JP2003292389A - Patterning method and article capable of patterning - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a patterning method capable of patterning surfaces of tiles and potteries after firing without losing aesthetic property of pictures and calligraphy, and to provide an article capable of patterning. <P>SOLUTION: After a resin composition 3 for ink fixing is impregnated into paper 2 and the paper 2 is attached to the surface of a substrate 1, the impregnated resin composition 3 is dried for adhering the paper 2 to the surface of the substrate 1 and a pattern is drawn on the paper 2 with ink 5. A decorative material may be put between the substrate 1 and the paper 2 from the viewpoint of the back decoration of the pattern. It is preferable that the surface of the paper 2 drawn with the pattern is coated with a protective layer 7 comprising a translucent resin from the viewpoint of improving the durability. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for drawing a pattern on the surface of a substrate and an article capable of drawing a pattern on the surface.

[0002]

2. Description of the Prior Art In order to attach a pattern to the surface of a tile or a ceramics, it is usually necessary to attach the pattern before firing. Since the hue of the design after firing is slightly different from that when the design was applied, a highly skilled technique of applying the design in consideration of the change in the hue due to firing was necessary. Also,
Since the patterns attached as described above inevitably have gloss, it was not possible to express paintings and calligraphy as if they were written on campus or on paper.

Therefore, a method has been proposed in which a sheet with a pattern is attached to the surface of a tile or ceramics with an adhesive. However, in the method of adhering a sheet with a pattern attached with an adhesive, there is a problem that the sheet peels off due to use.
Further, in a high humidity environment such as a bathroom, problems such as ink bleeding and water resistance occur.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of such conventional problems, and an object thereof is to provide a pattern on the surface of tiles or ceramics after firing. Moreover, it is to provide a method of designing a painting or calligraphy without losing its texture.

Another object of the present invention is to provide an article, such as a tile or a ceramic, on which a pattern having a texture such as a painting or a calligraphy can be drawn.

A further object of the present invention is to provide a patterning method and an article on which a pattern can be applied, which does not cause a problem even when used in a high humidity environment such as a bathroom and has excellent durability.

Another object of the present invention is to provide a patterning method and a patternable article in which the ink does not bleed and the definition of the pattern is high.

[0008]

According to the present invention, a paper or cloth is impregnated with an ink fixing resin composition, the paper or cloth is pasted on the surface of a substrate, and then the impregnated ink fixing resin composition is used. There is provided a patterning method which comprises drying a resin composition to fix the paper or cloth to the surface of a substrate, and drawing a pattern on the paper or cloth with ink.

According to the present invention, a paper or cloth impregnated with an ink fixing resin is fixed to at least a part of the surface of the article body with the ink fixing resin, and a pattern can be drawn with the ink. A featured article is provided. A tile is suitable as such an article body.

Here, in order to decorate the background of the drawn design, a decorative member may be sandwiched between the base material or article body and the paper or cloth. As such a decorative member,
Thin members are desirable.

From the viewpoint of improving durability, it is preferable that the surface of the paper or cloth on which the pattern is drawn is further covered with a protective layer made of a translucent resin.

From the viewpoint of eliminating ink bleeding and improving water resistance, it is desirable to use an aqueous solution or dispersion containing at least an aqueous binder resin and a cationic resin as the ink fixing resin composition. As the water-based binder resin, one containing at least one of water-based polyester resin and water-based polyurethane graft-polymerized with a hydrophilic vinyl monomer, and polyvinyl alcohol graft-polymerized with a hydrophilic vinyl monomer is preferable. As the above, a resin having a quaternary ammonium salt group on its side chain is preferable.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The inventor of the present invention is keenly aware of a designing method capable of providing a design on the surface of a tile, a ceramic or the like after firing and capable of drawing a painting or a calligraphy without losing its texture. As a result of repeated studies, the paper or cloth was impregnated with the ink fixing resin composition, the paper or cloth was pasted on the surface of the base material, and the impregnated ink fixing resin composition was dried. Alternatively, the inventors have found that it is sufficient to fix a cloth on the surface of a base material and draw a pattern on the paper or cloth with ink to complete the present invention. Hereinafter, the patterning method of the present invention and the article to which the pattern can be applied will be described in detail with reference to the drawings.

FIG. 1 is a process chart showing an example of the pattern attaching method of the present invention. A paper 2 is attached to the surface of a base material 1 such as a tile or a ceramics (FIG. 1A). The portion to which the paper 2 is attached may be the entire surface of the base material or a part of the surface of the base material. Although the paper 2 is attached to the surface of the base material in this figure, a cloth may be used instead of the paper 2. Figure 1
Let's take paper as an example. As the paper and cloth which can be used in the present invention, conventionally known ones can be used, and examples thereof include western paper, Japanese paper, tissue paper, non-woven fabric and woven cloth.

