JP2021050515A - Film laminate body - Google Patents

Abstract

To provide a film laminate body having both moisture permeability, anti-contamination properties, etc.SOLUTION: Provided are: 1. a film laminate body which is characterized by having a transparent film on a surface of a moisture-permeable material, and being formed by a composition containing a resin having a glass transition temperature of 30 to 80°C and having a contact angle with water is 60 to 110°; 2. the film laminate body described in 1. which is characterized by being formed by a composition containing a resin having a glass transition temperature of 30 to 80°C and a cross-linking agent; and 3. the film laminate body described in 1. or 2. which is characterized that the resin in the transparent film contains an acrylic silicone resin.SELECTED DRAWING: None

Description

The present invention relates to a novel coating laminate. The coating laminate of the present invention can be preferably applied as a constituent of an outer skin (for example, an exterior surface) of a building, a civil engineering structure, or the like.

Conventionally, as a material constituting an outer skin (for example, an exterior surface, etc.) of a building, a civil engineering structure, or the like, a material having moisture permeability is known (for example, Patent Document 1 and the like).

According to such a material, the water vapor generated on the back surface (base material side) can be discharged to the front surface side (outside), and the swelling of the material itself, 剝 and the like can be suppressed. However, contaminants are likely to adhere to the surface of the material described in Patent Document 1, and the initial aesthetic appearance may be impaired.

On the other hand, Patent Document 2 describes that a hydrophilic transparent film is provided on the surface of a building material in order to impart a contamination prevention function. By providing such a hydrophilic transparent film on the surface of the material of Patent Document 1, it can be expected to impart the effect of suppressing the adhesion of pollutants while making the best use of the appearance of the moisture permeable material.

Japanese Unexamined Patent Publication No. 7-1192272 Japanese Unexamined Patent Publication No. 2009-136727

However, a moisture-permeable material such as Patent Document 1 is often imparted with moisture permeability due to the presence of fine pores on its surface or inside. If a hydrophilic transparent film is present on the surface of such a material, the substance causing the contamination easily permeates into the fine pores, which in turn promotes the progress of the contamination, which may spoil the aesthetic appearance of the moisture permeable material. ..

The present invention has been made in view of such problems, and an object of the present invention is to obtain a film laminate having both moisture permeability, contamination prevention property, and the like.

As a result of diligent studies to achieve the above object, the present inventor has come up with a film laminate having a specific transparent film on the surface of a moisture-permeable material, and has completed the present invention.

That is, the present invention has the following features.
1. 1. A coating laminate having a transparent coating on the surface of a moisture-permeable material.
The transparent film is a film laminate characterized by containing a resin having a glass transition temperature of 30 to 80 ° C. and being formed of a composition having a contact angle of the film with water of 60 to 110 °.
2. The transparent film is characterized by being formed of a composition containing a resin having a glass transition temperature of 30 to 80 ° C. and a cross-linking agent. The film laminate according to the description.
3. 3. The resin in the transparent film contains an acrylic silicone resin. Or 2. The coating laminate according to.

The coating laminate of the present invention can exhibit excellent performance in terms of moisture permeability, antifouling property, etc., and can maintain the initial aesthetic appearance for a long period of time.

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

The coating laminate of the present invention has a specific transparent coating on the surface of the moisture-permeable material. It is desirable that such a coating laminate constitutes an outer skin of a building, a civil engineering structure, or the like. The outer skin referred to here is, for example, an exterior surface of a building, a civil engineering structure, or the like, and is a part exposed to the outdoor environment and affected by rainfall, sunlight, outside air, etc. (for example, wall surface, roof, eaves, rooftop, door). , Pillars, foundation beams, etc.).

As the moisture permeable material, a material having a property of allowing water vapor to pass through can be used. Specifically, examples of the breathable material include breathable base materials such as concrete, mortar, and wood, lightweight cellular concrete board, gypsum board, slate board, caucal board, wood wool cement board, ceramic siding board, and plywood. Breathable boards such as foamed foam boards, various moisture permeable sheets, moisture permeable coatings, and the like can be mentioned. As the moisture-permeable sheet or the moisture-permeable coating film, for example, a moisture-permeable material having an appearance such as plaster-like, earthen wall-like, stone-like, sandstone-like, or wood-like can be used. These can be used alone or in combination of two or more, and may be, for example, a moisture permeable base material and / or a moisture permeable board on which a moisture permeable sheet and / or a moisture permeable coating film is laminated. ..

