JPH01320282A - Method for coating cement-based base material - Google Patents

Abstract

PURPOSE:To improve the durability of a cement-based base material by coating the material with a specified solvent-type coating material. CONSTITUTION:From 1 to 100pts.wt. of a curing agent (e.g., hexamethylene diisocyanate) and/or 0.005-10pts.wt. of a hydrolysis-condensation catalyst (e.g., butylamine) for a hydrolyzable silyl group are incorporated, as required, into 100pts.wt. of a mixture consisting of 10-90wt.% of the polymer having a hydrolyzable silyl group shown by the formula [R1 is H, 1-10 C alkyl, aryl, and aralkyl, X is halogen, alkoxy, acyloxy, etc., and (a) is 0-2] on the terminal of the side chain and/or principal chain and having 2,000-600,000 weight average mol.wt. and 90-10wt.% of a fluoroolefinic polymer having 5,000-600,000 weight average mol.wt. and not contg. a hydrolyzable silyl group to obtain a solvent-type coating material. The coating material is applied on the cement-based base material undercoated, if necessary, and dried at room temp. or 60-250 deg.C.

Description

Detailed Description of the Invention [Objective of the Invention] (Industrial Field of Application) The present invention relates to a method of coating a cement base material, and more specifically, a coating method for coating a cement base material directly or in advance with an undercoat paint. A top coat is applied to a cement base material coated with a solution-type paint that contains as essential components both a vinyl polymer containing a hydrolyzable silyl group and a fluoroolefin polymer that does not contain a hydrolyzable silyl group. The present invention relates to a new coating method that can form a coating film with extremely high durability.

(Prior art and its problems) Cement-based materials such as concrete, asbestos slate, mortar, ALC board, calcium silicate-based materials, and plaster/slab-based materials are widely used in architecture and building material applications, and are used to impart cosmetic properties and For the purpose of improving durability, cross-linked paints such as acrylic urethane paints and acrylic melamine paints have been applied to the surface via an intermediate layer. However, such paints have the drawback that they have insufficient weather resistance and thus lose their gloss in a relatively short period of time, impairing their cosmetic properties.

In order to improve these defects, a coating such as an epoxy resin coating or a phenol alkyd resin coating is applied as an intermediate layer, and then a fluoroolefin polymer containing a functional group such as a hydroxyl group or an epoxy group and a curing agent are used as a top coating. A method of painting with paints made of polyisocyanate compounds, polyamine compounds, etc. has been proposed (Special Publications Publication No. 6).
2-16141). However, even in such a coating method, if a water-based paint is used as the paint that forms the intermediate layer, and if the intermediate layer is insufficiently dried and contains a large amount of water, the hardening will be inhibited by the moisture, so that it will not harden sufficiently. It has the disadvantage that a hard coating film is not formed and the gloss and adhesion deteriorate in a relatively short period of time. In addition, if a cement base material with a high moisture content is used as a base material, the above-mentioned problem will occur even if the paint is applied directly to such a base material, and if it is painted through an intermediate layer based on an organic solvent-based paint. It also has the disadvantage of a decrease in durability due to inhibition of curing by moisture. Furthermore, even when a so-called lacquer-type paint that does not contain a hardening agent is applied, there is a drawback that the adhesion decreases due to long-term exposure.

(Problem M to be solved by the invention) As a result of intensive research to improve this drawback, the present inventors have discovered that water can be added directly to a cement base material or to a cement base material coated with an undercoat in advance. By applying a solution-type paint as an overcoat that contains both a vinyl polymer containing a degradable silyl group and a fluoroolefin polymer not containing a hydrolyzable silyl group as essential components, long-term exposure can be avoided. The present inventors have discovered that coatings with excellent adhesion and extremely high durability can be obtained even after coating, and have completed the present invention.

[Structure of the invention]

(Means for Solving the Problems) To summarize the present invention, the present invention consists of a vinyl polymer (A) containing a hydrolyzable silyl group and a fluoroolefin polymer (A) containing no hydrolyzable silyl group. This invention relates to a method for coating a cement-based substrate, characterized in that a solution-type paint comprising B) as an essential component is applied to a cement-based substrate or a cement-based substrate to which an undercoat has been applied in advance. 6 Below, the configuration of the present invention will be explained in detail.

First, the hydrolyzable silyl group-containing vinyl polymer (A) component used in the present invention will be explained.

Vinyl polymer (A) containing the hydrolyzable silyl
The component has a general formula at the end of the side chain and/or main chain.

(X)3-a (Rt)asf (wherein, Ro is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a halogen atom,
Alkoxy group, acyloxy group, iminoxy group, phenoxy group, mercapto group, amino group, alkenyloxy group,
Alkoxyalkoxy group.

(a represents O or an integer of 1 to 2) A polymer containing a hydrolyzable silyl group represented by the following is commonly referred to.

Specific examples of such hydrolyzable silyl group-containing vinyl polymers (A) include hydrolyzable silyl group-containing fluoroolefin polymers, hydrolyzable silyl group-containing acrylic polymers, and hydrolyzable silyl group-containing acrylic polymers. Examples include carboxylic acid vinyl ester polymers.

