JP7109288B2 - Paint and decorative sheet using the same - Google Patents

Description

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

Conventionally, home appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; furniture such as decorative shelves, storage chests, cupboards, and desks; Substrates made of wood-based materials such as plywood, laminated wood, particle board, and hardboard; substrates made of resin-based materials such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate, and polyester; or Substrates made of metallic materials such as iron and aluminum; which are decorated with a decorative sheet laminated on the surface are used.

In recent years, more and more emphasis has been placed on design as a point of product differentiation. 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 coating material containing a matting agent (for example, Patent Documents 1 and 2). In addition, from the viewpoint of work environment and work safety, there is a demand for solvent-free paints for coating film formation. However, the adhesion between the coating film and the film substrate, especially the coating film formed using a substantially solvent-free coating material and a film substrate such as a polyethylene terephthalate-based resin film or a polybutylene terephthalate-based resin film. There was a problem that the adhesion to the material was not sufficient.

JP 2012-091487 A JP 2013-031995 A

An object of the present invention is to provide a paint capable of forming a coating film having excellent adhesion to a film substrate. A further object of the present invention is to provide a coating film-forming surface of a film substrate that is excellent in scratch resistance, crack resistance, bending resistance, and stain removability, and has good adhesion to the film substrate. To provide a coating material capable of forming an excellent coating film even with a polyethylene terephthalate-based resin or a polybutylene terephthalate-based resin, particularly preferably a substantially solvent-free coating material.

As a result of intensive research, the inventors of the present invention have found that the above problems can be achieved with a specific paint.

That is, the present invention provides (A) 100 parts by mass of a (meth)acrylate compound;
(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 (a2) (meth)acrylate other than epoxy-modified (meth)acrylate is 100% by mass.

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

A third invention is the paint according to the second invention, wherein the monofunctional (meth)acrylate other than (a2-2) the epoxy-modified (meth)acrylate comprises a phenoxy (meth)acrylate.

A fourth invention is the paint according to any one of the first to third inventions, wherein the paint does not contain inorganic particles.

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

A sixth invention is an article comprising a coating film formed using the paint according to any one of the first to fifth inventions.

A seventh invention is a decorative sheet comprising a coating film formed using the paint according to any one of the first to fifth inventions.

An eighth invention has a coating film formed using the paint according to any one of the first to fifth inventions and a layer of a film substrate; It is directly laminated; it is classified as 0, 1, or 2 in cross-cut test evaluation measured according to JIS K5600-5-6:1999; 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 composed of a polyethylene terephthalate-based resin or a polybutylene terephthalate-based resin.

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

A coating film formed using the coating material of the present invention has excellent adhesion to a film substrate. The coating film formed using the preferred coating material of the present invention is excellent in scratch resistance, crack resistance, bending resistance, and stain removability, and has excellent adhesion to the film substrate. Even if the forming surface is composed of a polyethylene terephthalate-based resin or a polybutylene terephthalate-based resin, the paint of the present invention is excellent even if it is substantially solventless. Therefore, the paint of the present invention can be suitably used as a paint film-forming paint for articles such as decorative sheets.

The term "film" is used herein interchangeably or interchangeably with "sheet." As used herein, the terms "film" and "sheet" are used for those that can be industrially wound into rolls. The term "plate" is used for those that cannot be industrially wound into rolls. The term "resin" is used as a term including resin mixtures containing two or more resins and resin compositions containing components other than resins. Further, in this specification, laminating a certain layer and another layer in order means directly laminating those layers, and interposing one or more layers such as an anchor coat between those layers. and lamination.

In this specification, the term "greater than or equal to" regarding a numerical range is used to mean a certain numerical value or more than a certain numerical value. For example, 20% or more means 20% or more than 20%. The term "up to" 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 numerical ranges is used to mean a certain numerical value, greater than a certain numerical value and less than another numerical value, or some other numerical value. Here, another certain numerical value is assumed to be a larger numerical value than the certain numerical value. For example, 10-90% means 10%, greater than 10% and less than 90%, or 90%.

Other than in the examples 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 trying to limit the application of the doctrine of equivalents to the claims, each numerical value should be interpreted in the light of significant digits and by applying conventional rounding techniques.

