JP2007090283A - Coating finishing method of ornamental face and ornamental layered product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating finishing method which is capable of increasing the contamination resistance properties and the weatherability of a multi-color pattern or unevenness pattern formed by an ornamental coating material. <P>SOLUTION: The coating finishing method of the ornamental face comprises applying a clear coating containing a modified silicate compound which contains 0.1-20 pts.wt. of the silicate compound calculated in terms of SiO<SB>2</SB>to 100 pts.wt. of the solid content of the resin for coating after forming the multi-color pattern or unevenness pattern by applying the ornamental coating material to the substrate and which has an equivalent ratio of 95:5-50:50 of a 1-2C linear alkyl group and a 3C or more branched alkyl group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for painting a decorative surface on the surface of a building or a civil engineering structure, and a decorative laminate.

  Conventionally, various decorative coating materials have been painted on the surface of buildings, civil engineering structures, and the like in order to enhance the aesthetics. As such a decorative coating material, a stone finish coating material in which a synthetic resin emulsion is blended with a pulverized natural stone, a colored aggregate, or the like, or two or more color particles in liquid or gel form are suspended in a dispersion medium. Various types of paints, thin finish coating materials and thick finish coating materials defined in JIS A6909 are known. Among these, examples of the stone finish finishing coating material include the coating materials described in Patent Document 1 (Japanese Patent Publication No. 2-40702). Moreover, as a colorful pattern coating material, the coating material etc. which were disclosed by patent document 2 (Japanese Patent Publication No. 1-19705) are mentioned, for example. In the coating of such decorative coating materials, a finishing method is generally adopted in which a clear coating is applied after the decorative coating material is applied in order to ensure coating properties such as contamination resistance and weather resistance. ing.

  Specifically, in Patent Document 3 (Japanese Patent Laid-Open No. 57-27177), as a decorative wall finishing method expressing a natural stone pattern, bones such as acrylic resin emulsion and marble powder, granite powder, colored cinnabar sand, colored ceramic powder, etc. After applying the spray material made by mixing the materials to form a concavo-convex pattern, the top of the convex part is cut flat after drying, and then the entire surface is coated with a transparent acrylic resin or transparent acrylic-urethane resin. The method of finishing is described.

  Patent Document 4 (Japanese Patent Laid-Open No. 5-177164) relates to a method for constructing a natural stone-like, polished stone-like finish surface, and a coating material composed of an emulsion resin, natural stone, and colored aggregate is applied to the gazette. In addition, a method is described in which a coated surface is flattened using a film sheet, plastering iron, or the like, and then a synthetic resin clear paint is applied to finish.

  Patent Document 5 (Japanese Patent Laid-Open No. 8-257490) relates to a natural stone finishing method. This publication describes a method in which a multicolor pattern paint made of an acrylic resin emulsion, a plurality of colored dispersed particles and mica is applied, and then a clear paint made of an acrylic resin or the like is applied to the surface.

  Patent Document 6 (Japanese Patent Laid-Open No. 2000-135471) applies a coating material containing a synthetic resin emulsion and aggregates and / or pigments, and further a coating material containing a synthetic resin emulsion, aggregates and mica flakes It is described that a decorative surface is formed by coating and then a clear paint made of a synthetic resin emulsion or the like is applied to the decorative surface in order to impart performance such as weather resistance and antifouling property.

  In the coating methods described in Patent Documents 3 to 6, the clear coating is a process necessary for improving the physical properties of the coating film such as contamination resistance. However, all of the clear paints described in the above-mentioned patent documents are obtained by using ordinary resins as they are or diluted, and may not provide a sufficient anti-contamination effect in an environment in which contamination tends to proceed. .

  On the other hand, Patent Document 7 (Japanese Patent Laid-Open No. 9-57186) discloses a multi-pattern paint finishing method in which a multi-color paint containing enamel dispersed particles of a plurality of colors is applied and then a clear paint is applied thereon. From the viewpoint of stain resistance, it is described that a clear coating material in which an organosilicate compound is blended with an acrylic resin, urethane resin, silicon resin, or fluororesin resin is described. If such a clear coating is used, the organosilicate compound imparts hydrophilicity to the surface of the coating and is expected to exhibit stain resistance by the action of washing away contaminants attached to the coating during rain. it can.

  However, the paint finish surface obtained by the method of Patent Document 7 has a problem that hydrophilicity is not expressed at the initial stage of coating film formation, and contaminants tend to adhere, and there is room for improvement in practice.

  The present invention has been made in view of such problems, and an object of the present invention is to improve the stain resistance, weather resistance, and the like of a multicolor pattern or an uneven pattern formed by a decorative coating material.

Japanese Patent Publication No. 2-40702 Japanese Patent Publication No. 1-19705 JP-A-57-27177 JP-A-5-177164 JP-A-8-257490 JP 2000-135471 A JP-A-9-57186

  As a result of intensive studies in order to solve these problems, the present inventor has conceived a method of applying a clear paint containing a specific silicate compound to a paint resin after applying a decorative coating material. The invention has been completed.

