JP7144169B2 - Face material - Google Patents

Description

The present invention relates to novel facings. The face material of the present invention can be applied to the surface coating of buildings, civil engineering structures, etc., and specifically, it can be applied to the pattern finishing of the walls of buildings.

Aesthetics are required for the walls of buildings and the like from the viewpoint of scenery. In recent years, from such a point of view, attention has been paid to pattern finishing, for example, in the image of natural stones, soil, plants, and the like.

In materials used for such pattern finishing, it is being studied to impart various functionalities in addition to aesthetics. As one of them, for example, Patent Literature 1 describes imparting moisture permeability. According to such a material, water vapor generated on the back surface (substrate side) can be discharged to the surface side (outside), and swelling, peeling, etc. of the material itself can be suppressed. However, contaminants tend to adhere to the surface of the material described in Patent Document 1, and there is a risk that the initial aesthetic appearance will be impaired.

On the other hand, Patent Document 2 describes that a hydrophilic film is provided on the surface of a building material in order to impart an antifouling function to the building material. By providing such a hydrophilic film on the surface of the material of Patent Document 1, an effect of suppressing adhesion of contaminants can be expected.

JP-A-7-119272 JP 2009-136727 A

However, the material disclosed in Patent Document 1 is often provided with moisture permeability due to the presence of fine pores on its surface or inside. If a hydrophilic coating is present on the surface of such a material, contamination-causing substances are likely to permeate into the fine pores, and there is a risk of accelerating the progress of contamination.

The present invention has been made in view of such problems, and an object of the present invention is to obtain a face material having moisture permeability, antifouling properties, and the like.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, this inventor thought about the face material which has a specific transparent layer in the surface of a pattern layer, and came to complete this invention.

That is, the face material of the present invention has the following characteristics.
1. A surface material having moisture permeability,
Having a moisture-permeable pattern layer and a moisture-permeable transparent layer covering the surface of the pattern layer,
The pattern layer is formed of a pattern layer composition containing granular inorganic particles and an acrylic silicone resin,
The transparent layer is formed of a transparent layer composition containing a carboxyl group-containing acrylic silicone resin having a glass transition temperature of 30 to 80° C.,
The transparent layer composition forms a film having a contact angle with water of 60 to 110°.
A surface material having moisture permeability (excluding a laminate in which a base layer and a design layer are laminated in order on the back surface of a transparent glass plate).
2. 1. The transparent layer is formed of a transparent layer composition containing a carboxyl group-containing acrylic silicone resin having a glass transition temperature of 30 to 80° C. and a cross-linking agent. A face material having moisture permeability as described.
3. 1. The acrylic silicone resin contained in the pattern layer has a lower glass transition temperature than the carboxyl group-containing acrylic silicone resin having a glass transition temperature of 30 to 80° C. contained in the transparent layer. or 2. A face material having moisture permeability according to 1.

The face material of the present invention can exhibit excellent performance in terms of moisture permeability, antifouling property, etc., and can retain the original aesthetic appearance for a long period of time.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated.

The face material of the present invention is a face material having moisture permeability, and has a pattern layer and a transparent layer covering the surface of the pattern layer.

Among them, the pattern layer is formed of a composition containing granular inorganic particles and a resin. Such a pattern layer can be formed by curing a composition containing granular inorganic particles and a resin (hereinafter also referred to as "pattern layer composition"). As a result, the granular inorganic particles are fixed by the resin to form a continuous surface, and a pattern layer having a color tone and/or uneven pattern based on the granular inorganic particles and having moisture permeability can be obtained. The moisture permeability of the pattern layer (water vapor permeability according to JIS Z0208) is preferably 40 to 1200 g/m ² 24h (more preferably 70 to 800 g/m ² 24h, still more preferably 100 to 600 g/m ² 24h). be.