1. paint:
The paint of the present invention contains (A) a (meth)acrylate compound; and (B) a compound having two or more isocyanate groups in one molecule. The component (A) contains (a1) an epoxy-modified (meth)acrylate. The component (A) consists of (a1) epoxy-modified (meth)acrylate; and (a2) (meth)acrylate other than epoxy-modified (meth)acrylate. (Meth)acrylate as used herein means methacrylate or acrylate. Each component will be described below.

(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) contains (a1) an epoxy-modified (meth)acrylate. The component (A) consists of (a1) epoxy-modified (meth)acrylate; and (a2) (meth)acrylate other than epoxy-modified (meth)acrylate.

(a1) epoxy-modified (meth)acrylate:
The above component (a1) is a (meth)acrylate modified with a compound having an epoxy group such as epichlorohydrin. The component (a1) acts 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 per molecule to form a urethane bond. It forms and works to improve 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; epichlorohydrin-modified alkyldiol di(meth)acrylates such as phosphorus-modified 1-4 butanediol di(meth)acrylate and epichlorohydrin-modified 1-6 hexanediol di(meth)acrylate; . Among these, epichlorohydrin-modified alkyldiol di(meth)acrylate is preferable as the component (a1) from the viewpoint of adhesion between the coating film and the film substrate. As the component (a1), one or a mixture of two or more thereof can be used.

In one typical embodiment, the epichlorohydrin-modified alkyldiol di(meth)acrylate may be a compound represented by the following general formula (1):

In formula (1), R ₁ represents hydrogen or a methyl group. _R2 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)acrylates:
The component (a2) is a (meth)acrylate other than the epoxy-modified (meth)acrylate. The component (a2) is preferably a polyfunctional other than (a2-1) epoxy-modified (meth)acrylate from the viewpoint of scratch resistance, crack resistance, bending resistance, stain removability, 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 an epoxy-modified (meth)acrylate and has two or more (meth)acryloyl groups in one molecule. The component (a2-1) functions to improve surface hardness, scratch resistance, and stain 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 (meth)acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate (Meth)acryloyl group-containing tetrafunctional reactive monomers such as; (meth)acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth)acryloyl group-containing octafunctional reactive monomers such as tripentaerythritol acrylate and polymers (oligomers and prepolymers) containing one or more of these as constituent monomers and having two or more (meth)acryloyl groups in one molecule.

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

As the component (a2-1), one or a mixture of two or more of these can be used.

The component (a2-2) is a (meth)acrylate other than the epoxy-modified (meth)acrylate and has one (meth)acryloyl group in one molecule. The above component (a2-2) functions to improve crack resistance and bending resistance. It also works 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. 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, trimethylsiloxyethyl methacrylate and the like can be mentioned.

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. phenoxy (meth)acrylate;

Examples of the component (a2-2) include prepolymers such as polyester (meth)acrylate, polyacrylic (meth)acrylate, polyalkylene glycol poly(meth)acrylate, epoxy (meth)acrylate, and polyether (meth)acrylate. Polymers or oligomers having one (meth)acryloyl group per molecule can be mentioned.

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

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)acrylamide N-substituted (meth)acryloylmorpholine, such as ethyl 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 and the like can be mentioned.

Among these, the component (a2-2) is preferably phenoxy(meth)acrylate, more preferably phenoxybenzyl(meth)acrylate, and m-phenoxybenzyl ( More preferred are meth)acrylates. As the component (a2-2), one or a mixture of two or more of these can be used.

The amount of the component (a1) in the component (A) is determined based on the sum of the component (a1) and the component (a2) being 100% by mass. From the viewpoint of crack resistance and bending resistance, usually 1% by mass or more (99% by mass or less of component (a2)), preferably 5% by mass or more (95% by mass or less of component (a2)), more preferably 10% by mass or more (90% by mass or less of component (a2)), more preferably 15% by mass or more (85% by mass or less of component (a2)). On the other hand, from the viewpoint of lowering the viscosity of the paint and improving the coatability, and from the viewpoint of the transfer film peelability, usually 90% by mass or less (10% by mass or more of the above component (a2)), preferably 70% by mass or less (the above Component (a2) 30% by mass or more), more preferably 60% by mass or less (component (a2) 40% by mass or more), still more preferably 45% by mass or less (component (a2) 55% by mass or more), most preferably is 40% by mass or less (60% by mass or more of component (a2)).

