. Functional groups are introduced into the surface to improve the compatibility with organic components such as the aforementioned matrix resin (B) and improve storage stability.

Examples of the aforementioned silane coupling agent system include: vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 -Methacryloxypropyltriethoxysilane, 3-propyleneoxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane , N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, 3-amino Propyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene) propylamine, N-phenyl- 3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3-urea Propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropane) Group) tetrasulfide, 3-isocyanate propyl triethoxy silane, allyl trichlorosilane, allyl triethoxy silane, allyl trimethoxy silane, diethoxy methyl vinyl silane , Trichlorovinyl silane, vinyl trichloro silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane and other vinyl silane coupling agents ； Diethoxy (glycidoxypropyl) methyl silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3- Epoxy silane coupling agent such as glycidoxypropyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane; styrene silane such as p-styryl trimethoxy silane Coupling agent; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methyl (Meth)acryloxy silane coupling agent such as acryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, etc.; N-2(aminoethyl )3-Aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyl Triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene Amino-based silane coupling agents such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc.; ureido-based silane coupling agents such as 3-ureapropyltriethoxysilane; 3 -Chloropropyl silane coupling agents such as chloropropyltrimethoxysilane; mercapto silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; bis( Triethoxysilyl propyl) tetrasulfide and other sulfide-based silane coupling agents; Isocyanate series silane coupling agent such as 3-isocyanate propyl triethoxy silane. These silane coupling agents may be used alone, or two or more of them may be used in combination. Among these, (meth)acrylic acid is preferred in terms of its excellent compatibility with organic components such as the aforementioned matrix resin (B) and the ability to obtain a cured coating film with high surface hardness and excellent smoothness. The oxy-based silane coupling agent is more preferably 3-propenoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane.

The matrix resin (B) used in the present invention contains a dendrimer type poly(meth)acrylate compound (B1) as an essential component. The dendrimer type poly(meth)acrylate compound refers to a compound having a regular multi-branched structure and having a (meth)acryloyl group at the end of each branch. In addition to the dendrimer type, it also It is called hyperbranched or star polymer. Examples of such compound systems include those represented by the following structural formulas (B-1) to (B-8), but are not limited to these, as long as they have a regular multi-branched structure and have at the end of each branch Any (meth)acryloyl compound can be used.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group having 1 to 4 carbon atoms.)

In the present invention, as the dendrimer type poly(meth)acrylate compound (B1) having such a molecular structure, "Viscoat #1000" manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500~2,000, the average number of (meth)acrylic acid groups per molecule is 14], "Viscoat 1020" [weight average molecular weight (Mw) 1,000 to 3,000], "SIRIUS501" [weight average molecular weight (Mw) 15,000 to 23,000], "SP-1106" manufactured by MIWON [Weight average molecular weight (Mw) 1,630, average number of (meth)acrylic acid bases per molecule 18], "CN2301", "CN2302" manufactured by SARTOMER [per The average number of (meth)acrylic groups per molecule is 16], "CN2303" [the average number of (meth)acrylic acid groups per molecule is 6], "CN2304" [the average number of (meth)acrylic acid groups per molecule is 18 ], "ESDRIMER HU-22" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "A-HBR-5" manufactured by Shin Nakamura Chemical Co., Ltd., "NEW FRONTIER R-1150" manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., Nissan Commercial products such as "HYPERTECH UR-101" manufactured by Chemical Corporation. These systems may be used alone, or two or more of them may be used in combination.

Among the aforementioned dendrimer-type poly(meth)acrylate compounds (B1), the active energy has excellent compatibility with various resin materials and excellent hardness, smoothness, and adhesion resistance of the cured product. From the viewpoint of a linear hardening resin composition, the average number of (meth)acrylic acid groups per molecule is preferably in the range of 5-50, particularly preferably in the range of 10-30. Moreover, the weight average molecular weight (Mw) is preferably in the range of 500 to 30,000.

In the present invention, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatography (GPC).

Measuring device: HLC-8220 manufactured by TOSOH Co., Ltd.

Column: Protection column H _XL -H manufactured by TOSOH Co., Ltd. + TSKgel G5000H _XL manufactured by TOSOH Co., Ltd. + TSKgel G4000H _XL manufactured by TOSOH Co., Ltd. + TSKgel G3000H _XL manufactured by TOSOH Co., Ltd. + TSKgel G2000H manufactured by TOSOH Co., Ltd. _XL

Detector: RI (differential refractometer)

Data processing: SC-8010 manufactured by TOSOH Co., Ltd.

Standard: Polystyrene

Sample: obtained by filtering a tetrahydrofuran solution of 0.4% by weight in terms of resin solid content with a microfilter (100μl)

In the present invention, a resin other than the dendrimer type poly(meth)acrylate compound (B1) may be used in combination as the matrix resin (B). Other resins include, for example, other (meth)acrylate compounds (B2) other than the aforementioned dendrimer-type poly(meth)acrylate compound (B1), or other resins that do not have a (meth)acryloyl group ( B3) etc.

The aforementioned other (meth)acrylate compound (B2) system includes, for example, various (meth)acrylate monomers, or urethane (meth)acrylate, and (meth)acrylic acid group-containing The acrylic resin and so on.

啉、N-乙烯吡咯啶酮、丙烯酸四氫糠酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸3-甲氧基丁酯、乙基卡必 醇(甲基)丙烯酸酯、磷酸(甲基)丙烯酸酯、經環氧乙烷改質之磷酸(甲基)丙烯酸酯、(甲基)丙烯酸苯氧酯、經環氧乙烷改質之(甲基)丙烯酸苯氧酯、經環氧丙烷改質之(甲基)丙烯酸苯氧酯、壬基苯酚(甲基)丙烯酸酯、經環氧乙烷改質之壬基苯酚(甲基)丙烯酸酯、經環氧丙烷改質之壬基苯酚(甲基)丙烯酸酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基丙二醇(甲基)丙烯酸酯、酞酸2-(甲基)丙烯醯氧基乙基-2-羥基丙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、酞酸氫-2-(甲基)丙烯醯氧基乙酯、酞酸氫2-(甲基)丙烯醯氧基丙酯、六氫酞酸氫2-(甲基)丙烯醯氧基丙酯、四氫酞酸氫2-(甲基)丙烯醯氧基丙酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟丙酯、(甲基)丙烯酸八氟丙酯、(甲基)丙烯酸八氟丙酯、單(甲基)丙烯酸金剛烷酯等單(甲基)丙烯酸酯；丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、乙氧化己二醇二(甲基)丙烯酸酯、丙氧化己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙氧化新戊二醇二(甲基)丙烯酸酯、羥三甲基乙酸新戊二醇二(甲基)丙烯酸酯等二(甲基)丙烯酸酯；三羥甲丙烷三(甲基)丙烯酸酯、乙氧化三羥甲丙烷三(甲基)丙烯酸酯、丙氧化三羥甲丙烷三(甲基)丙烯酸酯、參2-羥乙基異三聚氰酸酯三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯等三(甲基)丙烯酸酯； 新戊四醇三(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、二-三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二-三羥甲丙烷四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二-三羥甲丙烷五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二-三羥甲丙烷六(甲基)丙烯酸酯等4官能以上的(甲基)丙烯酸酯；及將上述之各種多官能(甲基)丙烯酸酯的一部分以烷基或ε-己內酯取代而成之(甲基)丙烯酸酯等。 The aforementioned (meth)acrylate single system includes, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth) ) N-butyl acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, glycidyl (meth)acrylate, acrylic

Morpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate Base) 2-ethoxyethyl acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phosphoric acid (meth)acrylate, modified by ethylene oxide High-quality phosphoric acid (meth)acrylate, phenoxy (meth)acrylate, phenoxy (meth)acrylate modified by ethylene oxide, phenoxy (meth)acrylate modified by propylene oxide Ester, nonylphenol (meth)acrylate, nonylphenol (meth)acrylate modified by ethylene oxide, nonylphenol (meth)acrylate modified by propylene oxide, methoxy Diethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, 2-(meth)acryloyloxyethyl phthalate 2-hydroxypropyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, hydrogen phthalate-2-(meth)propenoxyethyl, hydrogen phthalate 2-(methyl) Propyl acrylate, hydrogen hexahydrophthalate 2-(meth) propylene oxypropyl ester, hydrogen tetrahydrophthalate 2-(meth) propylene oxypropyl ester, dimethyl (meth)acrylate Ethyl aminoethyl, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, (meth) Mono(meth)acrylates such as octafluoropropyl acrylate and adamantyl mono(meth)acrylate; butanediol di(meth)acrylate, hexanediol di(meth)acrylate, hexamethylene oxide Alcohol di(meth)acrylate, propylene oxide hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Meth) acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, etc. (Meth) acrylate; trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, Ref. 2- Hydroxyethyl isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate and other tri(meth)acrylates; neopentyl erythritol tri(meth)acrylate, di-nephrine Alcohol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, two Neopentylerythritol tetra(meth)acrylate, dineopentaerythritol penta(meth)acrylate, di-trimethylolpropane penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate Esters, di-trimethylolpropane hexa(meth)acrylate and other (meth)acrylates with four or more functions; and the above-mentioned various polyfunctional (meth)acrylates (Meth)acrylate etc. in which part of acrylate is substituted with alkyl or ε-caprolactone.

Examples of the aforementioned urethane (meth)acrylate include a urethane (meth)acrylate using a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate compound as raw materials.

The polyisocyanate compound used in the raw material of the urethane (meth)acrylate may include various diisocyanate monomers, or cyanurates having an isocyanurate ring structure in the molecule (nurate) type polyisocyanate compound, etc.

Examples of the aforementioned diisocyanate single system include: butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl Aliphatic diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate; cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate Alicyclic diisocyanates such as isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, methylcyclohexane diisocyanate, etc.; 1,5-naphthylene diisocyanate (1,5-naphthylene diisocyanate), 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl Diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate (1,3-phenylene diisocyanate), 1,4-phenylene diisocyanate, toluene diisocyanate Aromatic diisocyanates such as isocyanates.

Examples of the cyanurate-type polyisocyanate compound system having an isocyanurate ring structure in the molecule include those obtained by reacting a diisocyanate monomer with a monool and/or diol. As for the diisocyanate monomer used in this reaction, the various diisocyanate monomers mentioned above can be mentioned, and each can be used individually or in combination of 2 or more types. In addition, the monoalcohols used in the reaction include hexanol, octanol, n-decyl alcohol, n-undecyl alcohol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol Alcohol, n-octadecyl alcohol, n-nonadecanol, etc. The diol series include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,3-butanediol , 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc. These monoalcohols or diols may be used alone, or two or more of them may be used in combination.

Examples of the hydroxyl group-containing (meth)acrylate compound used as the raw material of the urethane (meth)acrylate include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4- Aliphatic (meth)acrylate compounds such as hydroxybutyl ester, glycerol diacrylate, trimethylolpropane diacrylate, neopentylerythritol triacrylate, dineopentol pentaacrylate, etc.; 4-hydroxyphenyl acrylate , Β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, propylene 3-hydroxy-4-acetylphenyl acid and 2-hydroxy-3-phenoxypropyl acrylate are equivalent to (meth)acrylate compounds having an aromatic ring in the molecular structure. These systems may be used alone, or two or more of them may be used in combination.

The method for producing the urethane (meth)acrylate includes, for example, the molar ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound [( NCO)/(OH)] becomes the ratio of the range of 1/0.95~1/1.05 to use the aforementioned polyisocyanate compound and the aforementioned hydroxyl-containing (meth)acrylate compound, in the temperature range of 20~120℃, as needed The method is performed using a well-known and commonly used urethane catalyst.

The weight average molecular weight (Mw) of the aforementioned urethane (meth)acrylate is preferably in the range of 800 to 20,000, more preferably in the range of 900 to 1,000.

Examples of the aforementioned (meth)acrylic group-containing acrylic resin series include those obtained by reacting (meth)acrylic acid with a glycidyl-containing acrylic resin intermediate, or glycidyl (meth)acrylate It is obtained by reaction with carboxyl-containing acrylic resin intermediates.

The aforementioned glycidyl-containing acrylic resin intermediate system is obtained by, for example, acrylic polymerizing a glycidyl-containing acrylic monomer such as glycidyl (meth)acrylate and other (meth)acrylate compounds. Other (meth)acrylate compounds used here include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. , Tertiary butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate , (Meth)propylene Lauryl acid, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate Etc. (meth)acrylates having alkyl groups with carbon numbers 1-22; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl(meth) acrylate), dicyclopentenoxyethyl (meth)acrylate and other (meth)acrylates with alicyclic alkyl groups; benzyloxyethyl (meth)acrylate, benzyl (meth)acrylate Ester, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, (meth)acrylic acid (Meth)acrylates with aromatic rings such as 2-hydroxy-3-phenoxypropyl; hydroxyethyl (meth)acrylate; hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, Glycerol (meth)acrylate; hydroxyethyl (meth)acrylate modified by lactone, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate Polypropylene glycol (meth)acrylate and other (meth)acrylates having polyalkylene glycol groups, such as hydroxyalkyl acrylates; dimethyl fumarate, diethyl fumarate, fumaric acid Unsaturated dicarboxylic acid esters such as dibutyl ester, dimethyl iconate, dibutyl iconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itconate, etc.; benzene Styrene derivatives such as ethylene, α-methylstyrene and chlorostyrene; Diene compounds such as butadiene, isoprene, 1,3-pentadiene (piperylene), and dimethylbutadiene; vinyl chloride, vinyl bromide and other vinyl halides or vinylidene halides; methyl vinyl Unsaturated ketones such as ketones and butyl vinyl ketone; vinyl esters such as vinyl acetate and vinyl butyrate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; acrylonitrile, methacrylonitrile, and dicyandicyanide Vinylidene cyanide and other vinyl cyanides; acrylamide or its alkyd substituted amide; N-phenylmaleimide, N-cyclohexylmaleimide and other N-substituted maleimide Imidine; fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; such as trifluoromethyltrifluoroethylene Base ether, pentafluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether (per)fluoroalkyl group with carbon number of 1 to 18 (per)fluoroalkyl group‧perfluorovinyl ether ; Such as (meth)acrylate 2,2,2-trifluoroethyl, (meth)acrylate 2,2,3,3-tetrafluoropropyl, (meth)acrylate 1H,1H,5H-octafluoropentane Ester, (meth)acrylate 1H, 1H, 2H, 2H-heptadecafluorodecyl ester or (meth)acrylate perfluoroethoxyethyl (per)fluoroalkyl has a carbon number of 1 to 18 ( (Per)fluoroalkyl meth)acrylate; (meth)acrylates containing silyl groups such as 3-methacryloxypropyltrimethoxysilane; N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate or N,N-diethylaminopropyl (meth)acrylate (Meth)acrylic acid N,N-dialkylaminoalkyl esters, etc. These systems may be used alone, or two or more of them may be used in combination.