As the granular inorganic particles, both natural products and artificial products can be used as long as the base material is inorganic. As the granular inorganic particles, an embodiment containing at least granular colored inorganic particles is suitable. As such granular colored inorganic particles, those having a light transmittance of less than 3% are particularly preferable, and those having a light transmittance of 2% or less are more preferable. Specific examples of such granular colored inorganic particles include marble, granite, serpentinite, granite, sandstone, slate, basalt, gabbro, diorite, andesite, limestone, pulverized products thereof, and pulverized ceramics. , pulverized ceramics, metal particles, and the like. In addition, fluorite, cold water stone, feldspar, silica, silica sand, pulverized products thereof, pulverized glass, glass beads, etc., which are colored so as to satisfy the above conditions, can also be used. These can be used singly or in combination of two or more.

The above-mentioned light transmittance is a value of total light transmittance measured by a turbidity meter. In this measurement, a sample of granular inorganic particles is filled in a transparent glass cell having an inner thickness of 5 mm, water is then gradually filled, and air bubbles in the cell are removed by vibration.

The pattern layer may contain granular transparent inorganic particles in addition to the granular colored inorganic particles. The use of such granular transparent inorganic particles is suitable for improving the appearance. As the granular transparent inorganic particles, those having a light transmittance of 3% or more (more preferably 3 to 50%, still more preferably 10 to 30%) are suitable. Granular transparent inorganic particles include, for example, silica, cold water stone, feldspar, silica stone, pulverized products thereof, pulverized glass, glass beads, and the like. can be used. These can be used singly or in combination of two or more. In the present invention, "a to b" is synonymous with "a or more and b or less".

As the granular inorganic particles, a preferred embodiment includes particles having a particle size of 5 mm or less (more preferably 16 μm to 2 mm, still more preferably 20 μm to 850 μm). Within this range, various granular inorganic particles having different particle diameters, color tones, etc. can be used in combination. The particle size of the granular inorganic particles is measured by sieving using a metal mesh sieve specified in JIS Z8801-1:2000.

The resin for fixing the granular inorganic particles preferably has a transparent film. Examples of forms of such resins include solvent-soluble resins, non-water-dispersible resins, solvent-free resins, water-dispersible resins, and water-soluble resins. Examples of resin types include acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, vinyl acetate resins, acrylic silicon resins, fluorine resins, silicon resins, and composites thereof. These can be used singly or in combination of two or more. Such a resin may have the property of causing a cross-linking reaction.

As the resin in the pattern layer, one containing an acrylic silicon resin is suitable from the viewpoint of moisture permeability, durability, and the like. Examples of acrylic silicone resins include:
(1) a synthetic resin obtained by copolymerizing a monomer group containing a (meth)acrylic acid alkyl ester and a reactive silyl group-containing monomer;
(2) A resin obtained by copolymerizing a monomer group containing a (meth)acrylic acid alkyl ester and at least one monomer selected from reactive silyl group-containing monomers, hydroxyl group-containing monomers, and carboxyl group-containing monomers, and silicon; A synthetic resin obtained by adding a compound,
(3) a synthetic resin obtained by reacting a functional group in an acrylic resin with a silane coupling agent having a functional group capable of reacting with the functional group;
(4) a synthetic resin obtained by reacting a functional group in an acrylic resin with a silane coupling agent having a functional group capable of reacting with the functional group, and further adding a silicon compound;
etc. In the present invention, both acrylic acid alkyl ester and methacrylic acid alkyl ester are collectively referred to as (meth)acrylic acid alkyl ester. A monomer is a compound having a polymerizable unsaturated double bond. An acrylic resin is a synthetic resin obtained by polymerizing a group of monomers containing a (meth)acrylic acid alkyl ester.

Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. , isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate, ( 1-ethylpropyl meth)acrylate, 2-methylbutyl (meth)acrylate, 3-methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-(meth)acrylate Ethyl butyl, 2-methylpentyl (meth)acrylate, 4-methylpentyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate 2-ethylhexyl acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl (meth)acrylate, n-lauryl (meth)acrylate and the like. These can be used singly or in combination of two or more.