The amount of the component (a2-1) in the component (a2) is the sum of the component (a2-1) and the component (a2-2) as 100% by mass, and the surface hardness, scratch resistance, and From the viewpoint of stain removability, it is preferably 10% by mass or more (the above component (a2-2) is 90% by mass or less), more preferably 20% by mass or more (the above component (a2-2) is 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 coatability, crack resistance, and bending resistance, it is preferably 80% by mass or less (20% by mass or more of the component (a2)), more preferably It may be 65% by mass or less (35% by mass or more of component (a2)), more preferably 50% by mass or less (50% by mass or more of component (a2-2)).

(B) a compound having two or more isocyanate groups in one molecule:
Component (B) is a compound having two or more isocyanate groups (--N=C=O) in one molecule. The above component (B) reacts with the above component (a1) to form urethane bonds, and functions to improve the crack resistance and bending resistance of the coating film. It also works 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 methylenebis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, and isophorone. Polyisocyanates such as a trimethylolpropane adduct of diisocyanate, an isocyanurate of tolylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, an isocyanurate of isophorone diisocyanate, and a biuret of hexamethylene diisocyanate; and block types of the above polyisocyanates A urethane cross-linking agent such as isocyanate can be used.

From the viewpoint of the crack resistance and bending resistance of the hard coat, the above component (B) is preferably a compound having three isocyanate groups in one molecule. is more preferred. One or a mixture of two or more thereof can be used as the component (B). If desired, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as long as the object of the present invention is not compromised.

The 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, based on 100 parts by mass of the component (A), from the viewpoint of curability with active energy rays. parts or less, more preferably 25 parts by mass or less. On the other hand, from the viewpoint of reliably obtaining the effect of using 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 paint of the present invention may further contain a photopolymerization initiator from the viewpoint of improving curability with 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, and 4-benzoyl. -4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, benzophenone compounds such as 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; Acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenyl ketone; -anthraquinone compounds such as amyl anthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; alkylphenone compounds such as acetophenone dimethyl ketal; triazine compounds; biimidazole compounds; fin oxide-based compounds; titanocene-based compounds; oxime ester-based compounds; oxime phenylacetic ester-based compounds; hydroxyketone-based compounds; As the photopolymerization initiator, one or a mixture of two or more thereof can be used.

The paint of the present invention may optionally contain an active energy ray-curable resin other than the component (a1) or the component (a2), or an isocyanate group other than the component (B), as long as the object of the present invention is not violated. Compounds having, antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weather stabilizers, light stabilizers, UV absorbers, heat stabilizers, One or two or more optional components such as inorganic particles, organic particles, and colorants can be included.

If desired, the paint of the present invention may contain a solvent in order to dilute it to a concentration that facilitates coating. The solvent is particularly limited as long as it does not react with the components (A), (B), and other optional components and does not catalyze (promote) the self-reaction (including deterioration 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 thereof can be used.

The paints of the invention are preferably free of inorganic particles. In general, inorganic particles such as 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; useful from that point of view. On the other hand, the interaction with the resin component such as the 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 described later in order to impart a matte design, and the paint for forming a coating film does not contain inorganic particles to improve scratch resistance and bending resistance. It holds well.

Here, "free of" inorganic particles means not containing any significant amount of inorganic particles. In the field of film-forming paints, a significant amount of inorganic particles is usually about 1 part by mass or more per 100 parts by mass of component (A) from the viewpoint of imparting a matte design. Therefore, "does not contain" inorganic particles means that the amount of inorganic particles is usually less than 1 part by mass, preferably 0.5 parts by mass or less, more preferably 0.1 part by mass, relative to 100 parts by mass of the component (A). It can also be rephrased as 0.01 part by mass or less, more preferably 0.05 part by mass or less, and most preferably 0.01 part by mass or less.

The paints of the invention are preferably solvent-free. Since the paint of the present invention contains the above component (a1), and in one embodiment contains the above component (a1) and the above component (a2-2), it can be applied without containing a solvent. By not containing a solvent, it is possible to omit a drying process after coating and a process for treating the solvent recovered in a drying furnace. In addition, there is an effect that the risk of accidents due to explosion or combustion of the solvent is greatly reduced.

