TW201605990A - Actinic-ray-curable resin composition, coating composition, coating film, and layered film - Google Patents

Abstract

Provided are: an actinic-ray-curable resin composition which gives a cured coating film that has an extremely high surface hardness and that, despite this, can exhibit excellent processability; a coating composition comprising the resin composition; a coating film obtained from the coating composition; and a film having the coating film layer. The actinic-ray-curable resin composition is characterized by containing, as an essential component, an acrylic/acrylate resin (A) which is obtained by reacting an acrylic polymer (a) having glycidyl, hydroxy, and (meth)acryloyl groups with (meth)acrylic anhydride and which has a weight-average molecular weight (Mw) of 3,000-80,000. The film has a coating film layer obtained by curing the coating composition, which comprises the resin composition.

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 into the interior of a flat panel display, 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. So, coating. The hard coating agent hardened on 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 while having a very high surface hardness, and a coating material containing the resin composition; a coating film composed of the coating material; and a laminated film having the coating film layer.

The inventors of the present invention have devoted themselves to research to solve the above problems, and as a result, have found that an acrylic polymer containing (meth)acrylic anhydride and having a glycidyl group, a hydroxyl group, and a (meth)acryloyl group ( a) an active energy ray-curable resin composition characterized by an acrylic acrylate resin (A) having a weight average molecular weight (Mw) of 3,000 to 80,000 as a necessary component, which is cured after hardening The present invention has been completed by exhibiting a very high surface hardness while also being rich in workability (flexibility) at the time of coating hardening on a plastic substrate.

That is, the present invention provides a weight average molecular weight (Mw) obtained by reacting (meth)acrylic anhydride with an acrylic polymer (a) having a glycidyl group, a hydroxyl group, or a (meth)acryloyl group. An acrylic acrylate resin (A) having a range of 3,000 to 80,000, an active energy ray-curable resin composition characterized by an essential component, a coating film containing the same, a coating film obtained by curing the same, and a laminate having the coating layer film.

According to the present invention, it is possible to provide a cured coating film which has a very high surface hardness and transparency, and also has processability which can also be used as a flexible display; and can provide the active energy of the cured coating film. A wire hardening type resin composition; a coating containing the same.

[Formation of the Invention]

The active energy ray-curable resin composition of the present invention is characterized by containing a weight obtained by reacting (meth)acrylic anhydride with an acrylic polymer (a) having a glycidyl group, a hydroxyl group and a (meth)acryl fluorenyl group. The acrylic acrylate resin (A) having an average molecular weight (Mw) in the range of 3,000 to 80,000.

The acrylic acrylate resin (A) has a weight average molecular weight (Mw) of 3,000 to 80,000, and the crosslinking density after curing is appropriate, and high hardness and workability can be imparted to the cured coating film. 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.

Measurement conditions: column temperature 40 ° C

Solvent tetrahydrofuran

Flow rate 1.0ml/min

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, it is easy to obtain a cured film having a high surface hardness and excellent workability, and the (meth)acryl oxime equivalent of the acrylic acrylate resin (A) is preferably 150 g/eq to 600 g/ The range of eq is more preferably in the range of 160 g/eq to 450 g/eq, still more preferably in the range of 160 g/eq to 280 g/eq.

The acrylic acrylate resin (A) may, for example, be a homopolymer of a compound having a glycidyl group and a (meth)acryl fluorenyl group, or a copolymer of the compound and a (meth) acrylate (hereinafter, These are abbreviated as "precursor (1)".), which will be made with carboxyl groups and (methyl) A resin obtained by reacting an acrylic polymer (a) obtained by reacting a compound of an acrylonitrile group with (meth)acrylic anhydride. The acrylic acrylate resin (A) which can be used in the present invention can be obtained by reacting (meth)acrylic anhydride with a hydroxyl group formed by a reaction between a glycidyl group and a carboxyl group.

Here, examples of the compound having a glycidyl group and a (meth)acryloyl group as a raw material of the precursor (1) 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-epoxy ring Hexyl ester, vinyl cyclohexene oxide, and the like. Among these, it becomes easy to adjust the (meth)acryl oxime equivalent of the obtained acrylic polymer (a) to a preferable range to use (meth)acrylic acid propylene The ester, the epoxypropyl α-ethyl (meth)acrylate and the glycidyl α-n-propyl (meth)acrylate are preferred, and the use of glycidyl (meth)acrylate is more preferred.

