JPS6361191B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a decorative material having an uneven pattern.

Generally, decorative materials manufactured by various printing methods are extremely flat and have poor three-dimensional expressiveness. Mechanical or chemical embossing is known as a method to compensate for this drawback and give a three-dimensional effect, but mechanical embossing requires expensive embossing rolls and the process is complicated. There are drawbacks such as poor workability and the fact that the printed pattern and the embossed pattern are not in sync, and the chemical embossing method has the disadvantage that there are many restrictions on the patterns and materials that can be used, making it only usable for limited applications. .

The present invention eliminates the drawbacks of the conventional method described above, and provides a method for producing a decorative material having an uneven pattern, which is suitable in terms of cost, has almost no restrictions on the materials used, and is simple in terms of process. The purpose is to provide

As a result of intensive research for the above-mentioned purpose, the present inventors have found that utilizing the property of an ink coating layer containing a water-absorbing and swelling resin to absorb water and expand is extremely effective for achieving the above-mentioned purpose. I found it.

The present invention is based on the above-mentioned findings, and more specifically, after forming an ink coating layer containing a water-absorbing and swelling resin in addition to a binder and an organic solvent on a substrate, an aqueous liquid is applied onto the ink coating layer. The ink coating layer is expanded by absorbing water, and then dried by heating. The convex portions formed by the ink coating layer generated by water absorption and expansion tend to shrink when heated and dried, but this is due to the shape retention ability of the binder and, preferably, the shape retention ability of the additional resin coating layer formed thereon. Also, due to its moisture barrier properties, it remains as unevenness, and the unevenness that occurs on the surface due to shrinkage gives it a matte feel.

Hereinafter, a preferred embodiment of the method of the present invention will be described in more detail with reference to the drawings.

First, as shown in FIG. 1, a normal printing layer 2 and an ink pattern layer 3 containing a water-absorbing and swelling resin are formed on a base material 1. Note that the formation order of layers 2 and 3 is as follows: ink layer 3, in which the aqueous liquid contains a water-absorbing and swelling resin, which will be described later.
Although the illustrated order is preferred to facilitate contact of the aqueous liquid with the aqueous liquid, the reverse order is also possible.

Various materials can be used as the base material 1 depending on the end use, such as paper, plastic film, woven fabric, non-woven fabric, synthetic paper, plywood, wood veneer, other wood boards, metal plates, particle boards, and hard materials. Boards, cement boards, and other inorganic boards can be used alone or in combination of two or more types.

The normal printing layer 2 is a printing layer of normal ink that does not contain a water-absorbing and swelling resin, and is printed by screen printing, gravure printing, offset printing, letterpress printing, inkjet printing, etc. suitable for giving decorative effects to this type of decorative material. , usually formed as a single color or multicolor pattern printed layer. Of course, as shown in the figure, it is not necessary to provide it on the entire surface of the base material 1, nor does it need to overlap with the ink layer 3 containing the water-absorbing and swelling resin.

The water-absorbing and swelling resin (hereinafter simply referred to as "water-absorbing resin") contained in the ink layer 3 is a known hydrophilic resin that can absorb water and swell. As described on pages 25 to 29 (November 1974 issue), it is a polymer compound that contains a hydrophilic group such as a carboxyl group or a hydroxyl group in its molecule, and is usually moderately crosslinked. This resin absorbs water at room temperature or in a heated state and expands to several hundred times its own weight, but it does not dissolve in water and is able to maintain its elastic shape even when it absorbs water. . Since such water-absorbing resins are stable and do not dissolve in organic solvents, any organic solvent can be used as a medium in preparing the printing ink.