That is, the present invention has the following features.
1. After applying a decorative coating material to the base material to form a multicolor pattern or uneven pattern,
The silicate compound is contained in an amount of 0.1 to 20 parts by weight in terms of SiO ₂ with respect to 100 parts by weight of the solid content of the coating resin, and the silicate compound has a linear alkyl group having 1 to 2 carbon atoms and 3 or more carbon atoms. A method for painting a decorative surface, comprising applying a clear paint containing a modified silicate compound in which branched alkyl groups are mixed in an equivalent ratio of 95: 5 to 50:50.
2. A decorative laminate having a base material layer, a decorative layer, and a clear layer,
The decorative layer has a multicolor pattern or an uneven pattern,
The clear layer contains 0.1 to 20 parts by weight of a silicate compound in terms of SiO ₂ with respect to 100 parts by weight of the solid content of the coating resin, and the silicate compound has a linear alkyl group having 1 to 2 carbon atoms and A decorative laminate comprising a clear coating material containing a modified silicate compound in which branched alkyl groups having 3 or more carbon atoms are mixed at an equivalent ratio of 95: 5 to 50:50.

  The decorative surface formed by the paint finishing method of the present invention exhibits excellent stain resistance. In particular, it has a feature that contaminants hardly adhere even at the initial stage of coating film formation.

  Hereinafter, the best mode for carrying out the present invention will be described.

I. Coating Finishing Method First, of the embodiments of the present invention, a method for coating a base material with a decorative coating material and a clear coating in order will be described below.

[1] Substrate The present invention can be used mainly for surface finishing of buildings and civil engineering structures. Applicable base materials include, for example, concrete, mortar, porcelain tile, fiber mixed cement board, cement calcium silicate board, slag cement perlite board, asbestos cement board, ALC board, siding board, extrusion board, steel sheet, plastic board , Gypsum board, plywood and the like. The surface of these base materials can be coated after some surface treatment (for example, sealer, surfacer, filler, putty, etc.) is applied.

[2] Decorative coating material In the present invention, a multicolor pattern or an uneven pattern is formed by applying a decorative coating material to the substrate. Any decorative coating material can be used without particular limitation as long as it can form a multicolor pattern or an uneven pattern. The multicolor pattern referred to here is a pattern in which at least two or more colors are mixed in a visible state. The uneven pattern is a surface pattern having a height difference of about 0.2 to 5 mm.

  Specific examples of the decorative coating material include (1) stone finish finishing coating material, (2) JIS K5667 colorful pattern coating material, and (3) JIS A6909 thin finishing coating material / thickening finishing coating material. .

[Stone finish coating material]
The stone finish finishing coating material is a coating material capable of forming a multicolor pattern by coloring the aggregate, and is a coating material having a synthetic resin emulsion and an aggregate as essential components. Among these, examples of the synthetic resin emulsion include vinyl acetate resin, epoxy resin, silicone resin, acrylic resin, urethane resin, acrylic urethane resin, acrylic silicon resin, fluororesin, and a composite system thereof.

As the aggregate, an aggregate having a particle diameter of 0.05 to 5 mm is usually used. As such an aggregate, at least one selected from natural aggregates such as natural stones, pulverized natural stones, and artificial aggregates such as colored aggregates can be suitably used. Specifically, for example, marble, granite, serpentine, granite, fluorite, cryolite, feldspar, limestone, quartzite, quartz sand, crushed stone, mica, siliceous shale, and pulverized products thereof, ceramic pulverized products, ceramic pulverized products Products, crushed glass, glass beads, crushed resin, resin beads, rubber particles, metal particles, and the like. In addition, pulverized products such as shells, shells, wood, charcoal, activated carbon and the like can be used. Furthermore, those whose surfaces are colored and coated by performing surface treatment with pigments, dyes, glazes, and the like can also be used. By using two or more kinds of such aggregates in appropriate combination, various multicolor patterns can be expressed.
The aggregate is usually mixed at a ratio of 100 to 4000 parts by weight, preferably 150 to 3000 parts by weight, and more preferably 200 to 2000 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin emulsion. If the mixing ratio of the aggregate is within such a range, it is preferable in terms of design properties of the formed coating film, crack prevention properties, and the like.

  Components other than those described above can be mixed in the stone finish finishing coating material. Examples of such components include coloring pigments, extender pigments, fibers, film-forming aids, plasticizers, antifreezing agents, antiseptics, antifungal agents, antibacterial agents, antifoaming agents, pigment dispersants, thickeners. , Leveling agents, wetting agents, pH adjusting agents, matting agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents and the like.

As a method for applying the stone finish finishing coating material, for example, spray coating, roller coating, trowel coating, brush coating, and the like are possible, and one or more coating materials may be applied in layers. In such a stone finish finishing coating material, various uneven patterns can be imparted by appropriately selecting and adjusting a painting tool, coating conditions, and the like. Moreover, it is also possible to cut a convex part with a sander etc. after coating film drying. Tile patterns, geometric patterns, etc. can be formed by using joint rods or joint molds.
The coating amount of the stone finish finishing coating material is usually about 1 to 10 kg / m ² . At the time of application, a diluent such as water can be mixed to appropriately adjust the viscosity of the coating material. The dilution ratio is usually about 0 to 10% by weight. The stone finish finishing coating material may be usually dried at room temperature.

