WO2019124048A1 - Urethane (meth)acrylate resin, curable resin composition, cured product, and laminated film - Google Patents

Abstract

The present invention provides: a urethane (meth)acrylate resin characterized by containing an isocyanate compound (A) and a dipentaerythritol (meth)acrylate (B) as essential reaction raw materials, wherein the hydroxyl value of the dipentaerythritol (meth)acrylate (B) is in the range of 120-150 mgKOH/g(exclusive of 120); a curable resin composition containing said urethane (meth)acrylate resin; a cured product; and a laminated film. This urethane (meth)acrylate resin can form a cured coating film having excellent abrasion resistance, flexibility, curl resistance, and impact resistance.

Description

Urethane (meth) acrylate resin, curable resin composition, cured product and laminated film

The present invention relates to a urethane (meth) acrylate resin which is excellent in abrasion resistance, flexibility, curl resistance and impact resistance in a cured coating film, a curable resin composition containing the same, a cured product and a laminated film.

Plastic films manufactured using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc. are industrial applications such as a polarizing plate protective film incorporated in the inside of a flat panel display and a surface protective film of a touch panel Are often used. The surface of these plastic films is easily damaged by themselves, and the processability is low, so that there is a lack of performance such as cracking and cracking easily. Usually, a coat layer made of an active energy ray curable resin or the like is provided on the surface. To compensate for these performances.

As a coating agent for reinforcing a plastic film, for example, a resin composition containing a urethane acrylate obtained by reacting dipentaerythritol polyacrylate having a hydroxyl value of 80 to 120 mg KOH / g and hexamethylene diisocyanate is known. (See, for example, Patent Document 1). The resin composition is high in surface hardness of a cured product and excellent in abrasion resistance, but is easily curled and is not sufficiently tough or flexible of a coating film, so it is easily cracked by an external impact. there were.

Therefore, a material capable of forming a cured coating film having excellent scratch resistance and excellent in curl resistance, flexibility and impact resistance has been desired.

International Publication No. 2010/146801

The problem to be solved by the present invention is urethane (meth) acrylate resin capable of forming a cured coating film excellent in abrasion resistance, flexibility, curl resistance and impact resistance, and a curable resin composition containing the same. An object, a cured product and a laminated film are provided.

As a result of intensive studies to solve the above problems, the present inventor uses a urethane (meth) acrylate resin containing an isocyanate compound and dipentaerythritol (meth) acrylate having a specific hydroxyl value as essential reaction raw materials. As a result, the inventors have found that the above problems can be solved, and completed the present invention.

That is, the present invention is a urethane (meth) acrylate resin comprising an isocyanate compound (A) and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials, wherein the dipentaerythritol (meth) acrylate ( The present invention relates to a urethane (meth) acrylate resin characterized in that the hydroxyl value of B) is in the range of more than 120 mg KOH / g to 150 mg KOH / g, a curable resin composition containing the same, a cured product and a laminated film.

The urethane (meth) acrylate resin of the present invention can form a cured coating film excellent in scratch resistance, curl resistance, flexibility, and impact resistance, so it should be suitably used as a coating agent for protecting various substrate surfaces. Can. In addition, the laminated film having the cured coating film is excellent in abrasion resistance and curl resistance, and is highly flexible so that it is not easily cracked when it is bent or wound, and further, there is a drop on the film. Even in the case of impact resistance that is hard to break.

The urethane (meth) acrylate resin of the present invention uses the isocyanate compound (A) and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials.

Examples of the isocyanate compound (A) include aliphatic isocyanate compounds and isocyanate compounds having an aromatic ring or an alicyclic structure in the molecule.

Examples of the aliphatic isocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. It can be mentioned. Further, isocyanurate modified products, biuret modified products, allophanate modified products and the like which are modified products of these isocyanate compounds can also be used. These aliphatic isocyanate compounds can be used alone or in combination of two or more.

The isocyanate compound having an aromatic ring or an alicyclic structure in the molecule is, for example, an isocyanate compound (A1) represented by any of the following structural formulas (A1-1) to (A1-3);

（式中、Ｒ^１はそれぞれ独立に炭素原子数１～４のアルキル基であり、ｊは０または１～４の整数である。Ｒ^２はそれぞれ独立に水素原子、炭素原子数１～４のアルキル基の何れかである。）

Wherein R ¹ is each independently an alkyl group having 1 to 4 carbon atoms, and j is an integer of 0 or 1 to 4. R ² is independently a hydrogen atom or 1 to 4 carbon atoms. Any of the alkyl groups)

Isocyanate compound (A2) represented by the following structural formula (A2-1) or (A2-2);

（式中、ｌは０または１以上の整数であり、ｍは１または２である。Ｒ^３はそれぞれ独立に炭素原子数１～４のアルキル基、または式中括弧内で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかであり、ｋは０、１または２であり、ｎは０または１～８の整数である。）

(Wherein, l is an integer of 0 or 1 or more, m is 1 or 2. R ³ is each independently an alkyl group having 1 to 4 carbon atoms, or a structural portion represented in the parenthesis) And any of the bonding points linked via a methylene group marked with an asterisk (*), k is 0, 1 or 2 and n is an integer of 0 or 1 to 8.)

Alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc .; aromatic diisocyanate compounds such as diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate;

The polymethylene polyphenyl polyisocyanate etc. which have a repeating structure represented by following Structural formula (1) are mentioned. Further, isocyanurate modified products, biuret modified products, allophanate modified products and the like which are modified products of these isocyanate compounds can also be used. These isocyanate compounds having an aromatic ring or an alicyclic structure in their molecule can be used alone or in combination of two or more.

