TW201610014A - Active-energy-curing resin composition, coating material, coating film, and laminate film - Google Patents

Abstract

Provided are: an active-energy-curing resin composition that exhibits exceptional performance in terms of coating film workability, while a cured coating film obtained therefrom has extremely high surface hardness; a coating material containing said resin composition; a coating film comprising said coating material; and a film having a layer of said coating film. An active-energy-curing resin composition characterized by containing (A) an acrylic polymer having a weight-average molecular weight (Mw) within a range of 3,000-60,000, the acrylic polymer having hydroxyl groups and (meth)acryloyl groups within the polymer structure, and (B) an isocyanate compound; a coating material containing the same; and a film having a coating film layer obtained by curing said coating material.

Description

Active energy ray-curable resin composition, coating, coating film, and laminated film

The present invention relates to an active energy ray-curable resin composition capable of obtaining a coating film having a very high surface hardness and excellent workability, a coating material containing the resin composition, and a coating film comprising the coating material; And a laminated film having the coating layer.

Plastic films made of polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc., are mostly used for industrial purposes. These films are utilized as, for example, a polarizing plate protective film incorporated in the interior of a flat panel display or a surface protective film of a touch panel, but these films are required to have high scratch resistance.

In order to improve the scratch resistance, various methods have been studied, but from the viewpoint of environmental advantages such as reduction in energy required for hardening, in recent years, coating on a film has been gradually carried out to crosslink density. A highly polyfunctional acrylate is a main active energy ray-curable resin composition and is cured by an active energy ray such as ultraviolet (UV) or electron beam (EB) to form a hard coat layer.

Through the progress of weight reduction and thinning of the display, the film used is also thinned. Therefore, the hard coating agent applied to the film is required to have a higher hardness than before, and also corresponds to the requirements. Processability for flexible applications. In the case of a hard coating agent which can be suitably used for such a use, an acrylic polymer having a double bond in a side chain by reacting acrylic acid with an epoxy group-containing acrylic polymer, and a polyfunctional acrylic acid are known. An active energy ray-curable resin composition obtained by ester (see, for example, Patent Document 1).

However, in the active energy ray-curable resin composition using the acrylic polymer having a double bond and the polyfunctional acrylate provided in the aforementioned Patent Document 1, the reaction rate of the double bond contained in the composition is not Sufficient, although it has certain processability, the hardness of the coating film is still insufficient.

In addition, the inorganic fine particle-dispersion-type active energy ray-curable resin composition obtained by dispersing inorganic fine particles in a resin component as compared with a resin composition containing only an organic material is a high hardness capable of imparting a cured coating film. A novel material that imparts high performance or a new function to adjust the refractive index and impart conductivity (see, for example, Patent Document 2). The coating film obtained by dispersing the resin composition in which the inorganic fine particles are dispersed has a high hardness and can be used as a hard coat layer exhibiting scratch resistance, but on the other hand, it has processing. This is a side of poor performance, and it is difficult to apply to flexible display applications.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2011-207947

Patent Document 2 International Publication WO2013/047590

An object of the present invention is to provide an active energy ray-curable resin composition which exhibits excellent surface properties and transparency while having a very high surface hardness and transparency in a cured coating film, and contains the resin composition. Coating; a coating film composed of the coating; and a laminated film having the coating layer.

The inventors of the present invention have devoted themselves to research to solve the above problems, and have found that an acrylic polymer having a weight average molecular weight (Mw) in the range of 3,000 to 60,000 and having a hydroxyl group and a (meth) propylene in the polymer structure. The active energy ray-curable resin composition of the thiol-based acrylic polymer (A)" and the "isocyanate compound (B)" exhibits a very high surface hardness after hardening, and is also coated on a plastic substrate. The processability (flexibility) at the time of hardening is completed, and the present invention has been completed.

That is, the present invention provides an acrylic polymer (A) having an acrylic polymer having a weight average molecular weight (Mw) in the range of 3,000 to 60,000 and having a hydroxyl group and a (meth)acrylonitrile group in the polymer structure. An active energy ray-curable resin composition characterized by the "isocyanate compound (B)", a coating film containing the coating material, and a laminated film having the coating film layer.

According to the present invention, it is possible to provide a hardened coating film which has a very high surface hardness and transparency while also having It is a processability for use as a flexible display; an active energy ray-curable resin composition capable of providing the cured coating film; and a coating containing the same.

[Formation of the Invention]

The active energy ray-curable resin composition of the present invention is characterized by containing an acrylic polymer having a weight average molecular weight (Mw) in the range of 3,000 to 60,000 and having a hydroxyl group and a (meth) acrylonitrile group in the polymer structure. Acrylic polymer (A)" and "isocyanate compound (B)".

The acrylic polymer (A) has a weight average molecular weight (Mw) of 3,000 to 60,000, and a crosslinking density with a reaction of an isocyanate compound (B) to be described later is appropriate, and the cured film can be imparted high. Hardness and processability. The weight average molecular weight (Mw) is preferably in the range of 8,000 to 50,000, and the weight average molecular weight (Mw) is preferably from the viewpoint of improving the effect of the above-mentioned effects and the viscosity of the active energy ray-curable resin composition. The range of 20,000 to 40,000 is better.

Further, in the present invention, the weight average molecular weight (Mw) is a value obtained by measuring using a gel permeation chromatography (GPC) under the following conditions.

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

Pipe column: guard column HXL-H manufactured by TOSOH Co., Ltd.

+TOSOH Co., Ltd. TSKgel G5000HXL

+TOSOH Co., Ltd. TSKgel G4000HXL

+TSKgel G3000HXL made by TOSOH Co., Ltd.

+TOSOH Co., Ltd. TSKgel G2000HXL

Detector: RI (differential refractometer)

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

Standard: Polystyrene

Sample: Filtered by using a microfilter to filter a 0.4% by weight of a resin solid content in tetrahydrofuran (100 μl)

Moreover, the (meth)acryl oxime equivalent of the acrylic polymer (A) is preferably from 150 g/eq to 800 g/eq in view of the fact that it is easy to obtain a cured coating film having high surface hardness and excellent workability. The range is preferably in the range of 200 g/eq to 550 g/eq, and more preferably in the range of 220 g/eq to 320 g/eq.

The acrylic polymer (A) can be polymerized, for example, by using a compound (a-1) having a functional group such as a hydroxyl group, a glycidyl group or a carboxyl group and a (meth)acrylonyl group as an essential component. The obtained acrylic polymer (a) is reacted with a compound having a reactivity with such a functional group and a (meth)acryl fluorenyl compound (a-2), and introduced into a side chain of the acrylic polymer ( Methyl) acrylonitrile, and by the reaction A method of producing a hydroxyl group, or a compound having a hydroxyl group and a (meth)acryloyl group as an essential component of the acrylic polymer (a), such that the hydroxyl group is reacted with the compound (a-2) The acrylic polymer (A) is designed to remain as a functional group.

More specifically, a homopolymer of a compound having a hydroxyl group and a (meth)acryl fluorenyl group, or a compound obtained by using a hydroxyl group as a functional group in the compound (a-1) can be exemplified. a copolymer with (meth) acrylate (hereinafter referred to simply as "precursor (1)"), which is used with a compound having an isocyanate group and a (meth) propylene group, and an isocyanate group relative to a hydroxy group. The polymer (A-1) obtained by the reaction in a reduced manner.

Here, examples of the compound having a hydroxyl group and a (meth)acrylinyl group as a raw material of the precursor (1) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxy acrylate. Butyl ester, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxy propyl methacrylate Ester and the like. Among these, it is easy to adjust the (meth)acryl oxime equivalent in the obtained polymer (A) to the above preferred range and to obtain a polymer having a high hydroxyl value. It is preferred to use 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate.

In the case of producing the precursor (1), the (meth) acrylate which can be polymerized together with the compound having a hydroxyl group and a (meth) acryl fluorenyl group may, for example, be methyl (meth) acrylate or (meth). Ethyl acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (methyl) ) octyl acrylate, decyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (a) (meth) acrylate having a carbon number of 1 to 22, such as stearyl acrylate, octadecyl (meth) acrylate, or behenyl (meth) acrylate; (meth) acrylate ring ester, (meth) acrylate, isobornyl methacrylate, tricyclo [5.2.1.0 ^2,6] dec-8-yl ester (dicyclopentanyl (meth) acrylate), ( meth) acrylate, dicyclopentenyloxyethyl acetate (meth)acrylate having an alicyclic alkyl group such as dicyclopentenyloxyethyl (meth)acrylate; benzhydrylethyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid benzene Ethyl ester, phenoxyethyl (meth)acrylate, phenoxydiethylene (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. Acrylate; hydroxyethyl (meth)acrylate; hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycerol (meth)acrylate; modified by lactone (methyl) An acrylate having a hydroxyalkyl group such as a (meth) acrylate having a polyalkylene glycol group such as a hydroxyethyl acrylate, a (meth)acrylic acid polyethylene glycol or a (meth)acrylic acid polypropylene glycol; Separately, two or more types may be used in combination.

Among these, the (meth) acrylonitrile equivalent of the obtained polymer (A-1) is easily adjusted to the above preferred range, and while the obtained cured coating film has high hardness, From the viewpoint of easily obtaining a more processable coating film, a (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and a (meth) acrylate having an alicyclic alkyl group are preferable. In particular, it is particularly preferred to use methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and tertiary butyl (meth)acrylate.

Here, in order to adjust the (meth)acryl oxime equivalent of the obtained polymer (A-1) to an appropriate range, the mass ratio of both at the time of copolymerization [having a hydroxyl group and (methyl group) A compound in which a propylene fluorenyl compound: (meth) acrylate] is copolymerized at a ratio of from 10/90 to 90/10 is preferably used as a precursor, and is preferably 15/85 to 80. The range of /20 is better, and the range of 20/80 to 50/50 is even better, and it is preferably used in the range of 25/75 to 45/55.

