JP2019107827A - Laminated film, decorative film, and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film having high tack-free property and excellent scratch resistance, chemical resistance and substrate adhesion, a decorative film, and an article having the decorative film. A laminated film having a cured coating film of an active energy ray-curable resin composition on a substrate, wherein the active energy ray-curable resin composition is polyisocyanate (A) and dipentaerythritol (meth). ) A urethane (meth) acrylate resin containing acrylate (B) as an essential reaction raw material is contained, and the polyisocyanate (A) contains an isocyanurate form of isophorone diisocyanate, and the dipentaerythritol is contained. A laminated film characterized in that the hydroxyl value of the (meth) acrylate (B) is in the range of 70 to 150 mgKOH / g is used. [Selection diagram] None

Description

  The present invention relates to a laminated film, a decorative film, and an article having the decorative film.

  In recent years, in decorative molding of plastic products such as automobile interior parts and home electric appliance casings, a method using a decorative film has been developed because the degree of freedom of design is high and the processability is excellent. As the required characteristics for such a decorative film, not only processability applicable to three-dimensional molding, but also scratch resistance and chemical resistance for the purpose of surface protection of products, adhesion to a substrate, etc. are required. There is.

  Conventionally known decorative films include urethanes obtained by reacting polyisocyanate, polycarbonate diol having a structural unit derived from C 7-14 alkylene glycol, and hydroxyalkyl (meth) acrylate ( Although the thing using a meta) acrylate oligomer is known (for example, refer patent document 1), tack-free property is not enough and it did not satisfy now more and more required characteristic.

  Therefore, there has been a demand for a laminated film and a decorative film which have high tack free property and are excellent in abrasion resistance, chemical resistance and substrate adhesion.

Unexamined-Japanese-Patent No. 2014-231591

  The problem to be solved by the present invention is to provide a laminated film, a decorative film, and an article having the decorative film, having high tack free property and being excellent in scratch resistance, chemical resistance and substrate adhesion. It is to be.

  As a result of earnest research to solve the above problems, the inventors of the present invention have found that urethane (meth) acrylate resin essentially comprising a specific polyisocyanate and dipentaerythritol (meth) acrylate having a hydroxyl value within a specific range. The inventors have found that the above-mentioned problems can be solved by using an active energy ray-curable resin composition containing the present invention, and have completed the present invention.

  That is, the present invention is a laminated film having a cured coating film of an active energy ray curable resin composition on a substrate, wherein the active energy ray curable resin composition comprises polyisocyanate (A) and dipentaerythritol. It contains urethane (meth) acrylate resin which uses (meth) acrylate (B) as an essential reaction raw material, and the above-mentioned polyisocyanate (A) contains the isocyanurate body of isophorone diisocyanate, The present invention relates to a laminated film characterized by a hydroxyl value of pentaerythritol (meth) acrylate (B) being in the range of 70 to 150 mg KOH / g, a decorative film, and an article having the decorative film.

  The laminated film of the present invention has high tack free property and is excellent in scratch resistance, chemical resistance and substrate adhesion, so it is suitable for decorative molding of plastic products such as automobile interior parts and home electric appliance casings. It can be used for

  The laminated film of the present invention is characterized in that it has a cured coating film of an active energy ray-curable resin composition on a substrate.

  In the present invention, "(meth) acrylate resin" refers to a resin having one or both of an acryloyl group and a methacryloyl group in the molecule. Also, "(meth) acryloyl group" refers to one or both of an acryloyl group and a methacryloyl group, and "(meth) acrylate" refers to one or both of acrylate and methacrylate.

  The active energy ray curable resin composition contains a urethane (meth) acrylate resin.

  The urethane (meth) acrylate resin uses polyisocyanate (A) and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials.

  As the polyisocyanate (A), an isocyanurate of isophorone diisocyanate is essential because a laminated film having high tack free property and excellent in scratch resistance, chemical resistance and substrate adhesion is obtained. Use.

  Moreover, as said polyisocyanate (A), it can be used combining other polyisocyanate as needed.

  Examples of the other polyisocyanate include polyisocyanates having an aliphatic cyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc .; 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane Aromatic polyisocyanates such as diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate and naphthalene diisocyanate; and aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate. Moreover, these other polyisocyanates can be used alone or in combination of two or more.