A reactive silyl group is one in which one or more selected from, for example, an alkoxyl group, a hydroxyl group, a phenoxy group, a mercapto group, an amino group, and a halogen group are bonded to a silicon atom. Among these, one or more selected from an alkoxysilyl group in which an alkoxyl group is bonded to a silicon atom and a silanol group in which a hydroxyl group is bonded to a silicon atom is preferable.

The reactive silyl group-containing monomers in (1) and (2) above are compounds containing a reactive silyl group and a polymerizable double bond, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n- butoxysilane, vinyltris(β-methoxyethoxy)silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ-(meth)acryloyloxypropyltri Methoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethyl vinyl ether, methyldimethoxysilylpropyl vinyl ether, etc., and these 1 type, or 2 or more types can be used.

Examples of hydroxyl group-containing monomers in (2) above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, etc. These 1 type(s) or 2 or more types can be used.

Examples of the carboxyl group-containing monomer in (2) above include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, and itaconic anhydride. More than one species can be used.

As the silicon compound in (2) and (4) above, those having one or more reactive silyl groups in one molecule (excluding those having a polymerizable double bond) are used, and examples thereof include tetraethoxysilane, tetrafunctional alkoxysilanes such as tetramethoxysilane and tetrabutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, Trifunctional alkoxysilanes such as propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane , diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, methyl Bifunctional alkoxysilanes such as phenyldiethoxysilane; tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane; chlorosilanes such as chlorosilane; acetoxysilanes such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane, etc., and the like, and one or more of these are used. be able to. Moreover, a siloxane compound can also be used as a silicon compound. Examples of siloxane compounds include cyclic siloxane compounds, linear siloxane compounds, branched siloxane compounds, and derivatives thereof. Of these, cyclic siloxane compounds include, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.

Combinations of functional groups in (3) and (4) above include, for example, hydroxyl group and isocyanate group, amino group and isocyanate group, carboxyl group and epoxy group, amino group and epoxy group, and alkoxysilyl groups. The silane coupling agent is, for example, a compound having at least one or more reactive silyl groups and other substituents in one molecule, specifically β-(3,4 epoxycyclohexyl)ethyltrimethoxy Silane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ -aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, isocyanate-functional silane, and the like, and one or more of these can be used.

In the above (1) to (4), components other than the above, such as amino group-containing monomers such as dimethylaminoethyl (meth)acrylate and dimethylaminopropyl (meth)acrylate; (meth)acrylamide and ethyl (meth)acrylamide Nitrile group-containing monomers such as acrylonitrile; Epoxy group-containing monomers such as glycidyl (meth)acrylate; Aromatic vinyl monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene; sulfonic acid-containing vinyl monomers such as sulfonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride; chlorine-containing monomers such as vinyl chloride, vinylidene chloride and chloroprene; ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol mono Alkylene glycol monoallyl ethers such as allyl ether; vinyl ester monomers such as vinyl acetate and vinyl propionate; ethylene, propylene, isobutylene and the like can be used. These can be used alone or in combination of two or more. In addition, an ethylenically unsaturated double bond-containing ultraviolet absorber, an ethylenically unsaturated double bond-containing light stabilizer, and the like can also be used.

It is desirable that the glass transition temperature (hereinafter also referred to as “Tg”) of the resin in the pattern layer is lower than the glass transition temperature of the resin contained in the later-described transparent layer. In the present invention, by using such a resin, it is possible to improve the flexibility of the face material while ensuring physical properties such as antifouling properties. The glass transition temperature of the resin contained in the pattern layer is preferably -30 to 30°C, more preferably -25 to 25°C. The glass transition temperature of the resin is a value determined by the Fox formula.

The ratio of the above resin is preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, still more preferably 3 to 30 parts by weight, based on solid content, with respect to 100 parts by weight of the total amount of granular inorganic particles. Preferably 4-20 parts by weight, most preferably 5-19 parts by weight. With such a ratio, it is easy to impart a design property that takes advantage of the aesthetic appearance of the connection (aggregation) of the granular inorganic particles, and it is also suitable in terms of moisture permeability. That is, it is easy to obtain a moisture-permeable patterned layer composed of connected bodies (aggregates) of granular inorganic particles.