[Multicolored paint]
The multicolor paint is a liquid or gel-like color particle having two or more colors suspended in a dispersion medium. These are (1) oil-in-water type (O / W type), (2) water-in-oil type (W / O type), (3) oil-in-oil type (O / O type), (4) water-in-water type (W / W type). Among these, the oil-in-water type (O / W type) and the water-in-water type (W / W type) multicolored paints are both preferable in terms of environment and the like because the dispersion medium is aqueous.

The color particles in the multicolored paint are obtained by dispersing a colored paint containing a resin, a colorant, and various additives as required in a dispersion medium.
The resin in the colored paint is not particularly limited as long as it functions as a vehicle for the paint. Examples of such a resin include acrylic, urethane, vinyl acetate, vinyl acrylate, acrylic urethane, acrylic silicon, fluorine, polyvinyl alcohol, biogum, galactomannan derivatives, alginic acid derivatives, and cellulose derivatives. The form of these resins may be any of a solvent-soluble resin, a non-aqueous dispersion resin, a water-soluble resin, a water-dispersible resin, and the like. These resins may have a functional group that can be cross-linked by a curing agent or a curing catalyst.

  When the resin is a solvent-soluble resin and / or a non-water-dispersible resin, a solvent-type colored paint is obtained. When this resin is dispersed in an aqueous dispersion medium, an oil-in-water type (O / W type) is obtained. It becomes a multicolored paint. Further, when the resin is a water-soluble resin and / or a water-dispersible resin, an aqueous colored paint is obtained. When this resin is dispersed in an aqueous dispersion medium, a water-in-water type (W / W type) multicolor pattern paint and Become.

  As the colorant in the colored paint, those that can be generally added to the paint can be used. Specifically, for example, titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, brown, molybdate orange, permanent red, permanent Carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine A violet, an aluminum pigment, a pearl pigment, etc. are mentioned, These 1 type (s) or 2 or more types can be used.

  In the colored paint, known paint additives can be appropriately used. Such additives include, for example, viscosity modifiers, crosslinkers, catalysts, fillers, fibers, pigment dispersants, film-forming aids, antifreeze agents, drying regulators, plasticizers, matting agents, matting agents. Examples include foaming agents, ultraviolet absorbers, antioxidants, light stabilizers, antifungal agents, and preservatives.

The method for dispersing the colored paint in a granular form is not particularly limited, and a known method can be adopted. Specifically, a method of dispersing a colored paint in an aqueous dispersion medium containing a dispersion stabilizer or the like can be employed.
The dispersion stabilizer is a component that stabilizes the colored paint in a granular form, and can be selected according to the type of the colored paint. Specific examples of the dispersion stabilizer include, for example, a component that acts as a crosslinking agent for a colored paint. Examples of such components include epoxies, isocyanates, amines, alkoxysilanes, organic titanates, aluminum chelates, magnesium salts, calcium salts, barium salts, aluminum salts, sodium salts, potassium salts, boron Examples include acid salts and phosphates. Other dispersion stabilizers include polyvinyl alcohol, polyacrylic acid, polyethylene oxide, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, casein, cellulose acetate phthalate, bentonite, gelatin, sodium alginate, gum arabic, pectin, xanthan gum, starch Etc. can also be used.

The particle diameter and shape of the color particles can be set as appropriate. Specifically, the shape of the stirring blade at the time of manufacture, the size and position of the stirring blade with respect to the stirring tank, the rotation speed of the stirring blade, the viscosity of the colored paint, the method and concentration of the dispersion stabilizer, the viscosity of the aqueous dispersion medium, etc. What is necessary is just to select and adjust suitably.
Although the particle diameter of a color grain is not specifically limited, Usually, it is about 0.01-10 mm (preferably 0.1-5 mm).

For example, spray coating, roller coating, brush coating, or the like can be employed as a method for applying the multicolored paint. When a concavo-convex pattern is expressed using a multicolored paint, a desired concavo-convex pattern may be formed with an undercoat material, and then a multicolored paint may be applied. For example, as described in JP-A-8-173899 A method etc. can be adopted. Further, a tile-like pattern, a geometric pattern, or the like can be formed using a joint rod, a joint form frame, or the like.
The application amount of the multicolor paint is usually about 0.2 to 1 kg / m ² . At the time of application, the viscosity can be appropriately adjusted by mixing a diluent such as water. The dilution ratio is usually about 0 to 10% by weight. The multicolored paint is usually dried at room temperature.

[Thin finish coating material / Thick finish coating material]
The thin finish coating material and thick finish coating material specified in JIS A6909 use a synthetic resin emulsion as a binder, and color pigments, extender pigments, aggregates, and other admixtures (dispersants, thickeners). , Antifoaming agent, preservative, etc.)

  Among these, as the synthetic resin emulsion, for example, vinyl acetate resin, epoxy resin, silicone resin, acrylic resin, urethane resin, acrylic urethane resin, acrylic silicon resin, fluorine resin, or a composite system thereof can be used. .

