JP2010275339A - Curable composition and article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition giving a cured article excellent in surface hardness and moldability, and a film or a sheet having a cured coating of the curable composition. <P>SOLUTION: The active energy ray curable composition includes a polyurethane compound (A) obtained by reacting the following components (a1) to (a3), an ethylenically unsaturated compound (B) other than the compound (A), and a photopolymerization initiator (C): (a1) an epoxy (meth)acrylate having 2 hydroxyl groups in the molecule, which is synthesized from a diepoxy compound having a cyclic skeleton in the molecule, and a (meth)acrylic acid derivative; (a2) a compound other than the component (a1) having 2 hydroxyl groups in the molecule and a molecular weight of 50-500; (a3) a diisocyanate compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable composition capable of obtaining a cured product excellent in surface hardness and moldability, and a film or sheet having a cured film of the curable composition, and further a laminate comprising the film or sheet. About.

  Conventionally, cases such as mobile phones and personal computers have been decorated by molding with a thermoplastic resin kneaded with pigment or the like, or painting with a spray after molding. However, since these existing methods cannot meet the demands of the market for various design properties in recent years, injection molding simultaneous decorating methods such as transfer foil method and insert molding method have been often used. Yes. In the injection molding simultaneous decoration method, for example, in the insert molding method, a decorative film on which a pattern is printed in advance is vacuum-molded, inserted into a mold, and then a thermoplastic resin is melt-injected and molded. .

  For the purpose of imparting scratch resistance to such a decorative molded product, the decorative film is provided with a hard coat layer. However, in addition to high surface hardness, these hard coat layers also require flexibility that does not cause cracks even when molded into various shapes, which is inappropriate for conventional hard coat layers.

  Therefore, Patent Document 1 proposes a colored molded article having an acrylic polymer having a hydroxyl group and a photofunctional group and a protective layer made of polyisocyanate. The protective layer obtained by this method is rich in flexibility and has excellent moldability. However, in addition to insufficient surface hardness, it is a two-component paint composed of a main agent and a curing agent, so that the storage stability after mixing is poor.

  Therefore, Patent Document 2 proposes a composition using a polyurethane compound composed of epoxy (meth) acrylate having two hydroxyl groups in the molecule and diisocyanate. By using a polyurethane compound having a relatively high molecular weight and having a functional group in the side chain, both surface hardness and moldability are achieved. However, in order to apply to more complicated and large shapes, further improvement in formability has been desired.

JP 11-34248 A JP 2003-212938 A

  An object of the present invention is to provide a curable composition that becomes a cured film having a high degree of surface hardness and a degree of elongation that does not cause cracks or the like during decoration in the mold during injection molding, and an article having the cured film. Is to provide.

The present invention contains a polyurethane compound (A) obtained by reacting the following components (a1) to (a3), an ethylenically unsaturated compound (B) other than the compound (A), and a photopolymerization initiator (C). This is an active energy ray-curable composition.
(A1) An epoxy (meth) acrylate having two hydroxyl groups in the molecule synthesized from a diepoxy compound having a cyclic skeleton in the molecule and a (meth) acrylic acid derivative (a2) having two hydroxyl groups in the molecule The compound (a3) is a diisocyanate compound other than the component (a1) having a molecular weight of 50 to 500. In addition, the present invention provides the compound (A) having components (a1) to (a3) and one hydroxyl group in the molecule. And the above-mentioned active energy ray-curable composition obtained by reacting the component (a4) which is a compound having one or more photofunctional groups.

  The present invention is the above-mentioned active energy ray-curable composition further containing inorganic fine particles (D).

  Moreover, this invention is a film or sheet | seat which has the cured film which hardened the above-mentioned active energy ray curable composition.

  Furthermore, the present invention is a laminate comprising the above-described film or sheet.

  According to the present invention, there are provided a curable composition that is a cured product having a high surface hardness and a degree of elongation that does not cause cracks or the like during decoration in a mold during injection molding, and an article having the cured product layer. It is to be.

  Hereinafter, the present invention will be described in detail.

<Polyurethane compound (component A)>
The composition of the present invention contains a polyurethane compound (hereinafter referred to as “component A” as appropriate) for the purpose of maintaining low shrinkage during curing and imparting excellent moldability and surface hardness to the resulting cured product. Is done.

  Component A has (a1) component epoxy (meth) acrylate having two hydroxyl groups in the molecule, component (a2) has two hydroxyl groups in the molecule, and has a molecular weight of 50 to 500 ( It is a compound obtained by reacting a compound other than the component a1) and a diisocyanate compound as the component (a3).

  If necessary, a compound having one hydroxyl group and one or more photofunctional groups in the molecule as the component (a4) may be used in combination with the components (a1) to (a3).

<(A1) component: epoxy (meth) acrylate having two hydroxyl groups in the molecule>
The component (a1) is a component used for imparting surface hardness to the cured product by maintaining low shrinkage during curing of the composition and introducing a functional group into the molecular side chain of the component A.

  The component (a1) can be synthesized from a diepoxy compound having a cyclic skeleton in the molecule and a (meth) acrylic acid derivative. The synthesis method is not particularly limited, and a known synthesis method can be adopted. For example, a polymerization inhibitor such as a diepoxy compound, a (meth) acrylic acid derivative, a synthesis catalyst, or hydroquinone monomethyl ether is mixed. Then, this mixture can be synthesized by reacting under the condition of 95 ° C. Moreover, as long as it has two hydroxyl groups in a molecule | numerator, you may use the epoxy (meth) acrylate which has a commercially available cyclic | annular frame | skeleton.

  As a catalyst used for the synthesis of the diepoxy compound and the (meth) acrylic acid derivative, a known catalyst used for the esterification reaction of an acid group and an epoxy group can be used. Among them, a tertiary amine, a quaternary ammonium salt, a quaternary phosphonium salt, and the like are preferable because of excellent reaction rate. Specific examples thereof include dimethylaminoethyl methacrylate as the tertiary amine, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, tetraethyl as the quaternary ammonium salt and quaternary phosphonium salt. Examples thereof include phosphonium bromide, tetrabutylphosphonium bromide, benzyltriphenylphosphonium chloride, and benzyltriphenylphosphonium bromide.