  Further, as the other polyisocyanate, it is also possible to use a nurate modified product of the above-mentioned various other polyisocyanates than the isocyanurate of the isophorone diisocyanate, an adduct modified product, a biuret modified product, an allophanate modified product or the like.

  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 polyisocyanate (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.

  The dipentaerythritol (meth) acrylate (B) has high tack free property, and a laminated film excellent in abrasion resistance, chemical resistance and substrate adhesion can be obtained. It is preferable to contain acrylate (b1) as an essential component, and it is more preferable to contain dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (meth) acrylate (b2), and dipentaerythritol tetra ( It is particularly preferable to contain meta) 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 in the acrylate (B) is preferably in the range of 1 to 40% by mass because a laminated film having high tack free property and excellent in scratch resistance, chemical resistance and substrate adhesion can be obtained. The range of 3 to 35% by mass is more preferable, and the range of 5 to 30% by mass is particularly preferable.

  When the dipentaerythritol (meth) acrylate (B) contains the dipentaerythritol tetra (meth) acrylate (b1) and the dipentaerythritol penta (meth) acrylate (b2), it has high tack free property. And, since it is possible to obtain a laminated film excellent in scratch resistance, chemical resistance and substrate adhesion, it is possible to use the dipentaerythritol tetra (meth) acrylate (b1) and the dipentaerythritol penta (meth) acrylate (b2) The content ratio [(b1) / (b2)] is preferably in the range of 1/99 to 50/50, and more preferably in the range of 10/90 to 45/55.

  When the dipentaerythritol (meth) acrylate (B) contains the dipentaerythritol hexa (meth) acrylate (b3), it has high tack free property, and scratch resistance, chemical resistance and substrate adhesion The content of the dipentaerythritol (hexa) acrylate (b3) in the dipentaerythritol (meth) acrylate (B) is preferably in the range of 1 to 60% by mass because a laminated film excellent in 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. 30 seconds vortex
Leave for 30 minutes
4. Calculation of the area ratio as a measurement sample by passing through a 0.2 μm filter: Calculation at UV wavelength of 210 nm

  Further, the hydroxyl value of the dipentaerythritol (meth) acrylate (B) has high tack free property, and a laminated film excellent in scratch resistance, chemical resistance and substrate adhesion can be obtained. It is preferably in the range of -150 mg KOH / g, more preferably in the range of 100 to 150 mg KOH / g, and particularly preferably in the range of 120 to 150 mg KOH / g.

  In addition, the hydroxyl value of the said dipentaerythritol (meth) acrylate (B) is each measured from the actual value measured according to the neutralization titration method of JISK 0070 (1992), or the area ratio of the liquid chromatography chart. It is a calculated value calculated from the composition ratio of the components.

  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 dipentaerythritol (meth) acrylate (B) crude product is preferably in the range of 1 to 20% by mass.

  Although the said urethane (meth) acrylate resin makes the said polyisocyanate (A) and the said dipentaerythritol (meth) acrylate (B) an essential reaction raw material, as needed, the 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-acrylate Aromatic ring-containing (meth) acrylate compounds such as phenyl-2-hydroxyethyl, 3-hydroxy-4-acetylphenyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate; Polyether-modified (meth) obtained by ring-opening polymerization of a arylate 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; Lactone-modified (meth) acrylate compounds obtained by polycondensation of the (meth) acrylate compounds and lactone compounds 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, aliphatic (meth) acrylate compounds or polyether-modified products thereof, lactones are obtained because they have high tack free property and can obtain a laminated film excellent in scratch resistance, chemical resistance and substrate adhesion. Denatured 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, glycerol 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, sebacine By co-condensation with terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,4-cyclohexanedicarboxylic acid and other dicarboxylic acids Polyester polyol obtained; lactone type polyester polyol obtained by polycondensation reaction of the polyol monomer with various lactones such as ε-caprolactone, δ-valerolactone, 3-methyl-δ-valerolactone; The polyether polyol etc. which are obtained by ring-opening polymerization with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether and the like can be mentioned. 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 polyisocyanate (A) has, the polyisocyanate (A) and the dipentaerythritol (meth) acrylate (B), and the di- The molar ratio [(NCO) / (OH)] to the hydroxyl group possessed by pentaerythritol (meth) acrylate (B) is in the range of 1 / 1.05 to 1/2, and the temperature is 20 to 120 ° C. Within the scope, if necessary, a method using a urethanization catalyst can be mentioned.

