JP4377936B2 - Cosmetic material and method for producing the same - Google Patents

Description

  The present invention relates to a decorative material and a method for producing the same.

  Conventionally, as pre-coated decorative paper, an ink picture layer using acrylic nitrified cotton is provided on a paper substrate, and an ionizing radiation curable resin is provided thereon as a top coat layer.

  However, the above-mentioned conventional decorative paper has insufficient scratch resistance of the top coat layer and is insufficient in scratch resistance. In addition, the adhesion between the pattern layer and the top coat layer is insufficient, and the top coat layer may be peeled off from the pattern layer or the paper base material due to the cello tape test, scratch test, etc. Cannot be maintained in a good condition for a long time.

  In view of the above problems, the present invention has been made in order to eliminate the above-described conventional drawbacks, to provide a cosmetic material whose surface is hardly damaged, and to improve durability and maintain a good appearance for a long period of time. An object of the present invention is to provide a decorative material and a method for producing the same.

In the present invention, an ink layer comprising an ink containing (1) a resin obtained by crosslinking reaction using at least a urethane acrylate, an acrylic polyol, and a curing agent is provided on a substrate, and the ionization is performed on the ink layer. A cosmetic material comprising a topcoat layer obtained from a radiation curable resin, (2) obtained by crosslinking reaction on a base material using at least urethane acrylate, acrylic polyol and a curing agent. An ink solid layer made of an ink containing a resin is provided, and an ink pattern layer made of an ink containing at least a resin obtained by a crosslinking reaction using urethane acrylate, acrylic polyol and a curing agent is provided on the ink solid layer. Furthermore, a top coat layer obtained from an ionizing radiation curable resin is provided on the solid ink layer and the ink pattern layer. (3) The cosmetic material according to (1) or (2), wherein the topcoat layer is obtained from an ionizing radiation curable resin containing a matting agent (4) The cosmetic material according to any one of (1) to (3), wherein the hardness of the topcoat layer is 4H or more in terms of pencil hardness;
(5) An ink layer made of an ink containing at least a crosslinkable resin obtained from a urethane acrylate, an acrylic polyol, and a curing agent is provided on the substrate, and then the ion layer is made of an ionizing radiation curable resin on the ink layer. A topcoat layer is provided, and then the topcoat layer is cured by irradiating with ionizing radiation, and the polymerizable double bond remaining in the crosslinkable resin constituting the ink layer is polymerized to improve the hardness of the ink layer. (6) An ink solid layer comprising an ink containing a crosslinkable resin obtained from at least urethane acrylate, acrylic polyol and a curing agent is provided on a base material, and then the ink solid layer is formed. And an ink containing at least a crosslinkable resin obtained from urethane acrylate, acrylic polyol and a curing agent. An ink pattern layer is provided, and a top coat layer made of ionizing radiation curable resin is provided on the solid ink layer and the ink pattern layer, and then the top coat layer is cured by irradiating with ionizing radiation, and the ink layer is configured. The gist of the present invention is a method for producing a cosmetic material, characterized in that the polymerizable double bond remaining in the crosslinkable resin is polymerized to improve the hardness of the ink layer.

  Since the decorative material of the present invention is configured as described above, the top coat layer is excellent in scratch resistance and hardly damaged. Further, the adhesive strength between the topcoat layer and the ink layer or between the topcoat layer and the ink layer and the substrate is strong and excellent in durability, and excellent in appearance maintenance over a long period of time.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a longitudinal sectional view showing an example of the decorative material of the present invention. In the present invention, the decorative material is provided with an ink layer 2 made of a crosslinkable ink on the surface of the base material 1, and a topcoat layer 3 made of an ionizing radiation curable resin is provided on the surface of the ink layer 2. It is configured.

  The base material 1 is thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, so-called vinyl wallpaper original fabric obtained by sol coating or dry lamination of polyvinyl chloride on paper, or high-quality paper, coated paper, art paper , Sulfate paper, glassine paper, parchment paper, paper such as paraffin paper, glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, inorganic fiber such as carbon fiber, organic film such as polyester and vinylon Woven or non-woven fabrics using resins, polyolefin resins such as polyethylene and polypropylene, polyvinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, Such as polyethylene terephthalate, polybutylene terephthalate, etc. Reester resin, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, and other acrylic resins, polystyrene, acrylonitrile / butadiene-styrene copolymer (ABS), cellulose triacetate, cellophane, polycarbonate and other sheets or A metal foil such as a film, aluminum, iron, stainless steel, or copper can be used.

