TW201807107A - Composition for decorative sheets, decorative sheet and molded product - Google Patents

Abstract

Provided is a composition for decorative sheets, which contains (A) a furyl group-containing compound, (B) a polymerizable compound and (C) a polymerization initiator. Also provided are: a decorative sheet which has a cured film on a base, said cured film being formed from the composition; a molded product which is formed from the decorative sheet; and a method for producing a molded product, which comprises a first step for applying a composition for decorative sheets containing (A) a furyl group-containing compound, (B) a polymerizable compound and (C) a polymerization initiator to a base, a second step for curing the composition by means of irradiation of an active energy ray, and a third step for molding.

Description

Composition for decorative sheet, decorative sheet, and molded product

The present invention relates to a composition for a decorative sheet, a decorative sheet, and a molded product. This application is based on Japanese Patent Application Japanese Patent Application No. 2016-83470 filed on April 19, 2016, Japanese Patent Application Japanese Patent Application No. 2016-157132, filed on August 10, 2016, and April 3, 2017. The priority of Japanese Patent Application No. 2017-73495 is incorporated by reference into all the disclosures of these.

Previously, the surfaces of plastic casings used in various fields such as mobile phones such as smartphones, electronic devices such as notebook personal computers including mobile personal computers, and automotive interior and exterior parts, and building materials were processed by printing or painting. And give (decoration) high design (design, texture, aesthetics, etc.) and so on. In addition, in order to protect the decorative body or the soft plastic itself, in most cases, a protective layer (hard coating) is further provided.

In recent years, in the manufacture of decorative plastics, in order to cope with reduced environmental load, productivity or cost, and complicated product shapes, the method of directly connecting to the previous frame has been developed and replaced with film or sheet bonding. , Transfer decoration technology. That is, the lamination is used to join a decorative sheet such as a design pattern layer or a hard coat layer for protection to a substrate such as plastic. The conventional decorative sheet may be formed by laminating a single layer or a plurality of layers on a sheet base material, but it is configured such that the outermost layer after the final molding process is a protective layer (hard coat layer).

The decorative sheet provided with a protective layer on the film-like or sheet-like substrate is formed by various methods such as vacuum forming, pressure forming, film pressing forming, in-mold forming, insert mold forming, and cover vacuum forming. The decorative sheets are all extended or bent according to the shape of the object to be decorated (plastic frame) or the shape of the mold.

In the forming step, heat of several tens to hundreds of degrees is usually applied to the sheet. The main reason is to use the heat of the decorative sheet necessary for the step to join the object to be decorated (plastic frame), or to increase the extensibility of the decorative sheet by heating. However, in the case where the hard coat layer does not have sufficient flexibility and stretchability, the formability is deteriorated, whitening, scratches, cracks, peeling, etc. occur, and the designability is greatly lost, which is not preferable. (JP 5704929 B)

As a method generally used in a method for forming a hard coat layer on a film-like or sheet-like substrate, the invention described in JP 5524455 B, for example, forms a photosensitive coating composition on a film by utilizing active energy. The light is hardened (crosslinked) by irradiation of the light to form a hard coat layer. By using a polyfunctional photo-crosslinkable monomer in the composition, the degree of cross-linking after light irradiation is increased, thereby obtaining hard coatability. However, a film having a high degree of crosslinking is hard and brittle, and therefore lacks flexibility or stretchability. Therefore, in the conventional technique for obtaining a hard coat layer, it is extremely difficult to cope with processes such as bending, stretching and the like according to various product shapes in the step of forming the decorative sheet.

For such extremely high technical problems, materials such as urethane acrylate oligomers, which have both hardening and softness, have been previously proposed, but it is difficult to meet the requirements of the recent decorative films. A high level of coexistence of hard coating properties and softness and stretchability.

In addition, the technical problems are also avoided by using the decoration sheet or the entire manufacturing process including a molding step using the decorative sheet. For example, JP 2015-54886 A proposes a method of obtaining a hard coat layer by semi-hardening a photosensitive composition using an active energy ray to ensure stretchability necessary for molding, and then irradiating the active energy ray after molding. It is difficult to control the light irradiation conditions in order to obtain a semi-hardened state. The difference between ultraviolet (UV) irradiation machines or lamps significantly affects, or makes the processing industry bear the active energy ray irradiation equipment necessary for photocrosslinking. The disadvantage is big. In addition, JP 5389904 B proposes that a thermally crosslinkable composition be used in combination with a photosensitive composition to perform thermal crosslinking as a post-mold post-processing to improve the hard coatability. In order to obtain a sufficient hard coat, It requires a long time for thermal cross-linking, and also has disadvantages such as making the processing equipment bear the heating device necessary for thermal cross-linking.

In addition, JP 2007-290392 A proposes a hard coat composition for a decorative sheet in which a thermoplastic resin and an ionizing radiation resin are combined. The thermoplastic resin functions as an inert component to suppress the degree of cross-linking, thereby exhibiting stretchability. As a result, although a certain degree of moldability was shown, the level required in recent years has been insufficient. In addition, due to the adverse effects of non-hardened components, hard coat properties such as hardenability and chemical resistance are insufficient.

The control of the degree of cross-linking of the cross-linked film used in the forming process is critical, but the disadvantages of the technique of cross-linking control are high and the steps are complicated. Therefore, in the prior art, a soft crosslinked film is produced in order to show moldability, and as a result, hard coatability is lost, and self-crosslinked film formation is difficult to obtain a decorative molded article by a simple process such as forming processing. Therefore, the current situation is to deal with complicated methods.

Therefore, there is a need for a crosslinkable composition in which hard coatability and moldability, which are necessary for a decorative sheet, coexist, and a molded product can be obtained by a simple procedure.

The present invention has been made in view of the above-mentioned circumstances, and provides a novel composition for obtaining a high-level protective layer having both hard coatability and moldability necessary for an excellent decorative sheet that can cope with various molding processes. . Further, a composition for obtaining a decorative sheet that does not require a step such as light curing after forming processing is provided.

As a result of earnest research, the present inventors have found that the above-mentioned problems can be solved by including a furan group-containing compound, a polymerizable composition, and an initiator in the crosslinkable composition, thereby completing the present invention.

One embodiment of the present invention provides a composition for a decorative sheet, which includes a furanyl-containing compound (A), a polymerizable compound (B), and a polymerization initiator (C).

In one embodiment of the present invention, the furanyl-containing compound (A) may be a polymer having a weight average molecular weight of 1,000 or more.

In one embodiment of the present invention, the furan group-containing compound (A) may be a furan group-containing (meth) acrylic resin (A1). That is, in one embodiment of the present invention, there is provided a composition for a decorative sheet including a furan group-containing (meth) acrylic resin (A1), a polymerizable compound (B), and a polymerization initiator (C).

In one embodiment of the present invention, the furan group-containing compound (A) may be a polymer containing a furan group-containing monomer (a1-1).

In one embodiment of the present invention, the monomer (a1-1) may be furfuryl methacrylate.

In addition, in one embodiment of the present invention, the furan group-containing compound (A) may be a furan group-containing urethane resin (A2). That is, in one embodiment of the present invention, there is provided a composition for a decorative sheet including a furan group-containing urethane resin (A2), a polymerizable compound (B), and an initiator (C).

In one embodiment of the present invention, the furan group-containing urethane resin (A2) may be a furan group-containing (meth) acrylic copolymer (a2) having at least one active hydrogen group at one terminal and a poly (meth) acrylic copolymer (a2) Reactant of isocyanate (b2).

In one embodiment of the present invention, the furan group-containing urethane resin (A2) may be a furan group-containing (meth) acrylic copolymer (a2), a Reactant of isocyanate (b2) and polyol (c2) (except (a2)).

In one embodiment of the present invention, the (meth) acrylic copolymer (a2) may be a copolymer of a furan group-containing monomer, a furan group-free monomer, and a mercapto compound having at least one active hydrogen group. .

In addition, another embodiment of the present invention provides a decorative sheet having a cured film formed from the composition for a decorative sheet on a substrate.

In addition, still another embodiment of the present invention provides a molded article formed from the decorative sheet.

Furthermore, still another embodiment of the present invention provides a method for manufacturing a molded article, which includes coating a substrate with a furan group-containing compound (A), a polymerizable compound (B), and an initiator (C). The first step of the composition for a decorative sheet; the second step of curing by irradiating active energy rays; and the third step of forming.

The present invention will be described in detail below. In addition, in the present invention, the (meth) acrylate means an acrylate and / or a methacrylate, and the (meth) acrylic means an acrylic acid and / or a methacrylic acid.

In addition, in this specification, hardening (hard coating property) includes pencil hardness, abrasion resistance, and chemical resistance. In addition to these, it means that various external physical and chemical stimuli do not cause coating. The state of the membrane changes. In addition, the term "formability" refers to a problem that the designability is not significantly impaired, such as whitening, scratches, cracks, or peeling, caused by the forming process.

<Composition for Decorative Sheet> The composition for a decorative sheet of the present invention includes a furan group-containing compound (A), a polymerizable compound (B), and a polymerization initiator (C).

<Furan group-containing compound (A)> The furan group-containing compound (A) is a compound containing at least one furan group in a molecule, and may be a low-molecular compound or a high-molecular compound. The furan group-containing compound (A) may be a furan group-containing (meth) acrylic resin (A1) or a furan group-containing urethane resin (A2). In terms of hard coatability and processability of the composition for a decorative sheet, the furanyl-containing compound (A) is preferably 1 to 99 parts by weight based on 100 parts by weight of the total solid content of the composition for a decorative sheet. Used in parts by weight.

Examples of the low-molecular compound include compounds obtained by reacting a furan group-containing monomer or a (poly) isocyanate with a furan group-containing (poly) alcohol, and those obtained by reacting a (poly) isocyanate with a furan-containing amine. Compounds, compounds obtained by reacting glycidyl (meth) acrylate with a furan group-containing alcohol or amine, and the like, specifically, furfuryl (meth) acrylate, furfuryl alcohol, and 2- (methyl) ) Reactant of propylene ethoxyethyl isocyanate, reactant of furfuryl alcohol and diphenylmethane diisocyanate, reactant of furfuryl alcohol and hexamethylene diisocyanate, reactant of furfuryl alcohol and toluene diisocyanate , Reactants of furfuryl alcohol and isophorone diisocyanate, reactants of furfuryl alcohol and trimerized hexamethylene diisocyanate, reactants of furfuryl alcohol and trimerized toluene diisocyanate, furfurylamine and Reactant of 2- (meth) acryloxyethyl isocyanate, reactant of furfurylamine and diphenylmethane diisocyanate, reactant of furfurylamine and hexamethylene diisocyanate, furfurylamine and toluene Diisocyanate Reactants, reactants of furfurylamine and isophorone diisocyanate, reactants of furfurylamine and trimerized hexamethylene diisocyanate, reactants of furfurylamine and trimerized toluene diisocyanate, methyl group The reaction product of glycidyl acrylate and furfurylamine, the reaction product of glycidyl methacrylate and 2-furancarboxylic acid, and the like are not limited thereto. These may be used alone or as a mixture.

From the viewpoint of the hard coatability or processability of the composition for a decorative sheet, the furan group-containing compound (A) is preferably a polymer compound.

The polymer compound is usually a polymer having a weight average molecular weight (in terms of polystyrene) of 1,000 or more. Examples of the polymer compound include a poly (meth) acrylate having a furan group, a polyurethane, Polyester, polyamide, polyimide, polycarbonate, polyolefin, polystyrene, polysiloxane, polyether, copolymer of maleic anhydride, epoxy resin, etc., but it is not limited to these . These polymer compounds may be used alone or as a mixture. The polymer compound may have any shape such as a linear chain, a branch, or a star shape, and may also have any of thermoplastic and thermosetting properties. The polymer compound may further contain a photopolymerizable functional group in the furan group-containing compound (A). As the polymer compound, a furan group-containing (meth) acrylic resin (A1) and a furan group-containing urethane resin (A2) are preferably used.

<Furan group-containing (meth) acrylic resin (A1)> As a furan group-containing compound (A), a furan group-containing polymer compound is designed based on the starting properties of synthetic materials and the richness of species From the viewpoint of the range and the like, a furan group-containing (meth) acrylic resin (A1) as an acrylic polymer polymer compound is preferred. Examples of the furan-group-containing polymer compound include polymers containing a furan-group-containing monomer (a1-1) and those having an active reactive substituent such as an isocyanate group, a glycidyl group, or an anhydride group (structure). The reaction product of a polymer compound with a furan compound having an active hydrogen group such as an alcohol or an amine, and the like are not limited thereto.

In addition, as the furan-group-containing (meth) acrylic resin (A1) of the present invention, Japanese Patent Laid-Open No. 1994-271558, Japanese Patent Laid-Open No. 1994-293830, Japanese Patent Laid-Open No. 1996-239421, and Japanese Patent Laid-Open No. 1998-508655, Japanese Patent Laid-Open 2000-001529, Japanese Patent Laid-Open 2003-183348, Japanese Patent Laid-Open 2006-193628, Japanese Patent Laid-Open 2007-186684, Japanese Patent Laid-Open 2010-265377, Japanese Patent Laid-Open 2011 -170069 and other known compounds.

From the viewpoint of moldability and the like, the weight-average molecular weight (in terms of polystyrene) of the furan-group-containing (meth) acrylic resin (A1) of the present invention is preferably 10,000 or more, more preferably 50,000 to 2 million, Furthermore, it is more preferably 100,000 to 1 million. In this specification, a weight average molecular weight means the polystyrene conversion molecular weight measured by the gel permeation chromatography method.

From the viewpoint that the furanyl group can be easily introduced and the amount of the furanyl group can be easily controlled, the furanyl group-containing (meth) acrylic resin (A1) preferably contains a furanyl group-containing monomer (a1- The polymer of a monomer of 1) is more preferably a polymer of a furan group-containing monomer (a1-1) and a furan group-free monomer (a1-2). Furthermore, as a polymerization method, radical point polymerization is preferable from the point which is easy to control the characteristic requested | required of the composition for decorative sheets by control of molecular weight or a copolymerization composition.

The furanyl-containing monomer (a1-1) may be an ethylenically unsaturated monomer having at least one furanyl group. Specific examples include furfuryl alcohol and 2-propenyloxyethyl group. Reactant of isocyanate, reactant of furfuryl alcohol and 2-methacryloxyethyl isocyanate, reactant of furfurylamine and 2-propenyloxyethyl isocyanate, furfurylamine and 2-methylpropene Reactant of ethoxyethyl isocyanate, reactant of furfuryl alcohol and glycidyl methacrylate, reactant of furfurylamine and glycidyl methacrylate, 2-furancarboxylic acid and glycidyl methacrylate Reactant, succinate-modified furfuryl alcohol and glycidyl methacrylate reactant, succinate-modified furfurylamine and glycidyl methacrylate reactant, caprolactone-modified furfuryl alcohol Reactant with glycidyl methacrylate, reactant with caprolactone-modified furfurylamine and glycidyl methacrylate, reaction with caprolactone-modified furfuryl alcohol and 2-propenyloxyethyl isocyanate Compounds, caprolactone-modified furfurylamine and 2-propenyloxyethyl isocyanide Ester reactant, caprolactone modified furfuryl alcohol and 2-methacryloxyethyl isocyanate, caprolactone modified furfurylamine and 2-methacryloxyethyl isocyanate The reactants, furyl-containing (meth) acrylates such as furfuryl (meth) acrylate, vinyl furfuryl ether, allyl furfuryl ether, and the like are not limited thereto. The furanyl-containing monomer (a1-1) is preferably a furanyl-containing (meth) acrylate.

In terms of high monomer purity, few adverse effects during polymerization (molecular weight control, gelation, coloration, etc.) and stable synthesis of polymer compounds, the furan group-containing monomer (a1-1) is particularly preferred. Furfuryl methacrylate.

The furan group-containing monomer (a1-1) can be used in any amount of 100% by weight of the total monomers used in the polymerization, preferably 10% to 90% by weight, and more preferably 25% to 75% weight%.

The furan-group-free monomer (a1-2) is a monomer having an ethylenically unsaturated group that can be copolymerized with the furan-group-containing monomer (a1-1), and contains one ethylenically unsaturated monomer in one molecule. Saturated groups, specifically, compounds such as vinyl, allyl, (meth) acryl and the like.