The hydrolyzable silyl group-containing fluoroolefin polymers described above are disclosed in JP-A-62-81409 and JP-A-61.
It can be synthesized by methods such as those disclosed in Japanese Patent Application Laid-Open No. 14713-14713 and Japanese Patent Application Laid-open No. 149762-1982. In addition, hydrolyzable silyl group-containing acrylic polymers were disclosed in Japanese Patent Application Laid-open No. 57
It can be synthesized by methods such as those disclosed in Japanese Patent Application Laid-open No. 58-38766. In addition, for hydrolyzable silyl group-containing carboxylic acid vinyl ester polymers, the main component is carboxylic acid vinyl ester monomers, and copolymerizable monomers other than (meth)acrylic esters are used. It can be synthesized by introducing a hydrolyzable silyl group by a known and commonly used method.

The weight average molecular weight of the hydrolyzable silyl group-containing vinyl polymer (A) component obtained in this way is:
2,000 from the viewpoint of polymer film-forming properties and solubility in solvents.
0-600,000, preferably 4,000-300
,000 is desirable.

Next, the fluoroolefin polymer (B) component not containing a hydrolyzable silyl group used in the present invention includes vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, promotrifluoroethylene, and chlorotrifluoroethylene. At least a fluoroolefin monomer selected from the group consisting of fluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per)fluoroalkyl trifluorovinyl ether [wherein the (per)fluoroalkyl group has 1 to 18 carbon atoms] It is a polymer obtained by polymerizing one type of fluoroolefin monomer, and the amount of the fluoroolefin monomer used is preferably in the range of 10 to 100% by weight.

In the present invention, other copolymerizable monomers can be used when preparing the polymer (B) component from these fluoroolefin monomers. Such copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprate, vinyl caprylate, vinyl persate, vinyl laurate or stearate. Vinyl esters of linear or branched aliphatic carboxylic acids such as vinyl; alicyclic carboxylic acid vinyl esters such as cyclohexanecarboxylic acid vinyl ester; benzoic acid vinyl ester, p-t-butylbenzoic acid vinyl ester, Aromatic carboxylic acid vinyl esters such as salicylic acid vinyl ester; such as 2-trimethylsilyloxyethyl vinyl ether, 3-trimethylsilyloxypropyl vinyl ether, 4-trimethylsilyloxybutyl vinyl ether, 2-trimethylsilyloxyethyl methacrylate or 2-trimethylsilyloxyethyl acrylate Vinyl monomers containing a trialkyloxy group; monomers containing a carboxylic acid anhydride group such as maleic anhydride, itaconic anhydride or trimellitic anhydride monovinyl ester; vinyl isocyanate, allyl isocyanate or 2- Isocyanate: Monomers containing an isocyanate group such as methyl methacrylate; monomers containing a trialkylsilyloxycarbonyl group such as vinyl 4-trimethylsilyloxycarbonylpentanoate, trimethylsilyl methacrylate or trimethylsilyl acrylate; hydroxyethyl Hydroxy alkyl vinyl ethers such as vinyl ether, hydroxypropyl vinyl ether or hydroxybutyl vinyl ether; linear or branched such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether or cyclohexyl vinyl ether aliphatic or alicyclic vinyl ethers; monomers having epoxy groups such as glycidyl ether and glycidyl (meth)acrylate; acrylic acid, methacrylic acid.

Carboxyl group-containing monomers such as maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, monoethyl maleate, monobutyl maleate, monobutyl fumarate, monobutyl itaconate, monobutyl adipate, monovinyl sebacate, etc. Vinyl monomers containing basic nitrogen such as dimethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether, N-dimethylaminopropyl (meth)acrylamide, and dimethylaminoethyl (meth)acrylate; ethylene, propylene, butene- α-olefins such as 1 or hexene-1; halogenated olefins other than the above-mentioned fluoroolefin monomers such as vinyl chloride or vinylidene chloride; aromatic vinyl monomers such as styrene, α-methylstyrene or vinyltoluene; Class; Methyl (meth)acrylate, Ethyl (meth)acrylate,
Butyl (meth)acrylate, cyclohexyl (meth)
(meth)acrylic acid esters such as acrylate, β-hydroxyethyl (meth)acrylate or phosphate ester of β-hydroxyethyl (meth)acrylate; also (meth)acrylonitrile, (meth)acrylamide, N-methylol (meth)acrylate; ) acrylamide,
There is N-butoxymethyl (meth)acrylamide.

Polymerization is carried out in the presence of the above-mentioned monomers using a radical polymerization initiator, using known techniques such as bulk polymerization, solution polymerization, and emulsion polymerization, in batch, anti-continuous, or continuous operations. That's fine.

Such radical polymerization initiators include diacyl peroxides such as acetyl peroxide or benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide; hydrogen peroxide, t-butyl hydroperoxide or cumene hydro Hydroperoxides such as peroxide; dialkyl peroxides such as di-t-butyl peroxide or dicumyl peroxide; alkyl peroxy esters such as t-butyl peroxy acetate or t-butyl peroxy pivalate; Azo initiators such as azobisisobutyronitrile or azobisisovaleronitrile; or persulfates such as ammonium persulfate or potassium persulfate are used, and if necessary, sodium bisulfite or sodium pyrosulfite is used. Inorganic reducing agents such as or organic reducing agents such as cobalt naphthenate or dimethylaniline may also be used.

