JP7200657B2 - Methacrylate monomers, polymers, resin compositions, laminates and moldings - Google Patents

Description

The present invention relates to methacrylate monomers, polymers, resin compositions, laminates and molded articles.

BACKGROUND ART In recent years, environmental destruction has become a serious problem worldwide, and efforts to reduce the environmental load toward building a sustainable society have become active. One of them is the active use of natural materials to reduce the burden on the environment. A technique is disclosed to replace the material derived from In addition, instead of simply replacing petrochemical products, efforts are also being made to utilize the unique structure of natural products. An invention is disclosed in which superior mechanical properties and durability can be obtained.

On the other hand, the development of technology in recent years has been remarkable, with the spread of electronic devices such as smartphones, mobile phones, laptop computers, sensor devices, battery devices such as lithium-ion secondary batteries, mobility devices such as automobiles, etc., and the spread of IoT technology. The convenience of life has been greatly improved through collaboration with In general, a large amount of plastic molded products are used for the interior and exterior of these electronic devices that support our lives and mobility. In particular, in the exterior of molded plastic products, the surface is usually decorated by painting, printing, or the like, in order to enhance the design after molding. In addition, a protective coating layer having a hard coating property is further provided for the purpose of protecting the surface of the decorative body.

In such a plastic decoration method, from the viewpoint of reducing environmental impact and improving productivity, plastic films (hereinafter referred to as decorative films) that have undergone decoration processing and protective coating processing in advance are directly pasted and joined. Attempts have been made to actively replace the manufacturing method with Techniques for bonding such decorative films include, for example, vacuum molding, air pressure molding, membrane press molding, in-mold molding, insert molding, and overlay vacuum molding. Generally, it involves a step of stretching and bending the decorative film while applying heat of several tens to several hundred degrees according to the shape of the object to be decorated or the shape of the mold. However, since the protective coating layer with hard coat properties generally has a structure with a high degree of cross-linking, flexibility and extensibility are often insufficient, resulting in molding defects such as whitening, cracking, and peeling during molding. There is a problem that the design property is greatly impaired due to the occurrence of

As a method to solve this problem, Patent Document 3 discloses a decorative film having a hard coat layer in which a thermoplastic resin and a photosensitive resin are combined. I had a problem.
In addition, Patent Document 4 discloses a technique in which a composition capable of thermally cross-linking with a photosensitive composition is used in the hard coat layer, and a heat treatment is performed in a post-molding process. Therefore, it is not desirable from the viewpoint of productivity and reduction of environmental load.
In this way, in decorative films provided with a protective coating layer having hard coat properties, achieving both elongation and hard coat properties at a high level by a process with less environmental impact has become a major issue. In view of the construction of a sustainable society, it would be more preferable from the viewpoint of reducing the environmental burden if natural products could be effectively used for such plastic moldings.

Patent No. 5826814 WO2016/098898 WO2017/183634 Patent No. 5389904

The present invention has been made in view of the above-mentioned current situation, and a protective coating layer that utilizes natural products and has both excellent elongation and hard coat properties in a process with less environmental load for various molding processes. An object of the present invention is to provide a low-environmental load material comprising

The present invention relates to a methacrylate monomer (A) characterized by having a γ-oryzanol structure.

The present invention also relates to the methacrylate monomer (A) characterized by having a urethane bond.

Further, the present invention provides a polymer (P) of a monomer mixture containing 3 to 85% by weight of the methacrylate monomer (A) and 15 to 97% by weight of another copolymerizable monomer (B) with respect to 100% by weight of the monomer mixture. Regarding.

The present invention also relates to the polymer (P) characterized by having a weight average molecular weight of 50,000 to 1,000,000.

The present invention also relates to the polymer (P) characterized by having a glass transition temperature of 0 to 120°C.

The present invention also relates to a resin composition (R) comprising the polymer (P) and an acrylate group- and/or acrylamide group-containing polyfunctional monomer (Q).

The present invention also relates to a laminate (S) characterized by having a cured film made of the resin composition (R) on a substrate.

The present invention also relates to the laminate (S) for decorative molding.

The present invention also relates to a decorative molding formed from the laminate (S).

The polymer containing the methacrylate monomer (A) of the present invention has a structure derived from a natural product having extremely high cohesive strength while being non-crosslinked, and is a resin obtained by copolymerizing the methacrylate monomer (A) of the present invention. By using, it is possible to provide a laminate and a molded article having a protective coating layer that has both excellent elongation and hard coat properties while having a low environmental load.

Embodiments of the present invention will be described in detail below, but the following description is an example (representative example) of the embodiments of the present description, and the present invention is not limited to these contents unless it exceeds the gist.

（Ｒ_１～Ｒ_６は、水素原子、および不飽和結合を有していても良い炭素数１～１０のアルキル基からなる群より選ばれる少なくとも１種の基を示し、ただしＲ_５とＲ_６は互いに結合して環を形成してもよい。） <Methacrylate Monomer (A)>
The methacrylate monomer (A) of the present invention is a methacrylate having a γ-oryzanol-derived structure. γ-oryzanol is a general term for esters in which ferulic acid and sterols such as cycloartenol, 2,4-methylenecycloartanol, cyclopranol, campesterol, and β-sitosterol are linked via an ester bond, and have the general formula ( 1) has a typical structure as shown in γ-Oryzanol is present in naturally occurring raw materials, and is contained in, for example, lipids of rice bran.
General formula (1)

(R ₁ to R ₆ represent at least one group selected from the group consisting of hydrogen atoms and alkyl groups having 1 to 10 carbon atoms which may have an unsaturated bond, provided that R ₅ and R ₆ may combine with each other to form a ring.)

（Ｌは直接結合又はウレタン結合を有する分子量２００以下の２価の連結基を示し、Ｒ_１～Ｒ_６は、水素原子、不飽和結合を有していても良い炭素数１～１０のアルキル基からなる群より選ばれる少なくとも１種の基を示し、ただしＲ_５とＲ_６は互いに結合して環を形成してもよい。） As shown in the following general formula (2), the methacrylate monomer (A) of the present invention has a methacrylate group attached directly or via a divalent linking group to the hydroxyl group of the ferulic acid structure of γ-oryzanol. It is the structure introduced. In the case of an acrylate group instead of a methacrylate group, gelation tends to occur during production of the polymer.
general formula (2)

(L represents _{a divalent} linking group with a molecular weight of 200 or less having a direct bond or a urethane bond; represents at _least one group selected from the group consisting of, provided that R5 and _R6 may combine with each other to form a ring.)

Since the methacrylate monomer (A) of the present invention has a γ-oryzanol structure, it exhibits a high cohesive force even in a non-crosslinked state when it takes the form of a polymer (P) described later, and as a result, It can provide excellent hard coat properties as a protective coating agent. In addition, since it is in a non-crosslinked state, it is possible to exhibit excellent extensibility when heat is applied during molding. In addition, there are advantages in that gelation is less likely to occur when the methacrylate monomer (A) is polymerized, and in that a stronger cohesive force can be obtained after polymerization.