The precursor (1) can be used, for example, by separately polymerizing the compound having a hydroxyl group and a (meth)acryl fluorenyl group in the temperature range of 60 ° C to 150 ° C in the presence of a polymerization initiator, or a combination thereof. The compound is produced by addition polymerization with a (meth) acrylate, and in the case of a copolymer, it may be any of a random copolymer, a block copolymer, and a graft copolymer. The polymerization method can utilize a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like. Among these, it is possible to continuously carry out the production of the precursor (1) and the subsequent reaction of the precursor (1) with a compound having an isocyanate group and a (meth)acryl fluorenyl group. A solution polymerization method is preferred.

From the viewpoint of excellent solubility of the obtained acrylic polymer (A-1), the solvent used in the production of the precursor (1) by a solution polymerization method is preferably methyl ethyl ketone or methyl group. A ketone solvent such as isobutyl ketone.

Here, the catalyst system used in the production of the precursor (1) may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis-(2,4-dimethylpentyl) Azo compound such as nitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzammonium peroxide, laurel peroxide, peroxygen methyl Tertiary butyl acetate, tert-butyl peroxyethylhexanoate, 1,1'-bis(tri-butylperoxy)cyclohexane, peroxy-penta-ethylhexanoate, and An organic peroxide such as oxy-2-ethylhexanoic acid hexahexyl ester or hydrogen peroxide.

In the case where a peroxide is used as a catalyst, a peroxide may be used together with a reducing agent to form a redox type initiator.

The precursor (1) thus obtained can be reacted with a compound having an isocyanate group and a (meth) acrylonitrile group to cause an isocyanate group to be smaller than the molar amount with respect to the hydroxyl group, thereby obtaining a desired acrylic acid polymerization. (A-1). The reaction can be carried out, for example, by polymerizing a precursor (1) by a solution polymerization method, and adding a compound having an isocyanate group and a (meth)acryl fluorenyl group to the reaction system at a temperature of 50 to 120 ° C, suitably It is carried out by a method such as a catalyst such as tin (II) octoate.

The compound having an isocyanate group and a (meth) acryl fluorenyl group used herein may, for example, be a compound represented by the following formula, and examples thereof include a monomer having one isocyanate group and one (meth) acryl fluorenyl group. a monomer having one isocyanate group and two (meth)acryl fluorenyl groups, a monomer having one isocyanate group and three (meth)acryl fluorenyl groups, having one isocyanate group and four (methyl group) a monomer of an acrylonitrile group, a monomer having one isocyanate group and five (meth)acrylonyl groups, and the like.

In the formula, R ¹ is a hydrogen atom or a methyl group, R ³ is an alkylene group having 2 to 4 carbon atoms, and m is an integer of 1 to 5.

Specific examples of the product of the compound having an isocyanate group and a (meth) acrylonitrile group include 2-acryloyloxyethyl isocyanate (trade name: "KARENZ AOI" manufactured by Showa Denko Co., Ltd." Etc., 2-methylpropenyl oxirane ethyl isocyanate (trade name: "KARENZ MOI" manufactured by Showa Denko Co., Ltd.), 1,1-bis(acryloxymethyl)ethyl isocyanate (trade name: "KARENZ BEI" manufactured by Showa Denko Co., Ltd.).

Other examples include a compound obtained by adding a hydroxyl group-containing (meth) acrylate compound to one isocyanate group of a diisocyanate compound. The diisocyanate compound used in the reaction may, for example, be butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-three. Aliphatic diisocyanate such as methylhexamethylene diisocyanate, benzodimethyl diisocyanate or m-tetramethylbenzene diisocyanate; cyclohexane-1,4-diisocyanate, isophorone diisocyanate, amine Alicyclic diisocyanate such as diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate; diisocyanate 1 , 5-naphthyl ester, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-diphenylmethyl diisocyanate, dioxane Diphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, methyl phenyl diisocyanate An aromatic diisocyanate or the like. These may be used singly or in combination of two or more. Among these, from the viewpoint that the obtained acrylic polymer (A-1) becomes a more functional compound and is easy to obtain a coating film having a higher hardness, it is preferably one molecule. In the case of having two or more (meth) acrylonitrile groups, specifically, 1,1-bis(acryloxymethyl)ethyl isocyanate is preferred. Any of the foregoing can also be used for the addition of the hydroxyl group-containing (meth) acrylate compound.

The (meth) acrylonitrile group equivalent of the obtained polymer (A-1) is preferably in the range of 150 to 800 g/eq as described above, but it can be obtained by the precursor (1) and the foregoing. The reaction ratio of the isocyanate group to the (meth) fluorenyl group-based compound is adjusted. In general, it is easy to carry out the reaction of the obtained polymer (A-1) by reacting the isocyanate group with respect to the hydroxyl group of the 1 mol precursor (1) in a range of 0.7 to 0.9 mol. The methyl) acrylonitrile group equivalent is adjusted to the above preferred range, and the hydroxyl group is also allowed to remain.

Next, in the case of using a compound having a propylene group as a functional group, as the polymer (A), a homopolymer of a compound having a glycidyl group and a (meth) acryl fluorenyl group can be exemplified. Or a copolymer of the compound and (meth) acrylate (hereinafter referred to simply as "precursor (2)"), which is obtained by reacting a compound having a carboxyl group with a (meth) acryl fluorenyl group. Acrylic polymer (A-2).

Here, examples of the compound having a glycidyl group and a (meth)acryloyl group as a raw material of the precursor (2) include, for example, (meth)acrylic acid propyl acrylate and α-ethyl (methyl). Glycidyl acrylate, g-propyl α-n-propyl (meth) acrylate, g-propyl α-n-butyl (meth) acrylate, 3,4-butyl butyl (meth) acrylate , (meth)acrylic acid-4,5-epoxypentyl ester, (meth)acrylic acid-6,7-epoxypentyl ester, α-ethyl (meth)acrylic acid-6,7-epoxypentyl ester, Β-methylepoxypropyl (meth) acrylate, (meth)acrylic acid-3,4-epoxycyclohexyl ester, lactone-modified (meth)acrylic acid -3,4-epoxycyclohexyl ester, vinyl cyclohexene oxide, and the like. Among these, it is easy to adjust the (meth)acryl oxime equivalent of the obtained polymer (A) to the above preferred range, using (meth)acrylic epoxy. A propyl ester, a glycidyl α-ethyl (meth)acrylate, and a glycidyl α-n-propyl (meth)acrylate are preferred, and a glycidyl (meth)acrylate is more preferred.

When the precursor (2) is produced, any of the above may be used as the (meth) acrylate which can be polymerized with the compound having a glycidyl group and a (meth) acryl fluorenyl group, but it is easy to use The (meth)acrylonitrile group equivalent of the obtained acrylic polymer (A-2) is adjusted to the above preferred range, and the obtained hardened coating film is high in hardness, and is easy to obtain and has processability. From the viewpoint, it is preferably a (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and a (meth) acrylate having an alicyclic alkyl group, more preferably an alkyl group having 1 to 22 carbon atoms. Base (meth) acrylate. In particular, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tertiary butyl (meth)acrylate, (methyl) ) Cyclohexyl acrylate and isodecyl (meth) acrylate are particularly preferred.

Here, the (meth)acryl oxime equivalent of the obtained acrylic polymer (A-2) is easily adjusted to an appropriate range, and a cured coating film having high surface hardness and excellent curl resistance at the time of curing is obtained. From the point of view, the mass ratio of the two at the time of copolymerization [compound having a glycidyl group and a (meth) acrylonitrile group]: [(meth) acrylate] becomes 15/85 to 95/ It is preferable to use at a ratio of the range of 5, and it is more preferable to use it at a ratio of 30/90 to 90/10. Again, get from The active energy ray-curable resin composition having excellent stability over time is preferably in the range of 60/40 to 90/10, particularly preferably in the range of 80/20 to 90/10.

Although the precursor (2) has an epoxy group derived from the above compound having a glycidyl group and a (meth)acryl fluorenyl group, the acrylonitrile of the finally obtained acrylic polymer (A-2) is easily obtained. The epoxy equivalent of the precursor (2) is preferably in the range of 145 to 900 g/eq, more preferably in the range of 150 to 500 g/eq, from the viewpoint that the basis weight is adjusted to a range of from 150 to 800 g/eq. More preferably, it is in the range of 150 to 250 g/eq, and particularly preferably in the range of 150 to 180 g/eq.

The precursor (2) can be, for example, polymerized by the above-mentioned compound having a glycidyl group and a (meth)acryl fluorenyl group in the temperature range of 60 ° C to 150 ° C in the presence of a polymerization initiator. Alternatively, it can be produced by polymerization in combination with the above (meth) acrylate, but the precursor (2) can be continuously produced, and the precursor (2) and the carboxyl group and (meth) propylene can be continuously formed. From the viewpoint of the reaction of the mercapto compound, it is preferred to carry out the production by solution polymerization.

When the solvent used for the production of the precursor (2) by the solution polymerization method is considered to have a boiling point of 80 ° C or higher, the solvent is preferably used, and examples thereof include methyl ethyl ketone and methyl n-propyl ketone. , methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl n-hexyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-propyl Ketone solvents such as ketone, diisobutyl ketone, cyclohexanone, and phorbol; n-butyl ether, diisoamyl ether, and Ether solvent such as alkane; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethyl Glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl Glycol ether solvent such as propyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether; n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether An ester solvent such as an acid ester or ethyl-3-ethoxylate propionate; isopropanol, n-butanol, isobutanol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy- Alcohol solvent such as 1-butanol or 3-methyl-3-methoxybutanol; Hydrocarbon solvents such as benzene, xylene, SOLVESSO 100, SOLVESSO 150, SWASOL 1800, SWASOL 310, ISOPAR E, ISOPAR G, Exxon naphtha 5, Exxon naphtha 6. These may be used singly or in combination of two or more.