The composition for the pattern layer may optionally contain components (additives, etc.) other than those described above as long as the effects of the present invention are not significantly impaired. Examples of such components include plasticizers, film-forming aids, anti-algae agents, antibacterial agents, deodorants, adsorbents, flame retardants, thickeners, antifoaming agents, cross-linking agents, coloring pigments, and extender pigments. , luster pigments, phosphorescent pigments, fluorescent pigments, aggregates, fibers, ultraviolet absorbers, light stabilizers, antioxidants, silane coupling agents, catalysts, solvents, water, and the like.

The thickness of the pattern layer is preferably 0.3-6 mm, more preferably 0.5-5 mm. The thickness of the pattern layer is a value obtained by calculating the average thickness of the pattern layer (average of 10 randomly selected points).

It is desirable that each of the pattern layers exhibits a color tone resulting from juxtaposed color mixture. Juxtaposed color mixture means that when an observer looks at colors at a certain distance or more, a plurality of juxtaposed colors appear to be mixed without being distinguished individually. In the present invention, by adopting juxtaposed color mixture using two or more kinds (two colors) of granular inorganic particles instead of color mixture using pigments, dyes, etc., naturalness and the like can be enhanced.

The pattern layer may be of one color, or may be of a mixture of two or more colors. The color tone of the pattern layer can be appropriately set. Moreover, the surface of the pattern layer may be flat or may have an uneven pattern. As the uneven pattern, for example, various uneven patterns such as streaks and islands can be formed. The shape, arrangement, number, size, width, height difference, thickness, area, color tone, glossiness, etc. of the uneven pattern may be appropriately set according to the desired pattern.

The transparent layer in the present invention covers the surface of the pattern layer. The transparent layer can be formed from a composition (hereinafter also referred to as “transparent layer composition”) containing a resin having a glass transition temperature of 30 to 80° C. and having a coating film with a water contact angle of 60 to 110°. The transparent layer formed from such a composition makes the best use of the aesthetic appearance of the pattern layer and contributes to the improvement of antifouling property and the like.

The transparent layer composition contains a resin having a glass transition temperature of 30 to 80°C (preferably 35 to 75°C, more preferably 40 to 70°C). When the Tg is equal to or higher than the above lower limit, antifouling properties can be enhanced. In addition, since the Tg is equal to or less than the above upper limit, it is possible to prevent cracking of the transparent layer and the like while enhancing antifouling properties, and it is possible to maintain the aesthetic appearance of the pattern layer for a long period of time.

The transparent layer composition forms a film having a contact angle with water of 60 to 110° (preferably 70 to 105°, more preferably 75 to 100°). When this contact angle is equal to or greater than the above lower limit, it is possible to suppress permeation of contaminants and enhance anti-contamination properties. When the contact angle is equal to or less than the above upper limit, streaky contamination due to rainfall or the like can be suppressed. The contact angle is the angle formed by a water droplet dropped on the surface of the film formed from the transparent layer composition and the surface of the film, and is a value measured by a contact angle meter.

As the resin in the transparent layer composition, a resin having a transparent coating can be used. Examples of the form of such resins include solvent-soluble resins, non-water-dispersible resins, solvent-free resins, water-dispersible resins, water-soluble resins, etc. Among them, water-dispersible resins (resin emulsions ) is preferred. Examples of resin types include acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, vinyl acetate resins, acrylic silicon resins, fluorine resins, silicon resins, and composites thereof. These can be used singly or in combination of two or more.

The transparent layer composition desirably contains a cross-linking agent in addition to the above resins. In such an embodiment, a transparent layer composition containing a resin having a reactive functional group and a cross-linking agent capable of reacting with the reactive functional group can be used. In this case, the reaction between the resin and the cross-linking agent forms a film having a three-dimensional cross-linked structure, which makes it possible to improve physical properties such as antifouling properties and moisture permeability. As the cross-linking agent, those applicable to water-dispersible resins are preferable, and for example, water-soluble cross-linking agents, water-dispersible cross-linking agents, self-emulsifying cross-linking agents and the like are suitable.