（式中、Ｒ^４はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ^５はそれぞれ独立に炭素原子数１～４のアルキル基、又は構造式（１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｍは０又は１～３の整数であり、ｌは１以上の整数である。）

(Wherein, R ⁴ is each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁵ is each independently an alkyl group having 1 to 4 carbon atoms, or a structural formula (1 And m is an integer of 0 or 1 to 3, and l is an integer of 1 or more. )

The dipentaerythritol (meth) acrylate (B) is obtained by (meth) acrylated a part of hydroxyl groups of dipentaerythritol, as long as it has a hydroxyl group capable of reacting with the isocyanate compound (A), It may be a single compound or a mixture of a plurality of compounds. That is, in the case of the former, as the dipentaerythritol (meth) acrylate (B), dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Erythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate can be used alone respectively. In the latter case, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta ( One or more meta) acrylates may be contained and used as a mixture, and, if necessary, dipentaerythritol hexa (meth) acrylate may also be contained.

Since the dipentaerythritol (meth) acrylate (B) can form a urethane (meth) acrylate resin capable of forming a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance, It is preferable to contain dipentaerythritol tetra (meth) acrylate (b1) as an essential component, and it is more preferable to contain dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (meth) acrylate (b2) It is particularly preferable to contain dipentaerythritol tetra (meth) acrylate (b1), dipentaerythritol penta (meth) acrylate (b2), and dipentaerythritol hexa (meth) acrylate (b3).

When the dipentaerythritol (meth) acrylate (B) contains the dipentaerythritol tetra (meth) acrylate (b1), the dipentaerythritol (meth) of the dipentaerythritol tetra (meth) acrylate (b1) The content of the acrylate (B) is 10 to 50 because a urethane (meth) acrylate resin capable of forming a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance can be obtained. The range of mass% is preferable, the range of 12 to 45 mass% is more preferable, and the range of 15 to 40 mass% is particularly preferable.

When the dipentaerythritol (meth) acrylate (B) contains the dipentaerythritol tetra (meth) acrylate (b1) and the dipentaerythritol penta (meth) acrylate (b2), scratch resistance, flexibility, Since a urethane (meth) acrylate resin capable of forming a cured coating film excellent in curl resistance and impact resistance can be obtained, the dipentaerythritol tetra (meth) acrylate (b1) and the dipentaerythritol penta (meth) are obtained. The ratio of the content of acrylate (b2) [(b1) / (b2)] is preferably in the range of 20/80 to 80/20, and more preferably in the range of 30/70 to 60/40.

When the dipentaerythritol (meth) acrylate (B) contains the dipentaerythritol hexa (meth) acrylate (b3), a cured coating excellent in scratch resistance, flexibility, curl resistance, and impact resistance Since a urethane (meth) acrylate resin capable of forming a film can be obtained, the content of the dipentaerythritol (hexa) acrylate (b3) in the dipentaerythritol (meth) acrylate (B) is 1 to 60 mass. The range of% is preferable, and the range of 5 to 50% by mass is more preferable.

In the present invention, the content of each component in the dipentaerythritol (meth) acrylate (B) and the ratio of the content of each component are calculated from the area ratio of the liquid chromatography chart measured under the following conditions. Value.
[Measurement condition]
Device: "LCMS-2010 EV" manufactured by Shimadzu Corporation
Data processing: "LCMS Solution" manufactured by Shimadzu Corporation
Column: Tosoh Corp. “ODS-100V” (2.0 mm ID × 150 mm, 3 μm) 40 ° C.
Eluent: water / acetonitrile, 0.4 mL / min Detector: PDA, MS
Sample Preparation: 1. Dissolve 50 mg of the material in 10 ml of acetonitrile (for LC) 2. Stir by vortex for 30 seconds 3. Hold for 30 minutes 4. Pass through a 0.2 μm filter to calculate the area ratio: Calculated at UV wavelength of 210 nm

Further, the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is a urethane (meth) acrylate resin capable of forming a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance. Since it is obtained, it is more than 120 mg KOH / g and not more than 150 mg KOH / g, the range of 122 to 145 mg KOH / g is preferable, and the range of 122 to 140 mg KOH / g is more preferable.

The hydroxyl value of the dipentaerythritol (meth) acrylate (B) is an actual value measured according to JIS K 0070 (1992) neutralization titration method, or each component calculated from the area ratio of a liquid chromatography chart. Is a calculated value calculated from the composition ratio of

Examples of the method for producing the dipentaerythritol (meth) acrylate (B) include a method in which dipentaerythritol and acrylic acid are subjected to an esterification reaction. When produced by this method, a high molecular weight component (b ') or the like such as an addition reaction product of dipentaerythritol (meth) acrylates (B) may be generated as a by-product. b ′) may be used after purification and removal, or as a raw material of the urethane (meth) acrylate resin as it is a crude product of dipentaerythritol (meth) acrylate (B) containing the high molecular weight component (b ′) good. At this time, the content of the high molecular weight component (b ') in the crude product of the dipentaerythritol (meth) acrylate (B) is preferably in the range of 1 to 20% by mass.

Although the said urethane (meth) acrylate resin makes the said isocyanate compound (A) and the said dipentaerythritol (meth) acrylate (B) an essential reaction raw material, as needed, other monohydroxy (meta) may be used. Acrylate compounds, other polyol compounds, etc. can also be used.