Here, if a decorative member is sandwiched between the base material 1 and the paper 2, the background of the pattern can be effectively decorated by the shape and color of the decorative member or the shadow produced by the decorative member. . The decorative member that can be used is not particularly limited as long as it is a thin member, for example, pressed flowers, grass, leaves,
Natural products such as wood chips; metal and plastic sheet materials;
Examples include fibrous materials such as hair and plastic fibers.

Next, the ink fixing resin composition 3 is applied to the paper 2 attached to the surface of the substrate 1 with a brush to impregnate the paper 2 with the ink fixing resin composition 3 (see FIG. )). As a method for coating and impregnating the paper composition 2 with the ink fixing resin composition 3, a conventionally known method can be used, for example, a roll coater, a gravure coater, a bar coater, a knife coater, a dipping method, or the like can be used. . Also, FIG.
Then, after the paper 2 is attached to the surface of the base material 1, the paper 2 is impregnated with the ink fixing resin composition 3. However, after impregnating the paper 2 with the ink fixing resin composition 3, Of course, it may be attached to the surface of the base material 1.

The ink fixing resin composition usable in the present invention is not particularly limited as long as it absorbs and fixes the ink, and conventionally known ones can be used. Among them, an aqueous solution or an aqueous dispersion containing at least an aqueous binder resin and a cationic resin is preferable from the viewpoints of ink absorbency and water resistance. Here, the aqueous binder resin is preferably one containing at least one of an aqueous polyester resin and an aqueous polyurethane in which a hydrophilic vinyl monomer is graft-polymerized, and a polyvinyl alcohol in which a hydrophilic vinyl monomer is graft-polymerized, The cationic resin is preferably a resin having a quaternary ammonium salt group on its side chain. The ink fixing resin composition is usually used as water or a solution or dispersion containing water as a main component. Its concentration is 10-5
The range of 0 wt% is preferable. The aqueous binder resin and the cationic resin will be further described below.

The above aqueous binder resin is prepared by adding a polymerization initiator and optionally a small amount of an emulsifier to an aqueous solution or an aqueous dispersion obtained by mixing at least one of an aqueous polyester resin and an aqueous polyurethane with polyvinyl alcohol. It can be obtained by adding a hydrophilic vinyl monomer while maintaining the temperature at 70 to 80 ° C. and carrying out a polymerization reaction for about 2 to 5 hours. By this polymerization reaction, the hydrophilic vinyl monomer is graft-polymerized with the aqueous polyester resin, the aqueous polyurethane, and the polyvinyl alcohol, respectively.

The above-mentioned aqueous polyester resin is obtained mainly by polycondensation of polyhydric carboxylic acids and polyhydric alcohols, and examples of the polyhydric carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid and succinic acid. ,
Aromatic polycarboxylic acids such as 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and pyromellitic acid; maleic acid, fumaric acid, succinic acid Adipic acid,
Aliphatic dicarboxylic acids such as sebacic acid, malonic acid, azelaic acid, mesaconic acid, citraconic acid and glutaconic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexenedicarboxylic acid; anhydrides and lower alkyl esters of these carboxylic acids And one or more of these are used.

On the other hand, as the polyhydric alcohols used for the polyester resin, for example, ethylene glycol,
Alkylene glycols such as 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4-butenediol, neopentyl glycol, 1,5-pentane glycol and 1,6-hexane glycol Alkylene ether glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol;
Alicyclic polyhydric alcohols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; bisphenols such as bisphenol A, bisphenol F and bisphenol S, and alkylene oxides of bisphenols, and one of these Alternatively, two or more kinds can be used in combination.

If necessary, monocarboxylic acid or monoalcohol may be used for the purpose of adjusting the molecular weight or controlling the reaction. Examples of the monocarboxylic acid include benzoic acid, parahydroxybenzoic acid, toluenecarboxylic acid, salicylic acid, acetic acid, propionic acid and stearic acid. Examples of the monoalcohol include benzyl alcohol, toluene-4-methanol and cyclohexanemethanol.

The aqueous polyester resin of the present invention is
Since it has water solubility or water dispersibility, it has a hydrophilic group in the molecule. Examples of such a hydrophilic group include a sulfonic acid group and a carboxyl group. In order to introduce a sulfonic acid group into the polyester resin, a method of using sodium sulfoisophthalic acid as one of polyvalent carboxylic acid components is exemplified. In order to introduce a carboxyl group, a method of using a polyfunctional carboxylic acid having three or more functional groups as one of the polycarboxylic acid components is exemplified.

