JP2003011315A - Decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material excellent in environmental safety, solvent resistance, and water resistance. SOLUTION: In the decorative material 1, an ink layer 3 of an aqueous resin is formed on a base material 2, and a top coat layer 7 of an active energy ray curable solventless resin is formed on the ink layer. The ink layer has at least a pattern layer 5 and a primer layer 6, and a compound having at least two carbodiimide groups in a molecule is incorporated as a curing agent into at least one layer of the ink layer 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative material having excellent environmental safety, solvent resistance and water resistance, and more specifically to solvent resistance and water resistance having an ink layer made of a water-based resin. It relates to an excellent cosmetic material.

[0002]

2. Description of the Related Art In recent years, cosmetic materials such as house building materials and furniture have
Due to problems in the working environment in the manufacturing process and problems in the living environment, the use of ink that does not use organic solvents is required.

For example, in JP-A-11-227113, an ink layer made of a water-soluble ink is provided on a base material, and a top coat layer made of a solventless ionizing radiation curable resin is provided on the ink layer. The following cosmetic materials are disclosed.

[0004]

Problems to be Solved by the Invention
Although solvent resistance and water resistance are required, it cannot be said that the conventional decorative material provided with the ink layer made of the above water-soluble ink does not necessarily have sufficient solvent resistance and water resistance. It was

The present invention has been made to solve the above-mentioned problems, and provides a cosmetic material excellent in environmental safety such as working environment and living environment, solvent resistance and water resistance.

[0006]

According to a first aspect of the present invention, an ink layer made of a water-based resin is provided on a substrate, and a top coat layer made of a solventless active energy ray-curable resin is provided on the ink layer. The decorative material, wherein the ink layer has at least a pattern layer and a primer layer, and at least one layer in the ink layer contains a hydrophilic compound having two or more carbodiimide groups in the molecule as a crosslinking agent. Is characterized by.

The term "hydrophilic compound" as used herein has an affinity for water or a mixed solvent of water and an aliphatic lower alcohol in addition to a water-soluble compound which is completely soluble in water at room temperature. It also means a compound which is uniformly dispersed in the solvent to form an emulsion or suspension.

According to the present invention, a compound having two or more carbodiimide groups in a molecule as a cross-linking agent is provided in at least one layer of an ink layer containing a water-based resin as a main component, which comprises a primer layer, a pattern layer and, in some cases, a solid layer. By virtue of this, the adhesiveness of each layer is excellent, and the formed decorative material has excellent solvent resistance and water resistance, and is also excellent in environmental safety such as working environment and living environment.

The invention according to claim 2 is characterized in that, in the decorative material according to claim 1, the aqueous resin contains an anion-type water-dispersed resin as a main component, and the invention according to claim 3 is based on claim 1. The decorative material described above is characterized in that the aqueous resin containing an anionic water-dispersed resin as a main component has a carboxylic acid group. Furthermore, the invention of claim 4 is characterized in that, in the decorative material according to claim 1, an electron beam is used as an active energy ray.

[0010]

1 is a sectional view showing an example of the layer structure of a decorative material 1 of the present invention. Decorative material 1 shown in FIG.
Is a base material 2 and an ink layer 3 provided on the base material 2.
And a top coat layer 7 provided on the ink layer 3. The ink layer 3 is formed of a solid layer 4, a pattern layer 5, and a primer layer 6 in this order from the base material 2 side.

Hereinafter, the embodiments of the present invention will be described while describing each layer constituting the decorative material 1 in detail.

The base material 2 is an essential component of the decorative material 1 and forms the base of the decorative material 1. As the substrate 2, thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, or the like. A so-called vinyl wallpaper stock obtained by sol coating or dry laminating polyvinyl chloride on paper can be used. Further, a sheet or film made of an inorganic fiber such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber or carbon fiber can also be used. Further, woven or non-woven fabrics using organic resins such as polyester and vinylon, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer. Vinyl resins such as polymers, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS ), A sheet or film made of a resin such as cellulose triacetate, cellophane, or polycarbonate can also be used.
Alternatively, a metal foil such as aluminum, iron, stainless steel, or copper can be used. Further, a laminate of a plurality of such base material materials can be used as the base material 2.

