JPWO2015198788A1 - Active energy ray-curable resin composition, paint, coating film, and laminated film - Google Patents

Abstract

Active energy ray-curable resin composition, paint containing the resin composition, and paint capable of expressing excellent performance in paint film processability while the cured film obtained has a very high surface hardness And a film having the coating layer. An acrylic acrylate having a weight average molecular weight (Mw) in the range of 3,000 to 80,000, obtained by reacting an acrylic polymer (a) having a glycidyl group, a hydroxyl group and a (meth) acryloyl group with anhydrous (meth) acrylic acid. An active energy ray-curable resin composition comprising a resin (A) as an essential component, a paint containing the same, and a film having a coating layer obtained by curing the paint.

Description

  The present invention provides an active energy ray-curable resin composition, a paint containing the resin composition, and a paint film comprising the paint, which can obtain a paint film having an extremely high surface hardness and excellent workability. And a laminated film having the coating layer.

  Plastic films produced using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin and the like are widely used in industrial applications. These films are used as, for example, a polarizing plate protective film incorporated into a flat panel display, and these films are required to have high scratch resistance.

  Various methods have been studied as a method for improving the scratch resistance. However, in recent years, a polyfunctional acrylate having a high crosslinking density is mainly used on the film from the viewpoint of environmental advantages such as reduction of energy required for curing. A method of forming a hard coat layer by applying the active energy ray-curable resin composition and curing with active energy rays such as ultraviolet rays (UV) and electron beams (EB) has been implemented.

  With the progress of lighter and thinner displays, the films used are also made thinner. Therefore, a hard coating agent applied and cured on a film is required to have both higher hardness than before and workability compatible with applications requiring flexibility. Hard coating agents that can be used for such applications include acrylic polymers having a double bond in the side chain, obtained by reacting acrylic acid with an acrylic polymer containing an epoxy group, and polyfunctional acrylates. An active energy ray-curable resin composition obtained by the above is known (for example, see Patent Document 1).

  However, in the active energy ray-curable resin composition comprising an acrylic polymer having a double bond in the side chain and a polyfunctional acrylate provided in Patent Document 1, the reaction of the double bond contained in the composition Due to the insufficient rate, the coating film hardness was still insufficient, although it had a certain workability.

  In addition, the inorganic fine particle dispersed active energy ray curable resin composition obtained by dispersing inorganic fine particles in the resin component has a higher hardness of the cured coating film compared to a resin composition consisting of only an organic material, It is provided as a new material that can be improved in performance and impart new functions such as adjusting the refractive index and imparting conductivity (see, for example, Patent Document 2). A coating film obtained from a resin composition in which such inorganic fine particles are dispersed has a feature of high hardness and can be used as a hard coat layer exhibiting scratch resistance, but is inferior in processability. Therefore, it may be difficult to apply to flexible display applications.

JP 2011-207947 A International Publication WO2013 / 047590

  The problem to be solved by the present invention is that the cured coating film has an extremely high surface hardness and exhibits an excellent workability, and an active energy ray-curable resin composition, and a paint containing the resin composition Another object of the present invention is to provide a coating film comprising the coating material and a laminated film having the coating film layer.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have reacted an acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth) acryloyl group with anhydrous (meth) acrylic acid, An active energy ray-curable resin composition containing an acrylic acrylate resin (A) having a weight average molecular weight (Mw) in the range of 3,000 to 80,000 as an essential component has a very high surface after curing. The present invention was completed by finding out that it has high hardness and has excellent workability (flexibility) when applied and cured on a plastic substrate.

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

  According to the present invention, a cured coating film having a very high surface hardness and transparency, and a workability capable of being used as a flexible display, and an active energy ray-curable resin composition capable of providing the cured coating film A paint containing the same can be provided.

  The active energy ray-curable resin composition of the present invention comprises a weight average molecular weight (Mw) obtained by reacting an acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth) acryloyl group with anhydrous (meth) acrylic acid. ) Contains acrylic acrylate resin (A) in the range of 3,000-80,000.

  Since the acrylic acrylate resin (A) has a weight average molecular weight (Mw) in the range of 3,000 to 80,000, the crosslinking density after curing is appropriate, and the cured coating film has a high altitude and processing. Can be imparted. From the viewpoint that these effects are more excellent and the viscosity of the active energy ray-curable resin composition is easy to adjust to those suitable for coating, the weight average molecular weight (Mw) is in the range of 8,000 to 50,000. It is preferable that it is in the range of 20,000 to 40,000.

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

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Tosoh Corporation guard column HXL-H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 1.0 ml / min Standard; polystyrene sample; 0.4% by weight tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

  Further, the (meth) acryloyl group equivalent of the acrylic acrylate resin (A) is in the range of 150 g / eq to 600 g / eq in that a cured coating film having high surface hardness and excellent workability can be easily obtained. It is preferred that it is 160 g / eq to 450 g / eq, more preferred is 160 g / eq to 280 g / eq.

  The acrylic acrylate resin (A) is, for example, a homopolymer of a compound having a glycidyl group and a (meth) acryloyl group, or a copolymer of the compound and a (meth) acrylic ester (hereinafter referred to as “precursor”). (Abbreviated as “body (1)”), and an acrylic polymer (a) obtained by reacting this with a compound having a carboxyl group and a (meth) acryloyl group is reacted with anhydrous (meth) acrylic acid. The resin which consists of is mentioned. An acrylic acrylate resin (A) that can be used in the present invention can be obtained by reacting anhydrous (meth) acrylic acid with a hydroxyl group produced by the reaction of a glycidyl group and a carboxyl group.

  Here, the compound having a glycidyl group and a (meth) acryloyl group as a raw material of the precursor (1) is, for example, glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, α-n-propyl ( (Meth) acrylic acid glycidyl, α-n-butyl (meth) acrylic acid glycidyl, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid- 6,7-epoxypentyl, α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone modified (meth) Acrylic acid-3,4-epoxycyclohexyl, vinylcyclohexene oxide and the like can be mentioned. Among these, (meth) acrylic acid glycidyl, α-ethyl (meth) acrylic acid glycidyl, in that it becomes easy to adjust the (meth) acryloyl group equivalent of the obtained acrylic polymer (a) to a preferred range, And α-n-propyl (meth) acrylate glycidyl are preferably used, and glycidyl (meth) acrylate is more preferably used.