Examples of resins having reactive functional groups include carboxyl groups, carbodiimide groups, epoxy groups, aziridine groups, oxazoline groups, hydroxyl groups, isocyanate groups, carbonyl groups, hydrazide groups, epoxy groups, amino groups, and alkoxysilyl groups. Those having one or more selected reactive functional groups can be used. As the cross-linking agent, a combination of those capable of reacting with the reactive functional groups of such resins may be used. Combinations of reactive functional groups include, for example, a carboxyl group and a carbodiimide group, a carboxyl group and an epoxy group, a carboxyl group and an oxazoline group, a carboxyl group and an aziridine group, a hydroxyl group and an isocyanate group, a carbonyl group and a hydrazide group, an epoxy group and an amino group. groups, alkoxysilyl groups, etc., and one or more of these can be used.

When the resin in the transparent layer composition has a carboxyl group, a compound having one or more reactive functional groups selected from carbodiimide groups, epoxy groups, oxazoline groups and the like can be used as the cross-linking agent. Among these, as a cross-linking agent having a carbodiimide group, for example, JP-A-10-60272, JP-A-10-316930, JP-A-11-60667, JP-A-2000-7642, JP-A-2000- 119539, JP-A-2000-319351, JP-A-2013-112755, JP-A-2016-196612, JP-A-2016-196613, WO2017/6950, etc. . Examples of crosslinking agents having epoxy groups include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, and polyglycerol polyglycidyl ether. Ether, diglycerol polyglycidyl ether, polyhydroxyalkane polyglycidyl ether, sorbitol polyglycidyl ether and the like. Examples of cross-linking agents having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Examples thereof include resins obtained by copolymerizing a polymerizable oxazoline compound such as oxazoline with a monomer copolymerizable with the compound. These can be used singly or in combination of two or more.

When the resin in the transparent layer composition has a carbonyl group, for example, a compound having a hydrazide group can be used as the cross-linking agent. Examples of cross-linking agents having a hydrazide group include malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, and maleic dihydrazide. These can be used singly or in combination of two or more.

As the resin in the composition for the transparent layer, one containing an acrylic silicone resin is suitable from the viewpoint of moisture permeability, antifouling property, and the like. As the acrylic silicone resin, for example, the same resins as (1) to (4) described for the pattern layer can be used. The transparent layer composition may also contain a cross-linking agent in addition to such an acrylic silicone resin. In this case, an acrylic silicone resin having a reactive functional group may be used as the resin, and a cross-linking agent capable of reacting with the reactive functional group may be used as the cross-linking agent. Suitable combinations of reactive functional groups include, for example, a combination of a carboxyl group and a carbodiimide group, a carboxyl group and an epoxy group, a carboxyl group and an oxazoline group, a carbonyl group and a hydrazide group, etc. One or two of these more can be used.

The transparent layer composition in the present invention may contain a surfactant. In such an embodiment, both moisture permeability and antifouling properties can be further enhanced. Although the mechanism of action thereof is not clear, the composition for the transparent layer is likely to fill the fine pores of the pattern layer, effectively suppressing the seepage of contaminants, and the fine pores thus filled are In the pores, it is presumed that moisture permeability is imparted by the appropriate hydrophilicity of the surfactant, etc., contributing to this.

As such a surfactant, a compound having a structure having both a hydrophilic portion and a hydrophobic portion in the molecule can be used. For example, nonionic surfactants, anionic surfactants, cationic surfactants, , amphoteric surfactants, and the like. These can be used singly or in combination of two or more. As such a surfactant, for example, a compound having silicon and/or fluorine in the molecule can be used.

The ratio of the surfactant is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight in terms of solid content, with respect to 100 parts by weight of the resin solid content of the resin contained in the composition for the transparent layer. is. With such a ratio, both moisture permeability and antifouling properties can be sufficiently enhanced.