Next, the ink layer 3 will be described.

The ink layer 3 is composed of a solid layer 4, a pattern layer 5 and a primer layer 6.

As shown in FIG. 1, the solid layer 4 is provided in order to hide the background of the base material 2, and is usually formed in a solid pattern-free manner. The pattern layer 5 generally has a pattern or color composed of figures, characters, colors, combinations thereof, and the like, and is formed on the solid layer 4 as a planar, uneven, or convex (see FIG. 1) layer. To be done. The pattern layer 5 may also serve as the solid layer 4, and in this case, the solid layer 4 may be omitted. The solid layer 4 and the pattern layer 5 thus formed form colors and patterns on the decorative material 1.

A water-based resin is used for the ink used for forming the solid layer 4 and the pattern layer 5. In the present invention,
The use of the water-based resin can maintain a favorable working environment and living environment.

Aqueous resins are roughly classified according to the form in which they are present in water, and are divided into water-soluble resins that are dissolved in water and water-dispersed resins that are dispersed in water, and the aqueous resins are hydrated functional groups. It is dissolved or dispersed in water by hydrophilicity of the hydrated functional group alone or by using a neutralizing agent if necessary, but it is roughly classified by the ionicity of the hydrophilic group. , Cation type, nonion type, and anion type, and anion type water dispersion resin is particularly preferably used. As the cationic group, an amino group, an imino group, 3
Examples thereof include a primary amine group, a quaternary ammonium group, and a hydrazino group. As the nonionic group, a hydroxyl group,
Examples thereof include ether groups and amide groups. Examples of the anionic group include a carboxyl group, a sulfone group, a sulfuric acid ester group, and a phosphoric acid ester group.

As the water-soluble resin, starch, dextrin, natural products such as alginate, cellulose ester,
Examples include natural product derivatives such as cellulose ether, and synthetic resins such as polyvinyl alcohol, polyacrylate, polyvinylamine, acrylic nitrification cotton, polyurethane resin, and polyester resin.

As the water-dispersed resin, shellac, styrenated shellac, casein, stellene / maleic acid resin, rosin / maleic acid resin, acrylic resin, vinyl acetate thread resin, styrene resin, vinyl chloride resin, synthetic rubber latex , Polyurethane resin, polyester resin, alkyd resin, epoxy ester, rosin ester and the like.

A coloring agent such as a coloring pigment is added to the water-based resin used for the solid layer 4 and the pattern layer 5 as required.

As the color pigment, a commonly used organic or inorganic pigment can be used. Among these coloring pigments, as yellow pigments, monoazo, disazo, azo pigments such as polyazo, organic pigments such as isoindolinone, yellow lead, yellow iron oxide, cadmium yellow, titanium yellow, inorganic pigments such as antimony yellow. Can be used. As the red pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as quinacridone, and inorganic pigments such as Benji, vermilion, cadmium red and chrome vermilion can be used. As the blue pigment, organic pigments such as phthalocyanine blue and indanthrene blue, and inorganic pigments such as dark blue, ultramarine blue and cobalt blue can be used. Also, as the black pigment,
Organic pigments such as aniline black and inorganic pigments such as carbon black can be used. As the white pigment, inorganic pigments such as titanium dioxide, zinc oxide, antimony trioxide and the like can be used.