  The (meth) acryloyl group equivalent of the urethane (meth) acrylate resin has high tack free property, and can obtain a laminated film excellent in scratch resistance, chemical resistance and substrate adhesion, so 100 to 500 g The range of / eq is preferable, and the range of 100 to 200 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.

  In addition, the weight average molecular weight (Mw) of the urethane (meth) acrylate resin is high tack free, and a laminated film excellent in scratch resistance, chemical resistance and substrate adhesion can be obtained. The range of 1,000 to 100,000 is preferable, and the range of 10,000 to 100,000 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.

  In addition to the urethane (meth) acrylate resin, the active energy ray-curable resin composition may contain other photocurable compounds, organic solvents, ultraviolet absorbers, antioxidants, silicon-based additives, and fluorine-based additives. A silane coupling agent, a phosphoric acid ester compound, organic beads, inorganic fine particles, an inorganic filler, a rheology control agent, a defoamer, an antifogging agent, a colorant and the like may be contained.

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

  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) a Lilate, 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, 2 (Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (Meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyltetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (Meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, adamantine Mono (meth) acrylates such as lummono (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 polyisocyanate other than the said polyisocyanate (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 one 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], "SP-1106 manufactured by MIWON" [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 per molecule 18], "Esdrimer HU-22" manufactured by Nippon Steel Sumikin Chemical Co., Ltd., "A-HBR-5" manufactured by Shin-Nakamura Chemical Co., Ltd., "New Frontier R" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. A commercial product such as “−1150” or “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 be 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 manufacture by polymerizing various monomers in the temperature range of 60-150 degreeC in presence of a polymerization initiator. 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 of using a catalyst suitably, etc. are mentioned. Moreover, when this reaction is a urethanation reaction, the method etc. are made to react, dripping the said (meth) acrylate monomer ((alpha)) to an acrylic resin intermediate body in a temperature range of 50-120 degreeC.

  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 may be used alone or in combination of two or more. Above all, it is preferable to use various (meth) acrylate monomers (R1), since the composition is excellent in curability. When these other photocurable compounds are used, 5 parts by mass of the urethane (meth) acrylate resin 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. It is preferable to use in the ratio which becomes more than, it is more preferable to use in the ratio which becomes 20 mass parts or more, and it is especially preferable to become 80 mass parts 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. Moreover, although these organic solvents are mainly used in order to adjust the viscosity of a curable composition, it is preferable to adjust normally so that a non volatile matter may become the range of 10-80 mass%.

  Examples of the ultraviolet light 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-dodecyloxy benzophenone, 2-o-nitrobenzyloxy-4-dodecyloxy benzophenone 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- (a) Noethyl) -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 pro Triethoxysilane, 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-glycidoxypropyltriyl 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-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrile 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 compound include those having a (meth) acryloyl group in the molecular structure, and examples of commercially available products include “Kayamar PM-2” manufactured by Nippon Kayaku Co., Ltd., “Kayamer PM- 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 "SIPO" manufactured by SOLVAY, which is a phosphoric acid ester compound having ER 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 diameter 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. Further, 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 laminated film of the present invention has a cured coating film of the active energy ray curable resin composition on a substrate.

  As a method for producing a laminated film of the present invention, for example, a method of applying the active energy ray curable resin composition to at least one surface of the base material 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 active energy ray 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), etc.

  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.

  Examples of the active energy ray include ionizing radiation such as ultraviolet ray, electron beam, α ray, β ray, and γ ray. Moreover, when using an ultraviolet-ray as said active energy ray, in order to perform the curing reaction by an ultraviolet-ray efficiently, you may irradiate in inert gas atmospheres, such as nitrogen gas, and you may irradiate in an air atmosphere.

  As a source of the ultraviolet light, ultraviolet lamps are generally used in terms of practicality and economy. Specifically, low pressure mercury lamps, high pressure mercury lamps, super high pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs and the like can be mentioned.

  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, it is preferable normally that it is the range of 0.01-50 micrometers. .

  Moreover, it is preferable to add a photoinitiator to the said active energy ray curable resin composition from the ability to improve the hardenability of the cured coating film of the said active energy ray curable resin composition. In addition, if necessary, a photosensitizer can be further added to improve the curability.