The solvents used in the polymerization reaction include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; esters such as methyl acetate, ethyl acetate or butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or methyl amyl. Ketones such as ketones; amide solvents such as dimethylformamide or dimethylaradamide; alcoholic solvents such as methanol, ethanol, i-propanol, 5ee-butanol or ethylene glycol monoalkyl ether, or mixtures thereof are used.

In this polymerization, various chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol or α-methylstyrene dimer can also be used as molecular weight regulators.

The weight average molecular weight (wood) of the fluoroolefin polymer (B) that does not contain a hydrolyzable silyl group obtained in this way is 5,000 to 5,000 from the viewpoint of film-forming properties, solvent solubility, and workability of the polymer. 600,000 or even 7,000
0 to 300,000 is preferred.

The ratio of the vinyl polymer (A) containing a hydrolyzable silyl group and the fluoroolefin polymer (B) not containing a hydrolyzable silyl group used in the present invention is usually 10/ It is in the range of 90 to 90/10, more preferably in the range of 15/85 to 85/15.

In the present invention, the component (A) and/or (B)
) hydroxyl group, epoxy group, amino group in the ingredients.

When reactive functional groups such as carboxyl groups, phosphoric acid groups, amide groups, trialkylsilyloxy groups, and trialkylsilyloxycarbonyl groups are contained, a curing agent that can react with these functional groups ( C) can be blended, and by blending the curing agent, the crosslinking density of the coating film can be further increased and the coating film performance can be improved. In addition, in the present invention, when using such a curing agent (C), a curing catalyst that promotes the reaction with the reactive functional group and/or a catalyst for the hydrolysis-condensation reaction of the hydrolyzable silyl group ( By adding D), the curing of the coating film can be further accelerated.

Typical curing agents (C) that can react with the reactive functional groups constituting the top coat include polyisocyanate compounds, block polyisocyanate compounds, amino resins, and polyisocyanate compounds when the reactive functional groups are hydroxyl groups. 1 When the reactive functional group is a carboxyl group, use a polyepoxy compound, polyaziridine compound, polyisocyanate compound or block polyisocyanate compound, and when the reactive functional group is an amino group, use a polyepoxy compound. , a compound having both an epoxy group and a hydrolyzable silyl group in one molecule, a blocked isocyanate compound or a polyisocyanate compound, and when the reactive functional group is an epoxy group, a polycarboxy compound, a polycarboxylic acid anhydride compound, a polyketimine compound. Or, if the reactive functional group is a trialkylsilyloxy group, use a polyisocyanate compound, blocked isocyanate compound, amino resin, or polycarboxylic acid anhydride compound. In the case of carbonyl compounds, polyepoxy compounds, polyaziridine compounds, polyisocyanate compounds or block polyisocyanates (
- When the reactive functional group is a carboxyl group, use a polyepoxy compound, polyaziridine compound, polyisocyanate compound, or blocked polyisocyanate compound, and when the reactive functional group is an amide group, use a polyisocyanate compound, amino A resin or a blocked polyisocyanate compound can be blended.

In addition, when the 1-reactive functional group is a trialkylsilyloxy group, the trialkylsilyloxy group is hydrolyzed by moisture in the air after coating to generate a hydroxyl group, and a curing agent that can react with the hydroxyl group as described above. It is possible to harden it by. Furthermore, when the reactive functional group is a trialkylsilyloxycarbonyl group, the trialkylsilyloxycarbonyl group is hydrolyzed by moisture in the air to generate a carboxyl group after coating, so it does not react with the carboxyl group as described above. The resulting curing agent can be blended for curing. When the reactive functional group is a hydroxyl group, carboxyl group, trialkylsilyloxy group, or trialkylsilyloxycarbonyl group, aluminum,
Alkoxides or complex compounds of metals such as titanium, zirconium, and silicon may also be blended as curing agents.

Typical examples of the polyisocyanate compound as the curing agent (C) include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylene diisocyanate and isophorone diisocyanate; or tolylene diisocyanate,
4. Organic diisocyanates such as aromatic diisocyanates such as 4'-diphenylmethane diisocyanate;
Alternatively, adducts of these organic diisocyanates and polyhydric alcohols, as well as polymers of the above-mentioned organic diisocyanates and isocyanate/biuret compounds, etc. Isocyanate compounds are particularly preferred. Examples of typical commercially available polyisocyanate compounds include "Burnock, DN-950, -980"
, -9814 [Dainippon Ink Chemical Industry am product],
[Dismodule NJ (West German Bayer product)
, "Takenate D-14ONJ (Takeda Pharmaceutical @Product)", "Coronate EHJ [Japan Polyurethane Industries@Product]", "Duranate 24A-90cxJ (Kakasei Kogyo ■Repair product)" or vinyl polymers containing isocyanate groups. be.

On the other hand, typical examples of blocked polyisocyanate compounds refer to those obtained by blocking the various polyisocyanate compounds described above with known and commonly used blocking agents, and representative commercially available products of such blocked polyisocyanate compounds. For example, "Parnock B7-
671J (Dainippon Ink & Chemicals Product), Takenate B -815-NJ [Takeda Pharmaceutical Product],
“Azoitol (ADDITOL) VXL-80J
(Hoechst synthetic product) or “Coronate 2507J
C Nippon Polyurethane Industries ■ product] or a vinyl polymer having a blocked isocyanate group.