By "solvent free" is meant that it does not contain any significant amount of solvent. In the field of film-forming paints, a significant amount of the solvent is usually about 5 parts by weight or more per 100 parts by weight of component (A) from the viewpoint of diluting to a concentration that facilitates coating. Therefore, "not containing" a solvent means that the amount of solvent is usually less than 5 parts by mass, preferably 3 parts by mass or less, more preferably 1 part by mass, and still more preferably 100 parts by mass of component (A). It can also be rephrased as 0.5 parts by mass or less, most preferably 0.1 parts by mass or less.

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

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

Preferred methods for forming a coating film using the paint of the present invention include, for example,
(1) forming a wet coating film of the paint of the present invention on at least one surface of a film substrate;
(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 superimposing and temporarily attaching an active energy ray-transmitting film on the surface of the dry coating film obtained in the above step (2);
(4) A step of irradiating the laminate obtained in the step (3) with an active energy ray to cure the dried coating film;
A method including

The film substrate used in the step (1) is not particularly limited, and any resin film can be used as the film substrate. Examples of the resin film include polyester-based resins such as aromatic polyesters and aliphatic polyesters; acrylic-based resins; polycarbonate-based resins; poly(meth)acrylimide-based resins; Resin; cellulose-based resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose 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 resins; fluorine-containing resins such as polyvinylidene fluoride; In addition, resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, polyethersulfone; and the like can be mentioned. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. It also includes laminated films obtained by laminating two or more layers of one or more of these.

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

When the film base is one of the constituent layers of the decorative sheet, the thickness of the film base is not particularly limited, but it may be usually 20 μm or more, preferably 30 μm or more from the viewpoint of handling. From the viewpoint of designability, the thickness is usually 50 μm or more, preferably 80 μm or more. On the other hand, from the viewpoint of thinning the decorative sheet, the thickness is 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 substrate is transferred to another film substrate, the surface of the film substrate on which the wet coating film is formed must be subjected to an easy peeling treatment. you can

When the coating film formed on the surface of the film substrate is transferred to another film substrate, the thickness of the film substrate is not particularly limited. 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 step (1) is not particularly limited. Examples of the method include 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 form a dry coating film. For the preliminary drying, for example, it takes about 0.5 to 10 minutes for the web to pass through a drying oven set at a temperature of about 23 to 150° C., preferably at a temperature of 50 to 120° C., from the inlet to the outlet. , preferably by passing at a line speed of 1 to 5 minutes.

If the paint does not contain a solvent, like the paint described above as a preferred embodiment, the above step (2) can be omitted.

In the step (3), an active energy ray-transmitting film is superimposed on the surface of the dry coating film obtained in the step (2) and temporarily attached. This suppresses the oxygen hindrance of the curing reaction of the active energy ray-curable resin composition due to the irradiation of the active energy ray.

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

The active energy ray transmissive 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 nm with respect to the integral area of the transmission spectrum when it is assumed that the transmittance of the active energy ray in the entire wavelength range of 200 to 600 nm is 100%. It is the ratio of the integral area of the transmission spectrum of a line, and is a value measured by using a spectrophotometer “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation, with light incident on the film at an incident angle of 0°.

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

The surface of the active energy ray-transmitting film to be bonded to the dry coating film may be highly smooth or may be engraved with an embossed pattern. When a highly smooth one is used, a high-gloss design is imparted. When the embossed pattern is used, a design corresponding to the embossed pattern, such as a hairline design, a leather-like design, and a matte design, is imparted.

In the above step (4), the laminate obtained in the above step (3) is irradiated with an active energy ray, usually from the surface on the active energy ray-transmitting film side, to cure the dry coating film and form a coating film. It is formed.

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

The irradiation dose of the active energy ray in the step (4) is appropriately adjusted depending on the curing properties of the active energy ray-curable resin composition, the thickness of the hard coat, the line speed, and the like. The irradiation dose may be generally 10 to 10,000 mJ/cm ² , preferably 50 to 1,000 mJ/cm ² .

Preferred methods for forming a coating film using the paint of the present invention include, for example,
(1′) forming a wet coating film of the paint of the present invention on at least one surface of an active energy ray transparent 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 superimposing and temporarily attaching a film substrate on the surface of the dry coating film obtained in the above step (2');
(4') A step of irradiating the laminate obtained in the step (3') with an active energy ray to cure the dried coating film;
A method including

The method described later has the advantage over the method described above that it can also be applied to film substrates with low solvent resistance. Compared with the method described later, the aforementioned method has the advantage that it is easy to increase 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 step (1') is not particularly limited. Examples of the method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. The active energy ray-transmitting film has been described in the description of step (3) of the method described above.