  Among these, dimethylaminoethyl methacrylate having photofunctionality and effective as a later polyurethane forming catalyst is preferable.

  The diepoxy compound used for the component (a1) is a diepoxy compound having a cyclic skeleton in the molecule. Specifically, diepoxy compounds of aromatic glycols such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, and hydroquinone, and alkylene oxide adducts thereof; cyclopentanediol, cyclo Diepoxy compounds of alicyclic glycols such as pentanedimethanol, cyclopentanediethanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, norbornanediol, norbornanedimethanol, norbornanediethanol, decalindiol, decalindimethanol, decalindiethanol; phthalic acid, Diepoxy compounds such as isophthalic acid and terephthalic acid; 3,4-epoxycyclohexylmethylcarboxylate, 2- (3,4-ethylene Carboxymethyl-cyclohexyl-5,5-Supiro 3,4-epoxy) cyclohexane over meta-dioxane, bis (3,4-epoxycyclohexyl) alicyclic epoxy compounds such as adipate, etc. can be exemplified.

  Among these, a bisphenol diepoxy compound is preferable because high scratch resistance is obtained after curing, and among them, a bisphenol A diepoxy compound, a hydrogenated bisphenol A diepoxy compound, a bisphenol F diepoxy compound, a hydrogenation, among others. Bisphenol F diepoxy compounds are preferred.

  The diepoxy compound used for the component (a1) preferably has no hydroxyl group in the molecule. If the molecule has a hydroxyl group, the resulting epoxy (meth) acrylate has three or more hydroxyl groups in the molecule, and is not preferable because it gels during polyurethane formation.

<Component (a2): Compound other than component (a1) having two hydroxyl groups in the molecule and a molecular weight of 50 to 500>
The component (a2) is a compound having two hydroxyl groups in the molecule and a molecular weight of 50 to 500. The component (a2) is a component that is used to increase the amount of urethane bonds in the molecular chain of the component A, give the cured product with surface hardness and improve moldability. In the case of an epoxy (meth) acrylate having two hydroxyl groups in a molecule synthesized from a diepoxy compound having a cyclic skeleton in the molecule and a (meth) acrylic acid derivative, the molecular weight is 50 to 500. However, it is regarded as the component (a1).

  Specific examples of the component (a2) include aromatic glycols such as bisphenol A type, bisphenol F type, resorcin, and hydroquinone, and alkylene oxide adducts thereof; ethylene glycol, propylene glycol, neopentyl glycol, tetramethylene ether glycol. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, etc. Branched aliphatic glycols, polyalkylene glycols obtained by polymerizing these aliphatic glycols; hydrogenated bisphenol A type, hydrogenated bisphenol F type, cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, cyclohexa Alicyclic glycols such as diol, cyclohexanedimethanol, cyclohexanediethanol, norbornanediol, norbornanedimethanol, norbornanediethanol, decalindiol, decalindimethanol, decalindiethanol; alkanediols such as ethylene glycol adipate composed of ethylene glycol and adipic acid And polyester diols composed of dibasic acid. Other examples include compounds having two hydroxyl groups and one or more (meth) acryloyl groups in the molecule. Specifically, diepoxy resins obtained by a condensation reaction of a compound having two hydroxyl groups in its molecule and epichlorohydrin, such as the aforementioned aliphatic glycols or polyalkylene glycols obtained by polymerizing these aliphatic glycols Among these, epoxy (meth) acrylates obtained by reacting (meth) acrylic acid and the like are different from the a1 component. Other examples include glycerin mono (meth) acrylate.

  The molecular weight of component a2 is preferably 50 to 500. More preferably, it is 100-400. When the molecular weight of the component a2 is within the above range, the component A to be obtained is preferable from the viewpoint of low viscosity and excellent workability and the moldability of the resulting cured product. These can be used alone or in combination of two or more.

  Among these, polyalkylene glycols, alicyclic glycols, and epoxy (meth) acrylates and glycerin mono (meth) acrylates derived from them are preferable from the balance of surface hardness and moldability of the obtained cured product. More preferably, polyethylene glycol, polypropylene glycol, epoxy (meth) acrylate derived therefrom, hydrogenated products of cyclohexanedimethanol, bisphenol A and bisphenol F, and glycerin mono (meth) acrylate are preferable.

The molecular weight of component a2 is such as aromatic glycols, aliphatic glycols, alicyclic glycols, and other glycols, epoxy (meth) acrylates derived from these glycols, glycerin mono (meth) acrylate, and the like. In the case of a single component, the molecular weight calculated from the structural formula is used. Further, for the alkylene oxide adducts, polyalkylene glycols and polyester diols of the glycols, the molecular weight calculated from the hydroxyl value is used. The hydroxyl value is calculated according to JIS K1557-1 “Plastic-polyurethane raw material polyol test method”, or an inspection result value available from the manufacturer is used. In order to calculate the molecular weight from the hydroxyl value, the following formula is used.
Molecular weight = 56.1 × 1000 × 2 / hydroxyl value

<Polydiisocyanate (a3 component)>
The a3 component is an essential component used for introducing a urethane bond in the molecular chain of the A component into a polyurethane.

  As a specific example of a3 component, what is conventionally used for manufacture of urethane (meth) acrylate can be used. For example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, etc. Isocyanates; Aliphatic polyisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; isophorone diisocyanate, dicyclohexyl Alicyclic polyisocyanates such as methane-4,4-diisocyanate and methylcyclohexylene diisocyanate; Isocyanate, araliphatic polyisocyanates such as tetramethyl xylylene diisocyanate; these burette body, allophanate and the like can be mentioned. These can be used alone or in combination of two or more.

  Among these, alicyclic polyisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, and methylcyclohexylene diisocyanate are preferable from the viewpoint of physical properties of the obtained cured product. More preferred are dicyclohexylmethane-4,4-diisocyanate and methylcyclohexylene diisocyanate.

<Compound having one hydroxyl group and one or more photofunctional groups in the molecule (a4 component)>
The a4 component is used as necessary to block the terminal isocyanate group. The a4 component is a component that increases the number of functional groups of the A component and improves the surface hardness of the resulting cured product.