The solid layer 4 and the pattern layer 5 are formed by applying the above-mentioned aqueous resin by coating or printing and then drying and curing. More specifically, the solid layer 4 is usually formed by coating and printing and then drying and curing, and the pattern layer 5 is formed by printing and then drying and curing. As a coating method,
Various known methods such as roll coat, curtain flow coat, wire bar coat, reverse coat, gravure coat, gravure reverse coat, air knife coat, kiss coat, blade coat, smooth coat, comma coat, spray coat, flow coat, brush A method such as coating can be used, and the film thickness after drying is 0.1.
The coating is performed so as to have a thickness of about 10 μm. Also, as a printing method, gravure, letterpress, letterpress printing such as flexo,
Various known methods such as lithographic offset printing, lithographic printing such as dilithographic printing, stencil printing such as silk screen printing, electrostatic printing, and ink jet printing can be used.

The primer layer 6 is formed on the solid layer 4 and / or the pattern layer 5 described above and constitutes a part of the ink layer 3. The primer layer 6 is formed of a water-based resin, and as shown in FIG. 1, it is preferably adhered to both the solid layer 4 or the pattern layer 5 and the top coat layer 7 to improve the durability of the decorative material 1. And has the effect of improving the appearance and maintaining the appearance for a long time. Such an effect can hold the formed pattern for a long period of time and is extremely effective.

The aqueous resin used for forming the primer layer 6 mainly contains a binder component. Here, “primarily” means the primer layer 6
This is because, in some cases, the water-based resin forming the resin may contain a filler such as silica, a volume pigment such as organic beads, a neutralizing agent, and a surfactant in addition to the binder component. The water-based resin may be a type having both active energy ray-curing type and heat-curing type. Therefore, the water-based resin may have a binder component or a binder component according to the curing type,
When the binder component is an ultraviolet curing type, a curing agent (photopolymerization initiator) may be contained.

Therefore, in the present invention, the "binder component" is essentially a water-soluble binder component, a water-soluble treated binder component, an essentially water-dispersible binder component, and a water-dispersible treated binder component. Etc.
Furthermore, in the case of a UV-curing type binder component, the one containing a curing agent is called a "binder component", and in the case of an aqueous resin containing a filler or a volume pigment, the filler or volume pigment is used. Those removed are called "binder components".

The primer layer 6 formed of an aqueous resin mainly containing such a binder component is applied to both the pattern layer 5 or the solid layer 4 formed thereunder and the top coat layer 7 formed thereon. It is easy to follow, and the primer layer 6 is the pattern layer 5 or the solid layer 4
And originally has excellent adhesion to the top coat layer 7.

As the binder component mainly constituting the water-based resin, it is preferable to select and employ the binder component from the various resins exemplified in the solid layer 4 and the pattern layer 5 described above.

Examples of the binder component that can be selected include, as water-soluble binder components, natural products such as starch, dextrin and alginate, natural product derivatives such as cellulose ester and cellulose ether, polyvinyl alcohol and polyacrylate, Polyvinylamine,
Synthetic resins such as acrylic nitrification cotton, polyurethane resin, polyester resin and the like can be mentioned, and as the water-dispersible binder component, shellac, styrenated shellac, casein,
Styrene / maleic acid resin, rosin / maleic acid resin,
Acrylic resin, vinyl acetate resin, styrene resin,
Examples thereof include vinyl chloride resin, synthetic rubber latex, polyurethane resin, polyester resin, alkyd resin, epoxy ester and rosin ester.

The primer layer 6 is formed by coating the above-mentioned aqueous resin so as to be a solid surface so as to cover the pattern layer 5 or the solid layer 4, and is then cured by irradiation with active energy rays and / or heating. It is formed.

The coating method can be the same as that for the solid layer 4 described above. The thickness of the primer layer 6 is about 0.1 to 50 μm after drying, preferably 0.5 to 5 μm.
m is about 0.2 to 250 g / m ² .

The composition itself of the aqueous ink layer comprising the primer layer and the solid layer and / or the pattern layer as described above is not particularly limited, and water or water and an aliphatic lower alcohol such as methyl alcohol, ethyl alcohol, It is appropriately mixed in a mixed solvent with n-propyl alcohol, isopropyl alcohol, etc., and several kinds may be mixed as necessary. If you give a typical example as a general range, for example,
Alcohol / water (ratio by weight) = 0 to 20, preferably 0
About 7 is suitable.

