JP2002052681A - Decorative sheet and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having a ruggedness sharply reproduced in the sheet simultaneously having a cured film and the ruggedness so that a base is closely contacted with the cured film and the adhesive properties of the base with the cured film are not decreased by an increase in the depth of the ruggedness and a method for manufacturing the same. SOLUTION: The decorative sheet comprises a prime layer 3, a cured resin protective layer 4 laminated on a surface of a thermoplastic resin sheet 2 for constituting the sheet, and a ruggedness 5 formed on the surface of the layer 4 so that the layer 3 and the layer 4 are laminated along the ruggedness 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a decorative sheet having a thermoplastic resin sheet as a base material, having a protective layer made of a cured resin, and having irregularities on the surface, and a method for producing the same.

[0002]

2. Description of the Related Art Various decorative sheets using a thermoplastic resin sheet as a base material have hitherto been used.
For example, various decorative sheets have been manufactured by using a polyvinyl chloride resin sheet as a base material, performing printing, and then performing surface painting and unevenness imparting (= embossing) processing.

In these decorative sheets, the surface coating is
It is performed for the purpose of adjusting the gloss of the surface and improving the physical and chemical properties. In particular, for the latter purpose, it is often formed using a curable resin to form a cured film. The irregularities are provided for the purpose of giving a change to the surface or for reproducing the surface state by imitating the irregularities of the surface of an actual concrete object.

When the formation of a cured film and the embossing are performed on the same decorative sheet, the decorative sheet obtained by forming the cured film and then performing the embossing has sharp irregularities, but the irregularities are reproduced. As the depth increases, the adhesiveness tends to decrease, and after embossing, the decorative sheet obtained by performing surface painting has insufficient adhesiveness from the initial state, and moreover, to fill in irregularities In addition, the surface irregularities become dull. In particular, in the latter method in which the surface is coated after embossing is performed, it is difficult to form a cured film along the unevenness itself, and the cured film does not float from the unevenness or a part of the cured film is formed ( = Missing), the sharpness of the unevenness is impaired, and the adhesion strength cannot be obtained. That is, it is impossible to form a uniform and solid cured film unless it is a flat object by a method such as coating. The above tendency is more conspicuous in a polyolefin resin which cannot be said to originally have high adhesiveness.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a decorative sheet having a cured film and irregularities at the same time, in which the irregularities are sharply reproduced and the adhesion between the substrate and the cured film is excellent. , By increasing the depth of unevenness,
An object of the present invention is to provide a decorative sheet that does not cause a decrease in adhesion between a base material and a cured film, and to provide a method for producing such a decorative sheet.

[0006]

The above object is achieved by laminating a primer layer, preferably a primer layer having high adhesion and flexibility, and a cured film on a thermoplastic resin sheet as a base material, and then embossing. By processing,
It has been found that such a laminated structure solves the problem.

In the first invention, a primer layer forming composition and a curable resin composition layer are sequentially laminated on the surface of a thermoplastic resin sheet, and if necessary, a curing means is applied to both layers to provide a primer. Forming a cured resin protective layer in which the layer and the layer of the curable resin composition are cured, and then forming embossments on the cured resin protective layer to form irregularities. It is about. According to a second invention, in the first invention, the curable resin composition is an ionizing radiation-curable resin composition, and the curing means is performed by irradiating ionizing radiation. It is about the method. In a third aspect based on the first or second aspect, the thermoplastic resin sheet is a polyolefin-based resin sheet, and the primer layer is a reaction product of an acrylic resin-urethane resin copolymer and an isocyanate compound. And a method for producing a decorative sheet. According to a fourth aspect, in the third aspect, the copolymer of the acrylic resin and the urethane resin is a reaction product of an acrylic polymer component having a hydroxyl group at a terminal, a polyester polyol component, and a diisocyanate component. The present invention relates to a method for manufacturing a characteristic decorative sheet. In a fifth aspect based on the fourth aspect, the copolymer of the acrylic resin and the urethane resin is a polymethyl methacrylate having a hydroxyl group at a terminal and having a molecular weight of 5,000 to 7000, an adipate-based polyester polyol having a molecular weight of 500 to 5,000, and isophorone. The present invention relates to a method for producing a decorative sheet, which is a reaction product with a diisocyanate. In a sixth aspect, the third to fifth aspects are described.
In any one of the inventions, the ratio of the acrylic resin component / urethane resin component in the copolymer of the acrylic resin and the urethane resin constituting the primer layer is 40/60 to 60/4.
The present invention relates to a method for producing a decorative sheet characterized by being 0. According to a seventh aspect, a primer layer and a cured resin protective layer are laminated on the surface of a thermoplastic resin sheet, irregularities are formed from the surface of the cured resin protective layer, and the primer layer and the cured resin are formed. The protective layer is
The present invention relates to a decorative sheet which is laminated along the irregularities. An eighth invention is directed to the decorative sheet according to the seventh invention, wherein the thermoplastic resin sheet itself is a colored and / or patterned sheet. A ninth invention relates to the decorative sheet according to the eighth invention, wherein the thermoplastic resin sheet is a single-layer sheet colored and / or patterned. In a tenth aspect based on the eighth aspect, the thermoplastic resin sheet comprises:
The present invention relates to a decorative sheet comprising a laminate of multiple sheets and being colored and / or patterned. The eleventh invention is the seventh to ninth inventions.
In any one of the inventions, the present invention relates to a decorative sheet, wherein the cured resin protective layer is obtained by curing an ionizing radiation-curable resin composition. In a twelfth aspect based on any one of the seventh to eleventh aspects, the thermoplastic resin sheet is a polyolefin-based resin sheet, and the primer layer is formed by reacting a copolymer of an acrylic resin and a urethane resin with an isocyanate compound. The present invention relates to a decorative sheet comprising a product. According to a thirteenth aspect, in the twelfth aspect, the copolymer of the acrylic resin and the urethane resin is a reaction product of an acrylic polymer component having a hydroxyl group at a terminal, a polyester polyol component, and a diisocyanate component. It relates to a characteristic decorative sheet. The fourteenth invention is
In the thirteenth invention, the copolymer of the acrylic resin and the urethane resin has a molecular weight of 5,000 having a hydroxyl group at a terminal.
Polymethyl methacrylate of ~ 7000, molecular weight 500
The present invention relates to a decorative sheet characterized by being a reaction product with adipate-based polyester polyol of up to 5000 and isophorone diisocyanate. First
The invention of 5th is the invention according to any one of the 12th to 14th inventions
The present invention relates to a decorative sheet, wherein the ratio of acrylic resin component / urethane resin component in a copolymer of acrylic resin and urethane resin constituting a primer layer is 40/60 to 60/40.

