JPH0339752B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful method for forming a coating film, and more specifically, the present invention relates to a new and useful method for forming a coating film, and more specifically, it involves first applying an uneven pattern-forming coating material, and then applying a coating material containing a specific silyl group-containing polymer as an essential resin component. The present invention relates to a method for forming a so-called mastic coating film, which has an uneven pattern and excellent weather resistance. In recent years, mastic coatings have become widely used as interior and exterior materials for buildings.
An uneven pattern-forming paint containing a water-soluble resin and/or water-dispersible resin (hereinafter also collectively referred to as water-based resin) as a binder is applied to various base materials such as wood, plywood, slate, mortar, or concrete. After applying it and letting it dry for about 1 to 7 days,
The method used is to apply a paint that dries at room temperature as a top coat and let it dry. By the way, these room temperature drying paints are
Lutker type non-crosslinked paints and acrylic-urethane type paints that cure at room temperature are used, but the Lutker type paints are inferior in water resistance, stain resistance, weather resistance, etc. On the other hand, in the case of acrylic-urethane type, there is a problem of toxicity due to the free isocyanate of the hardening agent during painting, and water-based resin is used as uneven pattern forming paint. Due to the fact that water-based paint is used,
This undercoat always contains water, and the reaction between the polyisocyanate, which is a curing agent, and water occurs in parallel with the crosslinking reaction, which prevents the paint film from fully curing and can be applied in a short period of time. It has the drawbacks of causing cracks in the film and reducing its gloss. However, as a result of intensive research in view of the various drawbacks of the prior art as described above, the present inventors applied a paint containing a specific hydrolyzable silyl group-containing polymer as an essential resin component as a top coat paint. As a result, the present invention has been completed by discovering that it is possible to obtain a mastic coating film which has all the drawbacks of the prior art described above and is significantly improved. That is, the present invention provides an uneven pattern-forming paint containing a water-dispersible resin and/or a water-soluble resin as a binder to a base material coated with a primer, if necessary.
First, apply (A) to form an uneven surface, and then apply the general formula on this uneven surface. [However, R ¹ in the formula is a hydrogen atom or an alkyl group,
A monovalent organic group such as an aryl group or an aralkyl group, R ² is a halogen atom or an alkoxy group,
represents an acyloxy group, phenoxy group, mercapto group, amino group, iminooxy group or alkenyloxy group, and a is 0, 1 or 2
Let it be an integer. ] Hydrolyzable silyl group-containing polymer (b-
1), 100 parts by weight, a compound having at least two hydroxyl groups per molecule, and the general formula [However, R ³ , R ⁴ and R ⁵ in the formula each independently represent a linear or branched alkyl group, a cycloalkyl group, an aralkyl group, an alkyl group substituted with a halogen or alkoxy group, or a phenyl group. Alternatively, it represents an organic group such as a substituted phenyl group. ] 0 to 400 parts by weight of the alkoxysilane modified resin (b-2) obtained by reacting with the trialkoxysilyl group-containing compound represented by
~2500 parts by weight, curing catalyst (b-4) 0.001~50
The present invention provides a method for forming a mastic coating film, which comprises applying a paint (B) containing 20 to 8000 parts by weight of a solvent (b-5) and a solvent (b-5). Here, although there are various types of substrates mentioned above as typical substrates, the present invention is not limited to those mentioned above. Among these base materials, slate board,
For base materials such as wood or concrete that require large amounts of paint, first apply a primer such as lacquer type paint, unsaturated polyester resin paint, acrylic-urethane paint, or polyester-urethane paint. It is desirable to leave it there. Next, as the uneven pattern forming paint (A) described above,
Water-soluble resins such as vinyl polymer systems, polyester systems, alkyd systems or polyester-urethane systems and/or water dispersions such as vinyl polymer systems, epoxy resin systems, alkyd systems, polyester systems, polyester-urethane systems or polyether-urethane systems. Various aqueous resins such as polyester resins can be used alone or in combination of two or more types as typical binder components, but from the viewpoint of water resistance of the coating film, aqueous dispersions of vinyl polymers are the main binder components. Particularly preferred are those using a binder of In addition to these aqueous binders, various pigments such as titanium oxide, calcium carbonate or barium sulfate,
The uneven pattern forming paint (A) described above can be obtained by blending various fillers such as agarstone or clay, or dispersion stabilizers. Using a spray gun of approximately 5 to 7 mm, the substrate is air-sprayed as described above, and then dried at room temperature to provide a coating having the desired uneven surface. Next, the paint (B) used as a top coat in carrying out the method of the present invention will be explained in detail. First, the hydrolyzable silyl group-containing polymer, which can be called the first component constituting the paint (B) (b-1) is the general formula [However, R ¹ in the formula is a hydrogen atom or an alkyl group,
