JP2019194295A - Curable resin composition and laminate - Google Patents

Abstract

To provide a curable composition that can form a cured product layer having excellent chemical resistance, particularly resistance to a sunscreen agent, and a laminate having a cured product layer thereof.SOLUTION: A curable resin composition contains a hydroxy group-containing composition and a crosslinker, the hydroxy group-containing composition being a composition that has a break elongation at 80°C of less than 100% when cured with xylylene diisocyanate.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition capable of forming a cured product layer having excellent chemical resistance, particularly excellent resistance to sunscreen agents, and a laminate having the cured coating film.

Conventionally, for the purpose of improving the design of automobile interior parts, resin molded products in which decorative sheets are laminated are used on the surface of resin molded products. These molded articles are manufactured by, for example, integrating a decorative sheet, on which a pattern has been printed, with a resin by injection molding.
These decorative sheets are required to have chemical resistance against chemicals such as fragrances and sunscreens used in automobiles in addition to moldability. Especially, the request | requirement of the tolerance improvement with respect to a sunscreen agent is strong, and various proposals have been made | formed.

  For example, Patent Document 1 describes a laminate in which a paint having improved resistance to a sunscreen containing a binder resin and crosslinked resin particles is applied.

Japanese Patent Laid-Open No. 2006-89019

However, the method described in Patent Document 1 has insufficient resistance to sunscreen agents.
The present invention solves these problems, a curable resin composition capable of forming a cured product layer having excellent chemical resistance, in particular, resistance to sunscreen agents, and a laminate having the cured coating film thereof The purpose is to provide.

  That is, the gist of the present invention is the following [1] to [14].

[1] A curable resin composition containing a hydroxyl group-containing composition and a crosslinking agent, and when the hydroxyl group-containing composition is cured with xylylene diisocyanate, the elongation at break at 80 ° C. is less than 100%. A curable resin composition which is a composition.
[2] The curable resin composition according to [1], wherein the hydroxyl group-containing composition includes a polyurethane compound A having two or more hydroxyl groups.
[3] The curable resin composition according to [2], wherein the polyurethane compound A is a reaction product of a diol having a molecular weight of less than 500 and a diisocyanate.
[4] The curable resin composition according to [3], wherein the diol having a molecular weight of less than 500 has an amide group.
[5] The curable resin composition according to [2], wherein the polyurethane compound A is a reaction product of diamine, diisocyanate and polyol.
[6] The curable resin composition according to any one of [2] to [5], wherein the polyurethane compound A has three or more hydroxyl groups.
[7] The curable resin composition according to any one of [1] to [6], wherein the hydroxyl group-containing composition further includes an acrylic polymer B having two or more hydroxyl groups.
[8] The curable resin composition according to [7], wherein the acrylic polymer B includes a quaternary ammonium salt structure.
[9] The curable resin composition according to [8], wherein the content of the quaternary ammonium salt structure in the acrylic polymer B is 0.05 mmol / g or more.
[10] The curable resin composition according to any one of [1] to [9], wherein the crosslinking agent is a compound having an isocyanate group.
[11] A laminate having a layer made of a cured product of the curable resin composition according to any one of [1] to [10].
[12] A laminate having a surface protective layer on the surface of the cured product of the laminate according to [11].
[13] A laminate having a layer made of a cured product of the curable resin composition according to any one of [1] to [10] on the surface protective layer of the laminate.
[14] An article decorated with the laminate according to any one of [11] to [13].

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which can form the cured | curing material layer which has the outstanding chemical resistance, especially the tolerance with respect to a sunscreen agent can be provided.

  The curable resin composition of the present invention comprises a hydroxyl group-containing composition and a crosslinking agent, and when the hydroxyl group-containing composition is cured with xylylene diisocyanate, the elongation at break at 80 ° C. is less than 100%. It is a thing.

  In the curable resin composition of the present invention, the hydroxyl group of the hydroxyl group-containing composition reacts with the crosslinking agent to be cured to form a cured product.

  The present invention requires that the hydroxyl group-containing composition is a composition having an elongation at break of less than 100% at 80 ° C. when cured with xylylene diisocyanate.

  When the hydroxyl group-containing composition contains a crosslinking agent and the elongation at break is less than 100%, the chemical resistance of the cured product of the resulting curable resin composition is improved. The breaking elongation is preferably 70% or less, more preferably 60% or less, from the viewpoint of resistance to sunscreen agents.

In addition, when hardening the hydroxyl-containing composition of this invention, the xylylene diisocyanate amount with respect to 1 g of the said composition is calculated | required by following Formula.
Xylylene diisocyanate amount (g) = 1000 × 56.1 × 94.09 / hydroxyl value At this time, the hydroxyl value means neutralizing acetic acid bonded to a hydroxyl group when 1 g of the hydroxyl group-containing composition is acetylated. Is the amount of potassium hydroxide (mg) required for this, where 56.1 is the molecular weight of potassium hydroxide and 94.09 is the molecular weight per isocyanate group of xylylene diisocyanate.

  In the present invention, it is preferable that the hydroxyl group-containing composition contains a polyurethane compound A having two or more hydroxyl groups. By using the polyurethane compound A, high chemical resistance and high moldability can be obtained.

The polyurethane compound A is a reaction product of a polyol and a polyisocyanate.
In the present invention, a polyol is a compound having two or more hydroxyl groups in one molecule, and a polyisocyanate is a compound having two or more isocyanate groups in one molecule.

  The polyurethane compound A can be produced by reacting the total hydroxyl group mol amount of the polyol and the total isocyanate group mol amount of the polyisocyanate so that the total hydroxyl group mol amount> the total isocyanate group mol amount.

  Examples of the polyol include polyether polyol, polyester polyol, polycaprolactone polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol, silicon polyol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate, and bisphenol A. These may be used alone or in combination of two or more.

  Of these, polycaprolactone polyol and polycarbonate polyol are preferred. The polycaprolactone polyol can be obtained by ring-opening polymerization of a cyclic lactone compound with a low molecular polyol. Examples of the cyclic lactone compound include ε-caprolactone, γ-butyrolactone, δ-valerolactone, and the like. These can be used alone or in combination. The low molecular weight polyol has a molecular weight of about several tens to several hundreds, and has two or more hydroxyl groups in one molecule. Specifically, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1 , 5-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9- Nonanediol, 1,10-decanediol, neopentyl glycol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-hexyl-1,3-propanediol, cyclohexanedimethanol, Glycerin, trimethylolpropane, 1,2,6-hexanetriol, diglycerin, pe Low molecular weight compounds such as data erythritol, and oligomers and the like, such as alkylene oxide adducts of bisphenol A, to these can be used alone or may be used in combination. Examples thereof include Plaxel (registered trademark) 205, 210, 303, and 305 (manufactured by Daicel Chemical Industries).

  The polycarbonate polyol can be obtained, for example, by reacting at least one carbonate compound selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate with a diol or polyether polyol. Examples of the diol as a raw material for the polycarbonate polyol include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and 1,9- Nonanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, diethylene glycol, dipropylene glycol, polybutadiene diol and the like can be mentioned. Among these, it is preferable that at least one selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol is included from the viewpoint of wear resistance. Examples of the polycarbonate polyol include DURANOL (registered trademark) T4671, T4691, 5651, 6001 (manufactured by Asahi Kasei Corporation).

  Examples of the polyisocyanate include chain aliphatic polyisocyanate, aromatic polyisocyanate, and alicyclic polyisocyanate. These may be used alone or in combination of two or more.

  In the present invention, the polyurethane compound A is preferably a reaction product of a diol having a molecular weight of less than 500 and a diisocyanate. By using the diol having a molecular weight of less than 500, the chemical resistance of the cured product of the curable resin composition is improved.

  Examples of the diol having a molecular weight of less than 500 include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Linear forms such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol Diol having an aliphatic structure: propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2- Pentanediol, 3-methyl-1,5-pentanediol, 1,8-nonanediol, etc. Diols having a branched-chain aliphatic structure; cycloalkyl propanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecane diol, diols having an alicyclic structure, such as adamantyl diol.

  From the point that the cured product of the curable resin composition is excellent in chemical resistance, weather resistance, and moldability, those having a linear aliphatic structure are preferred, and at least one selected from ethylene glycol and 1,4-butanediol. Is more preferred. Among these, ethylene glycol is more preferable from the viewpoint of chemical resistance.

  Furthermore, in this invention, the chemical resistance of the hardened | cured material of the said curable resin composition becomes still better because the diol with a molecular weight of less than 500 has an amide group.

