JP6330123B2 - Composition for decorative sheet, decorative sheet, and molded product - Google Patents

Description

  The present invention relates to a composition for a decorative sheet, a decorative sheet, and a molded product.

  Conventionally, the surface of plastic casings used in various fields such as mobile phones such as smartphones, notebook computers including mobile PCs, interior and exterior parts for automobiles, and building materials are printed and painted. High designability (design, texture, luxury such as appearance) is given (decorated) by this processing. In addition, a protective layer (hard coat layer) is often provided for the purpose of protecting such a decorative body and the soft plastic itself.

  In recent years, in manufacturing for decorating such plastics, in order to cope with environmental burden reduction, productivity and cost, and complicated product shapes, film and sheet bonding / bonding can be performed directly from the conventional case. Replacement with transfer decoration technology is progressing. That is, a decorative sheet in which the above-described design layer for providing design properties, a hard coat layer for protection, and the like are laminated is bonded to a base material such as plastic. Conventional decorative sheets may be constructed by laminating a single layer or multiple layers on a sheet substrate, but the outermost layer after the final molding process is a protective layer (hard coat layer) Has been.

A decorative sheet with a protective layer on such a film or sheet-like substrate is molded by various methods such as vacuum molding, pressure molding, membrane press molding, in-mold molding, insert molding, overlay vacuum molding, etc. The In any case, the decorative sheet is stretched or bent in accordance with the shape of the object to be decorated (plastic casing) or the shape of the mold.
In the molding process, heat of several tens to several hundreds is generally applied to the sheet. The main reason is to increase the stretchability of the decorative sheet by heating the decorative sheet necessary for the process and the object to be decorated (plastic casing) or by heating. However, when the hard coat layer does not have sufficient flexibility and stretchability, whitening, scratches, cracks, peeling, and the like occur, and the design is greatly impaired (formability is poor). (Patent Document 1)

As a method generally used for forming a hard coat layer on a film or sheet-like substrate, for example, the invention described in Patent Document 2 forms a photosensitive coating composition on a film, The hard coat layer is formed by photocuring (crosslinking) by irradiation. By using a polyfunctional photocrosslinkable monomer in the composition, hard coat properties are obtained by improving the degree of crosslinking after light irradiation. However, highly cross-linked films are hard and brittle and therefore lack flexibility and extensibility. For this reason, it is extremely difficult to cope with processing such as bending and stretching performed in accordance with various product shapes in the decorative sheet molding process by the conventional technique for obtaining a hard coat layer.

  In response to the above extremely high technical problem, a material having both curability and flexibility like a urethane acrylate oligomer has been proposed, but at a very high level required for a decorative film in recent years, It is difficult to achieve both hard coat properties and flexibility / extension.

  Moreover, a technical subject is also avoided by the device of the whole manufacturing process including a decorating sheet and a shaping | molding process using the same. For example, Patent Document 3 proposes a method for ensuring the extensibility necessary for molding by semi-curing the photosensitive composition with active energy rays and obtaining a hard coat layer by further irradiating active energy rays after molding. However, it is difficult to control the light irradiation conditions to obtain a semi-cured state, and the difference between the UV irradiator and the lamp is greatly affected, and the active energy ray irradiation device necessary for post-photocrosslinking is burdened on the processor. The disadvantages are large. Further, Patent Document 4 proposes that hard coating properties are improved by performing thermal crosslinking as post-processing after molding by using a composition that can be thermally crosslinked in the photosensitive composition. In order to obtain sufficient hard coat properties, it takes a long time for thermal crosslinking, and there are significant disadvantages such as burdening a processor with a heating device necessary for thermal crosslinking.

In any case, control of the degree of cross-linking of the cross-linked film to cope with the molding process is the key, but the technical difficulty of cross-linking control is high, and there is a great disadvantage in that the process becomes complicated.
Therefore, in the prior art, the hard coat properties are lost as a result of creating a soft cross-linked film in order to achieve moldability. Difficult to get. Therefore, the current situation is that it is handled in a complicated manner.

Accordingly, there is a need for a crosslinkable composition that achieves both hard coat properties and moldability necessary for a decorative sheet and that enables a molded product to be obtained through a simple process.

Japanese Patent No. 5704929 Patent No. 580222 Japanese Patent Laying-Open No. 2015-54886 Patent No. 5389904

  The present invention has been made in view of the above-described present situation, and is for obtaining a protective layer having both a high level of hard coat properties and moldability necessary for an excellent decorative sheet capable of being applied to various molding processes. The object is to provide a novel composition. Furthermore, it aims at provision of the composition for obtaining the decorating sheet which does not require processes, such as photocuring, after a shaping | molding process.

As a result of intensive studies, the inventors have found that the above problem can be solved by including a compound containing a furyl group in the crosslinkable composition, a polymerizable composition and an initiator, and the present invention has been completed. It came to do.
That is, the present invention is a decorative sheet for molding having a cured film obtained by curing a decorative sheet composition with active energy rays on a plastic substrate, wherein the decorative sheet composition is a frill. The present invention relates to a decorative sheet for molding containing a compound (A) containing a group, a polymerizable compound (B), and an active energy ray polymerization initiator (C).

The present invention also relates to the decorative sheet for molding, wherein the compound (A) containing a furyl group is a polymer having a weight average molecular weight of 1000 or more.

Further, the present invention provides the molding decoration , wherein the furyl group-containing compound (A) is a monomeric acrylic polymer containing a furyl group-containing monomer (a-1). Regarding the sheet .
Further, the present invention is characterized in that the compound (A) containing a furyl group is a polymer of a monomer containing a monomer (a-1) containing a furyl group and a monomer having a hydroxyl group. The present invention relates to the decorative sheet for molding .

The present invention also relates to the decorative sheet for molding, wherein the monomer (a-1) is furfuryl methacrylate.
In the present invention, the compound (A) containing a furyl group is a monomer containing a furyl group, a reaction product of an isocyanate and an alcohol containing a furyl group, a reaction product of an isocyanate and an amine containing a furyl group, or The decorative sheet for molding is a reaction product of glycidyl (meth) acrylate and an alcohol or amine containing a furyl group.

  The present invention also relates to a molded product formed from the decorative sheet.

  Moreover, this invention is a 1st process of apply | coating to a base material the composition for decorating sheets containing the compound (A) containing a furyl group, a polymeric compound (B), and an initiator (C). And a second process for curing by irradiating active energy rays, and a third process for molding, and a method for producing a molded product.

  By using the crosslinked composition of the present invention as a protective layer for a decorative sheet, an excellent decorative sheet that can be used for various molding processes could be provided.

  The present invention is described in detail below. In the present invention, (meth) acrylate means acrylate and / or methacrylate, and (meth) auric acid means acrylic acid and / or methacrylic acid. Moreover, a furyl group means the group remove | excluding one hydrogen atom from furan and its substituent.

  In addition, in this specification, hard coat properties include pencil hardness, scratch resistance, chemical resistance, etc. In addition to these, the state of the coating changes with various physical and chemical external stimuli. It means not to cause. Moreover, moldability means that the problem which impairs designability, such as whitening, a crack, a crack, peeling, by a shaping | molding process does not generate | occur | produce.

<Composition for decorative sheet>
The composition for a decorative sheet of the present invention contains a compound (A) containing a furyl group, a polymerizable compound (B), and a polymerization initiator (C) as essential components.

<Compound containing furyl group (A)>
The compound (A) containing a furyl group is a compound containing at least one furyl group in the molecule, and may be a low molecular compound or a polymer compound.
The compound (A) containing a furyl group is 1 to 99 parts by weight in a total of 100 parts by weight of the solid content of the decorative sheet composition from the viewpoint of hard coat properties and processability of the decorative sheet composition. It is preferable to use in an amount.