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

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

In the step (3'), a film substrate is superimposed on the surface of the dry coating film obtained in the step (2') and temporarily attached. This suppresses the oxygen hindrance of the curing reaction of the active energy ray-curable resin composition due to the irradiation of the active energy ray. The above film substrate was explained in the explanation of step (1) of the above method.

In the step (4′), the laminate obtained in the step (3′) is irradiated with an active energy ray, usually from the surface on the active energy ray-transmitting film side, and the dried coating film is cured and coated. A film is formed. The active energy ray and its irradiation dose were explained in the explanation of step (4) of the above method.

2. Cosmetic 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 paint of the present invention is usually formed as a surface protective layer on the front side (the side that is normally visible in actual use) of the decorative sheet of the present invention. Here, the actual use state means a state in which the decorative sheet is used for decorating and decorating the surfaces of various articles.

Examples of the decorative sheet of the present invention include a decorative sheet having a coating film formed 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 that becomes the 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; ; 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; cellulose resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride Resin; In addition, resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulfone; These films include unstretched films, uniaxially stretched films, and biaxially stretched films. It also includes laminated films obtained by laminating two or more layers of one or more of these.

The thickness of the 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, the thickness is usually 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less. From the viewpoint of workability when applying the decorative sheet to an article, the thickness is usually 300 μm or less, preferably 250 μm or less.

As the 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 layer of a transparent thermoplastic resin film is provided on the printed layer. Furthermore, a decorative sheet having a hard coat formed using the paint of the present invention on the front side of the layer of the transparent thermoplastic resin film can be mentioned.

Examples of the colored thermoplastic resin film include, for example, 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-based resins such as styrene/ethylene/ethylene/propylene/styrene copolymers; cellulose-based resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polyvinylidene chloride-based resins; fluorine-containing resins; and resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulfone; These films include unstretched films, uniaxially stretched films, and biaxially stretched films. It also includes laminated films obtained by laminating two or more layers of one or more of these.

A coloring agent for coloring the colored thermoplastic resin film is not particularly limited, and any coloring agent can be used. Examples of the coloring agent include titanium oxide and carbon black. As the colorant, one or a mixture of two or more of these can be used. The amount of the colorant to be blended is usually 0.1 to 40 parts by mass, based on 100 parts by mass of the base resin used in the colored thermoplastic resin film, depending on the type of the colorant and the desired hiding 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 the production of decorative sheets. On the other hand, from the viewpoint of thinning the decorative sheet, the thickness is usually 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less. From the viewpoint of workability when applying the decorative sheet to an article, the thickness is usually 300 μm or less, preferably 250 μm or less.

Examples of the transparent thermoplastic resin film include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; Cellulose-based resins such as cellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene-butadiene-styrene copolymer, styrene-ethylene-butadiene-styrene copolymer Polyvinyl chloride resin; Polyvinylidene chloride resin; Fluorine resin such as polyvinylidene fluoride; Others, polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane , polyetherimide, polysulfone, polyethersulfone; and other transparent resin films. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. It also includes laminated films obtained by laminating two or more layers of one or more of these.

The thickness of the transparent 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 and from the viewpoint of design. On the other hand, from the viewpoint of thinning the decorative sheet, the thickness is usually 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less. From the viewpoint of workability when applying the decorative sheet to an article, the thickness is usually 300 μm or less, preferably 250 μm or less.

The printed layer is provided to impart a high degree of designability, and can be formed by printing any pattern using any ink and any 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 wholly or partially. Patterns include metallic patterns such as hairlines, wood grain patterns, stone grain patterns that imitate the surface of rocks such as marble, fabric patterns that imitate texture or cloth patterns, tile patterns, brickwork patterns, marquetry patterns, and patchwork. As the printing ink, a mixture of a binder, a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like 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, and polyamides. resins such as cellulose-based resins, butyral-based resins, polystyrene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins, and resin compositions thereof. In order to give a metallic design, aluminum, tin, titanium, indium and their oxides are applied directly or through an anchor coat onto the front surface of the colored thermoplastic resin film, or Vapor deposition may be performed entirely or partially on the surface opposite to the front side of the transparent thermoplastic resin film by a known method.