Specific examples of polycarboxylic anhydride compounds include trimellitic anhydride, pyromellitic anhydride, and vinyl polymers containing carboxylic anhydride groups.

Specific examples of polyepoxy compounds include ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, sorbitol polyglycidyl ether, phthalic acid glycidyl ester, and vinyl polymers containing epoxy groups.

Specific examples of compounds having both an epoxy group and a hydrolyzable silyl group in one molecule include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriicpropenyloxysilane, or glycidyl methacrylate and γ-glycidoxypropyltrimethoxysilane. There are acrylic copolymers containing methacryloxypropyltrimethoxysilane as an essential heptamer component.

Typical aminoplasts are produced by reacting an amino group-containing compound component such as melamine, urea, acetoguanamine, or benzoguanamine with an aldehyde compound component such as formaldehyde, paraformaldehyde, acetaldehyde, or glyoxal by a known and commonly used method. Condensates obtained by Of course.

Among these, those partially or completely etherified with alcohols C to C4 are preferable, and specific examples of such aminoplasts include hexamethyl etherified methylolmelamine, hexabutyl etherified methylolmelamine, and methylbutyl mixed ether. methylol melamine, methyl ether methylol melamine, butyl ether methylol melamine or 1so-
Examples include butyl etherified methylolmelamine and condensates thereof.

A specific example of a polyaziridine compound is a molar ratio of ethylene glycol diacrylate and ethyleneimine of 1:2.
Examples include adducts, adducts of trimethylolpropane triacrylate and ethyleneimine in a molar ratio of 1:3, and vinyl polymers containing aziridinyl groups.

When using the curing agent (C) component as described above, the amount used is 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, based on 100 parts by weight of the total amount of both components (A) and (B). is good.

In the present invention, when a polyisocyanate compound, a blocked isocyanate compound, or an aminoplast is used as the curing agent (C) component, the curing agent (C) component and the reactive group in the (A) component or (B) component are A curing catalyst can be included to accelerate the reaction.

Typical examples of such curing catalyst components include:

When a (block) polyisocyanate compound is used as the curing agent (C) component, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, triethylamine or dimethylaminoethanol may be used, and amino When using plasto, paratoenesulfonic acid, phosphoric acid, mono- or dialkyl ester of phosphoric acid, or [typically Nacure 155.2500X, Examples include dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, and organic amine block compounds thereof.

In addition, in the present invention, hydrolysis of the hydrolyzable silyl group in component (A) - hydrolysis to promote the condensation reaction -
A condensation reaction catalyst (D) can be used as necessary.

When component (A) or component (B) contains a group that promotes the hydrolysis-condensation reaction of a hydrolyzable silyl group, such as an amino group, a phosphoric acid group, or a sulfonic acid group, the hydrolyzable The curing reaction proceeds without adding the silyl group hydrolysis-condensation catalyst (D) component, and a cured coating film with excellent solvent resistance is formed.

However, if the above groups are not present in component A) or component CB), it is necessary to use component (D) of the hydrolysis-condensation catalyst.

Such a catalyst for hydrolysis-condensation of a hydrolyzable silyl group (D
) Typical components include basic compounds such as butylamine, dibutylamine, hexylamine, t-butylamine, ethylenediamine, triethylamine, inphoronediamine, imidazole, lithium hydroxide, sodium hydroxide, potassium hydroxide, and sodium methylate. Compounds: Tetrapropyl titanate, tetrabutyl titanate, tin octylate, lead octylate, cobalt octylate,
Metal-containing compounds such as zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin maleate; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, mono Acidic compounds such as alkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid ester of β-hydroxyethyl (meth)acrylate, monoalkyl phosphorous acid, and dialkyl phosphorous acid are mentioned, and in particular, dibutyltin diacetate and dibutyltin dioctate.

When adding a catalyst, tin compounds such as dibutyltin dilaurate and dibutyltin malate are preferred.

The amount of the catalyst used is generally 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing vinyl polymer (A).

The solution-type paint containing component (A) and component (B) as essential components used in the present invention may be used as a clear paint, or can be used as a colored paint by blending various coloring materials.

When used as a colored paint, typical colorants include phthalocyanine blue, phthalocyanine green,
Organic pigments such as quinacridone red, carbon black, etc. - Inorganic pigments such as titanium oxide, barium oxide, calcium carbonate, barium carbonate, barium sulfate and various calcined pigments; aluminum, brass, copper, silver, gold,
There are metal powders such as nickel.

When used as a clear paint, it is particularly preferable to add an ultraviolet absorber and/or an antioxidant in order to maintain a high degree of durability.

Ultraviolet absorbers that can be added to clear paints include (A)
It is not particularly limited as long as it is compatible with the component and component (B), and specifically, 2-(2'-hydroxy-5'-methyl-phenyl)benzotriazole, 2-(2'-Hydroxy-3'-t-butyl-
5'-methyl-phenyl)-5-chlorobenzotriazole,2-(2'-hydroxy-3',5'-di-
t-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-4'-n-octoxy.
phenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octyl-phenyl)benzotriazole, 2-(2'-hydroxy-3', 5'-bis(α
, α-dimethylbenzyl)phenyl) -2H-benzotriazole, 2- (3', 5'-di-t-butyl-2'-hydroxyphenyl)benzotriazole,
2(3'-t-butyl-5'-methyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(
3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-
57-t-butylphenyl)benzotriazole, 2-
(2',4'-dihydroxyphenyl)benzotriazole.