  Low molecular weight compounds include compounds containing furyl groups, compounds obtained by reacting (polyhydric) isocyanates with (polyhydric) alcohols containing furyl groups, and amines containing (polyhydric) isocyanates and furyl groups. Examples include compounds obtained by reaction, compounds obtained by reacting glycidyl (meth) acrylate and alcohols or amines containing furyl groups, specifically, furfuryl (meth) acrylate, furfuryl alcohol and 2 -(Meth) acryloyloxyethyl isocyanate reactant, furfuryl alcohol and diphenylmethane diisocyanate reactant, furfuryl alcohol and hexamethylene diisocyanate reactant, furfuryl alcohol and toluene diisocyanate reactant, furfuryl alcohol and isophorone diisocyanate Reactant reaction product, furfuryl alcohol and trimerized hexamethylene diisocyanate, furfuryl alcohol and trimerized toluene diisocyanate, furfurylamine and 2- (meth) acryloyloxyethyl isocyanate reaction, furfurylamine and diphenylmethane diisocyanate A reaction product of furfurylamine and hexamethylene diisocyanate, a reaction product of furfurylamine and toluene diisocyanate, a reaction product of furfurylamine and isophorone diisocyanate, a reaction product of furfurylamine and trimerized hexamethylene diisocyanate, furfurylamine and trimerized toluene diisocyanate, Reaction product of glycidyl methacrylate and furfurylamine, reaction product of glycidyl methacrylate and 2-furancarboxylic acid, etc. Including but not limited to. These may be used alone, or a mixture may be used.

  The compound (A) containing a furyl group is preferably a polymer compound from the viewpoint of hard coat properties and processability of the decorative sheet composition.

  As the polymer compound, a polymer having a weight average molecular weight (polystyrene conversion) of 1000 or more is preferable, and a poly (meth) acrylate, polyurethane, polyester, polyamide, polyimide, polycarbonate, polyolefin, polystyrene, polysiloxane having a furyl group, Examples thereof include polyethers, copolymers containing maleic anhydride, and epoxy resins, and these may be used alone or in a mixture. The polymer may be in any shape such as linear, branched or star shape, and may be either thermoplastic or thermosetting. Moreover, the photopolymerizable functional group may further be included in the compound (A) containing a furyl group.

Further, as the compound (A) containing a furyl group of the present invention, JP-A-1994-271558, JP-A-1994-293830, JP-A-1996-239421, JP-A-1998-508655, JP-A-2000-001529, JP-A-2003-183348 Also, known compounds described in JP-A-2006-193628, JP-A-2007-186684, JP-A-2010-265377, JP-A-2011-170069, and the like can be used.

From the viewpoint of moldability, the weight average molecular weight (polystyrene conversion) of the polymer compound (A) containing a furyl group of the present invention is preferably 10,000 or more, more preferably 50,000 to 2,000,000, and more preferably 100,000 to One million is particularly preferred.
In this specification, the weight average molecular weight indicates a polystyrene-equivalent molecular weight measured by gel permeation chromatography.

Among the high molecular compounds containing a furyl group, an acrylic polymerization high molecular compound is preferable from the viewpoint of the availability of synthetic raw materials and the range of design due to the variety of types.
As a polymer compound containing a furyl group, an active reaction such as a polymer of a monomer containing a monomer (a-1) containing a furyl group, an isocyanate group, a glycidyl group, or an anhydride group (structure) Examples include, but are not limited to, a reaction product of a polymer compound having an ionic substituent and a furyl compound having an active hydrogen group such as alcohol or amine.

From the viewpoint that a furyl group can be easily introduced and that the amount of furyl group introduced can be easily controlled, a monomer polymer containing a monomer (a-1) containing a furyl group is preferred, and a furyl group is contained. A polymer of the monomer (a-1) and the monomer (a-2) not containing a furyl group is more preferable. Furthermore, the polymerization method is preferably radical polymerization from the viewpoint of easy control of the characteristics required of the decorative sheet composition by controlling the molecular weight and copolymer composition.

  The monomer (a-1) containing a furyl group may be an ethylenically unsaturated group monomer having at least one furyl group, specifically, furfuryl alcohol and 2-acryloyloxyethyl isocyanate. Reaction product of furfuryl alcohol and 2-methacryloyloxyethyl isocyanate, reaction product of furfurylamine and 2-acryloyloxyethyl isocyanate, reaction product of furfurylamine and 2-methacryloyloxyethyl isocyanate, furfuryl alcohol and Reaction product of glycidyl methacrylate, reaction product of furfurylamine and glycidyl methacrylate, reaction product of 2-furancarboxylic acid and glycidyl methacrylate, reaction product of succinic acid-modified furfuryl alcohol and glycidyl methacrylate, succinic acid-modified furfurylamine Reaction product of glycidyl methacrylate, reaction product of caprolactone-modified furfuryl alcohol and glycidyl methacrylate, reaction product of caprolactone-modified furfurylamine and glycidyl methacrylate, reaction product of caprolactone-modified furfuryl alcohol and 2-acryloyloxyethyl isocyanate, caprolactone-modified furfurylamine and Reaction product of 2-acryloyloxyethyl isocyanate, reaction product of caprolactone-modified furfuryl alcohol and 2-methacryloyloxyethyl isocyanate, reaction product of caprolactone-modified furfurylamine and 2-methacryloyloxyethyl isocyanate, furfuryl (meth) acrylate, etc. (Meth) acrylate having a furyl group, vinyl furfuryl ether, allyl furfuryl ether, etc. Including but not limited to. Preferred is a (meth) acrylate having a furyl group.

  In particular, furfuryl methacrylate is preferred because it has high monomer purity, has little adverse effects during polymerization (molecular weight control, gelation, coloring, etc.), and can synthesize a polymer compound stably.

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

The monomer (a-2) not containing a furyl group is a monomer having an ethylenically unsaturated group copolymerizable with the monomer (a-1) containing a furyl group, A compound having one ethylenically unsaturated group, specifically, a vinyl group, an allyl group, a (meth) acryloyl group or the like is included.

Specific examples of the monomer (a-2) not containing a furyl group include (meth) acrylic acid,

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, or adamantyl (meth) acrylate Linear or branched alkyl (meth) acrylates such as bets;

Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, (meth) acrylic acid-2-hydroxy-3-allyloxypropyl, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 4-hydroxyvinylbenzene, polypropylene glycol mono (meth) acrylate or monomers of these monomers Rorakuton adduct (no moles 1-5) having a hydroxyl group such as (meth) acrylates;

(2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H-hexafluoroisopropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate, 2,6-dibromo-4-butylphenyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) Fluoroalkyl (meth) acrylates such as acrylate, 2,4,6-tribromophenol 3EO addition (meth) acrylate, or perfluorooctylethyl (meth) acrylate;

(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;

2-methoxyethyl (meth) acrylate, 1,3-butylene glycol methyl ether (meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, tetrahydro Furfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( T) acrylate, phenoxypolyethylene glycol (meth) acrylate, cresyl polyethylene glycol (meth) acrylate, (meth) acrylic acid-2- (vinyloxyethoxy) ethyl, p-nonylphenoxyethyl (meth) acrylate, p-nonylphenoxy Polyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, β-carboxyethyl (meth) acrylate, succinic acid mono (meth) acryloyloxyethyl ester, ω-carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyl Oxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate , 2- (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono ( (Meth) acrylate, phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol polypropylene glycol Mono (meta) acryl (Meth) acrylates having an ether group, such as n-butoxyethyl (meth) acrylate or 2-ethoxyethyl (meth) acrylate;

3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-hexyloxetane (Meth) acrylates having;

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

(Meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, morpholinoethyl (meth) acrylate, trimethylsiloxyethyl (meth) acrylate, diphenyl-2- (meth) ) Acryloyloxyethyl phosphate, 2- (meth) acryloyloxyethyl acid phosphate, caprolactone-modified-2- (meth) acryloyloxyethyl acid phosphate, 2-hydroxy-1- (meth) acryloxy-3-methacryloxypropane, (meth) ) Acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopro Le (meth) acrylamide, diacetone (meth) acrylamide, or (meth) acryloyl N-substituted, such as morpholine (meth) acrylamide;

Nitriles such as (meth) acrylonitrile;

Vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;

(Meth) acrylates having an isocyanate group such as 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate;

Product name “Silaplane FM-0711” (manufactured by JNC Corporation), product name “Silaplane FM-0721” (manufactured by JNC Corporation), trade name “Silaplane FM-0725” (manufactured by JNC Corporation) Polysiloxane (meth) acrylates such as
Alternatively, a mixture thereof can be mentioned.

Examples of other polymerizable monomers include vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, vinyl 2-ethylhexanoate, N-vinylcarbazole, and N-vinylpyrrolidone. Although it is mentioned, it is not limited to these.