Examples of the other monohydroxy (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, tri Aliphatic (meth) acrylate compounds such as methylolpropane di (meth) acrylate and pentaerythritol tri (meth) acrylate; 4-hydroxyphenyl acrylate; β-hydroxyphenethyl acrylate; 4-hydroxyphenethyl acrylate; 1- acrylic acid Aromatic ring-containing (meth) acrylate compounds such as phenyl-2-hydroxyethyl, 3-hydroxy-4-acetylphenyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate; the above (meth) Polyether-modified (meth) obtained by ring-opening polymerization of a acrylate compound with various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether Acrylate compounds; and lactone modified (meth) acrylate compounds obtained by polycondensation of the (meth) acrylate compound with a lactone compound such as ε-caprolactone and the like. These hydroxy (meth) acrylate compounds can be used alone or in combination of two or more. Among these, since an urethane (meth) acrylate resin capable of forming a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance can be obtained, aliphatic (meth) acrylate compounds or the compounds thereof Polyether modified products and lactone modified products are preferred. When these other monohydroxy (meth) acrylate compounds are used, the effects of the present invention are sufficiently exhibited, so the dipentaerythritol (meth) acrylate (B) and monohydroxy (meth) acrylate compounds It is preferable that the ratio of the said dipentaerythritol (meth) acrylate (B) with respect to the total mass of and becomes 70 mass% or more, and it is more preferable that it becomes 90 mass% or more.

Examples of the other polyol compound include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, and the like. 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono (meth) acrylate, trimethylolethane, trimethylolmethane mono (meth) acrylate, trimethylolpropane, trimethylolpropane mono (meth) ) Polyol monomers such as acrylate, pentaerythritol mono (meth) acrylate and pentaerythritol di (meth) acrylate; The above-mentioned polyol monomers and succinic acid, adipic acid, azelaic acid, sebaci Co-condensation with dicarboxylic acids such as acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,4-cyclohexanedicarboxylic acid A polyester polyol obtained by the above; a lactone type polyester polyol obtained by the polycondensation reaction of the polyol monomer with various lactones such as ε-caprolactone, δ-valerolactone, 3-methyl-δ-valerolactone; and the above-mentioned polyol monomer And polyether polyols obtained by ring-opening polymerization with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more. In addition, when these other polyol compounds are used, the effects of the present invention are sufficiently exhibited. Therefore, the dipentaerythritol with respect to the total mass of the dipentaerythritol (meth) acrylate (B) and the other polyol compound is sufficient. The proportion of erythritol (meth) acrylate (B) is preferably 70% by mass or more, and more preferably 90% by mass or more.

The method for producing the urethane (meth) acrylate resin is, for example, an isocyanate group which the isocyanate (A) has, the isocyanate compound (A) and the dipentaerythritol (meth) acrylate (B); The molar ratio [(NCO) / (OH)] to the hydroxyl group of erythritol (meth) acrylate (B) is in the range of 1 / 1.05 to 1/2, and the temperature range of 20 to 120 ° C. Inside, as needed, the method of performing using a urethanization catalyst is mentioned.

The (meth) acryloyl group equivalent of the urethane (meth) acrylate resin is in the range of 100 to 500 g / eq because it can form a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance. Preferably, the range of 100 to 250 g / eq is more preferable. In addition, the (meth) acryloyl group equivalent of urethane (meth) acrylate resin in this invention is a value calculated as a theoretical value from the reaction raw material.

Further, the weight average molecular weight (Mw) of the urethane (meth) acrylate resin is 1,500 to 100, because a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance can be formed. The range of 000 is preferable, and the range of 3,000 to 5,000 is more preferable.

In addition, the weight average molecular weight (Mw) of the said urethane (meth) acrylate resin shows the value measured by gel permeation chromatography (GPC) method.

The curable resin composition of the present invention contains the urethane (meth) acrylate resin and 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 such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, thioxanthones; various acyloethers 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-one Phenylpropan-1-one, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2 Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4′-methyldimethyl sulfide, 2,2′-diethoxyacetophenone, benzyl Dimethylketal, benzyl-β-methoxyethylacetal, 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-etoki) ) Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazine anthraquinone, 2-t-butyl anthraquinone, 2-amyl anthraquinone, β-chloroanthraquinone Etc. These photopolymerization initiators can be used alone or in combination of two or more.

Further, among the photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, which is active against light of a wider range of wavelengths and can improve the curing property of the cured coating film of the curable resin composition, 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-diphenylethan-1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-di Chiruamino -1- (4-morpholinophenyl) - it is preferable to use one or a mixture of two or more systems selected from the group consisting of butan-1-one.

As a commercial item of the said photoinitiator, For example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad- 2959", "Omnirad-369", "Omnirad-379", " Omnirad-907, Omnirad-4265, Omnirad-1000, Omnirad-651, Omnirad-TPO, Omnirad-819, Omnirad-2022, Omnirad-2100, Omnirad- 754 "," Omnirad-784 "," Omnirad-500 "," Omnirad-81 "(manufactured by IGM)," Kayacure-DETX "," Kayacure-MBP "," Kayacure-DMBI "," Kayacure-EP " , "Kayacure-OA" (Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (Stoufa Chemical), "Trigonal P1" (Akzo), "Sandley 1000" Sands Co., Ltd., "Deep" (Apjeong Co., Ltd.), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (made by Word Brenkin Sop), "Runtecture-1104" (Runtec) Company) and the like.

The addition amount of the photopolymerization initiator is an amount that can sufficiently exhibit the function as a photopolymerization initiator, and a range in which precipitation of crystals and deterioration of coating film properties do not occur is preferable, and specifically, The range of 0.05 to 20 parts by mass is preferable with respect to 100 parts by mass of the urethane (meth) acrylate resin, and the range of 0.1 to 10 parts by mass is more preferable.

Moreover, since the said curable resin composition can improve the curability of the cured coating film of the said curable resin composition, it can also contain a photosensitizer.

Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, and sulfur such as sodium diethyl dithiophosphate and s-benzyl isothiuronium-p-toluenesulfonate. A compound etc. are mentioned.

The curable resin composition of the present invention may further comprise, in addition to the urethane (meth) acrylate resin, other photocurable compounds (R), organic solvents, ultraviolet absorbers, antioxidants, silicone additives, fluorine It may contain a system additive, a silane coupling agent, a phosphoric acid ester compound, an organic bead, an inorganic fine particle, an inorganic filler, a rheology control agent, a defoamer, an antifogging agent, a colorant and the like.

Examples of the other photocurable compound (R) include various (meth) acrylate monomers, and other urethane (meth) acrylate resins other than the urethane (meth) acrylate resin, and epoxy (meth) acrylate resin And dendrimer type (meth) acrylate resins, (meth) acryloyl group-containing acrylic resins, and the like.

The (meth) acrylate monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate ) Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloyl morpholine, N-vinyl pyrrolidone, 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) Crylates, 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, Methoxy polyethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, -(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 tetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoro Propyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, adaman Mono (meth) acrylates such as chill mono (meth) acrylates;

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, hydroxypivalate neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylol Di (meth) acrylates such as propane di (meth) acrylate and pentaerythritol di (meth) acrylate;

Trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri Tri (meth) acrylates such as (meth) acrylates, dipentaerythritol tri (meth) acrylates;

Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate ) Acrylate, and tetrafunctional or higher (meth) acrylates such as ditrimethylolpropane hexa (meth) acrylate; some or all of the above-mentioned various polyfunctional (meth) acrylates modified with polyoxyalkylene chains or polyester chains (meta And the like.

As said other urethane (meth) acrylate resin, for example, urethane (meth) acrylate resin using isocyanate compounds other than the said isocyanate compound (A), and hydroxy (meta) other than dipentaerythritol (meth) acrylate (B) Urethane (meth) acrylate resin using an acrylate compound is mentioned.

Examples of the epoxy (meth) acrylate resin include those obtained by reacting various epoxy resins such as bisphenol-type epoxy resin and novolac-type epoxy resin with (meth) acrylic acid or a derivative thereof to (meth) acrylate .

The dendrimer type (meth) acrylate resin is a resin having a regular multi-branched structure and having a (meth) acryloyl group at the end of each branched chain. It is called a star polymer. Examples of such compounds include, but are not limited to, those represented by the following structural formulas (2-1) to (2-8), but the present invention is not limited thereto, and a multi-branched structure having regularity may be used. Any resin may be used as long as it is a resin having a (meth) acryloyl group at the end of each branched chain.

（式中Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素原子数１～４の炭化水素基である。）

(In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms.)

（式中Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素原子数１～４の炭化水素基である。）

(In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms.)

As such a dendrimer type (meth) acrylate resin, for example, “Biscoat # 1000” manufactured by Osaka Organic Chemical Co., Ltd. [weight-average molecular weight (Mw) 1,500 to 2,000, average (meth) acryloyl per molecule] Radical number 14], "Biscoat 1020" [Weight average molecular weight (Mw) 1,000 to 3,000], "SIRIUS 501" [Weight average molecular weight (Mw) 15,000 to 23,000], manufactured by MIWON "SP-1106 [Weight average molecular weight (Mw) 1,630, average (meth) acryloyl group number 18 per molecule], "CN 2301", "CN 2302" (average number (meth) acryloyl group number 16 per one molecule), manufactured by SARTOMER, " CN 2303 "[average (meth) acryloyl group number 6 per one molecule]," CN 2304 " Average (meth) acryloyl group number 18 per molecule], "Esdrimer HU-22" manufactured by Nippon Steel Sumikin Chemical Co., Ltd., "A-HBR-5" manufactured by Shin-Nakamura Chemical Co., Ltd., "New Frontier" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Commercially available products such as R-1150 "and" Hypertec UR-101 "manufactured by Nissan Chemical Industries, Ltd. may be used.

The weight average molecular weight (Mw) of the dendrimer type (meth) acrylate resin is preferably in the range of 1,000 to 30,000. The average number of (meth) acryloyl groups per molecule is preferably in the range of 5 to 30.

The (meth) acryloyl group-containing acrylic resin can be obtained, for example, by polymerizing a (meth) acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group or a glycidyl group as an essential component What is obtained by introducing a (meth) acryloyl group by further reacting a (meth) acrylate monomer (β) having a reactive functional group capable of reacting with these functional groups to an acrylic resin intermediate may be mentioned.

Examples of the (meth) acrylate monomer (α) having a reactive functional group include, for example, hydroxyl group-containing (meth) acrylate monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (meth) acrylic acid Carboxyl group-containing (meth) acrylate monomers; isocyanate group-containing (meth) acrylate monomers such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, etc .; glycidyl (meth) Examples thereof include glycidyl group-containing (meth) acrylate monomers such as acrylate and 4-hydroxybutyl acrylate glycidyl ether. These (meth) acrylate monomers (α) may be used alone or in combination of two or more.

The acrylic resin intermediate may be one obtained by copolymerizing other polymerizable unsaturated group-containing compounds, if necessary, in addition to the (meth) acrylate monomer (α). Examples of the other polymerizable unsaturated group-containing compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate ) Acrylic acid alkyl esters; Cyclocyclic (meth) acrylates such as cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl Aromatic ring-containing (meth) acrylates such as acrylates; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene and chlorostyrene It is below. These polymerizable unsaturated group-containing compounds may be used alone or in combination of two or more. Among these, (meth) acrylic acid alkyl ester is preferable.