When the precursor (1) is produced, any of the above (meth) acrylate which can be polymerized with the compound having a glycidyl group and a (meth) acryl fluorenyl group may be used, but it is easy to use The acrylic acrylate resin (A) having the (meth)acryl oxime equivalent of the obtained acrylic polymer (a) adjusted to the above preferred range and used for further addition of (meth)acrylic anhydride The obtained hardened coating film is preferably one which is high in hardness and also has processability, and 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 a (meth)acrylic acid having an alkyl group having 1 to 22 carbon atoms ester. 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, from the viewpoint of easily adjusting the (meth)acrylonitrile group-based equivalent of the obtained acrylic polymer (a) to an appropriate range, and obtaining a cured coating film having high surface hardness and excellent curl resistance at the time of curing, In view of the mass ratio of the two at the time of copolymerization [compound having a glycidyl group and a (meth)acryl fluorenyl group]: [(meth) acrylate] becomes 20/80 to 95/5 It is preferable to use it at a ratio of a range, and it is preferable to use it at a ratio of 30/70 to 90/10. In addition, from the viewpoint of obtaining an active energy ray-curable resin composition having excellent hardness of the coating film, it 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 (1) has an epoxy group derived from the above compound having a glycidyl group and a (meth)acryl fluorenyl group, it is easy to adjust the propylene oxime equivalent of the obtained acrylic polymer (a). The epoxy equivalent of the precursor (1) is preferably in the range of 150 to 500 g/eq, more preferably in the range of 150 to 250 g/eq, more preferably in the range of 145 to 750 g/eq. Range of 150~180g/eq.

The precursor (1) 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. Or before The (meth) acrylate is produced by using and polymerizing, but the precursor (1) can be continuously produced, and the precursor (1) and the carboxyl group and the (meth) acrylonitrile group can be continuously formed. In view of the reaction of the compound, it is preferably produced by solution polymerization.

When the solvent used for the production of the precursor (1) 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; n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene Ester monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxylate propionate ester solvent; toluene, xylene, SOLVESSO 100, SOLVESSO 150, SWASOL 1800, SWASOL 310, ISOPAR E, ISOPAR G, Exxon naphtha 5, Exxon naphtha 6 and other hydrocarbon solvents. These may be used singly or in combination of two or more.

Among the above solvents, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone or isopropyl acetate is preferred from the viewpoint that the solubility of the obtained precursor (1) is excellent. An ester solvent such as n-butyl acetate.

The catalyst system used in the production of the aforementioned precursor (1) may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis-(2,4-dimethylvaleronitrile). , 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), etc. Benzoyl peroxide, barium sulphate peroxide, tertiary butyl peroxytrimethylacetate, tertiary butyl peroxyethylhexanoate, 1,1'-bis (tertiary butyl peroxyl) An organic peroxide such as cyclohexane, peroxy-ethyl 2-ethylhexanoate or tertiary hexyl peroxy-2-ethylhexanoate, 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 a carboxyl group and a (meth) acrylonitrile group to obtain an acrylic polymer (a). The reaction method may, for example, be a method of polymerizing a precursor (1) by a solution polymerization method, and adding a compound having a carboxyl group and a (meth)acryl fluorenyl group to the reaction system at a temperature 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) is preferably in the range of 200 to 6,200 g/eq, but it is capable of having the carboxyl group and the (meth) propylene oxime by the aforementioned precursor (1) and the foregoing. The reaction ratio of the compound of the group is adjusted. In general, the reaction is carried out in such a manner that the carboxyl group has a range of from 0.1 to 0.9 mol with respect to 1 mol of the precursor (1), and the obtained acrylic polymer (a) is easily obtained. 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 modification; an unsaturated dicarboxylic acid such as maleic acid; A carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting an acid anhydride such as maleic anhydride with a hydroxyl group-containing polyfunctional (meth) acrylate monomer such as neopentyl alcohol triacrylate. These may be used singly or in combination of two or more. Among these, from the viewpoint of easily adjusting the (meth)acrylonitrile group equivalent of the obtained acrylic polymer (a) to the above preferred range, (meth)acrylic acid, (propylene) is preferred.醯oxy)acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, particularly preferably (meth)acrylic acid.