A monovalent organic group such as an aryl group or an aralkyl group, R ² is a halogen atom or an alkoxy group,
It represents a phenoxy group, a mercapto group, an amino group, an iminooxy group or an alkenyloxy group, and a is an integer of 0, 1 or 2. ] Halosilylalkyl group, alkoxysilylalkyl group, acyloxysilylalkyl group, phenoxysilylalkyl group, mercaptosilylalkyl group, aminosilylalkyl group, iminooxysilylalkyl group, or alkenyloxysilylalkyl group, etc. refers to a polymer containing a functional group that is easily hydrolyzed such as
polymers, saturated or unsaturated polyester resins,
Examples include alkyd resins, urethane resins, and polyether resins, but among these polymers, vinyl (co)polymers are particularly preferred from the viewpoint of weather resistance. In addition, as the hydrolyzable silyl group, which can also be called a characteristic group, in the polymer (b-1), among the various functional silyl groups listed above, one that does not produce undesirable volatile matter during curing is selected. , alkoxysilylalkyl groups are most preferred. Therefore, in order to introduce a hydrolyzable silyl group such as an alkoxysilylalkyl group into the above vinyl (co)polymer, a vinyl monomer containing an alkoxysilylalkyl group and a vinyl monomer that can be copolymerized with this are used. Copolymerizing a mixture with other vinyl monomers, radical polymerization of vinyl monomers using an alkoxysilane containing a mercapto group as a chain transfer agent, or copolymerizing a vinyl monomer with a separately prepared unsaturated group or A vinyl copolymer having an epoxy group in the side chain, aminosilanes containing an alkoxysilylalkyl group,
React with hydrosilanes and mercaptosilanes. Although well-known methods such as , etc. can be applied, it is most convenient to use only one of these methods, only the method , or a combination of the method and the method. Specific examples of the vinyl monomer containing an alkoxysilylalkyl group used when introducing an alkoxysilylalkyl group by the above copolymerization method include γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, ) Acryloyloxypropyltriethoxysilane, γ-
Examples include (meth)acryloyloxypropylmethyldimethoxysilane and allyltrimethoxysilane. Specific examples of alkoxysilanes containing a mercapto group that are used when introducing an alkoxysilylalkyl group by a method using a chain transfer agent include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The alkoxysilylalkyl group-containing monomer and/or mercapto group-containing alkoxysilane has a resin solid content of 1000 g from the viewpoint of curability and cost.
It is preferable to use an amount such that the amount of alkoxysilyl group introduced per unit is in the range of 0.1 to 3 moles. In this way, by copolymerizing the alkoxysilylalkyl group-containing vinyl monomer as described above with a vinyl monomer copolymerizable therewith, the hydrolyzable silyl group-containing polymer serving as the base resin component can be obtained. (b-1) is obtained. Typical examples of such copolymerizable vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid esters such as benzyl (meth)acrylate; hydroxyalkyl esters of (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; itaconic acid, fumaric acid or monoalkyl or dialkyl esters of dibasic acids such as maleic acid; aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene; and also vinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile, N,N-dialkyl Aminoalkyl methacrylate, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic anhydride, maleic acid, N-alkoxymethyl (meth)acrylamide, acrylamide, methacrylamide, N-methylolacrylamide, (meth)acrylic These include acid glycidyl ester, vinyltrimethoxysilane or vinyltriethoxysilane. Among the above copolymerizable vinyl monomers,
From the viewpoint of pigment dispersibility and adhesion, it is particularly preferred to copolymerize a small amount of a carboxyl group-containing monomer, a hydroxyl group-containing monomer, or an amide group-containing monomer. To prepare the above vinyl (co)polymer (b-1), any known method such as solution, bulk, or suspension polymerization can be used, but solution radical polymerization is the most preferred method. preferable. Typical solvents used in this case include toluene, xylene, cyclohexane, n-hexane,
Hydrocarbons such as octane; methanol, ethanol, i-propanol, n-butanol, i-
Alcohols such as butanol, sec-butanol, ethylene glycol monoalkyl ether;
Ester-based solvents such as ethyl acetate, methyl acetate, and butyl acetate, and ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are available, but the storage stability of the vinyl (co)polymer solution and the pot life of the composition of the present invention are In order to improve the performance of the solvent, it is preferable to use the alcoholic solvent in such a manner that at least 10% by weight of the total solvent amount is an alcoholic solvent. Polymerization may be carried out in a conventional manner using such a solvent and a polymerization initiator such as an azo or peroxide type polymerization initiator. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, and α-methylstyrene dimer can also be used during polymerization. The vinyl polymer (b-1) thus obtained
The number average molecular weight is suitably in the range of 1,000 to 30,000, preferably 3,000 to 20,000. Furthermore, in carrying out the method of the present invention, the above-mentioned paint