  When the precursor (1) is produced, any of the (meth) acrylic acid esters that can be polymerized with the compound having the glycidyl group and the (meth) acryloyl group can be used. Among them, it is easy to adjust the (meth) acryloyl group equivalent of the acrylic polymer (a) to be obtained within the above-mentioned preferable range, and an acrylic acrylate resin obtained by further adding anhydrous (meth) acrylic acid thereto ( A (meth) acrylic acid ester having an alkyl group having 1 to 22 carbon atoms and an alicyclic ring from the viewpoint that a cured film obtained using A) can be easily obtained while having high hardness and high workability. (Meth) acrylic acid ester having an alkyl group of the formula is preferable, and (meth) acrylic acid ester having an alkyl group having 1 to 22 carbon atoms is more preferable.Among others, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (n-butyl) (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, It is particularly preferred to use isobornyl (meth) acrylate.

  Here, it becomes easy to adjust the (meth) acryloyl group equivalent of the resulting acrylic polymer (a) to a suitable range, and a cured coating film having high surface hardness and excellent curling resistance at the time of curing. From the point obtained, the mass ratio of the two when copolymerized [compound having glycidyl group and (meth) acryloyl group]: [(meth) acrylic acid ester] is in the range of 20/80 to 95/5. It is preferable to use it in a ratio, and it is more preferable to use it in a ratio that is in the range of 30/70 to 90/10. Furthermore, it is preferably in the range of 60/40 to 90/10, more preferably in the range of 80/20 to 90/10, from the viewpoint of obtaining an active energy ray-curable resin composition having excellent coating film hardness. Is particularly preferred.

  The precursor (1) has an epoxy group derived from a compound having the glycidyl group and (meth) acryloyl group, and the epoxy equivalent of the precursor (1) is the acryloyl of the resulting acrylic polymer (a). It is preferably in the range of 150 to 500 g / eq, more preferably in the range of 150 to 250 g / eq, and more preferably in the range of 150 to 180 g in that it becomes easy to adjust the equivalent weight to the range of 145 to 750 g / eq. More preferably, it is in the range of / eq.

  The precursor (1) is, for example, a compound having the glycidyl group and the (meth) acryloyl group alone in the temperature range of 60 ° C. to 150 ° C. in the presence of a polymerization initiator, or the (meth) acrylic acid. Although it can manufacture by superposing | polymerizing in combination with ester, manufacture of the said precursor (1), the compound which has the said precursor (1) following this, a carboxyl group, and a (meth) acryloyl group, It is preferable to produce by solution polymerization in that it can be continuously performed.

  The solvent used when the precursor (1) is produced by the solution polymerization method is preferably a solvent having a boiling point of 80 ° C. or higher in consideration of the reaction temperature. For example, methyl ethyl ketone, methyl-n-propyl ketone, methyl 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, diisobutyl ketone, cyclohexanone, holon, etc. Ketone solvent; ether solvents such as n-butyl ether, diisoamyl ether, dioxane, etc .; acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, acetic acid-n-amyl, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Esters, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, etc .; toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1800, Swazol 310, Isopar E, Isopar G, Exxon naphtha No. 5, Exxon naphtha No. 6 and other hydrocarbon solvents. These may be used alone or in combination of two or more.

  Among the above solvents, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as isopropyl acetate and n-butyl acetate are preferred because of the excellent solubility of the resulting precursor (1).

  Examples of the catalyst used in the production of the precursor (1) include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 2,2′-azobis. Azo compounds such as-(4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate, 1,1'-bis- ( organic peroxides such as (t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, and t-hexylperoxy-2-ethylhexanoate, and hydrogen peroxide.

  When using a peroxide as a catalyst, it is good also as a redox type initiator using a peroxide with a reducing agent.

  The precursor (1) thus obtained can then be reacted with a compound having a carboxyl group and a (meth) acryloyl group to obtain an acrylic polymer (a). In the reaction method, for example, the precursor (1) is polymerized by a solution polymerization method, and a compound having a carboxyl group and a (meth) acryloyl group is added to the reaction system. Examples thereof include a method of appropriately using a catalyst such as phenylphosphine. The (meth) acryloyl group equivalent of the acrylic polymer (a) is preferably in the range of 200 to 6,200 g / eq. This is because the precursor (1), the carboxyl group and the (meth) acryloyl group It can adjust with the reaction ratio with the compound which has these. Usually, by reacting 1 mol of the epoxy group of the precursor (1) so that the carboxyl group is in the range of 0.1 to 0.9 mol, the acrylic polymer (a) ( It becomes easy to adjust the (meth) acryloyl equivalent to the preferred range.

  Examples of the compound having a carboxyl group and a (meth) acryloyl group used here include (meth) acrylic acid, (acryloyloxy) acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, and 1- [succinic acid]. Unsaturated monocarboxylic acids such as 2- (acryloyloxy) ethyl], 1- (2-acryloyloxyethyl) phthalate, hydrogen 2- (acryloyloxy) ethyl hexahydrophthalate, and lactone-modified products thereof; maleic acid, etc. Unsaturated dicarboxylic acid: carboxyl group-containing polyfunctional (meth) obtained by reacting acid anhydrides such as succinic anhydride and maleic anhydride with hydroxyl-containing polyfunctional (meth) acrylate monomers such as pentaerythritol triacrylate An acrylate etc. are mentioned. These may be used alone or in combination of two or more. Among these, (meth) acrylic acid, (acryloyloxy) acetic acid, acrylic acid 2 is easy in that the (meth) acryloyl group equivalent of the resulting acrylic polymer (a) can be easily adjusted to the above-mentioned preferable range. -Carboxyethyl and 3-carboxypropyl acrylate are preferred, and (meth) acrylic acid is particularly preferred.

  The acrylic polymer (a) thus obtained has in its molecular structure a hydroxyl group generated by a reaction between a glycidyl group and a carboxyl group. The acrylic acrylate resin (A) used in the present invention can be obtained by further reacting this hydroxyl group with anhydrous (meth) acrylic acid.

  Furthermore, from the viewpoint that it can be produced by a method that is easier to synthesize, glycidyl (meth) acrylate is used, and this is copolymerized with (meth) acrylate to obtain precursor (1). ) Is particularly preferably an acrylic polymer (a) obtained by reacting with (meth) acrylic acid.

  Next, a reaction of adding anhydrous (meth) acrylic acid to the acrylic polymer (a) obtained above is performed.