Specific examples of the furan-free monomer (a1-2) include (meth) acrylic acid;

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate Ester, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (formyl) Hexadecyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isotetradecyl (meth) acrylate, (meth) Linear or branched (meth) acrylates such as lauryl acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, and adamantyl (meth) acrylate Esters

Cyclohexyl (meth) acrylate, tert-butyl cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, (meth) acrylic acid Cyclic (meth) acrylic alkyl esters such as dicyclopentenyl ester, dicyclopentenyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate or cyclic (meth) acrylates ;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2 (meth) acrylate -Hydroxy-3-chloropropyl, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, (meth) acrylic acid- 2-hydroxy-3-allyloxypropyl, 2- (meth) acryloxyethyl-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, polyethylene glycol Alcohol mono (meth) acrylate, 4-hydroxyvinylbenzene, polypropylene glycol mono (meth) acrylate, and caprolactone adducts of these monomers (additional mole number is 1 to 5), etc. Hydroxyl (meth) acrylates;

2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H-hexafluoroisopropyl (meth) acrylate, (methyl ) 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate, 2,6-dibromo-4-butylphenyl (meth) acrylate , 2,4,6-tribromophenoxyethyl (meth) acrylate, 3EO addition of 2,4,6-tribromophenol 3 (meth) acrylate and perfluorooctyl ethyl (meth) acrylate Iso (meth) acrylates;

Tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetan (meth) acrylate (meth) acrylates having a heterocyclic ring;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, (methyl ) (Meth) acrylic esters having aromatic rings, such as p-cumylphenoxypolyethylene glycol of acrylic acid and nonylphenoxypolyethylene glycol (meth) acrylate;

2-methoxyethyl (meth) acrylate, 1,3-butanediol methyl ether (meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (methyl ) Acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol ( (Meth) acrylate, ethoxy diethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, (methyl ) Tetrahydrofurfuryl acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, cresol-based poly Ethylene glycol (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, p-nonylphenoxyethyl (meth) acrylate, p-nonylphenoxy poly Ethylene glycol (meth) acrylate, glycidyl (meth) acrylate, β-carboxyethyl (meth) acrylate, mono (meth) acrylic acid ethoxyethyl succinate, ω-carboxy polyhexyl Lactone mono (meth) acrylate, 2- (meth) acrylic acid Ethyl ethyl hydrophthalate, 2- (meth) acryloxypropylhydrophthalate, 2- (meth) acryloxypropyl hexahydrophthalate Ester, 2- (meth) acryloxypropyltetrahydrophthalate, octyloxyethylene glycol polypropylene glycol mono (meth) acrylate, lauryloxy polyethylene glycol mono (methyl) Base) acrylate, stearyloxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol polypropylene glycol mono (methyl) Acrylate, polyethylene glycol monomethyl ether (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol mono (meth) acrylate, nonyl (Methyl) phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, n-butoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, etc. ) Acrylates;

3- (propenyloxymethyl) 3-methyloxetane, 3- (methacryloxymethyl) 3-methyloxetane, 3- (propenyloxymethyl) ) 3-ethyloxetane, 3- (methacryloxymethyl) 3-ethyloxetane, 3- (propyleneoxyoxymethyl) 3-butyloxane Cyclobutane, 3- (methacryloxymethyl) 3-butyloxetane, 3- (propyleneoxymethyl) 3-hexyloxetane, and 3- (methyl (Meth) acrylic acid esters having oxetanyl groups such as allyloxymethyl) 3-hexyloxetane;

Styrene, α-methylstyrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, p-third butoxystyrene, p- Tertiary butoxycarbonylstyrene, p-tertiary butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene vinyl acetate, vinyl (meth) acrylate And vinyl such as allyl (meth) acrylate;

(Meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, morpholinyl (meth) acrylate Ethyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N N-substituted types such as N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and (meth) acrylfluorenylmorpholine (Meth) acrylamide;

(Meth) acrylonitrile and other nitriles;

Ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether have vinyl ethers with ether groups;

(Meth) acrylates with isocyanate groups such as 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate and 4-isocyanate butyl acrylate;

Trade name "Silaplane FM-0711" (manufactured by JNC), trade name "Silaplane FM-0721" (manufactured by JNC), and trade name "Saiplane Silicone (meth) acrylates such as Silaplane FM-0725 "(manufactured by JNC), or a mixture of these, but not limited to these.

Examples of other polymerizable monomers include vinyl acetate, vinyl monochloroacetate, vinyl benzoate, trimethyl vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl 2-ethylhexanoate. , N-vinylcarbitol, N-vinylpyrrolidone, and the like, but are not limited to these.

From the viewpoint of the synthesis stability when copolymerized with the furan group-containing monomer (a1-1), the furan group-free monomer (a1-2) is more preferably a (meth) acrylate compound.

Furthermore, in order to improve the chemical resistance required for automotive applications, especially for interior parts, it is preferred to use a monomer having a polar group as the monomer (a1-2). The furan-free monomer preferably has a hydroxyl group as a polar group, and specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (methyl) ) 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, (methyl ) 2-hydroxy-3-allyloxypropyl acrylate, 2- (meth) acryloxyethyl-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like are not limited thereto.

The furanyl-free monomer (a1-2) may be used alone, or two or more thereof may be used in any ratio.

The copolymerization of a furanyl-containing monomer (a1-1) and a furanyl-free monomer (a1-2) can be performed by a known method. That is, a polymer compound can be obtained by arbitrarily mixing a monomer with a polymerization initiator and heating.

The polymerization temperature is preferably adjusted appropriately according to the type of the polymerization initiator used or the boiling point of the solvent, and is preferably 20 ° C to 150 ° C, and more preferably 40 ° C to 120 ° C.

The environment in which the polymerization is performed is preferably performed in an inert gas environment for the purpose of preventing reduction in coloration or deactivation of the polymerization initiator. From the standpoint of ease of use and cost, nitrogen is preferred, but It is not limited to these.

As the polymerization initiator, an azo-based compound and an organic peroxide can be used. Examples of the azo-based compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 1,1'-azobis (cyclo Hexane 1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxy) Valeronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], etc., but it is not limited to these. Examples of the organic peroxides include benzoamidine peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxide dicarbonate, and di-n-propyl peroxydicarbonate. , Bis (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-butyl pervalerate, ( 3,5,5-trimethylhexyl) peroxide, dipropylfluorenyl peroxide, diethylfluorenyl peroxide, and the like are not limited thereto.

These polymerization initiators may be used singly or in combination of two or more kinds. The amount used may be 0.001 parts by weight to 100 parts by weight of the total of the monomer (a1-1) and the monomer (a1-2). Adjust arbitrarily within the range of 20 parts by weight.

During the polymerization, a chain transfer agent may be used for the purpose of adjusting the molecular weight. A chain transfer agent of 0.001 to 15 parts by mass can be arbitrarily used with respect to 100 parts by mass of the total of the monomer (a1-1) and the monomer (a1-2).

The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting molecular weight, and a known chain transfer agent can be used. Examples include: octyl mercaptan, n-dodecyl mercaptan, third-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, 1-thiol Glycerin, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3 -Mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), tri-[(3-mercaptopropionyloxy) -ethyl] -iso Cyanurate, pentaerythritol tetra (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), thiomalate, thio Thiols such as octyl glycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, butyl thioglycolate; dimethyl xanthate disulfide, diethyl xanthate disulfide, disulfide disulfide Disulfides such as isopropylxanthate, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide; carbon tetrachloride, dichloromethane, tribromomethane , Bromotrichloroethane, carbon tetrabromide, dibromoethane and other halogenated hydrocarbons; Secondary alcohols such as alcohols and glycerol; Phosphorous acid, hypophosphorous acid and its salts (sodium hypophosphite, potassium hypophosphite, etc.) or sulfurous acid, hydrogen sulfite, disulfite, metasulfite and their salts (hydrogen sulfite Sodium, potassium bisulfite, sodium disulfite, potassium disulfite, sodium metabisulfite, potassium metabisulfite, etc.) and lower oxides and their salts; and allyl alcohol, 2-ethylhexyl mercaptoacetate, α-formyl Butyl styrene dimer, terpineolene, α-terpinene, γ-terpinene, dipentene, anisole, and the like are not limited thereto. These can be used alone or in combination of two or more.

In addition, during the polymerization, an organic solvent may be used as a polymerization solvent. Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, and Ethoxydiethylene glycol, 3-methoxy-1-butanol, and the like are not particularly limited to these. These polymerization solvents may be used in combination of two or more kinds, and the solvent used for the end use is preferable.

<Furan group-containing urethane resin (A2)> As the furan group-containing compound (A), as described above, a furan group-containing urethane resin (A2) can also be used. The urethane-containing urethane resin (A2) is a urethane resin containing at least one or more furano groups in the molecule. The so-called urethane resin refers to a urethane bond in the molecule. Polymer.

In terms of hard-coating property and processability of the composition for a decorative sheet, the furan-group-containing urethane resin (A2) of the present invention is 100% by weight of the total solid content of the composition for a decorative sheet. It is preferably used in an amount of 1 to 99 parts by weight.

From the viewpoints of the moldability of the composition for a decorative sheet, the weight-average molecular weight (in terms of polystyrene) of the furan-containing urethane resin (A2) of the present invention is preferably a polymer of 1,000 or more, more preferably It is preferably 50 to 2 million, further preferably 10,000 to 1 million, and most preferably 100,000 to 1 million. In this specification, a weight average molecular weight means the polystyrene conversion molecular weight measured by the gel permeation chromatography method.

The furan group-containing urethane resin (A2) of the present invention may have any shape such as a linear chain, a branch, or a star shape, or may be compounded with other resins or the like. Specific examples of the other resins include copolymers including polyester, polyamidine, polyimide, polycarbonate, polyolefin, polystyrene, polysiloxane, polyether, and maleic anhydride, The epoxy resin is not limited to these.

As for the furan group-containing urethane resin (A2), the furan group may be included in a portion containing a polyol, a portion containing a polyisocyanate, a portion containing a chain extender such as a polyamine, and a portion containing a monoalcohol or a monoamine. Any of the parts of the polymerization stopper.

From the viewpoints of the starting range of synthetic raw materials and the design range brought by the richness of species, it is preferable that the furan group-containing urethane resin (A2) has a (meth) acrylic acid copolymer containing a furan group. The structural unit of the material, the furan group-containing (meth) acrylic copolymer has an active hydrogen group.

Here, the active hydrogen group refers to a nucleophilic substituent capable of reacting with an isocyanate group. Specific examples include a hydroxyl group, an amino group, a mercapto group, and a carboxyl group, but are not limited thereto. Among these, in terms of reactivity or ease of starting the raw material, a hydroxyl group and an amine group are preferred, and a hydroxyl group is particularly preferred. From the viewpoint of suppressing gelation during urethane resinization, the number of hydroxyl groups is preferably one to two, and more preferably one.

As a method of introducing an active hydrogen group into a (meth) acrylic copolymer, the method of copolymerizing the (meth) acrylic acid ester which has an active hydrogen group, etc. are mentioned.

From the viewpoint of the structure control of the urethane resin, the furan group-containing urethane resin (A2) is more preferably a structural unit containing a furan group-containing (meth) acrylic copolymer (a2). The (meth) acrylic copolymer (a2) containing a furan group has at least one active hydrogen group at a single end.

Here, the term "single terminal" refers to one terminal portion of the main chain of the (meth) acrylic copolymer. Examples of a method for introducing an active hydrogen group into the single terminal of the (meth) acrylic copolymer include an active hydrogen group. A method of copolymerizing a (meth) acrylate with a polymerization initiator, or a method of copolymerizing a (meth) acrylate in the presence of a mercapto compound having an active hydrogen group.

From the viewpoint of controlling the number of active hydrogen groups to be introduced or correctness of introduction of a single terminal, a method of copolymerizing (meth) acrylate in the presence of a mercapto compound having an active hydrogen group is preferred.

Specific examples of the furan group-containing urethane resin (A2) include, for example, a furan group-containing (meth) acrylic copolymer (a2) having at least one active hydrogen group at one terminal and a polyisocyanate. A reactant of (b2), or a furan-group-containing (meth) acrylic copolymer (a2) having at least one active hydrogen group at one terminal, a reactant of polyisocyanate (b2) and polyol (c2), and the like.

From the viewpoint that the physical properties required as a composition for a decorative sheet can be easily controlled, the (meth) acrylic copolymer (a2), polyisocyanate (b2), and polyisocyanate (b2) having a single terminal having at least one active hydrogen group are more preferable. Reactant of alcohol (c2).

A specific method for synthesizing the furan group-containing urethane resin (A2) is to mix the (a2), (b2), and (c2) in the presence of a catalyst or a solvent, and perform a heating reaction. The mixing method of (a2), (b2), and (c2) is not particularly limited, and all of them may be mixed and reacted, or a part of them may be reacted in advance. For example, (a2) and (b2) may be reacted after adding (c2), or (b2) and (c2) may be reacted after adding (a2).

The synthesis reaction of the furan group-containing urethane resin (A2) can be performed without a catalyst, and a catalyst can be used for the purpose of further promoting the reaction. Examples of the catalyst include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, bis (acetylacetonate) zinc, bis (tetrafluoroacetonylacetone) zinc, Zirconium monoacetamate, zirconium acetate, zirconium triacetate, zirconium acetate, zirconium tetraacetamate, zirconium tetramethoxyacetate, titanium titanium tetraethoxide, tetraisopropyl Organometallic compounds such as titanium oxytitanate and titanium tetrabutoxide; tin octylate, zinc hexanoate, zinc octoate, zinc stearate, zirconyl 2-ethylhexanoate, cobalt naphthenate, stannous oxide, Metal salts such as tin tetrachloride, potassium acetate; triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8 -Diazabicyclo [5,4,0] undecene, N, N, N ', N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethyl? Amine catalysts, such as phospholine; Bismuth nitrate, bismuth bromide, bismuth iodide, and bismuth sulfide; in addition, organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate; bismuth 2-ethylhexanoate , Bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, Bismuth catalysts such as organic acid bismuth salts such as bismuth fatty acid salts, bismuth oleate, bismuth linoleate, bismuth acetate, bisbisdecanoate, bismuth salicylate, bismuth digallate Etc., but it is not limited to these. As the catalyst, among these, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferred. These catalysts can be used alone or in combination of two or more.

The synthesis reaction of the furan group-containing urethane resin (A2) may be performed without a solvent, or may be performed using a solvent. When a solvent is used, as the usable solvent, an organic solvent which does not react with an isocyano group is preferred. Specific examples of usable solvents include: hydrocarbon solvents such as heptane, hexane, toluene, and benzene; ketone solvents such as ethyl acetate, methyl ethyl ketone, and cyclohexanone; diethyl ether and methyl formaldehyde Ether solvents such as cyclopentyl ether and tetrahydrofuran; polar solvents such as acetonitrile, dimethylformamide, and dimethylsulfenyl; halogen solvents such as dichloromethane and chloroform, but not limited thereto. In addition, one or more solvents may be used in combination.

The reaction temperature for the synthesis reaction of the furan group-containing urethane resin (A2) is usually 25 ° C to 120 ° C, preferably 40 ° C to 90 ° C, and the reaction time is usually 2 hours to 10 hours, preferably It is 3 to 8 hours. The progress of the reaction can be followed by NMR, IR, or the isocyanate residue in the reaction by titration or the like.

Examples of the method for introducing a furyl group into the (meth) acrylic copolymer (a2) include a method for copolymerizing a furan group-containing monomer, a method for introducing a furan group by a modification method, and the like. As an introduction method using a modification method, specifically, a method of copolymerizing glycidyl (meth) acrylate and then reacting furfurylamine or 2-furancarboxylic acid with an epoxy group may be mentioned; Or a method of adding an isocyanate group-containing methyl (acrylate) and then adding furfuryl alcohol or furfurylamine to an isocyanate group; after copolymerizing maleic anhydride, furfuryl alcohol or furfurylamine is opened. The method of cycloaddition to an anhydride structure and the like are not limited thereto. From the viewpoint of simplicity of synthesis, etc., as a method for introducing a furyl group into the (meth) acrylic copolymer (a2), a method of copolymerizing a furan group-containing monomer is preferred.