As mentioned above, the alkoxysilane-modified resin (b-2), which can also be called the second component of (B), is a compound having at least two hydroxyl groups per molecule, and a compound with the general formula [However, R ³ , R ⁴ and R ⁵ in the formula each independently represent a linear or branched alkyl group, a cycloalkyl group, an aralkyl group, an alkyl group substituted with a halogen or alkoxy group, or a phenyl group. Alternatively, it represents an organic group such as a substituted phenyl group. ] Refers to an alkoxysilane-modified resin obtained by reacting with a trialkoxysilyl group-containing compound shown in Typical examples of compounds having hydroxyl groups include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, 1,3-
Butanediol, 1,6-hexanediol, cyclohexanedimethanol, neopentyl glycol, glycerin, 3-methylpentane-1,
Polyhydric alcohols such as 3,5-triol, pentaerythritol, and sorbitol; saturated or unsaturated polyester resins, alkyd resins, vinyl polymers, polybutadiene glycol, and epoxy resins; and the above-mentioned polyhydric alcohols or various resins and ε - There are ester compounds containing hydroxyl groups obtained by reacting with caprolactone. Among the above-mentioned compounds containing hydroxyl groups, ε-
Particularly preferred are hydroxyl group-containing ester compounds obtained by adding caprolactone. The ε-caprolactone adduct of such a hydroxyl group-containing compound is preferably one in which ε-caprolactone is added at a ratio of about 1 to 20 moles per equivalent of hydroxyl group in the presence of a conventionally known catalyst. Typical examples of compounds containing at least one trialkoxysilyl group represented by the above general formula () per molecule, which is another component used in obtaining the alkoxysilane-modified resin, include tetramethyl silicate, tetraethyl Silicate, Tetrabutyl silicate, Tetra(2-
methoxyethyl) silicate or tetra(2
-tetra(substituted)alkyl silicates such as -chloroethyl)silicate; tetra(substituted)phenylsilicates such as tetraphenylsilicate or tetra(4-chlorophenyl)silicate; tetrabenzylsilicate or tetra(2-phenylethyl)silicate; Tetraaralkylsilicates; condensates of various monomers such as the above tetra(substituted)alkylsilicates such as tetraethysilicate dimer, tetraethylsilicate tetramer or tetraethylsilicate hexamer; vinyltrimethoxysilane, vinyltriethoxysilane or Silane coupling agents such as glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane or 3(β-aminoethyl)aminopropyltrimethoxysilane;
Trimethoxysilanes such as trimethoxysilane, triethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane; or 1 such as allyl acetate, allyl benzoate, diallyl phthalate, diallyl adipate, diallyl succinate or triallyl trimellitate Adducts of compounds having at least one allyl group per molecule and hydrosilanes such as trimethoxysilane or triethoxysilane; further examples include vinyl-based (co)polymers having alkoxysilyl groups in the side chains. , these may be used alone or in combination of two or more. Among these trialkoxysilyl group-containing compounds, tetramethylsilicate,
It is particularly preferable to use tetraalkyl silicates such as tetraethyl silicate or tetrabutyl silicate, or condensates such as tetraethyl silicate dimer, -trimer or -tetramer from the viewpoint of cost and the like. The desired alkoxysilane modified resin (b-
In order to prepare 2), for example, JP-A-58-173158
The method described in the specification may be followed. Furthermore, the pigment (b), which can be called the third component of the paint (B) used in carrying out the method of the present invention
-3) Any of the conventionally used materials can be used, but the most representative ones include titanium oxide, calcium carbonate,
These include inorganic pigments such as barium sulfate, carbon black, red lead, and yellow lead, and organic pigments such as azo, phthalocyanine, and quinacridine pigments. Furthermore, as the curing catalyst (b-4), which can be called the fourth component of the paint (B), it is preferable to use a known and commonly used catalyst for hydrolysis and condensation of silyl group-containing compounds; (b-
Typical examples of 4) include basic compounds such as butylamine, dibutylamine, hexylamine, t-butylamine, ethylenediamine, triethylamine, isophoronediamine, imidazole, lithium hydroxide, sodium hydroxide, potassium hydroxide, and sodium methylate; Isopropyl titanate, tetrabutyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin Metal-containing compounds such as malate; p-toluenesulfonic acid, trichloroacetic acid,
Phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, β-
Phosphate ester of hydroxyethyl acrylate,
Examples include acidic compounds such as monoalkyl phosphorous acid and dialkyl phosphorous acid, and particularly preferred are tin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, and dibutyltin maleate. Furthermore, the solvent (b-5), which can also be called the fifth component of the coating material (B) used in carrying out the method of the present invention, is used for the preparation of the vinyl (co)polymer (b-1). In addition to the compounds used in Examples include so-called hydrolyzable ester compounds, such as various tetra(substituted) alkyl silicates alone, the same effective alone of these silicates, and condensates of these various silicates, but the pot life of such paint (B) In order to increase the length of time, it is preferable to use an alcoholic solvent and a hydrolyzable ester compound together. (b-1) to (b-
5) When preparing the paint (B) by mixing the components, the ratio of each component used is (b-1) to 100 parts by weight of component (b-1).