Among the above solvents, methyl ethyl ketone or methyl isoform is preferred from the viewpoint that the solubility of the obtained precursor (2) is excellent and the reactivity with the isocyanate compound (B) is not obtained. A ketone solvent such as butyl ketone or an ester solvent such as n-propyl acetate, isopropyl acetate or n-butyl acetate.

The catalyst system used in the production of the aforementioned precursor (2) may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis-(2,4-dimethylvaleronitrile). , 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzammonium peroxide, lauryl peroxide, peroxytrimethyl B Tert-butyl butylate, butyl peroxyethylhexanoate, 1,1'-bis(tri-butylperoxy)cyclohexane, tert-amyl peroxy-2-ethylhexanoate, An organic peroxide such as oxy-2-ethylhexanoic acid hexahexyl ester or hydrogen peroxide.

In the case where a peroxide is used as a catalyst, a peroxide may be used together with a reducing agent to form a redox type initiator.

The precursor (2) thus obtained can be subsequently reacted with a compound having a carboxyl group and a (meth)acryl fluorenyl group to obtain a target acrylic polymer (A-2). The reaction method may, for example, polymerize the precursor (2) by a solution polymerization method, and add a compound having a carboxyl group and a (meth)acryl fluorenyl group to the reaction system at a temperature range of 60 to 150 ° C, suitably A method such as a catalyst such as triphenylphosphine is used. The (meth)acryl oxime equivalent of the acrylic polymer (A-2) is preferably in the range of from 150 to 800 g/eq, except that it can have a carboxyl group and a (meth) propylene oxime by the aforementioned precursor (2) and the foregoing. The reaction ratio of the compound of the group is adjusted. In general, the obtained acrylic polymer (A-2) is easily reacted by reacting the carboxyl group with respect to the epoxy group of the 1 mol precursor (2) in a range of 0.8 to 1.2 mol. The (meth)acrylonitrile group equivalent is adjusted to the above preferred range.

Examples of the compound having a carboxyl group and a (meth)acrylinyl group used herein include (meth)acrylic acid, (acryloxy)acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, and amber. 1-[2-(Propyloxy)ethyl ester of acid], 1-(2-propenyloxyethyl) phthalate, 2-(acryloxy)ethyl hexahydrophthalate, and the like An unsaturated monocarboxylic acid such as an ester modified product; an unsaturated dicarboxylic acid such as maleic acid; an acid anhydride such as succinic anhydride or maleic anhydride; and a hydroxyl group such as neopentyl alcohol triacrylate. A carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting a polyfunctional (meth) acrylate monomer. These may be used singly or in combination of two or more. Among these, it is preferable to adjust the (meth)acryl oxime equivalent of the obtained acrylic polymer (A-2) to the above preferred range, and it is preferably (meth)acrylic acid. (Propylene methoxy) acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, particularly preferably (meth)acrylic acid.

The acrylic polymer (A-2) thus obtained has a hydroxyl group which is produced by a reaction between an epoxy group and a carboxyl group in its molecular structure.

In the case of using a polymer having a carboxyl group as a functional group, the polymer (A) may be a homopolymer of a compound having a carboxyl group and a (meth)acryl fluorenyl group, or the compound. Acrylic acid obtained by reacting a copolymer with (meth) acrylate (hereinafter referred to simply as "precursor (3)") with a compound having a glycidyl group and a (meth) acryl fluorenyl group Polymer (A-3).

Here, examples of the compound having a carboxyl group and a (meth)acryloyl group as a raw material of the precursor (3) include (meth)acrylic acid, (acryloxy)acetic acid, and 2-carboxyethyl acrylate. 3-Carboxypropyl acrylate, 1-[2-(propylene methoxy)ethyl succinate], 1-(2-propenyl oxyethyl) phthalate, 2-(propylene oxy) hexahydrophthalate An unsaturated monocarboxylic acid such as an ethyl ester or a lactone modified product; an unsaturated dicarboxylic acid such as maleic acid; an acid anhydride such as succinic anhydride or maleic anhydride; and neopentyl alcohol triacrylate. The carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting a hydroxyl group-containing polyfunctional (meth) acrylate monomer.

Here, from the viewpoint of easily adjusting the (meth)acrylonitrile group equivalent of the obtained acrylic polymer (A-3) to the above preferred range, (meth)acrylic acid (acrylonitrile) is preferred. Oxy)acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, of which (meth)acrylic acid is particularly preferred.

When the precursor (3) is produced, any of the above may be used as the (meth) acrylate which can be polymerized with the compound having a carboxyl group and a (meth) acryl fluorenyl group, but it is easy to obtain the obtained one. The (meth)acrylonitrile group equivalent of the acrylic polymer (A-3)) is adjusted to the above preferred range, and the obtained hardened coating film is high in hardness, and it is easy to obtain a point which is also rich in workability. Preferably, it is preferably a (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and a (meth) acrylate having an alicyclic alkyl group, more preferably an alkyl group having 1 to 22 carbon atoms. (Meth) acrylate. In particular, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate and tertiary butyl (meth)acrylate, (methyl) Cyclohexyl acrylate and isodecyl (meth) acrylate are particularly preferred.

Here, the (meth) acrylonitrile base equivalent of the obtained acrylic polymer (A-3) is easily adjusted to an appropriate range, and a hard coating having high surface hardness and excellent curl resistance at the time of curing is easily obtained. From the viewpoint of the film, the mass ratio of the two at the time of copolymerization [compound having a carboxyl group and a (meth)acryloyl group]: [(meth) acrylate] is in the range of 15/85 to 95/5. It is preferably used at a ratio, and it is preferably used at a ratio of 30/90 to 90/10. Furthermore, from the point of obtaining an active energy ray-curable resin composition excellent in stability over time Look, it is preferably in the range of 60/40 to 90/10, and particularly preferably in the range of 80/20 to 90/10.

The precursor (3) can be used, for example, by separately polymerizing the compound having a carboxyl group and a (meth)acryl fluorenyl group in the temperature range of 60 ° C to 150 ° C in the presence of a polymerization initiator, or a combination thereof. The above compound is produced by polymerizing the above (meth) acrylate, but it is possible to continuously carry out the production of the precursor (3), and to continue the precursor (3) and have a propylene group and a (meth) propylene. From the viewpoint of the reaction of the mercapto compound, it is preferred to carry out the production by solution polymerization.

When the solvent used for the production of the precursor (3) by the solution polymerization method is a reaction temperature, the boiling point is 80 ° C or higher, and examples thereof include methyl ethyl ketone and methyl n-propyl ketone. Isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-propyl ketone a ketone solvent such as diisobutyl ketone, cyclohexanone or phorbolone; n-butyl ether, diisoamyl ether, and Ether solvent such as alkane; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethyl Glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl Glycol ether solvent such as propyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Ester solvent such as acid ester or ethyl-3-ethoxypropionate; isopropanol, n-butanol, isobutanol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy An alcohol solvent such as 1-butanol or 3-methyl-3-methoxybutanol; Benzene, xylene, SOLVESSO 100, SOLVESSO 150, SWASOL 1800, SWASOL 310, ISOPAR E, ISOPAR G, Exxon naphtha No. 5, Exxon naphtha No. 6 hydrocarbons vehicle. These may be used singly or in combination of two or more.

Among the above solvents, methyl ethyl ketone or methyl isoform is preferred from the viewpoint that the solubility of the obtained precursor (3) is excellent and the reactivity with the isocyanate compound (B) is not obtained. A ketone solvent such as butyl ketone or an ester solvent such as n-propyl acetate, isopropyl acetate or n-butyl acetate.

The catalyst system used in the production of the aforementioned precursor (3) may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis-(2,4-dimethylvaleronitrile). , 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzammonium peroxide, lauryl peroxide, peroxytrimethyl Tertiary butyl acetate, tert-butyl peroxyethylhexanoate, 1,1'-bis(tri-butylperoxy)cyclohexane, peroxy-penta-ethylhexanoate, and An organic peroxide such as oxy-2-ethylhexanoic acid hexahexyl ester or hydrogen peroxide.

In the case where a peroxide is used as a catalyst, a peroxide may be used together with a reducing agent to form a redox type initiator.

The precursor (3) thus obtained can be subsequently reacted with a compound having a glycidyl group and a (meth)acryl fluorenyl group to obtain a target acrylic polymer (A-3). The reaction method is an example For example, the precursor (3) is polymerized by solution polymerization, and a compound having a glycidyl group and a (meth)acryl fluorenyl group is added to the reaction system, and a temperature of 60 to 150 ° C is used, and three are appropriately used. A method such as a catalyst such as phenylphosphine.

The (meth)acryl oxime equivalent of the obtained acrylic polymer (A-3) is preferably in the range of 150 to 800 g/eq, except that it can be obtained by the aforementioned precursor (3) and having a propylene group. The reaction ratio with the (meth) acrylonitrile-based compound is adjusted. In general, the obtained acrylic polymer (A-3) is easily reacted by reacting a carboxyl group having a carboxyl group of from 0.9 to 1.25 mol with respect to 1 mol of the precursor (3). The (meth) acrylonitrile group equivalent is adjusted to the above preferred range.

Further, the obtained acrylic polymer (A-3) has a hydroxyl group produced by a reaction of a carboxyl group and a glycidyl group in its molecular structure.

