JP2019026832A - Coating and decorative sheet using the same - Google Patents

Abstract

To provide a coating excellent in scratch resistance, crack resistance, flexure resistance and contamination removal property, and capable of forming a coated film excellent in adhesiveness with a film substrate even when a polyethylene terephthalate resin film or polybutylene terephthalate resin constitutes a coated film forming surface of the film substrate, especially preferably containing no solvent.SOLUTION: There is provided a coating containing (A) a (meth)acrylate compound of 100 pts.mass and (B) a compound having two or more isocyanate groups in a molecule of 1 to 45 pts.mass, in which the (A) (meth)acrylate compound comprises (a1) epoxy modified (meth)acrylate of 1 to 90 mass% and (a2) (meth)acrylate other than epoxy modified (meth)acrylate of 99 to 10 mass%. The component (a2) is preferably (meth)acrylate other than the epoxy modified (meth)acrylate and is a mixture of polyfunctional (meth)acrylate and monofunctional (meth)acrylate.SELECTED DRAWING: Figure 1

Description

The present invention relates to a paint. More specifically, the present invention relates to a paint capable of forming a coating film excellent in adhesion to a film substrate, and a decorative sheet using the same.

Conventionally, household appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; furniture such as display cabinets, storage cabinets, cupboards, and desks; or building members such as floors, walls, and bathrooms; Substrates made of wood-based materials such as plywood, laminated wood, particle board, and hard board; base materials made of resin-based materials such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate, and polyester; or A substrate made of a metal-based material such as iron or aluminum is used in which a decorative sheet is pasted on the surface of the base material;

In recent years, as a point of differentiation of products, the design is increasingly emphasized. Therefore, it has been proposed to form a highly glossy coating film on the surface layer of the decorative sheet or to form a matte coating film made of a paint containing a matting agent (for example, Patent Documents 1 and 2). Moreover, solvent-free coating compositions are required from the viewpoint of work environment and work safety. However, the adhesion between the coating film and the film substrate, particularly a coating film formed using a substantially solvent-free coating film-forming coating film and a film substrate such as a polyethylene terephthalate resin film or a polybutylene terephthalate resin film. There was a problem that the adhesion to the material was not sufficient.

JP2012-091487A JP 2013-031995 A

The subject of this invention is providing the coating material which can form the coating film excellent in adhesiveness with a film base material. Further problems of the present invention are excellent in scratch resistance, crack resistance, bending resistance, and dirt removability, and constitute the coating film forming surface of the film base material for adhesion to the film base material. An object of the present invention is to provide a paint capable of forming an excellent coating film, particularly preferably a substantially solvent-free paint, even if it is a polyethylene terephthalate resin or a polybutylene terephthalate resin.

As a result of earnest research, the present inventor has found that the above-described problems can be achieved by a specific paint.

That is, the present invention comprises (A) (meth) acrylate compound 100 parts by mass; and
(B) 1 to 45 parts by mass of a compound having two or more isocyanate groups in one molecule;
Wherein the (A) (meth) acrylate compound is (a1) epoxy-modified (meth) acrylate 1 to 90% by mass; and
(A2) 99 to 10% by mass of (meth) acrylate other than epoxy-modified (meth) acrylate;
Here, the sum of (a1) epoxy-modified (meth) acrylate and (meth) acrylate other than (a2) epoxy-modified (meth) acrylate is 100% by mass.

In the second invention, (meth) acrylate other than the above (a2) epoxy-modified (meth) acrylate is
(A2-1) 10 to 80% by mass of polyfunctional (meth) acrylate other than epoxy-modified (meth) acrylate; and
(A2-2) monofunctional (meth) acrylate other than epoxy-modified (meth) acrylate, 90 to 20% by mass;
Here, the sum of the polyfunctional (meth) acrylate other than the (a2-1) epoxy-modified (meth) acrylate and the monofunctional (meth) acrylate other than the (a2-2) epoxy-modified (meth) acrylate is 100% by mass. The paint according to the first invention.

3rd invention is the coating material as described in 2nd invention in which monofunctional (meth) acrylates other than the said (a2-2) epoxy modified (meth) acrylate contain phenoxy (meth) acrylate.

4th invention is a coating material in any one of 1st-3rd invention, Comprising: It is a coating material which does not contain an inorganic particle.

A fifth invention is the paint according to any one of the first to fourth inventions, and does not contain a solvent.

6th invention is an article | item containing the coating film formed using the coating material in any one of 1st-5th invention.

7th invention is a decorative sheet containing the coating film formed using the coating material of any one of 1st-5th invention.

8th invention has the layer of the coating film formed using the coating material in any one of 1st-5th invention, and the film base material; The said coating film and the layer of said film base material are It is directly laminated; the evaluation of the cross cut test measured according to JIS K5600-5-6: 1999 is classification 0, 1, or 2; it is a decorative sheet.

A ninth invention is the decorative sheet according to the eighth invention, wherein the coating film-forming surface of the film substrate is a polyethylene terephthalate resin or a polybutylene terephthalate resin.

A tenth invention is an article including the decorative sheet according to any one of the seventh to ninth inventions.

The coating film formed using the coating material of this invention is excellent in adhesiveness with a film base material. The coating film formed using the preferred coating material of the present invention is excellent in scratch resistance, crack resistance, bending resistance, and dirt removal property, and has excellent adhesion to the film substrate, and the coating film of the film substrate. Even if the forming surface is composed of a polyethylene terephthalate resin or a polybutylene terephthalate resin, it is excellent even if the paint of the present invention is substantially solvent-free. Therefore, the paint of the present invention can be suitably used as a paint for forming a coating film on an article such as a decorative sheet.

