JPH01164477A - Production of inorganic decorative sheet - Google Patents

Abstract

PURPOSE:To improve the durability and decorative property of an inorg. decorative sheet by covering an underlayer and a specified colored layer formed on an inorg. base material with a clear coat layer of inorg. paint contg. a specified metal alkoxide as a binder. CONSTITUTION:An underlayer of synthetic resin is formed on the surface of an inorg. base material and a colored layer is partially formed on the surface of the underlayer with a nonaq. colorant and a solvent having <=12 solubility parameter. The underlayer and the colored layer are then covered with a clear coat layer of inorg. paint contg. a metal alkoxide represented by a formula M(OR)n (where M is Si, Ti, Al, Zr, Sr, Ba, Pb, Sn, La, Na or Fe, R is 1-10C alkyl and n is an integer of 1-4) as a binder to produce an inorg. decorative sheet.

Description

[Detailed Description of the Invention] r $ −L (1) ff1LIjl force! I! jThe present invention relates to an inorganic decorative laminate, particularly a method for manufacturing an inorganic decorative laminate with excellent durability and cosmetic properties, which is used for exteriors and the like.

Conventional technology and its problems Conventionally, inorganic decorative boards with patterns used for exteriors, etc. have been made by printing a coloring agent on the surface of an inorganic base material to form a pattern, and then forming a synthetic resin clear coat layer. However, when used for a long period of time, the colored layer and clear coat layer deteriorated due to ultraviolet rays, etc., resulting in a marked deterioration in appearance and poor durability.

Therefore, as a clear coat layer with excellent durability, for example, a clear coat layer made of an inorganic composition mainly containing a water-soluble alkali metal silicate described in JP-A-50-54 G2 (1';'; It has been proposed to cover the printed pattern with a clear coat layer to improve durability, but the adhesion with the colored layer of the undercoat coating 9 is poor and cracks occur in the printed pattern (+iif). , said printed pattern.”
- There was a problem in that lifting occurred in the clear coat layer at position ° and r, resulting in poor cosmetic properties.

On the other hand, in recent years, inorganic paints using metal alkoxide as a binder have been developed, but if fine patterns are dotted on the undercoat, the painted surface will be complicated. There was a problem in that poor adhesion of the coating layer was likely to occur.

Structure of the Invention In view of the above-mentioned problems, the present inventor conducted extensive research on improving the durability and cosmetic properties of inorganic decorative boards, and as a result, discovered a clear coat layer and a colorant that are interrelated with each other. We found the optimal conditions for the combination of the following and completed an inorganic decorative board with excellent durability and cosmetic properties.

In other words, the gist of the present invention is to provide an inorganic base material, an undercoat film formed on the surface of the inorganic base material, a colored layer partially laminated on the surface of the undercoat film, and at least the colored layer. In an inorganic decorative board consisting of a covering clear coat layer, the undercoat film is formed of a synthetic resin, the colored layer is formed of a non-aqueous coloring agent using a solvent with a solubility parameter of 12 or less, and the clear coat The layer is General 2M (
OR)n A method for producing an inorganic decorative board characterized by comprising an inorganic coating 1 [with a metal alkoxide expressed as a binder].

Inorganic J1 (Materials include asbestos slate board, asbestos silicate board, gypsum slag temporary, etc., and there are no particular restrictions on its specific gravity, but for inorganic base materials with a specific gravity of 1.3 or less, undercoat paint In order to prevent uneven suction and to reinforce the surface, it is preferable to apply a nola treatment in advance. Examples of the sealer include urethane, epoxy, or acrylic resin.

The undercoat film is porous! 1 (characteristic), r;
(In addition to concealing the pores and preventing uneven suction and coloring of non-aqueous colorants, which will be described later), metal alcoquid is used as a binder to coat the inorganic base material and be used in the clear coat layer, which will be described later. This prevents curing inhibition of inorganic paints.

Examples of the binder for the undercoat paint that forms the undercoat film include unsaturated polyester, polyester acrylate, epoxy acrylate, and urethane acrylate.

As a method for applying the undercoat, known methods such as spraying, application using a roll coater, or dipping may be employed.

A non-aqueous colorant using a solvent with a solubility parameter of 12 or less that forms a colored layer has excellent adhesion to the undercoat film, and uses a resin or a metal alkoxide described below as a binder for the colorant, and inorganic pigment or Dispersion can be avoided by adding a solvent, co-solvent, or diluent to a mixed and stirred mixture of organic pigments.

The resin used in the colorant binder includes cellulose which is compatible with solvents having a solubility parameter of 12 or less;
Examples include vinyl chloride, phenol, urethane, epoxy, alkyd, rubber, etc.

Examples of inorganic pigments include titanium white.

Examples include carbon black, chromium-based pigments, and iron oxide-based pigments.

(As a single pigment, for example, an azo compound type, a lid [1
Examples include dianiline type Rano.

For solvents, co-solvents, and diluents, solubility parameter 1
2 or less alcohols, ethers, ketones, aldehydes, etc., such as butanol, xylene, medilace [
1 solv, diezyl ether, benzene, diezyl ketone and the like.