The aforementioned carboxyl group-containing acrylic resin intermediate system is obtained by, for example, polymerizing carboxyl group-containing acrylic monomers such as (meth)acrylic acid with the aforementioned other (meth)acrylate compounds.

The weight average molecular weight (Mw) of the aforementioned (meth)acrylic acid resin group-containing acrylic resin is preferably in the range of 5,000 to 80,000, and its (meth)acrylic acid group equivalent is preferably 220 g/eq to 1650 g/eq. range.

The aforementioned other (meth)acrylate compounds (B2) may be used alone or in combination of two or more kinds. Among them, from the viewpoint of active energy ray curable resin composition having excellent properties such as hardness, smoothness, and adhesion resistance, the use of (meth)acrylate monomers or urethane (methyl) ) Acrylates are preferred, and trifunctional or higher is particularly preferred. The (meth)acrylate monomer with more than three functions is preferably neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dineopentitol penta(meth)acrylic acid Esters, dineopentaerythritol hexa(meth)acrylate. In addition, the urethane (meth)acrylate having trifunctional or higher functions is preferably a diisocyanate compound and glycerol diacrylate, trimethylolpropane diacrylate, neopentyl erythritol triacrylate, and di-neopentylene tetraacrylate. Alcohol pentaacrylate, etc. Urethane (meth)acrylate, which is a hydroxyl-containing (meth)acrylate compound having two or more (meth)acrylic groups in the molecular structure, as a raw material, more preferably Urethane (meth)acrylate using a diisocyanate compound and a hydroxyl-containing (meth)acrylate compound having 3 or more (meth)acrylic groups as raw materials.

Examples of the aforementioned other resin (B3) system that does not have a (meth)acrylic acid group include polyester resins, acrylic resins, and polyurethane resins. These systems may be used alone, or two or more of them may be used in combination. Among them, from the viewpoint of excellent adhesion or water resistance to various plastic films or plastic substrates, acrylic resins are preferred.

When a resin other than the dendrimer type poly(meth)acrylate compound (B1) is used in combination as the matrix resin (B), it has excellent compatibility with various resin materials and the hardness or smoothness of the cured product. In terms of active energy ray-curable resin composition with excellent properties such as durability and adhesion resistance, in 100 parts by mass of the matrix resin (B), the dendritic polymer type poly(meth)acrylate compound (B1) The content is preferably in the range of 5 to 100 parts by mass, more preferably in the range of 10 to 60 parts by mass.

酮、9-氧硫

、2-甲基-9-氧硫

、2-氯-9-氧硫

、2,4-二乙基-9-氧硫

等的

酮、9-氧硫

類；苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚等各種的醯偶姻醚；二苯乙二酮(benzil)、2,3-丁二酮(diacetyl)等α-二酮類；二硫化四甲胺硫甲醯基(tetramethylthiuram disulfide)、二硫化對甲苯基等硫化物類；4-二甲基胺基安息香酸、4-二甲基胺基安息香酸乙酯等各種的安息香酸；3,3'-羰基-雙(7-二乙基胺基)香豆素、1-羥基環己基苯基酮、2,2'-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-N-

啉基丙烷-1-酮、2-芐基-2-二甲基胺基-1-(4-N-

啉基苯基)-丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦(2,4,6-trimethylbenzoyldiphenylphosphine oxide)、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二基苯基)-2-羥基-2-甲基丙烷-1-酮、4-苯甲醯基-4'-甲基二甲基硫醚、2,2'-二乙氧基苯乙酮、芐基二甲基縮酮、芐基-β-甲氧基乙基縮醛、鄰苯甲醯基安息香酸甲酯、雙(4-二甲基胺基苯基)酮、對二甲基胺基苯乙酮、α,α-二氯-4-苯氧基苯乙酮、4-二甲基胺基苯甲酸戊酯(pentyl-4-dimethylaminobenzoate)、2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物、2,4-雙-三氯甲基-6-[二(乙氧基羰基甲基)胺基]苯基-S-三

、2,4-雙-三氯甲基-6-(4-乙氧基)苯基-S-三

、2,4-雙-三氯甲基-6-(3-溴-4-乙氧基)苯基-S-三

蒽醌、2-三級丁基蒽醌、2-戊基蒽醌、β-氯蒽醌等。此等係可各自單獨使用，亦可併用二種以上。 In addition to the aforementioned inorganic fine particles (A) and the aforementioned matrix resin (B), the active energy ray-curable resin composition of the present invention preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator system include: benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone , 4,4'-bisdiethylamino diphenyl ketone, 4,4'-dichlorodiphenyl ketone, Michelone, 3,3',4,4'-tetra(tertiary butyl) Peroxycarbonyl) benzophenone and various benzophenones;

Ketone, 9-oxysulfur

, 2-Methyl-9-oxysulfur

, 2-chloro-9-oxysulfur

, 2,4-Diethyl-9-oxysulfur

Waiting

Ketone, 9-oxysulfur

Classes; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and other various acetoin ethers; benzil, 2,3-butane Α-diketones such as diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; 4-dimethylaminobenzoic acid, 4-dimethyl Various benzoic acids such as ethyl aminobenzoate; 3,3'-carbonyl-bis(7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy -1,2-Diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-N-

Linylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-N-

(Hydroxyphenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzyldiphenylphosphine oxide (2,4,6-trimethylbenzoyldiphenylphosphine oxide), bis(2,4,6-trimethylbenzoyldiphenylphosphine oxide), 1-[4-(2-hydroxyethoxy)phenyl]-2 -Hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecyl) (Phenyl)-2-hydroxy-2-methylpropane-1-one, 4-benzyl-4'-methyl dimethyl sulfide, 2,2'-diethoxyacetophenone, benzyl Dimethyl ketal, benzyl-β-methoxyethyl acetal, phthalate methyl benzoate, bis(4-dimethylaminophenyl) ketone, p-dimethylamino Acetophenone, α,α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4, 5-Diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6-[bis(ethoxycarbonylmethyl)amino]phenyl-S-tri

, 2,4-Bis-trichloromethyl-6-(4-ethoxy)phenyl-S-tri

, 2,4-Bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-tri

Anthraquinone, 2-tertiary butyl anthraquinone, 2-pentyl anthraquinone, β-chloroanthraquinone, etc. These systems may be used alone, or two or more of them may be used in combination.

及9-氧硫

衍生物、2,2'-二甲氧基-1,2-二苯基乙烷-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-N-

啉基-1-丙酮、2-芐基-2-二甲基胺基-1-(4-N-

啉基苯基)-丁烷-1-酮之群組中之1種或2種以上的混合體系，而能夠得到對更廣範圍的波長的光顯示活性且硬化性高的塗料，故而較佳。 Among the aforementioned photopolymerization initiators, by using 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2 -Hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 9-oxysulfur

And 9-oxysulfur

Derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2, 4,6-Trimethylbenzyl)phenyl phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-N-

Linyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-N-

A mixed system of one or two or more of the group of (allophenyl)-butan-1-one can obtain a coating that exhibits activity to light of a wider range of wavelengths and has high curability, so it is preferred .