  Examples of the diol having an amide group and having a molecular weight of less than 500 include a reaction product of a cyclic hydroxycarboxylic acid ester and an amino alcohol compound containing a primary or secondary amino group.

  Cyclic hydroxycarboxylic acid esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ethanolamine, diethanolamine, N-methylethanolamine, etc. Reaction products of amino alcohol compounds containing primary or secondary amino groups are preferred.

  Examples of the diisocyanate include a chain aliphatic diisocyanate, an aromatic diisocyanate, an alicyclic diisocyanate, and an allohanate, isosinurate, burette, adduct, etc., and even if one of these is used, 2 You may use combining more than a seed. Among these, as the polyurethane compound A, an alicyclic diisocyanate is preferable from the viewpoint of enhancing the weather resistance and hardness of the obtained cured product.

  A chain aliphatic diisocyanate is a compound having a chain aliphatic structure and two isocyanate groups bonded thereto. The chain aliphatic diisocyanate can increase the weather resistance of the cured product of the curable composition and can impart stretchability. The chain aliphatic structure in the chain aliphatic diisocyanate is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of such chain aliphatic diisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate, and aliphatic diisocyanates such as adducts and dimers thereof. Can be mentioned. These may be used alone or in combination of two or more.

  An aromatic diisocyanate is a compound having an aromatic structure and two isocyanate groups bonded thereto. The aromatic structure in the aromatic diisocyanate is not particularly limited, but is preferably an aromatic structure having 6 to 13 carbon atoms. Examples of such aromatic diisocyanates include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate. The aromatic diisocyanate can increase the mechanical strength of the cured product of the curable composition. Examples of the aromatic diisocyanate include tolylene diisocyanate and diphenylmethane diisocyanate, and aromatic diisocyanates such as adducts and dimers thereof. These may be used alone or in combination of two or more.

  An alicyclic diisocyanate is a compound having an alicyclic structure and two isocyanate groups. The alicyclic structure in the alicyclic diisocyanate is not particularly limited, but preferably has 5 to 15 carbon atoms, more preferably 6 to 13 carbon atoms. The alicyclic structure is preferably a cycloalkylene group. Examples of the diisocyanate having an alicyclic structure include diisocyanates having an alicyclic structure such as bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, isophorone diisocyanate, and adducts and dimers thereof. And alicyclic diisocyanates such as Of these, isophorone diisocyanate is preferred.

In the present invention, the polyurethane compound may be a reaction product of diamine, diisocyanate and polyol. By using diamine, the chemical resistance of the resulting cured product is improved.

  Examples of the diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, It has a linear aliphatic structure such as 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, etc. Diamine; propylene diamine, 1,2-butanediamine, 1,3-butanediamine, 2,3-butanediamine, 2-methyl-1,3-propanediamine, neopentyldiamine, 1,2-pentanediamine, 3- Branched aliphatic structures such as methyl-1,5-pentanediamine and 1,8-nonanediamine Diamines having; cyclopropane diamine, cyclohexane diamine, cyclohexane diamine, tricyclodecane diamine, diamine having an alicyclic structure, such as adamantyl diamine.

  Among these, from the point that the cured product of the curable composition is excellent in chemical resistance, weather resistance, and moldability, those having a linear aliphatic structure are preferable, and are selected from ethylenediamine and 1,4-butanediamine. At least one is preferred.

  Further, the polyurethane compound A may be a reaction product of polyol, polyisocyanate and chain extender.

  The chain extender is a compound having two or more active hydrogens that react with isocyanate groups. Examples of the chain extender include low molecular weight diamine compounds having a number average molecular weight of 500 or less, and examples include aromatics such as 2,4- or 2,6-tolylenediamine, xylylenediamine, 4,4′-diphenylmethanediamine. Group diamine; ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4- or Aliphatic diamines such as 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine; And 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4′-dicyclohexylmethane Amine, isopropylidene cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bis-aminomethyl cyclohexane, alicyclic diamines such as tricyclodecane diamine. These may be used alone or in combination of two or more.

Moreover, it is preferable that the said polyurethane compound A of this invention has 3 or more of hydroxyl groups. When the polyurethane compound A has 3 or more hydroxyl groups, the chemical resistance and stretchability of the cured product of the curable resin composition are improved.
The polyurethane compound having 3 or more hydroxyl groups includes a reaction product of diol and diisocyanate having a molecular weight of less than 500, a reaction product of diamine, diisocyanate and polyol, a diol having a molecular weight of less than 500, a reaction product of diisocyanate and a polyol having a molecular weight of more than 500, and the like. Can be mentioned.

  Furthermore, the weight average molecular weight of the polyurethane compound A contained in the hydroxyl group-containing composition of the present invention is preferably greater than 1000 and less than or equal to 200,000 from the viewpoint of improving the chemical resistance and stretchability of the cured product of the curable resin composition. More than 3000 and 150,000 or less are more preferable, and more than 5000 and 100,000 or less are more preferable. If the weight average molecular weight is equal to or higher than the lower limit, the cured product of the curable resin composition exhibits sufficient chemical resistance, and if it is equal to or lower than the upper limit, the curable resin composition has a viscosity suitable for coating. Become. The weight average molecular weight of the polyurethane compound A is a value in terms of standard polystyrene measured by a gel permeation chromatography method (GPC method).

  In the present invention, the content of the polyurethane compound A is preferably 10 parts by weight or more and 100 parts by weight or less, more preferably 20 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the hydroxyl group-containing composition from the viewpoint of improving moldability. Is more preferable, and more preferably 70 parts by weight or less.

In addition, the polyurethane compound A of this invention can be manufactured by a well-known method. Usually, a polyol and a polyisocyanate are reacted in the presence of a catalyst.
The mixing ratio of the polyol and the polyisocyanate is preferably such that the equivalent ratio of the isocyanate group in the polyisocyanate with respect to the hydroxyl value in the polyol is 0.5 to less than 1.0, and is 0.8 or more. More preferably, it is used at a blending ratio of less than 1.0. If it is more than the said lower limit, chemical resistance can be made favorable. Moreover, if it is below the said upper limit, a moldability can be made favorable.

  Examples of the catalyst include tin-based catalysts such as dibutyltin laurate, dibutyltin dioctate, dioctyltin dilaurate, and dioctyltin dioctate; and bismuth-based catalysts such as bismuth tris (2-ethylhexanoate). . A catalyst may be used individually by 1 type and may be used in mixture of 2 or more types. Among these, dioctyltin dilaurate and bismuth tris (2-ethylhexanoate) are preferable from the viewpoint of environmental adaptability, catalytic activity, storage stability, and the like. The amount of the catalyst used is preferably 2000 ppm or less, more preferably 1000 ppm or less, based on the total content of the raw material compounds. Moreover, 10 ppm or more is preferable and 30 ppm or more is more preferable.

  An organic solvent can be used for the production of the polyurethane compound. As the solvent to be used, a solvent having no active hydrogen such as a hydroxyl group and an amino group is preferable, such as methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether, tetrahydrofuran and the like. Ether solvent: Swazol 1000 (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), Supersol 100 (trade name, manufactured by Nippon Petrochemical Co., Ltd.), Supersol 150 (trade name, manufactured by Nippon Petrochemical Co., Ltd.), benzene, toluene Aromatic solvents such as xylene; cyclic hydrocarbon solvents such as cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; ethyl acetate, n-butyl acetate, isobutyl Le acetate, n- amyl acetate, can be used acetate-based solvents such as propylene glycol acetate. Among these, a solvent composition containing either a ketone solvent or an acetate solvent is preferable in that it has good solubility in a polyurethane compound.

  In the present invention, the hydroxyl group-containing composition preferably further comprises a (meth) acrylic polymer having two or more hydroxyl groups. By using the (meth) acrylic polymer, chemical resistance is improved.

  Moreover, it is preferable that the said (meth) acrylic polymer contains the quaternary ammonium salt structure from the point which makes the chemical resistance of the hardened | cured material of the said curable resin composition favorable.

The content of the quaternary ammonium salt structure in the (meth) acrylic polymer is preferably 0.05 mmol / g or more, more preferably 0.1 mmol / g or more, from the viewpoint of improving the adhesion to the substrate. 0.2 mmol / g or more is more preferable. Further, from the viewpoint of water resistance and solvent solubility, it is preferably 2 mmol / g or less, more preferably 1 mmol / g or less, and further preferably 0.5 mmol / g or less.
The content of the quaternary ammonium salt structure in the (meth) acrylic polymer is a raw material of a monomer having a quaternary ammonium salt structure with respect to all monomers when the (meth) acrylic polymer is produced. It can be calculated from the mixing ratio.