  As a specific example of the a4 component, any compound having one hydroxyl group and one or more photofunctional groups may be used, but 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta ) Acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclopentanediol mono (meth) acrylate, cyclopentanedimethanol Mono (meth) acrylate, cyclopentanedimethanol mono (meth) acrylate, cyclohexanediol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, cyclohexanediethanol mono (meth) ) Acrylate, norbornanediol mono (meth) acrylate, norbornane dimethanol mono (meth) acrylate, norbornane diethanol mono (meth) acrylate, decalindiol mono (meth) acrylate, decalin dimethanol mono (meth) acrylate, decalin diethanol mono (meta) ) Acrylate, mono (meth) acrylates having a hydroxyl group such as hydrogenated bisphenol A mono (meth) acrylate; trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, bis ((meth) acryloxyethyl) ) Hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate, dipentaerythritol penta (meth) Monohydroxy poly (meth) acrylates such as acrylate and isocyanuric acid di (meth) acrylate; and alkylene oxide adducts thereof; monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl methacrylate and (meth) Addition reaction product with acrylic acid; addition reaction product with mono (meth) acrylic acid such as polyethylene glycol and polypropylene glycol; mono (meth) acrylic acid ester of polycaprolactone diol (repetition number n = 1 to 5) It is done.

  Among these, pentaerythritol tri (meth) acrylate and dipentaerythritol pentaacrylate are preferable from the viewpoint of the surface hardness of the obtained cured product.

  The synthesis method of the component A is not particularly limited, and various known polyurethane synthesis methods can be employed. For example, a component A can be obtained by mixing a1 component and a2 component and a polyurethane-forming catalyst, and dropping and reacting a3 component in this mixture on 50-90 degreeC conditions.

  At this time, a known catalyst such as an amine catalyst or an organometallic catalyst can be used as the polyurethane forming catalyst. Specific examples of the amine catalyst include triethylamine, N, N-dimethylcyclohexylamine, dimethanolamine and the like. As the organometallic catalyst, an organotin compound is preferably used, and examples thereof include stannous octoate, stannous laurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, and dioctyltin diacetate.

  Among these, since a high catalytic effect can be obtained in a small amount, an organometallic catalyst is preferable, and dibutyltin dilaurate is more preferable.

  Moreover, you may dilute with a solvent etc. as needed for the purpose of making temperature control at the time of a synthesis | combination easy, reducing the viscosity of the obtained A component, and improving workability | operativity.

  The ratio of the a1 component, the a2 component, and the a3 component when producing the A component is not particularly limited. However, it is preferable that the total epoxy group contained in the a1 component and the total carboxyl group amount of the a2 component are (total epoxy group amount) / (total carboxyl group amount) = 1. At that time, the ratio of the total epoxy group amount of the a1 component and the total isocyanate group amount contained in the a3 component is preferably 0.5 ≦ (total isocyanate group amount) / (total epoxy group amount) <1.0. .

  When the a4 component is used, the ratio of the total epoxy group amount of the a1 component and the total hydroxyl group amount contained in the a4 component and the total isocyanate group amount contained in the a3 component is 0.5 ≦ (total isocyanate Base amount) / (total epoxy group amount + total hydroxyl group amount) <1.0. At this time, the ratio between the a1 component and the a4 component can be appropriately selected depending on the molecular weight of the target compound, but 0 ≦ total hydroxyl group content in the a4 component / total epoxy group content of the a1 component <0.95 is preferable. .

  At this time, the amount of epoxy groups, the amount of carboxyl groups, the amount of isocyanate groups, and the amount of hydroxyl groups are obtained by multiplying the number of functional groups contained in one molecule by the number of moles to be used.

  The mass average molecular weight of the component A is preferably 5,000 to 100,000. If the mass average molecular weight of the A component is within the above range, it can be stably produced without gelation during production, which is preferable from the viewpoint of workability of the obtained A component and the moldability of the obtained cured product. . More preferably, the mass average molecular weight is 8000-30000. The weight average molecular weight of the component A is the same as that described above for a gel permeation chromatography apparatus manufactured by TOSO equipped with a TOSO column (GE4000HXL and G2000HXL) after adjusting a tetrahydrofuran solution (0.4% by mass) of the composition. 100 μl of the solution was injected, measured using a gel permeation chromatography method under conditions of flow rate: 1 ml / min, eluent: tetrahydrofuran, column temperature: 40 ° C., and converted to standard polystyrene.

  Although content of A component is not specifically limited, It is preferable that it is the range of 10-95 mass% in the total amount of 100 mass% of A component and B component, and it is more preferable that it is the range of 20-90 mass%. .

  When the content of the component A is within the above range, the viscosity can be easily reduced, the workability is excellent, and the moldability and surface hardness of the resulting cured product are good.

<An ethylenically unsaturated compound other than component A (component B)>
The composition of the present invention contains an ethylenically unsaturated compound other than the component A (hereinafter referred to as “component B” as appropriate) for the purpose of imparting surface hardness to the resulting cured product.

  Examples of the component B include di (meth) acrylate, polyfunctional (meth) acrylate, epoxy acrylate, urethane poly (meth) acrylate other than component A, polyester poly (meth) acrylate, and the like. These are specifically listed below.

  For example, as specific examples of di (meth) acrylate, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (repeating unit n = 2 to 15) di (meth) acrylate, polypropylene glycol (repeating unit n = 2 to 15) di (meth) Acrylate, polybutylene glycol (repeat unit n = 2-15) di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyl Oxydiethoxyphenyl) propane, trimethylo Propane di (meth) acrylate, tricyclodecane dimethanol diacrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2- (meth) acryloyloxypropyl) -2-ethoxypropyl isocyanurate, etc. Can be mentioned.