In the case of using the inorganic fine particles (D) to be described later, the acrylic microparticles (A) described above are excellent in compatibility with the inorganic fine particles, and the storage stability of the obtained composition is excellent. In view of the above, the acrylic polymers (A-2) and (A-3) are preferred. In view of the fact that the reactivity with the isocyanate compound (B) to be described later is good and the dispersibility of the inorganic fine particles (D) in the composition is more excellent, the polymer (A-2) and The hydroxyl value of A-3) is preferably in the range of 75 to 380 mgKOH/g, more preferably in the range of 110 to 360 mgKOH/g, still more preferably in the range of 230 to 360 mgKOH/g, and particularly preferably in the range of 300 to 360 mgKOH/g. range.

Further, from the viewpoint of synthesis capable of being produced by a simpler method, the acrylic polymer (A-2) is preferred, and particularly preferably, glycidyl (meth)acrylate is used. With (meth) acrylate The acrylic polymer obtained by polymerization to obtain the precursor (2) and reacting with the precursor (2) using (meth)acrylic acid.

Next, the isocyanate compound (B) used in the present invention will be described.

It is assumed that the active energy ray-curable resin composition of the present invention increases the crosslinking point by reacting the hydroxyl group in the acrylic polymer (A) with the isocyanate group in the isocyanate compound (B). The surface hardness of the obtained coating film is made to contain a urethane bond, and the workability of the coating film can be improved. Therefore, the isocyanate compound (B) is not particularly limited as long as it is a compound having an isocyanate group, but from the viewpoint of further increasing the crosslinking density, it is preferred to have an isocyanate selected from one molecule. a compound having two or more functional groups in the acryl group.

The isocyanate compound (B) may, for example, be hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate or 2,4,4-trimethylhexamethylene diisocyanate. Diisocyanate methyl diamine, triisocyanate, isophthalic diisocyanate, α,α,α',α'-tetramethylbenzene diisocyanate, bis(isocyanato) Methyl)naphthalene, 1,3,5-trimethylbenzene triisocyanate, sulfurized bis(isocyanatomethyl), bis(isocyanatoethyl) sulfide, bis(isocyanatomethyl) disulfide, Bis(isocyanatoethyl) disulfide, bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane, bis(isocyanatoethylthio)ethane, double (Isocyanatomethylthio)ethane, 2-propene oxirane ethyl isocyanate (trade name: "KARENZ AOI" manufactured by Showa Denko Co., Ltd.), 2-methylpropene oxynitride isocyanate Ester (trade name: "KARENZ MOI" manufactured by Showa Denko Co., Ltd.), 1,1-bis(acryloxymethyl)ethyl isocyanate (trade name: "KARENZ BEI" manufactured by Showa Denko Co., Ltd." Aliphatic polyisocyanate compound Isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2 ,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8 - bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane An alicyclic polyisocyanate compound such as 4,9-bis(isocyanatomethyl)tricyclodecane; an aromatic polyisocyanate compound such as diphenyl-4,4-diisocyanate; 2,5-diiso Cyanylthiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl)tetrahydrothiophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiazide 2,5-bis(isocyanatomethyl)-1,4-dithiazide 4,5-diisocyanato-1,3-dithiazide , 4,5-bis(isocyanatomethyl)-1,3-dithiazide a heterocyclic polyisocyanate compound, and a biuret, a nurate, a urea form, a polyol adduct, a blocked isocyanate, etc. of the derivatives of such isocyanate compounds, etc. Separately, two or more types may be used in combination.

Among these, from the viewpoint of excellent workability of the obtained coating film and not impairing transparency and yellowing, a biuret body using hexamethylene isocyanate or hexamethylene isocyanate is used. A cyanurate body of methylene isocyanate is preferred.

Further, in the present invention, the surface hardness of the obtained coating film is easily obtained from the viewpoint of easily preparing the viscosity of the coating material and having good curability. From the viewpoint of increasing the height, the (meth) acrylate (C) other than the acrylic polymer (A) may be used in combination.

The (meth) acrylate which can be used in the present invention is not particularly limited, and examples thereof include various (meth) acrylate monomers or urethane (meth) acrylates.

Examples of the (meth) acrylate single system include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (methyl). ) n-butyl acrylate, isobutyl (meth)acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, propylene fluorenyl Porphyrin, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, ( 2-Ethyl ethyl methacrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide (ethylene oxide) modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, oxiranyl (meth) acrylate modified by ethylene oxide, modified by propylene oxide Phenyloxy (meth)acrylate, nonylphenol (meth) acrylate, oxime phenol (meth) acrylate modified with ethylene oxide, decyl phenol modified with propylene oxide ( Methyl) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, phthalic acid 2- ( Methyl) propylene oxy ethoxylate 2-hydroxypropyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(methyl)propenyloxyethyl phthalate, 2-(methyl) phthalate Propylene methoxypropyl ester, 2-(meth) propylene methoxy propyl hexahydrophthalate, 2-(methyl) propylene methoxy propyl tetrahydro phthalate, dimethyl (meth) acrylate Aminoethyl ester, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, (methyl) Mono(meth)acrylate such as octafluoropropyl acrylate or adamantyl mono(meth)acrylate; butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ethoxylation Hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(a) Di(meth)acrylate such as acrylate; trimethylolpropane tri(meth)acrylate Ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, gin-2-hydroxyethyl isocyanurate tri(meth)acrylic acid Tris(meth)acrylate such as ester, tris(meth)acrylate, neopentyl alcohol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, di-trimethylolpropane Tris(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dioxane Tetraol penta (meth) acrylate, di-trimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane hexa (meth) acrylate A (meth) acrylate having a tetrafunctional or higher functional group; and a (meth) acrylate obtained by substituting a part of the above various polyfunctional (meth) acrylates with an alkyl group.

The urethane (meth) acrylate is exemplified by, for example, a urethane (meth) acrylate obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound.

The polyisocyanate compound used in the raw material of the urethane (meth) acrylate may be exemplified by various diisocyanate monomers or cyanurates having an isomeric cyanate ring structure in the molecule. Type polyisocyanate compound or the like.

Examples of the diisocyanate monosystem include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethyl. Aliphatic diisocyanates such as hexamethylene diisocyanate, benzodimethyl diisocyanate, m-tetramethyl dimethyl diisocyanate; cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine II Alicyclic diisocyanate such as isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate; diisocyanate 1,5 -Naphthyl ester, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-diphenyl methyl diisocyanate, dialkyl Aromatic compounds such as phenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and phenylphenyl diisocyanate Group diisocyanate and the like.

The polycyanate type polyisocyanate compound having a hetero-cyanate ring structure in the molecule may, for example, be obtained by reacting a diisocyanate monomer with a monool and/or a diol. The diisocyanate monomers to be used in the reaction include the above-mentioned various diisocyanate monomers, and they may be used alone or in combination of two or more. Further, the monool used in the reaction may, for example, be hexanol, octanol, n-decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-pentadecanol or n. Alcohol, n-octadecanol, n-nonadecanol, etc., and the diol type may, for example, be ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, or 1,3-butanediol. , 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and the like. These monools or diols may be used alone or in combination of two or more.

Among these polyisocyanate compounds, the diisocyanate monomer is more preferred as the hardened coating film having more excellent workability, and the aliphatic diisocyanate and the alicyclic diisocyanate are more preferred.

The hydroxyl group-containing (meth) acrylate compound used in the raw material of the urethane (meth) acrylate may, for example, be 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or acrylic acid 4- Aliphatic (meth) acrylate compounds such as hydroxybutyl ester, glycerin diacrylate, trimethylolpropane diacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate; 4-hydroxyphenyl acrylate , β-hydroxyphenylethyl acrylate, 4-hydroxyphenylethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-ethenyl phenyl acrylate, 2-hydroxy-3-benzene acrylate The oxypropyl ester is equivalent to a (meth) acrylate compound having an aromatic ring in its molecular structure. These may be used singly or in combination of two or more.

Among these hydroxy (meth) acrylate compounds, glycerin diacrylate, trimethylolpropane diacrylate, and new are preferable in terms of obtaining a cured coating film having excellent workability and high surface hardness. Pentaerythritol triacrylate and dipentaerythritol pentaacrylate are equal to an aliphatic (meth) acrylate compound having two or more (meth) acrylonitrile groups in a molecular structure. Further, in terms of obtaining a cured coating film exhibiting a higher surface hardness, it is more preferable that neopentyl alcohol triacrylate and dipentaerythritol pentaacrylate have three or more (methyl groups) in a molecular structure. An aliphatic (meth) acrylate compound of an acrylonitrile group.

The method of producing the aforementioned urethane (meth) acrylate is, for example, a molar ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound. [(NCO)/(OH)] is a ratio of the range of 1/0.95 to 1/1.05, and the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound are used in a temperature range of 20 to 120 ° C. A method of using various urethane-based catalysts as needed.

When the above-mentioned urethane (meth) acrylate is produced from the above polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group in the above molecular structure, the reaction may also be carried out in the presence of pentaerythritol IV (A) The system is carried out in a system of an acrylate compound such as acrylate or dipentaerythritol hexa(meth)acrylate. Specific examples of the urethane (meth) acrylate obtained by such a method include the above-mentioned polyisocyanate compound, pentaerythritol tri(meth)acrylate, and pentaerythritol IV ( a urethane (meth) acrylate obtained by reacting a raw material of a methyl acrylate; or containing the aforementioned polyisocyanate compound, A urethane acrylate obtained by reacting dipentaerythritol penta (meth) acrylate with a raw material of dipentaerythritol hexa (meth) acrylate.