The methacrylate monomer (A) of the present invention preferably has a urethane bond, which can be introduced into the divalent linking group portion represented by the general formula (2), in order to obtain a stronger cohesive force. The method for introducing the urethane bond is not limited to the following, but it can be obtained by reacting the isocyanate group of a compound having an isocyanate group and a methacrylate group with the hydroxyl group of the ferulic acid structure of γ-oryzanol. can. In addition, when reacting a hydroxyl group and an isocyanate group, you may use a well-known solvent and reaction catalyst.

Compounds having an isocyanate group and a methacrylate group include, for example, 2-isocyanatoethyl methacrylate, and commercially available products include Karenz MOI manufactured by Showa Denko KK.

<Polymer (P)>
The polymer (P) of the present invention is a polymer of a monomer mixture containing a methacrylate monomer (A) having a γ-oryzanol structure and another copolymerizable monomer (B). By containing the methacrylate monomer (A) having a γ-oryzanol structure, the polymer (P) can exhibit high cohesive strength, and when the polymer (P) is used as a protective coating agent, it is excellent. It is possible to achieve both hard coat properties and stretchability.

The polymer (P) of the present invention contains 3 to 85% by weight of the methacrylate monomer (A) having a γ-oryzanol structure and 15 to 97% by weight of the copolymer monomer (B) based on 100% by weight of the monomer mixture. It is preferably contained in the range, more preferably 10 to 65% by weight of the methacrylate monomer (A) and 35 to 90% by weight of the copolymerizable monomer (B).

Examples of copolymerizable monomers (B) include, but are not limited to, aromatics such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, and indene. group vinyl monomer;
methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) Alkyl (meth)acrylates such as acrylates, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate monomer;
(meth)acrylate monomers having an alicyclic structure such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate;
(meth)acrylate monomers having an aromatic ring such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate;
Carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and cinnamic acid;
Acid anhydride group-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride;
Styrenesulfonic acid, sodium styrenesulfonate, ammonium styrenesulfonate, lithium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, sodium 2-acrylamido-2-methylpropanesulfonate, methallylsulfonic acid, sodium methallylsulfonate , allylsulfonic acid, sodium allylsulfonate, ammonium allylsulfonate, vinylsulfonic acid, allyloxybenzenesulfonic acid, sodium allyloxybenzenesulfonate, ammonium allyloxybenzenesulfonate and other sulfonic acid group-containing monomers;
Phosphate group-containing monomers such as 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and dibutyl-2-acryloyloxyethyl phosphate ;
hydroxyl group-containing (meth)acrylate monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate;
Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate, dimethylaminostyrene, diethylaminostyrene, etc. Pentamethylpiperidinyl (meth)acrylate , amino group-containing monomers such as tetramethylpiperidinyl (meth)acrylate;
fluorinated alkyl group-containing monomers such as trifluoroethyl (meth)acrylate and heptadecafluorodecyl (meth)acrylate;
Keto group-containing monomers such as 2-acetoacetoxyethyl (meth)acrylate;
epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate;
γ-Methacryloxypropyltrimethoxysilane, γ-Methacryloxypropyltriethoxysilane, γ-Methacryloxypropyltributoxysilane, γ-Methacryloxypropylmethyldimethoxysilane, γ-Methacryloxypropylmethyldiethoxysilane, γ-Acryloxy Propyltrimethoxysilane, γ-Acryloxypropyltriethoxysilane, γ-Acryloxypropylmethyldimethoxysilane, γ-Methacryloxymethyltrimethoxysilane, γ-Acryloxymethyltrimethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane , alkoxysilyl group-containing monomers such as vinyltributoxysilane, vinylmethyldimethoxysilane;
Polyethylene glycol mono (meth) acrylate (manufactured by NOF Corporation, BLEMMER PE-90, 200, 350, 350G, AE-90, 200, 400, etc.) Polyethylene glycol/polypropylene glycol mono (meth) acrylate (manufactured by NOF Corporation, BLEMMER 50PEP-300, 70PEP-350, etc.), polyethylene oxide group-containing monomers such as methoxypolyethylene glycol mono (meth) acrylate (manufactured by NOF Corporation, Blenmer PME-400, 550, 1000, 4000, etc.);
(Meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-propyl (meth)acrylamide ) acrylamide, N-tert-butyl (meth)acrylamide, N-hexyl (meth)acrylamide, N-octyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N-hydroxy (meth)acrylamide-based monomers such as butyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-methoxypropyl (meth)acrylamide;
Allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 1,4-butanediol diol (meth)acrylates, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Glycerin dimethacrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, divinylbenzene, divinyl adipate, isophthalic acid Monomers having two or more ethylenically unsaturated groups such as diallyl, diallyl phthalate, and diallyl maleate are included. These may be used alone, or two or more of them may be used in any combination.

In the copolymer (B) used in the present invention, 80% by weight or more of 100% by weight of the copolymerized monomer (B) is a methacrylate monomer because gelation is unlikely to occur during the polymerization reaction of the polymer (P). Preferably.

The polymer (P) of the present invention can be obtained by polymerizing the above monomer mixture by a known polymerization method. Examples of known polymerization techniques include (living) radical polymerization, (living) anionic polymerization, (living) cationic polymerization, coordination polymerization, and the like.

When carrying out the above polymerization, the monomer mixture may be diluted with a solvent before carrying out the polymerization reaction. As the solvent, known solvents can be used, for example, ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as dioxane and tetrahydrofuran; - Aliphatic hydrocarbon solvents such as hexane, cyclohexane and methylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol and isopropanol; amide solvents such as dimethylformamide; mentioned. These may be used alone, or two or more of them may be used in any combination. Considering heat generation during the reaction, it is preferable to use a solvent during the polymerization.

For the polymer (P) of the present invention, a known polymerization initiator can be used in the above polymerization reaction. Examples of polymerization initiators include azo initiators and peroxides. Examples of the azo initiator include 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, and the like. Peroxides include t-butyl per Oxy-2-ethylhexanoate, benzoyl peroxide, di-t-butyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, sodium persulfate, ammonium persulfate, etc. mentions. These may be used alone, or two or more of them may be used in any combination.

The amount of the polymerization initiator used in the present invention is preferably 0.02 to 10% by weight, more preferably 0.05 to 5% by weight, based on 100% by weight of the monomer mixture. The reaction temperature during polymerization can be adjusted as appropriate, but is generally about 50 to 150°C.

A known chain transfer agent can be used for the polymer (P) of the present invention in order to adjust the weight average molecular weight. Examples of chain transfer agents include mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid, butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, and octadecane. Thiol, cyclohexylmercaptan, thiophenol, octyl thioglycolate, octyl 3-mercaptopropionate and the like. These may be used alone, or two or more of them may be used in any combination.