  Examples of color pigments include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, red potato, molybdate orange, permanent red, and permanent. Carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine Violet or the like can be used. A desired color can be expressed by using one or more of these in combination. The mixing ratio of the color pigment is usually about 1 to 300 parts by weight (preferably 2 to 200 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion.

  The extender pigment mainly acts as a filler, and is an effective component for forming a thick film. Specific examples of extender pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, porcelain clay, china clay, diatomaceous earth, hydrous finely divided silicic acid, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, carbonic acid Examples include magnesium, silica powder, and aluminum hydroxide. The particle size of the extender pigment is usually less than 50 μm (preferably 0.5 μm or more and less than 50 μm). The mixing ratio of the extender pigment is usually about 10 to 1000 parts by weight (preferably 20 to 500 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion.

  As the aggregate, for example, cryolite, feldspar, limestone, silica stone, silica sand, crushed stone, mica, siliceous shale, and pulverized products thereof, glass beads, resin beads, rubber particles, metal particles and the like can be used. The particle diameter of such aggregate is usually 0.05 to 5 mm. The mixing ratio of the aggregate is usually about 10 to 2000 parts by weight (preferably 30 to 1500 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion.

In the coating of such coating materials, various types of uneven patterns, such as sand wall, yuzu skin, fiber wall, ripple, stucco, uneven, can be selected by appropriately selecting the type of coating equipment and its usage. A pattern such as a lunar surface, a comb-like shape, or a worm-like shape can be formed. For example, a spray, a roller, a trowel, or the like can be used as the coating instrument. At this time, various uneven patterns can be formed by treating the coated surface with a design roller, a trowel, a brush, a comb, a spatula, or the like before the coating material is dried. Tile patterns, geometric patterns, etc. can be formed by using joint rods or joint molds. It is also possible to form a multicolor pattern by combining two or more kinds of coating materials having different colors.
The coating amount is usually about 0.3 to 10 kg / m ² although it depends on the type of pattern to be formed. At the time of application, a diluent such as water can be mixed to appropriately adjust the viscosity of the coating material. The dilution ratio is usually about 0 to 10% by weight. Drying is usually performed at room temperature.

[3] Clear paint In the present invention, after the decorative coating material is dried, the clear paint is applied. The clear coating material in the present invention includes a coating resin and a silicate compound, and the silicate compound has a linear alkyl group having 1 to 2 carbon atoms and a branched alkyl group having 3 or more carbon atoms in a ratio of 95: 5 to 50:50. A modified silicate compound mixed in an equivalent ratio is an essential component.

  In the present invention, the hydrophilicity of the coating film surface is increased by the action of such a specific modified silicate, and excellent performance in stain resistance can be exhibited. Furthermore, the inclusion of such a modified silicate in the clear coating is advantageous in terms of followability to the ground and crack resistance.

As the linear alkyl group in the modified silicate compound, one or more selected from a methyl group and an ethyl group can be used. Among these, a methyl group is preferable in the present invention.
On the other hand, as the branched alkyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isoheptyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1, 2-dimethylpropyl group, 1-ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl Group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2- Trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, Sookuchiru group, and the like. In the present invention, among them, a branched alkyl group having 3 to 6 carbon atoms is preferable, and a branched butyl group having 4 carbon atoms is particularly preferable.

  Specifically, the modified silicate having a linear alkyl group and a branched alkyl group can be produced by the method exemplified below.

(1) General formula Si (OR ¹ ) (OR ² ) (OR ³ ) (OR ⁴ )
(Wherein R ^{1 to} R ⁴ are a mixture of a linear alkyl group having 1 to 2 carbon atoms and a branched alkyl group having 3 or more carbon atoms) hydrolyzing a tetraalkoxysilane represented by Allow to condense. A known method can be adopted as the condensation method, and the average degree of condensation after the condensation may be about 2 to 100 (preferably 4 to 20). In this case, other tetraalkoxysilanes can be mixed and condensed during the condensation. Specific examples of the compound represented by the above general formula include monoisopropoxytrimethoxysilane, monoisopropoxytriethoxysilane, monoisobutoxytrimethoxysilane, monoisobutoxytriethoxysilane, diisobutoxydimethoxysilane, and the like. Can be mentioned.

(2) A tetramethoxysilane condensate and / or a tetraethoxysilane condensate is reacted with an alcohol having a branched alkyl group having 3 or more carbon atoms (transesterification reaction). Examples of the alcohol in this method include isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, isoamyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl- Examples include 1-butanol. As the tetramethoxysilane condensate and / or tetraethoxysilane condensate, those having an average degree of condensation of about 2 to 100 (preferably 4 to 20) may be used.

(3) Tetramethoxysilane and / or tetraethoxysilane are reacted with water and an alcohol having a branched alkyl group having 3 or more carbon atoms. In this method, the hydrolysis condensation reaction and the transesterification reaction can be performed in parallel. The average degree of condensation by the hydrolysis condensation reaction may be about 2 to 100 (preferably 4 to 20). As the alcohol, the same compound as the above (2) can be used.