The weight average molecular weight (Mw) of the obtained urethane (meth) acrylate is preferably in the range of 800 to 20,000, insofar as it is excellent in compatibility with the polymer (A). Good range from 900 to 1,000.

These compounds (C) may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining a coating film having a higher hardness, a polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups in one molecule is preferred. In the above polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups, pentaerythritol tri(meth) acrylate, neopentyl alcohol tetra (methyl) is preferred. Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Further, as the urethane (meth) acrylate having a polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups, a diisocyanate compound and glycerin are preferred. Diacrylate, trimethylolpropane diacrylate, neopentyl alcohol triacrylate, and dipentaerythritol pentaacrylate are equivalent to hydroxyl groups having two or more (meth) acrylonitrile groups in the molecular structure (A) A urethane (meth) acrylate obtained by reacting an acrylate compound, more preferably a diisocyanate compound and a hydroxyl group-containing (meth)acrylic acid having 3 or more (meth) acrylonitrile groups The urethane compound (meth) acrylate obtained by the reaction of the ester compound.

Further, the (meth) acrylate (C) which can be used in the present invention may be a multi-branched (meth) acrylate. In the case of such multi-branched (meth) acrylates, dendrimers can be used. Any one of the names provided by the name of the dendrimer, the core-shell, the hyperbranch, etc., for example, any of the following may be used as appropriate: in WO08/047620, JP-A-2012-111963 Japanese Laid-Open Patent Publication No. Hei 10-508052, the entire disclosure of which is incorporated herein by reference. In addition, as a commercial product of such a multi-branched (meth) acrylate, SIRIUS 501 manufactured by Osaka Organic Co., Ltd., etc. are mentioned.

In the present invention, the ratio of use of the acrylic polymer (A), the isocyanate compound (B), and other (meth) acrylate (C) used in combination as needed is not particularly limited, and it can be considered The hardness and workability of the target cured film, and the transparency and the scratch resistance are appropriately set. However, from the viewpoint of easily obtaining a coating film having a particularly high surface hardness and good workability, the above acrylic polymer ( A) and the mass ratio (A)/(B) of the isocyanate compound (B) are preferably in the range of 98/2 to 50/50, particularly preferably in the range of 98/2 to 70/30, more preferably The range of 98/2~80/20. The mass ratio (A)/(C) of the acrylic polymer (A) to the (meth) acrylate (C) is preferably in the range of 10/90 to 90/10, especially in the case of an acrylic polymer ( A), the mass ratio (A) / (B) / (C) of the isocyanate compound (B) to the (meth) acrylate (C) is preferably 10/88/2 to 62/7/31. range.

In the present invention, inorganic fine particles (D) can be used in combination for the purpose of further improving the surface hardness of the coating film or imparting other properties such as anti-blocking properties.

The blending ratio of the inorganic fine particles (D) can be appropriately set depending on the performance of the target. However, from the viewpoint of obtaining a coating film having a high coating film hardness and obtaining a coating film having high transparency, the active energy ray is relative to the active energy ray. It is preferable that the non-volatile matter is 100 parts by mass in the curable resin composition, and the inorganic fine particles (D) are contained in the range of 30 to 55 parts by mass. In other words, when the content of the inorganic fine particles (D) is 30 parts by mass or more, the effect of improving the coating film hardness and the scratch resistance at the time of curing becomes remarkable. In addition, when the content of the inorganic fine particles (D) is 55 parts by mass or less, the storage stability or transparency of the active energy ray-curable resin composition is improved. In the case of obtaining a cured coating film having high surface hardness, transparency, and curl resistance, the resin composition is excellent in storage stability, and 100 parts by mass of the nonvolatile matter in the composition is It is more preferable to contain inorganic fine particles (D) in the range of 35 to 50 parts by mass.

The average particle diameter of the inorganic fine particles (D) is a value measured by a dynamic light scattering method in a state of being dispersed in a composition, and is excellent in that the balance between the surface hardness and the transparency of the coating film is excellent. It is preferably in the range of 95 to 250 nm. In other words, when the average particle diameter is 95 nm or more, the surface hardness of the obtained coating film becomes higher. On the other hand, when it is 250 nm or less, the transparency of the obtained coating film becomes good. Among them, the average particle diameter is preferably in the range of 100 to 130 nm from the viewpoint of the hardness and transparency of the obtained coating film at a higher level.

In addition, the average particle diameter measured by the dynamic light scattering method of the inorganic fine particles (D) in the present invention is measured according to "ISO 13321" and is calculated by the cumulant method. Specifically, it is After diluting the active energy ray-curable resin composition with MIBK and adjusting it to a 1.0% concentration of MIBK solution, the MIBK solution was used to determine the value measured by a particle size measuring device ("ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.).

Specific examples of the inorganic fine particles (D) used herein include inorganic fine particles such as cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, barium titanate, and antimony trioxide. These may be used singly or in combination of two or more. Among the inorganic fine particles (D), preferred are cerium oxide fine particles, and examples of the cerium oxide fine particles include wet cerium oxide and dry cerium oxide. . The wet cerium oxide system may, for example, be a so-called sedimentation cerium oxide or a gelled cerium oxide obtained by reacting sodium citrate with mineral acid. Further, in the case of using the wet cerium oxide, it is easy to adjust the average particle diameter of the inorganic fine particles dispersed in the finally obtained resin composition to the above-mentioned preferable value. The average particle diameter in the state is preferably in the range of 95 to 250 nm.

On the other hand, the dry cerium oxide fine particles are obtained, for example, by burning ruthenium tetrachloride in an oxygen or hydrogen flame, and are easily adjusted from the average particle diameter of the inorganic fine particles (D) in the finally obtained resin composition. From the point of the range of 95 to 250 nm, it is preferred that the dry cerium oxide microparticles having an average primary particle diameter of 3 to 100 nm, particularly 5 to 50 nm, are agglomerated in a state before dispersion. Secondary particles.

Among the above-mentioned cerium oxide fine particles, dry cerium oxide fine particles are preferred from the viewpoint of obtaining a cured coating film having a higher surface hardness.

In the present invention, the inorganic fine particles (D) can be used by introducing a reactive functional group onto the surface of the inorganic fine particles by using a decane coupling agent for each of the above inorganic fine particles. By introducing a reactive functional group on the surface of the inorganic fine particles (D) to make the acrylic polymer with the foregoing (A) The organic component such as other (meth) acrylate (C) is improved in miscibility, and the dispersion stability and storage stability are improved.

The decane coupling agent used herein may, for example, be vinyl trichloromethane, vinyl trimethoxy decane, vinyl triethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy. Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, p-styryltrimethyl Oxydecane, 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxy Decane, 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethyl Oxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3 -Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl‧butylene)propylamine, N -Phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethyl Hydrazine hydrochloride, special amino decane, 3-ureidopropyl triethoxy decane, 3-chloropropyltrimethoxy decane, 3-mercaptopropylmethyldimethoxy decane, 3-mercaptopropyl Trimethoxy decane, bis(triethoxydecylpropyl) tetrasulfide, 3-isocyanate propyl triethoxy decane, allyl trichloro decane, allyl triethoxy decane, allyl Trimethoxy decane, diethoxymethyl vinyl decane, trichlorovinyl decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxy a vinyl-based decane coupling agent such as ethoxy) decane; Diethoxy(glycidoxypropyl)methylnonane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3 - epoxy propylene oxide methyl diethoxy decane, 3-glycidoxy propyl triethoxy decane, etc., epoxy decane coupling agent; p-styryl trimethoxy decane, etc., benzene a vinyl decane coupling agent; 3-methacryloxypropylmethyldimethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, a (meth)acryloxyl-type decane coupling agent such as 3-methacryl oxime propyl methyl diethoxy decane, 3-methyl propylene oxypropyl triethoxy decane or the like; N-2 (Aminoethyl) 3-aminopropylmethyldimethoxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane, N-2 (aminoethyl) 3 -Aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3- An amine-based decane coupling agent such as dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane or the like; 3-ureidotriethoxydecane, etc., urea-based decane coupling agent; 3-chloropropyltrimethoxydecane, etc., chloropropyl-based decane coupling agent; 3-mercaptopropylmethyldimethoxy a decane-based decane coupling agent such as decane, 3-mercaptopropyltrimethoxy decane or the like; a sulfonium-based decane coupling agent such as bis(triethoxydecylpropyl) tetrasulfide; Isocyanate-based decane coupling agent such as 3-isocyanate propyl triethoxy decane. These decane coupling agents may be used alone or in combination of two or more. Among these, a (meth)acryloxy-based decane coupling agent is preferred because it has excellent miscibility with an organic component and can obtain a cured coating film having high surface hardness and excellent transparency. More preferably, it is 3-propenyl methoxypropyl trimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane.

The resin composition of the present invention may contain a dispersing aid as needed. Examples of the dispersing aid include phosphate ester compounds such as acid isopropyl phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. These may be used singly or in combination of two or more. Among these, in view of excellent dispersibility and subsidence performance, phosphoric acid dimethacrylate modified with ethylene oxide is preferred.

For example, "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd., "KAYAMER PM-2", and "Light Ester P-2M" manufactured by Kyoeisha Chemical Co., Ltd., etc., may be mentioned. .

In the case of using the above-mentioned dispersing aid, it is preferable that the resin composition of the present invention contains 0.5 to 5.0 parts by mass in 100 parts by mass of the resin composition of the present invention.