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

Since the paint of the present invention has excellent adhesion to the film substrate, sufficient adhesion can be obtained even by forming a coating film directly on the front surface of the transparent thermoplastic resin film. can be obtained.

The thickness of the coating film formed using the paint of the present invention is not particularly limited, but from the viewpoint of scratch resistance, it may be usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more. From the viewpoint of the secondary processability and web handleability of the decorative sheet of the present invention, the thickness is 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-based, acrylic-based, polyurethane-based, acrylic-urethane-based, and polyester-urethane-based anchor coating agents. One or more of these can be used as the anchor coating agent.

The anchor coating agent may optionally contain antioxidants, weather stabilizers, light stabilizers, ultraviolet absorbers, heat stabilizers, antistatic agents, surfactants, One or two or more additives such as coloring agents, infrared shielding agents, leveling agents, thixotropic agents, and fillers may be included.

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

Although the thickness of the anchor coat is not particularly limited, it may generally be about 0.01 to 5 μm, preferably 0.1 to 2 μm.

In the decorative sheet of the present invention, from the viewpoint of improving adhesion to an adherend to be decorated and decorated using the decorative sheet of the present invention, the front side of the colored thermoplastic resin film is A pressure-sensitive adhesive layer or an adhesive layer may be formed directly or via an anchor coat on the opposite side.

FIG. 1 is a schematic cross-sectional view showing an example of the decorative sheet of the present invention. A coating film 1 formed using the coating material of the present invention, a layer 2 of a transparent thermoplastic resin film, a printed layer 3, a layer 4 of a colored thermoplastic resin film, and an adhesive layer 5 are sequentially formed from the surface side. have.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Measurement method (a) 60 degree gloss value (matte):
In accordance with JIS Z8741: 1997, Konica Minolta Co., Ltd.'s multi-angle gloss meter "GM-268 (trade name)" is used, and the 60 degree gloss value is measured under the condition that light is incident on the coating surface of the decorative sheet. did.

(b) Steel wool resistance (scratch resistance):
Place it on a JIS L0849: 2013 Gakushin-type tester so that the coating surface of the decorative sheet is the surface, and the reciprocating direction of the friction terminal and the machine direction of the decorative sheet are parallel, and the Gakushin-type tester After attaching #0000 steel wool to the friction terminal of No., a 200 g load was placed, and the surface of the test piece was rubbed back and forth 5 times under conditions of a moving distance of 60 mm and a speed of 1 reciprocation/second. The friction points were visually observed and evaluated 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) Stain removal:
Absorbent cotton having a length of 10 mm, a width of 10 mm, and a thickness of 2 mm was placed on the coated surface of the decorative sheet, and the red ink for fountain pens "Pilot Ink Red (trade name)" of Pilot Co., Ltd. was sufficiently soaked in the absorbent cotton. It is dropped onto the absorbent cotton until it reaches a state (usually about 1 mL), left for 24 hours in an environment with a room temperature of 25 ° C. and a relative humidity of 50%, and then the absorbent cotton is removed. Mama Lemon (trade name)" was used, and 3M's dishwashing sponge "Scotch-Bright antibacterial urethane sponge scourer, leaf type/three layers, no abrasive particles (trade name)" was used to wash the dishes with water. After that, the contaminated spots were visually observed and evaluated according to the following criteria.
⊚: The contamination was completely removed, and the contamination point was no longer visible.
O: Contamination was almost completely removed. However, a slight amount of contamination remained, and it was possible to determine the contamination location.
Δ: Contamination remained, and the contaminated area was reddish.
x: Contamination remained remarkably, and the contaminated part remained red even after washing with water.

(d) Mandrel test (crack resistance, bending resistance):
In compliance with JIS K5600-5-1:1999, a bending resistance test was performed by a cylindrical mandrel method using a sample taken from the decorative sheet so as to be 100 mm in the machine direction of the decorative sheet and 50 mm in the lateral direction. The diameter of the mandrel with the smallest diameter among the mandrels that did not crack was determined.