The weight-average molecular weight of the polymer (P) of the present invention is preferably in the range of 50,000 to 1,000,000, more preferably in the range of 100,000 to 800,000, from the viewpoint that excellent hard coat properties and elongation can be expressed. be. When the sample is soluble in tetrahydrofuran, the weight average molecular weight of the polymer (P) used in the present invention is determined by gel permeation chromatography (GPC) using polystyrene as a molecular weight standard and tetrahydrofuran as a developing solvent. It is a value measured by

The glass transition temperature of the polymer (P) of the present invention is preferably in the range of 0 to 120°C, more preferably in the range of 30 to 100°C, from the viewpoint of exhibiting excellent hard coat properties. In this specification, the glass transition temperature of the polymer (P) can be determined by DSC measurement according to JIS K7121.

<Resin composition (R)>
In the present invention, in the form of a resin composition (R) containing a polyfunctional monomer (Q) having an acrylate group and/or an acrylamide group in addition to the polymer (P), hard coating properties as a resin film can increase

<Acrylate group- and/or acrylamide group-containing polyfunctional monomer (Q)>
Examples of the polyfunctional monomer (Q) used in the present invention include, but are not limited to, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, Neopentyl glycol PO-modified diacrylate, neopentyl glycol hydroxypivalate diacrylate, caprolactone adduct diacrylate of neopentyl glycol hydroxypivalate, 1,6-hexanediol bis(2-hydroxy-3-acryloyloxypropyl) Ether, bis(4-acryloxypolyethoxyphenyl)propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO modified Bisphenol A diacrylate, PO-modified bisphenol A diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromobisphenol A diacrylate, tricyclodecanedimethylol diacrylate, isocyanuric acid Bifunctional acrylate monomers such as EO-modified diacrylates and 2-hydroxy-1,3-diacryloxypropane;
glycerin PO-modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, isocyanurate EO-modified triacrylate, isocyanate EO-modified ε-caprolactone-modified triacrylate, 1,3, trifunctional acrylate monomers such as 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate;
Tetrafunctional or higher such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris(acryloyloxy)phosphate, etc. an acrylate monomer of;
Bifunctional acrylamide monomers such as N,N'-diacryloyl-4,7,10-trioxa-1,13-tridecanediamine;
Trifunctional acrylamide monomers such as N,N',N''-triacryloyl-diethylenetriamine;
N,N',N'',N'''-tetraacryloyltriethylenetetramine, N,N'-{[(2-acrylamidopropoxy)methyl]propane-1,3-diyl ) tetrafunctional or higher acrylamide monomers such as bis(oxy)]bis(propane-1,3-diyl)}diacrylamide. These may be used alone, or two or more of them may be used in any combination.

The blending amount of the polyfunctional monomer (Q) in the present invention is preferably in the range of 20 to 80% by weight with respect to 100% by weight as the sum of the polymer (P) and the polyfunctional monomer (Q).

In the present invention, it is preferable to use active energy rays such as ultraviolet rays and electron beams to cure the resin composition (R).

When the active energy ray is ultraviolet rays, it is preferable to use a photopolymerization initiator that generates radical active species upon irradiation with ultraviolet rays in order to further enhance curability.

As the photopolymerization initiator used in the present invention, known photopolymerization initiators can be used. (2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, 2-hydroxy-1 Acetophenones such as -{4-(2-hydroxy-2-methylpropionyl)benzyl}phenyl}-2-methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, and benzoin ethyl ether;
phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide;
Other examples include phenylglyoxylic methyl ester and the like. These may be used alone, or two or more of them may be used in any combination.

Commercially available photopolymerization initiators used in the present invention include, but are not limited to, BASF Irgacure 651, Irgacure 184, Darocure 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01, ADEKA's Adeka Optomer N1414, Adeka Optomer N1717, La and Esacure 1001M manufactured by Co., Ltd., and the like.

The amount of the photopolymerization initiator used in the present invention is in the range of 0.1 to 15% by weight with respect to the sum of 100% by weight of the polymer (P) and the polyfunctional monomer (Q). preferable.

In the present invention, a photosensitizer can be used together with a photopolymerization initiator for the purpose of further enhancing curability. As the photosensitizer, known photosensitizers can be used, for example, unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketones such as benzyl and camphorquinone, and benzoin derivatives. , fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives , oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives , pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler ketone derivatives, biimidazole derivatives and the like. These may be used alone, or two or more of them may be used in any combination.

The amount of the photosensitizer used in the present invention is preferably in the range of 0.1 to 30% by weight with respect to 100% by weight of the sum of the polymer (P) and the polyfunctional monomer (Q). .

The resin composition (R) of the present invention can be used as a coating agent by adding a solvent to control the film thickness and smoothness.

As the solvent used in the present invention, known organic solvents can be used, for example, alcoholic solvents such as methanol, ethanol, isopropanol;
Glycol solvents such as ethylene glycol and propylene glycol;
Amide solvents such as diethylformamide such as dimethylformamide;
Ester-based solvents such as ethyl acetate, propyl acetate, and butyl acetate;
Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
Ether solvents such as dioxane and tetrahydrofuran;
Aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane;
aromatic hydrocarbon solvents such as toluene and xylene;
Water etc. are mentioned. These may be used alone, or two or more of them may be used in any combination.

The non-volatile content ratio of the resin composition (R) of the present invention can be adjusted using an organic solvent so as to have an optimum coating viscosity from the viewpoint of coating properties, film thickness, drying properties, leveling properties, etc., and is preferable. The range is 15-50% by weight.

Inorganic particles can be used in the resin composition (R) of the present invention in order to enhance the hard coat properties of the resin film. Examples of inorganic particles include silica particles such as colloidal silica, fumed silica, and precipitated silica, alumina particles, zirconia particles, titania particles, and metal oxides such as zinc oxide. These may be used alone, or two or more of them may be used in any combination.

The inorganic particles used in the present invention preferably have a radically polymerizable functional group on the particle surface from the viewpoint that the hard coat properties of the resin film can be further enhanced. Examples of radically polymerizable functional groups include vinyl groups, (meth)acrylate groups, and allyl groups. Methods for introducing radically polymerizable functional groups onto the particle surface include, for example, surface treatment with a silane coupling agent having these functional groups.

The resin composition (R) of the present invention may further contain known additives depending on the intended purpose as long as they do not impair the effects of the present invention. Known additives include, for example, dyes, pigments, dispersants, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, surface modifiers, viscosity modifiers, antiblocking agents and the like. These may be used alone, or two or more of them may be used in any combination.

<Laminate (S)>
A laminate can be obtained by forming a cured film comprising the resin composition (R) of the present invention on a substrate such as plastic or metal. Since the resin composition (R) of the present invention has excellent hard coat properties, the laminate (S) has excellent hard coat properties.