Therefore, as a method for obtaining a furyl group-containing (meth) acrylic copolymer (a2) having at least one active hydrogen group at one terminal, it is particularly preferable to use a furan group-containing monomer, a furan group-free monomer, and The thiol compound having at least one active hydrogen group is copolymerized.

The furan group-containing monomer may be an ethylenically unsaturated monomer having at least one furan group. Specific examples include a reactant of furfuryl alcohol and 2-propenyloxyethyl isocyanate, Reactant of furfuryl alcohol and 2-methacryloxyethyl isocyanate, reactant of furfurylamine and 2-propenyloxyethyl isocyanate, furfurylamine and 2-methacryloxyethyl isocyanate Isocyanate reactant, furfuryl alcohol and glycidyl methacrylate reactant, furfurylamine and glycidyl methacrylate reactant, 2-furancarboxylic acid and glycidyl methacrylate reactant, Reactant of diacid-modified furfuryl alcohol and glycidyl methacrylate, reactant of succinate-modified furfurylamine and glycidyl methacrylate, caprolactone-modified furfuryl alcohol and glycidyl methacrylate Reactant of glyceride, reactant of caprolactone-modified furfurylamine and glycidyl methacrylate, reactant of caprolactone-modified furfuryl alcohol and 2-propenyloxyethyl isocyanate, caprolactone Modified furfurylamine with 2-propenyloxyethyl isocyanate Reactants, reactants of caprolactone-modified furfuryl alcohol and 2-methacryloxyethyl isocyanate, reactants of caprolactone-modified furfurylamine and 2-methacryloxyethyl isocyanate Furfuryl-containing (meth) acrylates, such as furfuryl (meth) acrylate, vinyl furfuryl ether, allyl furfuryl ether, and the like are not limited thereto. The furanyl-containing monomer is preferably a furanyl-containing (meth) acrylate.

As a furan group-containing monomer, methyl is particularly preferable in terms of high monomer purity, little adverse effects (molecular weight control, gelation, coloring, etc.) during polymerization and stable synthesis of polymer compounds. Furfuryl acrylate.

The furan group-containing monomer can be used in any amount of 100% by weight of the total monomers used for polymerization, preferably 1% to 99% by weight, and more preferably 10% to 90% by weight.

A furan group-free monomer is a monomer having an ethylenically unsaturated group that can be copolymerized with a furan group-containing monomer, and contains one ethylenically unsaturated group in one molecule, specifically a vinyl group, Compounds such as allyl and (meth) acrylfluorenyl.

Specific examples of the furan-free monomer include (meth) acrylic acid, 2- (meth) acrylic acid ethoxyethyl succinate, and β-carboxyethyl (meth) acrylate. Carboxyl (meth) acrylates;

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate Ester, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (formyl) Hexadecyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isotetradecyl (meth) acrylate, (meth) Linear or branched (meth) acrylates such as lauryl acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, and adamantyl (meth) acrylate Esters

Cyclohexyl (meth) acrylate, tert-butyl cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, (meth) acrylic acid Dicyclopentenyl ester, dicyclopentenyloxyethyl (meth) acrylate, and cyclic (meth) acrylic alkyl esters such as isobornyl (meth) acrylate or cyclic (meth) acrylic acid Esters

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2 (meth) acrylate -Hydroxy-3-chloropropyl, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, (meth) acrylic acid- 2-hydroxy-3-allyloxypropyl, 2- (meth) acryloxyethyl-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, polyethylene glycol Alcohol mono (meth) acrylate, 4-hydroxyvinylbenzene, polypropylene glycol mono (meth) acrylate, and caprolactone adducts of these monomers (additional mole number is 1 to 5), etc. Hydroxyl (meth) acrylates;

2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H-hexafluoroisopropyl (meth) acrylate, (methyl ) 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate, 2,6-dibromo-4-butylphenyl (meth) acrylate , 2,4,6-tribromophenoxyethyl (meth) acrylate, 3EO addition of 2,4,6-tribromophenol 3 (meth) acrylate and perfluorooctyl ethyl (meth) acrylate Iso (meth) acrylates;

Tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetan (meth) acrylate (meth) acrylates having a heterocyclic ring;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, p-cumyl (Meth) acrylates with aromatic rings such as phenoxy polyethylene glycol (meth) acrylate and nonylphenoxy polyethylene glycol (meth) acrylate;

2-methoxyethyl (meth) acrylate, 1,3-butanediol methyl ether (meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (methyl ) Acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol ( (Meth) acrylate, ethoxy diethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, (methyl ) Tetrahydrofurfuryl acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, cresol-based poly Ethylene glycol (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, p-nonylphenoxyethyl (meth) acrylate, p-nonylphenoxy poly Ethylene glycol (meth) acrylate, glycidyl (meth) acrylate, β-carboxyethyl (meth) acrylate, mono (meth) acrylic acid ethoxyethyl succinate, ω-carboxy polyhexyl Lactone mono (meth) acrylate, 2- (meth) acrylic acid Ethyl ethyl hydrophthalate, 2- (meth) acryloxypropylhydrophthalate, 2- (meth) acryloxypropyl hexahydrophthalate Ester, 2- (meth) acryloxypropyltetrahydrophthalate, octyloxyethylene glycol polypropylene glycol mono (meth) acrylate, lauryloxy polyethylene glycol mono (methyl) Base) acrylate, stearyloxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol polypropylene glycol mono (methyl) Acrylate, polyethylene glycol monomethyl ether (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol mono (meth) acrylate, nonyl (Methyl) phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, n-butoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, etc. ) Acrylates;

3- (propenyloxymethyl) 3-methyloxetane, 3- (methacryloxymethyl) 3-methyloxetane, 3- (propenyloxymethyl) ) 3-ethyloxetane, 3- (methacryloxymethyl) 3-ethyloxetane, 3- (propyleneoxyoxymethyl) 3-butyloxane Cyclobutane, 3- (methacryloxymethyl) 3-butyloxetane, 3- (propyleneoxymethyl) 3-hexyloxetane, and 3- (methyl (Meth) acrylic acid esters having oxetanyl groups such as allyloxymethyl) 3-hexyloxetane;

Styrene, α-methylstyrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, p-third butoxystyrene, p- Tertiary butoxycarbonylstyrene, p-tertiary butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene vinyl acetate, vinyl (meth) acrylate And vinyl such as allyl (meth) acrylate;

(Meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, morpholinyl (meth) acrylate Ethyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N N-substituted types such as N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and (meth) acrylfluorenylmorpholine (Meth) acrylamide;

(Meth) acrylonitrile and other nitriles;

Ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether have vinyl ethers with ether groups;

(Meth) acrylates with isocyanate groups such as 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate and 4-isocyanate butyl acrylate;

Trade name "Silaplane FM-0711" (manufactured by JNC), trade name "Silaplane FM-0721" (manufactured by JNC), and trade name "Saiplane Silicone (meth) acrylates such as Silaplane FM-0725 "(manufactured by JNC), or a mixture of these, but not limited to these.

Examples of other polymerizable monomers include vinyl acetate, vinyl monochloroacetate, vinyl benzoate, trimethyl vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl 2-ethylhexanoate. , N-vinylcarbitol and N-vinylpyrrolidone, but are not limited to these.

As a furan group-free monomer, a (meth) acrylate compound is more preferable from a viewpoint of the synthesis stability at the time of copolymerization with a furan group containing monomer.

Furthermore, in order to improve the chemical resistance required for automotive applications, especially for the use of interior parts, it is preferred to use a monomer having a polar group as the furan-free monomer. The furan-free monomer preferably has a hydroxyl group as a polar group, and specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (methyl) ) 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, (methyl ) 2-hydroxy-3-allyloxypropyl acrylate, 2- (meth) acryloxyethyl-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like are not limited thereto.

The furanyl-free monomer may be used alone, or two or more thereof may be used in any ratio.

The mercapto compound having at least one active hydrogen group is not particularly limited as long as it has an active hydrogen group and a mercapto group in one molecule, and specific examples include 2-mercaptoethanol and 3-mercapto-1-propanol. , 4-mercaptobutanol, 3-mercapto-2-butanol, 3-mercapto-3-methyl-1-1-butanol, 3-mercapto-1-hexanol, 5-mercaptoheptanol, 6-mercapto Hexanol, 4-mercaptocyclohexanol, 2-hydroxybenzenethiol, thioglycerol, dithiothreitol, 2,3-dimercapto-1-propanol and other alcohols with thiol groups; thioglycolic acid, 2- Mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 4-mercaptobutyric acid, 5-mercaptovaleric acid, 6-mercaptohexanoic acid, thiosalicylic acid, 2-mercaptonicotinic acid, etc. have mercapto groups Carboxylic acids; 2-aminoethylthiol, 2- (methylamino) ethylthiol, 2-amino-2-methyl-1-propanol, 2-aminophenylthiol, 2- ( Methylamino) thiol, 3-aminopropylthiol, 3- (methylamino) propylthiol, 4-aminobutylthiol, 4- (methylamino) butylthiol, 5 -Aminopentyl mercaptan, 5- (methylamino) pentyl mercaptan, 6-aminohexyl mercaptan, 6- (methylamino) hexyl mercaptan, cysteine, cysteine, Cysteine A , And amines such as cysteine ester having a mercapto group, but is not limited to the these.

In order to introduce a furyl group-containing (meth) acrylic copolymer (a2) into a urethane resin, the mercapto compound having at least one active hydrogen group is preferably an alcohol having a mercapto group and an amine having a mercapto group.

By using a thiol compound having at least one active hydrogen group, a reaction in which a radical generated from a polymerization initiator takes hydrogen from a thiol group occurs. An active hydrogen group can be introduced into a single terminal by performing a polymerization reaction with a monomer from the generated mercapto radical.

The used amount of the mercapto compound having at least one active hydrogen group may be arbitrarily used in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the total of the furan group-containing monomer and the furan group-free monomer.

<Copolymerization of a furanyl-containing monomer and a furanyl-free monomer> The copolymerization of a furanyl-containing monomer and a furanyl-free monomer can be combined with the furan-containing monomer (a1-1 ) The copolymerization with the furan group-free monomer (a1-2) is performed by a known method in the same manner. That is, a polymer compound can be obtained by arbitrarily mixing a monomer with a polymerization initiator and heating.

The polymerization temperature is preferably adjusted appropriately according to the type of the polymerization initiator used or the boiling point of the solvent, and is preferably 20 ° C to 150 ° C, and more preferably 40 ° C to 120 ° C.

The environment in which the polymerization is performed is preferably performed in an inert gas environment for the purpose of preventing reduction in coloration or deactivation of the polymerization initiator. From the standpoint of ease of use and cost, nitrogen is preferred, but It is not limited to these.

As the polymerization initiator, an azo-based compound and an organic peroxide can be used. Examples of the azo-based compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 1,1'-azobis (cyclo Hexane 1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxy) Valeronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], etc., but it is not limited to these. Examples of the organic peroxides include benzoamidine peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxide dicarbonate, and di-n-propyl peroxydicarbonate. , Bis (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-butyl pervalerate, ( 3,5,5-trimethylhexyl) peroxide, dipropylfluorenyl peroxide, diethylfluorenyl peroxide, and the like are not limited thereto.

These polymerization initiators may be used singly or in combination of two or more. The amount used may be 0.001 to 20 parts by weight based on 100 parts by weight of the total of the furan group-containing monomer and the furan group-free monomer. It is arbitrarily adjusted within the range of weight part.

In addition, during the polymerization, an organic solvent may be used as a polymerization solvent. Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, and Ethoxydiethylene glycol, 3-methoxy-1-butanol, and the like are not particularly limited to these. These polymerization solvents may be used in combination of two or more kinds, and the solvent used for the end use is preferable.

The polyisocyanate (b2) is not particularly limited as long as it is a compound containing two or more isocyanate groups. From the viewpoint of suppressing gelation during synthesis of the urethane resin, diisocyanate is preferred. Specific examples of the diisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and a mixture thereof, crude toluene diisocyanate (Toluene Diisocyanate, TDI), and diphenylmethane-4,4'- Diisocyanate (Diphenyl Methane Diisocyanate (MDI), crude MDI, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (3, Aromatic diisocyanates such as 3'-Dimethyl-4,4'-biphenylene Diisocyanate (TODI), Polymethylene Polyphenyl Polyisocyanate (PMDI), cyanine diisocyanate, tetramethylxylene diisocyanate ; Xylene Diisocyanate (XDI), terephthalic acid diisocyanate, isophthalic acid diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 2,6-diisocyanate benzyl chloride, dichloro Aromatic aliphatics such as methyldiphenylmethane diisocyanate, diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, and tetraalkyldiphenylmethane diisocyanate Isocyanates; 4,4'-methylene dicyclohexyl diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), hydrogenated xylene diisocyanate (hydrogenated XDI), norbornene diisocyanate (Norbornene Diisocyanate NBDI), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane 40 Alicyclic diisocyanates such as diisocyanates; butane-1,4-diisocyanate, pentaethylene diisocyanate, hexamethylene diisocyanate (HDI), isopropylene diisocyanate, methylene diisocyanate, ionamine Acid diisocyanate, cyclohexane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate (Trimethyl Hexamethylene Diisocyanate TMDI), mixtures thereof, aliphatic diisocyanates such as dimer acid diisocyanate (DDI), lysine isocyanate, etc., but it is not limited to these. These diisocyanates can also be used as a block.

The compound having three or more isocyanate groups can be used within a range in which gelation does not occur during the reaction. Specifically, examples include the isotricyanate trimer of the diisocyanate, and urea trimerization. Polymer, trimethylolpropane addition compound, triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, etc., but it is not limited to this some.

These polyisocyanates may be used singly or in combination of two or more kinds. As the amount used, the ratio of the molar number of the isocyanate of the polyisocyanate (b2) to the molar number of the active hydrogen group of the (meth) acrylic copolymer (a2) having at least one active hydrogen group at one end, that is, NCO / The active hydrogen ratio is in the range of 0.1 to 10.0, and preferably 0.5 to 5.0.

The polyol (c2) is not particularly limited as long as it is a compound containing two or more hydroxyl groups.

From the viewpoint of suppressing gelation during synthesis of the urethane resin, the polyol (c2) is preferably a diol. As the diol, a low molecular weight diol can be used. Examples of the low-molecular-weight diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol. Glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1, 9-nonanediol, 2,2-dimethylolheptane, 1,3-propanediol, 1,4-butanediol, dipropylene glycol, 1,3-butanediol, 2-methyl-1 1,3-trimethylene glycol, 2,4-diethyl-1,5-pentamethylene glycol, hydrogenated bisphenol A, hydroxyalkylated bisphenol A, 1,4-cyclohexanedimethanol , 1,4-cyclohexanediol, 2,2,4-trimethyl-1,3-pentanediol, N, N-bis- (2-hydroxyethyl) dimethylhydantoin, etc. , But not limited to those.

Examples of the polyol (c2) include, but are not limited to, polyether polyols, polyester polyols, polycarbonate polyols, and polyolefin polyols.

Examples of the polyether polyol include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran, and specifically, polyethylene glycol, polypropylene glycol, and poly (ethylene / propylene) glycol. , Butylene glycol, etc., but is not limited to these. In addition, as the polyether polyol, hexanediol, methylhexanediol, heptanediol, octanediol, or polyether polyols obtained by condensation of these mixtures can also be used.

Examples of the polyester polyol include polyester polyols obtained by a condensation reaction of a polyol component and a dibasic acid component. Examples of the diol used as the polyol component include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butanediol, 1,6-hexanediol, and 3-methyl -1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl Alcohol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, bisphenol A, and the like are not limited thereto. As a dibasic acid component, terephthalic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic anhydride, isophthalic acid, 1 Aliphatic or aromatic dibasic acids, such as 2,3,4-tricarboxylic acid, and these anhydrides are not limited to these. In addition, as the polyester-based polyol, ring-opening using cyclic ester compounds such as ε-caprolactone, poly (β-methyl-γ-valerolactone), and lactones such as polyvalerolactone can also be used. Polyester polyol obtained by polymerization.