Further, the resin composition of the present invention may contain an organic solvent. In the case of producing the acrylic polymer (A) by a solution polymerization method, for example, the organic solvent may contain the solvent used at this time, and may further add another solvent in an additional manner. Or, once the organic solvent used in the production of the acrylic polymer (A) is removed, Use other solvents. Specific examples of the solvent to be used include a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a cyclic ether solvent such as tetrahydrofuran or dioxolane; methyl acetate and ethyl acetate; An ester such as butyl acetate; an aromatic solvent such as toluene or xylene; an alcohol solvent such as carbitol, celecoxime, methanol, isopropanol, butanol or propylene glycol monomethyl ether; ethylene glycol monoethyl ether, B A glycol ether solvent such as diol monobutyl ether, propylene glycol monomethyl ether or propylene glycol monopropyl ether. These may be used alone or in combination of two or more. Among these, a ketone solvent, more preferably methyl ethyl ketone or methyl isobutylene, is preferred as a resin composition which is excellent in stability and excellent in coating properties when used as a coating material. Ketone.

The resin composition of the present invention may further contain an ultraviolet absorber, an antioxidant, a polyoxonium additive, an organic bead, a fluorine-based additive, a rheology control agent, an antifoaming agent, a release agent, an antistatic agent, and an antifogging agent. Additives such as colorants, organic solvents, and inorganic fillers.

The above ultraviolet absorber may, for example, be 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis (2,4) -dimethylphenyl)-1,3,5-three ,2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-three Wait three Derivative, 2-(2'-dibenzopyranocarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl Benzenetriazole, 2-dibenzopyranocarboxy-4-dodecyloxydiphenyl ketone, 2-o-nitrobenzyloxy-4-dodecyloxydiphenyl ketone, and the like.

Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, and a phosphate ester. It is an antioxidant or the like. These may be used singly or in combination of two or more.

Examples of the polyfluorene-based additive include, for example, dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene, cyclic dimethyl polyoxyalkylene, methyl hydrogen polyoxyalkylene, and polyether. Modified dimethyl polyoxyalkylene copolymer, polyester modified dimethyl polyoxyalkylene copolymer, fluorine modified dimethyl polyoxyalkylene copolymer, modified by amine group a polyorganosiloxane having an alkyl group or a phenyl group such as a dimethyl polyoxyalkylene copolymer, a polydimethylsiloxane having an acrylic group modified by a polyether, and an acrylic modified with a polyester. Polydimethyl methoxy oxane and the like. These may be used singly or in combination of two or more.

Examples of the organic bead include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic acid styrene beads, polyoxyn beads, glass beads, acrylic beads, and benzoguanamine resin beads. And melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, polyethylene resin beads, and the like. The average particle diameter of these organic beads is preferably in the range of 1 to 10 μm. These may be used singly or in combination of two or more.

Examples of the fluorine-based additive include a DIC Corporation "MEGAFAC" series and the like. These may be used singly or in combination of two or more.

Examples of the release agent include "TEGO Rad 2200N" manufactured by EVONIK DEGUSSA, "TEGO Rad 2300", "TEGO Rad 2100", and BYK Chemie. "UV3500", "Peintadd 8526" and "SH-29PA" manufactured by Toray Dow Corning. These may be used singly or in combination of two or more.

Examples of the antistatic agent include pyridinium, imidazolium, sulfonium, ammonium, or a lithium salt of bis(trifluoromethanesulfonyl) quinone imine or bis(fluorosulfonyl) quinone imine. These may be used singly or in combination of two or more.

The amount of the above-mentioned various additives is preferably in the range of 0.01 to 40 parts by mass per 100 parts by mass of the resin composition of the present invention, in order to sufficiently exhibit the effect and not inhibit the ultraviolet curing. good.

The resin composition of the present invention is preferably further contained in a photopolymerization initiator. The photopolymerization initiator may, for example, be diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone or 4,4'-bisdimethylaminodiphenyl ketone. , 4,4'-bisdiethylaminodiphenyl ketone, 4,4'-dichlorodiphenyl ketone, mischrone, 3,3',4,4'-tetra (tributyl) Various diphenyl ketones such as 3,3',4,4'-tetra(t-butyl peroxycarbonyl)benzophenone; Ketone, 9-oxosulfur (thioxanthone), 2-methyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-diethyl 9-oxosulfur Wait Ketone, 9-oxosulfur a variety of acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; diphenylethylenedione, 2,3-butan Α-diketones such as diacetyl; tetramethyl thiuram disulfide, sulfides such as p-tolyl disulfide; 4-dimethylamino benzoic acid, 4-di Various benzoic acid such as methylamino benzoic acid ethyl ester; 3,3'-carbonyl-bis(7-diethylamino)coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'-di Methoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-N- Lolinylpropan-1-one, 2-benzyl-2-ethylamino-1-(4-N- Phenylphenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide , bis(2,4,6-trimethylbenzylidene)phenylphosphine, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1- Propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2- Methylpropan-1-one, 4-benzylidene-4'-methyldimethyl sulfide, 2,2'-diethoxyacetophenone, benzyldimethylketal, benzyl -β-methoxyethyl acetal, methyl benzylidene benzoate, bis(4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α,α-di Chloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2, 4-bis-trichloromethyl-6-[di-(ethoxycarbonylmethyl)amino]phenyl-S-three 2,4-bis-trichloromethyl-6-(4-ethoxy)phenyl-S-three 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-three 蒽醌, 2-tertiary butyl hydrazine, 2-pentyl hydrazine, β-chloropurine, and the like. These may be used singly or in combination of two or more.

Among the above 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-propan-1-one, 9-oxosulfur And 9-oxosulfur Derivative, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, oxidized double (2 ,4,6-trimethylbenzylidene)phenylphosphine, 2-methyl-1-[4-(methylthio)phenyl]-2-N- Lolinyl-1-propanone, 2-benzyl-2--2-methylamino-1-(4-N- It is preferred to use one or a mixture of two or more of the group of morphylphenyl)-butan-1-one to obtain a coating exhibiting light activity over a wider range of wavelengths and having high curability. .

The commercially available product of the photopolymerization initiator is, for example, "IRGACURE-184", "IRGACURE-149", "IRGACURE-261", "IRGACURE-369", "IRGACURE-500" manufactured by Ciba Specialty Chemicals Co., Ltd. "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 Co., Ltd.; "TRIGONAL P1" manufactured by AKZO Co., Ltd.; "SANDORAY 1000"; "DEAP" manufactured by APJOHN; "QUANTACURE-PDO", "QUANTACURE-ITX", "QUANTACURE-EPD" manufactured by WARD BLEKINSOP.

The amount of the photopolymerization initiator to be used is such that the amount of the function as a photopolymerization initiator can be sufficiently exhibited, and the range in which crystal precipitation or physical properties of the coating film are not deteriorated is preferable, specifically, the mass of the resin composition is 100. The fraction is preferably used in the range of 0.05 to 20 parts by mass, and particularly preferably used in the range of 0.1 to 10 parts by mass.

Further, the resin composition of the present invention may further use various photo sensitizers together with the above photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds or nitriles, and other nitrogen-containing compounds.

In the present invention, a thermal polymerization initiator can also be further used. The thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2' -Azo compound such as azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, lauryl peroxide, tertiary butyl peroxytrimethylacetate , tert-butyl peroxyethylhexanoate, 1,1'-bis(tri-butylperoxy)cyclohexane, per-pentyl peroxy-2-ethylhexanoate, peroxy-2-ethyl An organic peroxide such as hexyl hexanoate or a hydrogen peroxide or the like is preferably used in an amount of 0.05 to 20 parts by mass based on 100 parts by mass of the resin composition.

Further, the resin composition of the present invention may also use a urethane-based catalyst such as tin(II) octoate. The use ratio is preferably from 0.001 to 5 parts by mass based on 100 parts by mass of the resin composition.

In the method of producing the active energy ray-curable resin composition of the present invention, when the inorganic fine particles (D) are used in combination, for example, a disperser using a disperser, a stirring blade such as a turbine blade, or a pigment shaker a method of mixing and dispersing the inorganic fine particles (D) in the acrylic polymer (A) by a disperser such as a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, or a bead mill; or The method of mixing and dispersing the inorganic fine particles (D) in a resin component containing the acrylic polymer (A), the isocyanate compound (B), and the (meth) acrylate (C). In the case where the inorganic fine particles (D) are wet cerium oxide fine particles, a uniform and stable dispersion can be obtained by using any of the above dispersers. On the other hand, in the case where the inorganic fine particles (D) are dry cerium oxide fine particles, in order to obtain a uniform and stable dispersion, it is preferred to use a ball mill or a bead mill.

The ball mill to which the active energy ray-curable resin composition of the present invention is applied may, for example, be a wet ball mill having a container filled with a medium, a rotary bearing, and a rotary shaft coaxial with the rotary bearing. a stirring blade that is rotated by the rotation of the rotary bearing, a raw material supply port provided in the container, a dispersion discharge port provided in the container, and a shaft sealing device disposed in a portion of the rotary bearing penetrating the container, wherein The shaft sealing device is a shaft sealing device having two sets of mechanical sealing units and having a sealing portion of the two sets of mechanical sealing units sealed by an external sealing liquid.

In other words, the method of producing the active energy ray-curable resin composition containing the inorganic fine particles (D) includes, for example, the inorganic fine particles (D) and the polymer (A) from the supply port of the wet ball mill. The resin component containing the (meth) acrylate (C) as a component is supplied to the container, and the mixed medium and the raw material are stirred by rotating the rotary bearing and the stirring blade in the container to carry out the inorganic fine particles (D). powder Dispersing the dispersion of the resin component with the inorganic fine particles (D), and then discharging the same from the discharge port, wherein the wet ball mill has a container filled with a medium inside, a rotary bearing, and has a coaxial shape with the rotary bearing a rotating blade that rotates by the rotation of the rotary bearing, a material supply port that is provided in the container, a dispersion discharge port that is provided in the container, and a shaft seal that is disposed in a portion of the rotating bearing that passes through the container The device, the shaft sealing device is a shaft sealing device having two sets of mechanical sealing units and having a sealing portion of the two sets of mechanical sealing units sealed by an external sealing liquid.