The monomer (a-2) containing no furyl group is more preferably a (meth) acrylate compound from the viewpoint of synthesis stability at the time of copolymerization with the monomer (a-1) containing a furyl group.

  Furthermore, it is preferable to use a monomer having a polar group as the monomer (a-2) in order to improve chemical resistance required for automobile use, particularly interior parts use. The polar group is preferably a hydroxyl group, specifically 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, (meth) acrylic acid-2-hydroxy-3-allyloxypropyl, 2- (meth) acryloyloxyethyl-2-hydroxypropyl Examples include, but are not limited to, phthalate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate.

As the monomer (a-2) not containing a furyl group, only one type may be used, or two or more types may be used in any ratio.

  The copolymerization of the monomer (a-1) containing a furyl group and the monomer (a-2) containing no furyl group can be carried out by a known method. That is, a polymer can be obtained by optionally mixing a monomer with a polymerization initiator and heating.

  Although it is desirable to adjust suitably about polymerization temperature according to the kind of polymerization initiator to be used, and the boiling point of a solvent, 20 to 150 degreeC is preferable and 40 to 120 degreeC is more preferable.

  Regarding the environment in which the polymerization is carried out, it is desirable to carry out in an inert gas atmosphere for the purpose of preventing coloring reduction or deactivation of the polymerization initiator, and nitrogen gas is preferable from the viewpoint of availability, cost, etc. It is not limited.

  As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 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] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Dicarbonate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide And diacetyl peroxide.

These polymerization initiators can be used alone or in combination of two or more, and the amount used is 100 parts by weight in total of the monomer (a-1) and the monomer (a-2). Thus, it can be arbitrarily used in the range of 0.001 to 20 parts by weight.

During the polymerization, a chain transfer agent may be used for the purpose of adjusting the molecular weight. 0.001-15 mass parts chain transfer agent can be arbitrarily used with respect to a total of 100 mass parts of a monomer (a-1) and a monomer (a-2).
The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used. For example, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, 1-thioglycerol, 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-mercapto Propionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bi (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, butylthioglycolate, etc. Mercaptans; disulfides such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide; carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, carbon tetrabromide Halogenated hydrocarbons such as ethylene bromide; secondary alcohols such as isopropanol and glycerin; phosphorous acid and hypophosphorous acid And salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, bisulfite, dithionite, metabisulfite, and salts thereof (sodium bisulfite, potassium bisulfite, dithionite) Lower oxides and salts thereof such as sodium, potassium dithionite, sodium metabisulfite, potassium metabisulfite and the like; and allyl alcohol, 2-ethylhexyl thioglycolate, α-methylstyrene dimer, terpinolene, α- Examples include terpinene, γ-terpinene, dipentene, and anisole. These may be used alone or in combination of two or more.

In the polymerization, an organic solvent can be used as a polymerization solvent.
As an organic solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol, 3-methoxy-1-butanol and the like are used. However, it is not limited to these. These polymerization solvents may be used as a mixture of two or more kinds, but are preferably used for final use.

<Polymerizable compound (B)>
Next, as the polymerizable compound (B), a radical polymerizable compound can be used in order to improve curability associated with the reaction. The radical polymerizable compound in the present invention means a compound having at least one skeleton capable of radical polymerization in the molecule and having no furyl group. In addition, these have chemical forms of liquid or solid monomers, oligomers or polymers at normal temperature and normal pressure.

  Examples of such radically polymerizable compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, acid amides and acid anhydrides. Furthermore, urethane acrylates, epoxy acrylates, acrylic acrylates, ester acrylate acrylonitriles, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, and the like can be mentioned. It is not limited. Below, the specific example of the radically polymerizable compound in this invention is given.

Examples of acrylates:
Examples of monofunctional alkyl 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, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxy acrylates:
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, acrylic acid-2-hydroxy- 3-allyloxypropyl, 2-acryloyloxyethyl-2-hydroxypropyl phthalate.

Examples of monofunctional halogenated acrylates:
2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, acrylic Acrylic acid 2- (vinyloxy) ethyl, p- nonyl phenoxyethyl acrylate, p- nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl acrylates:
β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2- Acryloyloxypropyltetrahydrophthalate.

Examples of other monofunctional acrylates:
N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified-2-acryloyl Oxyethyl acid phosphate, 2-hydroxy-1-acryloxy-3-methacryloxypropane.

Examples of bifunctional acrylates:
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 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, neo Pentyl glycol diacrylate, ne Pentyl glycol PO-modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO Hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromobisphenol A diacrylate, tricyclodecane dimethylol Diacrylate, isocyanuric acid EO-modified diacrylate, 2-hydroxy-1,3-diacryloxypropane.

Examples of trifunctional acrylates:
Glycerin PO-modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, isocyanuric acid EO-modified triacrylate, isocyanuric acid EO-modified ε-caprolactone-modified triacrylate, 1,3 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetra- or higher functional acrylates:
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate.

Examples of methacrylates:
Examples of monofunctional alkyl methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate , Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxymethacrylates:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated methacrylates:
2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 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-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, Methacrylic acid-2- (vinyloxyethoxy) ethyl, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, Polyethylene glycol methacrylate, p- nonyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates:
β-carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2- Methacryloyloxypropyl tetrahydrophthalate.

Examples of other monofunctional methacrylates:
Dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone Modified-2-methacryloyloxyethyl acid phosphate and the like.

Examples of bifunctional methacrylates:
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopenty Glycol dimethacrylate, neopentyl glycol PO-modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct dimethacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3- (Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane , Bisphenol A dimethacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate, PO modified bisphenol F dimethacrylate, EO modified Tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane.

Examples of trifunctional methacrylates:
Glycerin PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate.

Examples of arylates:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

Examples of acid amides:
Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

Examples of styrenes:
Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene 2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds:
Vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone etc.

  Said radically polymerizable compound can be easily obtained as a commercial product of the manufacturer shown below. For example, `` Light acrylate '', `` Light ester '', `` Epoxy ester '', `` Urethane acrylate '' and `` Highly functional oligomer '' series manufactured by Kyoeisha Yushi Chemical Co., Ltd., Shin Nakamura Chemical Co., Ltd. "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Co., Ltd., manufactured by Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. “Kayarad” and “Kayamar” series manufactured by Nippon Kayaku Co., Ltd. “Acrylic acid / methacrylic acid ester monomer” series manufactured by Nippon Shokubai Co., Ltd., Nippon Synthetic Chemical Industry Co., Ltd. Made in "Nichigo-UV Shiko urethane acrylate oligomer" series, Shin-Etsu vinyl acetate Co., Ltd. "carboxylic vinyl ester monomers" series include Co. Kohjin Co. "functional monomer" series, and the like.

Moreover, the cyclic compound shown below is also mentioned as a radically polymerizable compound.
Examples of three-membered ring compounds:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Vol. 17, 3169 (1979), vinylcyclopropanes, Macromolecular Chemie Rapid Communication (Makromol. Chem. Rapid Commun.), Volume 5, p. 63 (1984), 1-phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition ( J. Polym. Sci. Polym. Chem. Ed.), 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed. 21), 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 (1985) Mounting No 2,3-vinyl oxirane.

Examples of cyclic ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Volume 20, p. 3021 (1982) and Journal of Polymer Science Polymer Letter Edition (J.Polym.Sci.Polym.Lett.Ed.), Vol. 21, 373 (1983), 2-methylene-1,3-dioxepane, polymer pre-prints (Polym. Preprints), No. 34, 152 (1985), dioxolanes, Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), 20, 361 (1982) 2) described in Macromolecular Chemie, 183, 1913 (1982) and Macromolecular Chem., 186, 1543 (1985). -Methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, polymer described in Macromolecules, Vol. 15, page 1711 (1982) -5,6-benzo-2-methylene-1,3-diosepane described in Polypre. Preprints, Vol. 34, page 154 (1985).

  Furthermore, the polymeric compound (B) can also mention the thing as described in the literature shown below. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyoto Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Association, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

As the polymerizable compound (B), only one kind may be used, or a mixture of two or more kinds in any ratio may be used in order to improve desired characteristics.