Examples of commercially available products of the aforementioned photopolymerization initiator include: "IRGACURE-184", "IRGACURE-149", "IRGACURE-261", "IRGACURE-369", "IRGACURE-500", manufactured by Ciba Specialty Chemicals, "IRGACURE-651", "IRGACURE-754", "IRGACURE-784", "IRGACURE-819", "IRGACURE-907", "IRGACURE-1116", "IRGACURE-1664", "IRGACURE-1700", "IRGACURE -1800", "IRGACURE-1850", "IRGACURE-2959", "IRGACURE-4043", "DAROCUR-1173"; "LUCIRIN TPO" manufactured by BASF Corporation; "KAYACURE-DETX", manufactured by Nippon Kayaku Co., Ltd. KAYACURE-MBP", "KAYACURE-DMBI", "KAYACURE-EPA", "KAYACURE-OA"; "VICURE-10" and "VICURE-55" manufactured by Stauffer Chemical; "TRIGONAL P1" manufactured by AKZO; manufactured by SANDOZ "SANDORAY 1000"; "DEAP" made by APJOHN; WARD BLEKINSOP Company-made "QUANTACURE-PDO", "QUANTACURE-ITX", "QUANTACURE-EPD", etc.

The amount of the aforementioned photopolymerization initiator used is an amount capable of fully exhibiting its function as a photopolymerization initiator, and is preferably within a range that does not cause crystal precipitation or deterioration of the physical properties of the coating film. Specifically, it is relative to the active energy The linear hardening resin composition is preferably used within a range of 0.05 to 20 parts by mass for 100 parts by mass, and more preferably used within a range of 0.1 to 10 parts by mass.

The active energy ray-curable resin composition of the present invention may further use various photosensitizers together with the aforementioned photopolymerization initiator. Examples of the photosensitizer system include amines, urea, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

The active energy ray-curable resin composition of the present invention may also contain an organic solvent. The organic solvents used here include, for example, ketone solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ether solvents such as tetrahydrofuran (THF) and dioxolane; Esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; alcohol solvents such as carbitol, celoxol, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Glycol ether solvents such as glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether. These systems may be used alone, or two or more of them may be used in combination. Among these, from the viewpoint of an active energy ray curable resin composition having excellent storage stability and smoothness of the cured coating film, a ketone solvent is preferred, and methyl ethyl ketone or methyl isobutyl is more preferred.基ketone. Organic solvents are mainly used to adjust active energy To measure the viscosity of the curable resin composition, any amount can be added depending on the intended use and the like.

The active energy ray-curable resin composition of the present invention may also contain various additives as needed. The additives used here include, for example, organic solvents, dispersing aids, ultraviolet absorbers, antioxidants, silicon-based additives, organic beads, fluorine-based additives, rheology control agents, defoamers, mold release agents, and antistatic Agents, anti-fogging agents, coloring agents, organic solvents, inorganic fillers, etc.

Examples of the aforementioned dispersion aid system include phosphate compounds such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. These systems may be used alone, or two or more of them may be used in combination. Among these, from the viewpoint of excellent dispersion assist performance, dimethacrylate phosphoric acid modified with ethylene oxide is preferred. Commercially available products of these dispersing aids include, for example, "KAYAMER PM-21" and "KAYAMER PM-2" manufactured by Nippon Kayaku Co., Ltd., and "LIGHT ESTER P-2M" manufactured by Kyoeisha Chemical Co., Ltd. Wait.

、2-[4-{(2-羥基-3-十三烷氧基丙基)氧基}-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三

等三

衍生物、2-(2'-二苯并哌喃羧基-5'-甲基苯基)苯并三唑、2-(2'-鄰硝基苄氧基-5'-甲基苯基)苯并三唑、2-二苯并哌喃羧基-4-十二烷氧基二苯基酮、2-鄰硝基苄氧基-4-十二烷氧基二苯基酮等。此等係可各自單獨使用，亦可併用二種以上。 Examples of the aforementioned ultraviolet absorber system include: 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4 -Dimethylphenyl)-1,3,5-tri

, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-Three

Wait three

Derivatives, 2-(2'-Dibenzopyrancarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl) Benzotriazole, 2-dibenzopiperanancarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These systems may be used alone, or two or more of them may be used in combination.

Examples of the antioxidant system include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants. These systems may be used alone, or two or more of them may be used in combination.

The aforementioned silicon-based additives include, for example, dimethyl polysiloxane, methyl phenyl polysiloxane, cyclic dimethyl polysiloxane, methyl hydrogen polysiloxane, modified by polyether Dimethylpolysiloxane copolymer, dimethylpolysiloxane copolymer modified by polyester, dimethylpolysiloxane copolymer modified by fluorine, dimethylpolysiloxane copolymer modified by amine group -Based polysiloxane copolymers, such as polyorganosiloxanes with alkyl or phenyl groups, polydimethylsiloxanes with acrylic groups modified by polyether, and acrylic groups modified with polyester Polydimethylsiloxane, etc. These systems may be used alone, or two or more of them may be used in combination.

Examples of the aforementioned organic beads include polymethylmethacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, polysiloxy beads, glass beads, acrylic beads, and benzoguanamine resin beads. , Melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, polyethylene resin beads, etc. The preferred value of the average particle diameter of these organic beads is in the range of 1-10 μm. These systems may be used alone, or two or more of them may be used in combination.

Examples of the fluorine-based additive system include DIC Corporation "MEGAFACE" series. These systems may be used alone, or two or more of them may be used in combination.

Examples of the aforementioned mold release agent include: "TEGO Rad 2200N", "TEGO Rad 2300", "TEGO Rad 2100" manufactured by Evonik Degussa, "UV3500" manufactured by BYK, "Paintad 8526" manufactured by TORAY-Dow Corning, and " SH-29PA" etc. These systems may be used alone, or two or more of them may be used in combination.

Examples of the antistatic agent system include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis(trifluoromethanesulfonyl)imide or bis(fluorosulfonyl)imide. These systems may be used alone, or two or more of them may be used in combination.

These various additives can be added in any amount according to the desired performance and the like, but it is generally preferable to use 0.01-40 parts by mass in 100 parts by mass of the active energy ray curable resin composition.

The active energy ray-curable resin composition system of the present invention can be used, for example, by using a disperser, a disperser having a stirring blade such as a turbine blade, a paint shaker, a roller mill, a ball mill, an attritor, and a sand mill. It is produced by mixing and dispersing the aforementioned inorganic fine particles (a) in the matrix resin (B) with a dispersing machine such as a bead mill or a bead mill. Among them, it is preferable to use a ball mill or a bead mill from the viewpoint of obtaining a uniform and stable dispersion. The method of mixing and dispersing the aforementioned inorganic fine particles (a) in the matrix resin (B) may be, for example, dispersing the inorganic fine particles (a) in the total amount of the matrix resin (B) to produce an active energy ray curable resin composition at one time. Method; or may be a method of dispersing inorganic fine particles (a) in a part of the matrix resin (B) to produce a pre-dispersion and then blending the remaining matrix resin (B). In addition, various additives may be added in the dispersion step, or may be added after the inorganic fine particles (a) are dispersed in the matrix resin (B).

The ball mill system that can be applied to the production of the active energy ray-curable resin composition of the present invention includes, for example, a wet ball mill, which has a container filled with a medium, a rotating shaft, and a rotating shaft that is coaxial with the aforementioned rotating bearing. A stirring blade that is rotated by the rotation drive of the rotary bearing, a raw material supply port provided in the container, a dispersion outlet provided in the container, and a shaft arranged in the portion where the rotary bearing penetrates the container The sealing device, wherein the aforementioned shaft sealing device is a shaft sealing device having two sets of mechanical seal units and a structure in which the sealing part of the two sets of mechanical seal units is sealed by an external sealing liquid.