The transparent film in the present invention covers the surface side of the moisture-permeable material. The transparent film contains a resin having a glass transition temperature (hereinafter, also referred to as "Tg") of 30 to 80 ° C., and a composition having a contact angle of the film with water of 60 to 110 ° (hereinafter, "composition for transparent film"). It can also be formed by). The transparent film formed by such a composition utilizes the aesthetic appearance of the moisture-permeable material and contributes to the improvement of antifouling property and the like.

The composition for a transparent film 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 Tg is at least the above lower limit value, the antifouling property can be enhanced. Further, when Tg is not more than the above upper limit value, it is possible to prevent cracking of the transparent film while improving the contamination prevention property, and it is possible to maintain the aesthetic appearance of the moisture permeable material for a long period of time.

The transparent coating composition forms a coating having a contact angle with water of 60 to 110 ° (preferably 70 to 105 °, more preferably 75 to 100 °). When this contact angle is at least the above lower limit value, it is possible to suppress the penetration of pollutants and enhance the anticontamination property. When the contact angle is not more than the above upper limit value, streak contamination due to rainfall or the like can be suppressed. The contact angle is the angle formed by the water droplets on the surface of the coating film formed by the transparent coating composition when the water droplets are dropped on the surface of the coating film, and is a value measured by a contact angle meter.

As the resin in the composition for a transparent film, a resin having a transparent film can be used. Examples of the form of such a resin include a solvent-soluble resin, a non-aqueous dispersion resin, a solvent-free resin, an aqueous dispersion resin, a water-soluble resin, and the like. Among them, an aqueous dispersion resin (resin emulsion). ) Is preferable. Examples of the type of resin include acrylic resin, urethane resin, epoxy resin, vinyl chloride resin, vinyl acetate resin, acrylic silicon resin, fluororesin, silicon resin, and the like, or a composite thereof. These can be used alone or in combination of two or more.

The average particle size of the water-dispersed resin is preferably 150 nm or less, more preferably 30 to 130 nm, and further preferably 40 to 100 nm. The water-dispersible resin having such an average particle size is suitable in terms of stain prevention, improvement of moisture permeability, and the like. The average particle size of the water-dispersed resin is a value measured using a dynamic light scattering type particle size distribution measuring device.

The transparent coating composition preferably contains a cross-linking agent in addition to the above-mentioned resin. In such an embodiment, a transparent film 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, a film having a three-dimensional crosslinked structure is formed by the reaction between the resin and the crosslinking agent, and it is possible to improve physical properties such as antifouling property 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 preferable.

Examples of the resin having a reactive functional group include a carboxyl group, a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group, a hydroxyl group, an isocyanate group, a carbonyl group, a hydrazide group, an epoxy group, an amino group, an alkoxysilyl group and the like. Those having one or more reactive functional groups selected can be used. As the cross-linking agent, one that can react with the reactive functional group of such a resin may be used in combination. Examples of the combination of reactive functional groups include 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, and an epoxy group and an amino. Examples thereof include a combination of groups, alkoxysilyl groups and the like, and one or more of these can be used.

When the resin in the transparent coating composition has a carboxyl group, as the cross-linking agent, for example, a compound having one or more reactive functional groups selected from a carbodiimide group, an epoxy group, an oxazoline group and the like can be used. Among these, examples of the cross-linking agent having a carbodiimide group include JP-A-10-60272, JP-A-10-316930, JP-A-11-60667, JP-A-2000-7642, and JP-A-2000-. Examples thereof include those described in JP-A-119539, JP-A-2000-31935, JP-A-2013-112755, JP-A-2016-196612, JP-A-2016-196613, WO2017 / 6950, and the like. .. Examples of the cross-linking agent having an epoxy group 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. Examples thereof include ether, diglycerol polyglycidyl ether, polyhydroxyalkane polyglycidyl ether, sorbitol polyglycidyl ether and the like. Examples of the cross-linking agent having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-. Examples thereof include a resin obtained by copolymerizing a polymerizable oxazoline compound such as oxazoline with a monomer copolymerizable with the compound. These can be used alone or in combination of two or more.

