JPS6299110A - Manufacture of decorative material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application gf) The present invention relates to a method for producing a decorative material having an arbitrary uneven pattern on the surface, and more specifically, a method for producing a decorative material having an uneven pattern on the surface using a simple method. The present invention relates to a method for economically providing decorative materials.

(Prior Art) Conventionally, as a method for imparting an uneven pattern to the surface of an inorganic material such as cement, concrete, mortar, etc., for example, a forming roller or a forming plate with an embossed pattern engraved on the surface is applied to an inorganic material before hardening. Methods such as pressing the material to harden it, and pouring slurry of 1#@ material into a mold with the desired uneven pattern and solidifying it are widely used, and these methods are faithful to the rollers and mold used. Although it is possible to form an uneven pattern, the rollers and molds used are expensive.

Furthermore, it has the disadvantage that it has poor workability and requires more complicated auxiliary equipment and work.

As a method to solve these various drawbacks, a water-swellable polymer is coated or printed in a pattern on a base sheet to create a patterned sheet with a coated pattern layer, and this patterned sheet is coated with a curable inorganic material. The slurry is laminated in a single layer and the coated pattern layer is expanded into a convex shape by the moisture in the curable inorganic slurry.
A method has been proposed in which recesses are formed on the surface of a single layer of curable inorganic slurry (see Japanese Patent Laid-Open No. 111613/1983).

This method is an excellent method that can extremely easily impart any uneven pattern to the surface of the decorative material without requiring expensive molding rollers or molds. The quality of the pattern depends on the expansion power of the water-swellable polymer used, the strength of the convex portions during expansion, the uniformity of expansion of the water-swellable polymer, and other factors.

(Problems to be Solved by the Invention) The method of using a patterned sheet as described above is an excellent method that solves most of the various drawbacks of the prior art. There is a problem in that the sharpness of the pattern, the depth of the recesses, the uniformity of the uneven pattern, etc. are inferior to those using conventional molding rollers or molds.

Therefore, the object of the present invention is to
Advantages of the method disclosed in the publication (economic efficiency, workability, cost)
The aim is to solve the above problems while maintaining the

(Means for Solving the Problems) As a result of intensive research in order to solve the problems of the above-mentioned conventional technology and achieve the above-mentioned object of the present invention, the present inventors have found that the water-swelling property used in the above-mentioned conventional method The present invention was completed based on the finding that when an elastic binder is used as a binder for a polymeric material, a molded sheet with excellent expansion speed, strength of the expansion part, uniformity of expansion, etc. can be obtained. .

That is, 1 the present invention provides a method for producing a decorative material from a curable inorganic slurry including the following steps a to e, in which the coated pattern layer of the patterned sheet used in step a below contains a water-swellable polymer and an elastic material. A method for producing a decorative material comprising a binder.

a. Step of preparing a patterned sheet having a coated pattern layer that absorbs water and expands on one side of the base sheet. Step of laminating the patterned sheet in contact with a curable inorganic slurry. c. Before 11 layers. Step d: expanding the coated pattern layer with moisture after or during lamination to form recesses corresponding to the coated pattern layer on the surface of the curable inorganic slurry. a step of curing the curable inorganic slurry, and e. a step of peeling the molded sheet from the cured layer.

Next, the present invention will be explained in detail with reference to the accompanying drawings.The basic principle of the method of the present invention, as schematically shown in FIG.
A step a is required in which a patterned sheet is prepared on the surface of the laver (material sheet) 1 with an optional coating pattern layer 2 formed of a composition comprising a water-swellable polymer and an elastic inder. Of course, this step a does not need to be performed consecutively with other steps,
It is preferable to form a molded sheet as shown in FIG. 1 in advance before starting other steps.

The main feature of the present invention lies in the structure of this base sheet, as will be described later.

As shown in FIG. 2, the process of the present invention includes the step of laminating the above-mentioned molded sheet on one layer 4 of curable inorganic slurry. Any method may be used as long as the layers are laminated, and the example shown in the second figure shows an example in which a molded sheet is placed on the bottom of a suitable mold 3 and a curable inorganic slurry 4 is injected thereon. It is suitable for cases where materials are produced in a factory, and the example shown in the third figure is an example in which a curable inorganic slurry is applied to a structure 5 such as a wall to form a layer 4, and a molded sheet is laminated on the surface of the layer 4. This example is suitable for on-site construction.