  Furthermore, in the present invention, the weight average molecular weight of the (meth) acrylic polymer is preferably more than 2000 and not more than 300000, preferably 3000, from the viewpoint of improving the chemical resistance and stretchability of the cured product of the curable resin composition. It is more preferably 200000 or less, and more preferably 50000 to 100000. When the weight average molecular weight is larger than the lower limit, the cured product exhibits sufficient chemical resistance, and when the weight average molecular weight is equal to or lower than the upper limit, the curable resin composition has a viscosity that is suitable for coating. In addition, the weight average molecular weight of the said (meth) acryl polymer is a value by standard polystyrene conversion measured by the gel permeation chromatography method (GPC method).

  In the present invention, the ratio of the polyurethane compound to the (meth) acrylic polymer is preferably 5/95 or more and 100/0 or less, more preferably 10/90 or more and 95/5 or less, and 15/85 or more and 90/10. More preferred are: If it is more than the said lower limit, the hardened | cured material which has sufficient moldability can be obtained. Moreover, if it is below the said upper limit, the hardened | cured material which has sufficient chemical resistance can be obtained.

  The (meth) acrylic polymer can be obtained by copolymerizing a (meth) acrylate having a hydroxyl group with another (meth) acrylate.

  In the present invention, “(meth) acryl” is a general term for acryl and methacryl, and means one or both of acryl and methacryl. “(Meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The “(meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group, and means one or both of them. (Meth) acrylic acid is a general term for acrylic acid and methacrylic acid, and means one or both of them.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxy. Hexyl acrylate, 1,2-dihydroxyethyl (meth) acrylate, 1,2-dihydroxypropyl (meth) acrylate, 1,2-dihydroxybutyl (meth) acrylate, 1,2-dihydroxy5-ethylhexyl (meth) acrylate, 1 , 1-dihydroxyethyl (meth) acrylate, 1,1-dihydroxypropyl (meth) acrylate, 1,1-dihydroxybutyl (meth) acrylate, 1,2,3-trihydroxypropyl (meth) acrylate, 1, , 3-trihydroxybutyl (meth) acrylate, 1,1,2-trihydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 1,1,2-trihydroxybutyl (meth) acrylate; 2-hydroxy Aromatic ring-containing hydroxy (meth) acrylates such as -3-phenoxypropyl (meth) acrylate; hydroxy polyethylene oxide mono (meth) acrylate, hydroxy polypropylene oxide mono (meth) acrylate, hydroxy (polyethylene oxide-polypropylene oxide) mono (meth) Acrylate, hydroxy (polyethylene oxide-propylene oxide) mono (meth) acrylate, hydroxy (polyethylene oxide-polytetramethylene oxide) mono (meth) acrylate Hydroxy (polyethylene oxide-tetramethylene oxide) mono (meth) acrylate, hydroxy (polypropylene oxide-polytetramethylene oxide) mono (meth) acrylate, hydroxy (polypropylene oxide-polytetramethylene oxide) mono (meth) acrylate, 1 1,2-dihydroxypolyethyl oxide (meth) acrylate, 1,2-dihydroxypolypropylene oxide (meth) acrylate, polyhydroxyalkyl (meth) acrylate; 1,2,3-trihydroxypropylene glycol (meth) acrylate, 1,1 , Hydroxypolyalkylene oxide (meth) acrylates such as 2-trihydroxypropylene glycol (meth) acrylate; Of these, hydroxyalkyl (meth) acrylate is preferred from the viewpoint of weather resistance and ease of polymerization with other monomer components, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. Is more preferable. These hydroxyl group-containing (meth) acrylic monomers may be used alone or in combination of two or more. In addition, when it is desired to impart high flexibility to the cured product of the resulting curable resin composition, it preferably contains a hydroxypolyalkylene oxide (meth) acrylate, and the hardness of the cured product of the resulting curable resin composition When it is desired to increase it, it is preferable to include those having two or more hydroxyl values.

  Examples of the other (meth) acrylates include carboxyl groups such as acrylic acid, methacrylic acid, succinic acid mono (2- (meth) acryloyloxyethyl), and ω-carboxy-polycaprolactone mono (meth) acrylate (meth). Acrylates: methyl (meth) acrylate, ether ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t- Butyl (meth) acrylate, n-pentyl (meth) acrylate, i-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) ) Acrylate, steari Alkyl (meth) acrylates having a linear or branched hydrocarbon skeleton such as (meth) acrylate and isostearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclo Alkyl (meth) acrylates having an alicyclic skeleton such as decanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate; glycidyl (meth) acrylate, hydroxybutyl (meth) Glycidyl group-containing (meth) acrylic esters such as acrylate glycidyl ether; phenoxy (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene Aromatic ring-containing (meth) acrylic esters such as glycol (meth) acrylate, nonylphenol EO adduct (meth) acrylate, o-biphenyloxyethyl (meth) acrylate; ammonium (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as sodium and potassium (meth) acrylate; cyclic ether-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate; N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meta) ) Amino group-containing (meth) acrylate such as acrylate; (meth) acrylamide, (meth) acrylamide diacetone acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (Meth) acrylamide derivatives such as ru (meth) acrylamide and N-butoxymethyl (meth) acrylamide; vinyl cyanides such as acrylonitrile, methacrylonitrile, α-cyanoacrylate, dicyanovinylidene and fumaronitrile; 2- (meth) acryloyl Oxyethyl acid phosphate, 2- (meth) acryloyloxyethyl acid phosphate monoethanolamine salt, diphenyl ((meth) acryloyloxyethyl) phosphate, (meth) acryloyloxypropyl acid phosphate, 3-chloro-2-acid phospho Oxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, acid phosphooxypolyoxypropylene glycol And phosphoric acid group-containing monomers such as diol (meth) acrylate. These can be appropriately selected according to the use of the cured product, but among these, alkyl (meth) acrylate and alicyclic having at least a linear or branched hydrocarbon skeleton particularly in terms of weather resistance It is preferable to include any one of alkyl (meth) acrylates having a skeleton. More preferably, it contains at least one of methyl (meth) acrylate, ether ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate. In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

  When the acrylic polymer B contains a quaternary ammonium salt structure, a (meth) acrylate containing a quaternary ammonium salt structure may be copolymerized.

  The cation of the quaternary ammonium salt has a quaternized amino group and a (meth) acryl group, and can be used for the production of a (meth) acrylic polymer. Are preferred, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate are more preferred, and dimethylaminoethyl (meth) acrylate is more preferred.

  As the anion of the quaternary ammonium salt, methyl chloride, methyl bromide, and methyl iodide are preferable, and methyl chloride is more preferable from the viewpoint of easy quaternization.

  Examples of the quaternary ammonium salt include trimethylaminoethyl (meth) acrylate chloride, trimethylaminoethyl (meth) acrylate bromide, and trimethylaminoethyl (meth) acrylate iodide. Trimethylaminoethyl (meth) acrylate chloride is more preferable from the viewpoint that the cationic property is easily developed.

  The acrylic polymer B may be copolymerized with an aromatic vinyl compound as necessary. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and the like.

  As the polymerization method of the acrylic polymer B, a known radical polymerization method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or a bulk polymerization method can be used. Among these, it is preferable to manufacture by the solution polymerization method from the point of the ease of reaction with the polyisocyanate which is a crosslinking agent.

  As the solvent used when the acrylic polymer B is produced by a solution polymerization method, a solvent having no active hydrogen such as a hydroxyl group or an amino group is preferable. Methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbide Ether solvents such as Tolu, diethyl carbitol, propylene glycol monomethyl ether, tetrahydrofuran, etc .; SWAZOL 1000 (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), SUPERSOL 100 (trade name, manufactured by Shin Nippon Petrochemical Co., Ltd.) Product name, manufactured by Nippon Petrochemical Co., Ltd.), aromatic solvents such as benzene, toluene and xylene; cyclic hydrocarbon solvents such as cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone Ethyl acetate, n- butyl acetate, isobutyl acetate, n- amyl acetate, can be used acetate-based solvents such as propylene glycol acetate. Among these, a solvent composition containing at least one of a ketone solvent or an acetate solvent is preferable in that it has good solubility in the polyurethane compound A and the acrylic polymer B.

  As the polymerization initiator used for producing the acrylic polymer B, those generally known as radical polymerization initiators can be used. Specific examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4 -Nitrile azo compounds such as dimethylvaleronitrile); Non-nitrile azo such as dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2,4,4-trimethylpentane) Compound: t-hexyl peroxypivalate, ter t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethyl Butylperoxy-2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5- Di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 4-methylbenzoyl peroxide, benzoyl peroxide, 1, 1'-bis- (tert-butylperoxy) organic peroxides such as cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be used as a redox polymerization initiator in combination with a reducing agent.