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

The ratio of the cross-linking agent is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 20 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 transparent coating composition. is there. With such a ratio, both moisture permeability and antifouling performance can be sufficiently enhanced.

As the resin in the composition for a transparent film, a resin containing an acrylic silicone resin is preferable from the viewpoint of moisture permeability, contamination prevention property, and the like. As the acrylic silicone resin, for example
(1) A synthetic resin obtained by copolymerizing a group of monomers containing a (meth) acrylic acid alkyl ester and a reactive silyl group-containing monomer.
(2) Silicone in a resin obtained by copolymerizing a (meth) acrylic acid alkyl ester and a monomer group containing at least one monomer selected from a reactive silyl group-containing monomer, a hydroxyl group-containing monomer, and a carboxyl group-containing monomer. 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.
And so on. In the present invention, the acrylic acid alkyl ester and the methacrylic acid alkyl ester are collectively referred to as (meth) acrylic acid alkyl ester. The monomer is a compound having a polymerizable unsaturated double bond. The acrylic resin is a synthetic resin obtained by polymerizing a group of monomers containing a (meth) acrylic acid alkyl ester.

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

The 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 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 are preferable.

The reactive silyl group-containing monomer in (1) and (2) above is a compound containing a reactive silyl group and a polymerizable double bond, and is, for example, 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 Examples thereof include methoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethyl vinyl ether, methyldimethoxysilylpropyl vinyl ether and the like. One type or two or more types can be used.

Examples of the hydroxyl group-containing monomer in (2) above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether and the like. One or more of these 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, itaconic anhydride, and the like, and one or two of these. More than seeds can be used.

As the silicon compound in the above (2) and (4), those having one or more reactive silyl groups in one molecule (excluding those having a polymerizable double bond) are used, for example, 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, methylphenyldi Chlorosilanes such as chlorosilane; acetoxysilanes such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane, etc., and one or more of these are used. be able to. Further, a siloxane compound can also be used as the silicon compound. Examples of the siloxane compound include cyclic siloxane compounds, linear siloxane compounds, branched siloxane compounds, and derivatives thereof. Among these, examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

Examples of the combination of the functional groups in the above (3) and (4) include a hydroxyl group and an isocyanate group, an amino group and an isocyanate group, a carboxyl group and an epoxy group, an amino group and an epoxy group, and an alkoxysilyl group. A silane coupling agent is, for example, a compound having at least one or more reactive silyl groups and other substituents in one molecule, and 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 can be mentioned, and one or more of these can be used.

In the above (1) to (4), components other than the above, for example, amino group-containing monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate; (meth) acrylamide and ethyl (meth) acrylamide. Amid group-containing monomer such as acrylonitrile; nitrile group-containing monomer such as acrylonitrile; epoxy group-containing monomer such as glycidyl (meth) acrylate; aromatic vinyl-based monomer such as styrene, methylstyrene, chlorostyrene, vinyltoluene; styrenesulfonic acid, vinyl Sulphonic acid-containing vinyl monomer such as sulfonic acid; Acid anhydride such as maleic anhydride and itaconic anhydride; Chlorine-containing monomer such as vinyl chloride, vinylidene chloride and chloroprene; ethylene glycol monoallyl ether, propylene glycol monoallyl ether and diethylene glycol mono An alkylene glycol monoallyl ether such as allyl ether; a vinyl ester-based monomer 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.

The composition for a transparent film may include a cross-linking agent in addition to such an acrylic silicone resin. In this case, an acrylic silicon 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, and one or two of these. The above can be used.