In the present invention, at least one of the above-mentioned ink layers contains a compound having two or more carbodiimide groups in the molecule as a crosslinking agent.

The compound having two or more carbodiimide groups exerts an effect as a cross-linking agent for the above-mentioned anionic aqueous emulsion, and also has the same action for the base material.

The compound having two or more carbodiimide groups in the molecule of the present invention is particularly preferably any compound having an affinity for dissolving or uniformly dispersing in water or a mixed solvent of water and an aliphatic lower alcohol. Although not limited, examples of typical compounds that are practically effective include the following.

[0035]

Embedded image X—O—CONH — [— R—N = C = N—] n
-R-NHCO-OX

In the formula, n represents an integer of 2 to 10, R is an organic diisocyanate residue, and X is a residue of an organic compound having at least one hydroxyl group capable of reacting with a hydrophilic isocyanate group or a mixture thereof. . In Formula 1, R is an aliphatic diisocyanate residue such as 1,6-hexamethylene diisocyanate, an alicyclic diisocyanate residue such as isophorone diisocyanate, or 4,
Alicyclic / aliphatic diisocyanate residues such as 4′-dicyclohexylmethane diisocyanate, aromatic diisocyanate residues such as tolylene diisocyanate, aromatic / aliphatic diisocyanate residues such as xylylene diisocyanate, or These mixture residues can be exemplified. Among these, those in which R contains aliphatic, alicyclic, or both aliphatic and alicyclic are preferable.

As the organic compound having at least one hydroxyl group capable of reacting with the above isocyanate group,
Various compounds can be used, for example, poly (ethylene oxide) whose end is blocked with an alkoxy group, specifically, poly (ethylene oxide) monomethyl ether, poly (ethylene oxide) monoethyl ether, etc. Can be mentioned. In addition, poly (alkylene oxide) whose ends are blocked with alkoxy groups, specifically, poly (propylene oxide) monomethyl ether, poly (propylene oxide) monoethyl ether, poly (propylene oxide) monophenyl ether, etc. You can Furthermore, dialkylamino alcohols, specifically 3-dimethylamino-1-
Propanol, 3-diethylamino-1-propanol, 3-diethylamino-2-propanol and the like can be mentioned.

In the present invention, the number of carbodiimide groups in the molecule of the above carbodiimide compound is 2
It is necessary to exist more than one. On the other hand, if the number of carbodiimide groups in the molecule is too large, it does not cause a decisive adverse effect, but generally, the flexibility of the formed coat layer is poor, and there is a problem in the adhesion of each layer. There are concerns. Therefore, the upper limit of the number of carbodiimide groups in the molecule is not always strictly defined, but is naturally limited. Usually, about 2 to 10, preferably 2
It can be said that about 8 is appropriate.

The addition amount of the carbodiimide group-containing compound in the ink layer is not necessarily limited, but usually,
It can be said that about 0.1 to 20% by weight, preferably about 0.5 to 15% by weight, is suitable for the anionic water-dispersed resin as the main component.

The carbodiimide group-containing compound may be added in at least one of the primer layer, the pattern layer and the solid layer in the ink layer. However, from a practical point of view, the effect is best exhibited when it is added to the primer layer and then to the solid layer.

Next, the top coat layer 7 will be described.

The top coat layer 7 is an indispensable layer formed as the outermost layer of the decorative material 1 in order to impart abrasion resistance that is less likely to be worn by rubbing. The top coat layer 7 is formed by curing the solventless active energy ray curable resin composition in consideration of the environmental safety of the decorative material 1.