Examples of the polycarbonate-based polyol include those obtained by reacting a polyol with a carbonate compound such as a dialkyl carbonate, an alkylene carbonate, or a diaryl carbonate, but the polycarbonate polyol is not limited thereto. As the polyol constituting the polycarbonate-based polyol, a polyol exemplified as a constituent component of a polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate. Examples of the alkylene carbonate include ethyl carbonate. Examples of the diaryl carbonate include diphenyl carbonate. The differences are not limited to these.

Examples of the polyolefin-based polyol include hydroxyl-containing polybutadiene, hydrogenated hydroxyl-containing polybutadiene, hydroxyl-containing polyisoprene, hydrogenated hydroxyl-containing polyisoprene, Hydroxyl-containing chlorinated polypropylene, hydroxyl-containing chlorinated polyethylene, and the like are not limited thereto.

As the polyol (c2), other than polybutadiene-based polyols, (meth) acrylic-based polyols, polycaprolactone-based polyols, polysiloxane-based polyols, and polyaminomethyl Ester-based polyols, castor oil polyols, and the like.

These polyols (c2) may be used singly or in combination of two or more kinds. As the amount used, the sum (XH) of the mole number of the hydroxyl group of the polyol (c2) and the mole number of the active hydrogen group of the (meth) acrylic copolymer (a2) having at least one active hydrogen group at one end, The ratio of the molar number to the isocyanate group of the polyisocyanate (b2), that is, NCO / (XH) is in the range of 0.1 to 10.0, and preferably 0.5 to 5.0.

In addition, the ratio of the molar number of the hydroxyl group of the polyol (c2) to the molar number of the active hydrogen group of the (meth) acrylic copolymer (a2) having at least one active hydrogen group at one end, that is, the hydroxyl group / active hydrogen group The range is preferably 0.1 to 10, and more preferably 0.5 to 5.

<Polymerizable Compound (B)> Next, as the polymerizable compound (B), a radical polymerizable compound can be used in order to improve the hardenability accompanying the reaction. The radical polymerizable compound in the present invention refers to a compound having at least one skeleton capable of radical polymerization in a molecule and not containing a furanyl group. In addition, these are chemical forms of monomers, oligomers, or polymers that are liquid or solid at room temperature and pressure.

Examples of the radically polymerizable compound include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylic acid, and maleic acid, and their salts, esters, amidines, Examples of the acid anhydride include urethane (meth) acrylate, (meth) acrylate epoxy, (meth) acrylate, ester (meth) acrylate, acrylonitrile, and styrene derivatives. , Various unsaturated polyesters, unsaturated polyethers, unsaturated polyamines, unsaturated polyurethanes, and the like, but are not limited to these. Hereinafter, specific examples of the radical polymerizable compound in the present invention will be listed.

Examples of acrylates: Examples of monofunctional alkyl acrylates, monofunctional cyclic alkyl acrylates or monofunctional cyclic acrylates: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, Butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, diacrylate Cyclopentenyl, dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxy-containing acrylates: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2 -Hydroxy-3-allyloxypropyl, 2-hydroxy-3-allyloxypropyl acrylate, 2-propenyloxyethyl-2-hydroxypropyl phthalate.

Examples of monofunctional halogen-containing acrylates: 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H acrylate, 5H-octafluoropentyl ester, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate Ester, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates: 2-methoxyethyl acrylate, 1,3-butanediol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methyl Oxypolyethylene glycol # 400 acrylate, methoxy dipropylene glycol acrylate, methoxy tripropylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy diethylene glycol acrylate, ethyl carbitol Acrylate, 2-ethylhexylcarbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresol group Polyethylene glycol acrylate, 2- (hydroxyethoxy) ethyl acrylate, p-nonylphenoxyethyl acrylate, p-nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl-containing acrylates: β-carboxyethyl acrylate, monopropylene ethoxyethyl succinate, ω-carboxy polycaprolactone monoacrylate, 2-propylene ethoxyethyl hydrogen o-benzene Diformate, 2-propenyloxypropylhydrophthalate, 2-propenyloxypropylhexahydrophthalate, 2-propenyloxypropyltetrahydrophthalate Diformate.

Examples of other monofunctional acrylates: N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinyl ethyl acrylate, trimethylsiloxyethyl acrylate Ester, diphenyl-2-propenyloxyethyl phosphate, 2-propenyloxyethyl acid phosphate, caprolactone modified 2-propenyloxyethyl acid phosphate, 2-hydroxy- 1-propenyloxy-3-methacryloxypropane.

Examples of difunctional acrylates: 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate Acrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate , Dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neopentyl glycol diacrylate, neopentyl glycol PO modification Diacrylate, neopentyl glycol hydroxytrimethylacetate diacrylate, caprolactone adduct dihydroxypentamethylene glycol diacrylate, 1,6-hexanediol bis (2- Hydroxy-3-propenyloxypropyl) ether, bis (4-propenyloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate Monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO modified bis A diacrylate, PO modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylic acid Ester, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A diacrylate, tricyclodecane dimethylol diacrylate, isocyanuric acid Acid EO modified diacrylate, 2-hydroxy-1,3-dipropenyloxypropane.

Examples of trifunctional acrylates: glycerol PO modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane PO modified triacrylate, isopropyl Tricyanic acid EO modified triacrylate, isotricyanic acid EO modified ε-caprolactone modified triacrylate, 1,3,5-tripropenyl hexahydro-tritriazine, pentaerythritol triacrylic acid Ester, dipentaerythritol triacrylate tripropionate.

Examples of tetrafunctional or higher acrylates: pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetra Acrylate, tris (acrylic acid) phosphate.

Examples of methacrylates: Examples of monofunctional alkyl methacrylates, monofunctional cyclic alkyl methacrylates, or monofunctional cyclic alkenyl methacrylates: methyl methacrylate, methacrylic acid Ethyl ester, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethyl methacrylate Hexyl ester, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate , Dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxy-containing methacrylates: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-methacrylate 3-phenoxypropyl, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloxyethyl-2-hydroxypropyl phthalate.

Examples of monofunctional halogen-containing methacrylates: 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate Propyl ester, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate , 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates: 2-methoxyethyl methacrylate, 1,3-butanediol methyl ether methacrylate, butoxyethyl methacrylate, methoxy Triethylene glycol methacrylate, methoxy polyethylene glycol # 400 methacrylate, methoxy dipropylene glycol methacrylate, methoxy tripropylene glycol methacrylate, methoxy polypropylene glycol methyl Acrylate, 2- (hydroxyethoxy) ethyl methacrylate, ethoxy diethylene glycol methacrylate, 2-ethylhexylcarbitol methacrylate, tetrahydrofurfuryl methacrylate , Phenoxyethyl methacrylate, phenoxy diethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, cresol-based polyethylene glycol methacrylate, methacrylic acid Nonylphenoxyethyl, p-nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates: β-carboxyethyl methacrylate, monomethacryloxyethyl succinate, ω-carboxy polycaprolactone monomethacrylate, 2-methyl Propylene ethoxyethyl hydrogen phthalate, 2-methacryl ethoxypropyl hydrogen phthalate, 2-methacryl ethoxypropyl hexahydrophthalic acid Ester, 2-methacryloxypropyl tetrahydrophthalate.

Examples of other monofunctional methacrylates: dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate Ester, morpholinyl ethyl methacrylate, trimethylsiloxy ethyl methacrylate, diphenyl-2-methacryloxyethyl phosphate, 2-methacryloxyethyl acid Phosphate esters, caprolactones modified 2-methacryloxyethyl ethyl phosphate and the like.

Examples of difunctional methacrylates: 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate Methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 dimethacrylate, poly Glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxytrimethyl acetate neopentyl glycol Dimethacrylate, caprolactone adduct of neopentyl glycol trimethylacetate, dimethacrylate, 1,6-hexanediol bis (2-hydroxy-3-methacryloxy) (Propyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate mono Fatty acid esters, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxy polyethoxyphenyl) propane, bisphenol A dimethacrylate, EO modified Modified bisphenol A dimethacrylate, PO modified bisphenol A dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bis Phenol A dimethacrylate, bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate, PO modified bisphenol F dimethacrylate, EO modified tetrabromobisphenol A di Methacrylate, tricyclodecane dimethylol dimethacrylate, isotricyanic acid EO modified dimethacrylate, 2-hydroxy-1,3-dimethylpropenyloxypropane.

Examples of trifunctional methacrylates: glycerol PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified Modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isotricyanic acid EO modified trimethacrylate, isotricyanic acid EO modified ε-caprolactone modified Trimethacrylate, 1,3,5-trimethacryl hexahydro-mesytriazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates: pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, Oligopolyester tetramethacrylate, tris (methacryloxy) phosphate.

Examples of aryl esters: allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, triaryl isocyanate.

Examples of amidoamines: acrylamide, N-methylol acrylamide, diacetone acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-iso Propyl allylamine, allyl morpholine, methacrylamide, N-methylol methacrylamide, diacetone methacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamidine, N-isopropylmethacrylamidine, methacrylamidomorpholine.

Examples of styrenes: styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, p-third butoxystyrene, p- Tributoxycarbonylstyrene, p-third-butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds: vinyl acetate, vinyl monochloroacetate, vinyl benzoate, trimethyl vinyl acetate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate Esters, vinyl butyrate, vinyl 2-ethylhexanoate, N-vinylcarbitol, N-vinylpyrrolidone and the like.

The radically polymerizable compound can be easily obtained as a commercially available product from a manufacturer shown below. Examples include "Light Acrylate", "Light ester", "epoxy ester", and "urethane acrylate" manufactured by Kyoeisha Oil Chemical Industry Co., Ltd. And "high-functional oligomer" series, "NK ester" and "NK oligomer" series manufactured by Shin Nakamura Chemical Co., Ltd., and "Fancryl" manufactured by Hitachi Chemical Industries, Ltd. Series, "Aronix M" series manufactured by Toa Synthetic Chemical Co., Ltd., "functional monomer" series manufactured by Daha Chemical Industry Co., Ltd., and manufactured by Osaka Organic Chemical Industry Co., Ltd. "Special acrylic monomer" series, "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., manufactured by Nippon Kayakusho Co., Ltd. "KAYARAD" and "Kayamer" series, "Acrylic acid / methacrylate monomer" series made by Japan Catalyst Corporation, Japan Synthetic Chemical Industry Co., Ltd. "NICHIGO" -UV ultraviolet light urethane acrylate oligomer series manufactured by the company, "Vinyl carboxylate monomer" series manufactured by Shin-Etsu vinyl acetate (stock) Co., Ltd. Stock) series of "functional monomers" made by the company.

In addition, the following cyclic compounds can also be cited as radical polymerizable compounds. Examples of three-membered cyclic compounds: Ethylene described in Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Volume 17, page 3169 (1979) Cyclopropanes, Macromolecular Chemistry Rapid communication (Makromol. Chem. Rapid Commun.) Vol. 5, p. 63 (1984), 1-phenyl-2-vinylcyclopropanes, polymers Journal of Polymer Science Sci. Polym. Chem. Ed., Vol. 23, p. 1931 (1985) and Journal of Polymer Science Polymer Letters Edition, J. Polym.Sci.Polym.Lett.Ed.) Vol. 21, 2-phenyl-3-vinyl oxide listed in page 4331 (1983), Japanese Chemical Society draft spring lecture 50, page 1564 (1985) 2,3-divinyl ethylene oxide.

Examples of cyclic ketene acetals: Journal of Polymer Science and Polymer Chemistry (J. Polym. Sci. Polym. Chem. Ed.) Vol. 20, p. 3021 (1982) and Polymer Science Polymer Express Journal of J. Polym. Sci. Polym. Lett. Ed., Vol. 21, p. 373 (1983), 2-Methylene-1,3-dioxane, Polymer Advance (Polymer Preprints, Polym. Preprints) Vol. 34, 152 (1985) Dioxolane, Polymer Science Polymer Letters Edition (J. Polym. Sci. Polym. Lett. Ed.) 20 Volume, p. 361 (1982), Macromolecular Chemistry (Makromol. Chem.) Vol. 183, 1913 (1982) and Makromol. Chem. Vol. 186, p. 1543 (1985 ) Described in 2-methylene-4-phenyl-1,3-dioxane, macromolecules, vol. 15, p. 1711 (1982) -2-Methylene-1,3-dioxepane, 5,6-benzo-2-methylene described in Polym. Preprints Vol. 34, 154 (1985) -1,3-dioxane.

Further, as the polymerizable compound (B), there may be mentioned those described in the following literature. For example, Yamashita and others edited the "Crosslinker Handbook" (1981, Daiseisha) or Kato Kiyoshi's "UV · EB Hardening Handbook (Raw Materials)" (1985, Polymer Journal), radiation curing ( radtech) Research Society, Akamatsu Kiyoshi "Practical Techniques for New Photosensitive Resins" (1987, CMC), Endo Takeshi, "Precision of Thermosetting Polymers" (1986, CMC), Biyama Eiichiro, "Gathering "Ester Resin Handbook" (1988, Nikkan Kogyo Shimbun), Radiation Curing Research Society, "Application and Market of UV · EB Hardening Technology" (2002, CMC).

As the polymerizable compound (B), only one kind may be used, and two or more kinds may be used in an arbitrary ratio in order to improve desired characteristics.

As the polymerizable compound (B), in addition to the monomers, those called oligomers and prepolymers can be used. Specific examples include: "Ebecryl 230, 244, 245, 270, 280 / 15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, etc., manufactured by Daicel UCB. , 8800, 254, 264, 265, 294 / 35HD, 1259, 1264, 4866, 9260, 8210, 1290.1290K, 5129, 2000, 2001, 2002, 2100, KRM7222, KRM7735, 4842, 210, 215, 4827, 4849, 6700, 6700-20T, 204, 205, 6602, 220, 4450, 770, IRR567, 81, 84, 83, 80, 657, 800, 805, 808, 810, 812, 1657, 1810, IRR302, 450, 670, 830, 835, 870, 1830, 1870, 2870, IRR267, 813, IRR483, 811, 436, 438, 446, 505, 524, 525, 554W, 584, 586, 745, 767, 1701, 1755, 740 / 40TP, 600, 601, 604, 605, 607, 608, 609, 600 / 25TO, 616, 645, 648, 860, 1606, 1608, 1629, 1940, 2958, 2959, 3200, 3201, 3404, 3411, 3412, 3415, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3703, 3702, RDX63182, 6040, IRR419 ｣, Sado 瑪 (Sart "omer" company made "CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN971, CN972, CN9782, CN981, CN9893, CN991｣, BASF), "Blue Mo (BAMO) Laromer) EA81, LR8713, LR8765, LR8986, PE56F, PE44F, LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, LR8967, LR8981, LR8982, LR8992, LR9004, LR8956, LR8985, LR8987, UP35D, UA19T, LR9005, PO83F, PO33F, PO84F, PO94F, LR8863, LR8869, LR8889, LR8997, LR8996, LR9013, LR9019, PO9026V, PE9027V "," Photomer "3005, 3015, 3016, 3072, 3982, manufactured by Cognis 3215, 5010, 5429, 5430, 5432, 5662, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6572, 3660 '', manufactured by Gensang Industrial Co., Ltd. "Art-Resin" UN-9000HP, 9000PEP, 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T, 1200TPK, 6060PTM, 6060P, manufactured by Nippon Synthetic Chemical Co., Ltd. `` UV-6630B, 7000B, 7510B, 7461TE, 3000B, 3200B, 3210EA, 3310B, 3500BA, 3520TL, 3700B, 6100B, 6640B, 1400B, 1700B, 6300B, 7550B, 7605B, 7610B, 7620EA, 7630B, 7640B, 2000B , 2010B, 2250EA, 2750B "," Kayarad R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, C-0011 TCR-1234, ZFR-1122, UX-2201, UX-2301, UX3204, UX-3301, UX-4101, UX-6101, UX-7101, MAX-5101, MAX-5100, MAX-3510, UX-4101 '' Wait.

In terms of the hard coatability and processability of the composition for a decorative sheet, the polymerizable compound (B) is preferably 1 to 99 parts by weight out of a total of 100 parts by weight of the solid content of the composition for a decorative sheet. The amount used.

In addition, in terms of hard coatability and processability of the composition for a decorative sheet, the polymerizable compound (B) is preferably 20 to 400 parts by weight based on 100 parts by weight of the furan group-containing compound (A). , More preferably 50 parts by weight to 200 parts by weight.