  Specific examples of the polyfunctional (meth) acrylate include, for example, trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and tris (2- (meth) acryloyloxypropyl) isocyanurate. Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

  Other specific examples include bisphenol type epoxy resin and (meth) acrylic acid obtained by condensation reaction of bisphenols selected from bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A and the like and / or hydrogenated products thereof with epichlorohydrin. Alkane selected from epoxy poly (meth) acrylates such as bisphenol-type epoxy di (meth) acrylates, polypropylene glycol (repeating units n = 2 to 15), polybutylene glycols (repeating units n = 2 to 15), etc. Epoxy poly (meth) acrylates obtained by reacting polyepoxy resins such as alkanediol polyepoxy resins obtained by condensation reaction of diols with epichlorohydrin and (meth) acrylic acid; organic diisocyanates One type of compound alone or a mixture of two or more types, one or more (meth) acryloyloxy groups in the molecule and one hydroxy group-containing (meth) acrylate having one hydroxy group Urethane (meth) acrylates obtained by reacting two or more mixtures; consisting of one or a mixture of two or more of alkane diol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, amide diol, spiroglycol compound, etc. An organic diisocyanate compound is added to the hydroxyl group of alcohols, and the resulting urethane prepolymer has an isocyanate group containing one (meth) acryloyloxy group and one hydroxy group (meth) in the molecule. Urethane reacted with acrylate (meta Acrylates: polybasic acids selected from phthalic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, azelaic acid, adipic acid, ethylene glycol, hexanediol, polyethylene glycol, polytetramethylene glycol, tri Examples thereof include polyhydric alcohols selected from methylolethane, trimethylolpropane, and the like, and polyester (meth) acrylates obtained by reaction with (meth) acrylic acid or derivatives thereof. These can be used individually by 1 type or in combination of 2 or more types.

  Among these, since the surface protection performance of the cured film can be improved, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, pentaerythritol tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate and the like are preferable. Further, in order to obtain good compatibility with other components in the coating composition of the present invention, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate and a mixture thereof, that is, a compound having at least three (meth) acryloyl groups in the molecule is particularly preferable.

  Although content of B component is not specifically limited, It is preferable that it is the range of 5-90 mass% in the total amount of 100 mass% of A component and B component, and it is more preferable that it is the range of 10-80 mass%. . When the content of the B component is within the above range, the surface hardness is good.

<Photopolymerization initiator (component C)>
The composition of the present invention contains a photopolymerization initiator (hereinafter appropriately referred to as “C component”) for the purpose of efficiently obtaining a cured product by an ultraviolet curing method.

  Specific examples of component C include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophene, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2- Ethyl anthraquinone, 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, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Tanone-1, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6 -Trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Examples include 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone and 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butan-1-one.

  Among these, since it is excellent in the sclerosis | hardenability of the resin composition of this invention especially, and the surface hardness of the hardened | cured material obtained, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl- Phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro One or more photopolymerization initiators selected from pan-1-one are preferred.

  In the present composition, the content of the component C is not particularly limited, but is preferably in the range of 0.01 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable components. More preferred is the range of parts. When content of C component exists in the said range, sclerosis | hardenability of this composition is favorable, and the hardened | cured material obtained has favorable surface hardness.

<Inorganic fine particles (component D)>
In the composition of the present invention, inorganic fine particles (hereinafter referred to as “component D” as appropriate) are used for the purpose of imparting surface protection performance such as scratch resistance to the cured film. The component D is preferably one in which inorganic fine particles are modified with an organic compound. Hydrolysis product of inorganic fine particles having an average primary particle diameter of 1 to 300 nm (hereinafter referred to as “(d1) component” as appropriate) and a polymerizable unsaturated double bond-containing organic silane compound (hereinafter referred to as “(d2) component as appropriate”) The polymerizable unsaturated double bond-containing inorganic fine particles obtained by condensation reaction of “)” are more preferable.

  The component (d1) preferably has an average primary particle diameter in the range of 1 to 300 nm, preferably 5 to 80 nm, and is dispersed in a colloidal state in a dispersion medium such as water or an organic solvent. As the component (d1), silica is preferable from the viewpoint of wear resistance and scratch resistance of the cured film to be obtained. The average primary particle size of the component (d1) is preferably 1 nm or more so as not to cause gelation during the reaction with the component (d2), and is preferably 300 nm or less from the viewpoint of the transparency of the resulting cured film.

  In addition, the average primary particle diameter in this invention means the gas adsorption method (Raw material manufacturer disclosure data: specific surface area equivalent diameter calculated | required by BET method).

  Specific examples of the component (d2) include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyldiethoxy. Silane, vinylphenylenetrimethoxysilane, vinylphenylenetriethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, vinyltris (3-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxy Silane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, β- (3,4-epoxycyclohexane E) Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltri Methoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltri Hydrolysis products such as methoxysilane and 3-isocyanatopropyltriethoxysilane can be mentioned. These can be used alone or in combination of two or more.

  Moreover, the silane compound which added (meth) acrylic acid to the epoxy group of these compounds and the glycidyl group, the silane compound which added the compound which has two (meth) acryloyloxy groups to an amino group, an amino group, and a mercapto group A silane compound obtained by adding a compound having a (meth) acryloyloxy group and an isocyanate group, a hydrolysis product of a silane compound obtained by adding a compound having a (meth) acryloyloxy group and a hydroxyl group to an isocyanate group, and the like can also be used.

  The most preferable compound as the component (d2) is a hydrolysis product of the monomer represented by the formula (1).

(In the formula, X represents a (meth) acryloyloxy group, vinylphenylene group or vinyl group, R ¹ represents a direct bond or a linear or branched alkylene group having 1 to 8 carbon atoms, and R ² and R ³ represent carbon. In the linear or branched alkyl group of formulas 1 to 8, a represents a positive integer of 1 to 3, b represents a positive integer of 0 to 2, and a + b is a positive integer of 1 to 3. )
As the monomer represented by the formula (1), a silane compound having a (meth) acryloyloxy group, a vinylphenylene group or a vinyl group, which exhibits polymerization activity when irradiated with active energy rays, is preferably used.

  By using such a silane compound, a photocurable B component capable of forming a chemical bond with the A component and the C component can be obtained, and a high degree of scratch resistance can be imparted to the resulting cured film. it can.

  Specific examples of the monomer represented by the formula (1) include, for example, 3- (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, and 3- (meth) acryloyloxypropyl. Triethoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, vinylphenylenetrimethoxysilane, vinylphenylenetriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc. Can be mentioned. These can be used alone or in combination of two or more.