The composition for a transparent coating in the present invention may contain a surfactant. In such an embodiment, both moisture permeability and antifouling performance can be further enhanced. Although the mechanism of action is not clear, the fine pores of the moisture-permeable material are easily filled by the transparent coating composition, which effectively suppresses the penetration of pollutants, and the fine pores filled in this way. It is presumed that in the pores, moisture permeability is imparted by the appropriate hydrophilicity of the surfactant, and the like contributes.

As such a surfactant, a compound having a structure having both a hydrophilic portion and a hydrophobic portion in the molecule can be used, and for example, a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used. , Amphoteric surfactant and the like. These can be used alone 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 transparent coating composition. Is. With such a ratio, both moisture permeability and antifouling performance can be sufficiently enhanced.

In addition to the above-mentioned components, the composition for a transparent film includes, for example, a matting agent, a coloring pigment, a bright pigment, a phosphorescent pigment, a fluorescent pigment, an aggregate, a fiber, a plasticizer, a film-forming auxiliary, and an algae-proofing agent. It contains antibacterial agents, deodorants, adsorbents, flame retardants, thickeners, defoaming agents, UV absorbers, light stabilizers, antioxidants, silane coupling agents, catalysts, solvents, water, etc. May be good. When the composition for a transparent film contains a coloring pigment, a colored transparent film can be formed. It is necessary to be careful to use the photocatalytic titanium oxide, colloidal silica, etc. within a range that does not significantly impair the effects of the present invention, and an embodiment in which these are not used is also preferable.

The coating laminate of the present invention can be obtained by coating a moisture-permeable material with such a transparent coating composition. Such a painting process can be performed by on-site painting, factory painting, or the like.

When performing on-site painting, a known instrument (for example, spray, roller, brush, etc.) is used to paint the transparent coating composition on the moisture-permeable material installed at the site such as a building or civil engineering structure. The coating laminate can be obtained by drying at room temperature (heating if necessary).

When factory coating is performed, a coating laminate is obtained by coating the moisture-permeable material with the transparent coating composition in the factory. The coating of the transparent coating composition in the factory may be applied using a known instrument (for example, a spray, a roller, a brush, a coater, etc.), and the drying may be performed at room temperature or in a heating environment. The coating laminate obtained by such a method can be carried to the site of a building, a civil engineering structure, or the like, and installed so as to constitute the outer skin thereof.

In the present invention, it is desirable that the transparent film formed by the transparent film composition is provided on the entire surface of the moisture permeable material. The weight per unit area (in terms of solid content) of the transparent film is preferably 5 to 200 g / m ² , and more preferably 10 to 100 g / m ² .

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

(Composition for transparent film 1)
Resin 1 (carboxyl group-containing acrylic silicon resin emulsion, Tg 66 ° C., average particle diameter 90 nm, 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 interface) Activator, solid content 30% by weight) 0.2 parts by weight, and 4 parts by weight of other additives (ultraviolet absorber, light stabilizer, thickener, defoamer, etc.) are uniformly mixed by a conventional method to make it transparent. The coating composition 1 was obtained. The contact angle of the transparent coating composition 1 with water was 82 °. The contact angle with water is 14 days in an atmosphere of a transparent film composition coated on an aluminum plate with a thickness of 150 μm, a temperature of 23 ° C., and a relative humidity of 50% (hereinafter, also referred to as “standard state”). It is a value measured by using a contact angle meter for a test piece obtained by drying and curing (the same applies hereinafter).

(Composition for transparent film 2)
Resin 1 (same as above) 200 parts by weight, film-forming aid 18 parts by weight, water 20 parts by weight, cross-linking agent (carbodiimide group-containing cross-linking agent, solid content 40% by weight) 10 parts by weight, and other additives (ultraviolet absorber, light Stabilizer, thickener, defoaming agent, etc.) 4 parts by weight were uniformly mixed by a conventional method to obtain a transparent film composition 2. The contact angle of the transparent coating composition 2 with water was 84 °.

(Composition for transparent film 3)
Resin 1 (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, and other additives (ultraviolet absorber) , Light stabilizer, thickener, defoamer, etc.) 4 parts by weight were uniformly mixed by a conventional method to obtain a transparent film composition 3. The contact angle of the transparent coating composition 3 with water was 81 °.