  In the production of the acrylic polymer B, a molecular weight modifier can be used to adjust the weight average molecular weight, and examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n -Mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid; xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide;

<Crosslinking agent>
As a crosslinking agent contained in the said curable resin composition, it can select from the compound which has a well-known isocyanate group suitably, and can be used.

  Examples of the compound having an isocyanate group include diisocyanates used in the production of the polyurethane compound A, and allophanate, isosinurate, burette, and adducts thereof. Although the kind in particular of diisoainate is not restrict | limited, A chain aliphatic polyisocyanate, aromatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned. Moreover, the copolymer of the isocyanate compound which has a (meth) acryloyl group, and another (meth) acrylate compound can also be used. Moreover, you may use the block body which blocked the said isocyanate compound by the well-known method as needed. One of these crosslinking agents may be used alone, or two or more thereof may be used in combination.

  The mixing ratio of the hydroxyl group-containing composition and the crosslinking agent contained in the curable resin composition is not particularly limited, but the equivalent ratio of the isocyanate group of the isocyanate compound to the hydroxyl value in the hydroxyl group-containing composition is , Preferably in a blending ratio of 0.5 to 2.0, more preferably in a blending ratio of 0.8 to 1.2. If it is more than the said lower limit, adhesiveness will become favorable. Moreover, if it is below the said upper limit, a moldability will become favorable.

  The curable resin composition of the present invention further includes a polyurethane resin other than the polyurethane compound A, a polyacryl resin other than the acrylic polymer B, a vinyl chloride-vinyl acetate copolymer, a phenol, contained in the hydroxyl group-containing composition. Resin, terpene phenol resin, polyester resin, polyether resin, polycarbonate resin, butyral resin, chlorinated polypropylene, chlorinated polyethylene and the like may be contained. Further, it may contain a (meth) acryl / urethane copolymer obtained by grafting a poly (meth) acrylic chain to a polyurethane chain or grafting a polyurethane chain to a poly (meth) acrylic chain.

The curable resin composition may contain an organic solvent.
The organic solvent is preferably a solvent having no active hydrogen such as a hydroxyl group or an amino group, such as methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether, tetrahydrofuran, etc. Ether solvent: SWAZOL 1000 (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), SUPERSOL 100 (trade name, manufactured by Nippon Petrochemical Co., Ltd.), SUPERSOL 150 (trade name, manufactured by Nippon Petrochemical Co., Ltd.), benzene, Aromatic solvents such as toluene and xylene; Cyclic hydrocarbon solvents such as cyclohexane; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; Ethyl acetate, n-butyl acetate, iso Chill acetate, n- amyl acetate, can be used acetate-based solvents such as propylene glycol acetate. Among these, a solvent composition containing either a ketone solvent or an acetate solvent is preferable in that it has good solubility in the polyurethane compound A and the acrylic polymer B.
The curable resin composition includes leveling agents, antistatic agents, plasticizers, surfactants, antioxidants, ultraviolet absorbers, inorganic particles such as silica, alumina, titania, smectite, silicone particles, melamine Resin particles, acrylic resin particles (for example, organic particles such as polymethyl methacrylate particles, acrylic-styrene copolymer particles, and polystyrene particles) may be contained.

<Viscosity / Coating method>
The viscosity of the curable resin composition is such that the viscosity at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24) is 5 mPa · s or more from the viewpoint of handleability, coatability, moldability and the like. Preferably, 10 mPa · s or more is more preferable. Moreover, 50000 mPa * s or less is preferable, 10000 mPa * s or less is more preferable, 5000 mPa * s or less is more preferable, 2000 mPa * s or less is especially preferable.

  The manufacturing method in particular of the said curable resin composition is not restrict | limited, It can manufacture by mixing each component with the stirrer normally used.

  The coating method of the curable resin composition is not particularly limited, and gravure method, gravure reverse method, gravure offset method, spinner coating method, roll coating method, reverse roll coating method, kiss coating method, wheeler coating method, dip coating method. It can be applied by any method such as silk screen method, wire bar coating method, flow coating method, comma coating method, curtain coating method, brush coating method, spray coating method and the like.

  The coating amount of the curable resin composition is not particularly limited, but in terms of adhesion to the substrate, it is preferable that the film thickness after drying is applied to be 0.1 μm or more and 20 μm or less, More preferably, the coating is performed so that the thickness is 0.5 μm or more and 3 μm or less.

  The curable resin composition is cured by drying to remove the organic solvent and reacting with a crosslinking agent. The drying condition is preferably 25 to 150 ° C. for 1 to 60 minutes, more preferably 30 to 120 ° C. for 1 to 10 minutes.

  The curable resin composition of this invention can obtain the laminated body of this invention by apply | coating and hardening a curable resin composition on a base material. The laminate of the present invention is not particularly limited as long as the cured product of the present invention is formed on the substrate, and a layer other than the substrate and the cured product of the present invention is interposed between the substrate and the cured product of the present invention. You may have, and you may have on the outer side. Moreover, the said laminated body may have multiple layers of the base material and the hardened | cured material of this invention.

  Examples of the base material that can be used in the laminate of the present invention include polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyolefins such as polypropylene and polyethylene; and other various plastics such as nylon, polycarbonate, and (meth) acrylic resin. , Glass, metal and the like. Among these, polyethylene terephthalate is preferable. Moreover, the shape of these base materials may be flat, such as a film shape or a sheet shape, or may be formed into various shapes.

  The thickness of the substrate that can be used in the laminate of the present invention is preferably 1.0 μm to 200 μm, and more preferably 10 μm to 100 μm. If the thickness of the substrate is too thin, the strength is insufficient, and therefore, the handleability is inferior when a protective layer is formed on the substrate or when the substrate is peeled off. On the other hand, if it is too thick, the followability to the mold during injection molding will be poor.

  In order to improve the releasability, the base material that can be used in the laminate of the present invention may be a substrate in which a release layer is formed by applying a release material to the release surface. Examples of release materials include epoxy resin release agents, epoxy melamine resin release agents, melamine resin release agents, amino alkyd resin release agents, silicone resin release agents, and fluororesin release agents. One or two or more of an agent, a cellulose derivative release agent, a urea resin release agent, a polyolefin resin release agent, a paraffin release agent, and the like can be used. As a method for forming the release layer, various printing methods and coating methods can be used.

  The laminate of the present invention may have an adhesive layer. The adhesive layer is a layer provided in order to improve the adhesion to the transfer target, and it is preferable to select the adhesive layer according to the material of the transfer target. Examples of the adhesive layer include acrylic resins, vinyl acetate resins, epoxy resins, polyester resins, polycarbonate resins, butyral resins, gelatin, cellulose resins, polyamide resins, vinyl chloride resins, and urethane resins. A resin having an appropriate softening temperature is selected from resins such as acrylonitrile-styrene resin.

  The thickness of the adhesive layer is preferably from 0.1 μm to 50 μm, and more preferably from 1 μm to 10 μm. When the adhesive layer is thinner than the range, the adhesive layer has poor adhesion, and when the range is exceeded, the foil breakage during transfer molding is reduced.

<Other layers>
In the laminate of the present invention, a pattern layer or a metal vapor deposition layer may be formed between the primer layer and the adhesive layer. The pattern layer is provided with a pattern, a pattern, a pattern, or the like using ink. Examples of the ink used for forming the pattern layer include azo pigments, organic pigments such as isoinsolin, quinacridone, phthalocyanine blue, and aniline black, cobalt blue Inorganic pigments such as petals, yellow lead, and titanium oxide, and various organic dyes can be used. Moreover, a metal vapor deposition layer is a layer which formed metals, such as aluminum, tin, silver, copper, chromium, and indium, by vacuum vapor deposition.

  The curable resin composition of the present invention is preferably used by being laminated with a surface protective layer. Examples of the surface protective layer include poly (meth) acrylic resin, polyester resin, polyurethane resin, epoxy resin, and silicone resin.

  A well-known thing can be used as an active energy ray-curable resin composition which forms the said surface protective layer. Examples of the active energy ray-curable resin composition for forming the surface protective layer include polymers having (meth) acryloyl groups, oligomers having (meth) acryloyl groups, and one or more (meth) acryloyl groups. The monomer which has can be used. These may be used alone or in combination of two or more.

  The polymer having the (meth) acryloyl group that can be used in the active energy ray-curable resin composition for forming the surface protective layer has a weight average molecular weight of 3000 to 1000000 having a photopolymerizable functional group in the side chain. The following (meth) acrylic copolymers can be mentioned.

