JP5812328B2 - Active energy ray-curable resin composition and film using the same - Google Patents

Description

  In particular, the present invention provides an active energy ray curable coating for coatings that provides a high hardness even when applied to a thin plastic substrate such as a film substrate, and also provides a cured coating with excellent flexibility. The present invention relates to a resin composition and a film substrate having a cured layer obtained by curing the composition.

  Protective films used for the purpose of protecting the surface of molded products and displays and making them difficult to scratch are polyethylene terephthalate resin film (hereinafter abbreviated as “PET film”) and acetylated cellulose resin film (hereinafter “TAC film”). It is obtained by applying a resinous hard coat agent on a plastic film substrate such as (abbreviated as) and setting a hard coat layer. The performance required for the hard coat layer is that the cured coating film has a high hardness so that it is difficult to be scratched, and also has a high flexibility so that cracking does not occur even when a protective film is used to protect the bent portion. And having curling resistance that does not cause curling due to curing shrinkage when cured.

  As a technique for increasing the hardness of the hard coat layer in order to improve the scratch resistance of the protective film, for example, a resin composition containing dipentaerythritol hexaacrylate and tripentaerythritol octaacrylate has a thickness of 80 μm. A technique is known in which a film obtained by applying and curing on a TAC film with a film thickness of 12 μm exhibits a hardness of about 5H pencil hardness (see Patent Document 1). However, although the cured coating film of such a resin composition has a high surface hardness, the curl generated at the time of curing is large, and since it is hard and brittle, cracking occurs when the coating film is bent. It was a thing.

JP 2009-286924 A

  Therefore, the problem to be solved by the present invention is to provide an active energy ray-curable resin composition in which a cured coating film has both high surface hardness and flexibility, and is excellent in curling resistance during curing. It is in.

  As a result of intensive studies to solve the above problems, the present inventors contain urethane (meth) acrylate (A), tripentaerythritol octa (meth) acrylate (B) and a polymerization initiator (C) as essential components. In order to complete the present invention, the active energy ray-curable resin composition characterized in that the cured coating film has both high surface hardness and flexibility and excellent curling resistance during curing. It came.

  That is, the present invention includes an active energy ray-curable resin characterized by containing urethane (meth) acrylate (A), tripentaerythritol octa (meth) acrylate (B) and a polymerization initiator (C) as essential components. Relates to the composition.

  The present invention also provides a film comprising a cured layer obtained by curing the active energy ray-curable resin composition.

  According to the present invention, compared with the conventional hard coating agent, the active energy ray curable type has a higher level of surface hardness and flexibility of the cured coating film and is excellent in curling resistance during curing. A resin composition can be obtained.

  In the present invention, by containing urethane (meth) acrylate (A) as an essential component of the resin composition, a cured coating film that is rich in flexibility and excellent in curling resistance during curing can be obtained.

  The urethane (meth) acrylate (A) is, for example, a urethane (meth) acrylate obtained by reacting a polyisocyanate compound (a1) with a (meth) acrylate compound (a2) having one hydroxyl group in the molecular structure. Urethane (meth) acrylate (A1), polyisocyanate compound (a3), (meth) acrylate compound (a4) having one hydroxyl group in the molecular structure, and polyol compound (a5) are reacted ( A2).

  First, the urethane (meth) acrylate (A1) will be described. Examples of the polyisocyanate compound (a1) used as a raw material for the urethane (meth) acrylate (A1) include various diisocyanate monomers and nurate type polyisocyanate compounds 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 (a1), the diisocyanate monomer is preferable, and the aliphatic diisocyanate and the alicyclic diisocyanate are more preferable in that a cured coating film having excellent flexibility is obtained.

  The (meth) acrylate compound (a2) having one hydroxyl group in the molecular structure used as a raw material for the urethane (meth) acrylate (A1) is, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxy Aliphatic (meth) acrylate compounds such as butyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, 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 (meth) acrylate compounds (a2) having one hydroxyl group in the molecular structure, glycerin diacrylate and trimethylolpropane diene are obtained in that a cured coating film having excellent flexibility 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, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like is preferable. Furthermore, an aliphatic (meth) acrylate compound having three or more (meth) acryloyl groups in the molecular structure such as pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. in that a cured coating film having higher surface hardness can be obtained. Is more preferable.