In any of the above cases, it is necessary to laminate the patterned sheet on the curable inorganic slurry layer 4 so that the coated pattern layer 2 of the patterned sheet is in contact with the curable inorganic slurry layer 4.

Step C of the method of the present invention is to absorb water and expand the coated pattern layer of the molded sheet, which is laminated in contact with one layer 4 of the curable inorganic slurry as described above, to form convex portions 2a, and to correspondingly harden and swell the patterned layer 4 of the curable inorganic slurry. This is a step of forming a recess 4b in the groove 4. The water absorption expansion of the patterned coating layer 2 can also be carried out by making the patterned coating layer 2 absorb water before laminating the patterned sheet on the curable inorganic slurry layer 4, but in a preferred example, the patterned sheet is made of a curable inorganic slurry. This is a method performed after laminating one layer 4 of slurry.

In this case, if the hardening inorganic slurry layer 4 is an aqueous slurry such as cement or mortar, the water in this slurry is absorbed by the coated pattern layer 2, and the coated pattern layer automatically expands to form the convex portions 2a. At the same time, a recess 4b is formed. If the water in the aqueous slurry is insufficient, you can use a water-permeable material, such as paper, as the base sheet and replenish water from behind the base sheet.Also, if the curable inorganic slurry is not water-based requires sufficient water supply from behind the base sheet.

Step d in the present invention may be carried out by leaving it for an appropriate period of time, or by heating it appropriately to promote curing.

(2) Step e is a step of peeling the patterned sheet from the curable inorganic slurry layer 4, as schematically shown in FIG. 5, and in this way the decorative material which is the object of the present invention is obtained.

Next, various materials used in the method of the present invention comprising the above steps will be explained.

The method of the present invention is mainly characterized by the structure of the patterned sheet prepared in step a above, especially the coated pattern layer thereof, and the object of the present invention is mainly achieved by the following specific structure.

The water-swellable polymer that constitutes the coated pattern layer is a polymer that absorbs water and swells when it comes into contact with water, but does not dissolve in water, such as starch-poly(meth)acrylic acid. Sodium grafted product, saponified starch-polyacrylonitrile grafted product, cellulose-sodium poly(meth)acrylate, cross-linked sodium poly(meth)acrylate, cross-linked potassium poly(meth)acrylate, vinyl alcohol-(meth)acrylic acid Any of the conventionally known products such as sodium-(meth)acrylic acid copolymer, alkali neutralized product of cross-linked isobutylene-maleic anhydride copolymer, sodium salt of cross-linked carboxymethyl cellulose, cross-linked polyethylene oxide, polyurethane containing polyoxyethylene chains, etc. can also be used.

Particularly preferred water-swellable polymers in the present invention include, for example, JP-A No. 54-83091, JP-A No. 54-8
No. 3989, No. 54-87791, No. 54-
(t7! Aqueous polymer segment)-(hydrophilic polymer segment)-(1
It is a block copolymer with a bond type of 1ili aqueous polymer segment).

The most preferred among such block copolymers are those in which the hydrophilic group of the hydrophilic polymer segment is an alkali metal salt of carboxylic acid or sulfonic acid.

The water-swellable polymer having the above-mentioned specific structure has excellent water-swellability, water absorption, water retention, strength when swollen, and water resistance (
Compared to other water-swellable polymers, it has excellent dispersibility in a hydrophobic elastic binder, and for the reasons mentioned above, it remains hydrophobic even after absorbing a large amount of water. Since the affinity with the elastic binder does not decrease,
There is almost no tendency to dissolve into the water added for expansion or into the water in the curable inorganic slurry, and it exhibits high water resistance.

Particularly preferred elastic binders in the present invention include:
Specific examples include natural rubber, styrene-butadiene rubber, styrene-isoprene rubber, butadiene-acrylonitrile rubber, chloroprene rubber, imprene rubber, polysulfide rubber, silicone rubber, acrylic rubber, and polyurethane elastomer. Among these, particularly preferred resins are polyurethane elastomers.