  The polymer having the (meth) acryloyl group is obtained by polymerizing a monomer mixture containing, for example, a (meth) acrylate monomer having at least one reactive group selected from a carboxyl group, an isocyanate group, an epoxy group, and a hydroxyl group. It is obtained by adding a (meth) acrylate monomer having a reactive group that reacts with the reactive group to the (meth) acrylic copolymer obtained in this manner.

A monomer having a reactive group that can be used for production of a polymer having a (meth) acryloyl group and a reactive group corresponding to the monomer are as follows.
(I) Monomer having an epoxy group Corresponding reactive group: carboxyl group
(ii) Monomer having a hydroxyl group Corresponding reactive group: Isocyanate group
(iii) Monomer having carboxyl group Corresponding reactive group: epoxy group (iv) Monomer having isocyanate group Corresponding reactive group: hydroxyl group

(i) Monomers having an epoxy group include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl. Examples include ether.
(ii) As a monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and addition of these ethylene oxide, propylene oxide and caprolactan Products, glycerin mono (meth) acrylate, and the like.
(iii) Examples of the monomer having a carboxyl group include hydroxyalkyl (meth) acrylate adducts of acid anhydrides such as (meth) acrylic acid and succinic anhydride.
(Iv) Examples of the monomer having an isocyanate group include 2-methacryloyloxyethyl isocyanate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate.

  Among these, (meth) acrylic polymer copolymerized with glycidyl methacrylate and acrylic acid added, and (meth) acrylic polymer copolymerized with 2-methacryloyloxyethyl isocyanate, acrylic acid, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and those added with ethylene oxide, propylene oxide, caprolactan adduct, and glycerin mono (meth) acrylate are preferable. It is preferable that 2-methacryloyloxyethyl isocyanate copolymerized (meth) acrylic polymer is 2-hydroxyethyl (meth) acrylate and its caprolactan adduct.

  As other (meth) acrylate monomers that can be used to produce the polymer having the (meth) acryloyl group, known monomers can be used. Specific examples of the other (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl ( (Meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, i-stearyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxytriethylene Recall (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, n-butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4,4, Examples include 4-hexafluorobutyl (meth) acrylate and perfluorooctylethyl (meth) acrylate. Among these, methyl (meth) acrylate is preferable from the viewpoint of excellent scratch resistance of the obtained cured film.

Examples of the oligomer having a (meth) acryloyl group that can be used in the active energy ray-curable resin composition for forming the surface protective layer include a urethane (meth) acrylate oligomer, and an epoxy (meth) acrylate oligomer, Examples include acrylic (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, polybutadiene (meth) acrylate oligomers, and polyether (meth) acrylates.
Among these, urethane (meth) acrylate oligomers are preferable from the viewpoint of scratch resistance and moldability.

  As the urethane (meth) acrylate oligomer, those produced by a known method from polyisocyanate, hydroxyl group-containing (meth) acrylate and polyol can be used.

  The isocyanate compound used for the production of the urethane (meth) acrylate oligomer is a compound having a total of two or more isocyanate groups or substituents containing isocyanate groups in one molecule. One type of isocyanate compound may be used, or two or more types may be used. Specific examples of the isocyanate compound include polyisocyanate used in the production of the polyurethane compound A, and its allophanate, isosinurate, burette, and adduct. The type of polyisocyanate is not particularly limited, and examples thereof include chain aliphatic polyisocyanate, aromatic polyisocyanate, and alicyclic polyisocyanate. Among these, alicyclic polyisocyanate is preferable from the viewpoint of excellent surface protection performance and weather resistance.

  The alicyclic polyisocyanate is a compound having a cyclic structure and two or more isocyanate groups. The alicyclic polyisocyanate preferably has 5 to 15 carbon atoms, and more preferably 6 or more carbon atoms. Moreover, it is more preferable that it is C14 or less, and it is especially preferable that it is C13 or less. Furthermore, the alicyclic structure is preferably a cycloalkylene group. Examples of the polyisocyanate having an alicyclic structure include diisocyanates having an alicyclic structure such as bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate, and tris (isocyanate isophorone) isocyanurate. And triisocyanate having an alicyclic structure. Among these, it is preferable to contain isophorone diisocyanate.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and cyclohexanedimethanol. Mono (meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, bisphenol A diglycidyl ether diacrylate, glycol mono ( (Meth) acrylate, glycerin (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipe Data erythritol penta (meth) acrylate and the like can be mentioned. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol A chain aliphatic structure, a cyclic aliphatic structure, and the like, such as a hydroxyalkyl (meth) acrylate having an alkylene group having 2 to 4 carbon atoms between a (meth) acryloyl group such as penta (meth) acrylate and a hydroxyl group, and Epoxy (meth) obtained by reacting an epoxy compound selected from epoxy compounds having an aromatic structure with a compound having a (meth) acryloyl group and a carboxyl group (in the present invention, (meth) acrylic acid is included). Acrylate etc. And the like.

  Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol A hydroxyalkyl (meth) acrylate having an alkylene group having 2 to 4 carbon atoms between a (meth) acryloyl group such as penta (meth) acrylate and a hydroxyl group, and an epoxy (meth) acrylate are obtained in the surface protective layer obtained. An epoxy (meth) acrylate obtained by reacting an epoxy compound having a chain aliphatic structure having 2 to 12 carbon atoms with a compound having a (meth) acryloyl group and a carboxyl group is particularly preferable from the viewpoint of mechanical strength. The Ureta (Meth) preferable because the curability of acrylate can be improved. The chain aliphatic structure may be a linear aliphatic structure or a branched aliphatic structure.

  Examples of the epoxy compound used to obtain an epoxy (meth) acrylate having a chain aliphatic structure having 2 to 12 carbon atoms include ethylene glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4 -Butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-heptanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9 An epoxy compound having a linear aliphatic structure such as nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether; Branched chain fats such as pyrene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether And epoxy compounds having a group structure.

  Among these, epoxy having a chain aliphatic structure having 4 to 6 carbon atoms, such as 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like A compound is preferable from the viewpoint of curability of the urethane (meth) acrylate.

  Examples of the compound having a (meth) acryloyl group and a carboxyl group used to obtain an epoxy (meth) acrylate having a chain aliphatic structure having 2 to 12 carbon atoms include (meth) acrylic acid; carboxymethyl (meta ) Acrylate, carboxyethyl (meth) acrylate, carboxypropyl (meth) acrylate, carboxypropyl (meth) acrylate and other carboxyalkyl (meth) acrylates; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) A reaction product of a hydroxyalkyl (meth) acrylate such as acrylate and a carboxylic anhydride such as phthalic anhydride, succinic anhydride or maleic anhydride. These may be used alone or in combination of two or more. Among these, a compound having an acryloyl group is preferable from the viewpoint of curability of the obtained urethane (meth) acrylate, and acrylic acid is particularly preferable.

Examples of the epoxy (meth) acrylate having a chain aliphatic structure having 2 to 12 carbon atoms include Kayarad R-167 (manufactured by Nippon Kayaku Co., Ltd.), NK Oligo EA-5520, EA-5321 (Shin Nakamura Chemical Co., Ltd.). Manufactured) and the like.
The polyol compound may be used alone or in combination of two or more.

  Examples of the polyol include the same polyols as those used for the polyurethane compound contained in the curable resin composition, such as low molecular weight polyols such as aliphatic diols and aromatic diols, and high molecular weight polyols.

  Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Linear fat such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol Diol having a family structure: propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-pentane Branching of diol, 3-methyl-1,5-pentanediol, 1,8-nonanediol, etc. Diols having Jo aliphatic structure; cycloalkyl propanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecane diol, diols having an alicyclic structure, such as adamantyl diol. Among these, those having a linear aliphatic structure are preferable, and in particular, the layer B obtained by using at least one selected from ethylene glycol and 1,4-butanediol has chemical resistance, weather resistance, and moldability. It is preferable in that it is excellent.

  Examples of the aromatic diol include bishydroxyethoxybenzene, bishydroxyethyl terephthalate, and bisphenol A. These may be used alone or in combination of two or more.

  Examples of the diol having an aromatic structure having a molecular weight of 500 or less include bishydroxyethoxybenzene, bishydroxyethyl terephthalate, and bisphenol A.

Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polyether ester polyol, polycaprolactone polyol, polycarbonate polyol, polyolefin polyol, and silicon polyol. These may be used alone or in combination of two or more.
When the above polymer polyol is used, polycarbonate polyol is preferable. Examples of the polycarbonate polyol include polycarbonate polyols similar to those used in the polyurethane compound contained in the curable resin composition.