The acrylic polymer (a) thus obtained has a hydroxyl group produced by a reaction of a glycidyl group and a carboxyl group in its molecular structure. The acrylic acrylate resin (A) used in the present invention is obtained by further reacting this hydroxyl group with (meth)acrylic anhydride.

Further, from the viewpoint that the synthesis can be produced in a simpler manner, it is particularly preferable to use a (meth)acrylic acid propylene acrylate to copolymerize with a (meth) acrylate to obtain a precursor. (1) An acrylic polymer (a) obtained by reacting the precursor (1) with (meth)acrylic acid.

Next, a reaction of adding (meth)acrylic anhydride to the acrylic polymer (a) obtained above is carried out.

The reaction of the above (meth)acrylic anhydride with the hydroxyl group in the acrylic polymer (a) is not particularly limited, and examples thereof include a glycidyl group of the precursor (1) and a carboxyl group and an acryl group. In the reaction of the compound, or after obtaining the acrylic polymer (a), (meth)acrylic anhydride is added to the reaction system, and a catalyst such as triphenylphosphine is suitably used at a temperature of 80 to 120 ° C. To carry out the method. The (meth)acrylonitrile group of the obtained acrylic acrylate resin (A) is thus treated The equivalent is preferably in the range of 150 to 600 g/eq, but it can be adjusted by the reaction ratio of the acrylic polymer (a) to (meth)acrylic anhydride. In general, the total of the carboxyl groups of (meth)acrylic acid produced by the cleavage of the carboxyl group of the compound having a carboxyl group and an acryloyl group, and the (meth)acrylic anhydride by the reaction with the hydroxyl group in the aforementioned acrylic polymer (a) The obtained carboxyl group is reacted in such a manner that the epoxy propyl group of the precursor (1) of the above-mentioned precursor (1) is in the range of 0.9 to 1.1 mol, and the obtained acrylic polymer (a) is easily used ( The methyl methacrylate oxime equivalent is adjusted to the above preferred range. In this case, the hydroxyl value of the acrylic acrylate resin (A) is preferably in the range of 5 to 230 mgKOH/g.

Furthermore, in the present invention, from the viewpoint of easily preparing the viscosity of the coating material and having good curability, and the surface hardness of the obtained coating film is high, it is also possible to use a combination other than the acrylic acrylate resin (A). (Meth) acrylate (B).

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

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 oxime 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)acrylic acid , ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ginsyl 2-hydroxyethyl isocyanurate tri (methyl) Tris(meth)acrylate such as acrylate or tris(meth)acrylate; pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, di-trihydroxyl Propane tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, two new Pentaerythritol 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 such as an ester; 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. (nurate) 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. An aliphatic diisocyanate such as hexamethylene diisocyanate, benzodimethyl diisocyanate or m-tetramethyl benzene diisocyanate; Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, octadecyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, Alicyclic diisocyanate such as methylcyclohexane diisocyanate; 1,5-naphthyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane Diisocyanate, 4,4'-diphenylmethyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, two An aromatic diisocyanate such as 1,4-phenylene isocyanate or methyl phenylisocyanate.

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 used in a ratio of 1/0.95 to 1/1.05 to use the aforementioned polyisocyanate compound and the aforementioned hydroxyl group-containing (A) The acrylate compound is a method in which a variety of urethane-based catalysts are used in a temperature range of 20 to 120 ° C, if necessary.

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 above polyisocyanate compound, dipentaerythritol penta (meth) acrylate and dipentaerythritol A urethane acrylate obtained by reacting a raw material of (meth) acrylate.

The weight average molecular weight (Mw) of the obtained urethane (meth) acrylate is preferably in the range of 800 to 20,000 in terms of excellent compatibility with the acrylic acrylate resin (A). More preferably, it is in the range of 900 to 1,000.

These compounds (B) 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, it is a polyfunctional (meth) propylene having three or more (meth) acrylonitrile groups. The acid ester urethane (meth) acrylate is preferably a diisocyanate compound, a glycerin diacrylate, a trimethylolpropane diacrylate, a neopentyl alcohol triacrylate, and a dipentane. Tetrahydrin pentaacrylate is equivalent to a urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound having two or more (meth) acrylonitrile groups in a molecular structure, more preferably A urethane (meth) acrylate obtained by reacting a diisocyanate compound with a hydroxyl group-containing (meth) acrylate compound having three or more (meth) acrylonitrile groups.