When the said acrylic resin intermediate is a thing obtained by copolymerizing the said (meth) acrylate monomer ((alpha)) and said other polymerizable unsaturated group containing compound, the reaction ratio of both makes curability In order to obtain an excellent (meth) acryloyl group-containing acrylic resin, the ratio of the (meth) acrylate monomer (α) to the total of both is preferably in the range of 20 to 70% by mass, and more preferably in the range of 30 to 60% by mass. .

The said acrylic resin intermediate can be manufactured by the method similar to a common acrylic resin. For example, it can be produced by polymerizing various monomers in the presence of a polymerization initiator in a temperature range of 60 to 150.degree. Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Further, as the polymerization mode, for example, a random copolymer, a block copolymer, a graft copolymer and the like can be mentioned. In the case of the solution polymerization method, for example, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether are used. Is preferred.

The (meth) acrylate monomer (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth) acrylate monomer (α), but from the viewpoint of reactivity, the following combination Is preferred. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the carboxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the glycidyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β). When the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the hydroxyl group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the glycidyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the carboxy group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β).

The reaction between the acrylic resin intermediate and the (meth) acrylate monomer (β) is, for example, an esterification such as triphenylphosphine in a temperature range of 60 to 150 ° C. when the reaction is an esterification reaction. The method etc. which use a catalyst suitably are mentioned. When the reaction is a urethanation reaction, the reaction may be carried out while dropping the (meth) acrylate monomer (α) to the acrylic resin intermediate at a temperature range of 50 to 120 ° C., and the like.

The weight average molecular weight (Mw) of the (meth) acryloyl group-containing acrylic resin is preferably in the range of 5,000 to 80,000. The (meth) acryloyl group equivalent is preferably in the range of 100 to 500 g / equivalent.

These other photocurable compounds (R) may be used alone or in combination of two or more. When these other photocurable compounds (R) are used, the urethane (meth) of the present invention is contained in 100 parts by mass in total of the urethane (meth) acrylate resin of the present invention and the other photocurable compounds (R). The acrylate resin is preferably used in a proportion of 5 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 80 parts by mass or more.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone and 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; Alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether And glycol ether solvents such as acetate. These organic solvents can be used alone or in combination of two or more. These organic solvents are mainly used for the purpose of adjusting the viscosity of the curable composition, but in general, it is preferable to adjust the nonvolatile content to be in the range of 10 to 80% by mass.

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, Triazine derivatives such as 3,5-triazine, 2- (2'-xanthene carboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2 And xanthene carboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like. These ultraviolet absorbers can be used alone or in combination of two or more.

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

Examples of the silicone-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether modified dimethylpolysiloxane copolymer, polyester modified dimethylpolysiloxane copolymer, fluorine modified Polyorganosiloxane having alkyl group or phenyl group such as dimethylpolysiloxane copolymer, amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxane having polyether modified acrylic group, polydimethylsiloxane having polyester modified acrylic group, etc. It can be mentioned. These silicon-based additives can be used alone or in combination of two or more.

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

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like. -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 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- Hydrochloride of N- (1,3-dimethyl butyrylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, special Aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanate ester Pirtriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, etc. Vinyl based silane coupling agent;

Diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethylsilane Epoxy based silane coupling agent such as ethoxysilane;

Styrene based silane coupling agents such as p-styryltrimethoxysilane;

(Meth) such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Acryloxy based silane coupling agent;

N-2 (aminoethyl) 3-aminopropylmethyl dimethoxysilane, N-2 (aminoethyl) 3-aminopropyl trimethoxysilane, N-2 (aminoethyl) 3-aminopropyl triethoxysilane, 3-aminopropyl trii Silane coupling of amino systems such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. Agents;

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

Chloropropyl based silane coupling agents such as 3-chloropropyltrimethoxysilane;

Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;

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

Examples thereof include isocyanate-based silane coupling agents such as 3-isocyanate propyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

Examples of the phosphate ester compounds include those having a (meth) acryloyl group in the molecular structure, and examples of commercially available products include “Kayamar PM-2”, “Kayamer PM-” manufactured by Nippon Kayaku Co., Ltd. 21 ", Kyoeisha Chemical Co., Ltd." Light Ester P-1 M "," Light Ester P-2 M "," Light Acrylate P-1 A (N) ", Solvay" SIPOMER PAM 100 "," SIPOMER PAM 200 "," SIPOMER PAM 300 "," SIPOMER PAM 4000 "," Viscoat # 3 PA "manufactured by Osaka Organic Chemical Industry Ltd.," Biscoat # 3 PMA "," New Frontier S-23A "manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; allyl ether group in molecular structure Is a phosphoric acid ester compound having IPOMER PAM 5000 ", and the like.

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 And polyester resin beads, polyamide resin beads, polyimide resin beads, polytetrafluoroethylene resin beads, polyethylene resin beads and the like. These organic beads can be used alone or in combination of two or more. The average particle size of these organic beads is preferably in the range of 1 to 10 μm.

Examples of the inorganic fine particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide and the like. These inorganic fine particles may be used alone or in combination of two or more. The average particle diameter of these inorganic fine particles is preferably in the range of 95 to 250 nm, and more preferably in the range of 100 to 180 nm.

When the inorganic fine particles are contained, a dispersion aid can be used. Examples of the dispersion aid include phosphoric acid ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, ethylene oxide modified phosphoric acid dimethacrylate, and the like. These dispersion adjuvants can be used alone or in combination of two or more. Moreover, as a commercial item of the said dispersion adjuvant, Nippon Kayaku Co., Ltd. "Kayamer PM-21", "Kayamer PM-2", Kyoeisha Chemical Co., Ltd. "light ester P-2M" etc. are mentioned, for example. .