(E) Cross-cut test (coating film adhesion):
According to JIS K5600-5-6: 1999, 100 grid cuts (1 grid = 1 mm × 1 mm) were made on the decorative sheet from the coating surface side, and then a tape for adhesion test was attached to the grid and applied with a finger. After scraping, I peeled it off. The evaluation criteria were in accordance with Table 1 of the JIS standard.
Class 0: The edges of the cut are completely smooth, and there is no detachment on any grid mesh.
Category 1: Small delamination of the coating at the intersection of cuts. No more than 5% is clearly affected in the crosscut portion.
Category 2: The coating is peeling along the edges of the cuts and/or at the intersections. The crosscut portion is affected by clearly more than 5%, but not more than 15%.
Class 3: The coating is partially or totally peeled off along the edge of the cut and/or partially or totally peeled off in various parts of the eye. The crosscut portion is affected by clearly more than 15% but not more than 35%.
Class 4: The coating film is partially or entirely peeled off along the edge of the cut, and/or some grains are partially or entirely peeled off. The crosscut portion is affected clearly above 35% but not above 65%.
Category 5: When the degree of peeling exceeds Category 4.

(f) Transfer film peelability:
A test piece was taken from the laminate of the decorative sheet and the transfer foil immediately after curing by UV irradiation so that the machine direction of the laminate coincided with the peeling direction, and the T-shaped peel strength between the decorative sheet and the transfer film was measured. , JIS K6854-3:1999. The following criteria evaluated from the value of T-peel strength.
A: Less than 5 g/25 mm.
◯: 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.
×: 200 g/25 mm or more.

Raw materials used (A) Active energy ray-curable resin:
(a1) epoxy-modified (meth)acrylate:
(a1-1) Nippon Kayaku Co., Ltd. epichlorohydrin-modified 1-6 hexanediol diacrylate "Kayarad R-167 (trade name)". A compound in which R ₁ is hydrogen, R ₂ is hydrogen, and R ₃ is (CH ₂ ) ₆ in the above general formula (1).

(a2) (meth)acrylates other than epoxy-modified (meth)acrylates:
(a2-1) Polyfunctional (meth)acrylates other than epoxy-modified (meth)acrylates:
(a2-1-1) Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate "Kayarad DPHA (trade name)".

(a2-2) Monofunctional (meth)acrylate other than epoxy-modified (meth)acrylate:
(a2-2-1) Kyoeisha Chemical Co., Ltd. m-phenoxybenzyl acrylate (CAS number 409325-06-0) "Light acrylate POB-A (trade name)".
(a2-2-2) Kyoeisha Chemical Co., Ltd. isobornyl acrylate "Light acrylate IB-XA (trade name)".

(B) a compound having two or more isocyanate groups in one molecule:
(B-1) Biuret form of hexamethylene diisocyanate (1,3,5-tris(6-isocyanatohexyl)biuret) “Duranate 24A-100 (trade name)” manufactured by Asahi Kasei Corporation.
(B-2) An isocyanurate form of hexamethylene diisocyanate "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)” from BASF.
(C-2) Acetophenone-based photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) “IRGACURE 1173 (trade name)” from BASF.
(C-3) Benzophenone from Wako Pure Chemical Industries, Ltd.;

(F) Transfer foil:
(F-1) High-gloss transfer foil "SH37 (trade name)" using biaxially oriented polyethylene terephthalate from SKC as a base film. Active energy ray transmittance 82%.
(F-2) Texture transfer foil "SWPP MAM-430 (trade name)" made of polypropylene resin manufactured by RIKEN TECHNOS CO., LTD. Active energy ray transmittance of 84%.

(G) Film substrate:
(G-1) White colored polybutylene terephthalate resin film "HR250 (WHT) (trade name)" having a thickness of 250 μm manufactured by RIKEN TECHNOS CORPORATION.
(G-2) 120 μm thick white colored polyvinyl chloride resin film “FC1814 (trade name)” manufactured by Riken Technos Co., Ltd.;
(G-3) 100 parts by mass of polyethylene terephthalate "PIFG5 (trade name)" from Bell Polyester Products Co., Ltd. and 12 parts by mass of titanium oxide (white pigment) "Tipaque CR-60-2 (trade name)" from 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.

Example 1
1. Preparation of paint:
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 (C-1) 2 parts by mass, the component (C-2) 3 parts by mass, and the component (C-3) 3 parts by mass were mixed and stirred to obtain a paint.