Benzotriazole compounds such as 2,4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4
-dimethoxybenzophenone, 2-hydroxy-4-
Methoxy-2'-carboxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecylbenzophenone, 2.2',
4゜4'-Tetrahydroxybenzophenone, 4-dobucyloxy-2-hydroxybenzophenone, 2-hydroxy-4-benzoxybenzophenone.

Benzophenone compounds such as 2-hydroxy-4-methoxy-2'-carboxybenzophenone; phenyl salicylate, p-octylphenyl salicylate,
Salicylic acid derivatives such as pt-butylphenyl salicylate, etc.: N-(2-ethoxyphenyl)-N'-(
4-Indodecylphenyl) ethanediamide, N-(2
-ethoxyphenyl) -N'-(2-ethyl)ethanediamide and other oxalic acid anilide derivatives; octyl 2-cyano-3,3-diphenylacrylate, ethyl 2-cyano-3,3-diphenylacrylate, 2- Cyano
3-phenyl-3-(3,4-dimethylphenyl)acrylic acid-(2-ethylhexyl), 2-cyano-3-(
unsaturated nitrile groups such as p-methoxyphenyl)-3-(3,4-dimethylphenyl)acrylic acid-2-(ethylhexyl), p-methoxy-α-(3,4-xylyl)benzylidenemalononitrile, etc. Contains ultraviolet absorber; other resorcinol monobenzoate, 2.4
-di-t-butylphenyl-3', 5'-di-t-butyl-4'-hydroxybenzoate, [2,2-thiobis(4-t-octylferulate)]-]n-butylamine nickel (If ), nickel dibutyl dithiocarbonate, etc.

Among the above-mentioned ultraviolet absorbers, benzotriazole compounds and hydroxybenzophenone compounds are particularly preferred for their effectiveness in improving durability.

Next, the antioxidant that can be added to the paint in the present invention is not particularly limited as long as it is compatible with component (A) and component (B), and specifically,
4,4'-methylenebis-(2,6-di-t-butylphenol), 2,2'-methylenebis-(4-methyl-
6-t-butylphenol), 1,3.5-)-listyl-2,4,6-tris(3,5-di-t-butyl-4
-hydroxybenzyl)benzene, 1. l,3-)-Lis-(2-methyl-5-t-butyl-4-hydroxyphenyl)propane, 2,2'-ethylidenebis-(4°6-di-t-butylphenol), triethylene glycol bis- 3-(3-t-butyl-4-hydroxy-5
-methylenyl)propionate, 3-(3',5'-
Octadecyl di-t-butyl-4'-hydroxyphenyl)propionate, 2,2'-methylenebis(4-ethyl-6-t-butylphenyl), pentaerythrityl-
Tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 2,6-di-butyl-4-methylphenol, 6-(3'-t-butyl-5'- Methyl-2'-hydroxybenzyl)-4
-t-butyl methylphenylacrylate, 4.4'-
Butylidenebis=(3-methyl-6-t-butylphenol), tetrakis-[methylene-3-(3', 5'
-di-t-butyl-4'-hydroxyphenyl)propionate comethane, N,N'-hexamethylenebis(3
, 5-di-t-butyl-4-hydroxyhydrocinnamamide), 1°6-hexanethiol bis-3-(3'
, 5'-di-t-butyl-4'-hydroxyphenyl)
Propionate, 2,2'-thiodiethylbis-[3
-(3',5'-t-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(3-methyl-6-thi-butylphenol), etc.; bis(1, 2,2゜6.6-bentamethyl-4-piperidyl) sebacate, bis(2,2,6
, 6-tetramethyl-4-piperidyl) sebacate,
l-42-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl] -
4-(3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxy)-2,2,6,6-titramethylpiperidine, 8-benzyl-7゜7,'9.
9-Tetramethyl-3-octyl-1゜3.8-triazaspiro(4,5)undecane-2,4-dione, 4-
Hindered amine compounds such as benzoyloxy-2,2゜6.6-titramethylpiperidine; Organic sulfur compounds such as myristylthiodipropionate, ditridecylthiopropionate, etc.; other 3,5-di, t-butyl-4
-Hydroxybenzyl phosphate diethyl ester, 3.5
-Di-t-butyl-4-hydroxybenzyl phosphate dioctadecyl ester and other phosphoric acid esters.

Among these antioxidants, hindered amine compounds and hindered phenol compounds are particularly preferred from the viewpoint of improving durability.

In the clear paint containing both components (A) and (B) as essential components of the present invention, (A) absorbs such ultraviolet light.

(B) 0.1 to 20 per 100 parts by weight of both components
By adding parts by weight, preferably 0.3 to 15 parts by weight, the antioxidant can be added to the total amount of both components (A) and (B) 1
By adding 0.1 to 10 parts by weight to 0.00 parts by weight, a coated product with excellent durability can be obtained. Moreover, although it is possible to obtain a coated product with excellent durability without adding an ultraviolet absorber and/or an antioxidant to the above-mentioned colored paint, the durability can be further improved by adding these. be able to.