Among the compounds that can be used as the polymerizable compound (B), a polyfunctional (meth) acrylate or a urethane (meth) is preferred from the viewpoints of hard coatability, processability, and cost. Acrylate.

<Polymerization Initiator (C)> Next, the polymerization initiator (C) is a compound that generates a radically active species that initiates a polymerization reaction by irradiation with active energy rays, and a previously known polymerization initiator can be used. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzylmethyl ketal, and 4- (2-hydroxyethoxy ) Phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl Propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane, oligomeric {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanyl) benzyl] phenyl} -2-methyl Acetophenones such as propane-1-one; benzoin such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoin-diphenyl-phosphine oxide Phosphines such as bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide; and methyl phenylglyoxylate, etc., but not limited to these. More specifically, they can be listed as: Irgacure 651, Irgacure 184, Irgacure 1173, Irgacure 500, Irgacure 1000, and Yanjia Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Ignacure ( Irgacure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01 (CGI124), CGI242 (BASF), Adeka Optomer N1414, Adeka Optomer N1717 (ADEKA), Esacure 1001M (Lan (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 61-9621, and Japanese Patent Application Laid-Open No. 60-60104. Triazine derivatives described in Japanese Patent Publication No. 60-60104. Gazette No. 59-1504 and Japanese Patent Laid-Open No. 61-243807 Of organic peroxides disclosed in the Japanese Patent, Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, and Diazonium Compound Publication of USP No. 3356453. The organic azide compounds described in USP No. 2848328, USP No. 2852379, and USP No. 2940853, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, and Japanese Patent Publication No. 38 -18015 and Japanese Patent Publication No. 45-9610, orthoquinonediazides, Japanese Patent Publication No. 55-39162, Japanese Patent Publication No. 59-140203, and "Macromolecules" "Volume 10, various onium compounds based on iodine compounds described in page 1307 (1977), azo compounds described in Japanese Patent Laid-Open No. 59-142205, Japanese Patent Laid-Open No. 1-54440, Europe Patent No. 109851, European Patent No. 126712, "Journal of Imaging Science (J.IMAG.SCI.)" Vol. 30, p. 174 (198 6 years), metal allene complex, titanocene described in Japanese Patent Application Laid-Open No. 61-151197, "COORDINATION CHEMISTRY REVIEW" Vol. 84, pages 85 to 85 Page 277 (1988) and Japanese Patent Application Laid-Open No. 2-182701, a transition metal complex containing a ruthenium and other metal, an aluminate complex described in Japanese Patent Laid-open No. 3-209477, and Japanese Patent Borate compounds described in Japanese Patent Application Laid-Open No. 2-157760, Japanese Patent Laid-Open Patent No. 55-127550, and Japanese Patent Laid-Open No. 60-202437 disclosed in 2,4,5-triarylimidazole dimer, Carbon bromide or organic halogen compounds described in Japanese Patent Laid-Open No. 59-107344, fluorene complex or oxo-fluorene complex described in Japanese Patent Laid-open No. 5-255347, Japanese Patent Laid-Open No. Sho 54- Aminoketone compounds described in Japanese Patent Laid-Open No. 99185, Japanese Patent Laid-Open No. 63-264560 and Japanese Patent Laid-Open No. 10-29977, Japanese Patent Laid-Open No. 2001-264530, Japanese Patent Laid-Open No. 2001-261761, Japan Patent Publication No. 2000-80068 Newspaper, Japanese Patent Laid-Open No. 2001-233842, Japanese Patent Laid-Open No. 2004-534797, Japanese Patent Laid-Open No. 2006-342166, Japanese Patent Laid-Open No. 2008-094770, Japanese Patent Laid-Open No. 2009-40762, Japanese Patent Laid-Open No. 2010-15025, Japanese Patent Laid-Open No. 2010-189279, Japanese Patent Laid-Open No. 2010-189280, Japanese Patent No. 2010-526846, Japanese Patent No. 2010-527338, Japanese Patent No. 2010-527339, USP3558309 Specification ( 1971), USP4202697 specification (1980), and oxime ester compounds described in Japanese Patent Laid-Open No. 61-24558.

In addition, as the polymerization initiator (C), a hydrogen abstraction type radical initiator may be used, and specifically, acetophenone, benzophenone, benzophenone, Michelin, thioxanthone, or anthracene Aromatic ketones, such as quinone, are not limited to these. In the technical field, these compounds usually use tertiary amines in combination. Specific examples include trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, and p-dimethylamine. And the like are not limited to these.

Among these polymerization initiators (C), acetophenones, phosphine oxides, and the like are preferably used.

These polymerization initiators (C) may be used singly or in combination of a plurality of kinds, and may be arbitrarily mixed and used according to the characteristics required for the reaction hardened product. Among 100 parts by weight of the total solid content of the composition for a decorative sheet, the use amount of these polymerization initiators (C) is preferably from 0.1 to 50 parts by weight, and more preferably from 1 to 20 parts by weight. Serving.

Furthermore, you may contain a sensitizer in the composition for decorative sheets of this invention. Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives or dibenzylidene acetone, 1,2-dione derivatives represented by benzophenone or camphorquinone, and benzoin. Derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, coumarinone derivatives Materials, polycyanine pigments such as cyanine derivatives, merocyanine derivatives, oxyalcohol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolinoline derivatives, Perylene derivatives, sulfonium derivatives, quatronium salt derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazine and porphyrazine Derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaline porphyrazine derivatives, naphthalocyanine derivatives, phthalocyanine derivatives, piperanium derivatives, thiopiperazine derivatives , Four-leaf clovelin derivatives, annulene derivatives, spiropyran derivatives, spiroxazine derivatives, Generation spiropyran derivatives, metal arene complexes, organic ruthenium complexes, which meters Le ketone derivative, imidazole derivative, but are not limited to the these.

Specific examples of sensitizers include "Pigment Handbook" edited by Shinoichi Ogawara et al. (1986, Kodansha), "Functional Pigment Chemistry" edited by Shinoichi Ogawara et al. (1981, CMC), and edited by Tadori Saburo, etc. The sensitizers described in "Special Functional Materials" (1986, CMC) are not limited to these. In addition, it may contain a sensitizer that shows absorption of light from the ultraviolet region to the near-infrared region. The sensitizer may be used alone, or two or more sensitizers may be contained in an arbitrary ratio.

The sensitizer is preferably used in an amount of 0.1 to 150 parts by weight, and more preferably used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the polymerization initiator (C).

In addition to the essential components of the composition for a decorative sheet of the present invention, a resin or a solvent may be added for the purpose of imparting coatability during the production of the decorative sheet or characteristics required as the composition for a decorative sheet for a decorative sheet. Or inorganic particles.

The resin that can be used in the composition for a decorative sheet of the present invention refers to a resin that does not contain a skeleton capable of undergoing radical polymerization in the molecule. In addition, these resins are those having a liquid or solid chemical form at normal temperature and pressure.

Examples of the resin having no backbone capable of radical polymerization in the molecule include alkyd resin, polyester resin, polyvinyl chloride, poly (meth) acrylate, epoxy resin, and polyurethane resin. , Cellulose derivatives (such as ethyl cellulose, cellulose acetate, nitro cellulose), vinyl chloride vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins , Butadiene-acrylonitrile copolymer-like synthetic rubber, etc., but are not limited to these. These resins may be used alone or in combination of two or more.

In terms of hard coatability or processability of the composition for a decorative sheet, these resins are preferably used in an amount of 1 to 99 parts by weight out of 100 parts by weight of the total solid content of the composition for a decorative sheet. . Meanwhile, it is preferably used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the polymerizable composition (B).

As the solvent that can be used in the composition for a decorative sheet of the present invention, a conventionally known organic solvent can be used, and specifically, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and Dibutanol, tertiary butanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene glycol), octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 2 -Ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, methylcyclohexanol, ethylene glycol monobutyl ether, diethylene glycol Monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol Alcohol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether Butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol phenyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2- Heptone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, γ-butyrolactone, isophor Ketones, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, isobutyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, ethylene glycol mono Butyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3 -Methoxybutyl acetate, n-propyl acetate, propylene glycol monomethyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, cyclohexanol acetate, propylene glycol monoethyl ether acetate, propylene Alcohol monobutyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol diacetate, 1,3-butanediol diacetate, glycerol triacetate, propylene glycol monomethyl ether propionate, 2, 2,4-trimethyl-1,3-pentanediol monoisobutyrate, diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether, ethylene glycol di Butyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, benzene, Toluene, ethylbenzene, o-xylene, m-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, second butylbenzene, third butylbenzene, ring Heptane, cyclohexane, pentane, hexane, octane, isohexane, isooctane, isononane, dicyclomethane, chloroform, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dioxane Chlorobenzene, 1,2,3-trichloropropane, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethylmethylene, N-methylpyrrolidone , 1,3-dimethyl-2-imidazolidone, and the like, but are not limited to these. These solvents may be used alone or in combination of two or more.

From the viewpoint of proper coating, the amount of the organic solvent used is preferably an amount such that the solid content concentration of the composition for a decorative sheet is 5 to 50% by weight. Outside the concentration range, problems such as a decrease in leveling property of the coating liquid, a decrease in smoothness of the coating film, and difficulty in controlling the thickness of the film are easily caused.

The inorganic particles that can be used in the composition for a decorative sheet of the present invention include silicon dioxide particles (colloidal silica, fumed silica, sedimentary silica, etc.), alumina particles, and zirconium particles. , Metal oxide particles such as titanium dioxide particles, zinc oxide particles, but are not limited to these.

From the viewpoint of crosslinkability, it is more preferable that the inorganic particles have a reactive functional group on the surface. Specific examples of the reactive functional group include vinyl such as vinyl, (meth) acryl, and allyl. The unsaturated bond, epoxy group, silanol group and the like are not limited thereto.

Examples of the shape of the inorganic particles include a sphere, an ellipsoid, a polyhedron, and a scaly shape. These shapes are preferably uniform and monolithic. The average particle diameter is preferably 0.005 μm to 0.5 μm, and more preferably 0.01 μm to 0.1 μm.

The composition for a decorative sheet of the present invention may further be used with dyes, organic and inorganic pigments, pigment dispersants, phosphine, phosphates, phosphites and other oxygen removing agents or reducing agents, mothproofing agents, anti-fading agents, etc., depending on the purpose. Halo inhibitors, fluorescent brighteners, surfactants, colorants, high-volume concrete, plasticizers, flame retardants, antioxidants, pigment precursors, ultraviolet absorbers, foaming agents, antifungal agents, antistatics Dispersants such as agents, magnetic bodies, resin-based dispersants, silane coupling agents, or storage stabilizers such as quaternary ammonium chloride, plasticizers, surface tension adjusters, lubricants, anti-blocking agents, light stabilizers, leveling agents Particles such as agents, defoamers, infrared absorbers, surfactants, thixotropic agents, antibacterial agents, silica, or other additives that impart various other properties, diluents, etc. are used in combination.

As described above, the composition for a decorative sheet of the present invention contains the furan group-containing compound (A), the polymerizable compound (B), and the initiator (C) as essential components. Moreover, the said composition for decorative sheets can be used suitably for manufacture of a molded article. It is preferable that the first step of applying a composition for a decorative sheet containing a furan group-containing compound (A), a polymerizable compound (B), and an initiator (C) on the substrate, and active energy by irradiation. The second step of curing is performed on a wire to form a decorative sheet, and the third step of forming is performed to produce a molded article.

The composition for a decorative sheet of the present invention undergoes a crosslinking reaction by reacting a polymerizable compound (B) with a radical generated from an initiator (C) at the stage of the second step. At this time, since the furanyl group in the compound (A) hardly reacts, it is considered to function as a so-called inert resin. Therefore, the furan group-containing compound (A) suppresses (controls) the degree of cross-linking of the entire photo-crosslinkable film, thereby obtaining a stretchable and flexible cross-linked film capable of coping with various molding processes.

The present invention is not limited to the manufacturing method or its action mechanism. After photocrosslinking (second step) using active energy rays, the furanyl group of the compound (A) and The photo-crosslinkable polymerizable group is thermally crosslinked, whereby a crosslinked film having an increased degree of crosslinking in the entire crosslinked film and having a hard coat property can be obtained. Here, the polymerizability possessed by the polymerizable compound (B) is based on the fact that 100% is not consumed in the technical field during photocrosslinking.

Thermal cross-linking of a furyl group and a polymerizable group is not particularly limited, and specifically a Diels-Alder reaction between a dienophile structure in the polymerizable group and a diene structure in the furan group . This reaction usually proceeds at room temperature or higher, but it is easier to proceed with heating. The reaction temperature is preferably 80 ° C or higher, and more preferably 100 ° C or higher.

In order to perform thermal crosslinking, the third step, that is, the forming process, is preferably a forming process accompanied by heating. The cross-linking can be sufficiently performed by utilizing the heat Diels-Alder reaction of the forming step, and the step of thermal cross-linking is not required in addition to the forming step. Therefore, from the viewpoint of productivity, Compared with other hot contacts, the advantages are high. The molding step is not limited to heating molding, and the manufacturing method of the present invention may further include a step of heating.

<Decorative sheet> The decorative sheet of the present invention is not particularly limited as long as it is formed by using the composition for a decorative sheet of the present invention for a cured film, and it may be provided on the substrate with a tackifier layer, a pattern layer, an adhesive layer, and a mold release as necessary. A layer, an antistatic layer, and the like are freely combined to constitute a layer. For example, the decorative sheet of the present invention is not limited, and preferable examples include a decorative sheet for lamination, a decorative sheet for transfer, and the like.

The decorative sheet for lamination is a decorative sheet having a structure in which a cured film using the composition for a decorative sheet of the present invention is provided on one side of a substrate, and a pattern layer or an adhesive layer is laminated on the other side, and It is decorated by sticking to the surface of the object to be decorated (plastic frame).

The decorative sheet for transfer is a decorative sheet in which a release layer is formed on one side of a substrate and a transfer layer is laminated on the release layer. Here, the transfer layer is a layer in which a cured film, a pattern layer, and an adhesive layer of the decorative sheet composition of the present invention are laminated in this order, and a tackifier layer, an antistatic layer, and ultraviolet absorption may be combined as necessary. Layers, low-reflection layers, near-infrared shielding layers, electromagnetic wave absorption layers, and the like, the layer configuration in the decorative sheet of the present invention is not limited to these.

In order to improve the adhesion between two different layers, the tackifier layer is, for example, a layer provided between the cured film and the adhesive layer or the pattern layer using the composition for a decorative sheet of the present invention. It is not limited to these, and may be set in any layer as needed.

As the tackifier layer, a two-liquid hardened urethane resin, a heat hardened urethane resin, a melamine resin, a cellulose ester resin, a chlorine-containing rubber resin, a vinyl chloride resin, and an acrylic resin are used. For resins, epoxy resins, and ethylene copolymer resins, gravure coating, gravure offset printing, anastomotic coating, rod coat, reverse gravure, and roll coating can be used. Method, corner coating method, surface coating method, die coating method, doctor blade coating method, lip coating method, spray coating method, spin coating method, bar coat method, slit coating method , Gravure printing, lithography, screen printing, transfer printing, sublimation transfer printing, inkjet printing and other known coating methods and printing methods.

The pattern layer is a layer necessary for obtaining the design required for the decorative sheet, and the pattern is not particularly limited, and examples thereof include wood grain, stone grain, cloth pattern, sand pattern, geometric pattern, text, Photos, illustrations, and other patterns can be freely combined. In addition, in addition to the lamination application, metal deposition may be performed on a part or the entire surface.

As an essential method for obtaining a pattern, a method of forming an ink containing a suitable colorant such as a pigment, a dye, and a binder resin using a known printing method is mentioned. Here, examples of the binder resin include polyethylene resin, polyester resin, polyacrylic resin, polyamide resin, polyvinyl acetal resin, cellulose resin, and alkyd resin. It is not limited to these. Examples of known printing methods include a gravure coating method, a gravure offset printing method, an anastomotic coating method, a bar coating method, a reverse gravure coating method, a roll coating method, and a notch wheel coating method. , Surface coating method, die coating method, doctor blade coating method, lip coating method, spray coating method, spin coating method, bar coating method, slit coating method, gravure printing, lithography, screen printing, transfer Print printing, sublimation transfer printing, inkjet printing, and the like are not limited to these.