The active energy ray-curable resin composition of the present invention can be used for coating applications. The coating can be used as a coating layer for protecting the surface of a substrate by being applied to various substrates and irradiated with an active energy ray to be cured. In this case, the coating material of the present invention may be applied directly to the surface protective member, or may be used as a protective film when applied to a plastic film. Alternatively, the coating material of the present invention may be applied to a plastic film, and the film-forming film may be used as an optical film such as an antireflection film, a diffusion film, and a ruthenium film. Since the coating film obtained by using the coating material of the present invention has a high surface hardness and excellent transparency, it can be applied to various plastic films in a film thickness depending on the intended use as a protective film or film. Shaped products are used.

Further, in order to obtain a coating film, a heat treatment step may be included before or after the irradiation of the active energy ray. By performing heat treatment, a coating film of higher hardness can be obtained. The heating temperature at this time can be appropriately selected depending on the heat resistance of the substrate (plastic film) to be used and the like. Alternatively, from the viewpoint of further improving the surface hardness, it is preferred to carry out the treatment in the range of 80 to 200 ° C for about 1 to 180 minutes.

Examples of the plastic film include polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, and AS resin. A plastic film or a plastic sheet made of a decene-based resin, a cyclic olefin, or a polyimide resin.

Among the above plastic films, the triacetyl cellulose film is a film which is particularly suitable for use in a polarizing plate of a liquid crystal display, but since it is usually thinner than 40 to 100 μm, it is possible even in the case of providing a hard coat layer. It is difficult to sufficiently increase the surface hardness and to easily cause curling characteristics. When the coating film composed of the resin composition of the present invention is used as a substrate, the coating film having high surface hardness, curl resistance, workability, and transparency is excellent. Quite applicable. When the triethylene fluorene cellulose film is used as a substrate, the coating amount in the coating of the present invention is such that the film thickness after drying is in the range of 1 to 20 μm, preferably in the range of 2 to 15 μm. Coating is preferred. 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. Printing, screen printing, etc.

Among the above-mentioned plastic films, the polyester film may, for example, be polyethylene terephthalate, and its thickness is usually about 100 to 300 μm. Because it is easy to process at low cost, it is a film that can be used for a variety of applications such as touch panel displays, but it is very soft even when In the case where a hard coat layer is provided, it is also difficult to sufficiently improve the characteristics of the surface hardness. When the polyethylene film is used as a substrate, the coating amount when the coating material of the present invention is applied is in a range of 5 to 100 μm, preferably 7 to 80 μm, in accordance with the use thereof. It is preferred to carry out the coating in the same manner. In general, when the coating material is applied at a film thickness of more than 20 μm, it tends to cause a large curl when coated with a thin film thickness. However, since the coating material of the present invention has a characteristic of excellent curl resistance, even In the case of coating at a film thickness of more than 20 μm, curling is less likely to occur, and it is quite suitable. The coating method at this time may, for example, be a bar coater coating, a Meyer bar coating, an air knife coating, a gravure coating, a reverse gravure coating, a lithography, a flexographic printing, a screen printing method, or the like.

Among the above-mentioned plastic films, since the polymethyl methacrylate film is usually thick and strong in thickness of about 100 to 2,000 μm, it is suitable for use in a front panel application such as a liquid crystal display, which requires a particularly high surface hardness. film. When the polymethyl methacrylate film is used as a substrate, the coating amount when the coating material of the present invention is applied is preferably in the range of 3 to 100 μm, preferably 7 in terms of the film thickness after drying. Coating is preferably carried out in a range of ~80 μm. In general, when a coating material is applied over a relatively thick film such as a polymethyl methacrylate film over a film thickness of more than 30 μm, it becomes a laminated film having a high surface hardness, and conversely, transparency tends to decrease, but the present invention The coating has a very high transparency compared to the conventional coating, so that a laminated film having high surface hardness and transparency can be obtained. The coating method at this time may, for example, be a bar coater coating, a Meyer bar coating, or a gas. Knife coating, gravure coating, reverse gravure coating, lithography, flexographic printing, screen printing, and the like.

Examples of the active energy ray which is irradiated when the coating material of the present invention is cured into a coating film include ultraviolet rays or electron beams. In the case of curing using ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, a metal halide lamp, or an LED lamp as a light source is used, and the amount of light, the arrangement of the light source, and the like can be adjusted as needed. In the case of using a high-pressure mercury lamp, it is usually preferable to perform hardening in a range of 5 to 50 m/min at a conveyance speed with respect to a lamp having a light amount in the range of 80 to 160 W/cm. On the other hand, in the case of hardening using an electron beam, it is usually performed by using an electron beam acceleration device having an acceleration voltage in the range of 10 to 300 kV, and curing is performed at a conveyance speed of 5 to 50 m/min.

Further, the substrate coated with the coating material 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 articles such as mobile phones, home electric appliances, automobile bumpers, and the like. In this case, examples of the method for forming the coating film include a coating method, a transfer method, and a sheet joining method.

The coating method is a method in which the coating material is spray-coated or applied to a molded article by using a printing machine such as a curtain coater, a roll coater, or a gravure coater, and then the active energy ray is irradiated and hardened. .

In the transfer method, the transfer material obtained by applying the coating material of the present invention on the release sheet having the release property is applied to the surface of the molded article, and then the base sheet is peeled off and the top coating is transferred. a method of hardening an active energy line on a surface of a molded article; or After the transfer material is applied to the surface of the molded article, the active energy ray is irradiated to be cured, and then the undercoat layer is transferred onto the surface of the molded article by peeling off the base sheet.

On the other hand, the sheet joining method is a method of "protecting sheet having a coating film comprising the coating material of the present invention on the base sheet" or "coating the substrate sheet with the coating material" The protective sheet of the film and the decorative layer is followed by a plastic molded article to form a protective layer on the surface of the molded article.

Among these, the coating of the present invention can be preferably used in the transfer method and the sheet joining method.

In the above transfer method, a transfer material is first produced. The transfer material can be produced, for example, by coating the above-mentioned coating material alone or by mixing it with a polyisocyanate compound, and heating it to semi-harden (B-stage) the coating film.

In order to manufacture a transfer material, the aforementioned coating material of the present invention is first coated on a substrate sheet. Examples of the method of applying the coating material include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a comma coat method, and the like; a gravure printing method, screen printing, and the like. Printing methods such as law. In view of the improvement in abrasion resistance and chemical resistance, the film thickness at the time of application is preferably such that the thickness of the coating film after curing is 1 to 50 μm, and coating is performed at 3 to 40 μm. good.

After the coating material was applied onto the substrate sheet by the above method, the coating film was semi-cured (B-tage) by heat drying. The heating is usually 55 to 160 ° C, preferably 100 to 140 ° C. The heating time is usually from 30 seconds to 30 minutes, preferably from 1 to 10 minutes, more preferably from 1 to 5 minutes.

The formation of the surface protective layer of the molded article using the transfer material is performed, for example, after the B-staged resin layer of the transfer material is bonded to the molded article, and then the active energy ray is irradiated to cure the resin layer. Specifically, for example, a B-staged resin layer of the transfer material is attached to the surface of the molded article, and then the B-stage of the transfer material is caused by peeling off the base sheet of the transfer material. After the resin layer is transferred onto the surface of the molded article, the energy beam is hardened by irradiation with an active energy ray to perform cross-linking hardening of the resin layer (transfer method); or the transfer material is inserted into the forming mold The resin is injected into the cavity, and the resin material is obtained, and the transfer material is subsequently peeled off on the surface of the substrate and transferred to the molded article, and then the energy is irradiated by the active energy ray. A method of performing cross-linking and hardening of a resin layer by wire hardening (forming simultaneous transfer method) or the like.

In the sheet-following method, the base sheet and the molded article of the sheet for forming a protective layer to be formed in advance are then thermally cured by heating to be "B-staged". Cross-linking hardening method of the formed resin layer (follow-up method); or inserting the protective layer forming sheet into a molding die to cause the resin to be injected into the cavity, and to obtain a resin molded article and to have a surface thereof After the protective layer forming sheet is followed by heat-hardening by heating, a method of crosslinking and curing the resin layer (forming simultaneous bonding method) or the like is performed.

Next, the coating film of the present invention is a coating film formed by applying the coating material of the present invention to the above-mentioned plastic film and hardening it, or coating and hardening the coating material of the present invention as a surface protective agent for a plastic molded article. The formed coating film, and the laminated film of the present invention is a film in which a coating film is formed on a plastic film.

Among the various uses of the above-mentioned film, as described above, a film obtained by applying the coating of the present invention to a plastic film and irradiating an active energy ray is used as a liquid crystal display or touch from the viewpoint of excellent hardness of the coating film. It is preferable to use a polarizing plate for a panel display or the like with a protective film. Specifically, when the coating material of the present invention is applied to a surface protective film used for a liquid crystal display, a touch panel display or the like and irradiated with an active energy ray to cure the film, the cured coating film becomes A protective film with high hardness and high transparency. In the use of the protective film of the polarizing plate, an adhesive layer may be formed on the other side of the coating layer on which the coating of the present invention is applied.

[Examples]

The present invention will be more specifically described by the following specific examples and examples, but the present invention is not limited by the examples. The parts and % in the examples are all based on quality unless otherwise specified.

In the examples of the present invention, the weight average molecular weight (Mw) is a value obtained by using a gel permeation chromatography (GPC) and measuring according to the following conditions.

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

Pipe column: protection column HXL-H made by TOSOH Co., Ltd.