  The method for producing the urethane (meth) acrylate (A1) includes, for example, the polyisocyanate compound (a1) and the (meth) acrylate compound (a2) having one hydroxyl group in the molecular structure. The molar ratio [(NCO) / (OH)] between the isocyanate group of the compound (a1) and the hydroxyl group of the (meth) acrylate compound (a2) having one hydroxyl group in the molecular structure is 1 / 0.0. Examples of the method include a method in which the catalyst is used at a ratio in the range of 95 to 1 / 1.05 and is used in a temperature range of 20 to 120 ° C. using a known and commonly used urethanization catalyst as necessary.

  When the urethane (meth) acrylate (A1) is produced from the polyisocyanate compound (a1) and the (meth) acrylate compound (a2) having one hydroxyl group in the molecular structure, the reaction is pentaerythritol tetra ( You may carry out by the type | system | group containing acrylate compounds other than the said (meth) acrylate compound (a2), such as a (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Specifically, the urethane (meth) acrylate (A1) obtained by such a method contains the polyisocyanate compound (a1), pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Reacting a raw material containing urethane (meth) acrylate obtained by reacting the raw material to be reacted, the polyisocyanate compound (a1), dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate And urethane acrylate obtained by the above method. The product obtained by the reaction preferably has a weight average molecular weight (Mw) in the range of 400 to 5,000, in that a cured coating film having both flexibility and high surface hardness is obtained, and 800 to A range of 3,500 is more preferable.

In the present invention, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) under the following conditions. The weight average molecular weight (Mw) of the composition can be measured by the same method as for ordinary resins.

Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

  Next, the urethane (meth) acrylate (A2) will be described. Examples of the polyisocyanate compound (a3) used as a raw material for the urethane (meth) acrylate (A2) include the polyisocyanate compound (a1) listed as a raw material for the urethane (meth) acrylate (A1).

  Among these polyisocyanate compounds (a3), the diisocyanate monomer is preferable in that a cured coating film having higher flexibility and high surface hardness can be obtained.

  The (meth) acrylate compound (a4) having one hydroxyl group in the molecular structure used as the raw material for the urethane (meth) acrylate (A2) is listed as the raw material for the urethane (meth) acrylate (A1). An acrylate compound (a2) etc. are mentioned. Among these, 2 (meth) acryloyl groups are present in the molecular structure of glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. in that a cured coating film having a higher surface hardness can be obtained. One or more aliphatic (meth) acrylate compounds are preferable, and an aliphatic (meth) acrylate compound having three or more (meth) acryloyl groups in a molecular structure such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate is more preferable.

  Examples of the polyol compound (a5) used as a raw material for the urethane (meth) acrylate (A2) include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,3-butanediol. Aliphatic polyols such as 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin;

  Hydroquinone, 2-methylhydroquinone, 1,4-benzenedimethanol, 3,3′-biphenyldiol, 4,4′-biphenyldiol, biphenyl-3,3′-dimethanol, biphenyl-4,4′-dimethanol Bisphenol A, bisphenol B, bisphenol F, bisphenol S, 1,4-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, naphthalene-2,6-dimethanol, 4,4 ', 4' '-Aromatic polyols such as methylidyne trisphenol;

  Polyether modification obtained by ring-opening polymerization of the aliphatic polyol and various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Aliphatic polyols;

  Polyether modification obtained by ring-opening polymerization of the aromatic polyol and various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Aromatic polyols;

  Lactone-modified aliphatic polyol obtained by polycondensation of the aliphatic polyol and a lactone compound such as ε-caprolactone:

  Lactone-modified aromatic polyol obtained by polycondensation of the aromatic polyol and a lactone compound such as ε-caprolactone:

  An aromatic ring-containing polyester polyol obtained by reacting an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid or pimelic acid with the aromatic polyol;

  Examples thereof include aromatic ring-containing polyester polyols obtained by reacting aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid and the like with the aliphatic polyols. These may be used alone or in combination of two or more. Among them, bisphenol compounds such as bisphenol A, bisphenol B, bisphenol S, and bisphenol F, and various cyclic ether compounds can be developed in that a cured coating film having excellent flexibility and excellent curling resistance during curing can be obtained. A polyether-modified bisphenol compound obtained by ring polymerization is preferred.