In the modified silicate compound in the present invention, a linear alkyl group having 1 to 2 carbon atoms and a branched alkyl group having 3 or more carbon atoms are usually 95: 5 to 50:50, preferably 90:10 to 55:45, more preferably. Are mixed at an equivalent ratio of 85:15 to 60:40. If the mixing ratio of the straight chain alkyl group and the branched alkyl group is within such a range, the effects of the present invention can be sufficiently exerted. When the ratio between the linear alkyl group and the branched alkyl group is out of the above range, the hydrophilic expression on the coating film surface becomes insufficient, and a remarkable effect cannot be obtained in stain resistance. In addition, followability to the ground, crack resistance, etc. tend to be insufficient.
In the method for producing the modified silicate compound exemplified in the above (1) to (3), the type and amount of the raw material compound are appropriately adjusted so that the equivalent ratio of the linear alkyl group to the branched alkyl group is within the above range. That's fine.

The clear coating in the present invention is obtained by mixing the above-described modified silicate compound with a coating resin.
Examples of the coating resin include acrylic resins, polyester resins, polyether resins, polyurethane resins, acrylic silicon resins, fluororesins, vinyl acetate resins, epoxy resins, and composites thereof. These can be used alone or in combination of two or more. Examples of the form of the coating resin include solvent-soluble resins, non-water dispersible resins, water-soluble resins, water-dispersible resins, and solvent-free resins.

  Among these, the solvent-soluble resin and / or the non-aqueous dispersible resin is a non-aqueous solvent as a medium, and 50% by weight or more (preferably 60% by weight or more) of the total solvent is aliphatic carbonized. A so-called weak solvent resin which is hydrogen is preferred. Such weak solvent resins are less toxic and have higher work safety compared to strong solvent resins that use aromatic hydrocarbon solvents as the main solvent, and when applied to existing coatings. It has a feature that the occurrence of lifting can be suppressed. Examples of the aliphatic hydrocarbon include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, and the like. In addition, terpine oil, mineral spirit, etc. Other aliphatic hydrocarbon solvents can also be used. In particular, those which do not contain toluene and xylene and correspond to the second petroleum having a flash point of 21 ° C. or higher are preferable in terms of safety and health. In the present invention, when such a weak solvent type resin is used as a coating resin, a particularly excellent effect can be obtained.

  The coating resin in the present invention may have crosslinking reactivity. When the coating resin is a cross-linking resin, the strength, water resistance, weather resistance, adhesion and the like of the coating film can be improved. The cross-linking reaction type resin may be one that causes a cross-linking reaction by itself or one that causes a cross-linking reaction by a cross-linking agent that is separately mixed. Such crosslinking reactivity includes, for example, hydroxyl group and isocyanate group, carbonyl group and hydrazide group, epoxy group and amino group, aldo group and semicarbazide group, keto group and semicarbazide group, alkoxyl group, carboxyl group and metal ion, carboxyl group It can be imparted by combining a reactive functional group such as a group and a carbodiimide group, a carboxyl group and an epoxy group, a carboxyl group and an aziridine group, a carboxyl group and an oxazoline group. Among these, a hydroxyl group-isocyanate group crosslinking reaction type resin is preferable.

  The glass transition temperature of the coating resin in the present invention is usually about -20 to 80 ° C (preferably -10 to 60 ° C).

  In the present invention, when the modified silicate compound is mixed with the coating resin, a silicate compound other than the modified silicate compound can be used in combination, but 80% by weight or more (preferably 95% by weight or more) of the entire silicate compound is the above. It is desirable to be composed of a modified silicate compound.

  In the clear paint, by using a specific modified silicate as described above, a sufficient hydrophilization function and a stain resistance effect can be obtained even with a small amount of silicate compound as compared with the prior art. This is also advantageous in terms of followability to the ground and crack resistance. That is, according to the present invention, it is possible to relatively reduce the amount of the silicate compound in the clear paint, and it is possible to design a paint that is extremely useful in practice.

The mixing ratio of the silicate compound, based on 100 parts by weight of the solid content of the coating resin, 0.1 to 20 parts by weight in terms of SiO ₂ (preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 It may be set within the range of (weight part). When the mixing ratio of the silicate compound is less than 0.1 parts by weight, the coating film is not imparted with hydrophilicity, so that the stain resistance is insufficient. On the other hand, when it exceeds 20 parts by weight, the followability of the formed coating film to the ground becomes insufficient, and cracks and the like are likely to occur.

The SiO ₂ conversion in the present invention means the weight remaining as silica (SiO ₂ ) when a compound having a Si—O bond such as alkoxysilane or silicate is completely hydrolyzed and then baked at 900 ° C. Expressed in minutes.
In general, alkoxysilanes and silicates have a property of reacting with water to cause a hydrolysis reaction to form silanol, and further causing a condensation reaction between silanols or between silanol and alkoxy. When this reaction is performed to the ultimate, silica (SiO ₂ ) is obtained. These reactions are RO (Si (OR) ₂ O) _n R + (n + 1) H ₂ O → nSiO ₂ + (2n + 2) ROH
(R represents an alkyl group. N is an integer.)
It is expressed by the reaction formula. In terms of SiO ₂ in the present invention are those obtained by converting the amount of silica component which remains to this scheme based.