In addition to the components described above, the composition for the transparent layer includes, for example, matting agents, coloring pigments, bright pigments, phosphorescent pigments, fluorescent pigments, aggregates, fibers, plasticizers, film-forming aids, anti-algae agents, Contains antibacterial agents, deodorants, adsorbents, flame retardants, thickeners, antifoaming agents, ultraviolet absorbers, light stabilizers, antioxidants, silane coupling agents, catalysts, solvents, water, etc. good too. When the transparent layer composition contains a color pigment, a colored transparent layer can be formed. Regarding photocatalytic titanium oxide, colloidal silica, etc., it is necessary to pay attention to use them within a range that does not significantly impair the effects of the present invention, and an aspect in which they are not used is also suitable.

It is desirable that the transparent layer formed from such a transparent layer composition is provided on the entire surface of the pattern layer. The weight per unit area of the transparent layer (in terms of solid content) is preferably 5 to 200 g/m ² , more preferably 10 to 100 g/m ² .

The face material of the present invention may have reinforcing material. Such reinforcements can be provided, for example, on the inside and/or on the back side of the pattern layer. Examples of reinforcing materials include woven fabrics, non-woven fabrics, ceramic papers, synthetic papers, meshes, cloths, plasterboards, plywoods, slate plates, and metal plates. In addition, for example, a layer of a composition containing granular inorganic particles, resin, etc. may be provided as a reinforcing material on the back surface of the pattern layer. The reinforcing material may be made of two or more of the above materials. Such reinforcing materials can be used singly or in combination of two or more. By using such a reinforcing material, the strength, flexibility, etc. of the face material can be enhanced.

The method for manufacturing the face material of the present invention is not particularly limited, and various methods can be adopted. One example is a method using a mold. In this method, for example, a mold is prepared on which unevenness corresponding to a desired pattern is formed. Then, the pattern layer is obtained by filling or applying the pattern layer composition into the mold, and removing the mold after curing. Then, a transparent layer can be provided by a method of coating a transparent layer composition on the surface of the pattern layer after demolding. For filling or applying each composition, known instruments such as sprayers, rollers, trowels, reciprocators, coaters and the like can be used.

As another example, a method of filling or coating the transparent layer composition and the pattern layer composition in order in the mold and removing the mold after curing can be employed. In this case, the pattern layer composition is desirably filled or applied after the transparent layer composition is cured.

In each of the above methods, when a reinforcing material is introduced, for example, the reinforcing material may be embedded inside the pattern layer or laminated on the rear surface of the pattern layer before the pattern layer composition is cured.

The face material of the present invention has moisture permeability. The face material of the present invention exhibits a moisture permeability according to JIS Z0208 of preferably 40 g/m ² ·24h or more, more preferably 70 g/m ² ·24h or more, still more preferably 100 g/m ² ·24h or more. The upper limit of the moisture permeability is preferably 1000 g/m ² ·24h or less, more preferably 600 g/m ² ·24h or less, still more preferably 400 g/m ² ·24h or less. If the moisture permeability is within such a range, the water vapor generated on the back side (base material side) of the face material can be discharged to the front side (outside), preventing swelling, peeling, etc. of the face material itself. can be suppressed.

The face material of the present invention can be used as a material for decorating the walls of buildings and the like. When fixing the face material of the present invention to a wall surface or the like, for example, an adhesive, an adhesive tape, a nail, a screw, a bolt, a rail, or the like may be used. Examples of base materials constituting building wall surfaces include concrete, mortar, siding boards, extruded boards, gypsum boards, perlite boards, plywood, bricks, plastic boards, metal plates, glass, and porcelain tiles. These substrates may be those on which a film (existing film, undercoat film, etc.) has already been formed, or to which wallpaper is pasted.

Examples are shown below to further clarify the features of the present invention.