In the present invention, for example, the following water-absorbing resins can be used: As described in Japanese Patent Publication No. 13495/1983,
Saponified product of copolymer of vinyl ester and ethylenically unsaturated carboxylic acid or its derivative; Japanese Patent Publication No. 53-46199 and Japanese Patent Publication No. 53-46200
A copolymer of starch or cellulose and an unsaturated carboxylic acid or a derivative thereof as described in Japanese Patent Publication No. 1983-4462; A copolymer of starch or cellulose and an unsaturated carboxylic acid or a derivative thereof as described in Japanese Patent Publication No. A mixture of a copolymer of and an insolubilized carboxymethyl cellulose salt;
Self-crosslinking type acrylic acid alkali metal salt polymer; as described in JP-A No. 53-50290,
A saponified product of a copolymer of vinyl ester and an acrylic ester or a methacrylic ester; a crosslinked product of a lower olefin-maleic anhydride copolymer and an ethylene- Mixtures with vinyl acetate copolymers or polybutadiene; and as described in JP-A-55-40749,
Copolymer of acrylic acid alkali metal salt or ammonium salt and acrylic acid.

Commercially available water-absorbing resins that can be used in the present invention include, for example, Hydrogel-S (Sumitomo Chemicals),
Examples include Sunwet IM-300 (Sanyo Chemical Products), Aqua Keep 4S (Steel Chemical Industry Products), and SGP Absorbent Polyar (General Chemicals Products).

The water-absorbing resin mentioned above is usually a fine powder with a maximum particle size of 350μ and a minimum of about 0.1μ, but 100μ~
Those having a particle size of 1μ are usually used.

The ink for forming layer 3 contains the above-mentioned water-absorbing resin, usually 5 to 70%, preferably 10%.
Contain ~30%. If the resin content is too low, the water absorption and swelling effect will be insufficient; on the other hand, if it is too high, the water absorption and swelling effect will be good, but the adhesion of the ink to the base material will decrease and the ink will not stick to the base material. This is not preferable because the printed layer 4 easily falls off due to friction.

As mentioned above, the water-absorbing resin used in the present invention is stable against organic solvents, so when preparing the ink, aliphatic hydrocarbons, aromatic Organic solvents such as hydrocarbons, hydrocarbons, alcohols, ketones, esters, alcohol ethers, chlorine-containing hydrocarbons, and nitrogen-containing hydrocarbons can be used as desired.

The ink further contains a binder for bonding the water-absorbing resin to the substrate, and the binder may be any of a variety of binders contained in conventional printing ink vehicles. Such binders include, for example, the following: natural or synthetic drying oils such as linseed oil, linseed oil, soybean oil, dehydrated castor oil, styrenated oils, vinyltoluenated oils, maleated oils, rosins, Natural resins or processed resins such as copal, dammar, silica, hardened rosin, and rosin esters,
Polyvinyl acetate resin, polyvinyl chloride resin,
polyvinyl alcohol, polyvinyl butyral,
Synthetic resins such as polystyrene resins, acrylic resins, phenolic resins or modified resins, unsaturated polyester resins, alkyd resins, polyamide resins, epoxy resins, polyurethane resins, aminoplast resins, petroleum resins, etc. , cellulose derivatives such as nitrocellulose, methyl, ethyl, carboxymethyl, or acetylbutyryl cellulose, rubber derivatives such as chlorinated rubber and cyclized rubber, and one or more types of glue, casein, dextrin, etc. blend. These binders are contained in the ink in a proportion of, for example, 3 to 50% in order to give the ink a viscosity suitable for printing and adhesion to various substrates.

In addition to the components described above, the ink may further contain colorants such as dyes or pigments. Such dyes or pigments include those used in common printing ink compositions, such as azo, anthraquinone, or diphenylamine disperse dyes, oil-soluble dyes, or basic dyes, or yellow lead, chrome vermilion, Inorganic pigments such as navy blue, Bengara, cadmium pigments, ultramarine, and carbon black, or insoluble mono- or polyazo pigments, azo lake pigments, phthalocyanine pigments, threne pigments such as thioindigo or anthraquinone pigments, quinacridone pigments, Organic pigments such as dioxazine pigments, irgazine pigments, dyed lake pigments, nitro and nitroso pigments, etc. can be used.

The ink further includes known auxiliary agents that are contained in ordinary printing inks, such as plasticizers, stabilizers, waxes, greases, desiccants, auxiliary desiccants, dispersants,
Thickeners, fillers, ultraviolet absorbers, etc. may also be included.