  As the polymerizable compound (B), in addition to the above monomers, those called oligomers and prepolymers can be used. Specifically, “Ebecryl 230, 244, 245, 270, 280 / 15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, 294 / 35HD, manufactured by Daicel UCB, 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, 1 30, 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 ", manufactured by Sartomer CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN971, CN972, CN9782, CN981, CN9873, CN991, "Laromar EA81L, F87" manufactured by BASF LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, LR8967, LR8981, LR8982, LR8992, LR9004, LR8956, LR8985, LR8987, UP35D, UA19T, LR9005, PO83F, PO33F, L8489, L9489 LR8996, LR9013 LR9019, PO9026V, PE9027V "manufactured by Cognis" Photomer 3005, 3015, 3016, 3072, 3982, 3215, 5010, 5429, 5430, 5432, 5662, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6572, 3660 "," Art Resin UN-9000HP, 9000PEP, 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T, manufactured by Negami Kogyo Co., Ltd. 1200TPK, 6060PTM, 6060P "," Nippon Gosei Chemical Co., Ltd. "" purple light UV-6630B, 7000B, 7510B, 7461TE, 3000B, 320 " 0B, 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 "and the like.

The polymerizable compound (B) is an amount of 1 to 99 parts by weight in a total of 100 parts by weight of the solid content of the decorative sheet composition from the viewpoint of hard coat properties and processability of the decorative sheet composition. It is preferable to use it.

  In addition, the polymerizable compound (B) is preferably 20 to 400 parts by weight with respect to 100 parts by weight of the compound (A) having a furyl group, from the viewpoint of hard coat properties and processability of the decorative sheet composition, More preferably, it is 50 to 200 parts by weight.

Of the above-mentioned compounds that can be used as the polymerizable compound (B), polyfunctional (meth) acrylates and urethane acrylates are preferable from the viewpoints of hard coatability, processability, and cost.

<Polymerization initiator (C)>
Next, the polymerization initiator (C) is a compound that generates a radical active species that initiates a polymerization reaction by irradiation with active energy rays, and a conventionally known polymerization initiator can be used. Specifically, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane , Oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl Acetophenones such as phenyl} -2-methylpropan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as benzoin isopropyl ether and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Examples include glyoxylic methyl ester. More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 Cure 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01 (CGI124), CGI242 (BASF), Adekaoptomer N1414, Adekaoptomer N1717 (ADEKA), Esacure1001M
Lamberti), JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104, triazine derivatives, JP-A-59-1504 and JP-A-61-243807. Organic peroxides described in Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604 and USP 3,567,453, Japanese Patent Publication No. 3,848,328, US Pat. No. 2,848,328, Organic azide compounds described in US Pat. No. 2,852,379 and US Pat. No. 2,940,853, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015 and Japanese Patent Publication No. 45-9610. Ortho-quinonediazides described, JP-B-55-391 Various onium compounds including iodonium compounds described in JP-A No. 62, JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977); -142205, an azo compound described in JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, "Journal of Imaging Science (J.IMAG.SCI.)" 30, vol. 174 (1986), titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, 85 ~ 277 (1988) and transition metal such as ruthenium described in JP-A-2-182701 Transition metal complexes, aluminate complexes described in JP-A-3-209477, borate compounds described in JP-A-2-157760, JP-A-55-127550 and JP-A-60-202437 2,4,5-triarylimidazole dimer, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, Aminoketone compounds described in JP-A-54-99185, JP-A-63-264560, and JP-A-10-29977, JP-A-2001-264530, JP-A-2001-261761, and JP-A-2000-80068. , JP 2001-233842 A, JP 2004-534797 A JP-A 2006-342166, JP-A 2008-094770, JP-A 2009-40762, JP-A 2010-15025, JP-A 2010-189279, JP-A 2010-189280, JP-T 2010-526846, JP-T 2010-527338, Examples include oxime ester compounds described in JP-T 2010-527339, USP 3558309 specification (1971), USP4202697 specification (1980), and JP-A No. 61-24558.

  Further, as the polymerization initiator (C), a hydrogen abstraction type radical initiator can be used, and specifically, aromatic ketones such as acetophenone, benzophenone, benzyl, Michler ketone, thioxanthone, or anthraquinone can be mentioned. It is done. These compounds generally use tertiary amines in combination with those skilled in the art. Specifically, trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, p-dimethylaminophenylalkyl ester, etc. However, it is not limited to these.

  Among these, Preferably, acetophenones, phosphine oxides, etc. are mentioned.

  These can be used singly or in combination, and can be mixed and used arbitrarily depending on the properties required for the reaction-cured product. The amount used when using these polymerization initiators (C) is The total solid content of the decorative sheet composition is preferably 100 to 50 parts by weight, more preferably 1 to 20 parts by weight.

Furthermore, a sensitizer can be contained in the composition for a decorative sheet of the present invention. Examples of sensitizers include:
Unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthenes Derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulene derivatives, Squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinopo Philazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran Derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives, biimidazole derivatives and the like.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained. The sensitizer may contain two or more sensitizers in any ratio.

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

  In addition to the essential components of the decorative sheet composition of the present invention described above, for the purpose of imparting the coating properties at the time of production of the decorative sheet and the properties required as a decorative sheet composition for the decorative sheet. Further, a resin, a solvent or inorganic particles may be added.

  The resin that can be used in the decorative sheet composition of the present invention means a resin that does not have a radically polymerizable skeleton in the molecule. In addition, these have a liquid or solid chemical form at normal temperature and normal pressure.

Examples of the resin having no skeleton capable of radical polymerization in the molecule include alkyd resin, polyester resin, polyvinyl chloride, poly (meth) acrylic ester, epoxy resin, polyurethane resin, cellulose derivative (for example, ethyl cellulose, cellulose acetate). , Nitrocellulose), vinyl chloride vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, and synthetic rubber such as butadiene-acrylonitrile copolymer. These resins can be used alone or in combination of two or more thereof.

  The resin is preferably used in an amount of 1 to 99 parts by weight in a total of 100 parts by weight of the solid content of the decorative sheet composition from the viewpoint of hard coat properties and processability of the decorative sheet composition. At the same time, 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 decorative sheet composition of the present invention, a conventionally known organic solvent can be used. Specifically, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert -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 mono Hexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoiso Propyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary 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-hept Non, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, γ-butyrolactone, isophorone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetic acid Amyl, isobutyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, ethylene glycol monobutyl 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 glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, Triacetin, 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 dibutyl 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, sec-butylbenzene, tert-butylbenzene, cycloheptane, cyclohexane, pentane, hexane, octane, isohexane, isooctane, isononane, dichloromethane, chloroform, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, 1,2,3-tri Examples include, but are not limited to, chloropropane, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. . These can be used alone or in combination.

  It is preferable from the viewpoint of coating suitability that the organic solvent is used in an amount that makes the solid content concentration of the decorative sheet composition 5 to 50% by weight. Outside the above-described concentration range, problems such as a decrease in leveling property of the coating liquid, a decrease in the smoothness of the coating film, and a difficulty in controlling the film thickness are likely to occur.

The inorganic particles that can be used in the decorative sheet composition of the present invention are metal oxides such as silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles, and the like. The particles are preferably exemplified, but not limited thereto.

  From the viewpoint of crosslinkability, the inorganic particles preferably have a reactive functional group on the surface, and specific examples of the reactive functional group include a vinyl group, a (meth) acryloyl group, and an allyl group. Examples thereof include, but are not limited to, an ethylenically unsaturated bond, an epoxy group, and a silanol group.

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

The decorative sheet composition of the present invention further comprises an oxygen remover and a reducing agent such as dyes, organic and inorganic pigments, pigment dispersants, phosphines, phosphonates, phosphites, antifoggants, antifading agents, depending on the purpose. Antihalation agent, optical brightener, surfactant, colorant, extender, plasticizer, flame retardant, antioxidant, dye precursor, ultraviolet absorber, foaming agent, antifungal agent, antistatic agent, magnetic substance , Dispersants such as resin-type dispersants, storage stabilizers such as silane coupling agents and quaternary ammonium chloride, plasticizers, surface tension modifiers, slipping agents, antiblocking agents, light stabilizers, leveling agents, antifoaming It may be used by mixing with an additive, an infrared absorbent, a surfactant, a thixotropic agent, an antibacterial agent, fine particles such as silica, an additive imparting various characteristics, a diluent solvent, and the like.