[0008]

FIG. 1 shows a basic structure of a decorative sheet 1. The decorative sheet 1 has a thermoplastic resin sheet 2 as a base material, a primer layer 3 on one surface thereof, and a hardened sheet. It is formed of a three-layer laminate in which the resin protective layers 4 are sequentially laminated. Then, this laminated body is formed from the outermost cured resin protective layer 4 to the primer layer 3 immediately below, and
It has irregularities 5 reaching the middle of its thickness from the upper surface of the lower thermoplastic resin sheet 2, and the primer layer 3 and the cured resin protective layer 4 are laminated along the irregularities 5. . Here, the unevenness 5 referred to here means the unevenness seen from the outermost surface and also refers to the unevenness that extends to the lower layer, particularly to the thermoplastic resin sheet, and when there are two thermoplastic resin sheets, the lower layer has thermoplasticity. It also refers to the unevenness of the resin sheet.

The base material of the decorative sheet 1 is basically made of the thermoplastic resin sheet 2, but if it has a sufficient thickness to be subjected to embossing, the lower side (= back side).
However, it may be lined with another material, for example, paper or nonwoven fabric laminated on the lower surface side.

As the thermoplastic resin constituting the thermoplastic resin sheet 2, general ones can be used. For example, general-purpose polyolefin resins such as polyethylene resin or polypropylene resin, cellulosic resins such as cellulose acetate, and polystyrene resins. A vinyl resin or vinyl copolymer resin such as a vinyl chloride resin, a polyvinylidene chloride resin, a polyvinyl alcohol resin, a vinyl chloride-vinyl acetate copolymer resin, an ethylene-vinyl acetate copolymer resin, or an ethylene-vinyl alcohol copolymer resin, Polyethylene terephthalate resin, polybutylene terephthalate resin,
Alternatively, an acrylic resin (including a methacrylic resin) such as a polyphthalic ester-based resin such as a polyethylene naphthalate-isophthalate copolymer resin, a polymethyl methacrylate resin, a polyethyl methacrylate resin, or a polybutyl acrylate resin, or a polyamide resin (Commonly referred to as nylon 6 or nylon 66), polycarbonate resin, polystyrene resin, ABS resin, or the like can be used.

[0011] Among the above general thermoplastic resins, in most cases, a polyvinyl chloride resin is conventionally used.
The reason is that when it is a polyvinyl chloride resin sheet,
It has good adhesiveness and thermal adhesiveness, so there is no problem in printing or laminating, it is easy to emboss, and it also has flame retardancy, and the degree of hardness and softness can be freely adjusted by adding a plasticizer. There are advantages. However, the polyvinyl chloride resin sheet contains chlorine in its structure, inevitably undergoes discoloration, emits toxic gas when burnt, and emits smoke when burned. There is also a problem caused by the contained plasticizer.

As a sheet other than a polyvinyl chloride resin sheet, an acrylic resin sheet is used when a high degree of weather resistance is required, and a fluororesin sheet is used when a stain resistance is required. However, none of them were enough to replace the polyvinyl chloride resin sheet.

[0013] Therefore, recently, polyolefin resin sheets have begun to be used in place of polyvinyl chloride resin sheets. Broadly speaking, (A) a sheet of a non-elastomeric polyolefin resin (B) a polyolefin thermoplastic resin There is an elastomer sheet.

One type of the polyolefin resin constituting the polyolefin resin sheet is the non-elastomer of the above (A). Specifically, polyethylene (low density or high density), polypropylene (isotactic type, syndiotactic type) (Tick type or mixed type thereof), polymethylpentene, polybutene, ethylene / propylene copolymer, propylene / butene copolymer and the like. Another type of polyolefin resin constituting the polyolefin resin sheet is the above (B)
(1) to (8) below.

(1) The main raw material is made of high-density polyethylene or isotactic polypropylene, which is a hard segment, and further contains an elastomer as a soft segment and, if necessary, an inorganic filler.

Here, as the elastomer, a diene rubber, a hydrogenated diene rubber, an olefin elastomer or the like is used. Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses crystallization of the polyolefin resin (high-density polyethylene or polypropylene in the present invention). It has improved flexibility. The olefin elastomer is an elastic copolymer obtained by adding at least one polyene copolymerizable with two or three or more olefins. As the olefin, ethylene, propylene, α-olefin, or the like is used. , 1,4-hexadiene, cyclic dienes, norbornene and the like are used. Preferred olefin copolymer rubbers include, for example, elastic copolymers containing an olefin as a main component, such as ethylene / propylene copolymer rubber. In addition, these elastomers may be appropriately cross-linked by using a cross-linking agent such as an organic peroxide or sulfur, if necessary.

(2) The hard segment is made of isotactic polypropylene and the soft segment is made of atactic polypropylene. Preferably, necking during film formation can be eliminated, and elongation, deformation and breakage during processing are minimized. In order to achieve the above, the latter has a ratio of 5 to 50%, preferably 20 to 40% (described in Japanese Patent Publication No. Hei 6-23278.
% By mass. ).

(3) A copolymer of ethylene / propylene / butene containing one of three structural isomers of 1-butene, 2-butene or isobutylene as butene. The following (3a) to (3c) are typical. (3a) A ternary random copolymer of ethylene / propylene / butene in which propylene in the monomer is preferably 90% or more (described in JP-A-9-111055). (3b) An amorphous material comprising a terpolymer of ethylene / propylene / butene and a crystalline polypropylene having a propylene component content of 50% or more (described in JP-A-5-77371). (3c) The content of propylene and / or 1-butene is 5
A product containing low-crystalline content of 0% or more and a crystalline polyolefin such as isotactic polypropylene, and further containing 0.5% of an oil gelling agent (Japanese Patent Application Laid-Open No. Hei 7-31635).
No. 8).