The cured product of the present invention is obtained by curing the curable resin composition.

Examples of the method for curing the curable composition include a method of heating and a method of irradiating active energy rays such as ultraviolet rays.

As the method of heating, curing can be performed by heating in a temperature range of 60 to 200 ° C. for 0.5 to 60 minutes.

Further, as a method of irradiating the active energy ray, for example, in the case of ultraviolet light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, LED It can be cured by a method using an ultraviolet lamp such as

As the active energy ray, ionizing radiation such as an electron beam, an alpha ray, a beta ray, and a gamma ray can be used in addition to the ultraviolet ray.

The exposure dose of the actinic energy ray is preferably in the range of 0.05 ~ 5J / cm ^2, more preferably in the range of ^{0.1 ~ 3J / cm 2, 0.1} ~ 1J / cm 2 It is particularly preferable to be in the range of The above-mentioned ultraviolet irradiation amount is based on a value measured in a wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Japan Battery Co., Ltd.).

The laminated film of the present invention has a layer comprising the cured product on a substrate.

As a method for producing the laminated film of the present invention, for example, a method of applying the curable resin composition to at least one surface of the substrate and then irradiating an active energy ray may be mentioned.

Examples of the substrate include metal substrates, plastic substrates, glass substrates, paper substrates, wood substrates, fibrous substrates and the like. Among these substrates, plastic substrates are preferable because they have excellent adhesion to the curable resin composition.

The material of the plastic base material is polyester, acrylic resin (polymethyl methacrylate etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin And polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), polyimide and the like.

Examples of the plastic base include plastic molded articles such as mobile phones, home appliances, automobile interior and exterior materials, OA equipment and the like. Also, a film base made of plastic can be used.

As a method of applying the active energy ray curable resin composition, for example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, spin coater, dipping, screen Coating methods include printing, spraying, brushing, an applicator, a bar coater, and the like.

Although the film thickness of the coating film formed using the said active energy ray curable resin composition can be suitably adjusted according to the use to be used, Usually, it is preferable that it is the range of 0.01-50 micrometers. .

The laminated film of the present invention may have a functional film layer such as an antireflection film, a diffusion film, a polarizing film, etc., in addition to the substrate and the layer made of the cured product.

The laminated film of the present invention can be used as a coating layer for protecting the substrate surface since it has a cured coating film excellent in scratch resistance, flexibility, curl resistance and impact resistance. For example, it can be suitably used for the front plate application of a liquid crystal display or an organic EL display.

Moreover, as an article which has a laminated film of this invention, plastic molded articles, such as a mobile telephone, a household appliance case, the bumper of a motor vehicle, OA apparatus, etc. are mentioned, for example.

Hereinafter, the present invention will be specifically described by examples and comparative examples.

In addition, in a present Example, a hydroxyl value is the actual value measured according to the neutralization titration method of JISK 0070 (1992).

In addition, in a present Example, a weight average molecular weight (Mw) is the value measured on condition of the following using gel permeation chromatography (GPC).

Measuring device; manufactured by Tosoh Corporation HLC-8220
Column; Tosoh Corp. guard column H _XL- H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000 HXL
Detector; RI (differential refractometer)
Data processing: Tosoh Corp. SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; Polystyrene sample; Tetrahydrofuran solution of 0.4% by mass in terms of resin solid content filtered with a microfilter (100 μl)

In the present example, the liquid chromatography chart was measured under the following conditions.
[Measurement condition]
Device: "LCMS-2010 EV" manufactured by Shimadzu Corporation
Data processing: "LCMS Solution" manufactured by Shimadzu Corporation
Column: Tosoh Corp. “ODS-100V” (2.0 mm ID × 150 mm, 3 μm) 40 ° C.
Eluent: water / acetonitrile, 0.4 mL / min Detector: PDA, MS
Sample Preparation: 1. Dissolve 50 mg of the material in 10 ml of acetonitrile (for LC) 2. Stir by vortex for 30 seconds 3. Hold for 30 minutes 4. Pass through a 0.2 μm filter and calculate the area ratio as the measurement sample: Calculated at UV wavelength 210 nm

Production Example 1: Production of dipentaerythritol (meth) acrylate (B1)
In a flask equipped with a thermometer, a stirrer, and a condenser, 280 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The produced water was 65 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water. Furthermore, the reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water. After hydroquinone monomethyl ether was added in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B1). The hydroxyl value of this dipentaerythritol (meth) acrylate (B1) was 125 mg KOH / g (measured value). Further, the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 23% by mass, the content of dipentaerythritol pentaacrylate (b2) is 36% by mass, and dipentaerythritol hexaacrylate The content of (b3) was 26% by mass, and the content of the high molecular weight component (b ') was 15% by mass.

Production Example 2: Production of dipentaerythritol (meth) acrylate (B2)
In a flask equipped with a thermometer, a stirrer, and a condenser, 250 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The generated water was 64 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water. Furthermore, the reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water. After hydroquinone monomethyl ether was added in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B2). The hydroxyl value of this dipentaerythritol (meth) acrylate (B2) was 130 mg KOH / g. Further, the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 26% by mass, the content of dipentaerythritol pentaacrylate (b2) is 39% by mass, and dipentaerythritol hexaacrylate The content of (b3) was 24% by mass, and the content of the high molecular weight component (b ') was 11% by mass.