That is, the method of manufacturing the active energy ray-curable resin composition of the present invention includes, for example, supplying the raw material containing the inorganic fine particles (a) and the matrix resin (B) from the supply port of a wet ball mill to In the container, the mixing medium and the raw materials are stirred by rotating the rotary bearing and the stirring blade in the container, and the pulverization of the inorganic fine particles (a) and the dispersion of the inorganic fine particles (a) on the matrix resin (B) are performed, Then the method of discharging from the aforementioned discharge port, wherein the wet ball mill has: a container filled with a medium, a rotating bearing, and a rotating shaft that is coaxial with the aforementioned rotating bearing and is rotated by the rotation drive of the aforementioned rotating bearing A stirring blade, a raw material supply port provided in the container, a dispersion outlet provided in the container, and a shaft sealing device arranged in the portion where the rotary bearing penetrates the container. The shaft sealing device has two sets of mechanical seal units and has The sealing part of the two groups of mechanical sealing units is sealed by an external sealing fluid.

This manufacturing method will be described in further detail based on the drawing showing an example of the specific structure of the aforementioned wet ball mill.

The wet ball mill shown in Figure 1 has: a container (p1) filled with a medium, a rotating bearing (q1), a rotating shaft that is coaxial with the rotating bearing (q1), and is driven by the rotation of the rotating bearing And the rotating stirring blade (r1), the raw material supply port (s1) provided in the container (p1), the dispersion outlet (t1) provided in the container (p1), and the part where the rotating bearing penetrates the container The shaft sealing device (u1). Here, the aforementioned shaft sealing device (u1) has two sets of mechanical seal units and has a structure in which the sealing portion of the two sets of mechanical seal units is sealed by an external sealing liquid. Such shaft sealing device (u1) may include, for example, a second The structure shown in the figure.

In the wet ball mill shown in Figure 1, the raw material is supplied to the container (p1) through the supply port (s1) in Figure 1. The container (p1) is filled with a medium, and the raw material and the medium are stirred and mixed by the stirring blade (r1) rotated by the rotation drive of the rotary bearing (q1), and the pulverization of the inorganic fine particles (a) and the inorganic fine particles (a) Dispersion to the aforementioned matrix resin (B). The inner side of the aforementioned rotating bearing (p1) becomes a cavity with an opening on the side of the discharge port (t1), and a screen-type separator 2 as a separator is installed in the cavity. The inner side is provided with a flow path leading to the discharge port (t1). The dispersion system in the container (p1) is pushed by the supply pressure of the raw material, and is transported from the opening of the rotation bearing (p1) to the separator 2 inside. The aforementioned separator 2 does not allow the medium with a large particle size to pass but only allows the dispersion containing the inorganic fine particles (A) with a small particle size to pass, thereby leaving the aforementioned medium in the container (p1), and only the dispersion from the discharge Exit (t1) discharge.

The aforementioned wet ball mill has a shaft seal device (u1) as shown in Figure 2, and the aforementioned shaft seal device (u1) has two sets of mechanical seal units with a rotating ring fixed to the aforementioned bearing (q1) 3 and the fixed ring 4 fixed to the housing 1 of the shaft seal device in Figure 1 are arranged to form a sealing part, and the rotating ring 3 and the fixed ring 4 of the unit are arranged in the same orientation in the two units direction. Here, the sealing part refers to a pair of sliding surfaces formed by the aforementioned rotating ring 3 and the fixed ring 4. In addition, there is a liquid sealing space 11 between the two sets of mechanical seal units, and there is an external sealing liquid supply port 5 and an external sealing liquid discharge port 6 communicating therewith. In the liquid sealing space 11, the external sealing liquid (R) supplied from the external sealing liquid tank 7 by the pump 8 is supplied through the external sealing liquid supply port 5, and returns to the aforementioned through the external sealing liquid discharge port 6. Slot 7 for circulating supply. Thereby, the external sealing liquid (R) is filled in the liquid sealing space 11 liquid-tightly, and the gap 9 formed between the rotating ring 3 and the fixed ring 4 is filled with the external sealing liquid (R) in the sealing portion. The sealing liquid (R) is used to lubricate and cool the sliding surfaces of the rotating ring 3 and the fixed ring 4.

In addition, the inflow pressure of the sealing liquid (R) and the pressure of the spring 10 are set so that the fixed ring 4 is pressed against the rotating ring 3 by the inflow pressure of the external sealing liquid (R), and the fixed ring 4 is pressed by the spring 10 The force P2 pressing the rotating ring 3 and the force P3 pulling the fixed ring 4 away from the rotating ring 3 by the inflow pressure of the external sealing liquid (R) are balanced. Thereby, the gap 9 between the fixed ring 4 and the rotating ring 3 as the sliding surface is filled with the external sealing liquid (R) liquid-tightly, and the aforementioned matrix resin (B) does not enter the gap 9. When the aforementioned matrix resin (B) flows into the gap 9, by the aforementioned rotation The sliding of the rotating ring 3 and the fixed ring 4 generates mechano radicals, and sometimes the (meth)acrylic acid group possessed by the matrix resin (B) may cause polymerization to cause gelation or thickening. This risk can be avoided by using the wet ball mill of the present invention with the shaft sealing device (u1) as described above.

Examples of the shaft sealing device system such as the aforementioned shaft sealing device (u1) include tandem mechanical seals. In addition, the commercially available product line of the wet ball mill Y having the aforementioned tandem mechanical seal as the shaft seal device includes, for example, the "LMZ" series manufactured by Ashizawa Finetech Co., Ltd., and the like.

The external sealing liquid (R) is a non-reactive liquid, and examples thereof include various organic solvents described above. Among these, from the viewpoint of becoming an active energy ray curable resin composition having excellent storage stability and smoothness of the cured coating film, a ketone solvent is preferred, and methyl ethyl ketone or methyl isobutyl is more preferred.基ketone.

The medium filled in the container (p1) in Figure 1 uses, for example, various microbeads. Examples of the material system of the beads include zirconia, glass, titanium oxide, copper, and zirconia silicate. Among these, from the viewpoint of being the hardest and having less abrasion, zirconia beads are preferred.

The separation between the slurry and the medium in the screen-type separator 2 in Figure 1 is good, and the dispersion time is short due to the high pulverization energy of the aforementioned inorganic particles (a), and the impact on the aforementioned inorganic particles (a) From the viewpoint that the over-dispersion phenomenon of the inorganic fine particles (a) is not too strong, the aforementioned medium is preferably one having an average particle diameter in the range of 10 to 1000 μm in terms of a median particle diameter.

The aforementioned over-dispersion phenomenon refers to the phenomenon that a new active surface is generated by the destruction of inorganic fine particles, which causes re-aggregation. When over-dispersion occurs, the dispersion will gel.

In terms of the minimum power required for dispersion and the most effective pulverization, the filling rate of the medium in the container (p1) in Figure 1 is preferably in the range of 75 to 90% by volume of the container's internal volume.

In view of the large impact when the medium collides with the aforementioned inorganic fine particles (a) and the improvement of dispersion efficiency, the aforementioned stirring blade (r1) is preferably rotationally driven so that the peripheral velocity of the tip part becomes in the range of 5-20 m/sec. More preferably, it is in the range of 8-20m/sec.

When using such a wet ball mill to manufacture the resin composition of the present invention, the manufacturing method may be a batch type or a continuous type. Moreover, in the case of a continuous type, it may be a circulating type in which the slurry is taken out and then supplied, or a non-circulating type. Among these, in terms of improved production efficiency and excellent homogeneity of the obtained dispersion, the circulation type is preferred.

In addition, when using such a wet ball mill to produce the resin composition of the present invention, it is preferably carried out in a two-stage step, which is to use larger particles with a median particle diameter in the range of 400 to 1000 μm as the medium. After the pre-dispersion step, smaller particles with a median diameter of 15 to 400 μm are used as the medium for the main dispersion step.