The ink containing this water-absorbing resin can be easily prepared by mixing the various components described above and then kneading the mixture in a suitable device. However, by adding and mixing the water-absorbing resin into various known printing inks containing the above-mentioned various components other than the water-absorbing resin, such as offset, gravure, letterpress, or silk screen inks, desired results can be obtained. It is convenient to prepare an ink.

The ink containing the water-absorbing resin obtained in this way can be printed using known printing methods such as screen printing, gravure printing, offset printing, letterpress printing, and inkjet printing, or by brush coating, knife coater, etc.
Using a coating method such as a roll coater, a water-absorbing resin is usually applied onto the printing layer 2 at a ratio of 3 to 50 g/m ² (dry weight) to form an ink layer 3 (hereinafter often referred to as "water-absorbing expansion"). As the printing method, screen printing method or gravure printing method is particularly suitable.

According to the present invention, as shown in FIG. 2, an aqueous liquid 4 is applied onto the normal printing layer 2 and the water-absorbing and swelling ink layer 3 of the structure shown in FIG. 1 by spraying, brush coating, gravure coating, roll coating, etc. Apply by. In addition to water or colored water, aqueous liquids include, for example, water-soluble acrylic resins, styrene/acrylic acid copolymer resins, styrene/maleic acid/acrylic acid copolymer resins, polyvinyl alcohol, melamine resins, polyacrylic acid amide,
Aqueous varnishes containing water-soluble resins such as casein, glue, dextrin, methylcellulose, and carboxymethylcellulose, or synthetic resins such as self-crosslinking acrylic resin emulsions, reactive acrylic resin emulsions containing crosslinking agents, epoxy resin emulsions, and urethane resin emulsions. It contains an aqueous emulsion of For aqueous liquids,
Dyes or pigments can also be added. In the example shown in FIG. 2, an aqueous liquid containing resin is used.

Another method for applying aqueous liquids is
It is also possible to immerse the illustrated structure in an aqueous liquid.

By applying aqueous liquid 5, 3a in FIG.
As shown in the figure, the ink layer containing the water-absorbing resin expands, and water is retained here.

Next, when the structure shown in FIG. 2 is introduced into a heating furnace or the like and the whole is heated, the resin-containing aqueous liquid forms a coating 4b, and the water-absorbing and swelling liquid containing water forms a coating 4b as shown in FIG. Some water evaporates from the ink layer 3a, resulting in a convex portion 3b whose height is somewhat reduced, but the shape retention and moisture permeation prevention ability of the resin coating 4b formed by heating and the binder in the ink layer 3b It remains as a convex portion due to its shape retention force. However, if only the holding power of the binder in the ink layer 3b is used, the convex portions tend to become smooth due to later absorption and release of water, so as in this example, the aqueous liquid is in the form of a water-based varnish or a water-based emulsion. Swelling-containing aqueous liquids are preferably used. Such a resin-containing aqueous liquid is applied onto the substrate 1 at a rate of, for example, 1 to 30 g/m ² (resin content).

Due to the shrinkage of the ink layer 3a, fine irregularities are formed in the convex portions of the coating 4b, and these fine irregularities are effective in imparting a matte texture.

In order to maintain the shape and prevent moisture permeation of the coating 4b described above, or to protect the surface of the decorative material, an overcoat varnish dissolved in an organic solvent may be applied thereon as shown in FIG. 4. . The overcoat varnish may be applied either before or after heating and drying. Examples of the solvent-based resin varnish include thermosetting resins such as unsaturated polyester resins, polyurethane resins, alkyd resins, epoxy resins, diallyl phthalate resins, and melamine resins; polyvinyl acetate resins, polyvinyl chloride resins, Thermoplastic resins such as polyvinyl alcohol, polyvinyl butyral, polystyrene resins, and acrylic resins are used.

Although one preferred embodiment of the present invention has been described above, the method of the present invention can also be implemented by variously modifying the above embodiment.