In this specification, the term “film” is used interchangeably or interchangeably with “sheet”. In this specification, the terms “film” and “sheet” are used for what can be rolled up in a roll form industrially. The term “plate” is used for those that cannot be rolled up industrially in roll form. The term “resin” is used as a term including a resin mixture containing two or more resins and a resin composition containing components other than resins. Further, in this specification, laminating a certain layer and another layer in order means laminating those layers directly and interposing one or more other layers such as anchor coats between these layers. Including both lamination.

In the present specification, the term “or more” relating to a numerical range is used in the sense of a certain numerical value or a certain numerical value. For example, 20% or more means 20% or more than 20%. The term “below” relating to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol “˜” relating to a numerical range is used to mean a certain numerical value, a certain numerical value and less than a certain other numerical value, or another certain numerical value. Here, it is assumed that some other numerical value is larger than a certain numerical value. For example, 10-90% means 10%, more than 10% and less than 90%, or 90%.

Unless otherwise specified, or unless otherwise specified, all numerical values used in the specification and claims are to be understood as being modified by the term “about”. Without attempting to limit the application of the doctrine of equivalents to the claims, each number should be interpreted in the light of significant figures and by applying conventional rounding techniques.

1. paint:
The coating material of the present invention includes (A) (meth) acrylate compound; and (B) a compound having two or more isocyanate groups in one molecule. The component (A) includes (a1) an epoxy-modified (meth) acrylate. The component (A) comprises (a1) epoxy-modified (meth) acrylate; and (a2) (meth) acrylates other than epoxy-modified (meth) acrylate. In the present specification, (meth) acrylate means methacrylate or acrylate. Hereinafter, each component will be described.

(A) (Meth) acrylate compound:
The component (A) is a (meth) acrylate having one or more (meth) acryloyl groups in one molecule. The component (A) functions to form a hard coat by being polymerized and cured by active energy rays such as ultraviolet rays and electron beams. The component (A) includes (a1) an epoxy-modified (meth) acrylate. The component (A) comprises (a1) epoxy-modified (meth) acrylate; and (a2) (meth) acrylates other than epoxy-modified (meth) acrylate.

(A1) Epoxy-modified (meth) acrylate:
The component (a1) is a (meth) acrylate modified with a compound having an epoxy group such as epichlorohydrin. The component (a1) works to improve the adhesion between the coating film and the film substrate; and the component (B) reacts with a compound having two or more isocyanate groups in one molecule to form a urethane bond. Forming and improving the crack resistance and bending resistance of the coating film.

Examples of the component (a1) include epichlorohydrin-modified trimethylolpropane tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, epichlorohydrin-modified phenoxy (meth) acrylate; epichlorohydride And phosphorous-modified 1-4 butanediol di (meth) acrylate and epichlorohydrin-modified 1-6 hexanediol di (meth) acrylate and other epichlorohydrin-modified alkyldiol di (meth) acrylates; . Among these, as the component (a1), epichlorohydrin-modified alkyl diol di (meth) acrylate is preferable from the viewpoint of adhesion between the coating film and the film substrate. As said component (a1), these 1 type, or 2 or more types of mixtures can be used.

The epichlorohydrin-modified alkyldiol di (meth) acrylate may be a compound represented by the following general formula (1) in one of typical embodiments.

In formula (1), R ₁ represents hydrogen or a methyl group. R ₂ represents hydrogen or a methyl group. R ₃ is a hydrocarbon group having 1 to 100 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms. The hydrocarbon group may be linear or branched. The hydrocarbon group may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group.

(A2) (Meth) acrylates other than epoxy-modified (meth) acrylate:
The component (a2) is a (meth) acrylate other than the epoxy-modified (meth) acrylate. The component (a2) is preferably a polyfunctional compound other than (a2-1) epoxy-modified (meth) acrylate, from the viewpoint of scratch resistance, crack resistance, bending resistance, dirt removal, and transfer film peelability. (Meth) acrylate; and (a2-2) monofunctional (meth) acrylate other than epoxy-modified (meth) acrylate.

The component (a2-1) is a (meth) acrylate other than the epoxy-modified (meth) acrylate, and is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule. The component (a2-1) functions to improve surface hardness, scratch resistance, and contamination resistance.

Examples of the component (a2-1) include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2, Bifunctional reactions containing (meth) acryloyl groups such as 2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane Monomer (trimethylolpropane tri (meth) acrylate), trimethylolethane tri (meth) acrylate, and (meth) acryloyl group-containing trifunctional reactive monomer such as pentaerythritol tri (meth) acrylate; pentaerythritol tet (Meth) acryloyl group-containing tetrafunctional reactive monomer such as (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomer such as dipentaerythritol hexaacrylate; (meth) acryloyl group-containing 8 such as tripentaerythritol acrylate 8 Examples of the functional reactive monomer and a polymer (oligomer or prepolymer) having one or more of these as constituent monomers and having two or more (meth) acryloyl groups in one molecule can be given.

Examples of the component (a2-1) include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. Examples thereof include (meth) acryloyl group-containing prepolymers or oligomers such as (meth) acrylates and having two or more (meth) acryloyl groups in one molecule.

As said component (a2-1), these 1 type, or 2 or more types of mixtures can be used.

The component (a2-2) is (meth) acrylate other than epoxy-modified (meth) acrylate, and is (meth) acrylate having one (meth) acryloyl group in one molecule. The component (a2-2) functions to improve crack resistance and bending resistance. It also serves to lower the viscosity of the paint and improve the coatability.

Examples of the component (a2-2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth). Acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxy Ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate DOO, and, and the like trimethylsiloxy ethyl methacrylate.

Examples of the component (a2-2) include phenoxyethyl (meth) acrylate, phenoxybutyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxybenzyl (meth) acrylate. And phenoxy (meth) acrylate.

Examples of the component (a2-2) include polyester (meth) acrylate, polyacrylic (meth) acrylate, polyalkylene glycol poly (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate. Examples of the polymer or oligomer include one having one (meth) acryloyl group in one molecule.