The base material used in the laminate (S) of the present invention includes known base materials, for example, polyester base material, nylon base material, polyethylene base material, polypropylene base material, polyvinyl acetal base material, polycarbonate base material, Plastic substrates such as polyacetate substrates, polyvinyl chloride substrates, and cellulose substrates, deposition plastic substrates obtained by subjecting these plastic substrates to metal deposition processing such as aluminum, aluminum foil, copper foil, SUS substrates, and glass , inorganic substrates such as ITO, and natural substrates such as paper, cotton, linen, silk, and wool. The thickness of the substrate is usually about 25-10000 μm.

The laminate (S) of the present invention can be produced by applying the resin composition (R) by a known printing method. Known printing methods include, but are not limited to, dip coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, and die coating. , a gravure coating method, an offset coating method, an inkjet printing method, and the like. If necessary, the substrate may be pre-dried or dried after printing using a known device such as a hot air oven, an electric oven, or an infrared heater.

The laminate (S) of the present invention can be cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam after forming a film of the resin composition (R) on a substrate, and a known active energy A line irradiation device can be used.

When ultraviolet rays are used as the active energy ray, the light source for generating ultraviolet rays is preferably a light source having a main emission wavelength in the wavelength range of 250 to 450 nm. lamp, mercury xenon lamp, metal halide lamp, high power metal halide lamp, xenon lamp, pulse emission xenon lamp, deuterium lamp, ND-YAG triple wave laser, HE-CD laser, nitrogen laser, XE-CI excimer laser, XE-F Excimer lasers, semiconductor-excited solid-state lasers, LED lamp light sources, and the like are included.

When an electron beam is used as the active energy beam, an electron beam irradiation apparatus that applies a high voltage to accelerate electrons and uses them as a beam is preferably used. Examples of electron beam sources include electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type accelerators. The acceleration voltage is preferably in the range of 10-150 kV, more preferably in the range of 60-100 kV.

In the laminate (S) of the present invention, layers such as an anchor layer, a pattern layer, an adhesive layer, a release layer, and an antistatic layer may be provided on the base material, if necessary. These layers are preferably positioned between the resin coating and the substrate, but are not particularly limited.

<Laminate for decorative molding>
As described above, the resin composition (R) of the present invention has excellent hard coat properties and excellent elongation when heat is applied. Suitable for use as a decorative sheet.

Examples of the types of the decorative sheet of the present invention include laminating decorative sheets and transfer decorative sheets. The decorative sheet for lamination has a laminate structure in which a layer comprising a cured film of the resin composition (R) of the present invention is provided on one side of a base material, and a pattern layer and an adhesive layer are laminated on the other side. . In addition, the decorative sheet for transfer forms a release layer on one side of the substrate, and on the release layer, a layer made of a cured film of the resin composition (R) of the present invention, a pattern layer, an adhesive It has a laminated structure in which a transfer layer is laminated in order of layers.

<Decorative molding>
Using the decorative sheet of the present invention, a decorative molded article can be produced by covering the surface of the molded article so that the layer of the cured film of the resin composition (R) in the decorative sheet faces outside. Examples of materials for the molded body include, but are not limited to, wood, paper, metal, plastic, fiber-reinforced plastic, rubber, glass, minerals, and clay.

Methods for molding a decorative molded body using the decorative sheet of the present invention are not limited to the following, but examples include insert molding, in-mold molding, vacuum molding, air pressure molding, TOM molding, and press molding. and other methods.

It is preferable that the molding of the decorative molded body using the decorative sheet of the present invention is accompanied by a heating step. The heating temperature is preferably in the range of 80 to 200° C., depending on the type of substrate used in the decorative sheet.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples. In the examples, "parts" means "parts by weight" and "%" means "% by weight".

<Measurement of weight average molecular weight>
The weight average molecular weight was measured by gel permeation chromatography (GPC) using the polymer (P) as a sample. Tetrahydrofuran was used as the eluent, and the HLC-8220 GPC system manufactured by Tosoh Co., Ltd., in which two columns of TSKgel superHZM-N were connected, was used as the measuring instrument. bottom. Samples were prepared by dissolving 2 mg of material in 5 ml of the above eluent. Also, the weight average molecular weight was calculated in terms of standard polystyrene.

<Measurement of glass transition temperature>
The glass transition temperature was determined by measurement with a differential scanning calorimeter (DSC) using the polymer (P) as a sample. A robot DSC (differential scanning calorimeter, "RDC220" manufactured by Seiko Instruments Inc.) was connected to "SSC5200 Disk Station" (manufactured by Seiko Instruments Inc.) and used for measurement. A sufficiently dried polymer (P) was used as a measurement sample. 10 mg of the measurement sample was placed in the differential scanning calorimeter, held at 100°C for 5 minutes, and then rapidly cooled to -140°C using liquid nitrogen. After that, the temperature was raised at a rate of temperature rise of 10° C./min until the temperature was raised to 250° C., and DSC measurement was performed. The glass transition temperature was determined from the obtained DSC chart.

<Non-volatile content ratio>
About 1 g of a sample was placed in a mentum can, and the non-volatile content ratio was obtained from the change in weight before and after drying in an electric oven at 200° C. for 10 minutes.
<Conversion rate>
The conversion rate was obtained from the following formula.
Conversion rate (%) = Measured non-volatile content ratio of reaction solution/Theoretical non-volatile content ratio of reaction solution x 100
Theoretical non-volatile content ratio (%) of the reaction solution = {mixed amount (g) of monomer (A) + mixed amount (g) of copolymerized monomer (B))/mixed amount of all raw materials (g) × 100

<Production of Monomer (A)>
A methacrylate monomer (A) having a γ-oryzanol structure was produced according to the method shown below.

<Example 1> Production of Monomer (A-1) While blowing air into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube, γ-oryzanol (manufactured by Tokyo Kasei Co., Ltd.) 329. 0 part, 2.5 parts of sodium acetate (manufactured by Tokyo Kasei Co., Ltd.), 0.3 parts of 4-methoxyphenol (manufactured by Tokyo Kasei Co., Ltd.), and 500 parts of n-propyl acetate were charged, and the temperature was raised to 90° C. while stirring. . Then, 168.3 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the reaction vessel from the dropping tube over 2 hours, and the reaction was performed at 90 ° C. for 24 hours. Thin layer chromatography (developing solvent: toluene / methanol = 100/2), the disappearance of the γ-oryzanol-derived spots was confirmed, and the reaction was terminated. After cooling the reaction vessel to 40° C., the solvent was distilled off under reduced pressure under the conditions of 40° C. and 5.2 kPa. After that, 800 parts of methanol was added to the reaction vessel, and the mixture was stirred at 40° C. for 1 hour, followed by filtration. Solids remaining on the filter paper were thoroughly washed with 200 parts of methanol, and the solids were recovered. The resulting solid was dried under reduced pressure to obtain the target methacrylate monomer (A-1). The resulting solid was subjected to ¹ H-NMR (solvent: heavy chloroform, standard: tetramethylsilane) measurement, and in addition to the signal derived from γ-oryzanol, the following spectrum derived from the methacrylic acid skeleton was obtained. Therefore, the obtained solid was identified as a methacrylic acid ester of γ-oryzanol.