As the solventless active energy ray-curable resin used for the top coat layer 7, a resin which is cured by active energy rays such as ultraviolet rays or electron rays having an energy quantum capable of polymerizing and crosslinking molecules is used. To be done. Specifically, a composition in which a prepolymer having a polymerizable unsaturated bond or a carbodiimide group in the molecule, an oligomer and / or a monomer is arbitrarily mixed and which is solvent-free is used. Examples of these compositions include acrylates such as urethane acrylate, polyester acrylate, and carbodiimide acrylate, silicon resins such as siloxane, polyester, and carbodiimide.

Such prepolymers, oligomers and / or
Alternatively, the monomers may be used alone or in admixture of two or more. In order to impart coating suitability and to adjust the flexibility and surface hardness of the topcoat layer 7 after curing, the compounding ratio thereof may be adjusted or a non-curable resin may be contained. preferable. As the non-curable resin, a thermoplastic resin such as urethane type, fiber type, polyester type, acrylic type, butyral, polyvinyl chloride, or polyvinyl acetate can be used.

When the active energy ray-curable resin composition is cured with ultraviolet rays, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthone are used as photopolymerization initiators. And /
Alternatively, it is preferable to add n-butylamine, triethylamine, tri-n-butylphosphine, or the like as a photosensitizer.

The active energy ray-curable resin composition contains
A matting agent may be included. The top coat layer 7 formed of the active energy ray-curable resin composition containing a matting agent also has a matting effect. Examples of the matting agent include silica, calcium carbonate, barium sulfate, alumina, glass balloons, inorganic or organic fillers such as polyethylene, and fine powder.

The above-mentioned solventless type active energy ray-curable resin composition is provided on the primer layer 6 of the ink layer 3 by coating or the like, and then cured by active energy rays. For the active energy ray-curable composition for the top coat layer, the same solid coating method as that for coating the ink for forming the primer layer 6 can be adopted. The active energy ray-curable composition for the top coat layer has a thickness of 0.1 to 130 so that the thickness of the formed top coat layer 7 is about 0.1 to 100 μm.
The coating amount is about g / m ² .

In the present invention, examples of active energy rays include electron rays and ultraviolet rays. As a UV source,
An ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp, etc. can be used. As the electron beam source, various electron beam accelerators such as Cockloft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, etc. are used, and 50 to 1000 keV, preferably 50 to 1000 keV are used. Irradiate with an electron beam having an energy of 300 keV. The irradiation dose of the electron beam is usually 0.5 to 30M.
It is about rad.

The decorative material 1 thus formed can be suitably used for members such as furniture and wall surfaces which require surface protection performance.

[0050]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. In the following, "part" means "part by mass" (the same as "part by weight").

(Example 1) Thin paper for building materials (Sanko papermaking print, basis weight 30 g / m ² ) was used as the base material 2, and solid layer ink A, pattern layer ink B and The primer layer ink C was applied and dried in order using a bar coater to form a top coat layer ink D having the following composition using a bar coater. Then, the coating film was cured by irradiating an electron beam with an acceleration voltage of 175 KV with an absorbed dose of 3 Mrad. Further, after that, by holding at 70 ° C. for 24 hours, Example 1
I got a cosmetic material.

(Ink Compositions A to D) Solid Layer Ink A: White water-based ink (42 white, carboxylic acid group-containing anionic polyurethane emulsion ink, manufactured by The Inktech Co., Ltd.) 100 parts, water 22
Part, isopropyl alcohol (IPA) 9 parts, ethanol 9 parts, water-dispersible carbodiimide compound (carbodiimide equivalent 445, water-dispersible nonionic type, non-yellowing type, carbodilite E-02, manufactured by Nisshinbo Co., Ltd.) 1
2.5 parts; Ink for pattern layer B: 100 parts of red aqueous ink (42 red, carboxylic acid group-containing anionic polyurethane emulsion, manufactured by The Inktech Co., Ltd.), 8 parts of water, IPA9
Part, ethanol 9 parts; Ink C for primer layer: aqueous polyester resin (carboxylic acid group-containing anionic polyester emulsion, trade name Pethresin A-160P, manufactured by Takamatsu Yushi Co., Ltd.) 1
00 parts, silica powder (trade name Sylysia 380, manufactured by Fuji Silysia Ltd.) 1.2 parts, water 22 parts, IPA 9 parts,
Ethanol 9 parts, carbodiimide compound (trade name Carbodilite E-02, manufactured by Nisshinbo Co., Ltd.) 12.5 parts; Topcoat layer ink D: electron beam curable ink (C4
1, manufactured by The Inktech Co., Ltd.) 100 parts