According to the detailed research conducted by the present inventor, the elastic binder described above is not only elastic, but also exhibits good water permeability when a water-swellable polymer is incorporated therein. The contained water-swellable polymer can easily absorb water, and since the binder is elastic, the water-swellable polymer can easily expand due to water absorption. , a patterned sheet with a coated pattern layer formed from the above water-swellable polymer and an elastic binder is laminated on a single layer of curable inorganic slurry.

When the coated pattern layer absorbs water and expands, its W expansion rate is high and it expands uniformly, and the physical strength of the expanding body is very high, so it is sharp and uniform in each layer of the curable inorganic slurry. It was possible to form a concave portion. On the other hand, when a water-swellable polymer is simply used to form a coated pattern layer as in the conventional technology, the expansion of the coated pattern layer is not uniform, making it impossible to form sharp recesses. The concavities formed by the soluble polymer dissolving into the supplied water or the water in the curable inorganic slurry were not uniform. In addition, in order to solve these shortcomings,
If a water-swellable polymer is used as a binder, such as a thermosetting resin, such as that used in general paints and inks, this resin may impede water absorption or hinder the expansion of the water-swellable polymer. This made it impossible to achieve sufficient and uniform expansion. Further, even when ordinary thermoplastic resins are used as binders, these binders have poor water permeability and lack elasticity at room temperature, so that sufficient expansion of the water-swellable polymer has not been achieved.

The composition for forming the coated pattern layer used in the present invention contains the above-mentioned water-swellable polymer and an elastic binder as essential components.
If it is 0 parts by weight, it is appropriate for the water-swellable polymer to account for 10 to 90 parts by weight, and if the amount used is less than 10 parts by weight, sufficient swelling of the coated pattern layer will not be achieved. In addition, if the amount exceeds 90 parts by weight, the elastic binder is insufficient and the water-swellable polymer cannot be sufficiently bound, resulting in uniform expansion of the coated pattern layer and poor expansion. cannot achieve sufficient physical strength.

In addition to the above two essential components, the composition used in the present invention may optionally contain various additives such as pigments, fillers, plasticizers, ultraviolet absorbers, stabilizers, flame retardants, foaming agents, etc. Agents etc. can be added arbitrarily.

The composition used in the present invention, which contains a water-swellable polymer and an elastic binder as essential components, may be applied to a wide material sheet in a molten state to form a coated pattern layer, but it is generally It is preferable to add an organic solvent that dissolves the above-mentioned elastic binder and use it in the form of a liquid composition, such as a paint or ink. Any organic solvent can be used as long as it can dissolve or uniformly disperse the elastic binder. Specifically, doluol, quidylol, cyclohexane, dioxane, dimethylformamide, methanol, ethanol, inproparol, butanol, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, methyl acetate, butyl acetate, tetrahydrofuran, 4m carbon , chloroform, trichlene, etc. alone or in combination.

When using a liquid composition as described above.

Any concentration may be used as long as it is liquid, but it is generally preferred to have a solid content of about 10 to 50% by weight.

The base sheet used to form a patterned sheet by coating or printing the above compositions may include paper, woven fabric,
Any sheet or plate-like material having a certain degree of strength, such as nonwoven fabric, plastic film or sheet, wood board, metal plate, etc., can be used. Particularly preferred are materials that have water permeability and air permeability, such as paper, woven fabric, nonwoven fabric, etc., or composites thereof. By using such a water-permeable and air-permeable base sheet, water can be supplied from the back side of the patterned sheet when expanding the coated pattern layer, and the curable inorganic slurry can be cured by drying. The preferred base sheet is paper, which does not hinder drying even if the base sheet is dry, and the most preferred is a composite sheet made by laminating paper with woven or non-woven fabric to strengthen the paper. As long as such a base sheet has enough strength to not be damaged during use,
Any thickness may be used.

Any known method may be used to form a coated pattern layer on the base sheet as described above with a composition comprising a water-swellable polymer and an elastic binder as described above, depending on the coated pattern layer to be formed. For example, intaglio printing, letterpress printing, planographic printing, screen printing, brush coating, spatula coating, spray coating, etc. can be used.