The above-mentioned aqueous polyurethane is mainly obtained by reacting a diisocyanate with a polyhydroxy compound, and examples of the diisocyanate include:
2,4-tolylene diisocyanate, 2,6-diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,5-naphthalene diisocyanate, 1, Examples include 5-tetrahydronaphthalenediisocyanate.

Examples of the polyhydroxy compound include dibasic acids such as phthalic acid / adipic acid / maleic acid, glycols such as ethylene glycol / propylene glycol / butylene glycol / diethylene glycol, trimethylolpropane / hexanetriol / glycerin / trimethylol. Polyester obtained by esterification reaction with dihydric or trihydric alcohol such as ethane / pentaerythritol; ring-opening polymerization of ethylene oxide or propylene oxide using polyhydric alcohol such as ethylene glycol, glycerin or sorbitol as an initiator Polyether; castor oil and the like can be mentioned.

The water-based polyurethane of the present invention has water-soluble or water-dispersible properties and therefore has a hydrophilic group such as a carboxyl group in the molecule.

Polyvinyl alcohol is obtained by saponifying polyvinyl acetate by an acid saponification method or an alkali saponification method. The degree of saponification is not particularly limited, but a range of 75 to 100% is preferable.

Hydrophilic vinyl monomers include, for example, hydroxyethyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; glycols such as ethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate. Ester; (meth) acrylamide,
Acrylamide compounds such as methylolacrylamide and methoxymethylolacrylamide; glycidyl (meth) acrylate compounds; nitrogen-containing vinyl compounds such as vinylpyridine, vinylimidazole and vinylpyrrolidone; (meth) acrylic acid, maleic anhydride, itaconic acid, croton Examples thereof include unsaturated acids such as acids and salts thereof.

On the other hand, examples of the above-mentioned cationic resin include a polymer or copolymer of a monomer having a quaternary ammonium salt group in its side chain, and such a monomer is (meth) acrylic acid aminoalkyl ester. Examples include quaternary compounds. Specifically, quaternary compounds of dimethylaminoethyl methacrylate with methyl chloride or dimethyl sulfate, quaternary compounds of dimethylaminopropyl (meth) acrylamide with methyl chloride, dimethyl sulfate, benzyl chloride, monochloroacetic acid, etc., acrylamide-3-methyl. Quaternary butyldimethylamine, vinylbenzylammonium salt, diallyldimethylammonium salt, etc.
Examples include monomers having a primary ammonium base. In addition, polyallylamine, polyethyleneimine, polyamine sulfone, cationic polystyrene copolymer and the like can be used as the cationic resin.

Commercially available resin compositions for fixing ink which can be used in the present invention include "NS-244LX" and "NS-246L".
X, NS-141LX, NS-282LX, NS-286LX, NS-155
"X", "NS-310XS-90" (all manufactured by Takamatsu Yushi Co., Ltd.)

In FIG. 1, next, the ink fixing resin composition 3 impregnated in the paper 2 is dried to fix the paper 2 to the surface of the substrate 1 (FIG. 1 (c)). As the drying conditions, for example, the drying temperature is in the range of 50 to 100 ° C. and the drying time is 0.2.
~ 1 hour range. As a result, the product of the present invention that can be patterned is obtained.

Then, a pattern is applied to the paper 2 impregnated with the ink fixing resin 4 with the ink 5 ((d) of the same figure). Of course, it does not matter if the user attaches this pattern. The ink 5 that can be used is not particularly limited, and may be water-based or oil-based, dye-based, or pigment-based. Examples thereof include water-based and oil-based paints, ink, red flesh and ink jet inks. There is also no particular limitation on the method of attaching the pattern to the above-mentioned paper, and the pattern may be attached using a brush, pen, brush or the like, or the pattern is processed as image data into a computer and processed by an ink jet method. You may print on paper by the drawing machine 6. In particular, when copying a picture or a drawing on the base material 1, it is preferable to use the inkjet type drawing machine 6.

Next, a translucent resin is applied to protect the pattern attached to the paper 2 to form a protective layer 7 on the paper (FIG. 2 (e)). The translucent resin that can be used here is preferably one having water resistance, abrasion resistance, and toughness, and examples thereof include urethane, acrylic resin, epoxy resin, and ionomer.

The patterning method of the present invention can be carried out on any substrate, and can be carried out not only on tiles and ceramics but also on molded products made of plastic, metal, ceramics, glass, wood and the like. Further, as the article of the present invention,
Examples include bathroom tiles, entrance tiles, decorative wall tiles, tableware such as plates and bowls.

[0034]

Example A commercially available tissue paper was placed on a 15 cm square tile surface, and then a "NS-141L" resin composition for fixing ink was used.
"X" (manufactured by Takamatsu Yushi Co., Ltd.) was applied with a brush to impregnate the tissue paper with the resin composition. Then, it was dried for about 20 minutes using a commercially available tableware dryer. Next, a famous landscape copy was drawn in full color on the surface of the tile using an ink jet type drawing machine. And urethane was sprayed on it with a gun type sprayer to provide a protective layer.