  The urethane (meth) acrylate has a weight average molecular weight (Mw) of preferably 1500 or more, and more preferably 3000 or more. Moreover, it is preferable that it is 60000 or less, It is more preferable that it is 50000 or less, It is further more preferable that it is 25000 or less. When the weight average molecular weight of the urethane (meth) acrylate is not less than the lower limit, the three-dimensional processability of the cured product of the resulting curable resin composition tends to be good. When the number average molecular weight of the urethane (meth) acrylate is not more than the upper limit value, the chemical resistance of the cured product of the resulting curable resin composition tends to be good. The weight average molecular weight of the urethane (meth) acrylate can be determined by gel permeation chromatography measurement (GPC measurement).

  The urethane (meth) acrylate is usually obtained by reacting the isocyanate compound and polyol compound under conditions such that the isocyanate group becomes excessive to obtain a precursor of urethane (meth) acrylate having an isocyanate terminal, and then isocyanate. It can be produced by a method of reacting a urethane urethane (meth) acrylate precursor having a terminal with the hydroxyl group-containing (meth) acrylate.

  The amount of all isocyanate groups and the amount of hydroxyl groups in the urethane (meth) acrylate is usually equimolar in theory. However, in the case where the hydroxyl group-containing (meth) acrylate has two or more hydroxyl groups, an excess amount of the hydroxyl group-containing (meth) acrylate is added in order to prevent the handling property from being lowered due to the increase in viscosity accompanying the increase in the molecular weight. It is preferable to use it. For this reason, the amount of isocyanate compound, polyol compound and hydroxyl group-containing (meth) acrylate used as a raw material and other raw material compounds is such that the amount of all isocyanate groups in the urethane (meth) acrylate and the amount of all functional groups reacting therewith. It is an amount that is equal to or greater than 50 equivalent% and equal to or less than 300 equivalent% in terms of equivalent equivalents or equivalent percentages of all functional groups relative to isocyanate groups.

  The content of urethane (meth) acrylate in the active energy ray-curable resin composition is preferably 60% by weight or more, more preferably 80% by weight or more based on the total amount of the active energy ray-curable resin composition. More preferably, it is more preferably 90% by weight or more, and particularly preferably 95% by weight or more. If it is more than this lower limit, sufficient scratch resistance and moldability are exhibited.

  Examples of the monomer having one or more (meth) acryloyl groups include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specifically, for example, styrene, α- Aromatic vinyl monomers such as methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene; vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam Vinyl ester monomers such as divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether and allyl glycidyl ether; (meth) acrylamide, N, N-dimethyla Kurylamide, N, N-dimethylmethacrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloyl (Meth) acrylamides such as morpholine and methylenebis (meth) acrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic acid-n- Butyl, (meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic Stearyl acid, tetrahydrofurfuryl (meth) acrylate (Meth) acrylic acid morpholyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid glycidyl, (meth) Dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, (meth) acrylic acid Dicyclopentenyl, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, Monofunctional such as phenyl (meth) acrylate Meth) acrylate; and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene di (meth) acrylate Glycol (n = 5-14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, di ( (Meth) acrylic acid polypropylene glycol (n = 5 to 14), di (meth) acrylic acid-1,3-butylene glycol, di (meth) acrylic acid-1,4-butanediol, di (meth) acrylic acid polybutylene Glycol (n = 3-16), di (meth) Poly (1-methylbutylene glycol) acrylate (n = 5 to 20), di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) Neopentyl glycol acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, dicyclopentanediol di (meth) acrylate, tricyclodecane di (meth) acrylate, bisphenol A diglycidyl ether diacrylate, 1 , 4-cyclohexanedimethanol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether diacrylate, 1,4-butanediol diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, trimethylol Lopantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane polyoxypropyl (meth) Acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxy) Ethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di ( And polyfunctional (meth) acrylates such as bisphenol A epoxy di (meth) acrylate, bisphenol F epoxy di (meth) acrylate, and the like.

  Among these, in particular, in applications where application properties are required for the active energy ray-curable resin composition of the present invention, (meth) acryloylmorpholine, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid benzyl, (Meth) acrylic acid cyclohexyl, (meth) acrylic acid trimethylcyclohexyl, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid tricyclodecane, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid isobornyl, (meta ) Monofunctional (meth) acrylates having a ring structure in the molecule, such as acrylamide, are preferred. On the other hand, in applications where the mechanical strength of the resulting surface protective layer is required, di (meth) acrylic acid-1,4 -Butanediol, di (meth) acrylic acid-1,6-hexanediol, di (meth) Acrylic acid-1,9-nonanediol, dipentaglycol di (meth) acrylate, tricyclodecane di (meth) acrylate, 1,4-cyclohexanedimethanol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether diacrylate 1,4-butanediol diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Multifunctional (medium) such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate ) Acrylate is preferred, and in applications where the resulting surface protective layer is required to be stretchable, polyethylene glycol di (meth) acrylate (n = 5-14), polypropylene glycol di (meth) acrylate (n = 5-14) , Polyether (meth) acrylates such as di (meth) acrylic acid polybutylene glycol (n = 3 to 16) and di (meth) acrylic acid poly (1-methylbutylene glycol) (n = 5 to 20) are preferable. .

  In the active energy ray-curable resin composition, the content of the monomer having one or more (meth) acryloyl groups depends on physical properties such as viscosity adjustment of the composition and hardness and elongation of the resulting surface protective layer. From the point of adjustment, it is preferably 50% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, based on the total amount of the active energy ray-curable resin composition. It is particularly preferably 10% by weight or less.

  Moreover, the active energy ray-curable resin composition forming the layer surface protective layer may contain an organic solvent. By using an organic solvent, it can be adjusted to an appropriate viscosity for forming a cured product, and a uniform cured product can be obtained.

  Examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2- Ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxy Ether esters such as ethyl acetate and 3-methoxypropyl acetate; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and propyl acetate Esters such as ethyl acetate and butyl acetate; and the like.

  Furthermore, the active energy ray-curable resin composition forming the surface protective layer may contain a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methylorthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, methyl benzoyl formate, 2-methyl-1- [4- (methylthio) Nenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one and the like. These photopolymerization initiators may be used alone or in combination of two or more.

  Among these, as the polymerization initiator, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl are used because the curing rate is high and the crosslinking density can be sufficiently increased. Ketones, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl -Propan-1-one is preferred, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl- Propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one is preferred There.

  When the active energy ray-curable resin composition forming the surface protective layer contains a compound having a cationic polymerizable group such as an epoxy group together with a radical polymerizable group, the polymerization initiator is a photo radical polymerization initiator. In addition, a photocationic polymerization initiator may be included. Any known cationic photopolymerization initiator may be used as long as it does not significantly impair the effects of the present invention.

  The active energy ray-curable resin composition forming the surface protective layer is composed of a leveling agent, an antistatic agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, silica, alumina, titania, smectite, and the like. Inorganic particles, silicone particles, melamine resin particles, polyolefin resin particles (for example, polyethylene particles, polypropylene particles), acrylic resin particles (for example, polymethyl methacrylate particles, acrylic-styrene copolymer particles, polystyrene) Organic particles), core-shell type composite resin particles, and the like.

  The surface protective layer can be obtained by applying and curing the active energy ray-curable polymer composition on a substrate or a cured product of the curable resin composition applied to the substrate. .

  Examples of the active energy ray used for curing the active energy ray-curable polymer composition include infrared rays, visible rays, ultraviolet rays, X rays, electron beams, α rays, β rays, γ rays, and the like. Among them, it is preferable to use an electron beam or ultraviolet rays from the viewpoint of apparatus cost and productivity. As the light source, electron beam irradiation device, ultra high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, Ar laser, He-Cd laser, solid laser, xenon lamp, high frequency induction mercury lamp, etc. Can be used.

The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when it hardens | cures by electron beam irradiation, it is preferable that the irradiation amount is 10 kGy or more and 150 kGy or less. Further, when cured by ultraviolet irradiation is preferably 50 mJ / cm ² or more 1500 mJ / cm ² or less. When curing, any atmosphere of air, inert gas such as nitrogen or argon may be used.

<Viscosity / Coating method>
What is necessary is just to adjust the viscosity and coating method of the said active energy ray curable polymer composition similarly to the said curable resin composition.

  The active energy ray-curable polymer composition is preferably applied such that the film thickness after drying is 0.1 μm or more and 20 μm or less, and is 0.5 μm or more and 10 μm or less. More preferably. If the film thickness is too thin, a sufficient surface protective layer cannot be obtained, and if it is too thick, the amount of residual solvent at the time of drying increases and the adhesion and moldability deteriorate.