(4) The hard segment is polyethylene,
A crystalline rubber such as polypropylene or polymethylpentene, and a monoolefin copolymer rubber such as an ethylene / propylene non-conjugated diene terpolymer rubber having a soft segment partially cross-linked (described in JP-B-53-21021) ).

(5) An olefin copolymer (crystalline) as a hard segment and an uncrosslinked monoolefin copolymer rubber as a soft segment are heated and subjected to a shear stress while being partially crosslinked (particularly). Kosho 53-34
No. 210).

(6) A peroxide-decomposable olefin polymer, such as isotactic polypropylene, propyne / ethylene copolymer, or propylene / butene, which has a reduced molecular weight and increased fluidity when mixed and heated with peroxide. (1) A peroxide-crosslinked monoolefin polymer in which fluidity is reduced by a similar operation using a copolymer as a hard segment, for example, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene terpolymer rubber Is a soft segment, and is obtained by mixing and heating a peroxide non-crosslinked hydrocarbon rubber which does not crosslink and does not change its fluidity by the same operation in the presence of a peroxide ( 56-1
No. 5741).

(7) Ethylene / styrene / butadiene copolymer (described in JP-A-2-139232).

(8) The olefin elastomer of the above (1) to (7) having a hydroxyl group or a carboxyl group.

As the polyolefin resin sheet, any of a stretched sheet and an unstretched sheet can be used. Various additives such as a filler, a foaming agent, a flame retardant, a lubricant, an antioxidant, a processing stabilizer, an ultraviolet absorber, and a light stabilizer are added to the polyolefin resin sheet as needed. The thickness of such a polyolefin resin sheet is 2
It is about 0 to 300 μm. In addition, since the polyolefin resin sheet has poor adhesiveness as it is, it is preferable to improve the adhesiveness by performing a corona discharge treatment on a surface involved in printing or adhesion.

The primer layer 3 generally comprises a polyester resin, a polyurethane resin, an acrylic resin, a polycarbonate resin, a vinyl chloride / vinyl acetate copolymer, a polyvinyl butyral resin, a nitrocellulose resin or the like as a resin component, and dissolves the resin component. Alternatively, it is formed using a dispersed composition for forming a primer layer.

When the thermoplastic resin sheet 2 is made of a non-elastomeric polyolefin resin or a polyolefin thermoplastic elastomer, the primer layer 3 comprises a copolymer of an acrylic resin and a urethane resin, and an isocyanate compound. It is more preferable to use the reaction product of (1) from the viewpoint of improving the adhesiveness.

The above-mentioned copolymer of acrylic resin and urethane resin comprises the following three components: (A) an acrylic polymer component having a hydroxyl group at the terminal, (B) a polyester polyol component, and (C) a diisocyanate component. Which is obtained by mixing and reacting these three components to produce a prepolymer, and further adding a chain extender such as a diamine to the prepolymer to extend the chain. It is. As described above, the polyester urethane is formed, and the acrylic polymer component is introduced into the molecule to form an acrylic / polyester urethane copolymer having a hydroxyl group at a terminal.

In the above-mentioned copolymer of an acrylic resin and a urethane resin, the mass ratio of the acrylic resin component to the urethane resin component is expressed as follows: acrylic resin component / urethane resin component =
A ratio of 40/60 to 60/40 is preferable because characteristics such as blocking resistance and recoating property are good. The acrylic resin component relates to the acrylic polymer in the copolymer, and the urethane resin component relates to the sum of the polyester polyol and the isocyanate component in the copolymer.

In the above-mentioned copolymer of acrylic resin and urethane resin, as the acrylic polymer component having a hydroxyl group at the terminal of (A), a linear acrylic ester polymer having a hydroxyl group at the terminal is used. For example, a linear poly (methyl methacrylate) polymer having a hydroxyl group at a terminal is excellent in weather resistance (particularly, durability against deterioration by sunlight), and is easy to be compatibilized by being copolymerized with urethane. Is preferably used.

In the above copolymer of an acrylic resin and a urethane resin, the polyester polyol component (B) reacts with the diisocyanate (C) to form a polyester urethane, which becomes a urethane resin component. . As the polyester polyol component, a polyester diol having a hydroxyl group at both ends is used.
Polyester compounds derived from a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof, or an addition reaction product of an epoxy compound, a condensation product of a dibasic acid and a diol, and a cyclic ester compound. No.

The above diols include ethylene glycol, propylene glycol, diethylene glycol,
Short-chain aliphatic diols such as butanediol, hexanediol, and methylpentanediol are exemplified. The dibasic acids include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like.

Preferred as the above polyester polyol is an acid component of adipic acid or a mixture of adipic acid and terephthalic acid, particularly adipic acid, and 3-methylpentanediol and 1,1 as diol components.
It is an adipate-based polyester diol using 4-cyclohexanedimethanol.

In the primer layer 3, an acrylic resin component composed of an acrylic polymer contributes to weather resistance and anti-blocking properties. In the case of polymethyl methacrylate having a hydroxyl group at a terminal, the molecular weight may be 5,000 to 7000. preferable. In the primer layer 3, the urethane resin component contributes to the flexibility of the layer and the adhesion to the adherend. In the urethane resin, the molecular weight of the polyester polyol component may be any range as long as a urethane resin capable of sufficiently exhibiting the flexibility of the primer layer can be obtained, and adipic acid or a mixture of adipic acid and terephthalic acid,
In the case of an adipate-based polyester diol comprising methylpentanediol and 1,4-cyclohexanedimethanol, 500 to 5000 is preferable.

In the above copolymer of acrylic resin and urethane resin, as the diisocyanate component (C), an aliphatic or alicyclic diisocyanate compound having two isocyanate groups in one molecule is used. Specifically, tetramethylene diisocyanate, 2,2,
4 (2,4,4) 1,6 hexamethylene diisocyanate, isophorone diisocyanate, 4,4'dicyclohexylmethane diisocyanate, or 1,4'cyclohexyl diisocyanate. Of these, isophorone diisocyanate is preferred because of its excellent physical properties and price.