Production Example 3 Production of Dipentaerythritol (Meth) Acrylate (B3)
In a flask equipped with a thermometer, a stirrer, and a condenser, 220 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The generated water was 61 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water. Furthermore, the reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water. After adding hydroquinone monomethyl ether in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B3). The hydroxyl value of this dipentaerythritol (meth) acrylate (B3) was 140 mg KOH / g. Further, the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 28% by mass, the content of dipentaerythritol pentaacrylate (b2) is 42% by mass, and dipentaerythritol hexaacrylate The content of (b3) was 22% by mass, and the content of the high molecular weight component (b ') was 8% by mass.

Comparative Production Example 1: Production of dipentaerythritol (meth) acrylate (B4)
In a flask equipped with a thermometer, a stirrer, and a condenser, 460 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The generated water was 71.8 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water. Furthermore, the reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water. After hydroquinone monomethyl ether was added in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B4). The hydroxyl value of this dipentaerythritol (meth) acrylate (B4) was 43 mg KOH / g. In addition, the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 0.2% by mass, the content of dipentaerythritol pentaacrylate (b2) is 35.2% by mass, The content of pentaerythritol hexaacrylate (b3) was 62.1% by mass, and the content of high molecular weight component (b ') was 2.5% by mass.

Comparative Production Example 2: Production of dipentaerythritol (meth) acrylate (B5)
In a flask equipped with a thermometer, a stirrer, and a condenser, 180 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The produced water was 50 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water. Furthermore, the reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water. After hydroquinone monomethyl ether was added in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B5). The hydroxyl value of this dipentaerythritol (meth) acrylate (B5) was 160 mg KOH / g. Further, the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 36% by mass, the content of dipentaerythritol pentaacrylate (b2) is 48% by mass, and dipentaerythritol hexaacrylate The content of (b3) was 8% by mass, and the content of the high molecular weight component (b ') was 8% by mass.

Example 1 Preparation of Urethane (Meth) Acrylate Resin (1)
In a four-necked flask, 84 parts by mass of hexamethylene diisocyanate ("50M-HDI" manufactured by Asahi Kasei Corp.), 135 parts by mass of butyl acetate, 0.25 parts by mass of dibutyltin dilaurate, 0.25 parts by mass of methoquinone, and dibutylhydroxytoluene 4.0 parts by mass was added, and the flask was heated until the internal temperature reached 60.degree. Subsequently, 460 parts by mass of the dipentaerythritol (meth) acrylate (B1) (hydroxyl value: 125 mg KOH / g) obtained in Production Example 1 is dividedly added over about 2 hours, and urethane 8 A meta) acrylate resin (1) was obtained. The weight average molecular weight (Mw) of this urethane (meth) acrylate resin (1) was 6,000, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 118 g / equivalent. .

Examples 2 to 4 Preparation of Urethane (Meth) Acrylate Resins (2) to (4)
Urethane (meth) acrylate resins (2) to ((2) to (5) in the same manner as in Example 1 except that dipentaerythritol (meth) acrylate, isocyanate compound and butyl acetate were changed to the compositions and amounts shown in Table 1. I got 4).

Comparative Examples 1 and 2: Preparation of Urethane (Meth) Acrylate Resins (C1) and (C2)
Urethane (meth) acrylate resins (C1) and (C4) were prepared in the same manner as in Example 1, except that dipentaerythritol (meth) acrylate, isocyanate compound and butyl acetate were changed to the compositions and amounts shown in Table 1. I got C2).

"Isocyanate compound (A1)" in Table 1 shows hexamethylene diisocyanate.

"Isocyanate compound (A2)" in Table 1 shows pentamethylene diisocyanate.

Example 5 Preparation of Laminated Film (1)
A curable resin composition was prepared by mixing 125 parts by mass of the urethane (meth) acrylate resin (1) obtained in Example 1, 3 parts by mass of a photopolymerization initiator ("Omnirad-184" manufactured by IGM), and 72 parts by mass of methyl ethyl ketone I got Next, the obtained curable resin composition was applied on a 125 μm thick polyethylene terephthalate film (hereinafter abbreviated as “PET film”) with a bar coater and dried at 80 ° C. for 2 minutes. Subsequently, 300 mJ / cm ² of ultraviolet light was irradiated with a 80 W high pressure mercury lamp in a nitrogen atmosphere to obtain a laminated film having a cured coating film with a film thickness of 5 μm on a PET film.

(Examples 6 to 8: Preparation of laminated films (2) to (4))
Example 5 except that the urethane (meth) acrylate resins (2) to (4) obtained in Examples 2 to 4 were used instead of the urethane (meth) acrylate resin (1) used in Example 5 Laminated films (2) to (4) were obtained in the same manner as in the above.

Comparative Examples 3 and 4: Preparation of Laminated Films (R1) and (R2)
Example 5 except that the urethane (meth) acrylate resins (C1) and (C2) obtained in Comparative Examples 1 and 2 were used instead of the urethane (meth) acrylate resin (1) used in Example 5 Laminated films (R1) and (R2) were obtained in the same manner as in the above.

The following evaluation was performed using the laminated film obtained by said Example and comparative example.

[Method of measuring coating film hardness]
In the laminated films obtained in Examples and Comparative Examples, the hardness of the cured film surface of the curable resin composition was measured under a load of 500 g in accordance with JIS K 5600-5-4 [Scratch hardness (pencil method)]. did. The measurement was performed five times for one hardness, and the hardness at which four or more measurements were not scratched was taken as the hardness of the cured coating.

[Evaluation method of abrasion resistance]
A disc-shaped indenter with a diameter of 2.4 cm is wrapped with 0.5 g of steel wool ("Bonstar # 0000" manufactured by Japan Steel Wool Co., Ltd.), a load of 500 g is applied to the indenter, and in the examples and comparative examples The cured film surface of the obtained laminated film was subjected to an abrasion test in which the surface was cured 200 times. The haze value of the coating film before and after the abrasion test was measured using an automatic haze computer ("HZ-2" manufactured by Suga Test Instruments Co., Ltd.), and the scratch resistance was evaluated by the value of the difference (dH). The smaller the difference value (dH), the higher the resistance to abrasion.