  Among them, a silane compound selected from 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane is polymerized by irradiation with active energy rays. It is particularly preferable in terms of excellent activity.

  Such a component D is obtained by obtaining a mixture of the component dispersion (d1) and the component (d2) in which the component (d1) is dispersed in a dispersion medium, and then subjecting the dispersion medium of the component (d1) to normal pressure or reduced pressure. And azeotropic distillation with a medium having a polarity lower than that of the dispersion medium, substituting the dispersion medium of component (d1) with a medium having a low polarity, and then reacting under heating. Specific methods include the following methods.

  Preparation of the mixture of (d1) component dispersion and (d2) component is either mixing (d1) component dispersion and (d2) component, or (d1) adding component dispersion, organosilane compound and water. What is necessary is just to mix a decomposition catalyst and to make an organosilane compound into the component (d2) in the presence of the component (d1).

  More specifically, in the presence or absence of an organic solvent such as an alcohol solvent, 0.5 to 6 mol of water or 0.001 to 0.1 as a hydrolysis catalyst with respect to 1 mol of the organic silane compound. (D2) component is prepared by adding normal hydrochloric acid or aqueous acetic acid solution, etc., and removing alcohol generated by hydrolysis out of the system while stirring under heating. Thereafter, the component (d2) and the component dispersion (d1) are mixed. Alternatively, by mixing an organic silane compound and a hydrolysis catalyst in the component dispersion (d1) in the same manner as described above to obtain a hydrolysis product of the organic silane compound, the component dispersion (d1) and the component (d2) Can be prepared.

  At this time, as a mixing ratio of the component (d1) and the component (d2), when the total of the component (d1) and the component (d2) is 100% by mass, the component (d1) is 5 to 90% by mass. Is preferred. More preferably, it is 20-80 mass%. If it is 5 mass% or more, it is preferable from the point of the surface protection performance of the cured film obtained, and if it is 90 mass% or less, it is preferable at the point of the dispersion stability and the intensity | strength of a cured film. Next, in the condensation reaction of the component (d1) and the component (d2), first, the dispersion medium of the component (d1) and the water generated by the condensation reaction are subjected to normal pressure or reduced pressure at 60 to 100 ° C., preferably 70 to 90. An azeotropic distillation is performed at a temperature of ° C., and the solid content concentration is adjusted to 50 to 90% by mass.

  Next, a solvent having a lower polarity than the dispersion medium of the component (d1) is added to the system, and the low polarity solvent, water, and the dispersion medium of the component (d1) are further azeotropically distilled, preferably 60 to 150 ° C., preferably While maintaining the solid concentration at 30 to 90% by mass, preferably 50 to 80% by mass at a temperature of 80 to 130 ° C., the mixture is stirred for 0.5 to 10 hours to perform a condensation reaction to obtain component D. At this time, a catalyst such as water, acid, base, salt or the like may be used for the purpose of promoting the reaction.

  The content ratio of the D component is in the range of 5 to 50 parts by mass, preferably in the range of 10 to 35 parts by mass as the solid content with respect to 100 parts by mass of the total amount of the A and B components. When content of D component exists in the said range, the moldability and transparency of the obtained hardened | cured material, and surface hardness are favorable.

  The composition of the present invention may contain a polymerization inhibitor without departing from the object of the present invention. Examples of the polymerization inhibitor include nitroso polymerization inhibitors such as nitrosophenylhydroxylamine ammonium salt, quinones such as hydroquinone, hydroquinone monomethyl ether and benzoquinone, N, N-diphenylpicrylhydrazyl (DPPH), and triphenylmethyl. And radical scavengers such as benzotriazole-based antioxidants. These can be used alone or in combination of two or more.

Furthermore, the composition of the present invention includes a rheology modifier such as a non-reactive thermoplastic polymer, an organic benton, polyamide, microgel, and a fiber-based resin, a surface modifier represented by silicone, and an ultraviolet absorber. Additives such as an agent, a light stabilizer, an antioxidant, a polymerization inhibitor, a silane coupling agent, an organic filler, and an anti-sagging agent can be appropriately blended as necessary using known means.

  In the composition of the present invention, an inorganic filler other than Component D can be blended as necessary for the purpose of imparting shape stability and heat resistance, or improving conductivity. Moreover, a well-known method can be used as a compounding method. Inorganic fillers include metal oxides such as silica, alumina, and titanium oxide, or composite oxides thereof, and those metal oxides or composites in terms of shape stability, heat resistance, flame retardancy, insulation, etc. of the cured product. A surface-treated metal oxide or surface-treated composite oxide obtained by coating an oxide with a silane coupling agent or the like, or a hydroxide such as aluminum hydroxide, magnesium hydroxide, or potassium hydroxide is preferable. In order to improve conductivity, the inorganic filler includes metal particles such as gold, silver, copper, nickel and alloys thereof, conductive particles such as carbon, carbon nanotube, carbon nanohorn, and fullerene, and glass, ceramic, and plastic. Particles obtained by coating the surface of a nucleus such as a metal oxide with metal, ITO (indium tin oxide) or the like are preferable. The conductive particles preferably have an aspect ratio of 5 or more in terms of conductivity. The aspect ratio is determined by (major axis) / (minor axis). As the particle diameter of the inorganic filler, an area average particle diameter of 1 μm or less is optically preferable. The compounding quantity of an inorganic filler can be adjusted according to the use for which a composition is used, the required mechanical strength, fluidity, etc.

  When the composition of the present invention is used as a coating material, the composition can be diluted with an organic solvent in order to adjust the viscosity of the composition according to the coating method.

  Examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, cyclohexyl alcohol, diacetone alcohol; methyl cellosolve, cellosolve, butyl cellosolve, methylcarbyl Ether solvents such as Toll, Carbitol, Butyl Carbitol, Diethyl Carbitol, Propylene Glycol Monomethyl Ether; “Swazole 1000” (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), “Supersol 100” (trade name, new Nippon Petrochemical Co., Ltd.), "Supersol 150" (trade name, Shin Nippon Petrochemical Co., Ltd.), aromatic solvents such as benzene, toluene and xylene; cyclic hydrocarbon solvents such as cyclohexane; Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ketone solvents and ethyl acetate and cyclohexanone, n- butyl acetate, isobutyl acetate, n- amyl acetate, include acetate-based solvents such as propylene glycol acetate. These organic solvents can be used alone or in combination of two or more.