When the above (A), (B), and (C) are reacted, the total hydroxyl group (including the case of amino group) of the acrylic polymer, polyester diol, and a chain extender described later and isocyanate are included. The reaction is performed such that the equivalent ratio of the groups is such that the isocyanate groups become excessive.

When the above three components are reacted at 60 to 120 ° C. for about 2 hours, the isocyanate group of the diisocyanate reacts with the hydroxyl group at the terminal of the polyester diol to form a polyester urethane resin component and the hydroxyl group at the terminal of the acrylic polymer. And a compound in which diisocyanate is added to the prepolymer, and a prepolymer in which excess isocyanate groups and hydroxyl groups remain is formed. A chain extender is added to the prepolymer, an isocyanate group is reacted with the chain extender, and the chain is extended, whereby an acrylic polymer component is introduced into the polyester urethane molecule, and a desired acrylic resin having a hydroxyl group at a terminal is obtained. A urethane copolymer is obtained.

A production example of an acrylic / urethane copolymer having a hydroxyl group at a terminal is shown below. (A) polymethyl methacrylate having a molecular weight of 6000 and hydroxyl groups at both ends, (B) a polyester diol obtained by polycondensation of 1,4-cyclohexanedimethanol and adipic acid, and 3-methylpentanediol, and (C) Isophorone diisocyanate is used, and isophorone diamine is used as a chain extender.

The above-described reaction vessel (A), (B) and (C) into which a dry nitrogen is introduced and which can be sealed and equipped with a stirrer are blended and reacted at a temperature of 75 ° C. for 6 hours. After the polymer was obtained, the obtained prepolymer was dissolved in methyl ethyl ketone, chain extension was performed by dropping isophoronediamine at a temperature of 60 ° C., and toluene and isopropyl alcohol were further added. -A urethane copolymer was obtained. The molecular weight of the acrylic / urethane copolymer is 53000, and the acrylic resin component /
The urethane resin component ratio was 50/50, and the solvent composition was methyl ethyl ketone / toluene / isopropyl alcohol =
55/40/5.

The isocyanate compound used in the primer layer 3 together with the above-mentioned copolymer of acrylic resin and urethane resin (= the desired acrylic-urethane copolymer having a hydroxyl group at the terminal) is the above-mentioned acrylic resin and urethane resin. Any compound can be used as long as it can react with the hydroxyl group of the copolymer of the above and crosslink and cure. For example, a divalent or higher valent aliphatic or aromatic isocyanate compound is desirable. Specifically, a monomer such as tolylene diisocyanate, xylylene diisocyanate, 4,4 ′ dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, or lysine isocyanate, a dimer, a trimer, or a multimer thereof, or Isocyanate compounds such as derivatives (adducts) obtained by adding these isocyanate compounds to polyols are exemplified.

In addition to the above resin, a filler such as silica fine powder or an additive such as a light stabilizer may be added to the primer layer 3. The primer layer 3 is prepared by mixing these components with a solvent or a diluent, if necessary, to prepare a composition for forming a primer layer. The obtained composition for forming a primer layer is applied to the thermoplastic resin sheet 2. above,
It is formed by applying by a known application method such as gravure coating or roll coating, and then, if necessary, drying and curing.
It may be heated or heated for curing. The thickness of the primer layer 3 is preferably 0.5 to 10 g / m ² .

In the present invention, the primer layer 3 is formed in order to bring the cured resin protective layer 4 into close contact with the thermoplastic resin sheet 2;
A primer layer may also be formed on the side to be laminated with the adherend, and the decorative sheet is not limited to the decorative sheet 1 described with reference to FIG. 1, but may be a decorative sheet described with reference to FIGS. 1
The same applies to. However, like the decorative sheet 1 shown in FIG. 3, a pattern layer is provided on the lower surface side via a primer layer,
In the case where the colored layer is formed, the lowermost primer layer does not necessarily have to be formed.

The cured resin protective layer 4 is obtained by curing a layer of the curable resin composition by using a curing means, and can be formed using a general thermosetting resin. In some cases, an unsaturated polyester resin, polyurethane resin, or epoxy resin that provides flexibility as a cured coating film is used, and particularly, a polyurethane resin is often used. These are mixed with a solvent or a diluent or the like to form a composition for forming a curable resin protective layer. The composition is coated on the primer layer 3 by a usual coating means, and then dried and cured as necessary. Then, the cured resin protective layer 4 is formed. It may be heated or heated for curing.

However, such as a melamine resin decorative panel or a diallyl phthalate resin decorative panel, the abrasion resistance and durability are as high as those of a decorative panel whose surface is made of a thermosetting resin prepared by using hot pressing means. To prepare on the surface of the decorative sheet, a layer is formed by application or the like using a so-called ionizing radiation-curable resin composition, which is ultraviolet-curable or electron-beam-curable, and cured by irradiating with ultraviolet light or an electron beam. It is more preferable that the cured resin protective layer 4 is formed by curing the ionizing radiation-curable resin composition obtained as described above.

The ionizing radiation-curable resin composition is obtained by appropriately mixing the following prepolymer, oligomer and / or monomer having a polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule. Ionizing radiation refers to electromagnetic waves or charged particle beams having energy quanta that can polymerize or crosslink molecules, and usually use ultraviolet rays or electron beams.

Among the examples of the above prepolymers and oligomers, those having a polymerizable unsaturated bond in the molecule include:
Unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, acrylates such as polyester acrylates, urethane acrylates, epoxy acrylates, polyether acrylates, polyol acrylates, melamine acrylates, silicone acrylates, triazine acrylates, or the aforementioned Methacrylates corresponding to each acrylate are included.

Among the above prepolymers and oligomers, those having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resins and novolak type epoxy resins, and vinyl ethers such as aliphatic vinyl ethers. And the like.

Further, examples of the above-mentioned monomers include monofunctional acrylates such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, and phenoxyethyl acrylate; For the corresponding monofunctional methacrylates and polyfunctional ones, diethylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide triacrylate, dipentaerythritol pentaacrylate Or polyfunctional acrylates such as dipentaerythritol hexaacrylate, or the corresponding polyfunctional methacrylate Over door acids and the like. In addition, examples of the monomer having a thiol group include trimethylolpropane trithioglycolate and dipentaerythritol tetrathioglycolate.