  The ink layer 2 is an ink layer obtained by adding a colorant such as a pigment to a crosslinkable resin as a main component, and examples of the crosslinkable resin used therein include urethane acrylate, epoxy acrylate, acrylic polyol, and polyester acrylate. Examples include resins obtained by crosslinking reaction using at least one kind and a curing agent, and resins obtained by crosslinking and curing an ionizing radiation curable resin described later as it is or using a curing agent. At least one selected from these resins can be used. Among these resins, a resin obtained by crosslinking reaction with at least one selected from urethane acrylate, epoxy acrylate, acrylic polyol and polyester acrylate and a curing agent is preferable.

  As a curing agent used to obtain a crosslinkable resin, usually isocyanates or organic sulfonates are used for unsaturated polyester resins and polyurethane resins, amines are used for epoxy resins, and further as a radical polymerization initiator, Methyl ethyl ketone peroxide or azobisisobutyl nitrile is used.

  As the isocyanate, divalent or higher aliphatic or aromatic isocyanate can be used. Specific examples include tolylene diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

  An ionizing radiation curable resin is a resin that has an energy quantum capable of polymerizing and crosslinking molecules among electromagnetic waves or charged particle beams, and can be cured by ionizing radiation such as ultraviolet rays and electron beams, and is not polymerizable in the molecule. A composition in which prepolymers, oligomers, and / or monomers having a saturated bond or an epoxy group are appropriately mixed is used. Examples of these compositions include acrylates such as urethane acrylate, polyester acrylate, and epoxy acrylate, silicon resins such as siloxane, polyester, and epoxy resin.

  Examples of the prepolymer and oligomer include unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates, polyester methacrylate, polyether methacrylate, polyol methacrylate, methacrylates such as melamine methacrylate, polyester acrylate, epoxy acrylate, Examples include acrylates such as urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate.

  When the epoxy resin, epoxy-based or urethane-based prepolymer or oligomer is used, a curing agent, amine or isocyanate used for each curing can be mixed and used as a two-component mixture.

  Examples of the monomer include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, Acrylic esters such as methoxybutyl acrylate and phenyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dibenzylamino) ethyl acrylate, methacrylic acid-2 -(N, N-dimethylamino) methyl, a Substituted aminoalcohol esters of unsaturated acids such as 2-hydroxy (N, N-diethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl Polyfunctional compounds such as glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, etc., dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc. And / or a polythiol compound having two or more thiol groups in the molecule, for example, trimethylolpropane trithioglycolate , Trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like.

  The above compounds are used alone or in combination of two or more as required. In order to impart ordinary coating suitability to the resin composition, 5% by weight or more of the prepolymer or oligomer, the monomer and It is preferable that the polythiol is 95% by weight or less.

  When selecting a monomer, if the flexibility of the cured product is required, the amount of the monomer is reduced within a range that does not hinder the suitability of coating, or a monofunctional or bifunctional acrylate monomer. To give a structure with a relatively low crosslink density. In addition, when the heat resistance, hardness, solvent resistance, etc. of the cured product are required, the amount of monomer is increased within a range that does not hinder coating suitability, or an acrylate monomer having three or more functions is added. It is preferable to use a high crosslink density structure. It is also possible to adjust coating suitability and physical properties of the cured product by mixing a 1,2-functional monomer and a tri- or higher functional monomer. Examples of the monofunctional acrylate monomer as described above include 2-hydroxy acrylate, 2-hexyl acrylate, phenoxyethyl acrylate, and the like. Examples of the bifunctional acrylate monomer include ethylene glycol diacrylate and 1,6-hexanediol acrylate, and examples of the trifunctional or higher acrylate monomer include trimethylolpropane triacrylate, pentaerythritol hexaacrylate, diester. Examples include pentaerythritol hexaacrylate.