As described above, the decorative sheet composition of the present invention contains a compound (A) containing a furyl group, a polymerizable compound (B), and an initiator (C) as essential components.
Moreover, the said composition for decorating sheets can be used conveniently for manufacture of a molded product. Preferably, the 1st process of apply | coating to a base material the composition for decorating sheets containing the compound (A) containing a furyl group, a polymeric compound (B), and an initiator (C), and activity A decorative sheet can be formed by the second step of curing by irradiating energy rays, and a molded product can be produced by a third step of molding.

In the decorative sheet composition of the present invention, the crosslinking reaction proceeds by the reaction of the polymerizable compound (B) with radicals generated from the initiator (C) in the stage of the second step. At this time, since the furyl group in the compound (A) hardly reacts, it seems to function as a so-called inert resin. Therefore, by suppressing (controlling) the degree of crosslinking of the entire photocrosslinked film with the compound (A) containing a furyl group, it is possible to obtain a crosslinked film having extensibility and flexibility that can be applied to various molding processes. Become.

Although this invention is not limited to a manufacturing method or its action mechanism, after the photocrosslinking (2nd process) by an active energy ray, the furyl group which a compound (A) has, and a polymeric compound (B) When the polymerizable group that is not involved in the photocrosslinking derived from is thermally crosslinked, the crosslinking degree of the entire crosslinked film is improved, and a crosslinked film having hard coat properties can be obtained. Here, it is a general fact for those skilled in the art that the polymerizable group of the polymerizable compound (B) is not consumed 100% during photocrosslinking.
The thermal crosslinking of the furyl group and the polymerizable group is not particularly limited, and specifically, it is a Diels-Alder reaction by a dienophile structure in the polymerizable group and a diene structure in the furyl group. This reaction can generally proceed at room temperature or higher, but the reaction is more likely to proceed when heated. The reaction temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher.

The molding process as the third step is preferably a molding process involving heating in order to thermally crosslink. The Diels-Alder reaction that utilizes the heat of the molding process allows the crosslinking to proceed sufficiently, and it is not necessary to perform a thermal crosslinking process in addition to the molding process. The advantage is high.
The molding step is not limited to thermoforming, and the production method of the present invention may further include a heating step.

<Decoration sheet>
The decorative sheet of the present invention is not particularly limited as long as the cured film is formed by using the decorative sheet composition of the present invention, and an anchor layer, a pattern layer, an adhesive layer on the substrate as necessary. The layer structure is freely combined with a release layer, an antistatic layer and the like. For example, the decorative sheet of the present invention is not limited, but preferred examples include a laminate decorative sheet and a transfer decorative sheet.

  The decorative sheet for laminate has a layer 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. It is a sheet and is decorated by sticking to the surface of a body to be decorated (plastic casing).

  The decorative sheet for transfer is a decorative sheet in which a release layer is formed on one side of a substrate, and the transfer layer is laminated on the release layer. Here, the transfer layer is a layer laminated in the order of a cured film, a pattern layer, and an adhesive layer using the decorative sheet composition of the present invention, but if necessary, an anchor layer, an antistatic layer, Although an ultraviolet absorption layer, a low reflection layer, a near infrared ray blocking layer, an electromagnetic wave absorption layer, and the like can be combined, the layer structure in the decorative sheet of the present invention is not limited to these.

The anchor layer is a layer provided between a cured film and an adhesive layer or a pattern layer using the decorative sheet composition of the present invention, for example, in order to enhance the adhesion between two different layers. Without being limited thereto, it can be provided between arbitrary layers as required.
As an anchor layer, two-component cured urethane resin, thermosetting urethane resin, melamine resin, cellulose ester resin, chlorine-containing rubber resin, chlorine-containing vinyl resin, acrylic resin, epoxy resin, vinyl copolymer Using coalesced resin, gravure coating method, gravure offset method, kiss coating method, rod coating method, reverse gravure coating method, roll coating method, comma coating method, top coating method, die coating method, knife coating method, lip coating method, It can be laminated using known coating methods and printing methods such as spray coating, spin coating, bar coating, slit coating, gravure printing, offset printing, screen printing, transfer printing, sublimation transfer printing, and ink jet printing. it can.

The above pattern layer is a layer necessary for obtaining a desired design on the decorative sheet, and there is no particular limitation on the pattern, for example, wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, There are pictures made of photographs, illustrations, etc., and the combination of the pictures is also free. In addition, the overcoating is also free, and it is also possible to perform metal deposition on a part or the entire surface.
As a method necessary for obtaining a pattern, a method of forming an ink composed of a suitable colorant such as a pigment and a dye and a binder resin by using a known printing method can be mentioned. Here, examples of the binder resin include, but are not limited to, a polyvinyl resin, a polyester resin, a polyacrylic resin, a polyamide resin, a polyvinyl acetal resin, a cellulose resin, and an alkyd resin. Known printing methods include gravure coating, gravure offset, kiss coating, rod coating, reverse gravure coating, roll coating, comma coating, top coating, die coating, knife coating, and lip coating. Examples thereof include, but are not limited to, methods, spray coating, spin coating, bar coating, slit coating, gravure printing, offset printing, screen printing, transfer printing, sublimation transfer printing, and ink jet printing.

The adhesive layer is a layer necessary for adhering when the transfer layer is transferred to the resin molding. 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 an adhesive resin, but is preferably an acrylic resin, polystyrene resin, polyamide resin, indene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate. Copolymer resin etc. are mentioned, It is also possible to mix and use 1 or more types as needed. Moreover, it is more preferable to select suitably from a viewpoint of affinity with a resin molding.

The release layer is a layer necessary for separating the transfer layer from the substrate, and includes a melamine resin release agent, a silicone resin release agent, a fluororesin release agent, a cellulose resin release agent, urea Examples include, but are not limited to, resin-based release agents, polyolefin resin-based release agents, paraffin resin-based release agents, and acrylic resin-based release agents. One or more of the above mold release agents can be freely mixed and used as necessary.

  The base material that can be used in the decorative sheet of the present invention is not particularly limited, but polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin. Preferred examples include plastic materials such as AS resin, norbornene resin, and vinyl resin.

  More preferably, the plastic material may be a film or a sheet formed by a casting method or non-stretching or biaxial stretching method, but is not limited to the production method. From the viewpoint of imparting adhesion, the substrate surface may be coated with an undercoat such as corona discharge treatment or a primer.

  The thickness of the substrate is not particularly limited, and it is desirable to select an optimum thickness depending on the molding method.

As a method for producing a decorative sheet, the composition for a decorative sheet of the present invention is formed on a substrate so as to be a uniform and predetermined film thickness, and is then dried as necessary, and further activated. It is formed by photocrosslinking by irradiation with energy rays.

As the film formation method, a known printing or coating method can be used, for example, a gravure coating method, a gravure offset method, a kiss coating method, a rod coating method, a reverse gravure coating method, a roll coating method, a comma coating method, Top coating method, die coating method, knife 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, etc. However, it is not limited to these.

As described in the description of the solvent that can be used in the decorative sheet composition of the present invention, a solvent may be used from the viewpoint of coatability. However, if crosslinking is performed by irradiation with active energy rays in a state where a large amount of solvent is contained in the coating film, it may adversely affect the control of crosslinking. Therefore, it is desirable to remove the coating film to some extent by drying. As a method of drying, it can be carried out by vacuum drying using a vacuum dryer or the like, drying by baking using a convection oven (hot air dryer), IR oven, hot plate or the like, or a combination thereof. is there. Although it is preferable to select baking from the viewpoints of equipment cost and productivity, it is more preferable that the baking be performed while paying attention to the following conditions.
The baking conditions (temperature, time) can be appropriately selected according to the boiling point and film thickness to be used, and the drying performance of the oven, but the decorative sheet composition of the present invention has a high temperature of 100 ° C. or higher. Since the above-mentioned thermal crosslinking reaction of the furyl group can proceed in the region, the temperature is preferably 100 ° C. or lower. Further, since a long-time baking may cause a thermal crosslinking reaction to proceed, it is preferably 10 minutes or less. If the thermal crosslinking reaction proceeds at the pre-baking time point, it is not preferable because it adversely affects the photocrosslinking by irradiation with active energy and the degree of crosslinking increases more than necessary, which may impair the extensibility.