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy -2-Methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4, 6 trimethyl benzoyl) phenyl phosphine oxide, 2-methyl 1- (4 methyl thio phenyl) 2-morpholinopropan 1 -one , 2-benzyl-2-dimethylamino-1- (4-morpholinophe) Le) - butan-1-one, and the like.
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  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 0.1-5 mass parts is preferable with respect to 100 mass parts of urethane (meth) acrylate resin, and the range of 1-3 mass parts is more preferable.

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

  As a decorative film of this invention, what is decorated is mentioned to the surface of the said laminated film, for example. In addition, the decorative film of the present invention can be suitably used for automobile interiors.

  Examples of the article of the present invention include plastic molded articles such as mobile phones, automobile interior and exterior materials, home electric appliance casings, and OA equipment.

  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: 0.4% by mass of tetrahydrofuran solution 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. 30 seconds vortex
Leave for 30 minutes
4. Calculation of the area ratio as a measurement sample by passing through a 0.2 μm filter: Calculation at UV wavelength of 210 nm

Production Example 1: Production of dipentaerythritol (meth) acrylate (B1)
In a flask equipped with a thermometer, a stirrer, and a condenser, 310 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 73.5 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 78 mg KOH / g (measured value). In addition, the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 5.2% by mass, the content of dipentaerythritol pentaacrylate (b2) is 44.8% by mass, The content of pentaerythritol hexaacrylate (b3) was 41.7% by mass, and the content of high molecular weight component (b ') was 8.3% by mass.

(Production Examples 2 to 5: Production of dipentaerythritol (meth) acrylate (B2) to (B5))
Dipentaerythritol (meth) acrylates (B2) to (B5) were obtained in the same manner as in Production Example 1 except that the preparation amount of acrylic acid and the reaction time were changed as shown in Table 1. The content of each component calculated from the hydroxyl value of dipentaerythritol (meth) acrylate (B2) to (B5), the area ratio of the liquid chromatography chart, dipentaerythritol (Meta calculated from the content ratio of each component Table 1 shows the hydroxyl value of the acrylates (B2) to (B5).

Production Example 6 Production of Urethane (Meth) Acrylate Resin (1)
In a four-necked flask, 242.8 parts by mass of an isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 331.5 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, and methoquinone 0.4 A mass part and 4.0 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Subsequently, 1078.8 parts by mass of dipentaerythritol (meth) acrylate (B1) (hydroxyl value: 78 mg KOH / g) obtained in Production Example 1 is dividedly introduced over about 2 hours, and reacted at 85 ° C. for 8 hours Urethane (meth) acrylate resin (1) was obtained. The weight average molecular weight (Mw) of this urethane (meth) acrylate resin (1) was 7,000, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 124 g / equivalent. .

Production Example 7 Production of Urethane (Meth) Acrylate Resin (2)
In a four-necked flask, 242.8 parts by mass of an isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 313.5 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, and methoquinone 0.4 A mass part and 3.8 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Next, 1006.9 parts by mass of the dipentaerythritol (meth) acrylate (B1) (hydroxyl value: 78 mg KOH / g) obtained in Production Example 1 is dividedly introduced over about 2 hours, and reacted at 85 ° C. for 8 hours Urethane (meth) acrylate resin (2) was obtained. The weight average molecular weight (Mw) of this urethane (meth) acrylate resin (2) was 11,700, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 126 g / equivalent. .

Production Example 8 Production of Urethane (Meth) Acrylate Resin (3)
In a four-necked flask, 242.8 parts by mass of an isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 280.8 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, 0.3 part of methoquinone A mass part and 3.4 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Next, 876.6 parts by mass of dipentaerythritol (meth) acrylate (B2) (hydroxyl value: 96 mg KOH / g) obtained in Production Example 2 is dividedly introduced over about 2 hours, and reacted at 85 ° C. for 8 hours Urethane (meth) acrylate resin (3) was obtained. The weight average molecular weight (Mw) of this urethane (meth) acrylate resin (3) was 14,200, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 131 g / equivalent. .