The adhesive layer is a layer necessary for performing adhesion when transferring a transfer layer to a resin molded body. The adhesive layer may be the entire surface or a part to be transferred.

The adhesive layer can be used without particular limitation as long as it is a resin having adhesive properties. Preferred examples include acrylic resins, polystyrene resins, polyamide resins, indene resins, and chlorinated polyolefin resins. , Vinyl chloride-vinyl acetate copolymer resin, etc., may also be used in combination of more than one. Moreover, it is more preferable to select from a viewpoint of the affinity with a resin molded object.

The release layer is a layer necessary to release the transfer layer from the substrate, and examples thereof include melamine resin-based release agents, silicone resin-based release agents, fluororesin-based release agents, and cellulose resin-based release agents. Agents, urea resin-based release agents, polyolefin resin-based release agents, paraffin resin-based release agents, acrylic resin-based release agents, and the like, but are not limited to these. The mold release agent may optionally be used in combination of more than one kind.

The base material that can be used in the decorative sheet of the present invention is not particularly limited, and preferably includes polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyester, and polyolefin. , Epoxy resin, melamine resin, triacetam cellulose resin, Acrylonitrile Butadiene Styrene (ABS) resin, acryl-styrene (AS) resin, norbornene series Plastic materials such as resin and vinyl resin.

As a base material which can be used for a decorative sheet, the film shape or sheet shape using the casting method or the unstretched, biaxially stretched method from the said plastic raw material is more preferable, It is not limited to this manufacturing method. In addition, from the viewpoint of imparting adhesion, it is also possible to apply a primer coating such as a corona discharge treatment or a primer to the surface of the substrate.

The thickness of the substrate is not particularly limited, and it is desirable to select an optimal thickness according to the molding method.

As a method for manufacturing a decorative sheet, the composition for a decorative sheet of the present invention is formed by forming a uniform and predetermined film thickness on a base material, and then, if necessary, dried, and then subjected to light irradiation by irradiation with active energy rays. Formed together.

As the film formation method, a known printing or coating method can be used, and examples thereof include a gravure coating method, a gravure offset printing method, an anastomotic coating method, a bar coating method, a reverse gravure coating method, and a roll coating method. Method, corner coating method, surface coating method, die coating method, doctor blade coating method, lip coating method, spray coating method, spin coating method, bar coating method, slit coating method, gravure printing, Offset printing, screen printing, transfer printing, sublimation transfer printing, inkjet printing, and the like are not limited to these.

As described in the description of the solvent usable in the composition for a decorative sheet of the present invention, a solvent may be used from the viewpoint of coating properties. However, if the crosslinking by active energy ray irradiation is performed in a state where a large amount of solvent is contained in the coating film, the control of the crosslinking may be adversely affected. Therefore, it is desirable to dry the coating film to Removed to some extent. As a method of drying, vacuum drying using reduced pressure using a vacuum dryer or the like, drying using a convection oven (hot air dryer), an infrared oven, a hot plate or the like, or a combination thereof To implement. From a viewpoint of equipment cost or productivity, it is preferable to select baking, and it is more preferable to implement it by paying attention to the following conditions.

The baking conditions (temperature, time) can be appropriately selected according to the boiling point or film thickness used, and the drying performance of the oven. The composition for a decorative sheet of the present invention can perform the furanyl group in a high temperature region of 100 ° C or higher. The thermal crosslinking reaction is preferably 100 ° C or lower. In addition, since it can be baked for a long time and can also perform a thermal crosslinking reaction, it is preferably 10 minutes or less. If the thermal cross-linking reaction is performed at the pre-baking time, it will adversely affect the photo-crosslinking with the active energy ray, and the degree of cross-linking must be increased by more than necessary. As a result, the stretchability may be impaired, which is not good.

The film thickness of the composition for a decorative sheet of the present invention is not particularly limited, but from the viewpoint of moldability or hard coatability, it is preferably 1 μm to 100 μm, and more preferably 5 μm to 50 μm.

The active energy ray necessary for photocrosslinking the composition of the present invention refers to heat, ultraviolet rays, visible rays, near infrared rays, etc., electron beams, and the like. The polymerization initiator (C) generates radicals by these active energy rays, and the polymerizable compound (B) is polymerized to perform a crosslinking reaction. The light source provided by the active energy ray is preferably a light source having a dominant wavelength of light emission in a wavelength range from 250 nm to 450 nm. Examples of the light source having a dominant wavelength in the wavelength range from 250 nm to 450 nm include an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high-performance metal halide lamp, Xenon lamp, pulsed xenon lamp, heavy hydrogen lamp, fluorescent lamp, ND-YAG 3x wave laser, HE-CD laser, nitrogen laser, XE-CI excimer laser, XE-F standard Various light sources such as molecular lasers, semiconductor-excited solid-state lasers, and LED lamp light sources with emission wavelengths at 365 nm, 375 nm, and 385 nm. The definition of ultraviolet, visible light, and near-infrared in this specification is based on "Iwahikari Dictionary of Chemistry 4th Edition" (1987, Iwahami) compiled by Kubo Ryo and others.

As described above, the cured film can be laminated together with other necessary layers to be used as a decorative sheet. By using the composition for a decorative sheet of the present invention using the action mechanism, it has moldability capable of coping with various moldings. Furthermore, the decorative sheet of the present invention is further thermally cross-linked by using the heat at the time of molding to obtain a final hard coat property. The thermal cross-linking can be sufficiently performed by using heat applied during molding, and an additional baking step may be added as necessary. Examples

The following describes the present invention in more detail through examples. The following examples do not limit the scope of rights of the present invention in any way. In addition, each evaluation in an Example is based on the following method. In the examples, parts represent parts by weight, and% represents wt%.

<Weight average molecular weight> The weight average molecular weight was measured using Gel Permeation Chromatography (GPC) "GPC-8020" manufactured by Tosoh Corporation, and two SHODEX KF-806L and one KF were used for the column. -804L, one KF-802, using tetrahydrofuran as solvent. The weight average molecular weight is based on standard polystyrene.

(Embodiment 1) Embodiment using furan group-containing acrylic resin (A1) as furan group-containing compound (A)

<Production of furan group-containing acrylic resin (A1)> Synthesis Example 1: Compound (A) -1 A reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone. , And heated to 70 ° C in a nitrogen environment. Then, 30 parts by weight of a reactant of methacryloxyethyl isocyanate and furfuryl alcohol as monomer (a-1) and methyl methacrylate as monomer (a-2) were added dropwise over 2 hours. A monomer solution prepared by mixing 70 parts by weight of an ester and 3 parts by weight of azobisisobutyronitrile in advance. Furthermore, after performing a reaction at 70 ° C. for 1 hour, a step of adding 0.3 parts by weight of azobisbutyronitrile and performing the reaction for 1 hour was performed until the monomer addition rate became 98% or more, and then the mixture was cooled to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing compound (A) -1 having a solid content of 50%. The weight average molecular weight was 60,000.

Synthesis Examples 2 to 17: (A) -2 to (A) -17 The monomers (a-1) and (a-2) in Synthesis Example 1 were changed to the types and formulations shown in Table 1. The compound (A) having a weight-average molecular weight shown in Table 1 was obtained at a solid content of 50% by synthesizing the solid content concentration at the time of the reaction or the amount of the polymerization initiator appropriately, and synthesizing in the same manner. -2 to compound (A) -17.

[Table 1]

Synthesis Example 18: Compound (A) -18 A reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. Then, a monomer solution prepared by mixing 60 parts by weight of n-butyl acrylate, 40 parts by weight of 2-propenyloxyethyl isocyanate, and 3 parts by weight of azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after performing reaction at 70 degreeC for 1 hour, the process of adding 0.3 weight part of azobisbutyronitrile and performing reaction for 1 hour was performed until the monomer addition rate became 98% or more.

Next, after adding 0.1 part by weight of tin octoate, it took 2 hours to dropwise add 30 parts by weight of methyl ethyl ketone solution of 28 parts by weight of furfuryl alcohol. After further reacting at 70 ° C for 3 hours, the reaction solution was cooled to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing compound (A) -18 having a solid content of 50%. The weight average molecular weight was 30,000.

Synthesis Example 19: Compound (A) -19 A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 70 parts by weight of methyl ethyl ketone and 30 parts by weight of maleic anhydride, and the temperature was raised in a nitrogen atmosphere. To 70 ° C. Subsequently, a monomer solution prepared by mixing 50 parts by weight of methyl acrylate, 20 parts by weight of styrene, 20 parts by weight of methyl ethyl ketone, and 3 parts by weight of azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after performing reaction at 70 degreeC for 1 hour, the process of adding 0.3 weight part of azobisbutyronitrile and performing reaction for 1 hour was performed until the monomer addition rate became 98% or more.

Next, a solution of 28 parts by weight of furfurylamine and 30 parts by weight of methyl ethyl ketone was added dropwise over 2 hours. After further reacting at 70 ° C for 3 hours, the reaction solution was cooled to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing compound (A) -19 having a solid content of 50%. The weight average molecular weight was 25,000.

Synthesis Example 20: Compound (A) -20 A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 50 parts by weight of propylene glycol monomethyl ether acetate, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. Next, a monomer solution prepared by mixing 40 parts by weight of n-butyl methacrylate, 60 parts by weight of glycidyl methacrylate, and 1 part by weight of azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after performing reaction at 70 degreeC for 1 hour, the process of adding 0.1 weight part of azobisbutyronitrile and performing reaction for 1 hour was performed until the monomer addition rate became 98% or more, and it cooled to room temperature. Next, 47 parts by weight of 2-furancarboxylic acid and 1 part by weight of tetramethylammonium bromide were added, and after reacting at 100 ° C for 6 hours, the reaction solution was cooled to room temperature. Propylene glycol monomethyl ether acetate was added to obtain a furan group-containing compound (A) -20 having a solid content of 50%. The weight average molecular weight was 80,000.

Synthesis Example 21: Compound (A) -21 Aside from changing n-methyl methacrylate to n-butyl methacrylate in Synthesis Example 7, synthesis was carried out in the same manner to obtain a furanyl group containing 50% solids. Compound (A) -8. The weight average molecular weight was 23,000.

Synthesis Example 22: Compound (A) -22 Except changing n-methyl methacrylate to benzyl methacrylate in Synthesis Example 7, synthesis was carried out in the same manner to obtain a furanyl-containing compound having a solid content of 50%. Compound (A) -9. The weight average molecular weight was 34,000.

Synthesis Example 23: Compound (A) -23 Aside from changing n-methyl methacrylate to butyl acrylate in Synthesis Example 7, synthesis was carried out in the same manner to obtain a furan group-containing compound having a solid content of 50% ( A) -10. The weight average molecular weight was 26,000.

Synthesis Example of Compound for Comparative Example: Compound (1) A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. Then, a monomer solution prepared by mixing 50 parts by weight of n-methyl methacrylate, 50 parts by weight of glycidyl methacrylate, and 3 parts by weight of azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after performing a reaction at 70 ° C. for 1 hour, a step of adding 0.3 parts by weight of azobisbutyronitrile and performing the reaction for 1 hour was performed until the monomer addition rate became 98% or more, and then the mixture was cooled to room temperature. Methyl ethyl ketone was added to obtain a glycidyl group-containing compound (1) having a solid content of 50%. The weight average molecular weight was 25,000.

Synthesis Example of Compound for Comparative Example: Compound (2) A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. Then, a monomer solution prepared by mixing 80 parts by weight of n-butyl methacrylate, 20 parts by weight of hydroxyethyl methacrylate, and 3 parts by weight of azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after performing a reaction at 70 ° C. for 1 hour, a step of adding 0.3 parts by weight of azobisbutyronitrile and performing the reaction for 1 hour was performed until the monomer addition rate became 98% or more, and then the mixture was cooled to room temperature. Methyl ethyl ketone was added to obtain a hydroxyl-containing compound (2) having a solid content of 50%. The weight average molecular weight was 20,000.

Synthesis Example of Compound for Comparative Example: Compound (3) A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. Then, a monomer solution prepared by mixing 50 parts by weight of n-methyl methacrylate, 50 parts by weight of tetrahydrofurfuryl methacrylate, and 3 parts by weight of azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after reacting at 70 ° C. for 1 hour, a step of adding 0.15 parts by weight of azobisbutyronitrile and performing the reaction for 1 hour was performed until the monomer addition rate became 98% or more, and then the mixture was cooled to room temperature. Methyl ethyl ketone was added to obtain a tetrahydrofurfuryl-containing compound (3) having a solid content of 50%. The weight average molecular weight was 54,000.

<Production of the composition for a decorative sheet> Examples 1 to 41, Comparative Examples 1 to 5 were compounded in a weight part shown in Table 2 to compound (A) or compound (1) to compound (3) and polymerizability Compound (B) and polymerization initiator (C) to obtain a composition for a decorative sheet.

[Table 2]

The abbreviations in Table 2 are as follows. PET-30: "KAYARAD PET-30" (trifunctional acrylate) manufactured by Nippon Kayaku Co., Ltd. DPGDA: "DPGDA" (difunctional acrylate) manufactured by DAICEL ALLNEX DPPA: "SR399" (pentafunctional acrylate) manufactured by Sartomer DPHA: "A-DPH" (hexafunctional acrylate) manufactured by Shin Nakamura Chemical Industry Co., Ltd. UV-7650B: manufactured by Nippon Synthetic Chemical Co., Ltd. "Ultraviolet UV-7650B" (urethane acrylate oligomer) UA-3061: "UA-3061" (urethane acrylate) manufactured by Kyoeisha Chemical Co., Ltd. V-5500: DIC Corporation "UNIDIC V-5500" (epoxy acrylate) manufactured by 8KX-012C: "Aqrit 8KX-012C" (acrylic acrylate) manufactured by Daisen Fine Chemicals Co., Ltd. (EBECRYL) ) 1830: "EBECRYL 1830" (ester acrylate) manufactured by DAICEL ALLNEX Corporation Irg184: "Irg184" (photopolymerization starting from BASF) (formerly Japan Ciba) Initiator) Irg369 "Irg369" (photopolymerization initiator) manufactured by BASF (formerly Japan Ciba) TPO: "TPO" (photopolymerization initiator) manufactured by BASF (formerly Japan Ciba) SI- 100: "Sunaide SI-100" (thermal cationic polymerization generator) manufactured by Sunaide B-7982: "7982" (block isocyanate) manufactured by Baxenden MEK: methyl ethyl ketone PGMAC: propylene glycol monomethyl ether acetate

<Evaluation of hardenability> The compositions obtained in Examples 1 to 41 and Comparative Examples 1 to 5 were applied to a PET substrate (thickness 100 μm using a bar coater: "COSMOSHINE" manufactured by Toyo Textile Co., Ltd. ) A4100 ″), and dried with a hot air dryer at 80 ° C. for 1 minute, thereby obtaining a coating film having a film thickness of 5 μm. Using a belt conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² lamp), the coating film is irradiated with ultraviolet rays at a conveying speed of 10 m / min (cumulative light amount is 400 mJ / cm ² ) and then cured, and then By using a hot-air drier, heating was performed at 160 ° C. for 10 minutes, thereby obtaining a cured film that was assumed to have a coating film state after being thermoformed. Table 3 shows the results of the pencil film hardness test and abrasion resistance test of the cured film.

(Pencil Hardness Test) The hardness was determined in accordance with the test method of JIS-K-5600. In the case of assuming a decorative film, H or higher is a usable level.

(Scratch resistance test) Using # 0000 steel wool, a load of 500 g / cm ^{2 was} applied, and after 10 scratches were repeated, the presence or absence of the scratch was visually determined. In the case of assuming a decorative film, it is desirable that there is no flaw.

(Criterion criteria) 〇: No scratch △: Slightly scratched ×: Mostly scratched

<Extensibility Evaluation> The compositions obtained in Examples 1 to 41 and Comparative Examples 1 to 5 were applied to a polycarbonate substrate (thickness: 1 mm: manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a bar coater. "IUPILON-Sheet NF-2000"), followed by drying at 80 ° C for 1 minute using a hot air dryer to obtain a coating film having a thickness of 5 µm. Using a belt conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² lamp), the coating film was irradiated with ultraviolet rays at a conveying speed of 10 m / min (the cumulative light amount was 400 mJ / cm ² ) to obtain a cured film. Table 3 shows the results of the tensile test using the hardened film for a hypothetical forming process, and the results of performing a chemical resistance test for a specific application in the hypothetical automotive field.