  Although there is no restriction | limiting in particular as a film thickness of the composition for decorating sheets of this invention, Preferably it is 1 micrometer-100 micrometers from a viewpoint of a moldability or hard-coat property, Preferably it is 5 micrometers-50 micrometers.

  The active energy rays necessary for photocrosslinking the composition of the present invention are heat, ultraviolet rays, visible rays, near-infrared rays, electron beams, and the like. By these active energy rays, the polymerization initiator (C) generates radicals, and the polymerizable compound (B) is subsequently polymerized to proceed a crosslinking reaction. As a light source for applying active energy rays, a light source having a dominant wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable. Examples of light sources having a main wavelength of light emission in the wavelength region of 250 nm to 450 nm include ultrahigh pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulsed light emission. Xenon lamp, deuterium lamp, fluorescent lamp, ND-YAG triple wave laser, HE-CD laser, nitrogen laser, XE-Cl excimer laser, XE-F excimer laser, semiconductor-excited solid laser, 365 nm, 375 nm, 385 nm Various light sources such as an LED lamp light source having The definitions of ultraviolet rays, visible light, near-infrared rays and the like in this specification are based on Kubo Ryogo et al., “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami).

  As described above, the cured film is laminated with other necessary layers and used as a decorative sheet. It has the moldability which can respond to various shaping | molding by using the composition for decorating sheets of this invention by the above-mentioned action mechanism. Furthermore, the decorative sheet of the present invention can obtain final hard coat properties by further thermally crosslinking the cured film with heat during molding. Thermal crosslinking can proceed sufficiently with the heat applied during molding, but a baking step may be added if necessary.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, a following example does not restrict | limit the right range of this invention at all. In addition, each evaluation in an Example followed the following method. In the examples, “part” means “part by weight” and “%” means “% by weight”.
<Weight average molecular weight>
For the measurement of the weight average molecular weight, GPC (Gel Permeation Chromatography) “GPC-8020” manufactured by Tosoh Corporation was used, the columns were 2 SHODEX KF-806L, 1 KF-804L, 1 KF-802, and the solvent. Used tetrahydrofuran. The weight average molecular weight was calculated in terms of standard polystyrene.

<Production of Compound (A) Having Furyl Group>

(Synthesis example of polymer compound)
Synthesis Example 1: Compound (A) -1
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone and heated to 70 ° C. in a nitrogen atmosphere. Next, 30 parts by weight of a reaction product of methacryloxyethyl isocyanate and furfuryl alcohol as the monomer (a-1), 70 parts by weight of methyl methacrylate as the monomer (a-2), and 3 parts by weight of azobisisobutyronitrile The monomer liquid in which the parts were mixed in advance was added dropwise over 2 hours. Furthermore, after reacting at 70 ° C. for 1 hour, a step of adding 0.3 parts by weight of azobisbutyronitrile and reacting for 1 hour was performed until the monomer addition rate reached 98% or more, and then cooled to room temperature. . Methyl ethyl ketone was added to obtain a compound (A) -1 containing a furyl group having a solid content of 50%. The weight average molecular weight was 60,000.

Synthesis Examples 2-17
The same except that the monomers (a-1) and (a-2) in Synthesis Example 1 are changed to the types and blends shown in Table 1 and the solid content concentration and the amount of the polymerization initiator are appropriately adjusted during the reaction. Were synthesized to obtain compounds (A) -2 to (A) -17 having a weight average molecular weight shown in Table 1 at a solid content of 50%.

Synthesis Example 18: Compound (A) -18
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone and heated to 70 ° C. in a nitrogen atmosphere. Next, a monomer solution in which 60 parts by weight of n-butyl acrylate, 40 parts by weight of 2-acryloyloxyethyl isocyanate, and 3 parts by weight of azobisisobutyronitrile were mixed in advance was added dropwise over 2 hours. Furthermore, after making it react at 70 degreeC for 1 hour, the process of adding 0.3 weight part of azobisbutyronitrile and making it react for 1 hour was performed until the addition rate of the monomer became 98% or more.
Next, 0.1 part by weight of tin octylate was added, and then a solution of 28 parts by weight of furfuryl alcohol and 30 parts by weight of methyl ethyl ketone was added dropwise over 2 hours. The reaction was further continued at 70 ° C. for 3 hours, and then the reaction solution was cooled to room temperature. Methyl ethyl ketone was added to obtain a compound (A) -18 containing a furyl group having a solid content of 50%. The weight average molecular weight was 30000.

Synthesis Example 19 Compound (A) -19
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, and 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 to 70 ° C. in a nitrogen atmosphere. Subsequently, a monomer solution in which 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 were mixed in advance was dropped over 2 hours. Furthermore, after making it react at 70 degreeC for 1 hour, the process of adding 0.3 weight part of azobisbutyronitrile and making it react for 1 hour was performed until the addition rate of the monomer 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. The reaction was further continued at 70 ° C. for 3 hours, and then the reaction solution was cooled to room temperature. Methyl ethyl ketone was added to obtain a compound (A) -19 containing a furyl group having a solid content of 50%. The weight average molecular weight was 25000.

Synthesis Example 20 Compound (A) -20
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube was charged with 50 parts by weight of propylene glycol monomethyl ether acetate and heated to 70 ° C. in a nitrogen atmosphere. Subsequently, a monomer liquid in which 40 parts by weight of n-butyl methacrylate, 60 parts by weight of glycidyl methacrylate, and 1 part by weight of azobisisobutyronitrile were mixed in advance was dropped over 2 hours. Furthermore, after reacting at 70 ° C. for 1 hour, the step of adding 0.1 part by weight of azobisbutyronitrile and reacting for 1 hour was performed until the monomer addition rate reached 98% or more, and then cooled to room temperature. .
Next, 47 parts by weight of 2-furancarboxylic acid and 1 part by weight of tetramethylammonium bromide were added and reacted at 100 ° C. for 6 hours, and then the reaction solution was cooled to room temperature. Propylene glycol monomethyl ether acetate was added to obtain a compound (A) -20 containing a furyl group having a solid content of 50%. The weight average molecular weight was 80000.

Synthesis Example 21 Compound (A) -21
The synthesis was carried out in the same manner except that n-methyl methacrylate in Synthesis Example 7 was changed to n-butyl methacrylate to obtain a compound (A) -8 containing a furyl group having a solid content of 50%. The weight average molecular weight was 23000.

Synthesis Example 22 Compound (A) -22
Synthesis was carried out in the same manner except that n-methyl methacrylate in Synthesis Example 7 was changed to benzyl methacrylate to obtain Compound (A) -9 containing a furyl group having a solid content of 50%. The weight average molecular weight was 34,000.

Synthesis Example 23: Compound (A) -23
Synthesis was carried out in the same manner except that n-methyl methacrylate in Synthesis Example 7 was changed to butyl acrylate, to obtain a compound (A) -10 containing a furyl group having a solid content of 50%. The weight average molecular weight was 26000.

(Synthesis example of low molecular weight compound)
Synthesis Example 1: Compound (A) -101
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube was charged with 60 parts by weight of methyl ethyl ketone, 50 parts by weight of furfuryl alcohol and 0.1 part by weight of dibutyl tin dilaurate, and the temperature was raised to 60 ° C. under a nitrogen atmosphere. After warming, a solution of 72 parts by weight of 2-acryloyloxyethyl isocyanate in 50 parts by weight of methyl ethyl ketone was added dropwise over 2 hours. Subsequently, the reaction was continued at 60 ° C. for 3 hours, and then the reaction solution was cooled to room temperature. Methyl ethyl ketone was added to obtain a compound (A) -101 containing a furyl group having a solid content of 50%. A molecular weight of 239.10 was confirmed by mass spectrometry using EI-MS (PolarisQ manufactured by Thermo). (Theoretical value 239.08)

Synthesis Example 2: Compound (A) -102
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube was charged with 50 parts by weight of methyl ethyl ketone, 50 parts by weight of furfurylamine, and 0.1 parts by weight of dibutyltin dilaurate. After that, a solution of 43 parts by weight of 1,6-hexamethylene diisocyanate in 40 parts by weight of methyl ethyl ketone was added dropwise over 2 hours. Subsequently, the reaction was allowed to proceed at 60 ° C. for 3 hours, and then the reaction solution was cooled to room temperature. Methyl ethyl ketone was added to obtain a compound (A) -102 containing a furyl group having a solid content of 50%. A molecular weight of 362.17 was confirmed by mass spectrometry using EI-MS (PolarisQ manufactured by Thermo). (Theoretical value 362.20)