-2) component 0 to 400 parts by weight, (b-3) component 0
A suitable proportion is 2500 parts by weight of component (b-4), 0.001 to 50 parts by weight of component (b-5), and 20 to 8000 parts by weight of component (b-5). Therefore, it goes without saying that the paint (B) can be used either as a clear paint or as a colored paint containing the pigment (b-3). At this time, the alkoxysilane modified resin (b
Although a sufficiently durable coating film can be obtained without using component (b-2), it is even more advantageous to incorporate component (b-2), as it can significantly improve crack resistance. Become. The paint (B) thus obtained is applied by air spraying, for example, onto a paint film with the above-mentioned uneven surface, that is, a paint film that is obtained by applying the uneven pattern forming paint (A) to a base material and drying it. It is then left to stand at room temperature for about 2 to 7 days to fully cure and provide a coating film with particularly excellent weather resistance. Next, the present invention will be specifically explained with reference to Reference Examples, Examples, and Comparative Examples. In the following, unless otherwise specified, all parts and percentages are based on weight. Reference Example 1 [Example of preparation of hydrolyzable silyl group-containing polymer (b-1)] 400 parts of toluene and n-butanol were placed in a reactor equipped with a stirring device, a thermometer, a nitrogen gas introduction tube, and a reflux condenser. 400 parts of styrene, 100 parts of methyl methacrylate, n
-420 parts of butyl methacrylate, 195 parts of n-butyl acrylate, 70 parts of γ-methacryloyloxypropyltrimethoxysilane, 15 parts of monobutyl maleate, 200 parts of toluene, 6 parts of azobisisobutyronitrile, t - A mixture of 10 parts of butyl peroxyoctoate and 5 parts of t-butyl peroxybenzoate is added dropwise over 3 hours, and then the temperature is raised to 110°C and kept at the same temperature.
The reaction was continued for 15 hours to obtain a solution of a trimethoxysilylmethyl group-containing vinyl copolymer (b-1) with a nonvolatile content (NV) of 50% and a number average molecular weight (n) of 9,000. Hereinafter, this will be abbreviated as polymer (b-1-1). Reference example 2 (Preparation example of hydrolyzable silyl group-containing polymer (b-1)) As a monomer to be copolymerized, 100% of styrene
parts, 390 parts of methyl methacrylate, 330 parts of n-butyl acrylate, 130 parts of γ-methacryloyloxypropyltrimethoxysilane and β
- A trimethoxysilylmethyl group-containing vinyl copolymer (b-1) with an NV of 50% and n of 9000 was prepared in the same manner as in Reference Example 1, except that 50 parts of hydroxypropyl methacrylate was used. A solution was obtained. Hereinafter, this will be referred to as polymer (b-1-2).