It goes without saying that the solution type paint used in the present invention may contain color separation inhibitors, leveling agents, and other commonly known additives.

Cement bases used in the coating method of the present invention include concrete, asbestos slate, mortar, AL
C board 1 front gypsum rug material, calcium silicate material,
Base materials manufactured using other cement-based raw materials as essential components are also referred to as base materials. In addition, in the method of the present invention, when using a base material that easily leaches out alkaline components, it is necessary to apply an undercoat such as a sealer in advance to prevent the leaching of the alkali components and to improve adhesion to the base material. Particular preference is given to applying paint. Typical examples of such undercoat paints include acrylic urethane resin paints, epoxy resin paints, acrylic lacquer type paints, lacquer type paints based on chlorinated polyolefins such as chlorinated polyethylene or chlorinated polypropylene, and moisture-curing urethane paints. resin paint,
There are acrylic emulsion paints, emulsion paints whose main component is carboxylic acid vinyl ester, etc.

In the present invention, the undercoating paint as described above may be applied by any known and commonly used method such as spray painting, brushing, roller coating, etc. Thereafter, it may be dried at room temperature, or it may be formed into a film by heating at about 60 to 150°C.

In addition, (A) and (B) of the present invention can be applied to a cement base material or a cement base material coated with an undercoat as described above.
To apply a top coat containing both components as essential components, it is sufficient to follow a known and commonly used method such as that used when applying the above-mentioned undercoat. Alternatively, baking may be performed at a temperature of about 60 to 250°C.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition,
In the following, unless otherwise specified, "1 part" is based on weight.

Reference Example 1 [Preparation of vinyl polymer containing hydrolyzable silyl group] 400 parts of toluene and 400 parts of n-butanol were charged into a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reflux condenser tube. , the temperature was raised to 105° C. under a nitrogen atmosphere. Then, at the same temperature, 700 parts of methyl methacrylate,
1.20 parts of n-butyl methacrylate, 110 parts of n-butyl acrylate, 70 parts of γ-methacryloyloxypropyltrimethoxysilane, 200 parts of toluene,
Mixture method (Fly) consisting of 6 parts of azobisisobutyronitrile, 810 parts of t-butylperoxyoctoate, and 5 parts of monobutylperoxybenzoate (Fly) A vinyl polymer containing 20,000 trimethoxysilyl groups. A solution of was obtained. Hereinafter, this will be abbreviated as A-1.

Reference Example 2 [Same as above] Beover 10 (vinyl ester of branched fatty acid C1, manufactured by Shell, Netherlands) 4 as a monomer to be copolymerized
00 parts, vinyl pivalate 350 parts, vinyl acetate 150 parts
The same reaction as in Reference Example 1 was carried out except that 100 parts of vinyltrimethoxysilane (hereinafter abbreviated as VTMS) was used to obtain a vinyl polymer containing trimethoxysilyl groups with a non-volatile content of 49% and a mass of 35,000 parts. A solution was obtained. Hereinafter, this will be abbreviated as A-2.

Reference Example 3 [Same as above] 60 g of VTMS and ethyl vinyl ether (hereinafter referred to as
(abbreviated as EVE) 90g, vinyl benzoate 210g,
Methyl isobutyl ketone 120g, methyl orthoformate 3
0 g, 4.2 g of t-butyl peroxyvivalate (abbreviated as TBPV), and 3 g of t-butyl peroxyoctoate were charged.

Next, the liquefied hexafluoropropylene (hereinafter referred to as R
(abbreviated as FP) was press-fitted and heated to 60°C while stirring.
The reaction was carried out at 85° C. for 15 hours and then for 2 hours at 85° C. to obtain a solution of a vinyl polymer containing trimethoxysilyl groups with a nonvolatile content of 77% and an Mw of 46,000.

Hereinafter, this will be abbreviated as A-3.

Reference Example 4 [Same as above] In a reactor similar to Reference Example 3, 60 g of EVE and Beover 9 (
Made by Shell (Netherlands), 150 g of C8 (branched fatty acid vinyl ester), 90 g of vinyltriisopropenyloxysilane, 120 g of methyl isobutyl ketone, 30 g of methi orthoformate, 4.2 g of TBP V,
3 g of TBPo was charged. Next, 300 g of chlorotrifluoroethylene (hereinafter abbreviated as CTFE) was injected under pressure, and a reaction was carried out in the same manner as in Reference Example 3 to reduce the nonvolatile content to 78.5.
A solution of a vinyl polymer containing hydrolyzable silyl groups was obtained. Below, this is A-4
It is abbreviated as

Reference Example 5 [Preparation of fluoroolefin polymer containing no hydrolyzable silyl group] 40 g of EVE and 91 Beover were placed in the same reactor as in Reference Example 3.
60g, toluene 270g and 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as ABNV)
) 6g was prepared. Next, after 200 g of CTFE was press-injected, a reaction was carried out in the same manner as in Reference Example 3, and the nonvolatile content was 59.
A solution of a fluoroolefin polymer having a concentration of 98,000% was obtained. Hereinafter, this will be abbreviated as B-1.