  The method for producing the urethane (meth) acrylate (A2) includes, for example, a polyol compound (a5) and a polyisocyanate compound (a3), a hydroxyl group of the polyol compound (a5), and a polyisocyanate compound (a3). The molar ratio [(OH) / (NCO)] with the isocyanate group it has is used in a ratio that is in the range of 1 / 1.5-1 / 2.5, within the temperature range of 20-120 ° C., if necessary Reaction is performed using a known and usual urethanization catalyst to obtain an isocyanate group-containing intermediate as a reaction product, and then the intermediate and the (meth) acrylate compound (a4) having one hydroxyl group in the molecular structure The mole of the hydroxyl group of the (meth) acrylate compound (a4) having one hydroxyl group in the molecular structure and the isocyanate group of the intermediate [(OH) / (NCO)] is used so as to be in the range of 1 / 0.95 to 1 / 1.05. The method performed using it etc. are mentioned.

  In addition, the method for producing the urethane (meth) acrylate (A2) includes, for example, the polyol compound (a5), the polyisocyanate compound (a3), and a (meth) acrylate compound having one hydroxyl group in the molecular structure. A method in which (a4) is charged all at once and reacted, or after reacting the polyisocyanate compound (a3) with the (meth) acrylate compound (a4) having one hydroxyl group in the molecular structure, the polyol compound (a5 ) Is reacted.

  When producing the urethane (meth) acrylate (A2) from the polyisocyanate compound (a3), the (meth) acrylate compound (a4) having one hydroxyl group in the molecular structure, and the polyol compound (a5), The reaction may be performed in a system containing an acrylate compound other than the (meth) acrylate compound (a4), such as pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa (meth) acrylate. Specifically, the urethane (meth) acrylate (A2) obtained by such a method includes the polyisocyanate compound (a1), pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Urethane (meth) acrylate obtained by reacting a raw material containing a polyol compound (a5), the polyisocyanate compound (a1), dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate And urethane (meth) acrylate obtained by reacting a raw material containing the polyol compound (a5). The product obtained by the reaction preferably has a weight average molecular weight (Mw) in the range of 400 to 5,000, in that a cured coating film having both flexibility and high surface hardness is obtained, and 800 to A range of 3,500 is more preferable.

  Among these urethane (meth) acrylates (A), the urethane (meth) acrylate is characterized in that a cured coating film having both higher flexibility and surface hardness and excellent curling resistance during curing can be obtained. (A1) is preferred.

  The (meth) acryloyl group equivalent of the urethane (meth) acrylate (A) is 100 to 350 g / eq in that a cured coating film exhibiting higher surface hardness and excellent curling resistance during curing can be obtained. Is preferable, it is more preferable that it is the range of 130-250 g / eq, and it is especially preferable that it is the range of 140-200 g / eq.

  In the present invention, by using tripentaerythritol octa (meth) acrylate (B) as an essential component of the resin composition, a cured coating film having very high surface hardness and excellent curling resistance at the time of curing is obtained. It is done.

  The resin composition of the present invention has the urethane (meth) acrylate (A) and the tripentaerythritol octa (meth) acrylate (B) in that a cured coating film having both high surface hardness and flexibility is obtained. The mass ratio [(A) / (B)] is preferably in the range of 90/10 to 10/90, and more preferably in the range of 80/20 to 40/60.

  Examples of the polymerization initiator (C) contained in the active energy ray-curable resin composition of the present invention include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4, Benzophenones such as 4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; xanthone, thioxanthone, 2-methylthioxanthone, Xanthone such as 2-chlorothioxanthone and 2,4-diethylthioxanthone, thioxanthone; acyloin ether such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; α such as benzyl and diacetyl -Diketones; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; 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-morpholinopropane-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-methylpropane- 1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethylketa , Benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylamino Benzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazoli 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-triazine anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, etc. . These may be used alone or in combination of two or more.

  Examples of commercially available polymerization initiators include Irgacure-184, 149, 261, 369, 500, 651, 754, 784, 819, 907, 1116, 1664, 1700, 1800, 1850, 2959, 4043, Darocur-1173 (Ciba Specialty Chemicals), Lucyrin TPO (BASFF), Kayacure-DETX, MBP, DMBI, EPA, OA [ Nippon Kayaku Co., Ltd.], VICURE-10, 55 (STAFFER Co. LTD), TRIGONALP1 (AKZO Co. LTD), SANDORY 1000 (SANDOZ Co. LTD), DEAP (APJOHN Co. LTD) , QUANTACURE-PDO, ITX, EP (Manufactured by WARD BLEKINSOP Co.LTD), and the like.