(Composition 1 for pattern layer)
Mixture of granular colored inorganic particles (mixture of brown silica sand and reddish brown silica sand, particle size 32-600 μm, light transmittance less than 1%) 80 parts by weight, granular transparent inorganic particles (Kansuiseki; particle size 106-425 μm, light transmittance 16%) 20 parts by weight, resin 1 (acrylic silicone resin emulsion, Tg 0°C, solid content 50% by weight) 30 parts by weight, and additives (thickener, antifoaming agent, etc.) were uniformly mixed by a conventional method. , a brown pattern layer composition 1 was obtained.

(Composition 2 for pattern layer)
80 parts by weight of a mixture of granular colored inorganic particles (same as above), 20 parts by weight of granular transparent inorganic particles (same as above), 30 parts by weight of resin 2 (acrylic silicone resin emulsion, Tg 38 ° C., solid content 50% by weight), and additives ( A thickener, an antifoaming agent, etc.) were uniformly mixed by a conventional method to obtain a brown pattern layer composition 2.

(Composition 1 for transparent layer)
Resin 3 (carboxyl group-containing acrylic silicone resin emulsion, Tg 66 ° C., solid content 50% by weight) 200 parts by weight, film-forming aid 18 parts by weight, water 20 parts by weight, surfactant (fluorine-containing amphoteric surfactant, solid content 30% by weight) and 4 parts by weight of other additives (ultraviolet absorbers, light stabilizers, thickeners, antifoaming agents, etc.) were uniformly mixed by a conventional method to obtain a transparent layer composition 1. got The contact angle of this transparent layer composition 1 to water was 82°. The contact angle with water was measured by applying the composition for transparent layer to a thickness of 150 μm on an aluminum plate and keeping it in an atmosphere of 23° C. and 50% relative humidity (hereinafter also referred to as “standard conditions”) for 14 days. It is a value measured using a contact angle meter for a specimen obtained by drying and curing (the same applies hereinafter).

(Composition 2 for transparent layer)
Resin 3 (same as above) 200 parts by weight, film-forming aid 18 parts by weight, water 20 parts by weight, crosslinking agent (carbodiimide group-containing crosslinking agent, solid content 40% by weight) 10 parts by weight, other additives (ultraviolet absorber, light A stabilizer, a thickener, an antifoaming agent, etc.) (4 parts by weight) were uniformly mixed by a conventional method to obtain a composition 2 for a transparent layer. The contact angle of this transparent layer composition 2 with water was 84°.

(Composition 3 for transparent layer)
Resin 3 (same as above) 200 parts by weight, film-forming aid 18 parts by weight, water 20 parts by weight, surfactant (same as above) 0.2 parts by weight, cross-linking agent (same as above) 10 parts by weight, other additives (ultraviolet absorber , a light stabilizer, a thickener, an antifoaming agent, etc.) were uniformly mixed by a conventional method to obtain a composition 3 for a transparent layer. The contact angle with water of this transparent layer composition 3 was 81°.

(Composition 4 for transparent layer)
Resin 4 (carboxyl group-containing acrylic silicone resin emulsion, Tg 57°C, solid content 50% by weight) 200 parts by weight, film-forming aid 18 parts by weight, water 20 parts by weight, surfactant (same as above) 0.2 parts by weight, crosslinking 10 parts by weight of the agent (same as above) and 4 parts by weight of other additives (ultraviolet absorber, light stabilizer, thickener, antifoaming agent, etc.) are uniformly mixed by a conventional method to obtain a transparent layer composition 4. rice field. The contact angle of this transparent layer composition 4 to water was 82°.

(Composition 5 for transparent layer)
Resin 5 (carboxyl group-containing acrylic silicone resin emulsion, Tg 48° C., solid content 50% by weight) 200 parts by weight, film-forming aid 18 parts by weight, water 20 parts by weight, surfactant (same as above) 0.2 parts by weight, crosslinking 10 parts by weight of the agent (same as above) and 4 parts by weight of other additives (ultraviolet absorber, light stabilizer, thickener, antifoaming agent, etc.) are uniformly mixed by a conventional method to obtain a transparent layer composition 5. rice field. The contact angle of this transparent layer composition 5 with water was 84°.