  About content of the organic solvent, it is preferable from the point of coating workability | operativity that the hardened | cured material component in a composition shall be 30 mass% or more of the final composition at the time of coating. For example, when spraying the composition of the present invention, the Ford Cup No. It is preferable to add an organic solvent using a 4 viscometer so that the viscosity is about 15 to 60 seconds at 20 ° C.

  As a coating method when using the composition of the present invention as a coating material, a bar coater coating method, a Mayer bar coating method, an air knife coating method, a gravure coating method, a reverse gravure coating method, a micro gravure coating method, a brush coating method, Known coating methods such as spray coating, shower flow coating, dip coating, curtain coating, offset printing, flexographic printing, screen printing, and potting can be used.

  The material of the support when the composition of the present invention is used as a coating material is not particularly limited, but is not limited to cellulose resin, polyester resin, methacrylic resin, polycarbonate resin, polystyrene resin, crystalline polyolefin resin, non-crystalline resin, Examples thereof include crystalline polyolefin resins, polyether sulfone resins, acrylonitrile-styrene copolymer resins, polyamide resins, polyarylate resins, and polymethacrylimide resins. Of these, polyester resins, methacrylic resins, and polycarbonate resins are preferable. Moreover, what provided the handle | pattern and the easily bonding layer on the base-material surface can also be used. In addition, as a support body, what mix | blended various additives, such as antioxidant, a light stabilizer, a ultraviolet absorber, a fluorescent whitening agent, a transesterification agent, and an antistatic agent, may be used.

  Although the thickness of a support body is not specifically limited, Between the points of 0.05-1 mm are preferable from the point of the surface hardness of the coating material obtained.

  The cured product of the present invention is obtained by curing the composition with active energy rays or the like.

  The thickness of the cured product can be appropriately selected according to the purpose. For example, when using hardened | cured material as a film | membrane, 0.001-0.1 mm is preferable at the point of sclerosis | hardenability and surface hardness.

  In the case of using an active energy ray when obtaining a cured product, examples of the active energy ray include α, β, γ ray, and ultraviolet rays, and ultraviolet rays are preferred from the viewpoint of versatility.

  Examples of the ultraviolet ray generation source include commonly used ultraviolet lamps from the viewpoint of practicality and economy. For example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless UV lamp using a magnetron, and other LEDs may be mentioned.

  In the case of using the active energy ray when obtaining the cured product of the present invention, the atmosphere to be cured may be either air or an inert gas such as nitrogen or argon, but in an air atmosphere in terms of practicality and economy. It is preferable to cure.

  The composition of the present invention is suitable for a hard coat film because of its excellent surface hardness, and particularly for a film for in-mold decoration during injection molding because of its excellent moldability. In-mold decoration during injection molding means that a film with a hard coat layer or printing layer is sandwiched in the mold during injection molding of plastics, etc., and at the same time as injection molding, the hard coat layer or printing is performed on the surface of the molded product in the mold. This is a technique for decorating layers. At this time, the cured product film of the present invention may or may not be preformed.

  As a support in the case where the composition of the present invention is used for in-mold decoration during injection molding, among the above-mentioned supports, a support made of a polyester resin, a methacrylic resin or a polycarbonate resin is preferable. By using these, the obtained laminate has excellent moldability. The thickness of the support is preferably from 0.05 to 1 mm from the viewpoint of the surface hardness of the resulting coating, and preferably from 0.05 to 0.2 mm from the viewpoint of moldability.

  When the cured product of the present invention is used for in-mold decoration during injection molding, the thickness of the coating is preferably 0.001 to 0.1 mm in terms of curability and surface hardness, and more preferably 0.001 from the viewpoint of moldability. -0.01 mm is preferable.

  The injection molding resin is not particularly limited as long as it is a thermoplastic resin that can be melted and integrated with the support. For example, a polycarbonate resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin), and a polymer alloy containing a polycarbonate resin. Etc. These injection molding resins include antioxidants, light stabilizers, UV absorbers, lubricants, plasticizers, stabilizers, mold release agents, antistatic agents, colorants, flame retardants, glass fibers, carbon fibers, and drip prevention. You may mix | blend various additives, such as an agent.

  Hereinafter, the present invention will be described in more detail by way of examples. In the examples, “part” means “part by mass”, and “%” other than haze means “% by mass”. Moreover, the evaluation method of the obtained hardened layer is as follows.

<Synthesis of component (a1)>
(Synthesis Example 1)
In a 5 liter four-necked flask, 3180 parts of bisphenol F diepoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Epototo YDF-8170C, epoxy equivalent: 159), acrylic acid (manufactured by Mitsubishi Chemical Corporation, product) Name: Acrylic acid) 1440 parts, Hydroquinone monomethyl ether 4.6 parts as a polymerization inhibitor, 23 parts dimethylaminoethyl methacrylate (product name: Acryester DM, manufactured by Mitsubishi Rayon Co., Ltd.) as a synthesis catalyst, and stirred. The temperature was raised to 95 ° C., and the reaction was continued for 14 hours while maintaining the temperature at 95 ° C. When the acid value became 1 mgKOH / g or less, the mixture was cooled to an internal temperature of 60 ° C. to obtain EA-1 as a component (a1).

(Synthesis Example 2)
In place of bisphenol F type diepoxy resin, 36.2 parts of bisphenol A type diepoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Epototo YD-8125, epoxy equivalent: 173.1) is used to obtain 4.9 hydroquinone monomethyl ether. EA-2 was obtained as component (a1) in the same manner as in Synthesis Example 1 except that 24 parts of dimethylaminoethyl methacrylate was used.