[ ¹ H-NMR spectrum]
(σ value) 6.42 (1H), 6.18 (1H), 2.01 (3H)

<Example 2> Production of Monomer (A-2) γ-oryzanol (manufactured by Tokyo Kasei Co., Ltd.) 288.8. 1 part, 0.2 parts of Neostan U-810 (manufactured by Nitto Kasei Co., Ltd., dioctyltin catalyst), 0.4 parts of 4-methoxyphenol (manufactured by Tokyo Kasei Co., Ltd.), and 600 parts of toluene are charged and heated to 70° C. while stirring. The temperature was raised to After that, 111.3 parts of 2-isocyanatoethyl methacrylate (Kalenz MOI manufactured by Showa Denko) was added dropwise to the reaction vessel from the dropping tube over 2 hours, and the reaction was performed as it was at 70 ° C. for 18 hours. Solvent: toluene/methanol = 100/2) was used to confirm that the γ-oryzanol-derived spots had disappeared, and the reaction was terminated. After cooling the reaction vessel to 50° C., 50 parts of methanol was added and stirred at 50° C. for 3 hours. Thereafter, the solvent was distilled off under reduced pressure under the conditions of 40°C and 5.2 kPa, 800 parts of methanol was added to the reaction vessel, and after stirring at 40°C for 1 hour, filtration was performed, and 200 parts of methanol was removed from the solid matter remaining on the filter paper. The solid was recovered after washing thoroughly with . The resulting solid was dried under reduced pressure to obtain the target methacrylate monomer (A-2). The resulting solid was subjected to ¹ H-NMR (solvent: heavy chloroform, standard: tetramethylsilane) measurement, and in addition to the signal derived from γ-oryzanol, the spectrum derived from the reaction product with the Karenz MOI shown below was obtained. The obtained solid was identified as a reaction product of γ-oryzanol and Karenz MOI.

[ ¹ H-NMR spectrum]
(σ value) 8.03 (1H), 6.41 (1H), 6.16 (1H), 2.01 (3H), 4.32 (2H), 3.21 (2H)

<Comparative Example 1> Production of Monomer (A-3) γ-oryzanol (manufactured by Tokyo Kasei Co., Ltd.) 295.5. 6 parts, 0.2 parts of Neostan U-810 (manufactured by Nitto Kasei Co., Ltd.), 0.4 parts of 4-methoxyphenol (manufactured by Tokyo Kasei Co., Ltd.) and 600 parts of toluene were charged, and the temperature was raised to 70° C. while stirring. After that, 103.8 parts of 2-isocyanatoethyl acrylate (Karenzu AOI manufactured by Showa Denko) was added dropwise to the reaction vessel from the dropping tube over 2 hours, and the reaction was performed at 70 ° C. for 18 hours. Solvent: toluene/methanol = 100/2) was used to confirm that the γ-oryzanol-derived spots had disappeared, and the reaction was terminated. After cooling the reaction vessel to 50° C., 50 parts of methanol was added and stirred at 50° C. for 3 hours. Thereafter, the solvent was distilled off under reduced pressure under the conditions of 40°C and 5.2 kPa, 800 parts of methanol was added to the reaction vessel, and after stirring at 40°C for 1 hour, filtration was performed, and 200 parts of methanol was removed from the solid matter remaining on the filter paper. The solid was recovered after washing thoroughly with . The obtained solid was dried under reduced pressure to obtain the target acrylate monomer (A-3). The resulting solid was subjected to ¹ H-NMR (solvent: heavy chloroform, standard: tetramethylsilane) measurement, and in addition to the signal derived from γ-oryzanol, the spectrum derived from the Karenz AOI reaction product shown below was obtained. The obtained solid was identified as a reaction product of γ-oryzanol and Karenz AOI.

[ ¹ H-NMR spectrum]
(σ value) 8.03 (1H), 6.38 (1H), 6.05 (1H), 5.59 (1H), 2.01 (3H), 4.34 (2H), 3.19 ( 2H)

<Production of polymer (P)>
Polymers (P-1) to (P-10) were produced according to the method shown below. Table 1 shows the raw materials and compounding amounts produced and the properties of the obtained compounds.

<Example 3> Production of polymer (P-1) 80 parts of n-butyl acetate was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube while blowing nitrogen gas. °C. Then, monomer (A-1) 6 parts, n-butyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 49 parts, benzyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 45 parts, V-65 as a polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ) and 20 parts of n-butyl acetate was added dropwise from the dropping tube over 2 hours. 0.02 parts of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour for 5 hours after the completion of the dropwise addition, and the reaction was further carried out at 70 ° C. The conversion rate of the reaction solution was 98. % or more, the reaction was terminated.
The polymer (P-1) thus obtained has a weight average molecular weight of 65,000, a glass transition temperature of 39° C., a content of the monomer (A) of 6% by weight with respect to 100% by weight of the monomer mixture, and a copolymer monomer The content of (B) was 94% by weight.

<Example 4> Production of polymer (P-2) 80 parts of n-butyl acetate was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube while blowing nitrogen gas. °C. Then, 6 parts of monomer (A-1), 54 parts of methyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), 40 parts of n-butyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), V-601 as a polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ) and 20 parts of n-butyl acetate was added dropwise from the dropping tube over 2 hours. After the completion of dropping, 0.02 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour, and the reaction was further carried out at 70°C until the conversion of the reaction solution reached 98% or more. The reaction was terminated immediately.
The polymer (P-2) thus obtained has a weight average molecular weight of 923,000, a glass transition temperature of 66° C., a content of the monomer (A) of 6% by weight with respect to 100% by weight of the monomer mixture, and a copolymerized monomer. The content of (B) was 94% by weight.

<Example 5> Production of polymer (P-3) 80 parts of n-butyl acetate was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube while blowing nitrogen gas. °C. Then, 75 parts of the monomer (A-1), 25 parts of n-butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.1 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 20 parts of methylcyclohexane. The mixed monomer solution was dropped from the dropping tube over 2 hours. After the completion of dropping, 0.02 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour, and the reaction was further carried out at 70°C until the conversion of the reaction solution reached 98% or more. The reaction was terminated immediately.
The polymer (P-3) thus obtained has a weight average molecular weight of 584,000, a glass transition temperature of 78° C., a monomer (A) content of 75% by weight with respect to 100% by weight of the monomer mixture, and a copolymerized monomer The content of (B) was 25% by weight.