(Composition 6 for transparent layer)
Resin 6 (acrylic resin emulsion, Tg 28 ° C., solid content 50% by weight) 200 parts by weight, film-forming aid 18 parts by weight, water 20 parts by weight, other additives (ultraviolet absorber, light stabilizer, thickener, eraser 4 parts by weight of foaming agents, etc.) were uniformly mixed by a conventional method to obtain a composition 6 for a transparent layer. The contact angle of this transparent layer composition 6 with water was 86°.

(Composition 7 for transparent layer)
Resin 7 (colloidal silica composite emulsion, solid content 40% by weight) 250 parts by weight, film-forming aid 18 parts by weight, surfactant (same as above) 4 parts by weight, other additives (ultraviolet absorber, light stabilizer, thickener agent, antifoaming agent, etc.) were uniformly mixed by a conventional method to obtain a composition 7 for a transparent layer. The contact angle of this transparent layer composition 7 with water was 38°.

(Composition 8 for transparent layer)
Resin 8 (acrylic resin emulsion, Tg 48° C., solid content 50% by weight) 200 parts by weight, water repellent agent (dimethylsiloxane compound, solid content 50% by weight) 50 parts by weight, film forming aid 18 parts by weight, water 20 parts by weight , and 4 parts by weight of other additives (ultraviolet absorber, light stabilizer, thickener, antifoaming agent, etc.) were uniformly mixed by a conventional method to obtain a transparent layer composition 8. The contact angle of this transparent layer composition 8 with water was 116°.

(Example 1)
A square formwork was prepared as the formwork. The mold was placed with the inner surface facing upward, the inner surface of the mold was filled with pattern layer composition 1, and after curing, the mold was removed to obtain a pattern layer (thickness: 2 mm). The transparent layer composition 1 was spray-coated on the entire surface of the pattern layer and cured to form a transparent layer (solid content weight per unit area: 40 g/m ² ).

(Examples 2 to 6, Comparative Examples 1 to 3)
Surface materials 2 to 9 were obtained in the same manner as in Example 1, using those shown in Table 1 as the composition for the pattern layer and the composition for the transparent layer.

(Test 1)
For each face material obtained by the above method, moisture permeability was measured according to JIS Z0208. Table 1 shows the test results.

(Test 2)
The face material obtained by the above method was exposed to the outdoors for 6 months, and the change in appearance of the surface of the face material was observed. B>C>D; inferior). Table 1 shows the test results. In Examples 1 to 6 (face materials 1 to 6), the antifouling property was superior to that of Comparative Examples 1 to 3 (face materials 7 to 9).

(Test 3)
After the face materials of Examples 1 to 6 (face materials 1 to 6) were wound around a cylinder with a diameter of 150 mm, the occurrence of cracks on the surface was checked. The evaluation was made on a four-grade scale (excellent; A>B>C>D; inferior), with A indicating that no cracking was observed. Table 1 shows the test results. Examples 1-5 (face materials 1-5) had sufficient flexibility.

Claims (3)

A surface material having moisture permeability,
Having a moisture-permeable pattern layer and a moisture-permeable transparent layer covering the surface of the pattern layer,
The pattern layer is formed of a pattern layer composition containing granular inorganic particles and an acrylic silicone resin,
The transparent layer is formed of a transparent layer composition containing a carboxyl group-containing acrylic silicone resin having a glass transition temperature of 30 to 80° C.,
The transparent layer composition forms a film having a contact angle with water of 60 to 110°.
A surface material having moisture permeability (excluding a laminate in which a base layer and a design layer are laminated in order on the back surface of a transparent glass plate). The moisture permeability according to claim 1, wherein the transparent layer is formed from a transparent layer composition containing a carboxyl group-containing acrylic silicone resin having a glass transition temperature of 30 to 80 ° C. and a cross-linking agent. Infill with. 2. The acrylic silicone resin contained in the pattern layer has a lower glass transition temperature than the carboxyl group-containing acrylic silicone resin having a glass transition temperature of 30 to 80° C. contained in the transparent layer. 3. The surface material having moisture permeability according to 2.