Further, the (meth) acrylate (B) which can be used in the present invention may be a multi-branched (meth) acrylate. In the case of such a multi-branched (meth) acrylate, any one of a name provided by a dendrimer, a core-shell, a hyperbranch, or the like can be used, for example, Any of the following can be used as appropriate in the production method of WO 08/047620, JP-A-2012-111963, and JP-A-10-508052. 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 acrylate resin (A) to other (meth) acrylate (B) is not particularly limited, and the hardness and processing of the cured coating film can be achieved in view of the target. The acryl acrylate resin (A) and other (methyl groups) are used in view of the ease of obtaining a coating film having a particularly high surface hardness and good workability. The mass ratio (A)/(B) of the acrylate (B) is preferably in the range of 10/90 to 100/0, particularly preferably in the range of 30/70 to 90/10, more preferably 30/. 70~80/20.

In the present invention, inorganic fine particles (C) may 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 and the like.

The blending ratio of the inorganic fine particles (C) can be appropriately set in accordance with the performance of the target, but the active energy ray-curable resin composition is obtained from the viewpoint of obtaining a cured film having high transparency. It is preferable that the nonvolatile matter contains 100 parts by mass of the inorganic fine particles (C) in the range of 30 to 55 parts by mass. In other words, when the content of the inorganic fine particles (C) is 30 parts by mass or more, the effect of improving the coating film hardness or the scratch resistance at the time of curing becomes remarkable. In addition, when the content of the inorganic fine particles (C) 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 (C) in the range of 35 to 50 parts by mass.

The average particle diameter of the inorganic fine particles (C) 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 (C) 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 (C) 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 (C), preferred are cerium oxide fine particles, and examples thereof 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 (C) 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 (C) 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 (C), the miscibility with the organic components such as the acrylic acrylate resin (A) and other (meth) acrylate (B) is improved to cause dispersion. Stability, preservation and stability.

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 Silane hydrochloride group of special amine Silane, 3-ureidopropyl triethoxysilane Silane, 3-chloropropyl trimethoxy Silane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxydecylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxydecane, allyl Trichloromethane, allyl triethoxy decane, allyl trimethoxy decane, diethoxymethyl vinyl decane, trichlorovinyl decane, vinyl trichloro decane, vinyl trimethoxy decane , vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, etc., vinyl decane coupling agent; diethoxy (glycidoxypropyl) methyl decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3- An epoxy-based decane coupling agent such as glycidoxypropyltriethoxysilane; a styrene-based decane coupling agent such as p-styryltrimethoxydecane; and 3-methylpropenyloxypropyl group Dimethoxy decane, 3-propenyl methoxypropyl trimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-methyl propylene oxypropyl methyl diethoxy decane, 3-A a (meth) propylene oxirane decane coupling agent such as propylene oxypropyl triethoxy decane; N-2 (aminoethyl) 3-aminopropyl methyl dimethoxy decane, 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-aminopropyl An amine-based decane coupling agent such as a trimethoxy decane; 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 a decane, a 3-decyltrimethoxydecane or the like; a bis-(triethoxydecylpropyl) sulfonate, a sulfide-based decane coupling agent; a 3-isocyanate propyl group An isocyanate-based decane coupling agent such as ethoxysilane. 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 acrylate resin (A) by a solution polymerization method, for example, the organic solvent may directly contain the solvent used at this time, and may further add another solvent in an additional manner. Alternatively, other solvents may be used once the organic solvent used in the production of the acrylic acrylate resin (A) is removed. 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 solvent 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 A glycol ether solvent such as ethylene glycol 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 or an ester solvent is preferred as a resin composition which is excellent in stability and excellent in coating properties when used as a coating material, and more preferably methyl isobutyl 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-based antioxidant. 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. Preferred values of the average particle diameter of the organic beads A 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", "UV3500" manufactured by BYK Chemie Co., Ltd., and "Peintadd 8526" manufactured by Toray Dow Corning Co., Ltd., SH-29PA" and so on. 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 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, sulfurized 4-benzylidene-4'-methyldimethyl, 2,2'-diethoxyacetophenone, benzyldimethylketal, benzate Benzyl-β-methoxyethyl acetal, methyl phthaloyl benzoate, bis(4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α,α- Dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2 ,4-bis-trichloromethyl-6-[bis(ethoxycarbonylmethyl)amino]phenyl-S-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.; SANDOZ "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.