Examples of the component (a2-2) include 2- (meth) acryloyloxyethyl-succinic acid, 2-acryloyloxyethylhexahydrophthalic acid, and 2-acryloyloxyethyl-2-hydroxyethyl-phthalate. Examples thereof include (meth) acrylic acid adducts of esters such as acids or ester derivatives.

Examples of the component (a2-2) include N-methyl (meth) acrylamide, N-methylol (meth) acrylamide butyl ether, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, and N-isopropyl. (Meth) acrylamide, N-cyclopropyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-methyl, N-ethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide methyl ether, N-methylol (meth) acrylic N-substituted such as midethyl ether, N-methylol (meth) acrylamide propyl ether, N-butoxymethyl (meth) acrylamide, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and (meth) acryloylmorpholine (Meth) acrylamide compounds can be mentioned.

Among these, the component (a2-2) is preferably phenoxy (meth) acrylate, more preferably phenoxybenzyl (meth) acrylate, and m-phenoxybenzyl (m) from the viewpoint of scratch resistance and soil removability. More preferred is (meth) acrylate. As said component (a2-2), these 1 type, or 2 or more types of mixtures can be used.

The amount of the component (a1) in the component (A) is such that the sum of the component (a1) and the component (a2) is 100% by mass, the adhesion between the coating film and the film substrate, From the viewpoint of crack resistance and bending resistance, it is usually 1% by mass or more (the component (a2) is 99% by mass or less), preferably 5% by mass or more (the component (a2) is 95% by mass or less), more preferably. It is 10 mass% or more (the said component (a2) 90 mass% or less), More preferably, it is 15 mass% or more (the said component (a2) 85 mass% or less). On the other hand, from the viewpoint of lowering the coating viscosity and improving the coating property and from the viewpoint of transfer film peelability, it is usually 90% by mass or less (the above component (a2) is 10% by mass or more), preferably 70% by mass or less (above Component (a2) 30% by mass or more), more preferably 60% by mass or less (the above component (a2) 40% by mass or more), further preferably 45% by mass or less (the above component (a2) 55% by mass or more), most preferably Is 40 mass% or less (60 mass% or more of the said component (a2)).

The amount of the component (a2-1) in the component (a2) is such that the sum of the component (a2-1) and the component (a2-2) is 100% by mass, surface hardness, scratch resistance, and From the viewpoint of soil removability, it is preferably 10% by mass or more (the above component (a2-2) 90% by mass or less), more preferably 20% by mass or more (the above component (a2-2) 80% by mass or less), and still more preferably. May be 30% by mass or more (the above component (a2-2) is 70% by mass or less). On the other hand, from the viewpoint of lowering the viscosity of the paint and improving the coating property, crack resistance, and bending resistance, it is preferably 80% by mass or less (the above component (a2) is 20% by mass or more), more preferably. It may be 65% by mass or less (35% by mass or more of the component (a2)), more preferably 50% by mass or less (50% by mass or more of the component (a2-2)).

(B) Compound having two or more isocyanate groups in one molecule:
The component (B) is a compound having two or more isocyanate groups (—N═C═O) in one molecule. The component (B) reacts with the component (a1) to form a urethane bond, and serves to improve the crack resistance and bending resistance of the coating film. It also serves to improve the adhesion between the coating film and the film substrate.

Examples of the component (B) include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, isophorone A polyisocyanate such as a trimethylolpropane adduct of diisocyanate, an isocyanurate of tolylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, an isocyanurate of isophorone diisocyanate, a biuret of hexamethylene diisocyanate; and a block type of the above polyisocyanate Can include urethane crosslinkers such as isocyanate .

The component (B) is preferably a compound having three isocyanate groups in one molecule from the viewpoint of crack resistance and bending resistance of the hard coat, and isocyanurate of hexamethylene diisocyanate, hexamethylene diisocyanate. The biuret body is more preferable. As said component (B), these 1 type, or 2 or more types of mixtures can be used. In addition, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as desired as long as the object of the present invention is not adversely affected.

The compounding amount of the component (B) is usually 45 parts by mass or less, preferably 35 parts by mass or less, more preferably 30 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint of curability by active energy rays. Part or less, more preferably 25 parts by weight or less. On the other hand, from the viewpoint of reliably obtaining the use effect of the component (B), it may be usually 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more.

The coating material of the present invention can further contain a photopolymerization initiator from the viewpoint of improving curability by active energy rays.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. it can. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

In the coating material of the present invention, an active energy ray-curable resin other than the above component (a1) and the above component (a2) and an isocyanate group other than the above component (B) are optionally added as long as they do not contradict the purpose of the present invention. Compounds, antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weathering stabilizers, lightfastness stabilizers, UV absorbers, heat stabilizers, One kind or two or more kinds of optional components such as inorganic particles, organic particles, and a colorant can be contained.

Since the coating material of the present invention is diluted to a concentration easy to apply, a solvent may be included if desired. The solvent is not particularly limited as long as it does not react with the above components (A), (B), and other optional components, and does not catalyze (promote) the self-reaction (including degradation reaction) of these components. Not. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As the solvent, one or a mixture of two or more of these can be used.

The paint of the present invention preferably does not contain inorganic particles. In general, inorganic particles (eg, silica (silicon dioxide); metal oxide particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Metal fluoride particles such as magnesium fluoride and sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles; etc.), especially inorganic particles of appropriate particle size impart a matte design. It is useful from the viewpoint. On the other hand, the interaction with the resin component such as the above component (A) is weak, which causes insufficient scratch resistance and bending resistance. Therefore, in one aspect of the present invention, a transfer foil is used as will be described later in order to impart a matte design, and the coating film-forming paint does not contain inorganic particles so as to have scratch resistance and bending resistance. Good holding.