  The reaction between the anhydrous (meth) acrylic acid and the hydroxyl group in the acrylic polymer (a) is not particularly limited. For example, the glycidyl group, the carboxyl group, and the acryloyl group of the precursor (1) During the reaction with the compound having, or after obtaining the acrylic polymer (a), (meth) acrylic anhydride is added to the reaction system, and a catalyst such as triphenylphosphine is appropriately used in the temperature range of 80 to 120 ° C. And so on. The acrylic acrylate resin (A) thus obtained preferably has a (meth) acryloyl group equivalent in the range of 150 to 600 g / eq. This is because the acrylic polymer (a) and anhydrous (meth) It can be adjusted by the reaction ratio with acrylic acid. Usually, with respect to 1 mol of glycidyl groups in the precursor (1), the carboxyl group of the compound having a carboxyl group and an acryloyl group, and the (meth) acrylic anhydride is a hydroxyl group in the acrylic polymer (a). Of the acrylic polymer (a) obtained by reacting so that the total carboxyl group of the (meth) acrylic acid and the carboxyl group of (meth) acrylic acid produced by the reaction of It becomes easy to adjust the (meth) acryloyl equivalent to the preferred range. At this time, the hydroxyl value of the acrylic acrylate resin (A) is preferably in the range of 5 to 230 mgKOH / g.

  Further, in the present invention, from the viewpoint of easy preparation of the viscosity as a paint and good curability, and from the viewpoint of increasing the surface hardness of the obtained coating film, other than the acrylic acrylate resin (A) ( You may use together a (meth) acrylate (B).

  The (meth) acrylate (B) that can be used in the present application is not particularly limited, and examples thereof include various (meth) acrylate monomers and urethane (meth) acrylate.

  Examples of the (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate Relate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate , Ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- ( (Meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrophthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl ( (Meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, adamantyl Mono (meth) acrylates such as mono (meth) acrylate;

  Butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Di (meth) acrylates such as polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate;

  Trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate Tri (meth) acrylates such as;

  Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) Tetrafunctional or higher functional (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylylpropane hexa (meth) acrylate;

  And the (meth) acrylate etc. which substituted a part of above-mentioned various polyfunctional (meth) acrylate by the alkyl group etc. are mentioned.

  Examples of the urethane (meth) acrylate include urethane (meth) acrylate obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound.

  Examples of the polyisocyanate compound used as a raw material for the urethane (meth) acrylate include various diisocyanate monomers and a nurate polyisocyanate compound having an isocyanurate ring structure in the molecule.

  Examples of the diisocyanate monomer include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene. Aliphatic diisocyanates such as range isocyanate;

  Cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate;

  1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate And aromatic diisocyanates such as 1,4-phenylene diisocyanate and tolylene diisocyanate.

  Examples of the nurate type polyisocyanate compound having an isocyanurate ring structure in the molecule include those obtained by reacting a diisocyanate monomer with a monoalcohol and / or a diol. Examples of the diisocyanate monomer used in the reaction include the various diisocyanate monomers described above, and each may be used alone or in combination of two or more. Monoalcohols used in the reaction are hexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol, n- Octadecanol, n-nonadecanol and the like can be mentioned, and the diol includes ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1, Examples include 3-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol. These monoalcohols and diols may be used alone or in combination of two or more.

  Among these polyisocyanate compounds, the diisocyanate monomer is preferable, and the aliphatic diisocyanate and the alicyclic diisocyanate are more preferable in that a cured coating film having excellent processability can be obtained.

  The hydroxyl group-containing (meth) acrylate compound used as a raw material for the urethane (meth) acrylate is, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, Aliphatic (meth) acrylate compounds such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate;

  4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxy Examples include (meth) acrylate compounds having an aromatic ring in the molecular structure such as propyl acrylate. These may be used alone or in combination of two or more.

  Among these hydroxyl (meth) acrylate compounds, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentane are obtained because a cured coating film having excellent processability and high surface hardness can be obtained. An aliphatic (meth) acrylate compound having two or more (meth) acryloyl groups in the molecular structure such as acrylate is preferred. Furthermore, an aliphatic (meth) acrylate compound having three or more (meth) acryloyl groups in the molecular structure such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate in that a cured coating film having higher surface hardness can be obtained. Is more preferable.

  The method for producing the urethane (meth) acrylate includes, for example, the polyisocyanate compound, the hydroxyl group-containing (meth) acrylate compound, the isocyanate group of the polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate compound. The molar ratio [(NCO) / (OH)] with the hydroxyl group to be used is within a range of 1 / 0.95 to 1 / 1.05, within a temperature range of 20 to 120 ° C., if necessary. Examples of the method include using various urethanization catalysts.

  When the urethane (meth) acrylate is produced from the polyisocyanate compound and the (meth) acrylate compound having one hydroxyl group in the molecular structure, the reaction is pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa You may carry out by the type | system | group containing acrylate compounds, such as (meth) acrylate. Specifically, the urethane (meth) acrylate obtained by such a method is obtained by reacting a raw material containing the polyisocyanate compound, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Examples thereof include urethane (meth) acrylate obtained, urethane acrylate obtained by reacting a raw material containing polyisocyanate compound, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. .

  The weight average molecular weight (Mw) of the urethane (meth) acrylate thus obtained 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 ˜1,000.

  These compounds (B) may be used alone or in combination of two or more. Among them, a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule is preferable because a coating film with higher hardness can be obtained. Examples of the polyfunctional (meth) acrylate having three or more (meth) acryloyl groups include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. (Meth) acrylate is preferred. Moreover, as urethane (meth) acrylate as polyfunctional (meth) acrylate having three or more (meth) acryloyl groups, diisocyanate compound, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipenta Urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound having two or more (meth) acryloyl groups in the molecular structure such as erythritol pentaacrylate is preferred, and the diisocyanate compound and (meth) acryloyl group are A urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound having three or more is more preferable.

  The (meth) acrylate (B) that can be used in the present invention may be a multi-branched (meth) acrylate. As such a multi-branched (meth) acrylate, any of those provided with names such as dendrimer, core-shell, hyperbranch and the like can be used, for example, WO08 / 047620, JP What is provided with the manufacturing method in 2012-111963 gazette, Japanese translations of PCT publication No. 10-508052 gazette, etc. can use all suitably. Moreover, as what is marketed as such a multi-branched (meth) acrylate, SIRIUS501 etc. by Osaka Organic Chemical Co., Ltd. are mentioned.