For example, the water-absorbing and swelling ink layer 3 can be formed on the entire surface of the base material 1. As mentioned above, the matte texture provided by the fine irregularities formed on the coating 4b due to the expansion of the water-swelling ink layer and subsequent contraction during heating and drying has a decorative effect in itself. Furthermore, in order to provide patterned convex portions, an aqueous liquid may be applied onto the water-absorbing and swelling ink layer 3 in a pattern. One method for this purpose is to form a regular printing layer containing a patterned water-impermeable binder on the water-swellable ink layer and then apply the aqueous liquid.

As described above, according to the present invention, an uneven pattern that matches the colored pattern can be obtained by a simple method of forming an ink layer containing a water-absorbing and swelling resin on a substrate and then applying an aqueous liquid.

Examples of the present invention are shown below.

Example 1 A water-absorbing resin and a pigment were added to a varnish prepared by dissolving nitrified cotton in a solvent, and the mixture was kneaded in a sand mill at 3000 rpm for 1 hour to produce a water-swellable coating ink consisting of the following components: were prepared: Nitrified cotton 4 parts by weight Sunwet IM-300 (manufactured by Sanyo Kasei Co., Ltd., a water-absorbing resin consisting of a copolymer of starch and acrylate) 20 Valve handle 5 parts by weight Toluene 30 Isopropanol 21 Methanol 10 〃 Ethyl acetate 10 〃 100 〃 23 g/m ² tissue paper is printed with a gravure printing machine using ordinary tissue paper ink to form a normal printing layer, and then the above-mentioned water-swellable coating ink is applied thereon. A water-absorbing and swelling ink layer was formed by printing at a rate of 10 g/m ² (wet). Then, a self-crosslinking acrylic emulsion (resin content: 30%) was coated on the surface of this printed layer using a roll coater, and then dried at 80° C. for 1 minute.

Furthermore, after applying thermosetting amino resin on top of it using a roll coater at a rate of 10g/m ² (resin)
A decorative material rich in three-dimensional effects was obtained by drying at 100°C for 30 seconds.

Example 2 A water-swellable coating ink consisting of the following components was prepared.

Vinyl chloride resin 10 Polyethyl methacrylate 4 Hydrogel S (manufactured by Sumitomo Chemical Co., Ltd., water-absorbing resin consisting of a copolymer of vinyl alcohol and acrylate) 30 Methyl ethyl ketone 27 Methyl isobutyl ketone 4 Ethyl acetate 13 Toluene 13 100 Gravure printing machine to form a normal ink layer, and then print with the water-swellable coating composition to form a water-swellable ink layer. do. Thereafter, a self-crosslinking acrylic emulsion was applied in the same manner as in Example 1, followed by drying at 80°C for 1 minute.

Furthermore, 4g/m ² of polyurethane resin is applied on top of it.
After roll coating at a ratio of (resin content) and drying, a wall covering material with abrasion resistance and rich in three-dimensional effect was obtained.

[Brief explanation of drawings]

FIGS. 1 to 4 are cross-sectional views in the thickness direction of a decorative material or an intermediate thereof for explaining intermediate steps of a preferred embodiment of the method for manufacturing a decorative material of the present invention. 1...Base material, 2...Normal printing layer, 3...Water-swelling ink layer (3a...after water-absorbing expansion, 3b...after heat drying), 4...Resin-containing aqueous liquid, 5...Solvent-based resin varnish.

Claims (1)

[Claims] 1. When forming an ink coating layer and an aqueous solution coating layer on a substrate, and forming either one of these coating layers into a pattern, first a binder and an organic solvent are used. After forming the ink coating layer containing a water-absorbing and swelling resin in addition to the above, the aqueous liquid is applied onto the ink coating layer to expand the ink coating layer by water absorption, and the ink coating layer is further heated and dried. , a method for producing decorative materials. 2. The method of claim 1, wherein the aqueous liquid is selected from water, an aqueous resin solution and an aqueous resin emulsion. 3. The method according to claim 1, wherein after applying the aqueous liquid, an overcoat resin varnish dissolved in an organic solvent is applied, followed by heating and drying. 4 After heating and drying, an overcoat resin varnish dissolved in an organic solvent is applied, Claim 1
The method described in section. 5. The method according to claim 1, wherein the ink containing the water-absorbing and swelling resin further contains a colorant.