<Synthesis of component A>
(Synthesis Example 3)
In a 5-liter four-necked flask, 298 parts of EA-1 obtained in Synthesis Example 1 and 711.3 parts of ethyl acetate were placed and heated to an internal temperature of 60 ° C. While adding 0.21 part of di-n-butyltin dilaurate as a synthesis catalyst and stirring, 199 parts of methylcyclohexylene diisocyanate (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name: Takenate 600) as a component (a3) The solution was added dropwise over 1 hour. The reaction was continued for 2 hours after completion of the dropping, and then 27.3 parts of diethylene glycol (reagent manufactured by Wako Pure Chemical Industries, Ltd., trade name: diethylene glycol, molecular weight 106) as a2 component, pentaerythritol tetraacrylate (Toagosei Co., Ltd.) as a4 component 187 parts of a mixture manufactured by Trade Name: Aronix M-306 was added dropwise over 1 hour. Reaction was continued for 5 hours after dripping, and the polyurethane compound PU-1 of the weight average molecular weight 19800 was obtained as A component.

(Synthesis Examples 4 to 14)
A polyurethane compound was produced in the same manner as in Synthesis Example 3 except that the raw materials and the amount of charge shown in the charge amount column of Table 1 were used.

(Synthesis Example 15)
In a 5-liter four-necked flask, 174 parts of tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name: Coronate T-100), 0.62 part of hydroquinone monomethyl ether as a polymerization inhibitor, and 1247 parts of ethyl acetate The inner temperature was 60 ° C. As a synthesis catalyst, 0.13 part of di-n-butyltin dilaurate was added, and 1072 parts of pentaerythritol tetraacrylate (trade name: Aronix M-306, manufactured by Toagosei Co., Ltd.) was stirred for 4 hours while stirring. It was dripped. Reaction was continued for 5 hours after dripping, and polyfunctional urethane acrylate MU-1 was obtained.

<Synthesis of D component>
(Synthesis Example 16)
To a 3 liter four-necked flask equipped with a stirrer, a thermometer and a condenser, isopropanol silica sol (dispersion medium; isopropanol, SiO ₂ concentration; 30% by mass, average primary particle size (data disclosed by raw material manufacturer: determined by BET method) Specific surface area equivalent diameter): 12 nm) (manufactured by Nissan Chemical Industries, trade name: IPA-ST) (hereinafter abbreviated as “IPA-ST”) 2,000 parts, 3-methacryloyloxypropyltrimethoxysilane ( 382 parts manufactured by Shin-Etsu Silicon Co., Ltd. (trade name: KBM-503) (hereinafter abbreviated as “KBM-503”) were added. Next, the temperature inside the flask is raised while stirring, and 150 parts of pure water is gradually added dropwise so as to maintain the reflux temperature at the same time as the reflux of the volatile components begins. Decomposition was performed. After completion of hydrolysis, volatile components such as alcohol and water are distilled off under normal pressure, and the solid content (total amount 917 parts of 600 parts of SiO _{2 of} IPA-ST and 317 parts of KBM-503) is about 60. At the time of mass%, 600 parts of toluene was added, and alcohol, water and the like were azeotropically distilled together with toluene. Furthermore, 1,500 parts of toluene was added, and the solvent was completely replaced with a toluene dispersion. The solid content concentration at this time was about 40% by mass. Further, the reaction was carried out at 110 ° C. for 4 hours while distilling toluene, so that the solid content concentration was about 60% by mass. The obtained polymerizable unsaturated double bond-containing inorganic fine particles (hereinafter abbreviated as “CS-1”) are yellow, Newtonian fluid transparent and viscous liquid, and the viscosity at 25 ° C. is 30 mPa · s. s. Moreover, solid content concentration was 60.0% by the heating residue. The solid content concentration is represented by (mass after heating (g) / mass before heating (g)) × 100 (mass%), and the heating condition is 105 ° C. for 3 hours.

[Example 1]
140 parts of PU-1 of Synthesis Example 3 as the A component, 20 parts of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayarad DPHA) as the B component, and 2-methyl-1- [ 5. 4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) with 5 parts and CS-1 of Synthesis Example 14 as 16. 7 parts and 168.3 parts of methyl isobutyl ketone (MIBK) as a diluent solvent were blended to obtain a paint curable composition having an active ingredient content of 30% by mass.

The obtained curable composition was coated on an easy-adhesion treated surface of an easy-adhesion-treated polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: Soft Shine A4100, thickness 0.188 mm) using a bar coater # 10. Subsequently, after drying for 1 minute with a 100 ° C. hot air dryer, using a high-pressure mercury lamp, the composition is irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm ² (wavelength integrated energy amount of 320 to 380 nm). The film A having a cured film of a smooth curable composition having a thickness of 3 μm (0.003 mm) was obtained.

  A thickness of 3 μm (0.003 mm) was used in the same manner as film A, except that an acrylic film (Mitsubishi Rayon, trade name: Acryprene HBX-N47, thickness 0.125 mm) was used as the support, and the drying conditions were 80 ° C. A film B having a cured film of the smooth curable composition was obtained.

  Appearance, adhesion, pencil hardness, scratch resistance and stretchability were evaluated using the obtained film A having a cured film, and moldability was evaluated using film B having a cured film. The results are shown in Table 2.

[appearance]
About the obtained film A, the haze value was measured using the haze meter corresponding to JISK7136. Based on the measurement results, transparency was evaluated according to the following criteria.
○: Haze is 1% or less. It is transparent.
X: Haze exceeds 1%. Not transparent.

[Adhesion]: In accordance with JIS K 5600, the cured film of the obtained film A is made into 4 × 25 = 100 grids by making 6 vertical and horizontal cuts at 1 mm intervals in 4 locations. It was. The cellophane tape (manufactured by Nichiban Co., Ltd., trade name: cellotape (registered trademark)) was adhered to the surface and then evaluated by the number of cells remaining without being peeled off at once.
○: Number of remaining cells = 100
X: Number of remaining cells <100

  [Pencil hardness]: The cured film of the obtained film A was scratched at an angle of 45 degrees using a Mitsubishi Pencil Uni in accordance with JIS K 5600, and the maximum hardness without damage was determined by pencil hardness.