  In the present invention, the use ratio of the acrylic acrylate resin (A) and the other (meth) acrylate (B) is not particularly limited, and the hardness and workability of the desired cured coating film, Can be appropriately set in view of transparency, scratch resistance, etc., but from the viewpoint of easily obtaining a coating film having particularly high surface hardness and good workability, the acrylic acrylate resin (A) and others The mass ratio (A) / (B) to (meth) acrylate (B) is preferably in the range of 10/90 to 100/0, particularly in the range of 30/70 to 90/10. Is preferable, and it is still more preferable that it is 30 / 70-80 / 20.

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

  The blending ratio of the inorganic fine particles (C) can be appropriately set according to the target performance, but from the point that a highly transparent cured coating film is obtained, the active energy ray-curable resin composition contains It is preferable to contain inorganic fine particles (C) in the range of 30 to 55 parts by mass with respect to 100 parts by mass of the nonvolatile content. That is, when the content of the inorganic fine particles (C) is 30 parts by mass or more, the effect of improving the hardness and scratch resistance of the coating film at the time of curing becomes remarkable. Moreover, when content of the said inorganic fine particle (C) is 55 mass parts or less, the storage stability and transparency of an active energy ray hardening-type resin composition will become favorable. Among them, the resin composition is excellent in storage stability, and a cured coating film having both high surface hardness, transparency, and curl resistance can be obtained, with respect to 100 parts by mass of the nonvolatile content in the composition. More preferably, the inorganic fine particles (C) are contained in the range of 35 to 50 parts by mass.

  The average particle diameter of the inorganic fine particles (C) is in the range of 95 to 250 nm as a value measured by a dynamic light scattering method in a state of being dispersed in the composition and the surface hardness and transparency of the coating film. From the point which is excellent in balance with property. That is, when the average particle diameter is 95 nm or more, the surface hardness of the obtained coating film is further increased. On the other hand, when it is 250 nm or less, the resulting coating film has good transparency. Especially, it is more preferable that the average particle diameter is in the range of 100 to 130 nm in that the hardness and transparency of the obtained coating film can be combined at a higher level.

  In the present invention, the average particle diameter of the inorganic fine particles (C) by the dynamic light scattering method is measured according to “ISO 13321”, calculated by the cumulant method, specifically, The active energy ray-curable resin composition is diluted with MIBK to prepare a MIBK solution having a concentration of 1.0%, and then this MIBK solution is used to measure a particle size (“ELSZ-2” manufactured by Otsuka Electronics Co., Ltd.). Is a measured value.

  Specific examples of the inorganic fine particles (C) used here include inorganic fine particles such as silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These may be used alone or in combination of two or more. Among these inorganic fine particles (C), silica fine particles are preferable because they are easily available and easy to handle. Examples of the silica fine particles include wet silica and dry silica. Examples of the wet silica include so-called precipitated silica or gel silica obtained by reacting sodium silicate with a mineral acid. Moreover, when using such wet silica, the average particle size of the inorganic fine particles dispersed in the resin composition finally obtained is that the average particle size in the dry state is 95 to 250 nm. It is preferable in that it is easy to adjust to a preferable value.

  On the other hand, dry silica fine particles are obtained, for example, by burning silicon tetrachloride in an oxygen or hydrogen flame, and have an average primary particle size of 3 to 100 nm, particularly 5 to 50 nm, before being dispersed. It is easy to adjust the average particle diameter of the inorganic fine particles (C) in the resin composition finally obtained to the above-mentioned range of 95 to 250 nm that the dry silica fine particles in the range are aggregated secondary particles. It is preferable from the point which becomes.

  Among the above-mentioned silica fine particles, dry silica fine particles are preferable in that a cured coating film having higher surface hardness can be obtained.

  In the present invention, the inorganic fine particles (C) may be those obtained by introducing a reactive functional group on the surface of the inorganic fine particles using a silane coupling agent to the various inorganic fine particles described above. By introducing a reactive functional group on the surface of the inorganic fine particles (C), the miscibility with the organic component such as the acrylic acrylate resin (A) and other (meth) acrylate (B) is increased, and dispersion stability is improved. Storage stability is improved.

  Examples of the silane coupling agent used here include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Minoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl- N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special Aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanate group Pyrtriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, etc. , Vinyl silane coupling agents;

  Diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-bridoxypropyl Epoxy-based silane coupling agents such as triethoxysilane;

  styrenic silane coupling agents such as p-styryltrimethoxysilane;

  3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (meth) Acryloxy silane coupling agent;

  N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltri Amino-based silane couplings such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane Agent;

  Ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane;

  Chloropropyl-based silane coupling agents such as 3-chloropropyltrimethoxysilane;

  Mercaptopropyl silane coupling agents, such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethinesilane;

  Sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide;

  Examples thereof include isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Among these, a (meth) acryloxy-based silane coupling agent is preferable in that a cured coating film having excellent miscibility with an organic component, high surface hardness, and excellent transparency is obtained, and 3-acryloxypropyltrimethyl is preferred. Methoxysilane and 3-methacryloxypropyltrimethoxysilane are more preferable.

  The resin composition of the present invention may contain a dispersion aid as necessary. Examples of the dispersion aid include phosphate ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, ethylene oxide-modified phosphate dimethacrylate, and the like. These may be used alone or in combination of two or more. Among these, ethylene oxide-modified phosphoric dimethacrylate is preferable because it is excellent in dispersion assist performance.

  Examples of commercially available dispersion aids include “Kayamar PM-21” and “Kayamer PM-2” manufactured by Nippon Kayaku Co., Ltd., “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd., and the like.

  When using the said dispersion | distribution adjuvant, it contains in 0.5-5.0 mass parts in 100 mass parts of resin compositions of this invention at the point used as a resin composition with higher storage stability. Is preferred.

  Moreover, the resin composition of this invention may contain the organic solvent. For example, in the case where the acrylic acrylate resin (A) is produced by a solution polymerization method, the organic solvent may contain the solvent used at that time as it is, or further add another solvent. May be. Or the organic solvent used at the time of manufacture of the said acrylic acrylate resin (A) may be removed once, and another solvent may be used. Specific examples of the solvent used include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether . These may be used alone or in combination of two or more. Among these, a ketone solvent and an ester solvent are preferable, and methyl isobutyl ketone is more preferable in that the resin composition has excellent storage stability and excellent paintability when used as a paint.