  The photopolymerization initiator is in the range of 0.05 to 20 parts by mass in 100 parts by mass of the active energy ray-curable resin composition of the present invention in that no crystal is precipitated and sufficient curability is exhibited. It is preferable to use in the range of 0.1 to 10 parts by mass.

  In addition to the urethane (meth) acrylate (A) and tripentaerythritol octa (meth) acrylate (B), the active energy ray-curable resin composition of the present invention includes (meth) acrylate monomers other than these (D) ) May be contained.

  The (meth) acrylate monomer (D) is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, 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, 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) acryloyloxypropylhexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyltetrahydrophthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexa Fluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, Adama Mono (meth) acrylates such as ntil 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 , Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, Di (meth) acrylates such as pentaerythritol di (meth) acrylate;

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

  Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta ( Examples thereof include tetra- or higher functional (meth) acrylates such as (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  Among these (meth) acrylate monomers (D), the above tri (meth) acrylate or tetrafunctional or higher (meth) acrylate is preferable, and a compound having an acryloyl group in that a coating film showing higher hardness can be obtained. Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripentaerythritol hepta (meth) acrylate are more preferable.

  When the resin composition of the present invention contains the (meth) acrylate monomer (D), the cured coating film has both flexibility and high surface hardness and is excellent in curling resistance during curing. Is obtained in a total of 100 parts by mass of the urethane (meth) acrylate (A), the tripentaerythritol octa (meth) acrylate (B), and the (meth) acrylate monomer (D). ) The acrylate monomer is preferably 60 parts by mass or less, and more preferably 50 parts by mass or less.

  The active energy ray-curable resin composition of the present invention may further contain various additives. Can be added. Examples of these compounds include solvents, photosensitizers, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, and antistatic agents.

  Examples of the solvent include acetone, 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. -Ketone solvents such as butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and holon;

Ether solvents such as ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran;

Ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl Ester solvents such as ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate;

Alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, 3-methoxy-1-butanol, 3-methyl-3-methoxybutanol;

  Hydrocarbon solvents such as toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1800, Swazol 310, Isopar E, Isopar G, Exxon Naphtha No. 5, Exxon Naphtha No. 6 and the like. These may be used alone or in combination of two or more. Among these, the ester solvent is preferable in that the urethane (meth) acrylate (A) and tripentaerythritol octaacrylate are excellent in solubility.

  Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

  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.

  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 thereof include polyorganosiloxanes having an alkyl group and a phenyl group, such as a polysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer.

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

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

  The various additives are preferably used within the range where the effects are sufficiently exhibited and ultraviolet curing is not inhibited. Specifically, in 100 parts by mass of the active energy ray-curable resin composition of the present invention, 0. It is preferable to use in the range of 01-10 mass parts.

  Furthermore, the active energy ray-curable resin composition of the present invention can be used in combination with other resins other than the urethane (meth) acrylate (A) for the purpose of improving adhesion to a film substrate.

  Examples of the other resins include acrylic resins such as methyl methacrylate resin and methyl methacrylate copolymer; polystyrene, methyl methacrylate-styrene copolymer; polyester resin; polyurethane resin; polybutadiene and butadiene-acrylonitrile copolymer. And polybutadiene resins such as bisphenol type epoxy resins, epoxy resins such as phenoxy resins and novolac type epoxy resins. These may be used alone or in combination of two or more. The other resin is preferably used in such a range that the effect is sufficiently exerted and ultraviolet curing is not inhibited. Specifically, 10 parts by mass in 100 parts by mass of the active energy ray-curable resin composition of the present invention. It is preferable to use in the following ranges.

  Furthermore, the active energy ray-curable resin composition of the present invention may contain silica fine particles for the purpose of obtaining a cured coating film that is superior in surface hardness and curling resistance during curing. The average particle diameter (primary particle diameter) of the silica fine particles is preferably 1 to 100 nm, more preferably 10 to 50 nm, in that a cured coating film having both surface hardness and transparency is obtained. The silica fine particles are preferably used in such a range that the effect is sufficiently exhibited and ultraviolet curing is not inhibited. Specifically, in 100 parts by mass of the active energy ray-curable resin composition of the present invention, 50 parts by mass or less. It is preferable to use in the range.

  The active energy ray-curable resin composition of the present invention is obtained by adding the urethane (meth) acrylate (A) in a solid content of 10 to 90 in that a coating film having excellent curling resistance and flexibility during curing can be obtained. It is preferable to contain in the range of mass%, and it is more preferable to contain in the range of 20-60 mass%.