Reference Example 6 [Same as above] In a reactor similar to Reference Example 3, 100 g of 4-hydroxybutyl vinyl ether, 70 g of ethyl vinyl ether, 30 g of cyclohexyl vinyl ether, and Beover 9 were added.
0 parts g 215 g of butyl acetate, 20 g of ABNV, 5 g of butylperoxy-2-ethylhexanoate and Mg4,5AQ2(OH) as solid base iico:i
- 10 g of hydrotalcite having the characteristic formula 3.5H,O was charged. Next, 250 g of chlorotrifluoroethylene was introduced under pressure, and the reaction was carried out in the same manner as in Reference Example 3. The hydrotalcite was then filtered to give an NV of 67.3%, h
A solution of a fluoroolefin polymer containing 75,000 hydroxyl groups was obtained. Hereinafter, this will be abbreviated as B-2.

Reference Example 7 [Same as above] Methyl isobutyl ketone 21 was placed in the same reactor as Reference Example 3.
5g, glycidyl vinyl ether 35g, ethyl vinyl ether 115g, Beover 9100g, ABNV
10 g and 5 g of TBPo were charged.

Next, 250 g of chlorotrifluoroethylene was introduced under pressure, and the reaction was carried out in the same manner as in Reference Example 3, resulting in NV of 68.0% and lh.
A solution of a fluoroolefin polymer containing 120,000 epoxy groups was obtained. Hereinafter, this will be abbreviated as B-3.

Reference Example 8 [Same as above] Methyl isobutyl ketone 21 was placed in the same reactor as Reference Example 3.
5g, N,N-dimethylaminoethyl vinyl ether 5
0g, 250g of vinyl 2,2-dimethylbutanoate, A
After charging 10 g of BNV and 5 g of TBPo, 50 g of vinylidene fluoride and 150 g of hexafluoropropylene were introduced under pressure, and the same reaction as in Reference Example 3 was carried out to obtain a tertiary amino group with an NV of 67.9% and a fi of 110.000. A solution of a fluoroolefin polymer was obtained. Hereinafter, this will be abbreviated as B-4.

Example I Tinuvin-900 (CIBA-GE
Manufactured by IGY, 2-(2'-hydroxy-3', 5'-
After adding and dissolving 35 parts of monoaluminum phenyl benzotriazole and 1 part of dibutyltin dioctate, the mixture was diluted to spray viscosity with a mixed solvent of 60 parts of xylene and 40 parts of butyl acetate to form a paint solution (hereinafter referred to as AT-4). (omitted) was obtained.6 The AT-1 was soaked in water for 1 day and then dried at 25°C for 1 day to give a dry film thickness of 5.
It was spray-painted so that the time was 0 μs.

The obtained coated plate was left at a temperature of 25° C. for 10 days and dried to obtain a coated plate for accelerated weather resistance testing. ``Du-Panel Light Control Weather Meter'' (
Accelerated weathering tester manufactured by Suga Test Instruments: Appearance after 2,000 hours of exposure using test conditions: UV irradiation at 70℃ for 8 hours, condensation at 50℃ for 4 hours and one cycle of repeated exposure. No change was observed. Furthermore, when a cut line was made in the coating film and a peel test was performed using cellophane tape to evaluate the adhesion, no peeling was observed, indicating excellent adhesion.

Examples 2 to 14 Components (A), (B), (C), and (D) were mixed in the proportions shown in Table 1 below to obtain coating compositions AT-2 to AT-11. Next, a dry film thickness of 50mm was applied to a concrete base material as shown in Table 2 below. It was spray coated as desired and cured under the conditions shown in Table 2 to obtain a coating film.

The coating performance of this coating film was evaluated as in Example 1. These results are also shown in Table 3.

Comparative Example I A-1200 parts, xylene 48.1 parts, Tybake C
Example 1: White room material made from W4 from 8 parts of R-9353
Dilute it to a spray viscosity with the mixed solvent used in , add 1 part of dibutyltin dioctate, soak it in water for 1 day, and dry it at 25℃ for 1 day to give a dry film thickness of 50 -. was spray painted. The obtained coated plate was left to stand at 25° C. for 10 days to dry and harden. When such a coated plate was subjected to the test as in Example 1, the gloss was significantly reduced and peeling was observed between the base material and the coating film.

Comparative Example 2 B-1200 parts, xylene 48.1 parts, Tybake C
Example 1 to a white paint prepared from 8 parts of R-9353'
It was diluted to spray viscosity with the mixed solvent used in .

On the other hand, the base material used was a lightweight concrete board that had been immersed in water for one day and then dried at 25°C for one day, and a vinyl polymer emulsion was applied in advance to a dry film thickness of 100 times.
An undercoat film was formed by drying at a temperature of 25°C for one day. Then, a white paint film diluted to the above spray viscosity was applied to the base material by spray painting to a dry film thickness of 50I3 at 25°C. It was dried for 10 days at a temperature of When the obtained coated plate was subjected to the test as in Example 1, the gloss was only slightly reduced, but significant peeling from the undercoat film was observed.

(Margin below) [Footnotes to Table 1] Note 1) Methyl ethyl ketone solution of a copolymer consisting of 50% by weight of vinylidene fluoride with a weight average molecular weight of 120,000 and 50% by weight of tetrafluoroethylene, non-volatile content: 3
0%.