  The resin composition of the present invention further comprises an ultraviolet absorber, an antioxidant, a silicon-based additive, organic beads, a fluorine-based additive, a rheology control agent, a defoaming agent, a release agent, an antistatic agent, and an antifogging agent. Further, additives such as a colorant, an organic solvent, and an inorganic filler may be contained.

  Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 Triazine derivatives such as 2,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like.

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

  Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl. Examples include polyorganosiloxanes having alkyl groups and phenyl groups, such as polysiloxane copolymers and amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes having polyether-modified acrylic groups, and polydimethylsiloxanes having polyester-modified acrylic groups. It is done. These may be used alone or in combination of two or more.

  Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads. The preferable value of the average particle diameter of these organic beads is in the range of 1 to 10 μm. These may be used alone or in combination of two or more.

  Examples of the fluorine-based additive include DIC Corporation “Megafac” series. These may be used alone or in combination of two or more.

  Examples of the release agent include “Tegorad 2200N”, “Tegorad 2300”, “Tegorad 2100” manufactured by Evonik Degussa, “UV3500” manufactured by BYK Chemie, “Paintad 8526” manufactured by Toray Dow Corning, and “SH-29PA”. Or the like. These may be used alone or in combination of two or more.

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

  The amount of the various additives used is preferably in a range where the effect is sufficiently exhibited and ultraviolet curing is not inhibited. Specifically, in each 100 parts by mass of the resin composition of the present invention, 0.01 to 40 masses are used. It is preferable to use within the range of parts.

  The resin composition of the present invention preferably further contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, Various benzophenones such as Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

  Xanthones, thioxanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;

  Α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

  3,3′-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Tylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethyl Ketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, 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- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine, 2 , 4-Bis-trichloromethyl-6- (4-ethoxy Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazineanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, etc. Is mentioned. These may be used alone or in combination of two or more.

  Among the photopolymerization initiators, 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, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino One or more mixed systems selected from the group of phenyl) -butan-1-one By are more active against a broad range of wavelengths of light is preferred because highly curable coating is obtained.

  Commercially available products of the photopolymerization initiator include, for example, “Irgacure-184”, “Irgacure-149”, “Irgacure-261”, “Irgacure-369”, “Irgacure-500”, “Irgacure-” manufactured by Ciba Specialty Chemicals. "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; "Kayacure-DETX", "Kayacure-MBP" manufactured by Nippon Kayaku Co., Ltd. ”,“ Kayaki “A-DMBI”, “Kayacure-EPA”, “Kayacure-OA”; “Bicure-10”, “Bicure-55” manufactured by Stowa Chemical Co., Ltd. “Trigonal P1” manufactured by Akzo Co., Ltd .; “Sandray 1000” manufactured by Sands Co .; “Deep” manufactured by Apjon; “QuantaCure-PDO”, “QuantaCure-ITX”, “QuantaCure-EPD”, etc. manufactured by Ward Brenkinsop.

  The amount of the photopolymerization initiator used is an amount that can sufficiently exhibit the function as a photopolymerization initiator, and is preferably within a range that does not cause precipitation of crystals and physical properties of the coating film. It is preferable to use in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the resin composition, and it is particularly preferable to use in the range of 0.1 to 10 parts by mass.

  The resin composition of the present invention may further use various photosensitizers in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

  In the present invention, a thermal polymerization initiator can also be used. Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-). Azo compounds such as 2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate, 1,1′-bis- (t-butylperoxy) cyclohexane , Organic peroxides such as t-amylperoxy-2-ethylhexanoate and t-hexylperoxy-2-ethylhexanoate, hydrogen peroxide, and the like. It is preferably used in the range of 0.05 to 20 parts by mass.

  The method for producing the active energy ray-curable resin composition of the present invention includes, for example, a disperser, a disperser having a stirring blade such as a turbine blade, a paint shaker, a roll mill, a ball mill, an attritor when the inorganic fine particles (C) are used in combination. , A method of mixing and dispersing the inorganic fine particles (C) in the acrylic acrylate resin (A) using a dispersing machine such as a sand mill, a bead mill, or the inorganic fine particles (C), the acrylic acrylate resin (A), The method of mixing and dispersing in the resin component which consists of said (meth) acrylate (B) is mentioned. When the inorganic fine particles (C) are wet silica fine particles, a uniform and stable dispersion can be obtained when any of the above-described dispersers is used. On the other hand, when the inorganic fine particles (C) are dry silica fine particles, it is preferable to use a ball mill or a bead mill in order to obtain a uniform and stable dispersion.

  The ball mill that can be preferably used in producing the active energy ray-curable resin composition of the present invention has, for example, a vessel filled with a medium inside, a rotating shaft, and a rotating shaft coaxial with the rotating shaft. A stirring blade that is rotated by the rotational drive of the rotating shaft, a raw material supply port installed in the vessel, a dispersion outlet installed in the vessel, and a portion where the rotating shaft passes through the vessel. The shaft seal device has a structure in which the shaft seal device has two mechanical seal units, and the seal portions of the two mechanical seal units are sealed with an external seal liquid. A wet ball mill is mentioned.

  That is, a method for producing an active energy ray-curable resin composition containing inorganic fine particles (C) includes, for example, a vessel filled with media inside, a rotating shaft, and a rotating shaft coaxially with the rotating shaft. A stirring blade that is rotated by the rotational drive of the rotating shaft, a raw material supply port installed in the vessel, a dispersion outlet installed in the vessel, and a portion where the rotating shaft passes through the vessel. A wet ball mill having a shaft seal device, wherein the shaft seal device has two mechanical seal units, and the seal portions of the two mechanical seal units are sealed with an external seal liquid. Components of the inorganic fine particles (C), the resin (A), and the (meth) acrylate (B) are supplied from the supply port of the wet ball mill as an apparatus. The resin component is supplied to the vessel, and the rotating shaft and the stirring blade are rotated in the vessel to stir and mix the medium and the raw material, whereby the inorganic fine particles (C) are pulverized and the inorganic fine particles ( C) is dispersed in the resin component, and then discharged from the outlet.