<Laminate>
The curable resin composition of the present invention is used as an intermediate layer in forming a plurality of layers such as a substrate and a surface protective layer, or a surface protective layer and a pattern layer, and imparts adhesion to each layer. Can be used for primer layer. The laminate provided with the primer layer does not cause interfacial delamination during the subsequent process or during the long-term durability test, and has good durability.

  Since the primer layer made of the curable resin composition of the present invention is excellent in stretchability, it is suitable as a primer for a film base material, particularly a decorative film.

  When using the curable resin composition of this invention for a decorating film, the layer obtained from the curable resin composition of this invention can be used in combination with the film which has a well-known design property. The decorative film is, for example, a transfer film that, after a surface protective layer is previously applied and cured by the application method, the curable resin composition of the present invention is applied and cured, and then the base film is peeled off after molding. Alternatively, after the curable resin composition of the present invention is applied and cured on a film or sheet, a surface protective layer may be provided and used as a laminate film for simultaneous decoration. Moreover, these laminated bodies may further provide a design layer with a printed layer or the like.

  When using the laminated body of this invention for a decorating film, the said laminated body can be shape | molded by arbitrary shaping | molding methods by arbitrary shaping | molding methods according to the objective and a use. Specifically, the decorative film is heated to an appropriate temperature, for example, 40 ° C. or more and 150 ° C. or less, and then an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method and an in-mold forming method. By using a TOM method using a vacuum forming apparatus, it is possible to decorate a molded body having a complicated three-dimensional structure. In addition, the laminate of the present invention is a molded product having unevenness by embossing or marking on the mold release surface of the base film when used as a transfer film or when used as a laminate film. You can also get

  As the adherend of the decorative film used in the article decorated with the laminate of the present invention, for example, a polyolefin polymer such as polypropylene, an acrylonitrile-butadiene-styrene copolymer, a polycarbonate polymer, Preferred examples include polyethylene terephthalate polymers, acrylic polymers, and metal materials such as ED steel plates, magnesium alloys, stainless steels, and aluminum alloys. Further, an adherend in which the polymer and the metal material are combined may be used.

  Examples of articles decorated with the laminate of the present invention include, for example, automotive interior members, automotive exterior members, various parts such as housings and display windows of personal computers and mobile phones, exterior materials for furniture, interior building materials, It can be suitably used for various applications such as exterior building materials and interior decoration materials for houses. Among these, since it has excellent chemical resistance, it is suitable for automobile interior members.

Hereinafter, the present invention will be described more specifically based on examples. In the following description, “part” means part by mass.
<Molecular weight>
The molecular weight of the polymer is a weight average molecular weight (Mw) in terms of standard polystyrene measured by the gel permeation chromatography method (GPC method) under the following conditions.
Apparatus: High-speed GPC apparatus manufactured by Tosoh Corporation HLC-8320GPC type UV detector: UV-8320 type manufactured by Tosoh Corporation Flow rate: 0.35 mL / min
Inlet temperature: 40 ° C
Oven temperature: 40 ° C
RI temperature: 40 ° C
UV wavelength: 254 nm
Sample injection volume: 10 μL
Column: Three are connected in the order of (1) to (3).
(1) TSKgel superHZM-M (4.6 mm ID × 15 cmL) manufactured by Tosoh Corporation
(2) TSKgel superHZM-M (4.6 mm ID × 15 cmL) manufactured by Tosoh Corporation
(3) TSKgel HZ2000 (4.6 mm ID × 15 cmL) manufactured by Tosoh Corporation
Guard column: TSK guard column Super HZ-L (4.6 mm ID × 3.5 cm L) manufactured by Tosoh Corporation
Solvent: THF (stabilizer BHT)
Sample concentration: resin content adjusted to 0.2% by mass The evaluation was performed by the following method.

[Evaluation methods]
<Laminate-1>
Each curable resin composition adjusted to the blending ratio shown in Table 3 is applied to a release PET film with an applicator of 350 μm, and the solvent is volatilized by drying with a hot air dryer heated to 80 ° C. for 3 hours. Together with heat curing. About the obtained laminated body 1, "breaking elongation" in 80 degreeC and 160 degreeC mentioned later was evaluated.

<Laminated body-2>
Each curable resin composition adjusted to the blending ratio described in Table 3 was applied to a black ABS plate having a thickness of 1.5 mm with a # 14 bar coater and dried for 3 hours with a hot air dryer heated to 80 ° C. As a result, the solvent was volatilized and cured. About the obtained laminated body 2, evaluation of the "resistance test with respect to a sunscreen agent" mentioned later was performed.

<80 ° C breaking elongation>
About the laminated body-1 of this invention, after cut | disconnecting only a cured film to 10 mm width and peeling, using a tensile load measuring machine ("MX2-500N" by Imada Co., Ltd.), temperature 80 degreeC and tensile speed 40mm / The elongation at break was measured under the condition of a distance between chucks of 40 mm, and the breaking elongation (elongation until a crack was visually observed) was measured and evaluated according to the following criteria.
○: Less than 50% elongation Δ: Elongation 50% or more and less than 100% ×: 100% or more

<160 ° C breaking elongation>
About the laminated body-1 of this invention, after cut | disconnecting only a cured film to 10 mm width and peeling, using a tensile load measuring machine ("MX2-500N" by Imada Co., Ltd.), temperature 160 degreeC and tensile speed 40mm / The elongation at break was measured under the condition of a distance between chucks of 40 mm, and the breaking elongation (elongation until a crack was visually observed) was measured and evaluated according to the following criteria.
○: Elongation 100% or more.
Δ: Elongation 50% or more and less than 100%.
X: Less than 50%.

<Test for resistance to sunscreens>
A sunscreen agent (Ultra Sheer Dry-TouchSunscreen SPF45, manufactured by Neutrogena) was applied onto the laminate-2 of the present invention with a 50 μm applicator and dried with a hot air dryer heated to 80 ° C. for 1 hour. Then, it washed with water using the detergent, the surface was evaluated visually, and the following references | standards evaluated.
○: No change △: Whitening but no swelling ×: There is swelling

<Production Example 1: Synthesis of polyurethane polyol component A-1>
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 146.8 parts of IPDI, 38.8 parts of PL205, and 0.02 part of U810 were placed and reacted at 75 ° C. for 3 hours.
Thereafter, 38.9 parts of ethylene glycol and 149.6 parts of methyl ethyl ketone were added and reacted for 4 hours, and then 269.4 parts of methyl ethyl ketone and 104.8 parts of isopropyl alcohol were added, thereby adding polymer A-1 having a solid content of 30%. Got.
The hydroxyl value contained in 100% solid content of the calculated polymer A-1 is 20 mgKOH / g, and the number of hydroxyl groups contained in one molecule is 2.

<Production Example 2: Synthesis of polyurethane polyol component A-2>
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 118.6 parts of IPDI, 16.6 parts of PL305, and 0.02 part of U810 were placed and reacted at 75 ° C. for 3 hours.
Thereafter, 33.1 parts of ethylene glycol and 111.2 parts of methyl ethyl ketone were added and reacted for 4 hours, and then 314.2 parts of methyl ethyl ketone and 78.6 parts of isopropyl alcohol were added, thereby adding polymer A-2 having a solid content of 30%. Got.
The hydroxyl value contained in 100% solid content of the calculated polymer A-1 is 30 mgKOH / g, and the number of hydroxyl groups contained in one molecule is 3.

<Production Example 3: Synthesis of polyurethane polyol component A-3>
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 114.1 parts of TMDI, 16.6 parts of PL305, and 0.02 part of U810 were placed and reacted at 75 ° C. for 3 hours.
Thereafter, 37.6 parts of ethylene glycol and 112.2 parts of methyl ethyl ketone were added and reacted for 4 hours to obtain a polymer A-3 having a solid content of 50%.
The hydroxyl value contained in 100% solid content of the calculated polymer A-1 is 30 mgKOH / g, and the number of hydroxyl groups contained in one molecule is 3.

<Production Example 4: Synthesis of polyurethane polyol component A-4>
N-methylethanolamine 75,1 g and γ-butyrolactone 86.1 g were mixed in a flask equipped with a thermometer, a stirrer, and a reflux condenser, and N-methyl-N ′ by heating and stirring at 90 ° C. for 12 hours. -(2-Hydroxyethyl) -3-hydroxypropylamide was obtained. The obtained amide diol had a hydroxyl value of 660 mgKOH / g.
Next, 114.6 parts of IPDI, 22.2 parts of PL305, and 0.02 part of U810 were placed in another flask equipped with a thermometer, a stirrer, and a reflux condenser, and reacted at 75 ° C. for 3 hours.
Thereafter, 87.7 parts of the amide diol obtained in the previous reaction and 149.6 parts of methyl ethyl ketone were added and reacted for 4 hours to obtain a polymer A-4 having a solid content of 60%.
The hydroxyl value contained in 100% solid content of the calculated polymer A-1 is 30 mgKOH / g, and the number of hydroxyl groups contained in one molecule is 3.