Production Example 9 Production of Urethane (Meth) Acrylate Resin (4)
In a four-necked flask, 242.8 parts by mass of an isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 268.2 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, 0.3 part of methoquinone A mass part and 3.2 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Subsequently, 826.3 parts by mass of the dipentaerythritol (meth) acrylate (B3) (hydroxyl value: 129 mg KOH / g) obtained in Production Example 3 is dividedly introduced over about 2 hours, and reacted at 85 ° C. for 8 hours Urethane (meth) acrylate resin (4) was obtained. The weight average molecular weight (Mw) of this urethane (meth) acrylate resin (4) was 12,000, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 138 g / equivalent. .

Production Example 10 Production of Urethane (Meth) Acrylate Resin (5)
In a four-necked flask, 242.8 parts by mass of an isocyanurate form of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 224.5 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, 0.3 part of methoquinone A mass part and 2.7 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Subsequently, 652.3 parts by mass of dipentaerythritol (meth) acrylate (B3) (hydroxyl value: 129 mg KOH / g) obtained in Production Example 3 is dividedly introduced over about 2 hours, and reacted at 85 ° C. for 8 hours Urethane (meth) acrylate resin (5) was obtained. The weight average molecular weight (Mw) of this urethane (meth) acrylate resin (5) was 28,900, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 146 g / equivalent. .

Production Example 11 Production of Urethane (Meth) Acrylate Resin (6)
In a four-necked flask, 242.8 parts by mass of an isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 213.6 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, 0.3 part of methoquinone A mass part and 2.6 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Next, 608.8 parts by mass of the dipentaerythritol (meth) acrylate (B3) (hydroxyl value: 129 mg KOH / g) obtained in Production Example 3 is dividedly introduced over about 2 hours, and reacted at 85 ° C. for 8 hours Urethane (meth) acrylate resin (6) was obtained. The weight-average molecular weight (Mw) of this urethane (meth) acrylate resin (6) was 96,300, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 150 g / equivalent. .

Production Example 12 Production of Urethane (Meth) Acrylate Resin (7)
In a four-necked flask, 242.8 parts by mass of an isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 331.5 parts by mass of butyl acetate, 0.2 parts by mass of dibutyltin dilaurate, and methoquinone 0.7 A mass part and 6.6 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Next, 1957.0 parts by mass of dipentaerythritol (meth) acrylate (B4) (hydroxyl value: 43 mg KOH / g) obtained in Production Example 4 is dividedly introduced over about 2 hours, and reacted at 85 ° C. for 8 hours Urethane (meth) acrylate resin (7) was obtained. The weight average molecular weight (Mw) of this urethane (meth) acrylate resin (7) was 3,700, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 110 g / equivalent. .

Production Example 13 Production of Urethane (Meth) Acrylate Resin (8)
In a four-necked flask, 242.8 parts by mass of an isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 185.8 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, and methoquinone 0.2 A mass part and 0.2 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Subsequently, 1957.0 parts by mass of the dipentaerythritol (meth) acrylate (B5) (hydroxyl value: 169 mg KOH / g) obtained in Production Example 5 was dividedly introduced over about 2 hours, and reacted at 85 ° C. Progressed.

Production Example 14 Production of Urethane (Meth) Acrylate Resin (9)
In a four-necked flask, 242.8 parts by mass of an isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 98.8 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, 0.1 part of methoquinone A mass part and 1.2 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Next, 174.2 parts by mass of 2-hydroxyethyl acrylate was dividedly charged over about 2 hours, and reacted at 85 ° C. for 4 hours to obtain a urethane (meth) acrylate resin (9). The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (9) was 700, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 279 g / equivalent.

Production Example 15 Production of Urethane (Meth) Acrylate Resin (10)
In a four-necked flask, 242.8 parts by mass of isocyanurate of isophorone diisocyanate ("VESTANAT T 1890/100" manufactured by Evonik Co., Ltd.), 244.5 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, and 0.3 A mass part and 2.9 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degreeC. Next, 731.7 parts by mass of pentaerythritol (meth) acrylate ("MIRAMER M340" manufactured by MIWON) is dividedly introduced over about 2 hours, and reacted at 85 ° C. for 8 hours to react with urethane (meth) acrylate resin (10) I got The weight-average molecular weight (Mw) of this urethane (meth) acrylate resin (10) was 2,400, and the theoretical value of the (meth) acryloyl group equivalent calculated from the feed ratio of the raw materials was 124 g / equivalent .