  In addition, the active energy ray-curable resin composition of the present invention is obtained by adding 10 to 50 masses of the above-mentioned tripentaerythritol octa (meth) acrylate (B) in the solid sentence in that a cured coating film having higher surface hardness can be obtained. % In the range of 15% to 40% by mass.

  The active energy ray-curable resin composition of the present invention can be used as a hard code agent that protects the surface of a molded product, a display, or the like. At this time, it may be applied directly to a molded product or a display and cured, or may be applied to various plastic film surfaces and cured to be used as a surface protecting film.

  When the surface protective film is produced using the active energy ray-curable resin composition of the present invention, the thickness of the cured coating layer made of the resin composition varies depending on the substrate to be applied and the application, The film thickness after curing is preferably in the range of 1 μm to 20 μm, and more preferably in the range of 5 μm to 20 μm, in terms of becoming a cured coating film having high hardness and excellent curling resistance during curing. .

  Examples of the plastic film substrate include PET film, acrylic resin film, polycarbonate resin film, TAC film, polymethyl methacrylate film, polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, ABS resin film, AS Examples thereof include a resin film and a norbornene resin film.

  Examples of the coating method of the co-active energy ray-curable resin composition of the present invention include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. Law.

  Examples of the active energy rays to be irradiated 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, and a metal halide lamp is used as a light source, and the amount of light and the arrangement of the light source are adjusted as necessary. It is preferable to cure at a conveyance speed of 5 to 50 m / min with respect to one lamp having a light quantity of ˜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 of usually 10 to 300 kV at a conveyance speed of 5 to 50 m / min.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Unless otherwise indicated, all parts and percentages in the examples are based on mass.

  In Examples of the present application, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

Production Example 1
Production of urethane (meth) acrylate (A-1) Nitrogen gas was blown into a 2 liter clean separable flask equipped with a stirrer, gas inlet tube, condenser, dropping funnel and thermometer, and the air in the flask was nitrogen gas. Then, 336 g of hexamethylene diisocyanate, 352 g of butyl acetate, 0.1 g of dibutyltin diacetate and 0.5 g of methoquinone were added to the flask, and the temperature was raised to 70 ° C. with stirring. Subsequently, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [“M-305” manufactured by Toagosei Co., Ltd., hydroxyl value: 110.0, pentaerythritol triacrylate / pentaerythritol tetraacrylate = 60/40 (mass %)] 1,071 g was added over 1 hour. Furthermore, it hold | maintained at 80 degreeC for 3 hours, and obtained 1,616 g of butyl acetate solutions of urethane (meth) acrylate (A-1). Each property value of the urethane (meth) acrylate (A-1) was as follows. Nonvolatile content: 80%, Gardner viscosity (25 ° C.): U, Gardner color: 1 or less, weight average molecular weight (Mw) of solid content: 1,250, (meth) acryloyl equivalent: 153 g / eq

Production Example 2
Production of urethane (meth) acrylate (A-2) Nitrogen gas was blown into a 2-liter clean separable flask equipped with a stirrer, gas inlet tube, condenser, dropping funnel and thermometer, and the air in the flask was nitrogen gas. Then, 444 g of isophorone diisocyanate, 379 g of butyl acetate, 0.1 g of dibutyltin diacetate and 0.5 g of methoquinone were added to the flask, and the temperature was raised to 70 ° C. with stirring. Next, a mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate [“M-305” manufactured by Toagosei Co., Ltd., hydroxyl value: 110.0, pentaerythritol triacrylate / pentaerythritol tetraacrylate = 60/40 (%) ] 1071 g was added over 1 hour. Furthermore, it hold | maintained at 80 degreeC for 3 hours, and obtained 1,616 g of butyl acetate solutions of urethane (meth) acrylate (A-2). Each property value of the urethane (meth) acrylate (A-2) was as follows. Nonvolatile content: 80%, Gardner viscosity (25 ° C.): O, Gardner color: 1 or less, weight average molecular weight (Mw) of solid content: 1,300, (meth) acryloyl equivalent: 170 g / eq

Tripentaerythritol octa (meth) acrylate (B-1): “Biscoat V # 802” manufactured by Osaka Organic Chemical Industry Co., Ltd. (polyfunctional acrylate composition containing 55% by mass of tripentaerythritol octaacrylate)

(Meth) acrylate monomer (D-1): “Aronix M-403” manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
(Meth) acrylate monomer (D-2): “Aronix M-450” manufactured by Toagosei Co., Ltd. (mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate)

Example 1
Formulation of active energy ray-curable resin composition Polyfunctional acrylate (B-1) containing acrylic (meth) acrylate (A-1), tripentaerythritol octaacrylate with the formulation shown in Table 1, and photopolymerization start An agent (“Irgacure 184” manufactured by BASF Corporation) was mixed to obtain an active energy ray-curable resin composition.