(Example 2) Instead of the solid layer ink A used in Example 1, a solid layer ink E having the following composition was used. Others were the same as in Example 1 to obtain a decorative material of Example 2.

(Ink Composition E) Solid Layer Ink E: White water-based ink (42 white, carboxylic acid group-containing anionic polyurethane emulsion-based ink, manufactured by The Inktech Co., Ltd.) 100 parts, water 22
Parts, isopropyl alcohol (IPA) 9 parts, ethanol 9 parts.

(Example 3) Instead of the solid layer ink A and the primer layer ink C used in Example 1, solid layer ink F and primer layer ink G having the following compositions were used, respectively. Others were the same as in Example 1 to obtain a decorative material of Example 3.

(Ink composition F, G) Solid layer ink F: white aqueous ink (42 white, carboxylic acid group-containing anionic polyurethane emulsion, manufactured by The Inktech Co., Ltd.) 100 parts, water 8 parts, IPA9
Part, ethanol 9 parts, water-soluble carbodiimide compound (carbodiimide equivalent 334, water-soluble nonion type, non-yellowing type, trade name Carbodilite V-04, manufactured by Nisshinbo Co., Ltd.) 12.5 parts Primer layer ink G: Water-based polyester resin (Carboxylic acid group-containing anionic polyester emulsion, trade name PESRESIN A-160P, manufactured by Takamatsu Yushi Co., Ltd.) 1
00 parts, silica powder (trade name Sylysia 380, manufactured by Fuji Silysia Ltd.) 1.2 parts, water 22 parts, IPA 9 parts,
9 parts ethanol, water-soluble carbodiimide compound (trade name Carbodilite V-04, manufactured by Nisshinbo Co., Ltd.) 12.5
Department

Comparative Example 1 Instead of the solid layer ink A and the primer layer ink C used in Example 1, a solid layer ink E having the above composition and a primer layer ink H having the following composition were used, respectively. Others are the same as Example 1, and Comparative Example 1
I got a cosmetic material.

(Ink Composition H) Ink H for Primer Layer: Aqueous polyester resin (carboxylic acid group-containing anionic polyester emulsion, trade name PESRESIN A-160P, manufactured by Takamatsu Yushi Co., Ltd.) 1
00 parts, silica powder (trade name Sylysia 380, manufactured by Fuji Silysia Ltd.) 1.2 parts, water 22 parts, IPA 9 parts,
9 parts ethanol

Comparative Example 2 In place of the solid layer ink A and the primer layer ink C used in Example 1, a solid layer ink I and a primer layer ink J having the following compositions were used, respectively. A decorative material of Comparative Example 2 was obtained in the same manner as in Example 1.

Solid Layer Ink I: White water-based ink (42
White, carboxylic acid group-containing anionic polyurethane emulsion, manufactured by The Inktech Co., Ltd.) 100 parts, water 22
Part, IPA 9 parts, ethanol 9 parts, isocyanate compound (nurate type isocyanate, X-9003, Nika Kagaku Co., Ltd.) 5 parts; Primer layer ink J: aqueous polyester resin (carboxylic acid group-containing anionic polyester emulsion, commercial product Name PES Resin A-160P, manufactured by Takamatsu Yushi Co., Ltd.) 1
00 parts, silica powder (trade name Sylysia 380, manufactured by Fuji Silysia Ltd.) 1.2 parts, water 22 parts, IPA 9 parts,
9 parts of ethanol, isocyanate compound (nurate type isocyanate, X-9003, manufactured by Nika Kagaku Co., Ltd.) 5
Department

(Performance Evaluation) Examples 1 to 3 and Comparative Examples 1 to 1
The performance evaluation of each decorative material obtained in 2 was performed by evaluating the solvent resistance and water resistance by the following methods.