Here, “does not contain” inorganic particles means that it does not contain a significant amount of inorganic particles. In the field of coating film-forming paints, the significant amount of inorganic particles is usually about 1 part by mass or more with respect to 100 parts by mass of the component (A) from the viewpoint of imparting a matte design. Therefore, “does not contain” inorganic particles means that the amount of the inorganic particles is usually less than 1 part by mass, preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass with respect to 100 parts by mass of the component (A). In other words, it can be paraphrased as not more than 0.05 parts by mass, more preferably not more than 0.05 parts by mass, most preferably not more than 0.01 parts by mass.

The paint of the present invention preferably contains no solvent. Since the coating material of the present invention includes the component (a1), in one embodiment, the coating material includes the component (a1) and the component (a2-2). Therefore, the coating can be applied without including a solvent. By not including the solvent, there is an effect that it is possible to omit the drying step after coating the paint, the treatment step of the solvent recovered in the drying furnace, and the like. In addition, the risk of accidents due to solvent explosion and combustion is greatly reduced.

Here, “does not contain a solvent” means that it does not contain a significant amount of solvent. In the field of coating film-forming paints, a significant amount of the solvent is usually about 5 parts by mass or more with respect to 100 parts by mass of the component (A) from the viewpoint of dilution to a concentration that facilitates coating. Therefore, “does not contain a solvent” means that the amount of the solvent is usually less than 5 parts by weight, preferably 3 parts by weight or less, more preferably 1 part by weight, and still more preferably, with respect to 100 parts by weight of the component (A) In other words, it can be paraphrased as 0.5 parts by mass or less, most preferably 0.1 parts by mass or less.

The paint of the present invention can be obtained by mixing and stirring these components.

The method for forming a coating film using the paint of the present invention is not particularly limited, and a known web coating method can be used. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

As a preferable method of forming a coating film using the paint of the present invention, for example,
(1) The process of forming the wet coating film of the coating material of this invention on the at least one surface of a film base material;
(2) A step of pre-drying the wet coating film obtained in the above step (1) to form a dry coating film;
(3) A step of overlaying and temporarily attaching an active energy ray-permeable film on the surface of the dried coating film obtained in the step (2); and
(4) A step of irradiating the laminate obtained in the step (3) with active energy rays to cure the dried coating film;
Can be mentioned.

The film base material used in the step (1) is not particularly limited, and any resin film can be used as the film base material. Examples of the resin film include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly (meth) acrylimide resins; polyolefins such as polyethylene, polypropylene, and polymethylpentene. Resins; Cellulosic resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / Styrene resins such as ethylene / propylene / styrene copolymers and styrene / ethylene / ethylene / propylene / styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride Resin films such as fluorinated resins such as polyvinylidene fluoride; polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, polyethersulfone; Can give. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the laminated film which laminated | stacked 2 or more of these 1 or more types is included.

When the film substrate is one of the constituent layers of the decorative sheet, the wet coating film-forming surface of the film substrate is corona discharge from the viewpoint of enhancing the adhesion between the film substrate and the hard coat. It may be subjected to easy adhesion treatment such as treatment or anchor coat formation.

Moreover, when the said film base material is one of the constituent layers of a decorative sheet, the thickness of the said film base material is although it does not restrict | limit in particular, From a handling viewpoint, it may be 20 micrometers or more normally, Preferably it may be 30 micrometers or more. From the viewpoint of design properties, it may be usually 50 μm or more, preferably 80 μm or more. On the other hand, from the viewpoint of thinning the decorative sheet, it may be usually 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less.

When the coating film formed on the surface of the film base material is transferred to another film base material and used, the wet coating film forming surface of the film base material has been subjected to easy peeling treatment. It's okay.

In addition, when the coating film formed on the surface of the film base material is transferred to another film base material and used, the thickness of the film base material is not particularly limited, but from the viewpoint of handling properties, usually 20 μm or more, Preferably, it may be 30 μm or more. On the other hand, from the viewpoint of economy, it may be usually 100 μm or less, preferably 75 μm or less.

The method for forming the wet coating film of the paint of the present invention in the step (1) is not particularly limited. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

In the step (2), the wet coating film obtained in the step (1) is pre-dried to become a dry coating film. In the preliminary drying, for example, the time required for the web to pass from the inlet to the outlet in the drying furnace set at a temperature of about 23 to 150 ° C., preferably 50 to 120 ° C. is about 0.5 to 10 minutes. , Preferably by passing at a line speed of 1 to 5 minutes.

In addition, when the coating material does not contain a solvent like the coating material mentioned above as a preferable aspect, the said process (2) can also be skipped.

In the step (3), the active energy ray-permeable film is overlaid and temporarily pasted on the surface of the dried coating film obtained in the step (2). Thereby, the oxygen disorder | damage | failure of hardening reaction by active energy ray irradiation of an active energy ray curable resin composition is suppressed.

An example of a method of stacking and temporarily pasting the active energy ray transmissive film on the surface of the dried coating film will be described with reference to FIG. The laminate 6 obtained in the above step (2) is opposite to the dry coating film of the laminate 5 obtained in the above step (2) on the rotating heating drum 7 preheated to a desired temperature. The active energy ray transmissive film 8 is placed on the surface of the dried coating film and is pressure-bonded by a pressure-bonding roll 9. The laminate 10 on which the active energy ray-permeable film 8 is laminated and temporarily attached on the surface of the dried coating film is released from the heating drum 7 by the guide roll 11 and sent to the step (4).

The active energy ray-permeable film is a film having an active energy ray transmittance of usually 70% or more, preferably 80% or more. Here, the active energy ray transmittance is the active energy at a wavelength of 200 to 600 nanometers with respect to the integral area of the transmission spectrum when the active energy ray transmittance is assumed to be 100% over the entire wavelength range of 200 to 600 nanometers. It is the ratio of the integral area of the transmission spectrum of the line, and is a value measured by using a spectrophotometer “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation and making light incident on the film at an incident angle of 0 °.