  When the ionizing radiation curable resin obtained as described above is used as a crosslinkable resin, it preferably has a functional group that reacts with a curing agent, and the functional group includes an OH group, an SH group, an amino group, a carboxyl group, and an epoxy group. Etc. However, even if it does not have these functional groups, it can be used after being cured by polymerization if it has a polymerizable unsaturated double bond. That is, the crosslinkable resin of the present invention includes a resin that is crosslinked using a curing agent and a resin that is cured by radical polymerization without using a curing agent. For example, urethane acrylate, epoxy acrylate, acrylic polyol, etc. When used, the OH group or epoxy group undergoes a crosslinking reaction with a curing agent to proceed with curing, and the double bond of the acrylic group undergoes radical polymerization to cure each. Therefore, in the crosslinkable resin after the production, the crosslinking reaction product and the polymerization product may be produced separately, or there may be a structure caused by crosslinking and a structure caused by polymerization in the same molecule. Further, if a polymerizable double bond exists in each of the crosslinking reaction product and the polymerization product, both reaction products may cause a polymerization reaction to form one molecule.

  The ink layer 2 contains a colorant such as a color pigment. As the coloring pigment, a commonly used organic or inorganic pigment can be used. As the yellow pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as isoindolinone, and inorganic pigments such as yellow lead, yellow iron oxide, cadmium yellow, titanium yellow and antimony yellow can be used. As the red pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as quinacridone, inorganic pigments such as petals, 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 bitumen, ultramarine blue and cobalt blue can be used. 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 white, and antimony trioxide can be used.

  When the ink layer 2 is applied to the substrate 1, as a mixture in which the functional group used for the crosslinkable resin or the resin, prepolymer or oligomer having a polymerizable double bond is mixed with a curing agent or a polymerization catalyst. It can also be applied. Moreover, it can also apply | coat after hardening of this mixture progresses and it reaches | attains viscosity suitable for application | coating.

  The ink layer 2 is coated with an ionizing radiation curable resin as the top coat layer 3. However, the crosslinkable resin constituting the ink layer 2 uses the ionizing radiation curable resin as a raw material as described above. Since all physical and chemical properties are very similar, it can be said that the adhesion is good and an almost integral layer is formed.

  Then, the top coat layer 3 is cured by irradiating the top coat layer 3 with ionizing radiation, but naturally the ionizing radiation is also applied to the ink layer 2 and remains in the crosslinkable resin constituting the ink layer 2. The polymerizable double bond is activated to cause a polymerization reaction. As a result, the ink layer 2 and the topcoat layer 3 containing the ionizing radiation curable resin are cured, and the hardness of the ink layer is improved, and the adhesion between both layers and between the two layers and the substrate is further improved. At the same time, since the surface hardness is increased, the top coat layer 3 is excellent in scratch resistance, is hardly damaged, and can maintain a beautiful appearance over a long period of time.

  As a result of curing as described above, the ink layer 2 has a high hardness, a difference in hardness from the top coat layer 3 is reduced, and the scratch resistance of the top coat layer 3 is further improved. In particular, if each layer is selected so that the hardness difference between the ink layer 2 and the topcoat layer 3 is H to 2H (pencil hardness), the scratch resistance can be further improved. Here, the hardness of the top coat layer 3 is preferably 4H or more, particularly preferably 7H or more. The ink layer 2 is the same as the resin used for the top coat layer 3 and is made of a pigment and a pigment, so that the adhesion between the top coat layer 3 is further improved and peeling between the two layers hardly occurs and the durability is excellent. Yes.

  In the present invention, the ink layer 2 may be configured as an ink solid layer 4 as shown in FIG. 1 or may be configured as an ink pattern layer 5 as shown in FIG. Any layer is made of the above-described crosslinkable resin, so that it has excellent adhesion to the topcoat layer 3.

  Of the ink layer 2, the solid ink layer is a layer made of full-surface ink without a pattern such as an ink pattern, and the layer is always continuous in the plane direction in an arbitrary cross section in the layer thickness direction. The ink pattern layer is a layer formed with a pattern composed of lines, surfaces, combinations thereof, patterns, figures, characters, combinations thereof, etc. by ink, and in an arbitrary section in the layer thickness direction, the layer is not necessarily in the plane direction. Not continuous.

  The ink layer 2 is formed by applying an ink containing a crosslinkable resin constituting the layer 2 by coating or printing, and then drying and curing the ink. When the ink layer 2 is an ink solid layer, it can be provided by coating or printing. When the ink layer 2 is an ink pattern layer, it is usually provided by printing. For coating the ink of the ink layer 2, various known methods such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, Using a method such as comma coating, spray coating, pouring coating, or brush coating, the coating is usually applied to a thickness of about 1.0 to 10.0 μm at the time of drying. In addition, when printing ink of the ink layer 2, well-known printing such as relief printing such as gravure, letterpress and flexo, lithographic printing such as lithographic offset and dilitho printing, stencil printing such as silk screen, electrostatic printing, ink jet printing, etc. These various methods can be used.