Synthesis Example 3: Compound (A) -103
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone, 50 parts by weight of furfurylamine, and 0.1 parts by weight of dibutyltin dilaurate. After that, a solution of 85 parts by weight of trimeric 1,6-hexamethylene diisocyanate in 50 parts by weight of methyl ethyl ketone was added dropwise over 2 hours. Subsequently, the reaction was allowed to proceed at 60 ° C. for 3 hours, and then the reaction solution was cooled to room temperature. Methyl ethyl ketone was added to obtain a compound (A) -103 containing a furyl group having a solid content of 50%. A molecular weight of 798.40 was confirmed by mass spectrometry using EI-MS (PolarisQ manufactured by Thermo). (Theoretical value 798.38)

Synthesis Example of Comparative Compound: Compound (1)
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone and heated to 70 ° C. in a nitrogen atmosphere. Next, a monomer solution in which 50 parts by weight of n-methyl methacrylate, 50 parts by weight of glycidyl methacrylate, and 3 parts by weight of azobisisobutyronitrile were mixed in advance was added dropwise over 2 hours. Furthermore, after reacting at 70 ° C. for 1 hour, a step of adding 0.3 parts by weight of azobisbutyronitrile and reacting for 1 hour was performed until the monomer addition rate reached 98% or more, and then cooled to room temperature. . Methyl ethyl ketone was added to obtain a compound (1) containing a glycidyl group having a solid content of 50%. The weight average molecular weight was 25000.

Synthesis Example of Comparative Compound: Compound (2)
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone and heated to 70 ° C. in a nitrogen atmosphere. Subsequently, a monomer solution in which 80 parts by weight of n-butyl methacrylate, 20 parts by weight of glycidyl methacrylate, and 3 parts by weight of azobisisobutyronitrile were mixed in advance was dropped over 2 hours. Furthermore, after reacting at 70 ° C. for 1 hour, a step of adding 0.3 parts by weight of azobisbutyronitrile and reacting for 1 hour was performed until the monomer addition rate reached 98% or more, and then cooled to room temperature. . Methyl ethyl ketone was added to obtain a compound (2) containing a hydroxyl group having a solid content of 50%. The weight average molecular weight was 20000.

Synthesis Example of Comparative Compound: Compound (3)
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube was charged with 80 parts by weight of methyl ethyl ketone and heated to 70 ° C. in a nitrogen atmosphere. Next, a monomer solution in which 50 parts by weight of n-methyl methacrylate, 50 parts by weight of tetrahydrofurfuryl methacrylate, and 3 parts by weight of azobisisobutyronitrile were mixed in advance 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 reacting for 1 hour was performed until the monomer addition rate reached 98% or more, and then cooled to room temperature. . Methyl ethyl ketone was added to obtain a compound (3) containing a tetrahydrofuryl group having a solid content of 50%. The weight average molecular weight was 54,000.

(Embodiment 1)
<Manufacture of composition for decorative sheet>
Examples 1-41 and Comparative Examples 1-5
Compound (A) or compounds (1) to (3), a polymerizable compound (B), and a polymerization initiator (C) were blended in parts by weight shown in Table 2 to obtain a composition for a decorative sheet.

Abbreviations in Table 2 are as follows.
PET-30: Nippon Kayaku Co., Ltd. “KAYARAD PET-30” (trifunctional acrylate) DPGDA: Daicel Ornex Co., Ltd. “DPGDA” (bifunctional acrylate)
DPPA: Sartomer "SR399" (pentafunctional acrylate)
DPHA: “A-DPH” (hexafunctional acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
UV-7650B: “Shikko UV-7650B” (urethane acrylate oligomer) manufactured by Nippon Synthetic Chemical Co., Ltd.
UA-3061: Kyoeisha Chemical Co., Ltd. "UA-3061" (urethane acrylate)
V-5500: "Unidic V-5500" (epoxy acrylate) manufactured by DIC
8KX-012C: “Acryt 8KX-012C” (acrylic acrylate) manufactured by Taisei Fine Chemical Co., Ltd.
EBECRYL 1830: “EBECRYL 1830” (ester acrylate) manufactured by Daicel Ornex
Irg184: “Irg184” (photopolymerization initiator) manufactured by BASF (formerly Ciba Japan)
Irg369: “Irg369” (photopolymerization initiator) manufactured by BASF (formerly Ciba Japan)
TPO: “TPO” (photopolymerization initiator) manufactured by BASF (formerly Ciba Japan)
SI-100: “Sine Aid SI-100” (thermal cationic polymerization generator) manufactured by Sun-Aid
B-7982: “7982” (block isocyanate) manufactured by Baxenden
MEK: methyl ethyl ketone PGMAC: propylene glycol monomethyl ether acetate

<Curability evaluation>

The compositions obtained in Examples 1-41 and Comparative Examples 1-5 were applied to a PET base material (thickness 100 μm: “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) using a bar coater, and then dried with hot air A coating film having a thickness of 5 μm was obtained by drying at 80 ° C. for 1 minute using a container. The coating film is cured by UV irradiation (accumulated light amount 400 mJ / cm ² ) at a conveyor speed of 10 m / min using a belt conveyor type UV irradiation device (high pressure mercury lamp 120 W / cm ² lamps), and then dried with hot air The cured film which assumed the coating-film state after heat molding was obtained by heating for 10 minutes at 160 degreeC using a container. Table 3 shows the results of the pencil hardness test and the scratch resistance test of the cured film.

(Pencil hardness test)
The hardness was determined according to the test method of JIS-K-5600. When a decorative film is assumed, H or higher is a usable level.

(Abrasion resistance test)
Using # 0000 steel wool, a load of 500 g / cm ² was applied, and after 10 reciprocal abrasions, the presence or absence of scratches was visually determined. When a decorative film is assumed, it is desirable that there is no scratch.
(Criteria)
○: No scratch △: Slightly scratched ×: Many scratches

<Extension evaluation>
The compositions obtained in Examples 1-41 and Comparative Examples 1-5 were applied to a polycarbonate substrate (thickness 1 mm: “Iupilon Sheet NF-2000” manufactured by Mitsubishi Gas Chemical Company) using a bar coater. Then, the coating film with a film thickness of 5 micrometers was obtained by drying at 80 degreeC for 1 minute using a hot air dryer. The coated film was irradiated with ultraviolet rays (integrated light amount 400 mJ / cm ² ) at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 120 W / cm ² lamps) to obtain a cured film. Table 3 shows the results of an extensibility test using this cured film, assuming a molding process, and a chemical resistance test assuming a specific application such as in the automobile field.

(Extension test)
Each cured film was cut together with a base material into a dumbbell shape conforming to JIS K6251-1 standard to obtain an extensible test piece. The distance between chucks is 4 cm and the width is 1 cm. A tensile test was performed using the dumbbell pieces. ("EZ-SX" manufactured by Shimadzu Corporation)
Elongation condition: It was carried out at room temperature with a pulling speed of 100 mm / min.
Elongation determination: Based on a distance of 4 cm between chucks as a reference, when pulled to 2.8 cm corresponding to 70% of the original length, 3.2 cm corresponding to 80%, and 3.6 cm corresponding to 90%, The presence or absence of scratches on the coating film was confirmed. When a decorative film is assumed, it is desirable that there is no scratch at all, and it is more desirable that the film can be stretched longer.
(Criteria)
◯: No scratch Δ: About 10 to 20 scratches enter ×: Many scratches enter

(Chemical resistance test)
Each cured film was cut into a 4 cm square with the substrate and then baked for 10 minutes in a hot air drier (160 ° C.) to obtain a cured film in which (ideally) thermal crosslinking proceeded.
A PET film (thickness 50 μm) cut into a 3 cm square after putting 30 mg of sunscreen cream (“UltraSheer, SPF # 55” manufactured by Neutrogena) on the center of the test piece
Over it. By applying a load uniformly from the upper part of the PET film, the cream was stretched into a uniform circular shape (diameter 1.8 cm).
Under the following conditions, leave it in a hot air dryer (80 ° C., 12 hours), allow it to cool to room temperature, wash off the cream with tap water, and visually observe the appearance of the surface of the test piece. Was judged.