  In the clear paint, an amine compound can be mixed in addition to the above components. By mixing such an amine compound, it is possible to improve the adhesion when the clear paint is applied (recoated). Furthermore, the amine compound contributes to improvement of physical properties such as stain resistance and curability by interaction with the modified silicate compound.

  Examples of amine compounds include ethylamine, dimethylamine, diamylamine, cyclohexylamine, aniline, hexamethylenediamine, ethylenediamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triphenylamine, dimethyldodecylamine, dimethylbenzylamine, dimethylcyclohexyl. In addition to amine, pyridine, morpholine, etc., ethanolamine, diethanolamine, dimethylethanolamine, N-methyldiethanolamine, triethanolamine, ethylphenylethanolamine and other alkanol group-containing amine compounds, triethylenediamine ([2,2,2] dia Abicyclooctane), tetramethylethylenediamine, pentamethyldiethylenetriamine, etc. Alkyl group-containing amine compound, aminomethyl triethoxysilane, diamino methyl diethoxy silane, .gamma.-amino isobutyl trimethoxy silane, alkoxysilyl group-containing amine compounds such as .gamma.-aminopropyl methyl diethoxy silane, and the like.

  In the present invention, as the amine compound, bis (2,2,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1- Octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2 , 2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2 , 2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like can also be used.

  As the amine compound, an amine compound having a base dissociation constant pKb of 3 or more and 11 or less (preferably 4 or more and 8 or less) is particularly preferable. By using such a compound, physical properties such as recoatability, stain resistance and curability can be further enhanced.

  The mixing ratio of the amine compound is usually 0.01 to 20 parts by weight, preferably 0.02 to 5 parts by weight with respect to 100 parts by weight of the solid content of the coating resin. Within such a range, sufficient effects can be obtained in recoatability, stain resistance, curability and the like, and it is also preferable in terms of securing pot life.

In addition, various additives that can be used in normal paints can be blended in the clear paint. Such additives include, for example, curing agents, plasticizers, antiseptics, antifungal agents, anti-algae agents, antifoaming agents, leveling agents, dispersants, anti-sagging agents, catalysts, curing accelerators, dehydrating agents, matting agents. Agents, ultraviolet absorbers, antioxidants and the like.
In addition, the clear paint can be colored by mixing with a color pigment or the like, if necessary. However, the degree of coloring must be suppressed to such an extent that the design of the decorative coating material is not impaired.

  The clear coating is not particularly limited as long as it has the above-mentioned coating resin and modified silicate compound as constituents, but it is usually from a main agent containing a coating resin and a curing agent containing a modified silicate compound. It is desirable to use a two-component paint. Such a form is preferable in terms of ensuring the stability of the coating material and exhibiting antifouling performance. When the coating resin has a crosslinking reactive group and a crosslinking agent capable of reacting with the reactive group is used, the crosslinking agent may be mixed with a curing agent. Specifically, when the coating resin has a hydroxyl group, an isocyanate compound can be mixed with the curing agent.

As a coating method of the clear paint, various methods such as spray coating, roller coating, and brush coating can be employed. The coating amount at the time of coating is usually about 0.1 to 0.5 kg / m ² . The viscosity of the paint can be appropriately adjusted by diluting with a solvent or the like at the time of application. The dilution ratio is usually about 0 to 20% by weight. The drying after applying the clear paint is usually performed at room temperature.

II. Decorative Laminate The present invention can also be applied to a decorative laminate in which a base material layer, a decorative layer, and a clear layer are laminated. Such a decorative laminated body can be suitably used as a plate-like building material for surface finishing such as a building or a civil engineering structure.

  Among these, as the base material layer, for example, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, asbestos cement board, ALC board, siding board, extrusion board, steel sheet, plastic board, gypsum board, plywood, woven Cloth, nonwoven fabric, ceramic paper, synthetic paper, glass cloth, mesh, etc. can be used. Moreover, the coating-film layer which consists of various coating materials can also be used as a base material layer. In the present invention, it is sufficient that at least one base material layer is included, and two or more base material layers may be included. The base material layer should just be laminated | stacked in the back surface side or decoration layer of a decoration layer, and may be sandwiched by the decoration layer.

The decoration layer should just have a multicolor pattern or an uneven | corrugated pattern. Such a decorative layer is formed by, for example, the above-described decorative coating material (stone-finish finish coating material, JIS K5667 multi-color paint, JIS A6909 thin finish coating material, thick finish coating material, etc.) Can be used. Moreover, what was obtained by shape | molding the composition comprised from a binder, a pigment, an aggregate, etc. can also be used.
The clear layer is formed by the above-described clear paint. This clear layer is laminated on the surface of the decorative layer.

As a method for producing the laminate of the present invention, a known method can be adopted, and for example, the following method can be adopted.
(I) A decorative coating material is poured into a mold, the base material layer is laminated and cured, and after curing, demolded, and a clear paint is applied to the surface of the decorative layer.
(Ii) A decorative coating material is applied to the base material layer, and then a clear paint is applied to the surface thereof.