[Abrasion resistance]: The cured film of the obtained film A was subjected to 20 reciprocations by applying a load of 500 g / cm ² on steel wool # 0000, and the abrasion resistance was evaluated according to the condition of the scratch observed visually. .
○: No scratch. Good scratch resistance x: Scratches occurred. Poor scratch resistance

  [Stretchability]: The obtained film A was subjected to a tensile test (sample size: 80 mm × 15 mm, distance between chucks: 50 mm, pulling speed: 20 mm / min) using a Tensilon universal testing machine RTC-1250A manufactured by Orientec. The film was cracked and the elongation at break (visual judgment) was defined as the elongation at break, and the extensibility was evaluated from the results. An elongation at break of 10% or more was accepted.

  [Moldability]: About the obtained film B, the cured product layer is placed in the mold so as to face the inner wall surface of the mold, then the infrared heater is set to 120 ° C., and the distance between the heater and the film is set to 30 mm. After preheating the film for about 20 seconds, the film was made to follow the mold shape by vacuum suction while further heating. The shape of this mold is a truncated pyramid, the size of the truncated surface is 100 mm × 100 mm, the size of the bottom surface is 108 mm × 117 mm, the depth is 10 mm, and the radius of curvature of the edge of the truncated surface is Was 3 mm.

Next, under conditions of a molding temperature of 220 to 240 ° C. and a mold temperature of 70 ° C., an acrylic resin (manufactured by Mitsubishi Rayon, trade name: Acrypet VH) is injected to perform insert molding, and a cured film of the curable composition is formed. A laminated molded product having was obtained. The mold following property at that time was visually evaluated.
○: There is no crack or the like on the edge of the truncated surface or the truncated surface. Δ: A crack or the like occurs only on the edge of the truncated surface. ×: A crack or the like occurs on the truncated surface.

[Examples 2 to 15, Comparative Examples 1 to 4]
A coating composition was prepared in the same manner as in Example 1 except that the composition and composition shown in Tables 2 and 3 were used, and a film having a cured film was obtained and evaluated.

  In Tables 2 and 3, the numbers in parentheses in the column of component A indicate the solid content.

The symbols and abbreviations in Tables 1, 2, and 3 are as follows.
PU-1: Polyurethane compound of Synthesis Example 3 PU-2: Polyurethane compound of Synthesis Example 4 PU-3: Polyurethane compound of Synthesis Example 5 PU-4: Polyurethane compound of Synthesis Example 6 PU-5: Polyurethane compound of Synthesis Example 7 PU-6: Polyurethane compound of Synthesis Example 8 PU-7: Polyurethane compound of Synthesis Example 9 PU-8: Polyurethane compound of Synthesis Example 10 PU-9: Polyurethane compound of Synthesis Example 11 PU-10: Polyurethane compound of Synthesis Example 12 PU-11: Polyurethane compound of Synthesis Example 13 PU-12: Polyurethane compound of Synthesis Example 14 DEG: Diethylene glycol (reagent manufactured by Wako Pure Chemical Industries, Ltd., trade name: diethylene glycol, molecular weight 106)
CHDM: 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Rika Co., Ltd., trade name: SKY CHDM, molecular weight 144)
PPEA: Acrylic acid adduct of propylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name: epoxy ester 70PA, molecular weight 332)
GLM: glycerin monomethacrylate (manufactured by NOF Corporation, trade name: Blemmer GLM, molecular weight 160)
HXDI: Methylcyclohexylene diisocyanate (Mitsui Chemical Polyurethane Co., Ltd., trade name: Takenate 600)
IPDI: Isophorone diisocyanate (manufactured by Sumitomo Bayer Co., Ltd., trade name: Death Module I)
H-MDI: Dicyclohexylmethane-4,4-diisocyanate (manufactured by Sumitomo Bayer Co., Ltd., trade name: Desmodur W)
CS-1: Organic coated colloidal silica PETA of Synthesis Example 16: Pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-306)
DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayarad DPHA)
TMMT: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-TMMT)
TAIC: Tris (2- (meth) acryloyloxyethyl) isocyanurate (manufactured by Toa Gosei Co., Ltd., trade name: Aronix M-315)
DCPA: tricyclodecane dimethanol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate DCPA)
MU-1: polyfunctional urethane acrylate of Synthesis Example 15 IT-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals) Product name: Irgacure 907)
IT-2: 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Ciba Specialty Chemicals) Product name: Irgacure 127)

  Since the polyurethane compound which does not contain the (a2) component was used for the comparative example 1, it was inferior to a drawability and a moldability. Since Comparative Example 2 did not contain the component A, it was inferior in stretchability and moldability. Since Comparative Example 3 did not contain the B component, it was inferior in pencil hardness and scratch resistance.

Claims (9)

Active energy rays containing a polyurethane compound (A) obtained by reacting the following components (a1) to (a3), an ethylenically unsaturated compound (B) other than the compound (A), and a photopolymerization initiator (C) Curable composition.
(A1) An epoxy (meth) acrylate having two hydroxyl groups in the molecule synthesized from a diepoxy compound having a cyclic skeleton in the molecule and a (meth) acrylic acid derivative (a2) having two hydroxyl groups in the molecule A compound other than the component (a1) having a molecular weight of 50 to 500 (a3) diisocyanate compound   The active energy ray-curable composition according to claim 1 or 2, wherein the component (a2) is an epoxy (meth) acrylate.   The compound (A) is obtained by reacting the components (a1) to (a3) with the component (a4) which is a compound having one hydroxyl group and one or more photofunctional groups in the molecule. The active energy ray-curable composition according to any one of -3.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the compound (A) has a mass average molecular weight of 5,000 to 100,000.   The active energy ray-curable composition according to any one of claims 1 to 4, wherein the compound (B) is a compound having at least three (meth) acryloyl groups in the molecule.   The active energy ray-curable composition according to any one of claims 1 to 5, further comprising inorganic fine particles (D).   The inorganic fine particles (D) undergo a condensation reaction between inorganic fine particles (d1 component) having an average primary particle diameter of 1 to 300 nm and hydrolysis products (d2 component) of polymerizable unsaturated double bond-containing organic silane compounds. The active energy ray-curable composition according to any one of claims 1 to 6, which is an inorganic fine particle containing a polymerizable unsaturated double bond to be obtained.   The film or sheet | seat which has the cured film which hardened the active energy ray curable composition of any one of Claims 1-7.   A laminate comprising the film or sheet according to claim 8.