Preferable examples of the active energy ray transmissive film include a biaxially stretched polyethylene terephthalate resin film, a biaxially stretched polypropylene resin film, and a fluorine-containing resin film.

The bonding surface of the active energy ray transmissive film with the dried coating film may be highly smooth or may be an engraved embossed pattern. When a highly smooth material is used, a high gloss design is imparted. In the case where an embossed pattern is engraved, a design corresponding to the embossed pattern, for example, a hairline design, a leather-like design, and a matte design are given.

In the step (4), active energy rays are usually irradiated from the surface on the active energy ray-permeable film side to the laminate obtained in the step (3), and the dry coating film is cured. It is formed.

Examples of the active energy ray used in the above step (4) include ultraviolet rays and ionizing radiation such as an electron beam. Examples of the active energy ray used in the step (4) include white active energy rays using a high pressure mercury lamp, a metal halide lamp, or the like as a light source. Alternatively, the white active energy ray may be monochromatized using a filter such as a 365 filter (short wave cut filter), a 254 filter (long wave cut filter), or a 300 filter.

The irradiation amount of the active energy ray in the step (4) is appropriately adjusted depending on the curing characteristics, hard coat thickness, line speed, and the like of the active energy ray curable resin composition. The said irradiation amount may be 10-10000 mJ / cm < ² > normally, Preferably it may be 50-1000 mJ / cm < ² >.

As a preferable method of forming a coating film using the paint of the present invention, for example,
(1 ′) a step of forming a wet coating film of the paint of the present invention on at least one surface of the active energy ray-permeable film;
(2 ′) a step of pre-drying the wet coating film obtained in the above step (1 ′) to form a dry coating film;
(3 ′) a step of stacking a film base material on the surface of the dried coating film obtained in the above step (2 ′) and temporarily attaching it; and
(4 ′) A step of irradiating the laminate obtained in the step (3 ′) with an active energy ray to cure the dried coating film;
Can be mentioned.

The method described later has an advantage that it can be applied to a film substrate having low solvent resistance as compared with the method described above. Compared to the method described later, the above-described method has an advantage that it is easy to improve the adhesion between the film substrate and the hard coat when the film substrate is one of the constituent layers of the decorative sheet. Have.

The method for forming the wet coating film of the paint of the present invention in the step (1 ') is not particularly limited. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. About the said active energy ray transparent film, it demonstrated in description of the process (3) of the above-mentioned method.

In the step (2 '), the wet coating film obtained in the step (1') is preliminarily dried to become a dry coating film. In the preliminary drying, for example, the time required for the web to pass from the inlet to the outlet in the drying furnace set at a temperature of about 23 to 150 ° C., preferably 50 to 120 ° C. is about 0.5 to 10 minutes. , Preferably by passing at a line speed of 1 to 5 minutes.

As a preferred embodiment, when the paint does not contain a solvent as in the paint described above, the step (2 ') can be omitted.

In the step (3 ′), a film base material is overlaid and temporarily attached on the surface of the dried coating film obtained in the step (2 ′). Thereby, the oxygen disorder | damage | failure of hardening reaction by active energy ray irradiation of an active energy ray curable resin composition is suppressed. The film substrate has been described in the description of the step (1) of the above-described method.

In the step (4 ′), active energy rays are usually applied to the laminate obtained in the step (3 ′) from the surface on the active energy ray-permeable film side to cure the dried coating film. A film is formed. The active energy ray and the irradiation amount thereof have been described in the description of the step (4) of the above method.

2. Makeup sheet:
The decorative sheet of the present invention is a decorative sheet having a coating film formed using the paint of the present invention. The coating film formed using the coating material of the present invention is usually formed as a surface protective layer on the front surface (the surface that is normally visually recognized in the actual use state) of the decorative sheet of the present invention. Here, the actual use state refers to a state in which the decorative sheet is used for makeup and decoration on the surface of various articles.

Examples of the decorative sheet of the present invention include a decorative sheet having a coating film formed by using the paint of the present invention on the front surface of a thermoplastic resin film. At this time, the thermoplastic resin film is a layer serving as a base material of the decorative sheet. The thermoplastic resin film is usually colored from the viewpoint of design and functions to conceal the adherend.

Examples of the thermoplastic resin film include polyvinyl chloride resins; polyester resins such as aromatic polyesters and aliphatic polyesters; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; acrylic resins; polycarbonate resins. Poly (meth) acrylimide resin; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / propylene / styrene copolymer, and styrene / Styrenic resins such as ethylene / ethylene / propylene / styrene copolymers; Cellulosic resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polychlorinated Vinylidene resins; fluorine-containing resins such as polyvinylidene fluoride; other resins such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone; You can raise a film. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the laminated film which laminated | stacked 2 or more of these 1 or more types is included.

The thickness of the thermoplastic resin film is not particularly limited, but may be preferably 50 μm or more, and more preferably 75 μm or more, from the viewpoint of handleability during production of a decorative sheet. On the other hand, from the viewpoint of thinning the decorative sheet, it may be usually 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less. From the viewpoint of workability when attaching a decorative sheet to an article, it may be usually 300 μm or less, preferably 250 μm or less.

As a decorative sheet of the present invention, for example, a printed layer is provided on the front surface of a colored thermoplastic resin film, and a transparent thermoplastic resin film layer is provided on the surface of the printed layer. Furthermore, a decorative sheet having a hard coat formed by using the coating material of the present invention can be mentioned on the front side of the transparent thermoplastic resin film layer.

Examples of the colored thermoplastic resin film include polyvinyl chloride resins; polyester resins such as aromatic polyesters and aliphatic polyesters; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; acrylic resins; Polycarbonate resin; poly (meth) acrylimide resin; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / propylene / styrene copolymer, And styrene resins such as styrene / ethylene / ethylene / propylene / styrene copolymers; cellulose resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate Polyvinylidene chloride resin; fluorinated resin such as polyvinylidene fluoride; others, polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone, etc. The resin film can be raised. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the laminated film which laminated | stacked 2 or more of these 1 or more types is included.