  In the present invention, as shown in FIG. 3, an ink solid layer 4 made of an ink containing a crosslinkable resin is provided on the surface of the substrate 1, and an ink pattern made of an ink containing a crosslinkable resin on the surface of the ink solid layer 4. The layer 5 may be provided, and the top coat layer 3 made of an ionizing radiation curable resin may be provided on the surfaces of the ink solid layer 4 and the ink pattern layer 5. If comprised in this way, a desired pattern can be provided and the adhesiveness of the topcoat layer 3 and its lower layer can be improved.

  In addition, in this invention, as shown in FIG. 4, the ink layer 2 which consists of ink containing a crosslinkable resin is comprised from the ink solid layer 4 and the ink pattern layer 5, and the ink pattern layer 5 is made into the base material 1 side. It is also possible to provide the ink solid layer 4 on the top coat layer 3 side. In this case, the solid ink layer 4 may be colorless or colored with the colorant as described above, but it is necessary to have at least transparency.

The top coat layer 3 is formed by applying the ionizing radiation curable resin composition described above onto an ink layer or an ink solid layer and then curing it by irradiation with ionizing radiation. The top coat layer 3 is usually coated so that the film thickness is 8 to 15 g / m ² . The coating is performed in the same manner as the coating of the ink layer 2 described above.

  The top coat layer 3 can contain a matting agent, thereby providing a matte effect. Examples of the matting agent include inorganic or organic fillers or fine powders such as silica, calcium carbonate, barium sulfate, alumina, glass balloon, and polyethylene. The shape of the matting agent is arbitrary, but is preferably spherical or substantially spherical. As the particle size of the matting agent, those having a size of about 0.1 to 10 μm can be used, but those having a maximum size of 9 to 10 μm are preferable. When the particle size is in the range of 9 to 10 μm, it can be uniformly dispersed to form a beautiful matte surface, and can be formed relatively smooth without forming conspicuous irregularities on the surface of the topcoat layer 3. Further, the content of the matting agent is preferably 5 to 20% by weight for sufficiently expressing the matting effect, and further preferably 5 to 20% by weight for improving scratch resistance.

If the top coat layer 3 contains 5 to 20% by weight of a matting agent having a particle size of 9 to 10 μm and is formed to a film thickness of 8 to 15 g / m ² , it can be excellent in scratch resistance and marring resistance.

  When the ionizing radiation curable resin composition as described above is cured with ultraviolet rays in particular, acetophenones, benzophenones, Michler benzoylbenzoate, α-amylo is used as a photopolymerization initiator for the ionizing radiation curable resin composition. Mixtures of n-butylamine, triethylamine, tri-n-butylphosphine, and the like can be used as oxime esters, tetramethylthiuram monosulfide, thioxanthones, and / or photosensitizers.

  When the top coat layer 3 contains a matting agent, the matting agent as described above is mixed and dispersed in the ionizing radiation curable resin composition described above.

  The top coat layer 3 is formed by applying the ionizing radiation curable resin composition as described above by coating or the like and then irradiating and curing the ionizing radiation. The ionizing radiation curable composition can use the same method as the method for coating the ink for forming the ink layer 2 in the form of a solid surface, and is usually about 0.1 to 100 μm at the time of drying. Apply to film thickness.

  Among the ionizing radiations, 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, or the like can be used. Also, as the electron beam source, various electron beam accelerators such as a Cockroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency, etc. are used, preferably 100 to 1000 keV, preferably An electron beam having an energy of 100 to 300 keV is irradiated. The irradiation dose of the electron beam is usually about 0.5 to 30 Mrad.

  As described above, even when the solid ink layer 4 and the ink pattern layer 5 are provided on the base material 1 and the topcoat layer 3 is provided thereon, the ink layer 2 is provided on the base material 1 described above. Similarly, the crosslinkable resin used for the ink solid layer 4 and the ink pattern layer 5 is cured by curing or polymerization, and further cured by ionizing radiation irradiated from the top coat layer 3. Adhesiveness with the ink pattern layer 5 and the top coat layer 3 is improved, and a durable decorative material that does not peel off is obtained. Furthermore, a top coat layer that is excellent in scratch resistance and hardly scratched can be obtained.