(Composition for transparent film 4)
Resin 2 (carboxyl group-containing acrylic silicon resin emulsion, Tg 57 ° C., average particle diameter 90 nm, 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, 10 parts by weight of a cross-linking agent (same as above), and 4 parts by weight of other additives (ultraviolet absorber, light stabilizer, thickener, defoamer, etc.) are uniformly mixed by a conventional method for a transparent film. Composition 4 was obtained. The contact angle of the transparent coating composition 4 with water was 82 °.

(Composition 5 for transparent coating)
Resin 3 (carboxyl group-containing acrylic silicon resin emulsion, Tg 48 ° C., average particle diameter 90 nm, 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, 10 parts by weight of a cross-linking agent (same as above), and 4 parts by weight of other additives (ultraviolet absorber, light stabilizer, thickener, defoamer, etc.) are uniformly mixed by a conventional method for a transparent film. Composition 5 was obtained. The contact angle of the transparent coating composition 5 with water was 84 °.

(Composition for transparent film 6)
Resin 4 (acrylic resin emulsion, Tg 28 ° C., average particle size 90 nm, solid content 50% by weight) 200 parts by weight, film-forming aid 18 parts by weight, water 20 parts by weight, and other additives (ultraviolet absorber, light stabilizer, (Thickener, antifoaming agent, etc.) 4 parts by weight were uniformly mixed by a conventional method to obtain a transparent film composition 6. The contact angle of the transparent coating composition 6 with water was 86 °.

(Composition for transparent film 7)
Resin 5 (coloidal silica composite emulsion, average particle size 120 nm, solid content 40% by weight) 250 parts by weight, film-forming aid 18 parts by weight, surfactant (same as above) 4 parts by weight, and other additives (ultraviolet absorber, light Stabilizer, thickener, defoamer, etc.) 4 parts by weight were uniformly mixed by a conventional method to obtain a transparent film composition 7. The contact angle of the transparent coating composition 7 with water was 38 °.

(Composition for transparent film 8)
Resin 6 (acrylic resin emulsion, Tg 48 ° C., average particle size 90 nm, solid content 50% by weight) 200 parts by weight, water repellent (dimethylsiloxane compound, solid content 50% by weight) 50 parts by weight, film forming aid 18 parts by weight , 20 parts by weight of water and 4 parts by weight of other additives (ultraviolet absorber, light stabilizer, thickener, defoamer, etc.) were uniformly mixed by a conventional method to obtain a transparent film composition 8. The contact angle of the transparent coating composition 8 with water was 116 °.

(Example 1)
The transparent coating composition 1 was spray-coated on the entire surface of the moisture-permeable sheet (sandstone-like cured product mainly composed of inorganic particles, resin, etc., thickness 2 mm), and at room temperature (23 ° C.). ) Was cured to provide a transparent film (solid content weight 40 g / m ² per unit area) to prepare a test piece.

(Examples 2 to 5, Comparative Examples 1 to 3)
As the transparent coating composition, a test piece was prepared in the same manner as in Example 1 except that the compositions shown in Table 1 were used instead of the transparent coating composition 1.

(Test 1)
The moisture permeability of each test piece obtained by the above method was measured according to JIS Z0208. The test results are shown in Table 1.

(Test 2)
Each test piece obtained by the above method was exposed outdoors for 6 months, the appearance change on the surface of the test piece was observed, and the one with a slight degree of stain was designated as "A"(excellent; A). >B>C>D; inferior). The test results are shown in Table 1.

Claims (3)

A coating laminate having a transparent coating on the surface of a moisture-permeable material.
The transparent film is a film laminate characterized by containing a resin having a glass transition temperature of 30 to 80 ° C. and being formed of a composition having a contact angle of the film with water of 60 to 110 °. The film laminate according to claim 1, wherein the transparent film is formed of a composition containing a resin having a glass transition temperature of 30 to 80 ° C. and a cross-linking agent. The coating laminate according to claim 1 or 2, wherein the resin in the transparent coating contains an acrylic silicone resin.