  The active energy ray-curable resin composition of the present invention can be used for coating applications. The coating material can be used as a coating layer that protects the surface of the substrate by applying the coating onto various substrates and irradiating and curing the active energy rays. In this case, the coating material of the present invention may be directly applied to the surface protection member, or a material applied on a plastic film may be used as the protective film. Or you may use what applied the coating material of this invention on the plastic film, and formed the coating film as optical films, such as an antireflection film, a diffusion film, and a prism sheet. The coating film obtained using the paint of the present invention is characterized by high surface hardness and excellent transparency, so it can be applied to various types of plastic film with a film thickness according to the application, and used as a protective film or film It can be used as a molded product.

  Furthermore, in order to obtain a coating film, a heat treatment step can be included before or after irradiation with active energy rays. By performing the heat treatment, a coating film with 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, but from the viewpoint of further increasing the surface hardness, it is in the range of 80 to 200 ° C. and 1 to 180. It is preferable to perform processing for about a minute.

  The plastic film is, for example, a plastic film made of polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, cyclic olefin, polyimide resin, or the like. And plastic sheets.

  Among the plastic films, the triacetyl cellulose film is a film that is particularly suitably used for the polarizing plate application of a liquid crystal display. However, since the thickness is generally as thin as 40 to 100 μm, the surface even when a hard coat layer is installed. It is difficult to make the hardness sufficiently high, and there is a feature that it is easily curled. The coating film made of the resin composition of the present invention has a high surface hardness, excellent curl resistance, workability, and transparency even when a triacetyl cellulose film is used as a base material. Can be used. When the triacetyl cellulose film is used as a substrate, the coating amount when applying the coating material of the present invention is applied so that the film thickness after drying is in the range of 1 to 20 μm, preferably in the range of 2 to 15 μm. It is preferable. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Among the plastic films, examples of the polyester film include polyethylene terephthalate, and the thickness thereof is generally about 100 to 300 μm. Although it is a cheap and easy to process film, it is a film used for various applications such as a touch panel display. However, it is very soft and has a feature that it is difficult to sufficiently increase the surface hardness even when a hard coat layer is provided. When the polyethylene film is used as a substrate, the coating amount when applying the coating material of the present invention is in the range of 5 to 100 μm, preferably 7 to 80 μm after drying, depending on the application. It is preferable to apply as described above. In general, when a paint is applied with a film thickness exceeding 20 μm, it tends to curl greatly compared to the case where it is applied with a relatively thin film thickness, but the paint of the present invention is excellent in curling resistance. Since it has characteristics, curling hardly occurs even when it is applied with a relatively high film thickness exceeding 20 μm, and it can be suitably used. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Among the plastic films, the polymethyl methacrylate film is generally relatively thick and strong, with a thickness of about 100 to 2,000 μm, so it is suitable for applications that require a particularly high surface hardness, such as applications for front plates of liquid crystal displays. It is the film used for. When the polymethylmethacrylate film is used as a base material, the coating amount when applying the coating material of the present invention is in the range of 3 to 100 μm, preferably 7 to 80 μm after drying, depending on the application. It is preferable to apply so that it becomes. In general, when a coating is applied on a relatively thick film such as a polymethyl methacrylate film to a film thickness exceeding 30 μm, it becomes a laminated film having a high surface hardness, but the transparency tends to decrease. However, since the coating material of the present invention has very high transparency as compared with the conventional coating material, a laminated film having both high surface hardness and transparency can be obtained. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Examples of the active energy rays irradiated when the coating material of the present invention is cured to form a coating film include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED lamp as a light source is used, and the amount of light, the arrangement of the light sources, and the like are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 50 m / min for one lamp having a light quantity that is usually in the range of 80 to 160 W / cm. On the other hand, in the case of curing with an electron beam, it is preferably cured with an electron beam accelerator having an accelerating voltage that is usually in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m / min.

  Moreover, the base material to which the paint of the present invention is applied can be suitably used not only as a plastic film but also as a surface coating agent for various plastic molded products, for example, cellular phones, 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 bonding method.

  The coating method is a method in which the paint is spray-coated or coated as a top coat on a molded product using a printing device such as a curtain coater, roll coater, gravure coater, etc., and then cured by irradiation with active energy rays. is there.

  In the transfer method, a transfer material obtained by applying the above-described coating material of the present invention on a substrate sheet having releasability is adhered to the surface of the molded product, and then the substrate sheet is peeled off to top coat the surface of the molded product. , And then curing by irradiation with active energy rays, or by bonding the transfer material to the surface of the molded article, curing by irradiation with active energy rays, and then peeling the substrate sheet A method of transferring the top coat to the surface is mentioned.

  On the other hand, in the sheet bonding method, a protective sheet having a coating film made of the paint of the present invention on a base sheet, or a protective sheet having a coating film made of the paint and a decorative layer on a base sheet is plastic molded. In this method, a protective layer is formed on the surface of the molded product by bonding to the product.

  Among these, the coating material of the present invention can be preferably used for the transfer method and the sheet adhesion method.

  In the transfer method, first, a transfer material is prepared. The transfer material can be produced by, for example, applying the paint alone or mixed with a polyisocyanate compound on a base sheet and heating to semi-cure (B-stage) the coating film. .

  In order to produce a transfer material, first, the above-described paint of the present invention is applied onto a base material sheet. Examples of the method for applying the paint include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a coating method such as a comma coating method, and a printing method such as a gravure printing method and a screen printing method. The coating thickness is preferably such that the thickness of the coated film after curing is 1 to 50 μm, since the wear resistance and chemical resistance are good, and 3 to 40 μm. It is more preferable to paint on.

  After coating the coating material on the substrate sheet by the previous method, the coating film is heat-dried and the coating film is semi-cured (B-tage). The heating is usually 55 to 160 ° C, preferably 100 to 140 ° C. The heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes.

  For example, the surface protective layer of the molded product using the transfer material may be formed by, for example, bonding the B-staged resin layer of the transfer material and the molded product, and then irradiating active energy rays to cure the resin layer. To do. Specifically, for example, the B-staged resin layer of the transfer material is adhered to the surface of the molded product, and then the B-staged resin layer of the transfer material is removed by peeling the base sheet of the transfer material. After transferring onto the surface of the molded product, energy rays are cured by irradiation with active energy rays to cure the resin layer by cross-linking (transfer method), or the transfer material is sandwiched in a mold and the resin is placed in the cavity. At the same time as injection filling to obtain a resin molded product, a transfer material is adhered to the surface, the substrate sheet is peeled off and transferred onto the molded product, and then the energy beam is cured by irradiation with active energy rays to crosslink and cure the resin layer. And the like (molding simultaneous transfer method).