In the aforementioned pre-dispersion step, a large medium with a median particle diameter in the range of 400 to 1000 μm is used. This medium exerts a large impact force when colliding with the inorganic fine particles (a), so the inorganic fine particles with a large particle size (a) ) Has high pulverization ability, and the inorganic fine particles (A) of the raw material can be pulverized to a certain particle size by using it. In the aforementioned main dispersion step, a medium with a small median particle size in the range of 15~400μm is used. This medium exerts a small impact force when colliding with the inorganic fine particles (a), but is compared with a medium with a large particle size. , The number of particles contained in the same volume increases, so it is The number of collisions of sub (a) will increase. Therefore, it is used to pulverize the inorganic fine particles (a) pulverized to a certain extent in the pre-dispersion step into finer particles. Here, if the aforementioned pre-dispersion step is too long, the aforementioned over-dispersion phenomenon may occur. Therefore, the pre-dispersion step is preferably performed in a range of 1 to 3 cycles of the slurry circulating in the aforementioned container (p1).

The active energy ray-curable resin composition of the present invention can be used for coating applications. This coating system can be used as a coating layer that protects the surface of the substrate by coating on various substrates and irradiating active energy rays to harden them. In this case, the coating material of the present invention can be directly coated on the surface-protected member to be used, or the coating obtained by coating on a plastic film can be used as a protective film. Alternatively, the coating of the present invention can be coated on a plastic film, and the coating film can be used as an optical film such as an anti-reflection film, a diffuser film, and a sheet. When the coating of the present invention is coated on a plastic film, it can be coated on one side or on both sides. In addition, a multilayer film having multiple layers including the coating film of the present invention can also be produced in accordance with the desired performance. The coating film obtained by using the coating of the present invention has the characteristics of high surface hardness and excellent transparency, so it can be coated on various plastic films with a film thickness depending on the application and used as a protective film or film Shaped molded products.

Examples of the aforementioned plastic film series include polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetate cellulose resin, ABS resin, AS resin, Plastic film or plastic sheet composed of norbornene resin, cyclic olefin, polyimide resin, etc.

Among the above-mentioned plastic films, the triacetyl cellulose film is particularly suitable for polarizing plates of liquid crystal displays. However, since it is usually as thin as 40-100 μm in thickness, it is difficult to provide a hard coat layer. Fully improve the surface hardness and easy to produce curl features. The coating film containing the resin composition of the present invention can still achieve the effects of high surface hardness, curl resistance or toughness, and excellent transparency when the triacetyl cellulose film is used as the substrate, and is therefore quite suitable. In the case of using the triacetyl cellulose film as a substrate, the coating amount when applying the coating of the present invention is such that the film thickness after drying is in the range of 4 to 20 μm, preferably in the range of 6 to 15 μm Coating is better. The coating method at this time includes, for example, bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. Law etc.

Among the above-mentioned plastic films, polyester films include, for example, polyethylene terephthalate, whose thickness is usually about 100 to 300 μm. Since it is easy to process at low cost, it is a film that can be used in various applications such as touch panel displays, but it is very soft and it is difficult to sufficiently increase the surface hardness even when a hard coat layer is provided. In the case of using the polyethylene film as a substrate, the coating amount when applying the coating of the present invention is adapted to the application and the film thickness after drying is in the range of 5 to 100 μm, preferably in the range of 7 to 80 μm. The method of coating is better. Generally, when a paint is applied with a film thickness of more than 30μm, it tends to produce larger curls more easily than when applied with a thinner film thickness. However, the paint of the present invention is characterized by excellent curl resistance. Coated with a higher film thickness exceeding 30μm Under the circumstances, curling is not easy to occur, and it is quite suitable. The coating method at this time includes, for example, bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.

Among the above-mentioned plastic films, polymethyl methacrylate films are usually thicker and firmer with a thickness of about 100 to 2,000 μm. Therefore, they are suitable for applications requiring particularly high surface hardness such as LCD front panel applications. film. In the case of using the polymethyl methacrylate film as a substrate, the coating amount when applying the coating of the present invention is based on the application and the film thickness after drying is in the range of 5 to 100 μm, preferably 7 It is better to coat in the range of ~80μm. When Tong Chang coats a paint with a thickness exceeding 30 μm on a relatively thick film such as a polymethyl methacrylate film, it becomes a multilayer film with high surface hardness, and vice versa, the transparency tends to decrease. However, the present invention The paint has very high transparency compared to the conventional paint, so it is possible to obtain a laminated film with high surface hardness and transparency. Examples of the coating method at this time include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.

Examples of the active energy rays to be irradiated when the coating material of the present invention is cured to form a coating film include ultraviolet rays or electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp as a light source is used, and the amount of light, the arrangement of the light source, etc. can be adjusted as necessary. In the case of using a high-pressure mercury lamp, it is usually relative to a lamp with a light quantity in the range of 80~160W/cm. The feeding speed is within the range of 5-50m/min to make it harden. On the other hand, in the case of using an electron beam for curing, it is usually better to use an electron beam acceleration device with an acceleration voltage in the range of 10 to 300 kV, and to perform curing at a conveying speed of 5 to 50 m/min.

In addition, the substrate coated with the coating of the present invention can be suitably used not only as a plastic film, but also as a surface coating agent for various plastic molded products, such as mobile phones, home appliances, and automobile bumpers. In this case, the method of forming the coating film includes, for example, a coating method, a transfer method, and a sheet bonding method.

The aforementioned coating method is to spray coating the aforementioned paint, or use a curtain coater, roll coater, gravure coater, or other printing machine as a topcoat to coat the molded product, and then irradiate active energy rays to make it Hardening method.

The aforementioned transfer method system includes: after the transfer material obtained by coating the coating material of the present invention on the base sheet with releasability and then on the surface of the molded article, the base sheet is peeled off and the upper coating layer is transferred The surface of the molded product is then irradiated with active energy rays to harden it; or the transfer material is adhered to the surface of the molded product, irradiated with active energy rays to harden, and then the substrate sheet is peeled off to coat the top Layer transfer method on the surface of molded products

On the other hand, the sheet bonding method is by applying a protective sheet made of the coating of the present invention on a base sheet, or a coating and decoration made of the coating on the base sheet. The protective sheet of the layer is then attached to the plastic molded product, and the protective layer is formed on the surface of the molded product.

Among these, the coating system of the present invention can be preferably used for transfer method and sheet bonding method applications.

In the aforementioned transfer method, the transfer material is first produced. This transfer material system can be manufactured by coating the aforementioned paint alone or by mixing with a polyisocyanate compound on a substrate sheet and heating to semi-harden (B-stage) the coating film.

Here, when the acrylic polymer (X) or the compound (c) contained in the active energy ray curable compound of the present invention is a compound having a hydroxyl group in the molecular structure, the B-staged step is performed more efficiently For the purpose, a polyisocyanate compound can also be used in combination.

In order to manufacture the transfer material, first, the coating of the present invention is applied on the substrate sheet. Examples of the method of applying the coating material include coating methods such as gravure coating, roll coating, spray coating, lip coating, and cut-off wheel coating, and printing methods such as gravure printing and screen printing. From the viewpoint of better abrasion resistance and chemical resistance, the film thickness during coating is preferably applied so that the thickness of the cured coating film becomes 0.5~30μm, and it is better to apply 1~6μm. good.

After the aforementioned coating material is coated on the base material sheet by the aforementioned method, it is heated and dried to semi-harden the coating film (B-staged). Heating is usually 55 to 160°C, preferably 100 to 140°C. The heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.