In order to adjust physical properties such as flexibility and surface hardness when the ionizing radiation-curable resin composition is applied and cured, a resin not cured by ionizing radiation irradiation is added to the ionizing radiation-curable resin composition. Can also be added,
Specifically, it is a thermoplastic resin such as a cellulose resin, an acrylic resin, a vinyl chloride / vinyl acetate copolymer resin, and a polyvinyl acetate resin.

When the ionizing radiation-curable resin composition is cured by ultraviolet irradiation after application, a photopolymerization initiator or a photopolymerization accelerator is added. As the photopolymerization initiator, in the case of a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether or the like is used alone or as a mixture. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. . The addition amount of the photopolymerization initiator,
0.1 to 1 based on the ionizing radiation-curable resin composition 100
0 (based on mass).

The cured resin protective layer 4 preferably contains spherical particles which are preferably inorganic and have a higher hardness than the cured resin in order to improve the wear resistance of the surface of the layer. Spherical particles do not necessarily have to be true spheres, and α-
Alumina, silica, chromium oxide, iron oxide, diamond, graphite and the like can be exemplified. Among them, spherical α-alumina (from spherical alumina AS-10 manufactured by Showa Denko KK) AS50) having an average particle diameter of 5 to 100 μm.

The above prepolymer, oligomer and / or
Or, a monomer, a resin to be added as necessary, a photopolymerization initiator, and spherical particles, if necessary, further mixed with a solvent or a diluent to obtain a composition for forming a cured resin protective layer. The obtained composition for forming a cured resin protective layer is applied onto the primer layer 3 by a known application method such as gravure coating or roll coating, and then, if necessary, dried, and then exposed to ultraviolet light or electrons. The cured resin protective layer is formed by irradiating with a line and curing. The thickness of the cured resin protective layer is
It is preferably ² to 20 g / m ² .

As an ultraviolet light source for curing, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, a black light, a fluorescent lamp, a metal halide lamp, or the like is used. In addition, as the electron beam source for curing, a Cockloft-Walton type, a bande graph type, a resonance transformer type,
Using various electron beam accelerators such as an insulating core transformer type, a linear type, a dynamitron type, or a high frequency type, 100 to 10
An electron beam having an energy of 00 KeV, preferably 100 to 300 KeV is irradiated.

The decorative sheet 1 shown in FIG. 1 has a laminate comprising a thermoplastic resin sheet 2, a primer layer 3 and a cured resin protective layer 4, and a primer layer 3 immediately below the cured resin protective layer 4 on the outermost surface. In addition, the primer layer 3 and the cured resin protective layer 4 have irregularities 5 that reach the middle of the thickness from the upper surface of the thermoplastic resin sheet 2 below.
Are stacked along the irregularities 5. This unevenness 5
Is a metal plate having irregularities on its surface, a concave and convex mold such as a metal roll is applied to the cured resin protective layer side of the above laminate, pressurized,
Usually, it is formed by heating and pressurizing, and when accompanied by heating, then by cooling. The heating may include heating the concavo-convex mold and / or heating the laminate.

Incidentally, it is preferable that the decorative sheet 1 is a thermoplastic resin sheet 2 serving as a base material having some kind of decoration applied thereto. Although the decorative sheet 1 described above has the unevenness 5, it is more preferable that the decorative sheet 1 is further colored or provided with a pattern. The base material of the decorative sheet 1 may be one sheet as shown in FIG. 1, but may be two sheets. Hereinafter, when the base material is composed of one sheet,
In the case where the sheet is composed of two sheets, a colored sheet or a sheet provided with a pattern will be described.

In the decorative sheet 1 shown in FIG. 2, a primer layer 3a, a colored layer 6a, a picture layer 6b, a primer layer 3, and a cured resin protective layer 4 are sequentially laminated on a colored colored thermoplastic resin sheet 2a. This laminate has irregularities 5 that reach the middle of the thickness when viewed from the upper surface side of the lowermost thermoplastic resin sheet 2 from the outermost cured resin protective layer 4. And primer layer 3
a, a colored layer 6 a, a picture layer 6 b, a primer layer 3, and a cured resin protective layer 4 are laminated along irregularities 5. This is a so-called "front print" type decorative sheet.

Here, both the primer layers 3 and 3a or at least the lower primer layer 3
Is formed using the same material as that of the primer layer 3 already described with reference to FIG.

The coloring layer 6a and the picture layer 6b can be formed to form either one or both. Since the picture layer 6b does not normally cover the lower layer, the lower layer can be seen through from above the picture layer 6b. Coloring layer 6a and picture layer 6
b is a thermoplastic resin, for example, a cellulose resin, an acrylic resin, a vinyl chloride / vinyl acetate copolymer resin, or a polyvinyl acetate resin or the like as a binder resin, a coloring agent made of a dye or a pigment, an additive, solvent,
It can be formed by a printing method using an ink composition prepared by adding and diluting a diluent and the like. Since the coloring layer 6a is a so-called solid layer formed uniformly and uniformly, it can be formed by a coating method.

The decorative sheet 1 shown in FIG. 3 has a primer layer 3 on the lower surface of a transparent transparent thermoplastic resin sheet 2b.
a, a pattern layer 6b, and a coloring layer 6a are sequentially laminated, and a primer layer 3 and a cured resin protective layer 4 are sequentially laminated on the upper surface of a transparent thermoplastic resin sheet. The laminate has irregularities 5 that reach the middle of the thickness from the outermost cured resin protective layer 4 when viewed from the upper surface side of the transparent thermoplastic resin sheet 2b,
The primer layer 3 and the cured resin protective layer 4 are laminated along the unevenness 5. This is a so-called “back printing” type decorative sheet.

In the example described with reference to FIG. 3, both the primer layers 3 and 3a are formed using the same material as that for forming the primer layer 3 already described with reference to FIG. The coloring layer 6a and the picture layer 6b are shown in FIG.
Are formed using the same materials and means as described with reference to FIG. In this case, the colored layer 6a is preferably formed rather than not provided in order to impart hiding power to the decorative sheet 1, and may be formed by adding a hiding pigment.