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

(Criteria)
○: No change in appearance (transparent)
△: Slightly cloudy ×: Whitening occurs (no transparency)

Compared with a system using thermal crosslinking by epoxy crosslinking using a thermal cation generator as in Comparative Example 1 and a system using thermal crosslinking with block isocyanate and hydroxyl group as in Comparative Example 2, the furan of the present invention. It was revealed that the system (Examples 1 to 41) using thermal crosslinking of acryl and acrylic is clearly superior in terms of hard coat properties (pencil hardness, scratch resistance) of the coating film. It is assumed that the difference in reaction form used for crosslinking is reflected in curability, but details are not clear.
Moreover, it became clear that the crosslinked film | membrane using the composition for decorating sheets of this invention was excellent in the extensibility, and has sufficient extensibility adaptable to a decorating film.

  As described above, the crosslinked film using the decorative sheet composition of the present invention has sufficient extensibility, but has furan groups in the decorative sheet composition as shown in Examples 7 to 11. It became clear that the extensibility can be further increased with the increase in the weight average molecular weight of the compound (A), and that a particularly preferable result is obtained when the weight average molecular weight is 100,000 or more.

  As shown in Examples 21 to 38, it was revealed that a cross-linked film having sufficient extensibility and hard coat properties was obtained by blending with various polymerizable compounds (B) and a polymerization initiator (C).

In addition, when the polyfunctional acrylate is used alone as in Comparative Example 3, the degree of cross-linking is increased, so that the hard coat properties such as pencil hardness and scratch resistance are very good, but the extensibility is very poor, so that it is decorated. It is difficult to adapt to the seat. Furthermore, when urethane acrylate, which is generally considered to have a good balance between curability and extensibility as in Comparative Example 4, is used alone, the pencil hardness is not a problem and the extensibility is improved as compared with Comparative Example 3, but it is not sufficient. The results are inferior compared with the case where the cross-linking composition of the present invention is used. On the other hand, when an acrylic resin having a tetrahydrofuryl group is used as in Comparative Example 5, it is difficult to adapt to a decorative sheet because the coating film has no hard coat property and slightly extensibility. As described above, it indicates that the thermal crosslinking reaction does not proceed unless it is a furyl group, and that the function as an inert component does not reach that of a compound having a furyl group.

  Therefore, the composition for a decorative sheet of the present invention can correspond to various thermoformings by being composed of a compound (A) having a furyl group, a polymerization composition (B), and a polymerization initiator (C). It was revealed that a crosslinked film having excellent extensibility and hard coat properties for obtaining a decorative film can be obtained.

<Vacuum formability test>
After coating the compositions obtained in Examples 1-41 and Comparative Examples 1-5 on a polycarbonate substrate (thickness 1 mm: “Iupilon Sheet NF-2000” manufactured by Mitsubishi Gas Chemical Company) using a bar coater Then, a coating film having a film thickness of 5 μm was obtained by drying for 1 minute at 80 ° C. using a hot air dryer, and the coating film was used using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 120 W / cm ² lamps). The decorative sheet was obtained by ultraviolet irradiation (accumulated light amount 400 mJ / cm ² ) at a conveyor speed of 10 m / min.
Subsequently, the decorative sheet is set on a vacuum molding machine (“300X” manufactured by Seiko Sangyo Co., Ltd.), and heated vacuum molding (heater) using a rectangular parallelepiped (length: 65 mm, width 65 mm, height 25 mm) Temperature 300 ° C., estimated substrate surface temperature 200 ° C.). Table 2 shows the results of observing the appearance and confirming that there are no cracks or cracks in the decorative sheet during molding.
(Criteria)
○: Clear without cracks or cracks △: Partially confirmed cracks or cracks ×: Confirmed overall cracks or cracks

The decorative sheet having a cured film formed from the composition for a decorative sheet of the present invention resulted in excellent moldability. Therefore, it became clear that it has the 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 showed excellent chemical resistance (Examples 1 to 41, Comparative Examples 1 to 5: Condition 1). By having resistance to sunscreen cream, it can be preferably used for automobile applications, particularly interior parts of automobiles.

  The decorative sheet having a cured film formed from the crosslinked composition for a decorative sheet of the present invention exhibits sufficient chemical resistance, but the polymer compound (A) having a furan group in the crosslinked composition is hydroxyl. It has been revealed that the presence of a group exhibits good chemical resistance even under severe conditions. (Examples 12-17, 32-38: Condition 2)

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

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

<Extension evaluation>
After coating the obtained composition for decorative sheets on a polycarbonate substrate (thickness 1 mm: “Iupilon sheet NF-2000” manufactured by Mitsubishi Gas Chemical Company) using a bar coater, a hot air dryer is used. A coating film having a thickness of 5 μm was obtained by drying at 80 ° C. for 1 minute. The coated film was irradiated with ultraviolet rays (integrated light amount 400 mJ / cm ² ) at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 120 W / cm ² lamps) to obtain a cured film. Table 5 shows the results of the following extensibility test using this cured film and assuming a molding process.

Each cured film was cut together with a base material into a dumbbell shape conforming to JIS K6251-1 standard to obtain an extensible test piece. The distance between chucks is 4 cm and the width is 1 cm. A tensile test was performed using the dumbbell pieces. ("EZ-SX" manufactured by Shimadzu Corporation)
Elongation condition: It was carried out at room temperature with a pulling speed of 100 mm / min.
Elongation determination: Based on the distance between chucks of 4 cm, the presence or absence of scratches on the coating film was confirmed when pulled to 2.8 cm corresponding to 70% of the original length and 3.2 cm corresponding to 80%. . When a decorative film is assumed, it is desirable that there is no scratch at all.
(Criteria)
○: No scratch Δ: About 10 to 20 scratches enter ×: Many scratches enter <Vacuum formability test>
Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

As shown in comparison with Comparative Examples 1 to 5, even when a low molecular compound is used as the compound (A) having a furan group, the decorative sheet composition of the present invention has good hard coat properties and extensibility. And moldability. On the other hand, in the case where more extensibility is required, the possibility of using a high molecular compound rather than a low molecular compound as the compound (A) having a furan group is indicated.

The cross-linked film obtained from the decorative sheet composition of the present invention is compatible with a high level of moldability and hard coatability, and therefore can be applied to various molding methods by using the composition of the present invention. It is possible to obtain an excellent decorative film.
The use of the decorative film is not particularly limited as long as it is a plastic decoration. For example, electronic devices such as mobile phones such as Martphones, notebook computers including mobile computers, interior and exterior parts for automobiles, It can be used in fields such as building materials.

Claims (8)

A decorative sheet for molding having a cured film obtained by curing a decorative sheet composition with active energy rays on a plastic substrate, wherein the decorative sheet composition contains a furyl group (A ), A polymerizable compound (B), and an active energy ray polymerization initiator (C) . The decorative sheet for molding according to claim 1, wherein the compound (A) containing a furyl group is a polymer having a weight average molecular weight of 1000 or more. The decorative sheet for molding according to claim 1 or 2, wherein the compound (A) containing a furyl group is a polymer of a monomer containing a monomer (a-1) containing a furyl group. . The compound (A) containing a furyl group is a polymer of a monomer containing a monomer (a-1) containing a furyl group and a monomer having a hydroxyl group. 3. The decorative sheet for molding according to any one of 3 above. The decorative sheet for molding according to claim 3 or 4, wherein the monomer (a-1) is furfuryl methacrylate. The compound (A) containing a furyl group is a monomer containing a furyl group, a reaction product of an isocyanate and an alcohol containing a furyl group, a reaction product of an isocyanate and an amine containing a furyl group, or glycidyl (meth) acrylate and The decorative sheet for molding according to claim 1, wherein the decorative sheet is a reaction product with an alcohol or an amine containing a furyl group. It claims 1-6 molding articles formed from the decorative sheet according to any one.   A first step of applying to the substrate a composition for a decorative sheet comprising a compound (A) containing a furyl group, a polymerizable compound (B), and a polymerization initiator (C); and active energy rays The manufacturing method of the molded product containing the 2nd process hardened | cured by irradiating, and the 3rd process to shape | mold.