<Example 6> Production of polymer (P-4) 80 parts of n-butyl acetate was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube while blowing nitrogen gas. °C. Then, 25 parts of the monomer (A-1), 25 parts of n-butyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), 50 parts of 2-ethylhexyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), V-601 as a polymerization initiator (Fujifilm Wako Pure Chemical A monomer solution prepared by mixing 0.1 part of n-butyl acetate (manufactured by Tokyo Kasei Co., Ltd.) and 20 parts of n-butyl acetate (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 2 hours. After the completion of dropping, 0.02 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour, and the reaction was further carried out at 70°C until the conversion of the reaction solution reached 98% or more. The reaction was terminated immediately.
The polymer (P-4) thus obtained has a weight average molecular weight of 566,000, a glass transition temperature of 7° C., a monomer (A) content of 25% by weight with respect to 100% by weight of the monomer mixture, and a copolymer monomer The content of (B) was 75% by weight.

<Example 7> Production of polymer (P-5) While blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube, 60 parts of n-butyl acetate and methyl isobutyl ketone were added. 20 parts were charged and the temperature was raised to 70°C. Then, 60 parts of monomer (A-1), 20 parts of methyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), 10 parts of benzyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), 10 parts of methacrylic acid, V-601 as a polymerization initiator (Fuji Film Wako Pure Yakusha Co., Ltd.) and 20 parts of methylcyclohexane (manufactured by Tokyo Kasei Co., Ltd.) were added dropwise over 2 hours. After the completion of dropping, 0.02 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour, and the reaction was further carried out at 70°C until the conversion of the reaction solution reached 98% or more. The reaction was terminated immediately.
The polymer (P-5) thus obtained has a weight average molecular weight of 712,000, a glass transition temperature of 107° C., a monomer (A) content of 60% by weight with respect to 100% by weight of the monomer mixture, and a copolymer monomer The content of (B) was 40% by weight.

<Example 8> Production of polymer (P-6) While blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube, 50 parts of n-butyl acetate and methyl isobutyl ketone were added. 30 parts were charged and the temperature was raised to 70°C. Then, 40 parts of monomer (A-1), 35 parts of methyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), 25 parts of 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), V-601 as a polymerization initiator (Fujifilm Wako Pure Chemical Industries, Ltd. A monomer solution prepared by mixing 0.1 part of the product (manufacturer) and 20 parts of methylcyclohexane was added dropwise from the dropping tube over 2 hours. After the completion of dropping, 0.02 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour, and the reaction was further carried out at 70°C until the conversion of the reaction solution reached 98% or more. The reaction was terminated immediately.
The polymer (P-6) thus obtained has a weight average molecular weight of 704,000, a glass transition temperature of 90° C., a content of the monomer (A) of 40% by weight with respect to 100% by weight of the monomer mixture, and a copolymerized monomer. The content of (B) was 60% by weight.

<Example 9> Production of polymer (P-7) While blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube, 50 parts of n-butyl acetate and methyl isobutyl ketone were added. 30 parts were charged and the temperature was raised to 70°C. Then, monomer (A-2) 20 parts, methyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 35 parts, benzyl methacrylate 20 parts, 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 25 parts, polymerization initiator V-601 (Fuji Film manufactured by Wako Pure Chemical Industries, Ltd.) and 20 parts of n-butyl acetate were added dropwise over 2 hours. After the completion of dropping, 0.02 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour, and the reaction was further carried out at 70°C until the conversion of the reaction solution reached 98% or more. The reaction was terminated immediately.
The polymer (P-7) thus obtained has a weight average molecular weight of 655,000, a glass transition temperature of 82° C., a monomer (A) content of 20% by weight with respect to 100% by weight of the monomer mixture, and a copolymer monomer The content of (B) was 80% by weight.

<Comparative Example 2> Production of polymer (P-8) 50 parts of n-butyl acetate and methyl isobutyl ketone were added while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube. 30 parts were charged and the temperature was raised to 70°C. Then, 20 parts of the monomer (A-3), 35 parts of methyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), 20 parts of benzyl methacrylate, 25 parts of 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), V-601 (Fuji Film manufactured by Wako Pure Chemical Industries, Ltd.) and 20 parts of n-butyl acetate (manufactured by Tokyo Kasei Co., Ltd.) were added dropwise over a period of 2 hours. Gelation occurred, and the desired polymer (P-8) could not be obtained. Polymer (P-8) was not subjected to the performance test described below.

<Comparative Example 3> Production of polymer (P-9) 50 parts of n-butyl acetate and methyl isobutyl ketone were added while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube. 30 parts were charged and the temperature was raised to 70°C. Next, 55 parts of methyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), 20 parts of benzyl methacrylate, 25 parts of 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), and 0.5 parts of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. A monomer solution containing 1 part of n-butyl acetate and 20 parts of n-butyl acetate was added dropwise from the dropping tube over 2 hours. After the completion of dropping, 0.02 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour, and the reaction was further carried out at 70°C until the conversion of the reaction solution reached 98% or more. The reaction was terminated immediately.
The polymer (P-9) thus obtained has a weight average molecular weight of 613,000, a glass transition temperature of 81° C., a content of the monomer (A) of 0% by weight with respect to 100% by weight of the monomer mixture, and a copolymerized monomer. The content of (B) was 100% by weight.

<Comparative Example 4> Production of polymer (P-10) 50 parts of n-butyl acetate and methyl isobutyl ketone were added while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen inlet tube. 30 parts were charged and the temperature was raised to 70°C. Then, 50.7 parts of methyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), 40 parts of benzyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.), V-601 as a polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) A monomer solution containing 0.1 part of n-butyl acetate and 20 parts of n-butyl acetate was added dropwise from the dropping tube over 2 hours. After completion of dropping, 0.02 part of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel every hour, and the reaction was further carried out at 70°C. When the conversion of the reaction solution reaches 98% or more, the reaction vessel is cooled to 50° C., 0.1 part of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) is added and stirred until uniform, and Karenz AOI (Showa Denko) is added. 4.3 parts of Neostan U-810 (manufactured by Nitto Kasei Co., Ltd.) were added and reacted at 50° C. for 8 hours. It was confirmed from the transmission IR measurement of the reactant that the peak derived from the isocyanate group had disappeared, and the reaction was terminated.
The polymer (P-10) thus obtained has a weight average molecular weight of 547,000, a glass transition temperature of 76° C., a content of the monomer (A) of 0% by weight with respect to 100% by weight of the monomer mixture, and a copolymerized monomer. The content of (B) was 100% by weight.

Abbreviations in Table 1 have the following meanings.
MMA: methyl methacrylate nBMA: n-butyl methacrylate 2EHMA: 2-ethylhexyl methacrylate BzMA: benzyl methacrylate MAA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate AOI: Karenz AOI
MCH: methylcyclohexane MIBK: methyl isobutyl ketone

<Production of resin composition (R)>
Using the polymers (P-1) to (P-10) of Examples 3 to 9 and Comparative Examples 2 to 4, resin compositions (R-1) to (R-10) were produced according to the method shown below. bottom. Table 2 shows the blending amounts of the raw materials produced and the properties of the resulting compound.