In the method of producing the active energy ray-curable resin composition of the present invention, when the inorganic fine particles (C) are used in combination, for example, a disperser using a disperser, a stirring blade such as a turbine blade, or a paint shaker may be used. a disperser such as a roll mill, a ball mill, an attritor, a sand mill, a bead mill, or the like, wherein the inorganic fine particles (C) are mixed and dispersed in the acrylic acrylate resin (A); or the inorganic fine particles are (C) A method of mixing and dispersing in a resin component containing the acrylic acrylate resin (A) and the (meth) acrylate (B). In the case where the inorganic fine particles (C) 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 (C) 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, a method of producing an active energy ray-curable resin composition containing inorganic fine particles (C) includes, for example, the aforementioned inorganic microparticles (C) and the polymer from the supply port of the wet ball mill. (A) The resin component containing the component (meth) acrylate (B) 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 ( C) pulverization and dispersion of the inorganic fine particles (C) to the resin component, and then discharging from the discharge port, wherein the wet ball mill has a container filled with a medium, a rotary bearing, and a rotary bearing a stirring blade that rotates by a rotation of the rotary bearing, a material supply port that is provided in the container, a dispersion outlet that is provided in the container, and a portion that is disposed in the container through the container The shaft sealing device is a shaft sealing device having a structure in which two sets of mechanical sealing units are provided and the sealing portions of the two sets of mechanical sealing units are 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, etc., but from the viewpoint of further improving the surface hardness, it is carried out at a temperature of 80 to 200 ° C. The treatment of about 180 minutes is better.

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. Since it is easy to process at a low cost, it is a film which can be used for various uses, such as a touch panel display, but it is very soft, and it is difficult to fully improve surface hardness even if a hard-coat layer is provided. 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. Generally, when a coating is applied over a relatively thick film such as a polymethyl methacrylate film with a film thickness exceeding 30 μm, it becomes a surface hardness. A high build-up film tends to have a lower transparency, but the paint of the present invention has a very high transparency compared to the conventional paint, and thus 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, an air knife coating, a gravure coating, a reverse gravure coating, a lithography, a flexographic printing, a screen printing method, or 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 the surface of the molded article by irradiating the active energy ray; or after the transfer material is applied to the surface of the molded article, irradiating the active energy ray to harden it, and then coating the substrate by peeling off the base sheet A method of transferring a layer onto a surface of a molded article.

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.

In the previous method, after the coating material was applied onto a substrate sheet, the coating film was semi-hardened (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, in the case of producing a film obtained by applying the coating material of the present invention to a protective film of a polarizing plate used in a liquid crystal display or a touch panel display, and irradiating an active energy ray to cure the film, the cured film is formed. It will become 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.

Measurement conditions: column temperature 40 ° C

Solvent tetrahydrofuran

Flow rate 1.0ml/min

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 (film thickness after curing: 15 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.), a laminated film was wound around a test bar, and a test for visually confirming the presence or absence of cracks in the cured coating layer of the film was carried out, and a test bar having no cracks was formed. The minimum diameter is used as the evaluation result. The smaller the minimum diameter, the more excellent the coating film is.

Synthesis Example 1: Production of Acrylic Acrylate Resin (A-1)

96 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. 130 parts by mass of glycidyl methacrylate, 14 parts by mass of methyl methacrylate, and tert-butyl peroxy-2-ethylhexanoate ("PERBUTYL O" manufactured by Nippon Emulsifier Co., Ltd.) were dropped from the dropping funnel. After 6 parts by mass of the mixed solution, it was kept at 110 ° C for 15 hours. Then, after cooling to 90 ° C, 0.1 parts by mass of 4-methoxyphenol, 33 parts by mass of acrylic acid and 70 parts by mass of methacrylic anhydride were charged, and after adding 3 parts by mass of triphenylphosphine, the temperature was further raised to 110 ° C. The acid value was confirmed to be 3 mgKOH/g or less. Subsequently, it was diluted with methyl isobutyl ketone to obtain a methyl isobutyl ketone solution of an acrylic acrylate resin (A-1) (nonvolatile matter 50.0% by mass). The properties of the acrylic acrylate resin (A-1) are as follows.