The reason why the solubility parameter is set to 12 or less is because if the solubility parameter exceeds 12, the compatibility with the undercoat film and clear coat will be low.
This is because experiments have shown that due to insufficient properties, it swells or peels off when exposed to water, etc., and lacks durability.

Also, if necessary, add a plasticizer to Moeki's non-aqueous stone coloring agent.

A surfactant may be mixed if necessary.

Examples of the coloring method using the non-aqueous colorant described in item 1 include screen printing and flexible printing.11. Offset printing.

Methods include graphia printing, letterpress printing, intaglio printing, and sputtering.

2M (Represented by OrOn) Inorganic paints (hereinafter referred to as "metal alkoxide-based inorganic paints") that use metal alkoxide as a binder for clear coating, specifically, M is silicon, titanium, aluminum, strondium, barium. , lead, tin, lanthanum, zirconium or iron, R or methyl, ethyl.

Alkyl group such as proyl, butyl, pendel, etc., n is 1 to
It is expressed as an integer of 4.

Note that the metal alkoxide-based inorganic paint may have a metal oxide or sulfide added thereto as a filler, if necessary.

When a catalyst such as ammonia is added to the Moeki metal alkoxide-based inorganic paint, it undergoes hydrolysis at a heating temperature of room temperature to 180°C, preferably 70°C to 150°C, and is cured by a polycondensation reaction.

Example 1 A white epoxy resin was applied to an inorganic base material consisting of an asbestos cement calcium silicate plate with a specific gravity of 1.6 and cured.
After obtaining an undercoat film with a thickness of approximately 20 μm, a blue ethyl cell-based printing ink containing butanol as the main solvent with a solubility parameter of 11.4 was patterned by screen printing on this undercoat film. . After the ink pattern has dried, a metal alkoxide-based clear paint mixed with a silicon alkoxide main liquid and an ammonia-based auxiliary liquid is applied to the inorganic base material, and this is coated in a furnace at a temperature of +20'C. Hold for 10 minutes at
(A sample having a D clear coat layer was obtained.

Example 2 Example! The same procedure as in Example 2 was carried out, except that instead of using the blue ethylcellulose-based printing ink, a red alkyd 11tr printing ink with a solubility parameter of 9.0 and xylene as the main solvent was used. A sample was obtained by performing the operation.

Comparative Example 1 Instead of applying the silicon alkoxide-based clear paint in Example I, a water-soluble alkali metal silicate-based clear paint (Jumin Kagaku (Aji); Sumiceram PU5017) was used.
) was applied in the same manner as in Example 1, and this was applied at a temperature of 270°C.
Heat and harden by holding in an oven at ℃ for 15 minutes to a thickness of 10~
Example 1 except that 208 m of clear coat layer was obtained.
A sample was obtained using the same procedure.

Comparative Example 2 Instead of using the blue ethylcellulose-based ink in Example 1, an acetyl-butylcellulose-based red paint mainly composed of ethanol with a solubility parameter of 12.7 and ethylene glycol with a solubility parameter of 14.2 was used. The same procedure as in Example I was carried out, except that

Experiment on each sample obtained as described above.

Table out the observed results! Shown below.

Table-1 *Microscope observation The results are shown when observed at a magnification of 20 times.

*Weather resistance: Shows the results of measuring the condition with a weather meter after being exposed for 1000 hours.

*The results are based on visual observation of the condition after rubbing 30,000 times with a wash-resistant brush.

From the above results, since no fine racking or lifting occurred in the clear coat layer of Example 1.2, Example 1.2 was superior to the comparative example in terms of transparency and adhesion of the clear coat layer. ing. In addition, since the colored pattern of Example 1.2 did not crack or fade,
It was found that Examples 1.2 and 2 were better in durability and cosmetic properties than the comparative examples.

Effects of the Invention As is clear from the above description, the portion appropriately colored with the non-aqueous young coloring agent is covered with a clear coat layer with good adhesion, so it is protected from rainwater, sunlight, etc. Because of this, the colored part cracks.

There is less deterioration over time such as fading, and durability is improved.

Moreover, the metal alkoxide paint that forms the clear coat layer is colored with a non-aqueous diluent to swell the l part.
It does not cause blurring and has good adhesion to the undercoat. For this reason, it is possible to prevent blurring and discoloration of colored areas, and it also provides good adhesion to the clear coat layer.
Prevents lifting of the clear coat layer and improves cosmetic properties.

As a result, in combination with the above-mentioned effects, it is possible to obtain an inorganic decorative board that maintains a beautiful and delicate pattern for a long period of time.

Claims (1)

[Claims] (1) Forming an undercoat film of synthetic resin on the surface of an inorganic base material, forming a colored layer partially on the surface of this undercoat film with a non-aqueous colorant using a solvent with a solubility parameter of 12 or less, The undercoat film and the colored layer are expressed by the general formula: M(OR)_n [where M is silicon, titanium, aluminum, zirconium, strontium, barium, lead, tin, lanthanum, sodium or iron, and R is the number of carbon atoms. 1-10 alkyl group, n represents an integer of 1-4. ] A method for producing an inorganic decorative board, characterized in that it is coated with a clear coat layer made of an inorganic paint containing a metal alkoxide represented by the following as a binder.