Note 2) 45% by weight of vinylidene fluoride with a weight average molecular weight of 100,000, 45% by weight of tetrafluoroethylene
and 10% by weight of hexafluoropropylene in methyl ethyl ketone solution, nonvolatile content 30%.

Note 3) Manufactured by Dainippon Ink & Chemicals Co., Ltd., aliphatic polyisocyanate, isocyanate group content 15%, non-volatile content 7
5%.

Note 4) Methyl etherified melamine resin manufactured by Susumu Kagaku Kogyo ■.

Note 5) Glycidyl methacrylate/n-butyl methacrylate with number average molecular weight s, ooo = 50150
(weight ratio) copolymer, non-volatile content 50%.

Note 6) Dimethylaminoethyl methacrylate/n-butyl methacrylate with number average molecular weight s, ooo =
50150 (weight ratio) copolymer.

Note 7) Organic sulfonic acid amine salt curing catalyst manufactured by King, USA.

Note 8) Rutile-type titanium oxide manufactured by Ishihara Sangyo@.

Note 9) Manufactured by Nippon Ferro Co., Ltd., yellow fired pigment.

Note 10) Manufactured by Mitsubishi Kasei ■, carbon black.

Attention) Manufactured by AMERICAN CIANAMID,
2-Hydroxy-4-n-octoxybenzophenone 6
Note 12) Bis(1,2,2,6,6-bentamethyl-4-piperidyl) sebacate, manufactured by Sankyo ■.

Note 13) Pentaerythrityl-tetrakis (3-(3,5-di-butyl-4-hydroxyphenyl)propionate) manufactured by CIIIA-GEIGY.

(The following is a blank space) Table 3 [Effects of the Invention] The method of coating a cement base material of the present invention, that is, vinyl containing a hydrolyzable silyl group is applied to a cement base material or a cement base material coated with an undercoat in advance. By applying and curing a solution-type paint that contains as essential components a polymer and a fluoroolefin polymer that does not contain hydrolyzable silyl groups, a coating film with extremely excellent durability and adhesion is formed. can be done.

Therefore, the coating method of the present invention can be applied to various cement base materials, and can improve the cosmetic properties and durability of the cement base materials over a long period of time, and its utility value is extremely high.

Patent applicant: Dainippon Ink & Chemicals Co., Ltd. Agent: Yoshio Mizuno, patent attorney

Claims (1)

[Scope of Claims] 1. A vinyl polymer (A) containing a hydrolyzable silyl group and a fluoroolefin polymer (B) containing no hydrolysable silyl group as essential components in a cement base material A method for coating a cement-based substrate, characterized by coating with a solution-type paint comprising: 2. A vinyl polymer (A) containing a hydrolyzable silyl group and a fluoroolefin polymer (B) not containing a hydrolyzable silyl group are required on a cement base material coated with an undercoat in advance. A method for coating a cement base material, characterized by coating a solution-type paint comprising the following: 3. The solution-type paint contains a curing agent (C) and/or a catalyst for hydrolysis-condensation of the hydrolyzable silyl group (D)
The coating method according to claim 1 or 2, which comprises: 4. The coating method according to claim 1 or 2, wherein the vinyl polymer (A) containing a hydrolyzable silyl group is a fluoroolefin copolymer. 5. The coating method according to claim 1 or 2, wherein the vinyl polymer (A) containing a hydrolyzable silyl group is an acrylic polymer. 6. The coating method according to claim 1 or 2, wherein the vinyl polymer (A) containing a hydrolyzable silyl group is a vinyl polymer containing carboxylic acid vinyl ester as a main component. 7. The coating method according to claim 2, wherein the undercoat paint is a solution-type acrylic resin paint. 8. The coating method according to claim 2, wherein the undercoat paint is an acrylic resin emulsion paint. 9. The coating method according to claim 2, wherein the undercoat paint is a chlorinated polyolefin paint. 10. The fluoroolefin polymer (B
) is (a) fluoroolefin monomer 10 to 100
%, and (b) 90 to 0% of the other copolymerizable monomer. 11. The coating method according to claim 10, wherein the other copolymerizable vinyl monomer contains a monomer having a reactive functional group. 12. The fluoroolefin polymer (B) containing no hydrolyzable silyl group is vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and (per)fluoroethylene. Claim 10, wherein the essential component is at least one fluoroolefin monomer selected from the group consisting of alkyl trifluorovinyl ether (wherein the (per)fluoroalkyl group has 1 to 18 carbon atoms). How to paint. 13. The reactive functional group is a hydroxyl group, a carboxyl group,
Isocyanate group, amino group, epoxy group, amide group,
The coating method according to claim 11, wherein the coating is at least one selected from the group consisting of a trialkylsilyloxy group, a trialkylsilyloxycarbonyl group, and a carboxylic acid anhydride group. 14. The curing agent (C) is at least one selected from the group consisting of polyisocyanate compounds, blocked polyisocyanate compounds, amino resins, polyepoxy compounds, and compounds having both an epoxy group and a hydrolyzable silyl group in one molecule. The coating method according to claim 3, wherein the coating method is a seed. 15. The solution-type paint comprising the vinyl polymer (A) containing a hydrolyzable silyl group and the fluoroolefin polymer (B) not containing a hydrolyzable silyl group contains an ultraviolet absorber and/or The coating method according to claim 1 or 2, which contains an antioxidant.