  The decorative material of the present invention can be suitably used for members that require surface protection performance such as furniture and wall surfaces.

Next, the present invention will be described in more detail with specific examples.
[Example]
An ink solid layer in which a pigment is added to a resin having the following composition is formed by gravure printing on general paper (manufactured by Sanko Paper: print 30 g / m ² ), and an ink pattern layer having the same composition is formed on the ink solid layer. Laminated.
Ink layer resin composition Urethane acrylate 50 parts by weight Acrylic polyol 50 parts by weight Hexamethylene diisocyanate 3 parts by weight Next, an epoxy acrylate resin (manufactured by The Inktec Co., Ltd .: EB40) is coated as a top coat layer by roll coating, and electronic The solid line, the ink pattern layer, and the topcoat layer were cured by irradiating a line (5 Mrad).

[Comparative example]
From solid paper made of acrylic nitrifying cotton-based ink [manufactured by Showa Ink Co., Ltd .: UE, 6 parts of FW curing agent added] to general paper (manufactured by Sanko Paper: print 30 g / m ² ); The pattern layer is applied by gravure printing, and then the top coat layer is coated with an epoxy acrylate resin (manufactured by The Inktec Co., Ltd .: EB40) by roll coating, and the top coat layer is irradiated with an electron beam (5 Mrad). Cured.

  For the decorative materials obtained in Examples and Comparative Examples, a cross-cut cello tape peeling test was performed. The results are shown in Table 1.

注）比較例はいずれもトップコート層剥離を起こしていた。

Note) In all the comparative examples, the topcoat layer was peeled off.

[Evaluation of scratch resistance]
About the decorative material obtained by the Example and the comparative example, the pencil hardness, the Hoffman scratch, and the Tabers clutch were measured. The results are shown in Table 2.

It is a longitudinal cross-sectional view which shows an example of the decorative material of this invention. It is a longitudinal cross-sectional view which shows another example of the decorative material of this invention. It is a longitudinal cross-sectional view which shows another example of the decorative material of this invention. It is a longitudinal cross-sectional view which shows another example of the decorative material of this invention.

Explanation of symbols

1: Base material 2: Ink layer 3: Top coat layer 4: Ink solid layer 5: Ink pattern layer

Claims (6)

  An ink layer made of an ink containing at least a resin obtained by a crosslinking reaction using urethane acrylate, acrylic polyol and a curing agent is provided on a base material, and obtained from an ionizing radiation curable resin on the ink layer. A cosmetic material comprising a top coat layer.   On the substrate, an ink solid layer made of an ink containing at least a resin obtained by crosslinking reaction using urethane acrylate, acrylic polyol and a curing agent is provided, and on the ink solid layer, at least urethane acrylate and acrylic polyol are provided. An ink pattern layer made of an ink containing a resin obtained by crosslinking reaction with a curing agent is provided, and a top coat layer obtained from an ionizing radiation curable resin is further provided on the ink solid layer and the ink pattern layer. A cosmetic material characterized by being made.   3. The cosmetic material according to claim 1, wherein the top coat layer is obtained from an ionizing radiation curable resin containing a matting agent.   The decorative material according to any one of claims 1 to 3, wherein the hardness of the top coat layer is 4H or more in terms of pencil hardness.   An ink layer made of an ink containing at least a crosslinkable resin obtained from urethane acrylate, acrylic polyol and a curing agent is provided on the base material, and then a top coat layer made of an ionizing radiation curable resin is provided on the ink layer. Then, the top coat layer is cured by irradiating with ionizing radiation, and the polymerizable double bond remaining in the crosslinkable resin constituting the ink layer is polymerized to improve the hardness of the ink layer. A method for producing a cosmetic material.   An ink solid layer made of an ink containing a crosslinkable resin obtained from at least urethane acrylate, acrylic polyol and a curing agent is provided on a substrate, and then obtained from at least urethane acrylate, acrylic polyol and a curing agent on the ink solid layer. An ink pattern layer made of an ink containing a crosslinkable resin, and a top coat layer made of an ionizing radiation curable resin on the solid ink layer and the ink pattern layer, and then irradiated with ionizing radiation to form a top coat layer And a method for producing a cosmetic material, wherein the hardness of the ink layer is improved by polymerizing a polymerizable double bond remaining in the crosslinkable resin constituting the ink layer.

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