2. Production of decorative sheets:
(1) The paint obtained in 1 above is applied onto one side of the film substrate (G-1) using a film Meyer bar type coating device so that the thickness after curing is 10 μm. , to form a wet coating.
(2) The drying step was omitted because the paint used contained no solvent.
(3) Next, using an apparatus whose conceptual diagram is shown in FIG. On top of this, the surface of the laminate 6 opposite to the dried coating film is placed on the heating drum 7 side, and a transfer foil (F-1) 8 is placed on the surface of the dried coating film. Then, the transfer foil (F-1) 8 was superimposed on the surface of the dried coating film and temporarily adhered by pressing with the pressure roller 9 . Next, the laminate 10 having the film substrate (G-1), the dried coating film, and the transfer foil (F-1) in this order was released from the heating drum 7 by the guide rolls 11 .
(4) Next, using a high-pressure mercury lamp type ultraviolet irradiation device, an active energy ray is irradiated from the transfer foil (F-1) surface side of the laminate 10 under the condition of an integrated light amount of 240 mJ/cm ² , and the drying is performed. 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 transfer foil (F-1) was peeled off to obtain a decorative sheet having a coating film directly on one side of the film substrate (G-1). The above tests (a) to (e) were performed. Table 1 shows the results.

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

Example 17
The procedure of Example 1 was repeated except that the transfer foil (F-2) was used instead of the transfer foil (F-1). Table 3 shows the results.

Example 18
The procedure was carried out in the same manner as in Example 1, except that the film substrate (G-2) was used instead of the film substrate (G-1). Table 3 shows the results.

Example 19
The procedure was carried out in the same manner as in Example 1, except that the film substrate (G-3) was used instead of the film substrate (G-1). Table 3 shows the results.

A decorative sheet having a coating film made of the coating material of the present invention has excellent adhesion between the coating film and the film substrate. A decorative sheet having a coating film made of the preferred paint of the present invention is further excellent in scratch resistance, crack resistance, bending resistance, and stain removability. In addition, even if the coating film forming surface of the film substrate is made of polyethylene terephthalate resin or polybutylene terephthalate resin, sufficient adhesion between the coating film and the film substrate can be obtained by directly laminating the coating film. It is expressed. Moreover, the paint used for forming the coating film does not contain a solvent, and the drying process can be omitted.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional conceptual diagram which shows an example of the decorative sheet of this invention. 1 is a conceptual diagram of a lamination device used in Examples. FIG.

1: Coating film 2: Transparent thermoplastic resin film layer 3: Printed layer 4: Colored thermoplastic resin film layer 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 transparent film 9: Pressing roll 10: Laminate having film base material, predried coating film, and texturing transfer film in this order 11: Guide roll

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) 10 to 90% by mass of epichlorohydrin-modified alkyldiol di (meth)acrylate; and
(a2) 90 to 10% by mass of (meth)acrylate other than epoxy-modified (meth)acrylate;
Here, the sum of (a1) epichlorohydrin-modified alkyldiol di (meth)acrylate and (a2) (meth)acrylate other than epoxy-modified (meth)acrylate is 100% by mass ,
The (a2) (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) 90 to 20% by mass of a monofunctional (meth)acrylate other than an epoxy-modified (meth)acrylate;
Here, the sum of (a2-1) polyfunctional (meth)acrylate other than epoxy-modified (meth)acrylate and (a2-2) monofunctional (meth)acrylate other than epoxy-modified (meth)acrylate is 100% by mass. is paint.
2. The paint according to claim 1 , wherein the (a2-2) monofunctional (meth)acrylate other than the epoxy-modified (meth)acrylate includes phenoxy (meth)acrylate.
3. The paint according to claim 1, wherein the (a2-2) monofunctional (meth)acrylate other than the epoxy-modified (meth)acrylate includes phenoxybenzyl (meth)acrylate.
The paint according to any one of claims 1 to 3, which does not contain inorganic particles.
A paint according to any one of claims 1 to 4, which does not contain a solvent.
An article comprising a coating film formed using the coating material according to any one of claims 1 to 5.
A decorative sheet comprising a coating film formed using the coating material according to any one of claims 1 to 5.
Having a coating film formed using the coating material according to any one of claims 1 to 5 and a layer of a film substrate;
The coating film and the layer of the film substrate are directly laminated;
The cross-cut test evaluation measured according to JIS K5600-5-6: 1999 is classified as 0, 1, or 2;
cosmetic sheet.
9. The decorative sheet according to claim 8, wherein a polyethylene terephthalate-based resin or a polybutylene terephthalate-based resin constitutes the coating film forming surface of the film substrate.
An article comprising the decorative sheet according to any one of claims 7-9.

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