The formation of the surface protective layer of the molded article using the transfer material is performed, for example, by bonding the B-staged resin layer of the transfer material to the molded article, and then irradiating the resin layer with active energy rays to cure the resin layer. Specifically, for example, the transfer material is B-staged The resin layer is then applied to the surface of the molded product, and then by peeling off the base sheet of the transfer material, the B-staged resin layer of the transfer material is transferred on the surface of the molded product, and then activated by active energy rays The method of cross-linking and hardening the resin layer by irradiation with energy rays (transfer method); or sandwiching the aforementioned transfer material into a molding mold, and filling the mold with resin injection, while obtaining a resin molded product, The transfer material is then attached to the surface, the base sheet is peeled off and transferred to the molded product, and then the energy ray is irradiated with active energy rays to harden the resin layer to crosslink and harden the resin layer (molding while transferring Law) and so on.

Next, specifically, the sheet bonding method system includes: bonding the base sheet of the protective layer forming sheet prepared in advance to the molded product, and then heat-curing the molded product to perform B-stageization. The method of cross-linking and hardening of the resin layer (post-adhesive method); or sandwich the sheet for forming the protective layer in the forming mold, so that the resin is injected to fill the cavity, and the surface of the resin molded product is After the protective layer forming sheet is adhered, it is heat-cured by heating to perform a method of cross-linking and hardening the resin layer (molding simultaneous bonding method).

Next, the coating film of the present invention is a coating film formed by applying the coating material of the present invention on the aforementioned plastic film and curing it, or applying the coating material of the present invention as a surface protective agent of a plastic molded product and curing it. The formed coating film, and the film of the present invention is a film with a coating film formed on a plastic film.

Among the various uses of the aforementioned films, as described above, from the point of view of the excellent hardness of the coating film, the film obtained by coating the coating of the present invention on a plastic film and irradiating active energy rays is used as a liquid crystal display It is better to use the protective film for the polarizing plate used in the monitor or touch panel display. Specifically, when the coating of the present invention is coated on a polarizing plate protective film used in a liquid crystal display, a touch panel display, etc., and then cured by irradiating active energy rays, the cured coating film will It becomes a protective film with both high hardness and high transparency. In the use of a protective film for a polarizing plate, an adhesive layer may be formed on the other side of the coating layer formed by applying the paint of the present invention.

[Example]

Specific manufacturing examples and examples are listed below to explain the present invention more specifically, but the present invention is not limited by these examples. The parts and% in the examples are quality standards unless otherwise stated.

In the examples of the present invention, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatography (GPC).

Measuring device: HLC-8220 manufactured by TOSOH Co., Ltd.

Column: Protection column H _XL- H by TOSOH Co., Ltd. + TSKgel G5000H _{XL by} TOSOH Co., Ltd. + TSKgel G4000H _{XL by} TOSOH Co., Ltd. + TSKgel G3000H _{XL by} TOSOH Co., Ltd. + TSKgel G2000H by TOSOH Co., Ltd. _XL

Detector: RI (differential refractometer)

Data processing: SC-8010 manufactured by TOSOH Co., Ltd.

流速 1.0ml/分鐘

Flow rate 1.0ml/min

Standard: Polystyrene

Sample: obtained by filtering a tetrahydrofuran solution of 0.4% by weight in terms of resin solid content with a microfilter (100μl)

Inorganic particles used in the examples of this case (a)

‧(A-1): "NIPSIL SS-50F" wet silica made by TOSOH SILICA Co., Ltd.

‧(A-2): "NIPSIL SAZ-20B" wet silica made by TOSOH SILICA Co., Ltd.

‧(A-3): "AEROSIL R7200" manufactured by NIPPON AEROSIL Co., Ltd. has a (meth)acrylic acid smoked silica on the particle surface

‧(A-4): "AEROSIL R8200" smoked silicon made by NIPPON AEROSIL Co., Ltd.

The dendrimer type poly(meth)acrylate compound (B1) used in the examples of this case

‧(B1-1): "Miramer SP-1106" manufactured by MIWON, with a weight average molecular weight (Mw) of 1,630 and an average number of (meth)acrylic acid bases per molecule of 18

‧(B1-2): "Viscoat#1000" manufactured by Osaka Organic Chemical Co., Ltd., weight average molecular weight (Mw) 1,500~2,000, average number of (meth)acrylic acid bases per molecule 14

‧(B1-3): "SIRIUS 501" manufactured by Osaka Organic Chemical Co., Ltd. Weight average molecular weight (Mw) 15,000~23,000

Other (meth)acrylate compounds (B2) used in the examples of this case

‧(Meth)acrylate monomer (B2-1): "ARONIX M-404" manufactured by Toagosei Co., Ltd. contains dineopentaerythritol pentaacrylate and dineopentyl in a mass ratio of 30/70~40/60 Mixture of tetraol hexaacrylate

‧Urethane (meth)acrylate (B2-2)

In a reaction device equipped with a stirring device, 85 parts by mass of hexamethylene diisocyanate, 0.2 part by mass of dibutyltin dilaurate, and 0.2 part by mass of 4-methoxyphenol were added, and the temperature was raised to 60° C. while stirring. Next, 493 parts by mass of neopentylerythritol triacrylate ("ARONIX M-305" manufactured by Toagosei Co., Ltd.) was put in 10 times, once every 10 minutes. The reaction was further continued for 10 hours, and after confirming the disappearance of the absorption of the isocyanate group at 2250 cm ^-1 by infrared spectroscopy, the reaction was terminated, and a urethane (meth)acrylate (B2-2) was obtained. The property values of the urethane (meth)acrylate (B2-2) are as follows: weight average molecular weight (Mw): 1,500, theoretical acryl equivalent: 120g/eq

‧Acrylic resin containing (meth)acrylic acid group (B2-3)

A reaction device equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube was charged with 181 parts by mass of methyl isobutyl ketone, and the temperature in the system was raised to 110°C while stirring, and it took 3 hours to start the dripping process. The dropping funnel contains 288 parts by mass of glycidyl methacrylate, 192 parts by mass of methyl methacrylate, and tertiary butyl peroxy-2-ethylhexanoate ("PERBUTYL O" manufactured by Japan Emulsifier Co., Ltd.) After 19.2 parts by mass of the mixed solution, keep it at 110°C for 15 hours. Then, after cooling to 90°C, 0.64 parts by mass of 4-methoxyphenol was charged After adding 147 parts by mass of acrylic acid and 3.1 parts by mass of triphenylphosphine, the temperature was raised to 100°C and kept at 100°C for 8 hours to obtain (meth)acrylic acid group-containing acrylic resin (B2-3) methyl isobutyl 1200 parts by mass of the base ketone solution (50.0% by mass of non-volatile matter). The property values of the (meth)acrylic acid resin (B2-3) are as follows: weight average molecular weight (Mw): 12,000, acrylic equivalent in terms of solid content: 321g/eq, hydroxyl value 86mgKOH/g

Other resins (B3) without (meth)acrylic groups used in the examples of this case

‧Acrylic resin (B3-1): "ACRYDIC WFU-580" manufactured by DIC Co., Ltd.

‧Acrylic resin (B3-2): "ACRYDIC BL-616" manufactured by DIC Co., Ltd.

‧Acrylic resin (B3-3): "ACRYDIC WXU-880" manufactured by DIC Co., Ltd.

Example 1

The active energy ray-curable resin composition was adjusted in the following manner, and various evaluations were performed. The results are shown in Table 1.