  Next, the sheet bonding method is specifically a resin layer formed by bonding a base sheet and a molded product of a protective layer forming sheet prepared in advance and then thermosetting by heating to form a B-stage. A method of performing cross-linking curing (post-adhesion method), and the protective layer forming sheet is sandwiched in a molding die, and a resin is injected and filled in the cavity to obtain a resin molded product, and at the same time, the surface and the protective layer are formed. For example, there may be mentioned a method in which a resin sheet is bonded and then thermally cured by heating to crosslink and cure the resin layer (molding simultaneous bonding method).

  Next, the coating film of the present invention is a coating film formed by applying and curing the coating material of the present invention on the above-described plastic film, or coating and curing the coating material of the present invention as a surface protective agent for plastic molded products. 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 film, as described above, a film obtained by applying the paint of the present invention on a plastic film and irradiating an active energy ray is used as a protective film for a polarizing plate used for a liquid crystal display, a touch panel display or the like. It is preferable to use as the coating film hardness. Specifically, when the paint of the present invention is applied to a protective film of a polarizing plate used for a liquid crystal display, a touch panel display, etc., and the film is formed by irradiating and curing active energy rays, the cured coating film has a high hardness. It becomes a protective film that combines high transparency. In the use of a protective film for a polarizing plate, an adhesive layer may be formed on the opposite surface of the coating layer to which the paint of the present invention is applied.

  Hereinafter, the present invention will be described more specifically with reference to specific production examples and examples, but the present invention is not limited to these examples. Unless otherwise indicated, all parts and percentages in the examples are based on mass.

  In the Example of this invention, a weight average molecular weight (Mw) is the value measured on condition of the following using a gel permeation chromatograph (GPC).

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Tosoh Corporation guard column HXL-H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 1.0 ml / min Standard; polystyrene sample; 0.4% by weight tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

[Pencil hardness test]
1. Preparation method of test piece The active energy ray-curable resin composition obtained in each Example and Comparative Example was applied on a film with a bar coater so as to have a predetermined film thickness after curing, and irradiated with active energy rays. And the laminated film which has a cured coating film by the heat processing was obtained.
2. Pencil Hardness Test Method The surface of the cured coating film obtained above was evaluated by a pencil scratch test with a load of 500 g according to JIS K 5400. The test was conducted five times, and the hardness one degree lower than the hardness at which scratches were made once or more was defined as the pencil hardness of the coating film.

[Abrasion resistance test]
1. Preparation method of cured coating film A coating film was prepared in the same manner as in the pencil hardness test.
2. Steel Wool Resistance Test Steel Wool (Japan Steel Wool Co., Ltd. “Bonster # 0000” 0.5 g is wrapped with a disc-shaped indenter with a diameter of 2.4 cm, and a 1 kg weight load is applied to the indenter to coat the film. The film surface was reciprocated 100 times, and the haze value of the coating film before and after the test was measured using “Haze Computer HZ-2” manufactured by Suga Test Instruments Co., Ltd. and evaluated by the difference δH. It is a cured coating film with excellent scratch resistance.

[Bendability test]
1. Preparation method of cured coating film A coating film was prepared on a polyester film (film thickness 75 μm) by the same method as in the pencil hardness test (film thickness after curing: 15 μm).
2. Bendability test Using a mandrel tester (TP Tester's “Bend Tester”), the laminated film is wrapped around a test bar, and a test is performed to visually check whether a cured coating layer of the film is cracked. The minimum diameter of the test bar that does not cause cracks was taken as the evaluation result. The smaller the minimum diameter, the better the bendability.

Synthesis Example 1: Production of acrylic acrylate resin (A-1) 96 parts by mass of methyl isobutyl ketone was charged in a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, and the system temperature was 110 while stirring. The temperature was raised to 0 ° C., and then from 130 parts by mass of glycidyl methacrylate, 14 parts by mass of methyl methacrylate and 6 parts by mass of t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Emulsifier Co., Ltd.) The resulting mixture was dropped from the dropping funnel over 3 hours, and then maintained at 110 ° C. for 15 hours. Next, after the temperature was lowered to 90 ° C., 0.1 part by weight of methoquinone, 33 parts by weight of acrylic acid and 70 parts by weight of methacrylic anhydride were added, 3 parts by weight of triphenylphosphine was added, and the temperature was further raised to 110 ° C. It was confirmed that the acid value was 3 mgKOH / g or less. Subsequently, it diluted with methyl isobutyl ketone and the methyl isobutyl ketone solution (nonvolatile content 50.0 mass%) of acrylic acrylate resin (A-1) was obtained. Each property value of the acrylic acrylate resin (A-1) was as follows.
Weight average molecular weight (Mw): 36,000,
Theoretical acryloyl group equivalent: 180 g / eq,
Hydroxyl value 104 mg KOH / g.

Synthesis Examples 2-6
In Synthesis Example 1, acrylic acrylate resins (A-2) and (A) are prepared in the same manner as in Synthesis Example 1 except that the usage ratios of glycidyl methacrylate, methyl methacrylate, acrylic acid, and methacrylic anhydride are as shown in Table 1. -3) and (A-4) were obtained. Further, as Synthesis Examples 5 and 6 in which methacrylic anhydride was not used, synthesis was performed at the usage ratio shown in Table 1 to synthesize comparative resins (A′-1) and (A′-2). The property values of the resins obtained in each synthesis example are also shown in Table 1.

Footnotes in Table 1 (Meth) acryloyl group equivalent g / eq: Theoretical (meth) acryloyl group equivalent in terms of solid content derived from acrylic acid and methacrylic anhydride Hydroxyl value mgKOH / g: Reaction between acrylic acid and glycidyl group Calculated by subtracting the hydroxyl value of the reaction of methacrylic anhydride with this hydroxyl group from the hydroxyl value generated by

Example 1
Active energy ray curable resin by adding 40 parts by mass of PETA (Aronix M-305, manufactured by Toagosei Co., Ltd.) and 4 parts by mass of Irgacure 184 to 120 parts by mass of the acrylic acrylate resin (A-1) obtained in Synthesis Example 1. A composition was obtained.

This active energy ray-curable resin composition was applied onto a PET film (Toyobo 75 μA 4300) so as to have a dry film thickness of 15 μm, and cured at 500 mJ / cm ² with an irradiator equipped with a high-pressure mercury lamp. A laminated film was obtained.