(Extensibility Test) Each of the cured films was cut into a dumbbell shape according to JIS K6251-1 with the base material to obtain an extensibility test piece. Furthermore, the distance between the chucks is 4 cm, and the width is 1 cm. A tensile test was performed using "EZ-SX" manufactured by Shimadzu Corporation as a testing machine using this dumbbell piece.

Stretching conditions: The stretching was performed at a stretching speed of 100 mm / min at room temperature.

Elongation determination: Based on the distance between the chucks of 4 cm, confirm that the coating film is scratched when it is stretched to 2.8 cm equivalent to 70% of the original length, 3.2 cm equivalent to 80%, and 3.6 cm equivalent to 90% Is there. In the case of assuming a decorative film, it is desirable that there are no flaws at all, and further it is desirable that the film can be stretched longer.

(Criterion Criteria) 〇: No scratches △: About 10 to 20 scratches are generated ×: Many scratches are generated

(Chemical resistance test) After cutting each cured film together with the substrate to a 4 cm square, it was baked in a hot air dryer (160 ° C) for 10 minutes, and (ideally) thermally crosslinked, and A hardened film was obtained.

Apply 30 mg of sunscreen ("UltraSheer, SPF # 55" manufactured by Neutrogena) to the central part of the test piece, and cut and cut it into 3 cm square squares. PET film (50 μm thickness). The cream was uniformly rounded (1.8 cm in diameter) by applying a uniform load from the top of the PET film.

Under the following conditions, a hot air dryer (80 ° C, 12 hours) was left to stand, and after cooling to room temperature, the cream was rinsed with tap water, and the appearance of the surface of the test piece was visually observed to determine the chemical resistance.

Condition 1: The PET film, the test piece, and the cream are released. Condition 2: A state in which a PET film is not peeled, a test piece is sandwiched between a 10 cm square glass substrate (thickness 5 mm), and a load of 500 g is applied from the top of the glass substrate (closed state).

(Criterion criteria) 〇: No change in appearance (transparent) △: Slightly blurred ×: Whitening occurred (no transparency)

[table 3]

It can be seen that the present invention is compared with a system using thermal cross-linking using a thermal cation generator as in Comparative Example 1 and utilizing epoxy crosslinking, or a system using thermal cross-linking using block isocyanate and hydroxyl groups as in Comparative Example 2. The system (Examples 1 to 41) using thermal cross-linking of furan and acrylic acid is remarkably excellent in terms of the hard coatability (pencil hardness, scratch resistance) of the coating film. It is presumed that the difference in the reaction form used in the cross-linking reflects the hardenability, but the details are not clear.

In addition, the crosslinked film using the composition for a decorative sheet of the present invention was excellent in stretchability, and it was found that it has sufficient stretchability suitable for a decorative film.

As described above, the crosslinked film using the composition for a decorative sheet of the present invention has sufficient stretchability, but as shown in Examples 7 to 11, a furan group-containing compound ( A) As the weight average molecular weight increases, the extensibility can be further increased. When the weight average molecular weight is 100,000 or more, it is found that a particularly good result is imparted.

It can be seen that, as in Examples 21 to 38, a crosslinked film having sufficient stretchability and hard coatability in the preparation of various polymerizable compounds (B) or polymerization initiators (C) was obtained.

In addition, as in Comparative Example 3, when a polyfunctional acrylate is used alone, the degree of cross-linking becomes high. Therefore, hard coating properties such as pencil hardness and abrasion resistance are very good, but stretchability is very poor, making it difficult to adapt to decoration sheet. Furthermore, as in Comparative Example 4, when a urethane acrylate having a good balance between hardenability and extensibility is used alone, there is no problem in pencil hardness and the extensibility is improved as compared to Comparative Example 3. However, it is not sufficient, and the result is inferior compared with the case where the crosslinked composition of this invention is used. On the other hand, as in Comparative Example 5, when an acrylic resin having a tetrahydrofuran group is used, the hard coating property without a coating film and the stretchability are also slightly inferior, and therefore it is difficult to adapt to a decorative sheet. As described above, it means that if it is not a furanyl group, a cross-linking reaction is not performed, or its function as an inert component is inferior to that of a furanyl-containing compound.

Therefore, it is understood that the composition for a decorative sheet of the present invention is obtained by containing a furan group-containing compound (A), a polymer composition (B), and a polymerization initiator (C) to obtain a decorative film that can cope with various thermoforming processes. Crosslinked film with excellent stretchability and hard coatability.

<Vacuum Formability Test> The compositions obtained in Examples 1 to 41 and Comparative Examples 1 to 5 were applied to a polycarbonate substrate (thickness: 1 mm: manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a bar coater. "IUPILON-Sheet NF2000"), and dried with a hot air dryer at 80 ° C for 1 minute, thereby obtaining a coating film having a thickness of 5 μm. A belt conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² lamp) was used to irradiate the coating film with ultraviolet rays at a conveying speed of 10 m / min (cumulative light amount is 400 mJ / cm ² ) to obtain a decorative sheet. Next, the decorative sheet was set on a vacuum forming machine ("300X" manufactured by Singko Kogyo Co., Ltd.), and a cuboid (vertical: 65 mm, horizontal 65 mm, and height 25 mm) mold was used to perform heating and vacuum forming (heater temperature) 300 ° C, assuming a substrate surface temperature of 200 ° C). The appearance was observed, and the results of confirming the presence or absence of cracks or cracks in the decorative sheet accompanying molding are shown in Table 3.

(Criterion criteria) 〇: Transparent without cracks or cracks △: Partial cracks or cracks confirmed △: Cracks or cracks confirmed as a whole

A decorative sheet having a cured film formed from the composition for a decorative sheet of the present invention is a result of excellent moldability. Therefore, it turns out that it has moldability which can respond to various molding methods.

A decorative sheet having a cured film formed from the crosslinked composition for a decorative sheet of the present invention exhibits excellent chemical resistance (Examples 1 to 41, Comparative Examples 1 to 5: Condition 1). By being resistant to sunscreen, it can be preferably used for automotive applications, especially automotive interior parts and the like.

The decorative sheet having a cured film formed from the crosslinked composition for a decorative sheet of the present invention exhibits sufficient chemical resistance, and the furan group-containing polymer compound (A) in the crosslinked composition has a hydroxyl group. Furthermore, it shows good chemical resistance under severe conditions. (Example 12 to Example 17, Example 32 to Example 38: Condition 2)

(Embodiment 2) Embodiment using a low-molecular compound as a furanyl-containing compound (A)

Synthesis Example 1: Compound (A) -101 A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 60 parts by weight of methyl ethyl ketone, 50 parts by weight of furfuryl alcohol, and dibutyltin dilaurate. 0.1 part by weight, and after raising the temperature to 60 ° C. in a nitrogen atmosphere, a solution of 72 parts by weight of 2-propenyloxyethyl isocyanate and 50 parts by weight of methyl ethyl ketone was added dropwise over 2 hours. Then, after reacting at 60 ° C for 3 hours, the reaction liquid was cooled to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing compound (A) -101 having a solid content of 50%. The molecular weight of 239.10 was confirmed by mass analysis using EI-MS (Polaris Q manufactured by Thermo Corporation). (Theoretical value 239.08)

Synthesis Example 2: Compound (A) -102 A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 50 parts by weight of methyl ethyl ketone, 50 parts by weight of furfurylamine, and dibutyltin dilaurate. After 0.1 weight part was heated up to 60 ° C in a nitrogen atmosphere, 40 weight parts of a solution of 43 weight parts of 1,6-hexamethylene diisocyanate was added dropwise over 2 hours. Then, after reacting at 60 ° C for 3 hours, the reaction liquid was cooled to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing compound (A) -102 having a solid content of 50%. The molecular weight of 362.17 was confirmed by mass analysis using EI-MS (Polaris Q manufactured by Thermo). (Theoretical value 362.20)

Synthesis Example 3: Compound (A) -103 A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone, 50 parts by weight of furfurylamine, and dibutyltin dilaurate. 0.1 part by weight, and after raising the temperature to 60 ° C. in a nitrogen atmosphere, it took 2 hours to dropwise add 50 parts by weight of a solution of 85 parts by weight of trimerized 1,6-hexamethylene diisocyanate to methyl ethyl ketone. Then, after reacting at 60 ° C for 3 hours, the reaction liquid was cooled to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing compound (A) -103 having a solid content of 50%. The molecular weight of 798.40 was confirmed by mass analysis using EI-MS (Polaris Q manufactured by Thermo Corporation). (Theoretical value 798.38)

<Production of composition for decorative sheet> Examples 101 to 103 The compound (A), the polymerizable compound (B), and the polymerization initiator (C) were prepared by weight parts shown in Table 4 to obtain a decorative sheet.组合 物。 Composition. The abbreviations in Table 4 are the same as those in Table 2.

[Table 4]

<Evaluation of hardenability> The composition obtained in Examples 101 to 103 was applied to a PET substrate (thickness: 100 μm: "COSMOSHINE" manufactured by Toyo Textile Co., Ltd.) using a bar coater in the same manner as in Example 1. ) A4100 ″), and dried with a hot air dryer at 80 ° C. for 1 minute, thereby obtaining a coating film having a film thickness of 5 μm. Using a belt conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² lamp), the coating film is irradiated with ultraviolet rays at a conveying speed of 10 m / min (cumulative light amount is 400 mJ / cm ² ) and then cured, and then By using a hot-air drier, heating was performed at 160 ° C. for 10 minutes, thereby obtaining a cured film that was assumed to have a coating film state after being thermoformed. Table 5 shows the evaluation results of the cured film subjected to a pencil hardness test and an abrasion resistance test.

<Extensibility Evaluation> The composition for the decorative sheet obtained in Examples 101 to 103 was applied to a polycarbonate substrate (thickness: 1 mm: Mitsubishi Gas Chemical) using a bar coater in the same manner as in Example 1. "IUPILON-Sheet NF-2000" manufactured by the company was applied, and then dried at 80 ° C for 1 minute using a hot air dryer to obtain a coating film having a thickness of 5 μm. Using a belt conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² lamp), the coating film was irradiated with ultraviolet rays at a conveying speed of 10 m / min (the cumulative light amount was 400 mJ / cm ² ) to obtain a cured film. Table 5 shows the results of the following elongation test using this cured film under a hypothetical forming process.

Each cured film was cut into a dumbbell shape according to JIS K6251-1 with a base material to obtain a tensile test piece. Furthermore, the distance between the chucks is 4 cm, and the width is 1 cm. A tensile test was performed using "EZ-SX" manufactured by Shimadzu Corporation as a testing machine using this dumbbell piece.

Stretching conditions: The stretching was performed at a stretching speed of 100 mm / min at room temperature.

Elongation determination: Based on the distance between chucks of 4 cm, the presence or absence of scratches on the coating film when stretched to 2.8 cm equivalent to 70% of the original length and 3.2 cm equivalent to 80% was confirmed. In the case of assuming a decorative film, it is desirable that there is no flaw at all.

(Criterion Criteria) 〇: No scratches △: About 10 to 20 scratches are generated ×: Many scratches are generated

<Vacuum Formability Test> Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

[table 5]

As can be seen from Example 101 to Example 103 compared with Comparative Example 1 to Comparative Example 5 described in (Embodiment 1), even when a low-molecular compound is used as the furanyl-containing compound (A) Next, the composition for a decorative sheet of the present invention also exhibits good hard coatability, stretchability, and moldability. On the other hand, when further extensibility is required, it is possible to use polymer compounds such as a furan group-containing acrylic resin (A1) as the furan group-containing compound (A) compared to low-molecular compounds. Sex.

(Embodiment 3) Embodiment using furan group-containing urethane resin (A2) as furan group-containing compound (A)

<Production of a furan group-containing urethane resin (A2)> (Synthesis of a furan group-containing (meth) acrylic copolymer (a2) having at least one active hydrogen group at one terminal)

Synthesis Example 201: (meth) acrylic acid copolymer (a2) -1 A reaction container provided with a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone as a furan group-containing unit. 20 parts by weight of furfuryl methacrylate and 80 parts by weight of methyl methacrylate as a furan group-free monomer were heated at 50 ° C. Thereafter, 2-mercaptoethanol was added as a mercapto compound having an active hydrogen group, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. Thereafter, 0.1 part of a methyl ethyl ketone solution of 2,2'-azobis (2,4-dimethylvaleronitrile) was added in portions over 6.5 hours and allowed to react. After confirming that the conversion of the monomer was 98% or more, it was cooled to room temperature. Methyl ethyl ketone was added to obtain a (meth) acrylic copolymer (a2) -1 solution having a solid content of 50%. The weight average molecular weight was 51,000.

Synthesis Example 202 to Synthesis Example 212: (meth) acrylic copolymer (a2) -2 to (meth) acrylic copolymer (a2) -12 Comparative Synthesis Example 201 to Comparative Synthesis Example 202: (meth) acrylic copolymer (201), (meth) acrylic copolymer (202) The monomers in Synthesis Example 1 were changed to the types and formulations shown in Table 6, and the solid content concentration at the time of the reaction or the amount of the polymerization initiator was appropriately adjusted. (Meth) acrylic copolymer (a2) -2 to (meth) acrylic copolymer having a weight-average molecular weight shown in Table 6 was obtained from a solution having a solid content of 50% by synthesizing in the same manner. (A2) -12, (meth) acrylic copolymer (201), (meth) acrylic copolymer (202).

[TABLE 6]

Synthesis Example 213: Furan group-containing urethane resin (A2) -1 A (meth) acrylic copolymer (a2) -1 was charged into a reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube. 200 parts by weight of a methyl ethyl ketone solution (50% solids content), 1.8 parts by weight of hexamethylene diisocyanate (HDI), and 0.01 part by weight of dibutyltin dilaurate as a catalyst. It was heated to 60 ° C. for 3 hours in this state (NCO / active hydrogen ratio = 1.05). After the disappearance of the isocyanate group was confirmed by IR, it was left to cool to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing urethane resin (A2) -1 solution having a solid content of 40%. The weight average molecular weight was 123,000.

Synthesis Example 214 to Synthesis Example 224: Furan group-containing urethane resin (A2) -2 to Furan group-containing urethane resin (A2) -12 Synthesis Example 202 to Synthesis Example 212 ( The combination of the (meth) acrylic copolymer (a2) -2 to (meth) acrylic copolymer (a2) -12 and the raw materials shown in Table 7 was set to the NCO / active hydrogen ratio by the method according to Synthesis Example 13. = 1.05 to obtain a furan group-containing urethane resin (A2) -2 solution to a urethane resin (A2) -12 solution at a molecular weight shown in Table 7.

Synthesis Example 225: Furan group-containing urethane resin (A2) -13 A reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with (meth) acrylic copolymer (a2)- 500 parts by weight of a methyl ethyl ketone solution (50% solids content), 0.9 parts by weight of hexamethylene diisocyanate (HDI), and 0.01 parts by weight of dibutyltin dilaurate as a catalyst, and the temperature was raised in a nitrogen atmosphere Heat to 60 ° C for 3 hours under this condition (NCO / active hydrogen ratio = 2.1)

0.21 parts by weight of 1,4-butanediol was added, and the mixture was further heated and stirred for 3 hours. After the disappearance of the isocyanate group was confirmed by IR, it was left to cool to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing urethane resin (A2) -13 solution having a solid content of 40%. The weight average molecular weight was 141,000.

Synthesis Examples 226 to 235: Furan group-containing urethane resin (A2) -14 to Furan group-containing urethane resin (A2) -23 were changed to the raw materials shown in Table 7, Otherwise, synthesis was carried out according to the method of Example 25, whereby furan group-containing urethane resin (A2) -14 solution to urethane resin (A2) -23 solution was obtained with the molecular weight shown in Table 7. .