The decorative sheet 1 shown in FIG. 4 has a primer layer 3a, a colored layer 6a, and a pattern layer 6b sequentially laminated on a colored colored thermoplastic resin sheet 2a. It has a common part with the decorative sheet 1 described by reference. On the picture layer 6b, a transparent thermoplastic resin sheet 2b is laminated via an adhesive layer 7, and on the transparent thermoplastic resin sheet 2b, the same as in the decorative sheet 1 described with reference to FIG. , A primer layer 3 and a cured resin protective layer 4 are sequentially laminated to form a laminate. This laminate has irregularities 5 reaching the middle of its thickness from the outermost cured resin protective layer 4 as viewed from the upper surface side of the colored thermoplastic resin sheet 2a.
a, a colored layer 6 a, a picture layer 6 b, an adhesive layer 7, a transparent thermoplastic resin sheet 2 b, a primer layer 3, and a cured resin protective layer 4 are laminated along irregularities 5. Because two sheets are laminated, "doubling sheet", and because it is also embossed,
Also referred to as "doubling embossed sheet". In the case where two sheets are used, both of the two sheets may be formed of a transparent thermoplastic resin sheet. In this case,
There is a case where only the pattern layer 6b is formed between the two sheets, and a case where the coloring layer 6a is provided below the pattern layer 6b. Also,
Only the picture layer 6b may be formed between the two sheets, and the colored layer 6a may be formed on the lower surface of the lower transparent thermoplastic resin sheet.

Here, the newly added adhesive layer 7 can be omitted, but when a polyolefin resin sheet is used as a base material, it is better that the adhesive layer is interposed. Various layers can be used,
It is preferable to use a two-component polyurethane-based resin adhesive composed of a main component of a polyol and a curing agent of an isocyanate compound, since it is easy to wet, can obtain flexibility, and can perform dry lamination.

It is also conceivable to form the decorative sheet 1 by laminating three or more thermoplastic resin sheets. However, the required thickness cannot be obtained unless three or more thermoplastic resin sheets are used. Since it is not economical to use such a sheet, it is preferable to use one or two sheets to form the decorative sheet 1 unless a special effect is aimed at.

By the way, according to the present invention, when the primer layer is formed by using a reaction product of a copolymer of an acrylic resin and a urethane resin with an isocyanate compound, it has flexibility and adhesiveness. Is excellent, so that the primer layer 3 and the cured resin protective layer 4 are laminated on the thermoplastic resin sheet 2 (the decorative sheet described with reference to FIG. 1, FIG. 2, FIG. 3, and FIG. 4). When the unevenness is formed by embossing the cured resin protective layer 4 to obtain the unevenness in the cured resin protective layer 4, even if the laminate is distorted at the lamination interface, the strain is not affected. Is easily absorbed, so that embossing can form not only shallow unevenness but also considerably deep unevenness. As an example, the pitch of the unevenness is 50 to 150 μm, preferably 5 μm.
Deep irregularities such as 0 to 100 μm and a height difference of 50 to 300 μm, preferably 50 to 150 μm can be sufficiently obtained. Further, when forming a concave portion on a flat surface, the minor diameter of the concave portion is 3
Deep recesses having a depth of 0 to 200 μm, preferably 30 to 150 μm, and a depth of 30 to 300 μm, preferably 30 to 150 μm can also be formed.

[0064]

(Example 1) A corona discharge treatment was applied to both front and back surfaces of a polyolefin resin sheet having a thickness of 60 μm, and the following ink compositions were used. And a pattern layer composed of a picture layer were sequentially laminated. (Ink composition for forming a primer layer)-28 parts by mass of polyurethane resin-4 parts by mass of hexamethylene diisocyanate-4 parts by mass of silica-34 parts by mass of methyl ethyl ketone-34 parts by mass of toluene

On the picture surface of the obtained printed sheet,
Using the following adhesive composition, by a roll coating method, applied so that the coating amount when dried becomes 10 g / m ² ,
After drying to form an adhesive layer, a polypropylene resin is melt-extruded on the adhesive layer to a thickness of 80
A transparent layer having a thickness of μm was formed, and a multilayer sheet having a pattern layer interposed between the colored sheet and the transparent layer was obtained. (Adhesive composition) ・ Polyester polyol 50 parts by mass ・ Hexamethylene diisocyanate 7 parts by mass ・ Ethyl acetate 50 parts by mass

The surface of the transparent layer of the multilayer sheet obtained above is subjected to a corona discharge treatment, and the primer layer-forming coating composition having the following composition is applied to the treated surface so that the coating amount when dried becomes 1 g / m ^2. The urethane acrylate-based electron beam curable resin composition for forming a surface protective layer is applied in an amount of 1 when dried.
After coating so as to be 5 g / m ² , an electron beam was irradiated using an electron beam irradiation apparatus under the conditions of an acceleration voltage of 125 KV, an irradiation dose of 5 Mrad, and an oxygen concentration of 200 ppm or less, and both coating films were cured. A surface protection layer was formed. (Coating composition for forming a primer layer) 48 parts by mass of acrylic / urethane copolymer (Examples of the production examples in paragraphs 0037 to 0038) 5 parts by mass of hexamethylene diisocyanate 4 parts by mass of silica 4 parts by mass of methyl isobutyl ketone 7 parts by mass Methyl ethyl ketone 41 parts by mass (ink composition for forming a picture layer)-polyurethane resin 3 parts by mass-acrylic polyol 12 parts by mass-pigment 10 parts by mass-silica 1 part by mass-methyl ethyl ketone 37 parts by mass-methyl isobutyl ketone 37 parts by mass (surface protection) Urethane acrylate-based electron beam curable resin composition for layer formation) Bifunctional urethane acrylate oligomer 40 parts by mass Hexafunctional urethane acrylate oligomer 10 parts by mass Silica 5 parts by mass Ethyl acetate 45 parts by mass

The sheet on which the surface protective layer had been formed was embossed using an embossing machine, using a satin embossing plate having a plate depth of 100 μm or more from the surface side. The coating film on the surface of the obtained product had no peeling in the evaluation of the initial adhesion and the adhesion after the weather resistance test, and the reproducibility of the embossed plate unevenness was sufficient.