Also, in forming such a coated pattern layer.

An anchor coat layer may be formed on the base sheet in advance in order to improve the adhesion between the coated pattern layer and the base sheet.
Such an anchor coat layer may be formed from any resin, but preferred is an anchor coat agent consisting of an elastic binder as described above. By forming a thin anchor coat layer using such an anchor coat agent, the adhesiveness between the coated pattern layer and the base sheet can be improved.

The thickness of the coated pattern layer to be formed varies depending on the depth of the concave portions of the uneven pattern to be formed in a single layer of the curable inorganic slurry; to form deep concave portions, a relatively thick coated pattern layer is used, and to form shallow concave portions. To achieve this, a relatively thin coated pattern layer is required. Generally, it is about 0.001 mm to 10 mm before expansion, preferably about 0.005 fflIl to lsm. The thickness of the coated pattern layer formed in this way increases due to water absorption, and the thickness varies depending on the type and ratio of the water-swellable polymer and/or elastic binder used.
Generally, the thickness increases by about 1.2 to 200 times due to expansion.

The curable inorganic slurry used in the method of the present invention includes:
Both water-based and non-aqueous systems can be used, but water-based systems are preferred, such as hydraulic cements such as portland cement and magnesia cement, and hydraulic substances such as gypsum hemihydrate and other inorganic binders. , fillers, aggregates, pigments or colorants such as silk, plasticizers, stabilizers, hardening accelerators or retarders, as necessary;
It is made by adding additives such as hydrating agents, emulsifiers, thickeners, blowing agents, and natural or synthetic resins and mixing them with water. All of these curable inorganic slurries are conventionally known and can be easily obtained and used on the market.

The method of the present invention is carried out using the materials as described above and following the steps as described above, and provides a decorative material of excellent quality that overcomes the drawbacks of the prior art.

The surface of the decorative material according to the present invention as described above may be further subjected to various treatments as necessary, such as polishing with Kenfu, coloring with paint, waterproofing, or polishing.

(Operation effect) In the method of the present invention as described above, since the coated pattern layer of the patterned sheet used is formed from a material with a specific composition, the rate of expansion of the coated pattern layer due to water absorption is high and the expansion rate is is uniform and has a high strength when expanded, so a sharp, uniform, and deeply carved arbitrary beautiful uneven pattern can be formed on the surface of a single layer of hardening inorganic slurry. This problem is solved, and a decorative decorative material useful as interior and exterior materials for buildings and the like can be economically provided.

Next, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the text are based on weight.

Example 1 96 parts of a 25% polyether-type polyurethane elastomer solution (methyl ethyl ketone:toluene=11) and 50 parts
A rubber solution was prepared by stirring and mixing 1 part of methyl ethyl ketone in a homogenizer, and 184.6 parts of a 19.5% organic solvent fine dispersion of a water-swellable polymer (described later) was added to this solution.
cyclohexane:toluene:dioxane=a:i:t)
were added and stirred to prepare a coating liquid.

Further, 100 parts of a 25% polyether type polyurethane elastomer solution was diluted with 50 parts of methyl ethyl ketone to prepare an anchor coating agent.

Next, the above anchor coating agent was applied to the paper surface of a composite sheet made of rayon/polyester nonwoven fabric and paper using a #40 bar coater at a rate of 5 g/rrI' based on solid content, and the mixture was coated at 50° C. It was further dried at 120° C. for 5 minutes to form an anchor coat layer. Next, the above coating liquid was applied to the surface in stripes using a wire at a rate of about 100 g/rn' based on solid content, and dried to obtain a patterned sheet having a striped coating pattern layer. .

Place the molded sheet above on the bottom of the mold with the coated pattern layer facing upwards, pour mortar containing 1+2:0.65 of Portland cement, sand and water onto it, and allow the mortar to completely harden. Ta. After curing, the mold was removed, and the molded sheet was then peeled off from the cured mortar, yielding a decorative material in which a clear and sharp uneven pattern with a depth of 1.6 mm was formed on the mortar surface.