It is abbreviated as Reference Example 3 (Preparation example of hydrolyzable silyl group-containing polymer (b-1)) 400 parts of toluene and 300 parts of n-butanol were charged into the same reactor as in Reference Example 1, and the temperature was raised to 105°C. and then 200 parts of styrene, 500 parts of n-butyl methacrylate, 90 parts of n-butyl acrylate, 200 parts of γ-methacryloyloxypropyltrimethoxysilane, 200 parts of toluene, and 6 parts of azobisisobutyronitrile. , 30 parts of t-butyl peroxyoctoate and 5 parts of t-butyl peroxybenzoate;
- 100 parts of butanol and 10 parts of acrylamide
The mixture was added dropwise over 4 hours, heated to 110°C, and kept at the same temperature for 15 hours to continue the reaction, forming a trimethoxysilylmethyl group with NV of 50% and n of 6000. A vinyl copolymer (b-1) having the following properties was obtained. Hereinafter, this will be referred to as a polymer (b-
It is abbreviated as 1-3). Reference Example 4 (Preparation example of hydrolyzable silyl group-containing polymer (b-1)) As monomers to be copolymerized, 490 parts of methyl methacrylate, 50 parts of n-butyl methacrylate,
330 parts of n-butyl acrylate and γ-methacryloyloxypropyltrimethoxysilane
In the same manner as in Reference Example 1, NV
A solution of a vinyl copolymer (b-1) having a trimethoxysilylmethyl group with n of 50% and n of 13,000 was obtained. Hereinafter, this will be abbreviated as polymer (b-1-4). Reference Example 5 (Preparation example of polyisocyanate-curing acrylic polyol) 400 parts of toluene and 400 parts of butyl acetate were used as the solvent to be initially charged in the reactor, and 200 parts of styrene was used as the monomer to be copolymerized. 100 parts of methyl methacrylate, 400 parts of n-butyl methacrylate, 155 parts of n-butyl acrylate
140 parts of β-hydroxyethyl methacrylate
NV was 50 in the same manner as in Reference Example 1, except that 1 part and 5 parts of methacrylic acid were used.
% and n of 9000 was obtained. Hereinafter, this will be abbreviated as acrylic polyol (b'-1). Reference Example 6 [Preparation example of alkoxysilane modified resin (b-2)] Trimethylolpropane was added to a reactor equipped with a stirring device, a thermometer, a nitrogen gas introduction pipe, and a cooling pipe.
134 parts (1 mol), 684 parts (6 mol) of ε-caprolactone and 0.04 parts of tetrabutyl titanate.
The mixture was reacted at 180° C. for 6 hours under a nitrogen atmosphere to obtain an adduct with a molar ratio of trimethylolpropane-ε-caprolactone of 1:6. then
After cooling the temperature to 90°C, add 936 parts of this tetraethyl silicate and further add 5.3 parts of tetrabutyl titanate so that the equivalent ratio of the tetraethyl silicate to be added and the hydroxyl group in the above adduct is 1.5. The reaction was then carried out at 110 to 120° C. until the distillation of ethanol stopped, that is, for 3 hours, to obtain the desired modified resin (b-2). Hereinafter, this will be abbreviated as resin (b-2-1). Reference example 7 (same as above) Trimethylolpropane obtained in reference example 6
818 parts of a 1:6 molar ratio adduct of ε-caprolactone and "ethyl silicate 40" [manufactured by Colcoll Co., Ltd.]
2230 parts of a thick compound of tetramers, pentamers and hexamers of ethyl silicate and 9.2 parts of tetrabutyl titanate
The resulting mixture was heated at a temperature of 100 to 135° C. for 2 hours, and the produced ethanol was distilled out of the system to obtain the desired resin (b-2) modified with a tetraethoxysilane condensate. Hereinafter, this will be referred to as resin (b
-2-2). Examples 1 to 6 and Comparative Example 1 “Boncourt 5450” [Dainippon Ink and Chemicals Co., Ltd.
vinyl polymer emulsion; NV=55%]
100 parts of calcium carbonate, 247 parts of anhydrite, 248 parts of anhydrite
PWC of 90% and 52 parts of water, and
After diluting the uneven pattern forming paint with an NV of 85% with water to a spray viscosity, use a spray gun with a diameter of 5 mm to apply it to a slate board that has been previously coated with a commercially available Lutzker type acrylic resin clear paint as a primer. Air spray, at room temperature 2
After drying for several days, a coating film having an uneven surface was obtained. Next, each top coat paint prepared from components (b-1) to (b-5) as shown in Table 1 was diluted to the spray viscosity with a predetermined dilution thinner on this coating film having an uneven surface. Each layer was painted separately and dried at room temperature for 7 days to obtain each cured coating. The above is the explanation about Examples 1 to 6,
Comparative Example 1 was prepared using acrylic polyol (b'-1) as shown in the same table and "Burnock DN-950" [non-yellowing type polyisocyanate manufactured by Dainippon Ink and Chemicals Co., Ltd.; NV = 75%, isocyanate A cured coating film for control was obtained using the same procedure as in Examples 1 to 6 using titanium oxide and thinner. The performance of each cured coating film obtained in each example and comparative example is evaluated and shown in the same table.