  As the mold used in the above (i), for example, a mold made of silicon resin, urethane resin, or the like, or a mold provided with release paper can be used. In the method (i), since the mold frame side is the surface of the laminate, a desired uneven pattern can be imparted to the laminate surface by adjusting the shape inside the mold. In the method (i), a method using a means such as a spray, a trowel, a reciprocator, or a coater can be employed instead of pouring.

The dimensions of the decorative laminate can be adjusted by appropriately cutting after laminating each layer. In the above method (i), it is also possible to manufacture using a mold having dimensions determined in advance without cutting the manufactured laminate.
Although the thickness of each layer which comprises a decoration laminated body is not specifically limited, Usually, a base material layer is about 0.1-10 mm, a decoration layer is about 0.1-10 mm, and a clear layer is about 10-300 micrometers.

Specifically, the decorative laminate of the present invention can be applied to inner and outer walls, partitions, doors, ceilings, pillars, and the like in houses, apartments, schools, hospitals, stores, offices, factories, warehouses, restaurants, and the like. What is necessary is just to stick using an adhesive agent, an adhesive, an adhesive tape, a nail, a hook, etc. when constructing this invention laminated body in such a site | part. In addition, it can also be fixed using pins, fasteners, rails or the like.
Moreover, you may cut | disconnect and use a laminated body for arbitrary shapes at the time of construction. In this case, the side surface of the laminate after cutting can be appropriately treated with a paint or the like.

  Examples are given below to clarify the features of the present invention.

<Decorative coating material>
For 200 parts by weight of acrylic resin emulsion (methyl methacrylate-styrene- (2-ethylhexyl acrylate) -methacrylic acid copolymer, pH 7.6, solid content 50 wt%, minimum film forming temperature 0 ° C.) 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate) 3 parts by weight, polyurethane-based thickener 5 parts by weight, silicone-based antifoaming agent 3 parts by weight, coloring with a particle diameter of 0.1 to 2 mm 380 parts by weight of the aggregate mixture (white: grey: black = 3: 3: 1) was uniformly mixed by a conventional method to produce a decorative coating material A.

<Clear paint>

・ Modified silicate compound (1)
To 100 parts by weight of methyl silicate condensate (weight average molecular weight 1000, average condensation degree 8, nonvolatile content 100%), 52 parts by weight of isobutyl alcohol and 0.03 part by weight of dibutyltin dilaurate as a catalyst were added and mixed. Demethanol reaction was carried out at 75 ° C. for 8 hours to produce a modified silicate compound (1). In this modified silicate compound (1), the equivalent ratio of methyl group to isobutyl group was 62:38, and the residual silica ratio obtained by firing at 900 ° C. was 43% by weight.

・ Modified silicate compound (2)
52 parts by weight of n-butyl alcohol and 0.03 parts by weight of dibutyltin dilaurate as a catalyst are added to and mixed with 100 parts by weight of a methyl silicate condensate (weight average molecular weight 1000, average degree of condensation 8, nonvolatile content 100%). Thereafter, a demethanol reaction was performed at 75 ° C. for 8 hours to produce a modified silicate compound (2). In this modified silicate compound (2), the equivalent ratio of methyl group to n-butyl group was 62:38, and the residual silica ratio obtained by baking at 900 ° C. was 43% by weight.

・ Main agent (1)
Non-water-dispersed acrylic polyol (hydroxyl value 50 KOHmg / g, weight average molecular weight 80000, glass transition temperature 40 ° C., solid content 50% by weight, medium: mineral spirit, aliphatic hydrocarbon 70% by weight) The main agent (1) was produced by uniformly mixing and stirring 104 parts by weight of spirit and 1 part by weight of a silicone-based antifoaming agent by a conventional method.

・ Main agent (2)
Non-water-dispersed acrylic polyol (hydroxyl value 50KOHmg / g, weight average molecular weight 80000, glass transition temperature 40 ° C, solid content 50% by weight, medium: mineral spirit, aliphatic hydrocarbon 70% by weight) with 200 parts by weight 2 parts by weight of (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508, pKb 5.5), 102 parts by weight of mineral spirits, and 1 part by weight of a silicone-based antifoaming agent are uniformly used in a conventional manner. The main component (2) was produced by mixing and stirring.

・ Curing agent (1)
40 parts by weight of Solvesso 100 (manufactured by Exxon Chemical) and 20 parts by weight of the modified silicate compound (1) are uniformly added to 40 parts by weight of polyisocyanate containing isocyanurate structure (non-volatile content: 100% by weight, NCO content: 21% by weight). The curing agent (1) was produced by mixing.

・ Curing agent (2)
40 parts by weight of Solvesso 100 (manufactured by Exxon Chemical) and 20 parts by weight of the modified silicate compound (2) are uniformly added to 40 parts by weight of the polyisocyanate containing isocyanurate structure (non-volatile content: 100% by weight, NCO content: 21% by weight). The curing agent (2) was produced by mixing.