Comparative Example Directly applied to the same tile surface as in the example, "NS-141LX" (manufactured by Takamatsu Oil & Fat Co., Ltd.) as a resin composition for fixing ink, and dried. A copy of such a landscape painting was drawn on the tile surface, and a protective layer made of urethane was provided on it.

(Evaluation of texture) As a result of visually observing the tiles of Examples and Comparative Examples produced as described above, the depth feeling which the original landscape image had in the tiles of Comparative Example was completely lost due to the gloss of the tiles. On the other hand, in the tiles of the example, the gloss of the tiles was suppressed and the depth and texture close to the original image were produced.

(Evaluation of Durability) After placing the tile of the example in the bathroom for one month, the surface condition of the tile was visually observed.
As a result, the tissue paper was not peeled off from the surface of the tile body, and ink bleeding was not observed.

[0038]

According to the patterning method of the present invention, a paper or cloth is impregnated with the ink fixing resin composition, the paper or cloth is pasted on the surface of the substrate, and then the ink fixing resin composition is impregnated. An object is dried to fix the paper or cloth to the surface of the base material, and a pattern is drawn on the paper or cloth with ink. Therefore, it is possible to attach a pattern to the surface of tiles or ceramics after firing. You can draw calligraphy without losing the texture.

Further, in the article to which a pattern can be attached according to the present invention, a paper or cloth impregnated with an ink fixing resin is fixed to at least a part of the surface of the article main body with the ink fixing resin, and the pattern is printed with the ink here. Since it can be drawn, it can be widely used for decoration and the like as an article on which a picture having a texture such as a painting or a calligraphy can be drawn. In particular, when the article is a tile, it is possible to apply a decoration having a texture that is not available in the past to a bathroom wall, an entrance wall, or the like.

If a decorative member is sandwiched between the base material or article body and the paper or cloth, the background decoration effect of the design is exhibited. In this case, it is also possible to form the pattern only by the decorative member without drawing the pattern.

The durability can be improved by further coating the surface of the paper or cloth on which the pattern is drawn with a transparent resin.

When an aqueous solution or dispersion containing at least an aqueous binder resin and a cationic resin is used as the ink fixing resin composition, ink bleeding can be eliminated and water resistance can be improved. As the aqueous binder resin, at least one of an aqueous polyester resin and an aqueous polyurethane graft-polymerized with a hydrophilic vinyl monomer, and a polyvinyl alcohol graft-polymerized with a hydrophilic vinyl monomer is used, and the cationic resin is If a resin having a quaternary ammonium salt group on the side chain is used,
The ink absorbency and water resistance are further improved.

[Brief description of drawings]

FIG. 1 is a process drawing showing an example of a patterning method of the present invention.

[Explanation of symbols]

1 Base material (main body of article) 2 paper 3 Ink fixing resin composition 4 Ink fixing resin 5 ink 6 Inkjet type drawing machine 7 protective layer

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C04B 41/89 C04B 41/89 DG

Claims (10)

[Claims] 1. A paper or a cloth is impregnated with an ink fixing resin composition, the paper or cloth is attached to the surface of a substrate, and the impregnated ink fixing resin composition is dried to obtain the paper or the cloth. A method for attaching a pattern, which comprises fixing a cloth to a surface of a base material and drawing a pattern on the paper or cloth with ink. 2. The patterning method according to claim 1, wherein a decorative member is sandwiched between the paper or cloth and the surface of the base material. 3. The patterning method according to claim 1, wherein the surface of the paper or cloth on which the pattern is drawn is further covered with a protective layer made of a translucent resin. 4. An article, wherein a paper or cloth impregnated with an ink fixing resin is fixed on at least a part of the surface of the article body with the ink fixing resin, and a pattern can be drawn with the ink. 5. The article according to claim 4, wherein a decorative member is sandwiched between the article body and the paper or cloth. 6. The article according to claim 4, wherein a pattern is drawn with ink on the paper or cloth. 7. The article according to claim 4, wherein a protective layer made of a translucent resin is further formed on the surface of the paper or cloth. 8. The ink fixing resin contains at least an aqueous binder resin and a cationic resin.
Item 7. 9. The aqueous binder resin contains at least one of an aqueous polyester resin and an aqueous polyurethane obtained by graft-polymerizing a hydrophilic vinyl monomer, and polyvinyl alcohol obtained by graft-polymerizing a hydrophilic vinyl monomer. The listed article. 10. The article according to claim 8 or 9, wherein the cationic resin is a resin having a quaternary ammonium salt group in a side chain.