Production Example 16 Production of Urethane (Meth) Acrylate Resin (11)
In a four-necked flask, 111.0 parts by mass of isophorone diisocyanate (Evonik "VESTANAT IPDI", 191.5 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, 0.2 parts by mass of methoquinone, and dibutyl hydroxytoluene 2.3 parts by mass was added, and the flask was heated until the internal temperature reached 60 ° C. Then, dipentaerythritol (meth) acrylate (B3) (hydroxyl value: 129 mg KOH / g) 652 obtained in Production Example 3. A urethane (meth) acrylate resin (11) was obtained by separately charging 3 parts by mass over about 2 hours and reacting for 8 hours at 85 ° C. The weight average molecular weight of this urethane (meth) acrylate resin (11) Mw) is 3,700 and is a theoretical value of (meth) acryloyl group equivalent calculated from the feed ratio of raw materials Was 124 g / equivalent.

Production Example 17 Production of Urethane (Meth) Acrylate Resin (12)
In a four-necked flask, isocyanurate of hexamethylene diisocyanate (178.7 parts by mass of "Barnock DN-901S" manufactured by DIC, 208.3 parts by mass of butyl acetate, 0.1 parts by mass of dibutyltin dilaurate, 0.3 parts by mass of methoquinone A mass part and 2.5 mass parts of dibutyl hydroxytoluenes were added, and it heated until the internal temperature of a flask became 60 degrees C. Then, the dipentaerythritol (meth) acrylate (B3) (hydroxyl value) obtained by manufacture example 3 A urethane (meth) acrylate resin (12) was obtained by separately charging 652.3 parts by mass of 129 mg KOH / g) over about 2 hours and reacting for 8 hours at 85 ° C. This urethane (meth) acrylate resin ( The weight average molecular weight (Mw) of 12) is 9,300, which is calculated from the feed ratio of the raw materials (meth) acrylic Theoretical value of yl group equivalent was 135 g / equivalent.

Example 1 Preparation of Laminated Film (1)
125 parts by mass of the urethane (meth) acrylate resin (1) obtained in Production Example 6, 3 parts by mass of a photopolymerization initiator ("Omnirad-184" manufactured by IGM Corporation), and 72 parts by mass of methyl ethyl ketone A resin composition was obtained. Then, the obtained active energy ray 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. Then, under a nitrogen atmosphere, ultraviolet light was irradiated at 300 mJ / cm ² with an 80 W high pressure mercury lamp to obtain a laminated film (1) having a cured coating film with a film thickness of 5 μm on a PET film.

(Examples 2 to 6 and Comparative Examples 1 to 5: Preparation of laminated films (2) to (6) and (C1) to (C5))
Example except that urethane (meth) acrylate resin (1) used in Example 1 was changed to urethane (meth) acrylate resins (2) to (7) and (8) to (12) as shown in Table 2, respectively In the same manner as Example 1, an active energy ray-curable resin composition and a laminated film using the active energy ray-curable resin composition were obtained.

  The following evaluation was performed using the active energy ray curable resin composition and laminated | multilayer film which were obtained by said Example and comparative example.

[Evaluation method of tack freeness]
The active energy curable resin composition was coated on a 125 μm-thick PET film by a bar coater and dried at 80 ° C. for 2 minutes. Subsequently, the presence or absence of tack was confirmed by overlapping the finger touch test and another PET film and applying a load, and evaluation was made according to the following criteria.

A: There is no change in appearance in the finger touch test, and the films do not adhere to each other even if the PET films are stacked.
B: The appearance does not change in the finger touch test, but when the PET films are stacked, the films adhere to each other.
C: A slight mark remains on the appearance in the finger touch test.
D: Marked tack is observed in the finger touch test.

[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 chemical resistance]
A sunscreen cream ("Neutrogena Ultra Shear Sunscreen" manufactured by Johnson & Johnson Consumer Inc.) is applied on the laminated film obtained in Examples and Comparative Examples to a concentration of 0.1 g / cm ² and the inside of an oven at 80 ° C. Left for 6 hours. After taking out from the oven and returning to normal temperature, the sunscreen cream was wiped off with a cloth, and the state of the coated film surface after wiping was evaluated according to the following criteria.