・ Curing agent (3)
10 parts by weight of Solvesso 100 (manufactured by Exxon Chemical) and 50 parts by weight of the modified silicate compound (2) are uniformly added to 40 parts by weight of polyisocyanate containing isocyanurate structure (non-volatile content: 100% by weight, NCO content: 21% by weight). The curing agent (3) was produced by mixing.

・ Clear paint A
The base agent (1) and the curing agent (1) produced by the above method were uniformly mixed at a weight ratio of 86:14 to obtain a clear coating material A. The mixing ratio of the modified silicate compound in the coating material A is 4.3 parts by weight in terms of SiO _{2 with} respect to 100 parts by weight of the resin solid content.

・ Clear paint B
The base agent (2) and the curing agent (1) produced by the above method were uniformly mixed at a weight ratio of 86:14 to obtain a clear coating material B. The mixing ratio of the modified silicate compound in the paint B is 4.3 parts by weight in terms of SiO _{2 with} respect to 100 parts by weight of the resin solid content.

・ Clear paint C
The base agent (1) and the curing agent (2) produced by the above method were uniformly mixed at a weight ratio of 86:14 to obtain a clear coating material C. The mixing ratio of the modified silicate compound in the coating material C is 4.3 parts by weight in terms of SiO _{2 with} respect to 100 parts by weight of the resin solid content.

・ Clear paint D
The base agent (1) and the curing agent (3) produced by the above method were uniformly mixed at a weight ratio of 86:14 to obtain a clear coating material D. The mixing ratio of the modified silicate compound in the coating material D is 10.7 parts by weight in terms of SiO _{2 with} respect to 100 parts by weight of the resin solid content.

<Contamination resistance test>
A 300 × 150 × 3 mm aluminum plate bent at a third position from the upper end so that the inner angle was 135 degrees was used as a test substrate. After spraying SK # 1000 primer at a coating amount of 0.15 kg / m ² on the convex surface of the test substrate and drying for 8 hours in a standard state, spray the decorative coating material A at a coating amount of 4 kg / m ² . It was painted and cured for 24 hours under standard conditions. Next, each of the clear paints obtained by the above method was spray-coated at a coating amount of 0.3 kg / m ² and dried and cured in a standard state for 7 days.
The test specimen obtained by the above method was installed in the Ibaraki city, Osaka, facing the south side with the wide area of the specimen vertical, and exposed outdoors for 3 months. At this time, when the contamination state on the vertical surface was visually observed, the stain resistance evaluation was the best for the clear paint B specimen, followed by the clear paints A and D, and then the clear paint C.

<Hot and cold repeat test>
SK # 1000 primer is spray-coated at a coating amount of 0.15 kg / m ² on a 300 mm × 150 mm × 6 mm slate plate, dried for 8 hours in a standard state, and then a decorative coating material A is applied at a coating amount of 4 kg / m. ² and spray-cured for 24 hours under standard conditions. Next, each of the clear paints obtained by the above method was spray-coated at a coating amount of 0.3 kg / m ² and dried and cured in a standard state for 7 days.
About the test body obtained by the above method, after performing a total of 10 cycles of hot and cold repeated tests in which water immersion (23 ° C.) 18 hours → −20 ° C. 3 hours → 80 ° C. 3 hours is one cycle, The presence or absence of cracks in the film was confirmed visually. As a result, no abnormality was observed in the specimens coated with the clear paints A, B, and C, but the clear paint D specimens were slightly cracked.

<Decorative laminate>
After applying a release agent to a silicone resin mold having a rock-like surface pattern (length 150 mm x width 70 mm x depth 5 mm), pouring decorative coating material A, placing a mesh on it, roller The sample was lightly pressed and smoothed, dried at room temperature for 48 hours, and demolded. Next, the clear coating B was spray-coated on the surface at a coating amount of 0.3 kg / m ² and dried and cured in a standard state for 7 days.
About the decorative laminated body obtained by the above method, when it tested by the above-mentioned test method, it became a result excellent in stain resistance and crack resistance.

Claims (2)

After applying a decorative coating material to the base material to form a multicolor pattern or uneven pattern,
The silicate compound is contained in an amount of 0.1 to 20 parts by weight in terms of SiO ₂ with respect to 100 parts by weight of the solid content of the coating resin, and the silicate compound has a linear alkyl group having 1 to 2 carbon atoms and 3 or more carbon atoms. A method for painting a decorative surface, comprising applying a clear paint containing a modified silicate compound in which branched alkyl groups are mixed in an equivalent ratio of 95: 5 to 50:50. A decorative laminate having a base material layer, a decorative layer, and a clear layer,
The decorative layer has a multicolor pattern or an uneven pattern,
The clear layer contains 0.1 to 20 parts by weight of a silicate compound in terms of SiO ₂ with respect to 100 parts by weight of the solid content of the coating resin, and the silicate compound has a linear alkyl group having 1 to 2 carbon atoms and A decorative laminate comprising a clear coating material containing a modified silicate compound in which branched alkyl groups having 3 or more carbon atoms are mixed at an equivalent ratio of 95: 5 to 50:50.