<Example 10> Production of resin composition (R-1) While blowing nitrogen gas into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tube, and a nitrogen introduction tube, polymer (P-1) solution 160 Part, KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd., trifunctional acrylate) 120 parts, Irgacure 184 (manufactured by BASF, photopolymerization initiator) 5 parts, n-butyl acetate 300 parts, charged with methyl isobutyl ketone 220 parts, Stirring was carried out for 1 hour. The coating agent thus obtained was designated as a resin composition (R-1).

<Example 11> Production of resin composition (R-2) While blowing nitrogen gas into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tube, and a nitrogen introduction tube, polymer (P-2) solution 160 120 parts of SR399 (Sartomer, pentafunctional acrylate), 5 parts of TPO (manufactured by BASF, photopolymerization initiator), 300 parts of n-butyl acetate, and 220 parts of methyl isobutyl ketone were charged and stirred for 1 hour. The coating agent thus obtained was designated as a resin composition (R-2).

<Example 12> Production of resin composition (R-3) While blowing nitrogen gas into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tube, and a nitrogen introduction tube, polymer (P-3) solution 240 Part, SR399 (Sartomer, pentafunctional acrylate) 80 parts, Irgacure 184 (BASF, photopolymerization initiator) 5 parts, n-butyl acetate 200 parts, methylcyclohexane 180 parts, methyl isobutyl ketone 100 parts charged, 1 Stirring was performed for hours. The coating agent thus obtained was designated as a resin composition (R-3).

<Example 13> Production of resin composition (R-4) Polymer (P-4) solution 200 while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube. Part, A-DPH (Shin-Nakamura Chemical Co., Ltd., hexafunctional acrylate) 100 parts, TPO (manufactured by BASF, photopolymerization initiator) 5 parts, n-butyl acetate 300 parts, methyl isobutyl ketone 200 parts charged, 1 hour Agitation was performed. The coating agent thus obtained was designated as a resin composition (R-4).

<Example 14> Production of resin composition (R-5) Polymer (P-5) solution 200 while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube. Part, A-DPH (Shin Nakamura Chemical Co., Ltd., hexafunctional acrylate) 100 parts, Irgacure 184 (manufactured by BASF, photopolymerization initiator) 5 parts, n-butyl acetate 300 parts, methyl isobutyl ketone 200 parts charged, 1 Stirring was performed for hours. The coating agent thus obtained was used as a resin composition (R-5).

<Example 15> Production of resin composition (R-6) Polymer (P-6) solution 200 while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube. Part, A-DPH (Shin-Nakamura Chemical Co., Ltd., 6-functional acrylate) 80 parts, Shikou UV-7650B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., urethane acrylate oligomer) 20 parts, Irgacure 184 (manufactured by BASF, photoinitiator) 5 200 parts of n-butyl acetate, 50 parts of methylcyclohexane, and 250 parts of methyl isobutyl ketone were charged and stirred for 1 hour. The coating agent thus obtained was designated as a resin composition (R-6).

<Example 16> Production of resin composition (R-7) Polymer (P-7) solution 200 while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube. Part, A-DPH (Shin-Nakamura Chemical Co., Ltd., 6-functional acrylate) 80 parts, Shikou UV-7650B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., urethane acrylate oligomer) 20 parts, Irgacure 184 (manufactured by BASF, photoinitiator) 5 200 parts of n-butyl acetate, 50 parts of methylcyclohexane, and 250 parts of methyl isobutyl ketone were charged and stirred for 1 hour. The coating agent thus obtained was designated as a resin composition (R-7).

<Comparative Example 5> Production of resin composition (R-8) While blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube, A-DPH (Shin Nakamura Chemical , hexafunctional acrylate) 160 parts, Shikou UV-7650B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate oligomer) 40 parts, Irgacure 184 (manufactured by BASF, photopolymerization initiator) 5 parts, n-butyl acetate 200 parts, methylcyclohexane 50 parts of methyl isobutyl ketone and 250 parts of methyl isobutyl ketone were added and stirred for 1 hour. The coating agent thus obtained was used as a resin composition (R-8).

<Comparative Example 6> Production of resin composition (R-9) Stirrer, thermometer, reflux condenser, dropping tube, polymer (P-9) 200 parts while blowing nitrogen gas into a reaction vessel equipped with a nitrogen introduction tube , A-DPH (Shin-Nakamura Chemical Co., Ltd., hexafunctional acrylate) 80 parts, Shikou UV-7650B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., urethane acrylate oligomer) 20 parts, Irgacure 184 (manufactured by BASF, photopolymerization initiator) 5 parts , 200 parts of n-butyl acetate, 50 parts of methylcyclohexane and 250 parts of methyl isobutyl ketone were charged and stirred for 1 hour. The coating agent thus obtained was designated as a resin composition (R-9).

<Comparative Example 7> Production of resin composition (R-10) Stirrer, thermometer, reflux condenser, dropping tube, polymer (P-10) 200 parts while blowing nitrogen gas into a reaction vessel equipped with a nitrogen introduction tube , A-DPH (Shin-Nakamura Chemical Co., Ltd., hexafunctional acrylate) 80 parts, Shikou UV-7650B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., urethane acrylate oligomer) 20 parts, Irgacure 184 (manufactured by BASF, photopolymerization initiator) 5 parts , 200 parts of n-butyl acetate, 50 parts of methylcyclohexane and 250 parts of methyl isobutyl ketone were charged and stirred for 1 hour. The coating agent thus obtained was designated as a resin composition (R-10).

<Production of test piece>
Using the resin compositions (R-1) to (R-10) of Examples 10 to 16 and Comparative Examples 5 to 7, test laminates (S-1) to (S-10) were prepared according to the methods described below. ) and moldings (T-1) to (T-10) were produced.

<Production of laminate (S)>
After drying each of the resin compositions (R-1) to (R-10) of Examples 10 to 16 and Comparative Examples 5 to 7, a 1 mm thick polycarbonate substrate (Mitsubishi "Iupilon Sheet NF-2000" manufactured by Gas Kagaku Co., Ltd.) and dried in a hot air oven at 100° C. for 1 minute. Next, a belt conveyor type ultraviolet irradiation device (120 W/cm ² high-pressure mercury lamp) was applied to the coating film using a resin composition other than Example 10 at a conveyor speed of 10 m/min, and the integrated light amount was 400 mJ/min. A curing treatment was performed by irradiating ultraviolet rays so as to obtain a thickness of cm ² . Further, the coating film using the resin composition of Example 10 was subjected to electron beam irradiation using an electron beam irradiation apparatus under the conditions of an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad), and a curing treatment was performed. went. Thus, a laminate (S) for testing was obtained.