A: There is no change compared with the laminated film before a test.
B: A thin and transparent mark remains on the coating.
C: Whitening or cracks occur in a part of the coated part.
D: Whitening or cracks occur on the entire surface of the coated part.

[Method of evaluating adhesion to substrate]
The active energy ray-curable resin composition was applied on a 60 μm thick acrylic film with a bar coater and dried at 80 ° C. for 2 minutes. Subsequently, 50 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 an acrylic film. The cured coating film surface of this laminated film is cut with a cutter knife to make 100 grids of 1 mm × 1 mm, and after sticking cellophane adhesive tape from above, perform an operation of rapidly peeling it away The number of grids remaining without being counted was counted and evaluated according to the following criteria.

A: The remaining number of grids was 80 or more.
B: The number of remaining cells in the grid was 50 or more and less than 80.
C: The number of remaining cells in the grid was 30 or more and less than 50.
D: The number of remaining grids was less than 30.

  The evaluation results of the laminated films (1) to (6) manufactured in Examples 1 to 6 and the laminated films (C1) to (C5) manufactured in Comparative Examples 1 to 5 are shown in Table 2.

  Although Examples 1 to 6 shown in Table 2 are examples using the active energy ray curable resin composition containing the urethane (meth) acrylate of the present invention, the coating of the active energy ray curable resin composition is It is confirmed that the film has high tack free property, and further, the laminated film using the active energy ray curable resin composition has excellent scratch resistance, chemical resistance and substrate adhesion. did it.

  On the other hand, Comparative Example 1 is an example using dipentaerythritol (meth) acrylate having a hydroxyl value of 43 mg KOH / g as a raw material of urethane (meth) acrylate, but the active energy ray curing containing the urethane (meth) acrylate It was confirmed that the coating film of the base resin composition had an insufficient tack free property.

  Comparative Example 2 is an example using 2-hydroxyethyl acrylate as a raw material of urethane (meth) acrylate, but the coating film of the active energy ray curable resin composition containing the urethane (meth) acrylate has high tack free property Although it had, it was confirmed that the obtained laminated film was extremely insufficient in abrasion resistance, chemical resistance and substrate adhesion.

  Comparative Example 3 is an example in which pentaerythritol (meth) acrylate is used as a raw material of urethane (meth) acrylate, but the coating film of the active energy ray curable resin composition containing the urethane (meth) acrylate is tack free Was confirmed to be inadequate.

  Comparative Example 4 is an example using isophorone diisocyanate as a raw material of urethane (meth) acrylate, but the coating film of the active energy ray-curable resin composition containing the urethane (meth) acrylate is the same as Comparative Example 2 It was confirmed that tack freeness was insufficient. In addition, it was confirmed that the obtained laminated film was inferior in abrasion resistance and chemical resistance to the laminated film of the present invention.

  Comparative Example 5 is an example using a nurate body of hexamethylene diisocyanate as a raw material of urethane (meth) acrylate, but the coating film of the active energy ray curable resin composition containing the urethane (meth) acrylate is compared As in Examples 2 and 3, it was confirmed that the tack free property was insufficient.

Claims (8)

A laminated film having a cured coating film of an active energy ray curable resin composition on a substrate,
The active energy ray-curable resin composition contains a urethane (meth) acrylate resin containing polyisocyanate (A) and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials,
The polyisocyanate (A) contains an isocyanurate of isophorone diisocyanate,
The laminated film characterized in that the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is in the range of 70 to 150 mg KOH / g.   The lamination according to claim 1, wherein the dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (meth) acrylate (b2). the film.   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 laminated film according to claim 2, wherein b2) is in the range of 1/99 to 50/50.   The laminated film according to claim 2, wherein the dipentaerythritol (meth) acrylate (B) further contains dipentaerythritol hexa (meth) acrylate (b3).   The laminated film according to claim 4, wherein a content of the dipentaerythritol hexa (meth) acrylate (b3) in the dipentaerythritol (meth) acrylate (B) is in a range of 1 to 60% by mass.   The laminated film according to any one of claims 1 to 5, wherein the weight average molecular weight of the urethane (meth) acrylate resin is in the range of 5,000 to 100,000.   A decorative film characterized in that the surface of the laminated film according to any one of claims 1 to 6 is decorated.   An article comprising the decorative film according to claim 7.