Weight average molecular weight (Mw): 36,000, theoretical propylene oxime equivalent: 180 g/eq, and hydroxyl value 104 mg KOH/g.

Synthesis Example 2~6

In the synthesis example 1, except that the ratio of use of glycidyl methacrylate, methyl methacrylate, acrylic acid, and methacrylic anhydride was made as shown in Table 1, the acrylic acrylate was obtained in the same manner as in Synthesis Example 1. Resins (A-2), (A-3), (A-4). Further, Synthesis Examples 5 and 6 in which methacrylic anhydride was not used were synthesized in the use ratios shown in Table 1, and the comparative resins (A'-1) and (A'-2) were synthesized. The resin property values obtained in the respective synthesis examples are also shown in Table 1.

Footnotes of Table 1

(Meth) propylene fluorenyl equivalent g/eq: theoretical (methyl) acrylonitrile equivalent derived from solid content of acrylic acid and methacrylic anhydride

The hydroxyl value mgKOH/g: the theoretical hydroxyl value converted from the solid content calculated from the hydroxyl value generated by the reaction of acrylic acid with the epoxy propyl group minus the hydroxyl value of the portion of the methacrylic anhydride reacted with the hydroxyl group.

Example 1

40 parts by mass of PETA (ARONIX M-305, manufactured by Toagosei Co., Ltd.) and 4 parts by mass of IRGACURE 184 were added to 120 parts by mass of the acrylic acrylate resin (A-1) obtained in the above Synthesis Example 1 to obtain active energy. A wire hardening type resin composition.

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 15 μ, and was cured at 500 mJ/cm ² using an irradiation machine equipped with a high-pressure mercury lamp to obtain a laminated film.

Examples 2-8 and Comparative Examples 1~2

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 Example 7, the cured coating film was further subjected to heat treatment at 150 ° C for 30 minutes. In the eighth embodiment, the inorganic fine particles (C) were blended, and the preparation method was carried out by dispersion using a wet ball mill. The results are shown in Table 2.

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

The abbreviations of Table 2 are as follows.

ARONIX M-305: Made in East Asia Synthetic Co., Ltd. Neopentyltetraol tetraacrylate/dipentaerythritol triacrylate

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

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 (15)

An active energy ray-curable resin composition comprising: reacting (meth)acrylic anhydride with an acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth)acryl fluorenyl group; An acrylic acrylate resin (A) having a weight average molecular weight (Mw) of from 3,000 to 80,000 is contained as an essential component. The active energy ray-curable resin composition of claim 1, wherein the (meth)acryl oxime equivalent of the acrylic acrylate resin (A) is in the range of 150 to 600 g/eq. The active energy ray-curable resin composition according to claim 1 or 2, which further contains a (meth) acrylate (B) other than the acryl acrylate resin (A). The active energy ray-curable resin composition of claim 3, wherein the (meth) acrylate (B) is a polyfunctional (meth) acrylate having 3 or more (meth) acrylonitrile groups in one molecule. ester. The active energy ray-curable resin composition of claim 3, wherein the (meth) acrylate (B) has a hydroxyl group. The active energy ray-curable resin composition of claim 3, wherein the (meth) acrylate is dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, Neopentyl alcohol tetraacrylate, neopentyl alcohol triacrylate or neopentyl alcohol diacrylate. The active energy ray-curable resin composition according to any one of claims 1 to 6, which further contains inorganic fine particles (C). The active energy ray-curable resin composition of claim 7, wherein the inorganic fine particles (C) are dry cerium oxide. The active energy ray-curable resin composition of claim 1, wherein the acrylic acrylate resin (A) is a resin obtained by reacting (meth)acrylic acid and (meth)acrylic anhydride 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 9, wherein the acrylic polymer has a hydroxyl value in the range of 5 to 230 mgKOH/g. A coating material comprising the active energy ray-curable resin composition according to any one of claims 1 to 10. A coating film characterized in that it is obtained by hardening a coating material as claimed in claim 11. The coating film of claim 12, wherein the hardening comprises a heat treatment step of 60 ° C or higher. A laminated film characterized by having a coating film as claimed in claim 12 or 13 on one or both sides of a plastic film. The laminate film of claim 14, wherein the film thickness of the coating film is in the range of 1 to 100 μm.