(Evaluation of Solvent Resistance) Solvent resistance was measured by using a gauze containing methyl ethyl ketone (MEK) or thinner on the surface of the top coat layer of each of the obtained decorative materials and applying a load of 0.98 N (100 gf). Rubbing under the conditions of
The appearance change of the top coat layer due to the solvent was visually observed.
If the number of rubbing was less than 100 reciprocations, the change was X. If the number of rubbing was more than 100 reciprocations and less than 200 reciprocations, the change was △. No change was observed after 300 round trips was marked with ◎. The evaluations of Δ, ○, and ◎ are practically problem-free.

(Evaluation of Water Resistance) With respect to water resistance, a urea-emulsion type adhesive was used on a particle board having a thickness of 10 mm, and each obtained decorative material was adhered so that the top coat layer was on the surface. After that, leave the cup with water on the surface upside down and leave it for 24 hours. Then, after removing the cup, wipe the surface of the decorative plate with a dry cloth to swell the decorative plate with water. The change was visually observed. Those with no change in appearance were marked with ◯, those with slight changes were marked with Δ, and those with significant changes were marked with X.
The evaluations of Δ and ○ have no practical problems.

(Evaluation Results) The results are summarized in Table 1.

[0065]

[Table 1]

The decorative materials of Examples 1 to 3 were made of an aqueous resin having excellent environmental safety, and all had excellent solvent resistance and water resistance. On the other hand, the decorative materials of Comparative Examples 1 and 2 were composed of a water-based resin having excellent environmental safety, but were poor in solvent resistance and water resistance.

[0067]

As described above, according to the present invention, at least one layer in an ink layer containing a water-based resin as a main component, which comprises a primer layer, a pattern layer and optionally a solid layer,
As a cross-linking agent, a compound having two or more carbodiimide groups in the molecule is contained, whereby the adhesion followability of each layer is excellent, and the formed cosmetic material has excellent solvent resistance and water resistance, as well as a work environment and Excellent in environmental safety such as residential environment.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a layer structure of a decorative material of the present invention.

[Explanation of symbols]

1 Cosmetic materials 2 base materials 3 ink layer 4 solid layers 5 picture layers 6 Primer layer 7 Top coat layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masataka Takemoto             1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo             Dai Nippon Printing Co., Ltd. (72) Inventor Akihiko Katashima             450 Aoto-cho, Midori-ku, Yokohama-shi, Kanagawa The             Inktech Co., Ltd. F term (reference) 4F100 AA20 AH03B AK01B AK01C                       AK41 AR00D AT00A BA04                       BA07 BA10A BA10C CA02B                       DG10 EJ53C EJ65D GB08                       HB31B HB32 HB35 JB07                       JB09B JB14C JL00

Claims (4)

[Claims] 1. A decorative material, comprising a base material provided with an ink layer made of a water-based resin, and a top coat layer made of a solventless active energy ray-curable resin provided on the ink layer. Has at least a pattern layer and a primer layer,
At least one layer of the ink layer contains a hydrophilic compound having two or more carbodiimide groups in the molecule as a cross-linking agent. 2. The decorative material according to claim 1, wherein the aqueous resin contains an anion-type water-dispersed resin as a main component. 3. An aqueous resin containing an anionic water-dispersed resin as a main component has a carboxylic acid group.
Or the cosmetic material according to 2. 4. The decorative material according to claim 1, wherein an electron beam is used as the active energy ray.