<Production Example 5: Synthesis of polymer B-1>
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 27.0 g of isopropanol and 1.8 g of dimethylaminoethyl methacrylate quaternized product are added, and the temperature is raised to 75 ° C. and stirred to dissolve. Thereafter, 55.8 g of methyl ethyl ketone, 54.0 g of methyl methacrylate, and 4.2 g of hydroxyethyl methacrylate are added, and then the temperature is kept at 75 ° C. A solution prepared by dissolving 0.6 g of 2,2′-azobisisobutylnitrile in 2.4 g of methyl ethyl ketone is added and reacted for 2 hours. The same operation was carried out twice after 2 hours and 3 hours, and further reacted at 75 ° C. for 6 hours to obtain a polymer B-1 having a solid content of 40%.
The calculated hydroxyl value contained in 100% solid content of the polymer B-1 was 30 mg KOH / g, and the amount of the quaternary ammonium salt added to the acrylic resin was 0.14 mmol / g.

<Production Example 6: Synthesis of polyurethane polyol component P-1>
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 15.6 parts of IPDI, 9.4 parts of PL305, and 0.01 part of U810 were placed and reacted at 75 ° C. for 3 hours. Thereafter, 70.3 parts of T4691 and 63.6 parts of methyl ethyl ketone were added and reacted for 4 hours to obtain a polymer P-1 having a solid content of 60%. The hydroxyl value contained in 100% solid content of the calculated polymer P-1 is 30 mgKOH / g, and the number of hydroxyl groups contained in one molecule is 3.

<Production Example 7: Synthesis of polymer P-2>
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 27.9 parts of methyl ethyl ketone, 15.9 parts of methyl methacrylate, 12 parts of normal butyl methacrylate, 2.1 parts of 2-hydroxyethyl methacrylate, 2,2′- To add 0.09 part of azobis (2-methylbutyronitrile), raise the temperature to 75 ° C., react for 2 hours, and further increase the polymerization rate, 2,2′-azobis (2-methylbutyrate) was added as an additional initiator. (Ronitrile) 0.06 parts, 0.09 parts, and 0.15 parts were added every 2 hours. Thereafter, the temperature was raised to 80 ° C., 0.15 part of 2,2′-azobis (2-methylbutyronitrile) was added, and the reaction was continued for 2 hours. The reaction solution was cooled to 40 ° C., and 41.6 parts of methyl ethyl ketone was added to obtain a polymer P-2. This polymer had a glass transition temperature of 63 ° C., a hydroxyl value of 30 mg KOH / g, and a weight average molecular weight of 53,500.

<Example 1>
In a flask equipped with a stirrer, A-1 as polyurethane polyol A is 100 parts in resin solids (333 parts as a 30% solids solution), xylylene diisocyanate is 25.2 parts as a crosslinking agent, and as a urethanization catalyst. 0.06 part of U-810 and 26.3 parts of methyl ethyl ketone were added to prepare a coating solution having a solid content of 30%.
About the laminated body-1 obtained by the above-mentioned method from the said coating liquid, the above-mentioned "breaking elongation" in 80 degreeC and 160 degreeC was performed. The results are shown in Table-3.

In a flask equipped with a stirrer, A-1 as polyurethane polyol A is 100 parts in resin solids (333 parts as a 30% solids solution), xylylene diisocyanate is 25.2 parts as a crosslinking agent, and as a urethanization catalyst. 0.06 part of U-810 and 212 parts of methyl ethyl ketone were added to prepare a coating solution having a solid content of 20%.
About the laminated body-2 obtained by the above-mentioned method from the said coating liquid, the "resistance test with respect to a sunscreen agent" mentioned later was evaluated. The results are shown in Table-3.

<Examples 2 to 4 and Comparative Examples 1 to 3>
A curable resin composition was prepared in the same manner as in Example 1 except that the composition of the curable resin composition was changed to the blending ratio shown in Table 3, and a resin laminate with a cured film was produced using the curable resin composition. And evaluated. The evaluation results of Examples 2 to 4 and Comparative Examples 1 to 3 are shown in Table 3.

<Raw materials and solvents>
The raw materials and solvents used in Examples and Comparative Examples and their abbreviations are as follows.
-EG: ethylene glycol-IPDI: isophorone diisocyanate (trade name "VESTANAT (registered trademark) IPDI" manufactured by Evonik Degussa Japan)
TMDI: trimethylhexamethylene diisocyanate (Evonik Degussa Japan, trade name “VESTANAT (registered trademark) TMDI”
PL205: polycaprolactone diol ("Plexel (registered trademark) 205" manufactured by Daicel Chemical Industries)
Number average molecular weight: 528.6
Hydroxyl value: 212.3 mg KOH / g
PL305: Polycaprolactone triol ("Plexel (registered trademark) 305" manufactured by Daicel Chemical Industries)
Number average molecular weight: 553.7
Hydroxyl value: 304.0 mgKOH / g
T4691: Polycarbonate polyol ("Duranol (registered trademark) T4691" manufactured by Asahi Kasei Corporation)
1,4-butanediol / 1,6-hexanediol = 9/1 (weight ratio)
Number average molecular weight: 1000
Hydroxyl value: 119.4 mg KOH / g
MMA: methyl methacrylate nBMA: normal butyl methacrylate 2HEMA: 2-hydroxyethyl methacrylate DQ100: quaternized dimethylaminoethyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester (registered trademark) DQ100”)
MEK: methyl ethyl ketone A-1: polyurethane polyol of component (A) obtained in Production Example 1 A-2: polyurethane polyol of component (A) obtained in Production Example 2 A-3: obtained in Production Example 3 (A ) Component polyurethane polyol A-4: obtained in Production Example 4 (A) component polyurethane polyol B-1: obtained in Production Example 5 (B) component polyacryl polyol P-1: obtained in Production Example 6 Polyurethane polyol P-2: Polyacrylic polyol P-3 obtained in Production Example 7: Polyester polyol (“Byron (registered trademark) GK250” manufactured by Toyobo Co., Ltd.)
Molecular weight 10,000, Tg 60 ° C, hydroxyl value 11mgKOH / g
XDI: xylylene diisocyanate (“Takenate (registered trademark) 500” manufactured by Mitsui Chemicals, Inc.)

In Comparative Examples 1 to 3 having a breaking elongation at 80 ° C. of 100 or more, the resistance test against the sunscreen was poor.

Claims (14)

  A curable resin composition comprising a hydroxyl group-containing composition and a cross-linking agent, wherein the hydroxyl group-containing composition has a breaking elongation at 80 ° C. of less than 100% when cured with xylylene diisocyanate. A curable resin composition.   The curable resin composition of Claim 1 in which the said hydroxyl-containing composition contains the polyurethane compound A which has a 2 or more hydroxyl group.   The curable resin composition according to claim 2, wherein the polyurethane compound A is a reaction product of a diol having a molecular weight of less than 500 and a diisocyanate.   The curable resin composition according to claim 3, wherein the diol having a molecular weight of less than 500 has an amide group.   The curable resin composition according to claim 2, wherein the polyurethane compound A is a reaction product of diamine, diisocyanate and polyol.   The curable resin composition according to any one of claims 2 to 5, wherein the polyurethane compound A has three or more hydroxyl groups.   The curable resin composition according to any one of claims 1 to 6, wherein the hydroxyl group-containing composition further contains an acrylic polymer B having two or more hydroxyl groups.   The curable resin composition according to claim 7, wherein the acrylic polymer B includes a quaternary ammonium salt structure.   The curable resin composition according to claim 8, wherein the content of the quaternary ammonium salt structure in the acrylic polymer B is 0.05 mmol / g or more.   The curable resin composition according to claim 1, wherein the crosslinking agent is a compound having an isocyanate group.   The laminated body which has a layer which consists of a hardened | cured material of the curable resin composition in any one of Claims 1-10.   The laminated body which has a surface protective layer on the surface of the said hardened | cured material of the laminated body of Claim 11.   The laminated body which has a layer which consists of a hardened | cured material of the curable resin composition in any one of Claims 1-10 on the surface protective layer of the said laminated body.   An article decorated with the laminate according to any one of claims 11 to 13.