+TOSOH Co., Ltd. TSKgel G5000HXL

+TOSOH Co., Ltd. TSKgel G4000HXL

+TSKgel G3000HXL made by TOSOH Co., Ltd.

+TOSOH Co., Ltd. TSKgel G2000HXL

Detector: RI (differential refractometer)

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

Standard: Polystyrene

Sample: Filtered by using a microfilter to filter a 0.4% by weight of a resin solid content in tetrahydrofuran (100 μl)

[Pencil hardness test]

1. Method for preparing test piece

The active energy ray-curable resin composition obtained in each of the examples and the comparative examples was applied onto the film by a bar coater so as to have a predetermined film thickness after curing, and was obtained by active energy ray irradiation and heat treatment. A laminated film having a hardened coating film.

2. Pencil hardness test method

The surface of the hardened coating film obtained above was passed through a pencil scratch test of a load of 500 g in accordance with JIS K 5400. The test was performed 5 times, and the hardness lower than the hardness of one or more scratches was used as the pencil hardness of the coating film.

[Abrasion resistance test]

1. Method for preparing hardened coating film

A coating film was produced in the same manner as in the case of the pencil hardness test described above.

2. Steel wool resistance test

A disk-shaped indenter having a diameter of 2.4 cm was wrapped with 0.5 g of steel wool ("BONSTAR #0000" manufactured by NIPPON STEEL WOOL Co., Ltd.), and a weight of 1 kg was applied to the indenter to return the film surface 100 of the film. The haze value of the coating film before and after the test was measured by "HAZE COMPUTER HZ-2" manufactured by SUGA Testing Machine Co., Ltd., and the difference was evaluated by the difference δH. The smaller the δH value, the more excellent the scratch resistance. Hardened coating film.

[Flexibility test]

1. Method for preparing hardened coating film

A coating film (thickness after curing: 18 μm) was formed on a polyester film (film thickness: 75 μm) in the same manner as in the above pencil hardness test.

2. Flexibility test

Using a mandrel tester ("bending tester" manufactured by TP Technik Co., Ltd.), the coated film was wound on the test bar, and the test film was visually confirmed to have a crack in the cured coating film. The minimum diameter of the test rod without cracks was used as the evaluation result. The smaller the minimum diameter, the more excellent the coating film is.

Synthesis Example 1: Production of Acrylic Polymer (A1)

229 parts by mass of methyl isobutyl ketone was placed in a reaction apparatus equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature in the system was raised to 110 ° C while stirring, and then it took 3 hours to drip. 309 parts by mass of glycidyl methacrylate, 34 parts by mass of methyl methacrylate, and butyl peroxy-2-ethylhexanoate ("PERBUTYL O" manufactured by Nippon Emulsifier Co., Ltd.) were added dropwise to the liquid funnel. After 10 parts by mass of the mixed solution, it was kept at 110 ° C for 15 hours. Then, cool down to After 90 ° C, 0.1 parts by mass of 4-methoxyphenol and 157 parts by mass of acrylic acid were charged, and after adding 3 parts by mass of triphenylphosphine, the mixture was further heated to 100 ° C for 8 hours, and then methyl isobutyl ketone was used. The mixture was diluted to obtain 1000 parts by mass of a methyl isobutyl ketone solution of the acrylic polymer (A1) (nonvolatile content: 50.0% by mass). The properties of the acrylic polymer (A) are as follows.

Weight average molecular weight (Mw): 35,000, Theoretical propylene sulfhydryl equivalent in terms of solid content: 230 g/eq, The hydroxyl value was 244 mgKOH/g.

Synthesis Example 2: Acrylic Polymer (A2)

In Synthesis Example 1, 283 parts by mass of methyl isobutyl ketone, 149 parts by mass of glycidyl methacrylate, 276 parts by mass of methyl methacrylate, and tertiary butyl peroxy-2-ethylhexanoate were prepared. In the same manner as in Synthesis Example 1, except that 25 parts by mass of the ester ("PERBUTYL O" manufactured by Nippon Emulsifier Co., Ltd.) was obtained, 76 parts by mass of acrylic acid was used immediately after the precursor was obtained, and the reaction was carried out in the same manner as in Synthesis Example 1. 1000 parts by mass of a methyl isobutyl ketone solution of the acrylic polymer (A2) (nonvolatile matter 50.0% by mass). The properties of the acrylic polymer (A2) are as follows.

Weight average molecular weight (Mw): 15,000, Theoretical propylene sulfhydryl equivalent in terms of solid content: 478 g/eq, The hydroxyl value was 117 mgKOH/g.

Example 1

To 160 parts by mass of the methyl isobutyl ketone solution of the acrylic polymer (A) obtained in the above Synthesis Example 1, 5 parts by mass of DURANATE 24A-100 as an isocyanate compound (B) and 20 parts by mass were added. An active energy ray-curable resin composition was obtained by DPHA (ARONIX M-404 East Asia Synthetic) of (meth) acrylate (C) and IRGACURE 184 as a polymerization initiator of 4 parts by mass.

The active energy ray-curable resin composition was applied onto a PET film (75 μA 4300 manufactured by Toyobo Co., Ltd.) so as to have a dry film thickness of 18 μ, and was cured at 500 mJ/cm ² using an irradiation machine equipped with a high-pressure mercury lamp, and at 80 ° C. The heat treatment was performed for 30 minutes to obtain a laminated film.

Examples 2 to 11 and Comparative Examples 1 to 2

The active energy ray-curable resin composition was prepared by blending each material in the same manner as in Example 1 and blending the amounts (mass basis) described in Table 1. Further, in the eleventh embodiment, the inorganic fine particles (D) were blended, and the preparation method was carried out by dispersion using a wet ball mill. The results are shown in Table 1.

The above various conditions for dispersion using a wet ball mill are as follows.

Medium: zirconia beads with a median diameter of 100 μm

Filling ratio of the resin composition relative to the inner volume of the mill: 70% by volume

Peripheral speed of the tip end of the stirring blade: 11m/sec

Flow rate of resin composition: 200 ml/min

Dispersion time: 60 minutes

Also, the abbreviations in Table 1 are as follows.

DURANATE 24A-100: Biuret body of hexamethylene isocyanate manufactured by ASAHI KASEI CHEMICALS Co., Ltd.

BURNOCK DN-980S: Isocyanate type polyisocyanate manufactured by DIC Corporation

KARENZ MOI: Foundry Electric Co., Ltd. 2-Methylpropenyl oxirane ethyl isocyanate

ARONIX M-404: manufactured by Toagosei Co., Ltd. dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate

SIRIUS 501: Dendritic Polyfunctional Acrylate, Osaka Organic Chemical Industry Co., Ltd.

AEROSIL R7200: "AEROSIL R7200" manufactured by NIPPON AEROSIL Co., Ltd. has a primary particle diameter of 12 nm and has (meth)acrylonitrile-based cerium oxide microparticles on the surface of the particle.

Claims (18)

An active energy ray-curable resin composition characterized by comprising an acrylic polymer having a weight average molecular weight (Mw) in the range of 3,000 to 60,000 and having a hydroxyl group and a (meth) acrylonitrile-based acrylic acid in the polymer structure Polymer (A) and isocyanate compound (B). The active energy ray-curable resin composition of claim 1, wherein the isocyanate compound (B) is hexamethylene isocyanate, a biuret of hexamethylene isocyanate, or a cyanuric acid of hexamethylene isocyanate (nurate) )body. The active energy ray-curable resin composition according to claim 1 or 2, further comprising a (meth) acrylate (C) other than the polymer (A) having the (meth) acrylonitrile group. The active energy ray-curable resin composition of claim 3, wherein the (meth) acrylate (C) is a polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups in one molecule. ester. The active energy ray-curable resin composition of claim 3, wherein the (meth) acrylate (C) has a hydroxyl group. The active energy ray-curable resin composition of claim 3, wherein the (meth) acrylate is dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, pentaerythritol triacrylate or new Pentaerythritol diacrylate. The active energy ray-curable resin composition according to any one of claims 1 to 6, which further contains inorganic fine particles (D). The active energy ray-curable resin composition of claim 7, wherein the inorganic fine particles (D) are selected from the group consisting of cerium oxide, aluminum oxide, and oxidation. One or more inorganic fine particles in the group of zirconium, titanium oxide, barium titanate, and antimony trioxide. The active energy ray-curable resin composition of claim 8, wherein the inorganic fine particles (D) are dry cerium oxide. The active energy ray-curable resin composition of claim 1, wherein the (meth)acryl oxime equivalent of the acrylic polymer (A) is in the range of 150 to 800 eq/g. The active energy ray-curable resin composition of claim 1, wherein the acrylic polymer (A) has a hydroxyl value in the range of 75 to 380 mgKOH/g. The active energy ray-curable resin composition of claim 1, wherein the acrylic polymer (A) is a polymer obtained by reacting a compound having a carboxyl group and a (meth) acrylonitrile group with an acrylic polymer described below: An acrylic polymer obtained by polymerizing a compound having a glycidyl group and a (meth)acryl fluorenyl group as an essential component. The active energy ray-curable resin composition of claim 1, wherein the ratio of the acrylic polymer (A) to the isocyanate compound (B), (A) / (B) (mass ratio) is 98/2 to 50/50 The scope. A coating material comprising the active energy ray-curable resin composition according to any one of claims 1 to 13. A coating film characterized in that it is obtained by hardening a coating material as claimed in claim 14. The coating film of claim 15, wherein the hardening comprises a heat treatment step of 60 ° C or more. A laminated film characterized by having a coating film as claimed in claim 15 or 16 on one or both sides of a plastic film. The laminate film of claim 17, wherein the film thickness of the coating film is in the range of 1 to 100 μm.