-93'' is rutile type titanium oxide manufactured by Ishihara Sangyo Co., Ltd.
Moreover, the solvent (b-5-1) is xylene/toluene/
n-butanol/trimethyl orthoformate/cellosolve acetate = 30/20/30/10/10 (weight ratio)
Solvent (b-5-2) is xylene/toluene/n-butanol/tetraethylsilicate/cellosolve acetate = 30/20/30/
A mixed solvent of 10/10 (same as above) was added to the solvent (b-5-
3) is xylene/toluene/n-butanol/tetraethylsilicate/trimethyl orthoformate/
Solve acetate = 30/15/30/5/10/10 (same as above) and solvent (b-5-4)
represents a mixed solvent of xylene/toluene/butyl acetate/cellosolve acetate = 30/30/30/10 (same as above). Furthermore, the "adhesiveness" shown in the same table
is a cut made in the painted surface and the cut is removed with cellophane tape, and the state of adhesion between the uneven paint film and the top coat film is visually judged,
One cycle of the "cold/thermal cycle" consists of immersing the coating in 20℃ water for 18 hours, then holding it in a -20℃ thermostatic bath for 3 hours, and then holding it in a 50℃ thermostatic bath for 3 hours. It shows the number of cycles until cracks occur on the painted surface, and the "paint film appearance after outdoor exposure" is the visual judgment of the appearance after one year of outdoor exposure in Miyazaki Prefecture.

【table】

[Table] As is clear from Table 1, it is known that the coating film obtained by the method of the present invention has extremely excellent durability.

Claims (1)

[Scope of Claims] 1. First, an uneven pattern forming paint (A) containing a water-dispersible resin and/or a water-soluble resin as a binder is applied to a base material to form an uneven surface. , the general formula [However, R ¹ in the formula is a hydrogen atom or an alkyl group, a monovalent organic group such as an aryl group or an aralkyl group, and R ² is a halogen atom or an alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, represents an iminooxy group or an alkenyloxy group, and a is 0, 1
or an integer of 2. ] 100 parts by weight of a polymer (b-1) containing a hydrolyzable silyl group, a compound containing at least two hydroxyl groups per molecule, and the general formula [However, R ³ , R ⁴ and R ⁵ in the formula are each,
It represents an organic group such as a linear or branched alkyl group, a cycloalkyl group, an aralkyl group, an alkyl group substituted with a halogen atom or an alkoxy group, a phenyl group, or a substituted phenyl group. ] 0 to 400 parts by weight of an alkoxysilane modified resin (b-2) obtained by reacting with a compound containing a trialkoxysilyl group shown in
0 to 2500 parts by weight of 3) and curing catalyst (b-4)
0.001 part by weight, and 20 to 8000 parts of solvent (b-5)
1. A method for forming a mastic coating film, which comprises applying a paint (B) comprising parts by weight. 2 The hydrolyzable silyl group-containing polymer described above (b
The method according to claim 1, wherein -1) is a vinyl polymer having a number average molecular weight of 1000 to 30000. 3 The above-mentioned alkoxysilane modified resin (b-
2) is at least one hydrolyzable ester compound selected from the group consisting of a single tetraalkyl silicate, a single tetra-substituted alkyl silicate, a monomer of these silicates with the same effect, and a condensate thereof, The modified resin (b-2)
The method according to claim 1, wherein the trialkoxysilyl group-containing compound is used as the trialkoxysilyl group-containing compound. 4. The method according to claim 1, wherein the solvent (b-5) contains an alkyl alcohol and/or a hydrolyzable ester compound. 5 The hydrolyzable silyl group-containing polymer described above (b
The method according to claim 1 or 2, wherein -1) is a vinyl polymer containing at least one polar group selected from the group consisting of a carboxyl group, an amide group, and a hydroxyl group. 6 The above-mentioned solvent (b-5) is selected from orthoformates, orthoacetates, simple tetraalkyl silicates, simple tetra-substituted alkyl silicates, the same effective simple substances of both of these silicates, and condensates thereof. Claim 1 or 4 contains at least one hydrolyzable ester compound selected from the group consisting of:
The method described in section. 7. The method according to claim 1, wherein the base material is coated with a primer.