The water-swellable polymer used above is a block copolymer (polystyrene content: 30
%) to which sodium thioglycolate has been added to the unsaturated double bonds, which alone absorbs about 50 times its own weight of water and expands.

Example 2 A base sheet made of polypropylene/polyester nonwoven fabric and paper was used as the base sheet in Example 1, and the other conditions were the same as in Example 1. A mortar decorative material having an uneven pattern with a depth of 1.4 mm was prepared. I got it. This decorative board is also Example 1
It also had an uneven pattern with excellent sharpness.

Example 3 A molded sheet was prepared in the same manner as in Example 1 except that a toluene solution of acrylic rubber was used instead of the polyurethane elastomer solution in Example 1. Meanwhile, Portland cement, sand and water were mixed in a ratio of 1:2:0 to the formwork coated with a mold release agent.
．． After pouring mortar No. 65 and smoothing the surface, the above molded sheets were laminated so that the coated pattern layer was in contact with the mortar slurry. After completely curing in this state, when the above molded sheet was peeled off, a sharp and clear depth of 2.
．． A mortar decorative material having an uneven pattern of 0 mm+ was obtained.

Example 4 The thickness of the 1nMl repair layer of the green sheet in Example 1 was 120g7m? When the same procedure as in Example 1 was carried out except that the values were 210g/rn' and 210g/rn', the depth of the uneven pattern was 3.0+m and 5.5mm, respectively, and a mortar decorative material with a sharp and clear uneven pattern was obtained. It was done.

Example 5 A 100 micron thick polyvinyl chloride film is used as a base sheet, and on one side of the base sheet, a silk screen ink consisting of a cross-linked sodium polyacrylate-based water-swellable polymer, a urethane elastomer, and a solvent is prepared. Then, a coated pattern layer was provided by screen printing, and a patterned sheet was created by drying.

After that, using a 12 mm gypsum board as a base, a slurry of calcined gypsum with water added to the optimal hydration amount of 75% was applied to the base using a roll coater to a thickness of 1011111 mm, and the coated surface was further coated with the above-mentioned coating. The patterned sheet was closely attached so that the surface of the coated pattern layer was in contact with one layer of the slurry. ii* After the slurry was completely cured in a close contact state, the molded sheet was peeled off.

The decorative material thus obtained was a noncombustible gypsum decorative board having a clear uneven pattern that completely matched the screen-printed coating pattern layer.

[Brief explanation of drawings]

1 to 5 are cross-sectional views schematically illustrating each step of the method of the present invention. ■...Base sheet 2...Coating pattern layer 3...Formwork 4...Curable inorganic material Slurry 5...
...Basic patent applicant Dai Nippon Printing Co., Ltd. and one other person Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 b Procedural amendment (voluntary) October 31, 1985

Claims (4)

[Claims] (1) In a method for producing a decorative material from a curable inorganic slurry including the following steps a to e, the coated pattern layer of the patterned sheet used in step a below is made of a water-swellable polymer and an elastic binder. A method for producing a decorative material characterized by: a. Step of preparing a patterned sheet having a coated pattern layer that absorbs water and expands on one side of the base sheet; b. Step of laminating the patterned sheet in contact with a curable inorganic slurry; c. Before lamination; step d of expanding the coated pattern layer with moisture after or during lamination to form a recess corresponding to the coated pattern layer on the surface of the curable inorganic slurry; a step of curing the curable inorganic slurry; and e. a molded sheet. The process of peeling off the hardened layer. (2) The method for producing a decorative material according to claim (1), wherein the coated pattern layer comprises 10 to 90 parts by weight of a water-swellable polymer and 90 to 10 parts by weight of an elastic binder. (3) The water-swellable polymer is a water-swellable polymer having a bonding format of (hydrophobic polymer segment)-(hydrophilic polymer segment)-(hydrophobic polymer segment) 1) The method for producing the decorative material described in item 1). (4) Claim No. 1, wherein the elastic binder is a urethane elastomer, acrylic rubber, natural rubber, chloroprene rubber, imprene rubber, styrene-butadiene rubber, thermoplastic elastomer, or a mixture thereof.
The method for manufacturing the decorative material described in section.