<Production of molded body (T)>
Laminates (S-1) to (S-10) were set in the center of a vacuum forming machine divided into upper and lower chambers so that the cured film side faced upward. In the lower chamber box, a tray-shaped mold for deep drawing molding was set, which had a size of 80 mm square, a rise of 10 mm, and corner portions of 3R. Next, the inside of the chamber box was evacuated with a vacuum pump, and the laminate (S) was heated by the heater at the top of the chamber until the surface temperature of the laminate (S) reached 160°C. When the laminate (S) was sufficiently thermally softened, the mold in the lower chamber box was lifted so that the laminate (S) covered the mold.
Next, the upper chamber box was opened to the atmosphere, and compressed air was supplied to the upper chamber box to sufficiently bring the laminate (S) and the mold into close contact with each other. Then, the lower chamber box was opened to the atmosphere, the upper chamber box was raised, and after cooling in the atmosphere, the molded laminate (S) was removed from the mold. A molding (T) for testing was thus obtained.

<Performance test>
Using the laminates (S-1) to (S-10) and the moldings (T-1) to (T-10), the following performance tests were performed. Table 3 shows the results of various performance tests.

<Evaluation of hard coat property>
The laminates (S-1) to (S-10) were heat-treated at 160° C. for 10 minutes using a hot air oven. After that, the laminate (S) was cooled to room temperature, and then tested according to JIS K7204 and K6264 [abrasion resistance test]. The hard coat property of the laminate (S) was evaluated from the results of abrasion resistance. Evaluation criteria are shown below. The apparatus used for the test was a "Rotary Abrasion Tester" manufactured by Toyo Seiki Co., Ltd. Using "CS-10" as an abrasion wheel, the amount of abrasion was evaluated after 500 rotations under a load of 500 g.
A: Amount of wear is less than 5 mg. excellence.
◯: Abrasion amount is 5 mg or more and less than 20 mg. Good.
Δ: The amount of wear is 20 mg or more and less than 50 mg. lower practical limit.
x: The amount of wear is 50 mg or more. Not practical.

<Evaluation of elongation>
The extensibility of the laminate (S) was evaluated by visually observing the appearance after molding of the moldings (T-1) to (T-10). Evaluation criteria are shown below.
⊚: No change in appearance such as wrinkles or cracks. excellence.
◯: There are no wrinkles or cracks, but some floats are observed. Good.
Δ: Appearance changes such as wrinkles and cracks are observed in a range of less than 10% of the whole. lower practical limit.
x: Appearance changes such as wrinkles and cracks are observed in a range of 10% or more of the whole. Not practical.

<Evaluation of chemical resistance>
The cured coating surface (smooth part) of the laminates (S-1) to (S-10) and the cured coating surface (molding part), 30 mg of sunscreen cream (manufactured by Johnson & Johnson, "Neutrogena Ultra Sheer DRY-TOUCH SUNSCREEN SPF55") is applied, the cream is evenly stretched into a circle with a diameter of 1.8 cm, and aluminum is applied from above. The foils were placed on top of each other and allowed to stand for 12 hours in a constant temperature oven at 80° C. After that, the test piece was taken out and cooled to room temperature in the atmosphere, after which the cream was washed off with deionized water, and the cured film on which the cream had been applied was removed. The chemical resistance was evaluated by visually observing changes in the appearance of the surface portion.The evaluation criteria are shown below.
O: No change in appearance. excellence.
△: Slightly cloudy. lower practical limit.
x: Whitening or floating occurred between the cured film and the substrate. Not practical.

As shown in Table 3, since Comparative Example 8 did not contain the polymer (P), the balance between the hard coat property and the extensibility was poor, and the extensibility and the chemical resistance of the molded portion were significantly deteriorated.

In Comparative Example 9, since the polymer (P) did not contain the methacrylate monomer (A) having a γ-oryzanol structure, the balance between the hard coat property and the elongation property was poor, and the hard coat property and the chemical resistance of the molded part were poor. deteriorated markedly.

In Comparative Example 10, the polymer (P) has a radically polymerizable functional group in the side chain, but as in Comparative Example 9, it does not contain a methacrylate monomer (A) having a γ-oryzanol structure. The balance between coatability and extensibility was poor, and extensibility and chemical resistance of the molded part deteriorated remarkably.

On the other hand, Examples 17 to 23 are resins containing a polymer (P) having a methacrylate monomer (A) having a γ-oryzanol structure or a polymer (P) containing a copolymer monomer (B) within a suitable range. Since it is a cured film of the composition, it satisfies hard coat property, extensibility and chemical resistance in a well-balanced manner.

Among them, Example 23 showed the most excellent performance. In Example 23, the content of the methacrylate monomer (A) having a γ-oryzanol structure in the polymer (P) is within the preferred range of 10 to 65% by weight. In comparison, it had an excellent balance between hard coat property and elongation, and had excellent elongation and chemical resistance of the molded part. In addition, in Example 19, since the weight average molecular weight of the polymer (P) is in the preferred range of 100,000 to 800,000, the balance between hard coat property and elongation is excellent compared to Examples 17 and 18 outside the range. , also showed excellent performance in chemical resistance.
In addition, in Example 23, the glass transition temperature of the polymer (P) is in a suitable range of 30 to 100 ° C., and therefore, compared to Examples 20 and 21, which are outside the range, the balance between hard coat property and elongation is excellent. , showed excellent performance in both hard coat property and elongation.
In addition, in Example 23, the polymer (P) contains a methacrylate monomer (A) having a γ-oryzanol structure with a urethane bond. showed excellent performance.

The polymer and resin composition containing the methacrylate monomer of the present invention is coated on the surface of a substrate made of a material such as glass, metal, resin, etc., and cured by irradiation with active energy rays to give a hard coat property to the surface of the substrate. Since it is possible to form a cured film with excellent elongation, it can be used in injection molded products such as equipment bodies such as daily necessities and daily necessities, food containers, housings such as electronic equipment and office supplies. It is suitably used for applications that require hard coat properties on the surface, and is particularly suitable for applications that require both hard coat properties and elongation properties.

Claims (8)

A methacrylate monomer (A) represented by the following general formula (2).
general formula (2)

(Wherein, L represents a divalent linking group with a molecular weight of 200 or less having a direct bond or a urethane bond, and R ₁ ～R ₆ represents at least one group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms which may have an unsaturated bond, with the proviso that R ₅ and R ₆ may combine with each other to form a ring. ) A polymer (P) of a monomer mixture containing 3 to 85% by weight of the methacrylate monomer (A) according to claim 1 and 15 to 97% by weight of another copolymerizable monomer (B) based on 100% by weight of the monomer mixture. 3. The polymer (P) according to claim 2 , which has a weight average molecular weight of 50,000 to 1,000,000. The polymer (P) according to claim 2 or 3 , which has a glass transition temperature of 0 to 120°C. A resin composition (R) comprising the polymer (P) according to any one of claims 2 to 4 and an acrylate group- and/or acrylamide group-containing polyfunctional monomer (Q). A laminate (S) comprising a cured film comprising the resin composition (R) according to claim 5 on a substrate. The laminate (S) according to claim 6 , which is for decorative molding. A decorative molding formed from the laminate (S) according to claim 7 .