Examples 2-8 and Comparative Examples 1-2
In the same manner as in Example 1, an active energy ray-curable resin composition was prepared by blending each material with the blending amount (mass basis) shown in Table 1. In Example 7, the cured coating film was further subjected to a heat treatment at 150 ° C. for 30 minutes. In Example 8, the inorganic fine particles (C) were blended, and the preparation method was dispersion by a wet ball mill. The results are shown in Table 2.

Each condition of dispersion by the wet ball mill is as follows.
Media: Zirconia beads having a median diameter of 100 μm Filling ratio of resin composition with respect to the inner volume of the mill: 70% by volume
Peripheral speed at the tip of the stirring blade: 11 m / sec
Flow rate of resin composition: 200 ml / min
Dispersion time: 60 minutes

Abbreviations in Table 2 are as follows.
Aronix M-305: Pentaerythritol tetraacrylate / dipentaerythritol triacrylate manufactured by Toagosei Co., Ltd. Aronics M-404: Dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate manufactured by Toagosei Co., Ltd. Aerosil R7200: Nippon Aerosil Co., Ltd. “Aerosil R7200” manufactured by “Aerosil R7200” having a primary average particle diameter of 12 nm and having a (meth) acryloyl group on the particle surface

As a result of intensive studies to solve the above problems, the present inventors have made a weight average molecular weight obtained by reacting methacrylic anhydride with an acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth) acryloyl group. The active energy ray-curable resin composition containing an acrylic acrylate resin (A) having an (Mw) in the range of 3,000 to 80,000 as an essential component exhibits a very high surface hardness after curing. In addition, the present inventors have found that the processability (flexibility) when coated and cured on a plastic substrate is high, and thus completed the present invention.

That is, in the present invention, the acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth) acryloyl group is reacted with methacrylic anhydride , and the weight average molecular weight (Mw) is in the range of 3,000 to 80,000. An active energy ray-curable resin composition containing an acrylic acrylate resin (A) as an essential component, a paint containing the same, a cured coating film, and a laminated film having the coating layer To do.

The active energy ray-curable resin composition of the present invention has a weight average molecular weight (Mw) of 3 obtained by reacting an acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth) acryloyl group with methacrylic anhydride. The acrylic acrylate resin (A) is in the range of 8,000 to 80,000.

The acrylic acrylate resin (A) is, for example, a homopolymer of a compound having a glycidyl group and a (meth) acryloyl group, or a copolymer of the compound and a (meth) acrylic ester (hereinafter referred to as “precursor”). Resin obtained by reacting methacrylic anhydride with the acrylic polymer (a) obtained by reacting a compound having a carboxyl group and a (meth) acryloyl group. Is mentioned. An acrylic acrylate resin (A) that can be used in the present invention can be obtained by reacting methacrylic anhydride with a hydroxyl group produced by a reaction between a glycidyl group and a carboxyl group.

Next, a reaction of adding methacrylic anhydride to the acrylic polymer (a) obtained above is performed.

The reaction between the methacrylic anhydride and the hydroxyl group in the acrylic polymer (a) is not particularly limited. For example, a compound having a glycidyl group, a carboxyl group, and an acryloyl group in the precursor (1) Or after the acrylic polymer (a) is obtained, methacrylic anhydride is added to the reaction system, and the reaction is carried out using a catalyst such as triphenylphosphine in a temperature range of 80 to 120 ° C. Can be mentioned. The acrylic acrylate resin (A) thus obtained preferably has a (meth) acryloyl group equivalent in the range of 150 to 600 g / eq. This is because the acrylic polymer (a), methacrylic anhydride and The reaction ratio can be adjusted. Usually, with respect to 1 mol of the glycidyl group of the precursor (1), a carboxyl group of a compound having a carboxyl group and an acryloyl group and methacrylic anhydride are reacted with a hydroxyl group in the acrylic polymer (a). The (meth) of the acrylic polymer (a) obtained by reacting so that the total carboxyl group of the (meth) acrylic acid generated by cleavage is in the range of 0.9 to 1.1 mol. It becomes easy to adjust the acryloyl equivalent to the above preferred range. At this time, the hydroxyl value of the acrylic acrylate resin (A) is preferably in the range of 5 to 230 mgKOH / g.

Claims (15)

An acrylic acrylate having a weight average molecular weight (Mw) in the range of 3,000 to 80,000, obtained by reacting an acrylic polymer (a) having a glycidyl group, a hydroxyl group and a (meth) acryloyl group with anhydrous (meth) acrylic acid. An active energy ray-curable resin composition comprising a resin (A) as an essential component. The active energy ray-curable resin composition according to claim 1, wherein the acrylic methacrylate resin (A) has a (meth) acryloyl group equivalent in a range of 150 to 600 g / eq. The active energy ray-curable resin composition according to claim 1 or 2, further comprising (meth) acrylate (B) other than the acrylic acrylate resin (A). The active energy ray-curable resin composition according to claim 3, wherein the (meth) acrylate (B) is a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule. The active energy ray-curable resin composition according to claim 3, wherein the (meth) acrylate (B) has a hydroxyl group. 4. The activity according to claim 3, wherein the (meth) acrylate is dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, pentalysitol tetraacrylate, pentaerythritol triacrylate, or pentaerythritol diacrylate. Energy ray curable resin composition. The active energy ray-curable resin composition according to any one of claims 1 to 6, further comprising inorganic fine particles (C). The active energy ray-curable resin composition according to claim 7, wherein the inorganic fine particles (C) are dry silica. The acrylic acrylate resin (A) reacts (meth) acrylic acid and anhydrous (meth) acrylic acid with an acrylic polymer obtained by polymerizing a compound having a glycidyl group and a (meth) acryloyl group as essential components. The active energy ray-curable resin composition according to claim 1, which is a resin obtained by allowing the resin to be obtained. The active energy ray-curable resin composition according to claim 9, wherein the acrylic polymer has a hydroxyl value in the range of 5 to 230 mgKOH / g. A paint comprising the active energy ray-curable resin composition according to any one of claims 1 to 10. A coating film obtained by curing the paint according to claim 11. The coating film according to claim 12, wherein the curing includes a heat treatment step of 60 ° C. or higher. A laminated film comprising the coating film according to claim 12 or 13 on one side or both sides of a plastic film. The laminated film according to claim 14, wherein the thickness of the coating film is in the range of 1 to 100 μm.