The colorant for coloring the colored thermoplastic resin film is not particularly limited, and any colorant can be used. Examples of the colorant include titanium oxide and carbon black. As said coloring agent, these 1 type, or 2 or more types of mixtures can be used. The blending amount of the colorant is usually 0.1 to 40 parts by mass, although the base resin used for the colored thermoplastic resin film is 100 parts by mass, depending on the type of colorant and the desired concealing property. Degree.

The thickness of the colored thermoplastic resin film is not particularly limited, but may be preferably 50 μm or more, more preferably 75 μm or more, from the viewpoint of handleability during production of the decorative sheet. On the other hand, from the viewpoint of thinning the decorative sheet, it may be usually 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less. From the viewpoint of workability when attaching a decorative sheet to an article, it may be usually 300 μm or less, preferably 250 μm or less.

Examples of the transparent thermoplastic resin film include polyester resins such as aromatic polyester and aliphatic polyester; acrylic resins; polycarbonate resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cellophane and triacetyl. Cellulosic resins such as cellulose, diacetylcellulose, acetylcellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / butadiene / styrene copolymer Styrene resins such as coalescence; polyvinyl chloride resins; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; other, polyvinyl alcohol, ethylene vinyl It may be mentioned a film of transparent resin and the like; alcohols, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the laminated film which laminated | stacked 2 or more of these 1 or more types is included.

The thickness of the transparent thermoplastic resin film is not particularly limited, but may be preferably 50 μm or more, and more preferably 75 μm or more, from the viewpoint of handleability during the production of a decorative sheet and from the viewpoint of design. On the other hand, from the viewpoint of thinning the decorative sheet, it may be usually 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less. From the viewpoint of workability when attaching a decorative sheet to an article, it may be usually 300 μm or less, preferably 250 μm or less.

The printing layer is provided for imparting high designability, and can be formed by printing an arbitrary pattern using an arbitrary ink and an arbitrary printing machine.

The printed layer is directly or via an anchor coat on the front surface of the colored thermoplastic resin film, or on the surface opposite to the front surface of the transparent thermoplastic resin film. Can be applied in whole or in part. The patterns include metal-like patterns such as hairlines, wood grain patterns, stone patterns imitating the surface of rocks such as marble, fabric patterns imitating cloth and cloth-like patterns, tiled patterns, brickwork patterns, parquet patterns, And patchwork. As printing ink, what mixed the pigment, the solvent, the stabilizer, the plasticizer, the catalyst, the hardening | curing agent, etc. in the binder suitably can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamides. Resins such as resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used. Moreover, in order to give a metallic design, aluminum, tin, titanium, indium and oxides thereof are directly or via an anchor coat on the front surface of the colored thermoplastic resin film, or You may vapor-deposit by the well-known method in full or part on the surface on the opposite side to the front side of the said transparent thermoplastic resin film.

A method of forming a coating film directly or via an anchor coat on the front surface of the transparent thermoplastic resin film using the paint of the present invention is not particularly limited, and a known web coating method is used. can do. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

In addition, since the coating material of the present invention has excellent adhesion to the film base material, sufficient adhesion can be obtained even by a method of directly forming a coating film on the front surface of the transparent thermoplastic resin film. Can be obtained.

The thickness of the coating film formed using the coating material of the present invention is not particularly limited, but may be usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more from the viewpoint of scratch resistance. Moreover, from the viewpoint of secondary processability and web handling properties of the decorative sheet of the present invention, it may be preferably 100 μm or less, more preferably 50 μm or less.

The anchor coating agent for forming the anchor coat is not particularly limited, and any anchor coating agent can be used. Examples of the anchor coating agent include polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane anchor coating agents. One or more of these can be used as the anchor coating agent.

In the above anchor coating agent, as long as it does not contradict the purpose of the present invention, an antioxidant, a weather resistance stabilizer, a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a surfactant, One or more additives such as a colorant, an infrared shielding agent, a leveling agent, a thixotropic agent, and a filler may be included.

The method for forming the anchor coat using the anchor coat agent is not particularly limited, and a known web coating method can be used. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

The thickness of the anchor coat is not particularly limited, but is usually about 0.01 to 5 μm, preferably 0.1 to 2 μm.

The decorative sheet of the present invention is a surface which is the front side of the colored thermoplastic resin film from the viewpoint of improving the adhesion with the adherend to be decorated and decorated using the decorative sheet of the present invention. An adhesive layer or an adhesive layer may be formed on the opposite surface directly or via an anchor coat.

FIG. 1 is a conceptual cross-sectional view showing an example of the decorative sheet of the present invention. In order from the surface side, a coating film 1, a transparent thermoplastic resin film layer 2, a printing layer 3, a colored thermoplastic resin film layer 4, and an adhesive layer 5 formed using the coating material of the present invention. Have.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measuring method (a) 60 degree gloss value (matte):
Based on JIS Z8741: 1997, Konica Minolta Co., Ltd. multi-angle gloss meter “GM-268 (trade name)” was used, and the 60-degree gloss value was measured under conditions where light was incident on the coating surface of the decorative sheet. did.

(B) Steel wool resistance (scratch resistance):
Placed in a JIS L0849: 2013 Gakushin type testing machine so that the reciprocating direction of the friction terminal and the machine direction of the decorative sheet are parallel so that the coating surface of the decorative sheet is the surface, After attaching # 0000 steel wool to the friction terminal, a 200 g load was placed, and the surface of the test piece was rubbed back and forth 5 times under the conditions of a moving distance of 60 mm and a speed of 1 reciprocation / second. The friction part was visually observed and judged according to the following criteria.
A: No scratch was observed.
○: There were 1 to 5 scratches.
Δ: There were 6 to 20 scratches.
X: There were 21 or more scratches.