[Method of evaluating flexibility]
Using a mandrel tester (“Bending Tester” manufactured by TP Giken Co., Ltd.), the laminated film obtained in Examples and Comparative Examples is wound around a test rod, and a test is performed to visually confirm whether or not a crack occurs. The minimum diameter of the test rod where no crack occurs was taken as the evaluation result. The test rods used had a diameter of 2 mm to 12 mm in 1 mm steps.

[Evaluation method of curl resistance]
The coating film of 5 cm square was cut out from the laminated film obtained by the Example and the comparative example, the test piece was obtained, the float from the level of a square was measured about this test piece, and the average value (mm) evaluated. The smaller the value, the smaller the curl and the better the curl resistance.

[Evaluation method of impact resistance]
The test was performed with reference to JIS K5600-5-3 (weight drop resistance). Specifically, it is as follows.
[apparatus]
Weight: A ball bearing steel ball (mass: 300.0 ± 0.5 g, diameter: 25.40 mm, grade: 60) specified in JIS B 1501 “Steel ball for five bearings” is suspended at the end by a thread.
Steel stand: A 300 mm long, 200 mm wide, and 30 mm thick steel stand horizontally installed on a concrete floor.
[operation]
1. The cured coated film surface of the laminated film was fixed upward on a steel table.
2. The weight was suspended at a position where the distance from the surface of the laminated film to the lower end of the weight was 50 mm, and after confirming that the swing or rotation had stopped, it was dropped onto the laminated film.
3. After the laminated film after the drop test was allowed to stand in the room for 1 hour, damage to the coated surface was examined.
4. The distance between the surface of the laminated film and the lower end of the weight was separated by 10 mm, and the test was continued to evaluate the maximum distance at which no cracking or peeling of the cured coating occurs.

The evaluation results of the laminated films (1) to (4) prepared in Examples 5 to 8 and the laminated films (R1) and (R2) prepared in Comparative Examples 3 and 4 are shown in Table 2.

Although Examples 5 to 8 shown in Table 2 are examples of the laminated film using the urethane (meth) acrylate resin of the present invention, the cured coating film of the urethane (meth) acrylate resin is excellent in the coating film hardness. It was also confirmed that the laminated film had excellent scratch resistance, flexibility, curl resistance and impact resistance.

On the other hand, Comparative Example 3 is an example using dipentaerythritol (meth) acrylate having a hydroxyl value of 43 mg KOH / g as a raw material of urethane (meth) acrylate resin, but the cured coating film of the urethane (meth) acrylate resin is Although excellent in coating film hardness, it was confirmed that the laminated film using the urethane (meth) acrylate resin was extremely insufficient in flexibility, curl resistance and impact resistance.

Comparative Example 4 is an example using dipentaerythritol (meth) acrylate having a hydroxyl value of 160 mg KOH / g as a raw material of urethane (meth) acrylate resin, but the cured coating film of the urethane (meth) acrylate resin is coated It was confirmed that the film hardness was insufficient, and that the laminated film using the urethane (meth) acrylate resin was extremely insufficient in abrasion resistance.

Claims (10)

It is urethane (meth) acrylate resin which uses an isocyanate compound (A) and dipentaerythritol (meth) acrylate (B) as an essential reaction raw material,
The urethane (meth) acrylate resin, wherein the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is in the range of more than 120 mg KOH / g and 150 mg KOH / g or less. The urethane (meth) acrylate resin according to claim 1, wherein the isocyanate compound (A) is an aliphatic isocyanate compound. The urethane (meth) according to claim 1, wherein the isocyanate compound (A) is an isocyanate compound (A1) represented by any one of the following structural formulas (A1-1) to (A1-3), or a modified product thereof. Acrylate resin.

Wherein R ¹ is each independently an alkyl group having 1 to 4 carbon atoms, and j is an integer of 0 or 1 to 4. R ² is independently a hydrogen atom or 1 to 4 carbon atoms. Any of the alkyl groups) The urethane (meth) acrylate resin according to claim 1, wherein the isocyanate compound (A) is an isocyanate compound (A2) represented by the following structural formula (A2-1) or (A2-2), or a modified product thereof.

(Wherein, l is an integer of 0 or 1 or more, m is 1 or 2. R ³ is each independently an alkyl group having 1 to 4 carbon atoms, or a structural portion represented in the parenthesis) And any of the bonding points linked via a methylene group marked with an asterisk (*), k is 0, 1 or 2 and n is an integer of 0 or 1 to 8.) The dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (meth) acrylate (b2). The urethane (meth) acrylate resin according to any one of the items. The urethane (meth) acrylate resin according to claim 5, wherein the content of the dipentaerythritol tetra (meth) acrylate (b1) is in the range of 10 to 50% by mass in the dipentaerythritol (meth) acrylate (B). . The content ratio of the dipentaerythritol tetra (meth) acrylate (b1) in the dipentaerythritol (meth) acrylate (B) to the dipentaerythritol penta (meth) acrylate (b2) [(b1) / ((b)) The urethane (meth) acrylate resin according to claim 5, wherein b2) is in the range of 20/80 to 80/20. A curable resin composition comprising the urethane (meth) acrylate resin according to any one of claims 1 to 7 and a photopolymerization initiator. A cured product characterized in that it is a cured reaction product of the curable resin composition according to claim 8. A laminated film having a layer comprising the cured product according to claim 9 on the surface of a substrate.