Synthesis Example 236: Furan group-containing urethane resin (A2) -24 was placed in a reaction vessel equipped with a stirrer, thermometer, reflux cooler, and gas introduction tube, and P-2010 Kuraray polyol 1.4 was charged. Parts by weight, 0.6 parts by weight of XDI, and 0.01 parts by weight of dibutyltin dilaurate as a catalyst were heated to 60 ° C. in a nitrogen atmosphere, and heated and stirred in this state for 3 hours (residual NCO / (XH) = 1). Further, 400 parts by weight of a methyl ethyl ketone solution (solid content: 50%) of the (meth) acrylic copolymer (a2) -10 was added, and the mixture was heated and stirred for 3 hours. After the disappearance of the isocyanate group was confirmed by IR, it was left to cool to room temperature. Methyl ethyl ketone was added to obtain a furan group-containing urethane resin (A2) -24 solution having a solid content of 40%. The weight average molecular weight was 184,000.

Synthesis Example 237: Furan group-containing urethane resin (A2) -25 was changed to the raw materials shown in Table 7, and was synthesized by the method according to Synthesis Example 36, whereby the molecular weights shown in Table 7 were obtained. A furanyl-containing urethane resin (A2) -25 solution was obtained.

Comparative Synthesis Example 203, Comparative Synthesis Example 204: Furan group-free urethane resin (203), Furan group-free urethane resin (204) In addition to using a (meth) acrylic copolymer (1 ) Or (meth) acrylic copolymer (2) instead of (meth) acrylic copolymer (a2), and synthesized by the method according to Synthesis Example 13 to obtain a furan group-containing Urethane resin (203) and furan group-containing urethane resin (204).

Comparative Synthesis Example 205, Comparative Synthesis Example 206: Furan group-free urethane resin (205), Furan group-free urethane resin (206) Except the use of (meth) acrylic copolymer (201 ) Or (meth) acrylic copolymer (202) instead of (meth) acrylic copolymer (a2), and synthesized in accordance with the method of Synthesis Example 225, thereby obtaining a furan-free group at a molecular weight shown in Table 7 Urethane resin (205), furan-free urethane resin (206).

[TABLE 7]

The abbreviations in Table 7 are as follows. HDI: hexamethylene diisocyanate MDI: diphenylmethane diisocyanate IPDI: isophorone diisocyanate XDI: m-xylylene diisocyanate TDI: toluene diisocyanate P2010: "P2010" (polyester poly Alcohol, the number of functional groups is 2, the hydroxyl value is 56, the molecular weight is 2000) PTG-2000SN: "PTG-2000SN" (polyether polyol, the number of functional groups is 2, the hydroxyl value is 57 and the molecular weight is 2000) manufactured by Hodogaya Chemical ) G-2000: "G-2000" (polybutadiene-based polyol, functional group number 2, hydroxyl value: 45) manufactured by Japan's Chanda Co., Ltd. NL2000B: "BENEBiOL" NL2000B manufactured by Mitsubishi Chemical Corporation "(Polycarbonate diol, the number of functional groups is 2, the hydroxyl value is 56)

Synthesis Example 207 of Compound for Comparative Example: Compound (207) A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. Then, a monomer solution prepared by mixing 50 parts by weight of n-methyl methacrylate, 50 parts by weight of glycidyl methacrylate, and 3 parts by weight of azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after performing a reaction at 70 ° C. for 1 hour, a step of adding 0.3 parts by weight of azobisbutyronitrile and performing the reaction for 1 hour was performed until the monomer addition rate became 98% or more, and then the mixture was cooled to room temperature. Methyl ethyl ketone was added to obtain a glycidyl group-containing compound (7) having a solid content of 50%. The weight average molecular weight was 25,000.

Synthesis Example 208 of Compound for Comparative Example: Compound (208) A reaction vessel including a stirrer, a thermometer, a reflux cooler, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. Then, a monomer solution prepared by mixing 80 parts by weight of n-butyl methacrylate, 20 parts by weight of hydroxyethyl methacrylate, and 3 parts by weight of azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after performing a reaction at 70 ° C. for 1 hour, a step of adding 0.3 parts by weight of azobisbutyronitrile and performing the reaction for 1 hour was performed until the monomer addition rate became 98% or more, and then the mixture was cooled to room temperature. Methyl ethyl ketone was added to obtain a hydroxyl-containing compound (8) having a solid content of 50%. The weight average molecular weight was 20,000.

<Production of composition for decorative sheet> Examples 201 to 230, Comparative Example 201 to Comparative Example 208 A furan group-containing urethane resin (A2) was prepared in a weight part shown in Table 8 and furan-free Group urethane resin (203) to furan group-free urethane resin (206) or compound (207) to compound (208), polymerizable compound (B), and polymerization initiator (C ) To obtain a composition for a decorative sheet.

[TABLE 8]

The abbreviations in Table 8 are as follows. (Polymerizable compound (B)) PET-30: "KAYARAD PET-30" (trifunctional acrylate) manufactured by Nippon Kayaku Co., Ltd. DPGDA: "DAICEL ALLNEX" DPGDA "(difunctional acrylate) DPPA:" SR399 "(pentafunctional acrylate) made by Sartomer DPHA:" A-DPH "(hexafunctional acrylate) made by Shin Nakamura Chemical Industry Co., Ltd. UV- 7650B: "Ultraviolet UV-7650B" (urethane acrylate oligomer) manufactured by Nippon Synthetic Chemical Co., Ltd. UA-3061: "UA-3061" (urethane acrylic acid) manufactured by Kyoeisha Chemical Co., Ltd. Ester) V-5500: "UNIDIC V-5500" (epoxy acrylate) manufactured by DIC Corporation 8KX-012C: "Aqrit 8KX-012C" (acrylic acid) manufactured by Dacheng Fine Chemicals Co., Ltd. Acrylate) EBCRYL 1830: "EBECRYL 1830" (Ester Acrylate) (Ester Acrylate) (Starter (C)) manufactured by DAICEL ALLNEX Irg184: BASF (BASF) (Formerly Ciba) "Irg184" (photopolymerization initiator) manufactured by Irg369: "Irg369" (photopolymerization initiator) manufactured by BASF (formerly Japan Ciba) TPO: BASF (formerly Japan Ciba) "TPO" (photopolymerization initiator) (thermal crosslinker) manufactured by SI-100: "Sunaide SI-100" (thermal cationic polymerization generator) manufactured by Sunaide Corporation B -7982: "7982" (block isocyanate) (solvent) manufactured by Baxenden Corporation MEK: methyl ethyl ketone PGMAC: propylene glycol monomethyl ether acetate

<Evaluation of hardenability> The composition obtained in Examples 201 to 230 and Comparative Examples 201 to 208 was applied to a PET substrate (thickness: 100 μm: Toyo) using a bar coater in the same manner as in Example 1. "COSMOSHINE A4100" manufactured by the textile company was applied, and then dried with a hot air dryer at 80 ° C for 1 minute, thereby obtaining a coating film having a thickness of 5 μm. Using a belt conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² lamp), the coating film was irradiated with ultraviolet rays (cumulative light amount is 400 mJ / cm ² ) at a conveying speed of 10 m / min, and then hot air was used. The dryer was heated at 160 ° C. for 10 minutes, thereby obtaining a cured film that was assumed to have a coating film state after being thermoformed. Table 9 shows the results of the pencil hardness test and the scratch resistance test of the cured film.

(Pencil Hardness Test) In the same manner as in Example 1, the hardness was determined in accordance with the test method of JIS-K-5600. In the case of assuming a decorative film, H or higher is a usable level.

(Abrasion resistance test) As in Example 1, using # 0000 steel wool, a load of 500 g / cm ^{2 was} applied, and after abrasion was repeated 10 times, the presence or absence of a flaw was determined visually. In the case of assuming a decorative film, it is desirable that there is no flaw.

(Criterion criteria) 〇: No scratch △: Slightly scratched ×: Mostly scratched

<Extensibility Evaluation> As in Example 1, a polycarbonate substrate (thickness: 1 mm: composition obtained in Examples 201 to 230 and Comparative Examples 201 to 208) was applied to a polycarbonate substrate using a bar coater. After applying "IUPILON-Sheet NF-2000" manufactured by Mitsubishi Gas Chemical Co., Ltd., it was dried at 80 ° C for 1 minute using a hot air dryer to obtain a coating film having a thickness of 5 μm. . Using a belt conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² lamp), the coating film was irradiated with ultraviolet rays at a conveying speed of 10 m / min (the cumulative light amount was 400 mJ / cm ² ) to obtain a cured film. Table 9 shows the results of the tensile test using the hardened film for a hypothetical molding process, and the results of performing a chemical resistance test for a specific application in the automotive field.

(Extensibility Test) Each of the cured films was cut into a dumbbell shape according to JIS K6251-1 with the base material to obtain an extensibility test piece. Furthermore, the distance between the chucks is 4 cm, and the width is 1 cm. A tensile test was performed using "EZ-SX" manufactured by Shimadzu Corporation as a testing machine using this dumbbell piece.

Stretching conditions: The stretching was performed at a stretching speed of 100 mm / min at room temperature.

Elongation determination: Based on the distance between chucks of 4 cm, the presence or absence of scratches on the coating film when stretched to 2.8 cm equivalent to 70% of the original length and 3.2 cm equivalent to 80% was confirmed. In the case of assuming a decorative film, it is desirable that there are no flaws at all, and further it is desirable that the film can be stretched longer.

(Criterion Criteria) 〇: No scratches △: About 10 to 20 scratches are generated ×: Many scratches are generated

(Chemical resistance test) After cutting each cured film together with the substrate to a 4 cm square, it was baked in a hot air dryer (160 ° C) for 10 minutes, and (ideally) thermally crosslinked, and A hardened film was obtained.

Apply 30 mg of sunscreen ("UltraSheer, SPF # 55" manufactured by Neutrogena) to the central part of the test piece, and cut and cut it into 3 cm square squares. PET film (50 μm thickness). The cream was uniformly rounded (1.8 cm in diameter) by applying a uniform load from the top of the PET film.

Under the following conditions, a hot air dryer (80 ° C, 12 hours) was left to stand, and after cooling to room temperature, the cream was rinsed with tap water, and the appearance of the surface of the test piece was visually observed to determine the chemical resistance.

Condition: Peeling off the PET film, test piece and cream.

(Criterion criteria) 〇: No change in appearance (transparent) △: Slightly blurred ×: Whitening occurred (no transparency)

[TABLE 9]

It can be seen that the composition for a decorative sheet using the furan-group-containing urethane resin of the present invention is the same as that of Examples 201 to 230, compared to the use of furan-free aminomethyl in Comparative Examples 201 to 204. The composition for an ester resin decorative sheet can have excellent hard coatability (pencil hardness, abrasion resistance) and stretchability in the physical properties of the obtained crosslinked film.

It can be seen that the present invention is compared with a system using thermal crosslinking using a thermal cation generator such as Comparative Example 205 and utilizing epoxy crosslinking, or a system using thermal crosslinking using block isocyanate and hydroxyl groups as Comparative Example 206. The system (Example 201 to Example 230) using thermal cross-linking of furan and acrylic acid is remarkably excellent in terms of the hard coatability (pencil hardness, scratch resistance) of the coating film. It is presumed that the difference in the reaction form used in the cross-linking reflects the hardenability, but the details are not clear.

In addition, the crosslinked film using the composition for a decorative sheet of the present invention was excellent in stretchability, and it was found that it has sufficient stretchability suitable for a decorative film.

It can be seen that, as in Examples 226 to 230, a crosslinked film having sufficient stretchability and hard coatability can be obtained in the preparation of various polymerizable compounds (B) or polymerization initiators (C).

In addition, as in Comparative Example 207, when a polyfunctional acrylate is used alone, the degree of cross-linking becomes high, so the hard coat properties such as pencil hardness and abrasion resistance are very good, and the stretchability is very poor, so it is difficult to adapt to decorative sheets . Furthermore, as in Comparative Example 8, when a urethane acrylate having a good balance between hardenability and extensibility is used alone, there is no problem in pencil hardness, and the extensibility is also better than that in Comparative Example 7. However, it is not sufficient, and the result is inferior compared with the case where the crosslinked composition of this invention is used.

Therefore, it is understood that the composition for a decorative sheet of the present invention is obtained by containing a furan group-containing urethane resin (A2), a polymerization composition (B), and a polymerization initiator (C) to obtain a composition that can cope with various conditions. A crosslinked film of a thermoformed decorative film that has both excellent stretchability and hard coatability.

<Vacuum Formability Test> The compositions obtained in Examples 201 to 230 and Comparative Examples 201 to 208 were applied to a polycarbonate substrate (thickness: 1 mm: manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a bar coater. "IUPILON-Sheet NF-2000"), and dried at 80 ° C for 1 minute using a hot air dryer to obtain a coating film having a thickness of 5 μm. A belt conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² lamp) was used to irradiate the coating film with ultraviolet rays at a conveying speed of 10 m / min (cumulative light amount is 400 mJ / cm ² ) to obtain a decorative sheet.

Next, the decorative sheet was set on a vacuum forming machine ("300X" manufactured by Singko Kogyo Co., Ltd.), and a cuboid (vertical: 65 mm, horizontal 65 mm, and height 25 mm) mold was used to perform heating and vacuum forming (heater temperature). 300 ° C, assuming a substrate surface temperature of 200 ° C). The appearance was observed, and the results of confirming the presence or absence of cracks or cracks in the decorative sheet accompanying molding are shown in Table 9.

(Criterion criteria) 〇: Transparent without cracks or cracks △: Partial cracks or cracks confirmed △: Cracks or cracks confirmed as a whole

A decorative sheet having a cured film formed from the composition for a decorative sheet of the present invention is a result of excellent moldability. Therefore, it turns out that it has moldability which can respond to various molding methods.

The decorative sheet having a cured film formed from the crosslinked composition for a decorative sheet of the present invention exhibits excellent chemical resistance (Examples 1 to 30, Comparative Examples 1 to 8). By being resistant to sunscreen, it can be preferably used for automotive applications, especially automotive interior parts and the like.

The crosslinked film obtained from the composition for a decorative sheet of the present invention coexists with a high level of moldability and hard coatability. Therefore, by using the composition of the present invention, an excellent decorative film that can cope with various molding methods can be obtained.

The use of the decorative film is not particularly limited as long as it is a plastic decoration. For example, it can be used in mobile phones such as smart phones, electronic devices such as notebook personal computers including mobile personal computers, automotive interior and exterior parts, and building materials. Used in the field.

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Claims (12)

A composition for a decorative sheet includes a furanyl-containing compound (A), a polymerizable compound (B), and a polymerization initiator (C). The composition for a decorative sheet according to item 1 of the scope of patent application, wherein the furan group-containing compound (A) is a polymer having a weight average molecular weight of 1,000 or more. The composition for a decorative sheet according to claim 1 or claim 2, wherein the furanyl-containing compound (A) is a furanyl-containing (meth) acrylic resin (A1). The composition for a decorative sheet according to claim 1 or claim 2, wherein the furanyl-containing compound (A) is a polymer of a monomer containing a furanyl-containing monomer (a1-1). The composition for a decorative sheet according to item 3 of the scope of patent application, wherein the monomer (a1-1) is furfuryl methacrylate. The composition for a decorative sheet according to item 1 of the scope of patent application, wherein the furan group-containing compound (A) is a furan group-containing urethane resin (A2). The composition for a decorative sheet according to item 6 of the scope of patent application, wherein the furan group-containing urethane resin (A2) is a furan group-containing (meth) acrylic acid having at least one active hydrogen group at a single terminal. Reactant of copolymer (a2) and polyisocyanate (b2). The composition for a decorative sheet according to item 6 of the scope of patent application, wherein the furan group-containing urethane resin (A2) is a furan group-containing (meth) acrylic acid having at least one active hydrogen group at a single terminal. Copolymer (a2), reactant with polyisocyanate (b2) and polyol (c2) (except (a2)). The composition for a decorative sheet according to item 7 or item 8 of the scope of patent application, wherein the (meth) acrylic copolymer (a2) is a furan-group-containing monomer, a furan-group-free monomer, and has Copolymer of at least one active hydrogen-based thiol compound. A decorative sheet having a cured film formed on the substrate of the composition for a decorative sheet according to any one of claims 1 to 9. A formed article is formed from a decorative sheet according to item 10 of the scope of patent application. A method for manufacturing a molded product, comprising: a first step of applying the composition for a decorative sheet according to any one of claims 1 to 9 on a substrate; and irradiating active energy The second step of hardening; and the third step of forming.