In the above, the initial adhesiveness was determined by using a cutter knife to cut eleven vertical and horizontal cuts at 2 mm intervals from the cured resin protective layer, the primer layer, and the transparent layer therebelow to 100 grids. It is a result of observing the presence or absence of peeling by rapidly affixing a cellophane adhesive tape thereon in a 45 ° direction. In addition, weather resistance test,
Using a super UV tester (manufactured by Iwasaki Electric Co., Ltd.)
Temperature; 63 ° C., relative humidity; 70%, irradiation intensity; 60 mW
/ Cm ² , DEW cycle; irradiation 20 hours / DEW 4 hours. After the test, the same adhesion evaluation was performed as above, and the adhesion after the weather resistance test was determined. Furthermore, the reproducibility of the embossed plate's uneven shape was visually checked, "sufficient"; one having sufficient depth and shape, "slightly insufficient"; one having slightly insufficient depth and shape, and "sufficient"": Insufficient depth and shape.

(Comparative Example 1) The multilayer sheet was first embossed with a satin embossing plate having a plate depth of 100 μm or more from the surface side, and then subjected to a corona discharge treatment on the embossed surface, and thereafter a primer layer Formation, protection layer formation,
Otherwise, the procedure was the same as in Example 1. The coating film on the surface of the obtained product had considerable peeling in the initial adhesion and the evaluation after the weather resistance test, and the reproducibility of the embossed plate unevenness was "slightly insufficient".

Comparative Example 2 The embossing was carried out in the same manner as in Comparative Example 1, except that a grained embossing plate having a plate depth of 20 μm was used. The coating on the surface of the obtained product is
In the evaluation of the initial adhesion and the adhesion after the weather resistance test, there was slight peeling, and the reproducibility of the concave-convex shape of the embossed plate was "insufficient".

Comparative Example 3 The same procedure as in Example 1 was carried out except that the following coating composition for forming a primer layer was used. (Coating composition for forming a primer layer)-30 parts by mass of polyester polyol-4 parts by mass of hexamethylene diisocyanate-35 parts by mass of methyl ethyl ketone-35 parts by mass of toluene

The coating film on the surface of the obtained product did not peel off in the evaluation of the initial adhesion, but did peel off considerably in the evaluation of the adhesion after the weather resistance test. In addition, the reproducibility of the embossed plate unevenness was “sufficient”.

Comparative Example 4 The same procedure as in Example 1 was carried out except that the following coating composition for forming a primer layer was used. (Coating composition for forming a primer layer)-17 parts by mass of polyester polyol-17 parts by mass of acrylic resin-4 parts by mass of hexamethylene diisocyanate-33 parts by mass of methyl ethyl ketone-33 parts by mass of toluene

The coating film on the surface of the obtained product did not peel off in the evaluation of the initial adhesion, but did peel off slightly in the evaluation of the adhesion after the weather resistance test. In addition, the reproducibility of the embossed plate unevenness was “sufficient”.

[0075]

According to the first aspect of the present invention, since the cured resin protective layer is formed on the surface of the thermoplastic resin sheet via the primer layer, the embossing is performed. As compared with the case of forming the cured resin protective layer, the unevenness is reproduced sharply, the adhesion between the thermoplastic resin sheet and the cured resin protective layer is excellent, and even if the unevenness is formed deeply, the cured resin protective layer is Since it can be formed, it is possible to provide a method of manufacturing a decorative sheet capable of obtaining a decorative sheet in which the adhesion between the base material and the cured film is hardly reduced even if the unevenness is formed deeply. According to the invention of claim 2, in addition to the effect of the invention of claim 1, the curable resin protective layer is formed using an ionizing radiation curable resin composition, and can be easily cured by irradiation with ionizing radiation. A method for producing a decorative sheet can be provided. According to the invention of claim 3, in addition to the effects of the invention of claim 1 or 2, the primer layer is formed of a copolymer of an acrylic resin and a urethane resin while using a polyolefin-based resin sheet whose adhesiveness is not always good. And a reaction product of a polyisocyanate compound and an isocyanate compound, thereby providing a method for producing a decorative sheet having excellent adhesion, flexibility, and weather resistance between a polyolefin-based resin sheet and a cured resin protective layer. According to the fourth aspect of the present invention, it is possible to provide a method of manufacturing a decorative sheet capable of promoting substantially the same effect as the effect of the third aspect of the present invention. Claim 5
According to the invention, in addition to the effect of the invention of claim 4, since the components of the copolymer of acrylic resin and urethane resin are specified, by using polymethyl methacrylate having a hydroxyl group at a terminal and a molecular weight of 5,000 to 7000, , Weather resistance and adhesion are particularly good, and the molecular weight is 500 to 5
The use of an adipate-based polyester polyol of 000 provides particularly good flexibility, and the use of isophorone diisocyanate provides a method for producing a decorative sheet that can provide a primer layer excellent in physical properties and cost. it can. According to the invention of claim 6, in addition to the effect of any of claims 3 to 5, the ratio of acrylic resin component / urethane resin component in the copolymer of acrylic resin and urethane resin constituting the primer layer is specified. Therefore, it is possible to provide a method for producing a decorative sheet excellent in blocking resistance and recoating property of the coating film of the primer layer. According to the invention of claim 7, irregularities are formed in the laminate of the thermoplastic resin sheet, the primer layer, and the cured resin protective layer, and the primer layer and the cured resin protective layer are laminated along the irregularities. Since it has a structure, it is possible to provide a decorative sheet in which the irregularities are deep and sharp, yet the adhesiveness between the thermoplastic resin sheet and the cured resin protective layer can be ensured. According to the invention of claim 8, in addition to the effect of the invention of claim 7, it is possible to provide a decorative sheet having a higher decorative effect, in which the thermoplastic resin sheet itself is colored or patterned. According to the ninth aspect of the present invention, in addition to the effects of the eighth aspect of the present invention, it is possible to provide a decorative sheet having a thermoplastic resin sheet having a single layer structure. According to the tenth aspect, in addition to the effects of the eighth aspect, it is possible to provide a decorative sheet having a two-layer thermoplastic resin sheet. According to the invention of claim 11, in addition to the effects of any of claims 7 to 9, the cured resin protective layer is formed by curing the ionizing radiation-curable resin composition, so that the surface has abrasion resistance, A durable decorative sheet can be provided. Claim 1
According to the second invention, in addition to the effects of the seventh to eleventh inventions, in addition to the base material being a polyolefin-based resin sheet, the primer layer is formed of a copolymer of an acrylic resin and a urethane resin, and an isocyanate compound. Because of the formation of the reaction product, the adhesion between the substrate and the cured resin protective layer,
A decorative sheet having excellent flexibility and weather resistance can be provided. According to the invention of claim 13, it is possible to provide a decorative sheet in which the effect of the invention of claim 12 is further promoted. Claim 14
According to the invention, in addition to the effect of the invention of claim 13, in the copolymer of acrylic resin and urethane resin, polymethyl methacrylate having a hydroxyl group at the terminal and having a molecular weight of 5000 to 7000 is used, Adhesiveness is particularly good, and adipate-based polyester polyol having a molecular weight of 500 to 5,000 is used, so that flexibility is particularly good, and isophorone diisocyanate is used, so that the primer layer is excellent in physical properties and cost. Can be provided. According to the invention of claim 15, in addition to the effect of any of claims 12 to 14, the ratio of acrylic resin component / urethane resin component in the copolymer of acrylic resin and urethane resin constituting the primer layer is specified. As a result, a decorative sheet having excellent blocking resistance and recoating property of the coating film of the primer layer can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a basic structure of a decorative sheet.