(C) Dirt removal:
Absorbent cotton of 10 mm length, 10 mm width, 2 mm thickness was left on the coating surface of the decorative sheet, and the pilot cotton red ink “Pilot Ink Red (trade name)” was sufficiently contained in the absorbent cotton. Drop it onto the absorbent cotton until it reaches a state (usually about 1 mL) and leave it for 24 hours in an environment at room temperature of 25 ° C. and a relative humidity of 50%. Then, the absorbent cotton is removed, and the contaminated area is washed with a dishwashing detergent “ Using Mama Lemon (trade name), 3M's dishwashing sponge "Scotch Bright Antibacterial Urethane Sponge, Leaf Type / 3 Layers, No Abrasive Particles (trade name)" was washed with water to wash dishes. Then, the contaminated part was visually observed and evaluated according to the following criteria.
A: Contamination was completely removed, and the contaminated part was not known.
○: Contamination was almost completely removed. However, a slight amount of contamination remained and the contaminated part could be identified.
Δ: Contamination remained, and the contaminated portion was reddish.
X: Contamination remained remarkably, and the contaminated portion remained red after washing with water.

(D) Mandrel test (crack resistance, bending resistance):
In accordance with JIS K5600-5: 1999, a sample taken from the decorative sheet so that the decorative sheet had a machine direction of 100 mm × lateral direction of 50 mm was subjected to a bending resistance test by a cylindrical mandrel method. The diameter of the mandrel with the smallest diameter among the mandrels that did not crack was determined.

(E) Cross cut test (coating adhesion):
In accordance with JIS K5600-5-6: 1999, 100 squares (1 square = 1 mm × 1 mm) of grid cuts are made on the decorative sheet from the coating surface side, and then a tape for adhesion test is applied to the grid with fingers. After crushing, it was peeled off. Evaluation criteria were in accordance with Table 1 of the above JIS standard.
Classification 0: The edges of the cuts are completely smooth, and there is no peeling in any lattice eye.
Classification 1: Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
Classification 2: The coating film is peeled along the edge of the cut and / or at the intersection. The cross-cut portion is clearly affected by more than 5% but not more than 15%.
Classification 3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
Classification 4: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 35% but not more than 65%.
Category 5: When the degree of peeling exceeds Category 4.

(F) Transfer film peelability:
From the laminate of the decorative sheet and transfer foil immediately after UV irradiation curing, a test piece is collected so that the machine direction of the laminate coincides with the peeling direction, and the T-shaped peel strength between the decorative sheet and the transfer film is measured. , Measured according to JIS K6854-3: 1999. The T-type peel strength was evaluated according to the following criteria.
A: Less than 5 g / 25 mm.
A: 5 g / 25 mm or more and less than 50 g / 25 mm.
Δ: 50 g / 25 mm or more and less than 200 g / 25 mm.
X: 200 g / 25 mm or more.

Raw materials used (A) Active energy ray curable resin:
(A1) Epoxy-modified (meth) acrylate:
(A1-1) Epichlorohydrin-modified 1-6 hexanediol diacrylate “Kayarad R-167 (trade name)” of Nippon Kayaku Co., Ltd. In the above general formula (1), a compound in which R ₁ is hydrogen, R ₂ is hydrogen, and R ₃ is (CH ₂ ) ₆ .

(A2) (Meth) acrylates other than epoxy-modified (meth) acrylate:
(A2-1) Polyfunctional (meth) acrylates other than epoxy-modified (meth) acrylate:
(A2-1-1) Dipentaerythritol hexaacrylate “Kayarad DPHA (trade name)” manufactured by Nippon Kayaku Co., Ltd.

(A2-2) Monofunctional (meth) acrylate other than epoxy-modified (meth) acrylate:
(A2-2-1) m-phenoxybenzyl acrylate (CAS No. 409325-06-0) “Light acrylate POB-A (trade name)” of Kyoeisha Chemical Co., Ltd.
(A2-2-2) Isobornyl acrylate “Light acrylate IB-XA (trade name)” of Kyoeisha Chemical Co., Ltd.

(B) Compound having two or more isocyanate groups in one molecule:
(B-1) Hexamethylene diisocyanate biuret (1,3,5-tris (6-isocyanatohexyl) biuret) “Duranate 24A-100 (trade name)” manufactured by Asahi Kasei Corporation.
(B-2) Hexamethylene diisocyanate isocyanurate "Duranate TPA-100 (trade name)" manufactured by Asahi Kasei Corporation.

(C) Other ingredients:
(C-1) Acylphosphine oxide photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) “IRGACURE TPO (trade name)” manufactured by BASF.
(C-2) An acetophenone photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) “IRGACURE 1173 (trade name)” manufactured by BASF.
(C-3) Benzophenone from Wako Pure Chemical Industries, Ltd.

(F) Transfer foil:
(F-1) High-gloss transfer foil “SH37 (trade name)” using biaxially stretched polyethylene terephthalate manufactured by SKC as a base film. Active energy ray transmittance 82%.
(F-2) A textured transfer foil “SWPP MAM-430 (trade name)” made by polypropylene resin of Riken Technos Co., Ltd. Active energy ray transmittance 84%.

(G) Film substrate:
(G-1) Riken Technos Co., Ltd., thickness 250 μm, white colored polybutylene terephthalate resin film “HR250 (WHT) (trade name)”.
(G-2) Riken Technos Co., Ltd., 120 μm thick, white colored polyvinyl chloride resin film “FC1814 (trade name)”.
(G-3) 100 parts by mass of polyethylene terephthalate “PIFG5 (trade name)” manufactured by Bell Polyester Products Co., Ltd., and 12 masses of titanium oxide (white pigment) “Taipaque CR-60-2 (trade name)” manufactured by Ishihara Sangyo Co., Ltd. A white resin film having a thickness of 250 μm was obtained by a T-die extrusion film forming method using the polyester resin composition with the part.