-Manufacture of Evaluation Sample 1 The active energy ray-curable resin composition obtained by the above blending was applied onto a triacetylcellulose film having a thickness of 80 μm, dried at 70 ° C. for 5 minutes, and then using a high-pressure mercury lamp in a nitrogen atmosphere. Irradiated with 200 mJ / cm ² , a coating film having a cured film thickness of 7 μm was prepared.

-Production of evaluation sample 2 An evaluation sample 2 was prepared in the same manner as in the production of the evaluation sample 1 except that the base material was changed to a glass plate.

-Evaluation About the obtained evaluation samples 1 and 2, various evaluations described below were performed, and the results are shown in Table 1.

Evaluation 1: Evaluation of curling resistance A 5 cm square coating film was cut out from the evaluation sample 1 to obtain a test piece. The test piece was measured for floating from four sides horizontally, and the average value was evaluated. The smaller the value, the smaller the curl and the better the curl resistance.

Evaluation 2: Measurement of pencil hardness [Pencil hardness]
About the said evaluation sample 1, based on JISK5600-5-4, the pencil hardness measurement was performed on 500-g load conditions. The measurement was performed 5 times per hardness, and the hardness of the cured coating film was determined as the hardness at which the measurement without scratches was 4 times or more.

Evaluation 3: Measurement of universal hardness Using the micro hardness tester ("Fischerscope H100C" manufactured by Fischer Instruments Co., Ltd.), the universal hardness was measured under the following conditions. Indentation strength: 100 mN, indentation depth: 1 μm, indentation speed: 1 μm / 15 sec, measurement environment temperature: 25 ° C.

Evaluation 4: Evaluation of the flexibility of the coating film Using a mandrel tester (“Flex Tester” manufactured by TP Giken Co., Ltd.), when the sample for evaluation is wound around the test bar, it is visually confirmed whether or not the sample 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 more flexible the coating film.

Example 2-4
Except for changing the formulation of the active energy ray-curable resin composition as shown in Table 1, the active energy ray-curable resin composition, the evaluation sample 1 and the evaluation sample 2 were obtained in the same manner as in Example 1, and various evaluations were made. Went. The results are shown in Table 1.

Comparative Examples 1-3
Except for changing the formulation of the active energy ray-curable resin composition as shown in Table 1, the active energy ray-curable resin composition, the evaluation sample 1 and the evaluation sample 2 were obtained in the same manner as in Example 1, and various evaluations were made. Went. The results are shown in Table 2.

Claims (7)

An active energy ray-curable resin composition containing urethane (meth) acrylate (A), tripentaerythritol octa (meth) acrylate (B) and a polymerization initiator (C) as essential components , the solid content The content of the urethane (meth) acrylate (A) is in the range of 20 to 60% by mass, and the content of the tripentaerythritol octa (meth) acrylate (B) is in the range of 15 to 40% by mass. An active energy ray-curable resin composition. The mass ratio [(A) / (B)] of the urethane (meth) acrylate (A) and the tripentaerythritol octa (meth) acrylate (B) is in the range of 80/20 to 40/60. Item 2. The active energy ray-curable resin composition according to Item 1. The active energy ray-curable resin composition according to claim 1, wherein the urethane (meth) acrylate (A) has a (meth) acryloyl group equivalent in the range of 100 to 350 g / eq. 2. The urethane (meth) acrylate (A) is a reaction product of a raw material containing a polyisocyanate compound (a1), pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Active energy ray-curable resin composition. The active energy ray-curable resin composition according to claim 4, wherein the reaction product has a weight average molecular weight (Mw) in the range of 400 to 5,000. The active energy ray according to claim 1, further comprising a (meth) acrylate monomer (D) other than these in addition to the urethane (meth) acrylate (A) and the tripentaerythritol octa (meth) acrylate (B). A curable resin composition. The film which has a hardened layer obtained by hardening the active energy ray hardening-type resin composition of any one of Claims 1-6.