FIG. 2 is a cross-sectional view of a “front printing” type decorative sheet.

FIG. 3 is a cross-sectional view of a “back printing” type decorative sheet.

FIG. 4 is a cross-sectional view of a “doubling embossed sheet” type decorative sheet.

[Explanation of symbols]

 Reference Signs List 1 decorative sheet 2 thermoplastic resin sheet 3 primer layer 4 cured resin protective layer 5 unevenness 6 pattern layer (6a; coloring layer, 6b; picture layer) 7 adhesive layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/40 B32B 27/40 31/22 31/22 // B29K 23:00 B29K 23:00 33:04 33:04 75:00 75:00 B29L 9:00 B29L 9:00 F-term (reference) 4F100 AK01A AK01C AK03A AK07 AK25B AK41B AK51B AL01B AL01C BA03 BA10A BA10C BA15 CA13A DD01 EH112 EH17 EH462 EJ55B EJ39 EJ392 EJ39 EJ392 HB21 JA07B JB12C JB14C JB16A JK06 JL09 JL10A JL11 JN01 YY00B 4F209 AA03 AA24A AA36 AA42 AA43A AA44 AD05 AD20 AD32 AD34 AF01 AG03 AG05 AH48 PA01 PA15 PB02 PB13 PC01 PC05 PG02 PG02 PG02 PG02 PG02

Claims (15)

[Claims] 1. A primer layer forming composition and a layer of a curable resin composition are sequentially laminated on the surface of a thermoplastic resin sheet, and if necessary, a curing means is applied to both layers to form a primer layer, and A method for producing a decorative sheet, comprising: forming a cured resin protective layer in which a layer of a curable resin composition has been cured; and thereafter, embossing is performed on the cured resin protective layer to form irregularities. 2. The method for producing a decorative sheet according to claim 1, wherein said curable resin composition is an ionizing radiation curable resin composition, and said curing means is performed by irradiating ionizing radiation. 3. The thermoplastic resin sheet is a polyolefin resin sheet, and the primer layer comprises a reaction product of a copolymer of an acrylic resin and a urethane resin with an isocyanate compound. Or the method for producing a decorative sheet according to 2. 4. The method according to claim 3, wherein the copolymer of the acrylic resin and the urethane resin is a reaction product of an acrylic polymer component having a hydroxyl group at a terminal, a polyester polyol component, and a diisocyanate component. Method for producing a decorative sheet. 5. The copolymer of an acrylic resin and a urethane resin has a hydroxyl group-terminated molecular weight of 5,000 to 700.
0 polymethyl methacrylate, molecular weight 500-500
The method for producing a decorative sheet according to claim 4, wherein the cosmetic sheet is a reaction product with an adipate-based polyester polyol of 0 and isophorone diisocyanate. 6. The copolymer of acrylic resin and urethane resin constituting the primer layer, wherein the ratio of acrylic resin component / urethane resin component is 40/60 to 60/40. Or a method for producing a decorative sheet according to the above. 7. A primer layer and a cured resin protection layer are laminated on the surface of a thermoplastic resin sheet, and irregularities are formed from the surface of the cured resin protection layer, and the primer layer and the cured resin protection are formed. A decorative sheet, wherein layers are laminated along the irregularities. 8. The decorative sheet according to claim 7, wherein the thermoplastic resin sheet itself is a colored and / or patterned sheet. 9. The decorative sheet according to claim 8, wherein the thermoplastic resin sheet is a colored and / or patterned single-layer sheet. 10. The decorative sheet according to claim 8, wherein the thermoplastic resin sheet is formed of a laminate of a plurality of sheets and is colored and / or patterned. 11. The decorative sheet according to claim 7, wherein the cured resin protective layer is formed by curing an ionizing radiation-curable resin composition. 12. The thermoplastic resin sheet is a polyolefin-based resin sheet, and the primer layer is made of a reaction product of a copolymer of an acrylic resin and a urethane resin with an isocyanate compound. ~ 1
The decorative sheet according to any one of claims 1 to 7. 13. An acrylic polymer component having a terminal hydroxyl group, wherein the copolymer of acrylic resin and urethane resin has
13. A reaction product with a polyester polyol component and a diisocyanate component.
The decorative sheet according to the above. 14. The copolymer of an acrylic resin and a urethane resin has a hydroxyl group-terminated molecular weight of 5,000 to 70.
Polymethyl methacrylate having a molecular weight of 500 to 50
14. The decorative sheet according to claim 13, which is a reaction product of No. 00 with an adipate-based polyester polyol and isophorone diisocyanate. 15. An acrylic resin component in a copolymer of an acrylic resin and a urethane resin constituting a primer layer.
The decorative sheet according to any one of claims 12 to 14, wherein the ratio of the urethane resin component is 40/60 to 60/40.