◆Adjustment of active energy ray curable resin composition

Blending of 55 parts by mass of the aforementioned inorganic particles (a-1) ("NIPSIL SS-50F") and 15 parts by mass of the aforementioned dendrimer-type poly(meth)acrylate compound (B1-1) ("Miramer SP1106") , (Meth)acrylate monomer (B2-1) ("ARONIX M-404") 30 parts by mass, 80 parts by mass of methyl isobutyl ketone, and 20 parts by mass of propylene glycol monomethyl ether, using a wet ball mill ( Ashizawa Co., Ltd. made "Starmill LMZ015") will A slurry of 50% by mass of non-volatile matter was mixed and dispersed to obtain a dispersion.

The conditions for the dispersion using the wet ball mill are as follows.

Medium: Zirconia beads with a median diameter of 100μm

The filling rate of the resin composition with respect to the inner volume of the mill: 70% by volume

The circumferential velocity of the tip of the mixing blade: 11m/sec

Flow rate of resin composition: 200ml/min

Dispersion time: 50 minutes

2 parts by mass of a photoinitiator ("IRGACURE #184" manufactured by Ciba Specialty Chemicals) was added to the obtained dispersion, and methyl isobutyl ketone was added to adjust the non-volatile matter ratio to 40% by mass to obtain Active energy ray curable resin composition.

◆Measurement of average particle size of inorganic fine particles (A)

The average particle size of the inorganic fine particles (A) in the active energy ray-curable resin composition was measured using a particle size measuring device ("ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.).

◆Assessment of storage stability

The active energy ray-curable resin composition was allowed to stand for 1 month under a temperature condition of 40°C, and the presence or absence of deposits was evaluated for each elapsed time.

○: No sediment is observed

△: Sediment was observed after 3 weeks

×: Sediment was observed after 1 week

◆Assessment of coating appearance

1. Production of laminated film

Use a bar coater to coat the active energy ray-curable resin composition on a polyethylene terephthalate film with a thickness of 3 μm so that the cured film thickness becomes 3 μm, and dry it at 70°C for 1 minute. A high-pressure mercury lamp was used to harden it with an irradiation amount of 250mJ/cm ² to obtain a laminated film with a hardened coating film.

2. Evaluation

The appearance of the coating film on the laminated film was visually observed. Those with a smooth surface were rated as ○, and those with unevenness, such as unevenness, lumps, interference fringes, etc., were rated as ×.

◆Assessment of coating transparency

1. Production of laminated film

The evaluation of the appearance of the aforementioned coating film was performed in the same manner as the above-mentioned evaluation of the appearance of the coating film to obtain a laminated film.

2. Evaluation

The haze value of the hardened coating film on the laminated film was measured using "Haze Computer HZ-2" manufactured by Suga Test Instruments Co., Ltd.

◆Assessment of adhesion resistance

1. Production of laminated film

The evaluation of the external appearance of the coating film described above was carried out in the same manner, and a laminated film A was obtained. An ultraviolet curable hard coat agent ("UNIDIC 17-806" manufactured by DIC Co., Ltd.) was used instead of the active energy ray curable resin composition, and laminated film B was obtained in the same manner.

2. Evaluation

Laminate the two films so that the coating surfaces of the laminated films A and B are in contact with each other, and apply a load to rub against each other. The smooth sliding condition (with anti-blocking property) is judged as ○, and the non-sliding condition (with Adhesion) is judged as ×.

◆Assessment of curl resistance

1. Production of laminated film

Use a bar coater to apply the active energy ray-curable resin composition on a polyethylene terephthalate film with a thickness of 50 μm so that the cured film thickness becomes 3 μm, and dry it at 70°C for 1 minute. A high-pressure mercury lamp was used to harden it with an irradiation amount of 250mJ/cm ² to obtain a laminated film with a hardened coating film.

2. Evaluation

The laminated film was cut into 10 cm squares, the four corners were measured for floating from the horizontal, and the average value was evaluated. The smaller the value, the smaller the curl, which is a coating film with excellent curl resistance.

◆Assessment of surface hardness

1. Production of laminated film

Use a bar coater to apply the active energy ray-curable resin composition to a 125μm thick polyethylene terephthalate (PET) film so that the cured film thickness becomes 2μm, and dry it at 70°C for 1 minute , Use a high-pressure mercury lamp under nitrogen, and cure it with an irradiation of 250mJ/cm ² to obtain a PET laminated film with a cured coating film.

Similarly, using a bar coater, the active energy ray-curable resin composition was coated on a 60-μm-thick triacetyl cellulose (TAC) film so that the cured film thickness became 5μm, and dried at 70°C for 1 minute , Use a high-pressure mercury lamp under nitrogen, and cure it with an irradiation amount of 250mJ/cm ² to obtain a TAC laminate film with a cured coating film.

2. Evaluation

Regarding the hardened coating film on the above-mentioned laminated film, in accordance with JIS K 5400, the polyethylene terephthalate film as the base material was evaluated through a pencil scratch test with a load of 750 g, and the triacetyl cellulose film as the base was evaluated. The materials were evaluated by a pencil scratch test weighing 500g. The test was performed 5 times, and the hardness that was one level lower than the hardness of one scratch or more was set as the pencil hardness of the coating film.

◆Compatibility with acrylic resin

1. Evaluation of compatibility

When 80 parts by mass of the active energy ray curable resin composition and 20 parts by mass of any of the aforementioned acrylic resins (B3-1) to (B3-3) are blended and mixed, the transparent mixture is evaluated as ○, and Those who developed turbidity were rated as ×.

2. Evaluation of coating film

Using a bar coater, a mixture of 80 parts by mass of the aforementioned active energy ray-curable resin composition and 20 parts by mass of any of the aforementioned acrylic resins (B3-1) to (B3-3) was used to obtain a cured film thickness of 3 μm It is coated on a polyethylene terephthalate film with a thickness of 75μm and dried at 70°C for 1 minute. Under nitrogen, a high-pressure mercury lamp is used to cure the film at an irradiation dose of 250mJ/cm ² to obtain a hardened film. Laminated film of coating film. The appearance of the coating film on the laminated film was visually observed, and those with a smooth surface were rated as ○, and those with unevenness such as unevenness, lumps, interference fringes, etc., were rated as ×.

Examples 2~8, Comparative Examples 1~5

Except that the blending composition at the time of dispersion adjustment was adjusted to the ratio shown in Tables 1 and 2, the same procedure as in Example 1 was carried out to adjust the active energy ray-curable resin composition, and the same was carried out as in Example 1 The results are shown in Tables 1 and 2. In addition, the active energy ray-curable resin composition adjusted in Comparative Examples 3 and 4 was dispersed and precipitated during the storage stability test, so no other evaluation was performed.

Claims (6)

An active energy ray-curable resin composition containing inorganic fine particles (A) and matrix resin (B) with an average particle diameter in the range of 80 to 250 nm. The mass of the inorganic fine particles (A) and the matrix resin (B) The ratio [(A)/(B)] is in the range of 30/70 to 70/30, and the matrix resin (B) is made of dendrimer type poly(meth)acrylate compound (B1) as an essential component Active energy ray-curable resin composition, characterized in that the dendrimer-type poly(meth)acrylate compound (B1) is selected from those represented by the following structural formulas (B-1) to (B-8) More than one group of compounds,

(In formulas (B-1) to (B-8), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group having 1 to 4 carbon atoms). The active energy ray-curable resin composition of claim 1, wherein the inorganic fine particles (A) are silicon dioxide. The active energy ray curable resin composition of claim 1, wherein the average number of (meth)acrylic acid groups per molecule of the dendrimer-type poly(meth)acrylate compound (B1) is 10 to 30 range. A paint containing the active energy ray-curable resin composition according to any one of claims 1 to 3. A coating film formed by hardening the paint of claim 4. A laminated film having one or more layers including the coating film of claim 5.

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