Example 1
1. Paint preparation:
Component (a1-1) 20 parts by mass, Component (a2-1-1) 30 parts by mass, Component (a2-2-1) 50 parts by mass, Component (B-1) 10 parts by mass, Component above (C-1) 2 parts by mass, 3 parts by mass of the component (C-2) and 3 parts by mass of the component (C-3) were mixed and stirred to obtain a paint.

2. Production of decorative sheets:
(1) Apply the paint obtained in 1 above on one side of the film base (G-1) using a film Mayer bar type coating device so that the thickness after curing is 10 μm. A wet paint film was formed.
(2) Since the paint used did not contain a solvent, the drying step was omitted.
(3) Next, using the apparatus whose conceptual diagram is shown in FIG. 2, the rotating drum 7 in which the laminate 6 of the film base (G-1) and the dried coating film is preheated to a temperature of 30 ° C. is used. On the surface of the laminate 6, the surface opposite to the dry coating film is placed on the heating drum 7 side, and the transfer foil (F-1) 8 is further placed on the surface of the dry coating film. Then, the transfer foil (F-1) 8 was stacked on the surface of the dried coating film and temporarily attached by pressure bonding with the pressure-bonding roll 9. Next, the laminated body 10 which has the said film base material (G-1), the said dry coating film, and the said transfer foil (F-1) in this order was released from the heating drum 7 with the guide roll 11. FIG.
(4) Next, using a high-pressure mercury lamp type ultraviolet irradiation device, the active energy ray is irradiated from the side of the transfer foil (F-1) of the laminate 10 under the condition of an integrated light amount of 240 mJ / cm ² , and the drying The coating film was cured to form a coating film.
(5) Subsequently, the test (f) was performed using the laminate of the decorative sheet and the transfer foil obtained in the step (4). Next, the said transfer foil (F-1) was peeled and removed, and the decorative sheet which has a coating film directly on the one side of the said film base material (G-1) was obtained. The above tests (i) to (e) were conducted. The results are shown in Table 1.

Examples 2-16
The same procedure as in Example 1 was performed except that the formulation of the paint was changed as shown in any one of Tables 1 to 3. The results are shown in any one of Tables 1-3.

Example 17
It carried out similarly to Example 1 except having used the said transfer foil (F-2) instead of the said transfer foil (F-1). The results are shown in Table 3.

Example 18
It carried out similarly to Example 1 except having used the said film base material (G-2) instead of the said film base material (G-1). The results are shown in Table 3.

Example 19
It carried out similarly to Example 1 except having used the said film base material (G-3) instead of the said film base material (G-1). The results are shown in Table 3.

The decorative sheet having a coating film made of the paint of the present invention is excellent in adhesion between the coating film and the film substrate. The decorative sheet having a coating film made of the preferred coating material of the present invention is further excellent in scratch resistance, crack resistance, bending resistance, and soil removability. Moreover, even if the film-forming surface of the film substrate is composed of a polyethylene terephthalate resin or a polybutylene terephthalate resin, sufficient adhesion between the coating film and the film substrate is achieved by directly laminating the coating film. It is expressed. However, the paint used for forming the coating film does not contain a solvent, and the drying step can be omitted.

It is a conceptual diagram of the cross section which shows an example of the decorative sheet of this invention. It is a conceptual diagram of the lamination apparatus used in the Example.

1: Coating film 2: Layer of transparent thermoplastic resin film 3: Printing layer 4: Layer of colored thermoplastic resin film 5: Adhesive layer 6: Laminate having a film substrate and a pre-dried coating film in this order 7: Heating drum 8: Active energy ray permeable film 9: Press roll 10: Laminate 11: Guide roll having a film base material, a pre-dried coating film, and a textured transfer film in this order

Claims (10)

(A) (Meth) acrylate compound 100 parts by mass; and
(B) 1 to 45 parts by mass of a compound having two or more isocyanate groups in one molecule;
Wherein the (A) (meth) acrylate compound is (a1) epoxy-modified (meth) acrylate 1 to 90% by mass; and
(A2) 99 to 10% by mass of (meth) acrylate other than epoxy-modified (meth) acrylate;
Here, the sum of (a1) epoxy-modified (meth) acrylate and (meth) acrylate other than (a2) epoxy-modified (meth) acrylate is 100% by mass.
(A) A (meth) acrylate other than the epoxy-modified (meth) acrylate is
(A2-1) 10 to 80% by mass of polyfunctional (meth) acrylate other than epoxy-modified (meth) acrylate; and
(A2-2) monofunctional (meth) acrylate other than epoxy-modified (meth) acrylate, 90 to 20% by mass;
Here, the sum of the polyfunctional (meth) acrylate other than the (a2-1) epoxy-modified (meth) acrylate and the monofunctional (meth) acrylate other than the (a2-2) epoxy-modified (meth) acrylate is 100% by mass. The paint according to claim 1, wherein
The coating material according to claim 2, wherein the monofunctional (meth) acrylate other than the (a2-2) epoxy-modified (meth) acrylate includes phenoxy (meth) acrylate.
The paint according to any one of claims 1 to 3, wherein the paint does not contain inorganic particles.
The paint according to any one of claims 1 to 4, wherein the paint does not contain a solvent.
An article comprising a coating film formed using the paint according to any one of claims 1 to 5.
A decorative sheet comprising a coating film formed using the paint according to any one of claims 1 to 5.
Having a layer of a coating film and a film substrate formed by using the paint according to any one of claims 1 to 5;
The coating film and the film substrate layer are directly laminated;
The evaluation of the cross cut test measured according to JIS K5600-5-6: 1999 is classification 0, 1, or 2;
Makeup sheet.
The decorative sheet according to claim 8, wherein the coating film forming surface of the film base material is a polyethylene terephthalate resin or a polybutylene terephthalate resin.
An article comprising the decorative sheet according to any one of claims 7 to 9.