JP2000327996A - Coating method and silicon-containing liquid composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating material requiring no primer coating, capable of improving coating film functions such as stain resistance and resistance to weathering only by coating directly on the surfaces of structures such as building structures and civil engineering structures or coating on the existing coating films. SOLUTION: This coating method comprises applying a silicon-containing liquid composition obtained by formulating the following components A to D on the surface of a structure, and preventing the surface of the structure from staining. Component A: an organosilicate 100 pts.wt. calculated as SiO2 Component B: catalyst 0.1-10 pts.wt., Component C: water 100-50,000 pts.wt., Component D: solvent 100-50,000 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing dirt such as dust and oily components generated on painted or unpainted surfaces of building structures, civil engineering structures, industrial equipment, traffic signs, etc. The present invention relates to a coating method that can be easily removed by wiping or the like, and a liquid composition suitably used for such coating.

[0002]

2. Description of the Related Art In recent years, landscapes of architectural structures, civil engineering structures, and the like have been regarded as important, and various types of low-contamination paint finishing have been performed with the aim of improving the contamination resistance of the surface of the structures. Have been. As a method of finishing the low-contamination coating, conventionally, a highly weather-resistant organic coating such as a fluororesin-based coating, an acrylic silicon-based coating, or a urethane-based coating has been used for the finish coating (top coating).

In recent years, a small amount of an alkyl silicate has been added to these paint systems to make the surface of the coating film hydrophilic, thereby making it difficult for dust and oily contaminants to adhere. Something like washing out is being done. On the other hand, compared with the above-mentioned organic paints, development of inorganic paints containing an organopolysiloxane as a main component, which is generally superior in weather resistance, durability, chemical resistance, heat resistance, and the like, has been actively promoted. Some have been converted.

[0004] However, when these topcoats are applied, in order to further improve the adhesion between the structure or the like (substrate) and the coating film, an undercoat, or even a primer, is provided between the substrate and the topcoat. It is a common coating method to use an intermediate coating as required, and it is a problem common to organic coatings and inorganic coatings that it takes time. In particular, a coating film of an organic paint is easily contaminated by dust, metal powder, rain (acid rain or the like) or an exhaust gas during exposure, and is likely to cause a decrease in landscape.

[0005] In addition, these topcoats, in which a small amount of alkyl silicate is added to these organic coatings, tend to cause problems in the physical properties of the coatings, such as an increase in viscosity during storage of the coatings and the occurrence of cracks in the coatings. Need attention.
Inorganic paints, like organic paints to which a small amount of alkyl silicate is added, often require heat curing, such as storage stability of paints, cracks in thick films, etc. At present, there is a problem that requires attention.

[0006] Further, since these paint systems contain a large amount of volatile organic solvents, they fall under hazardous materials under the Fire Service Law and require careful handling for safe handling. At present, it is desired to solve the problems of the stability of the coating material, the function of the coating film, and the workability and safety during coating as described above.

[0007]

DISCLOSURE OF THE INVENTION The present invention does not require a primer coating, and can be applied to a structure such as an architectural structure, a civil engineering structure or the like directly or on an existing coating film.
An object of the present invention is to provide a coating material and a coating method capable of improving a coating function such as weather resistance.

[0008]

Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, have found that architectural structures, civil engineering structures,
Industrial equipment, transportation equipment, on the surface of painted or unpainted structures such as traffic signs, the following specific silicon-containing composition paper,
The coating obtained by impregnating cloth, non-woven fabric, etc. and wiping, or aerosolizing this silicon-containing composition, spraying and applying, prevents or prevents contamination and is easy to remove even if contaminants adhere. This led to the present invention.

That is, the present invention relates to (1) a method of applying a silicon-containing liquid composition comprising the following components (A) to (D) to the surface of a structure to prevent the surface of the structure from being stained. Method, Component (A) 100 parts by weight of organosilicate SiO ₂ Component (B) 0.1 to 10 parts by weight of component (C) 100 to 50,000 parts by weight of water Component (D) 100 to 50,000 parts by weight of solvent (2) A coating method for applying a silicon-containing liquid composition comprising the following components (A) to (E) to the surface of the structure to prevent the surface of the structure from being stained: Component (A) organosilicate SiO ₂ conversion 100 parts by weight Component (B) catalyst 0.1 to 10 parts by weight Component (C) water 100 to 50,000 parts by weight Component (D) solvent 100 to 50,000 parts by weight Component (E) pigment, filler, additive for paint At least one of them

(3) The coating according to the above (1), wherein the silicon-containing liquid composition comprising the components (A) to (D) is aerosolized and sprayed onto the surface of the structure to apply the composition. Method (4) The coating method according to the above (2), wherein the silicon-containing liquid composition obtained by blending the components (A) to (E) is aerosolized and sprayed onto the surface of the structure for application. , (5) the component (A) has the chemical formula SiOx (OR) y
The coating method according to any one of the above (1) to (4), wherein 0 ≦ x ≦ 1.2, 1.4 ≦ y
≦ 4, R is an alkyl group having 1 to 4 carbon atoms, and 2
x + y = 4. (6) The coating method according to any one of (1) to (5), wherein the organosilicate is methylsilicate.

(7) A silicon-containing liquid composition obtained by blending the following components (A) to (D): Component (A) 100 parts by weight of organosilicate SiO ₂ Component (B) catalyst 0.1 to 10 Parts by weight Component (C) 100 to 50,000 parts by weight of water Component (D) 100 to 50,000 parts by weight of solvent (8) Silicon-containing liquid composition obtained by blending the following components (A) to (E) on the surface of the structure Component, component (A) 100 parts by weight of organosilicate SiO ₂ component (B) catalyst 0.1 to 10 parts by weight component (C) water 100 to 50,000 parts by weight component (D) solvent 100 to 50,000 parts by weight component (E) ) One or more of pigments, fillers and paint additives

(9) The component (A) has the chemical formula SiOx
(7) or (8) above, which is represented by (OR) y
The silicon-containing liquid composition according to the above (where 0 ≦ x ≦ 1.
2.1.4 ≦ y ≦ 4, R is an alkyl group having 1 to 4 carbon atoms, and 2x + y = 4. (10) The silicon-containing liquid composition according to any one of (7) to (9), wherein the organosilicate is methyl silicate.

According to the present invention, the specific silicon-containing liquid composition is applied directly to the surface of an unpainted structure, or is simply applied on the existing coating film on the surface of the painted structure, thereby obtaining stain resistance and weather resistance. It has become possible to improve the coating function such as properties. Particularly as a silicon-containing liquid composition, pigments, fillers,
And / or anti-sagging agents, leveling agents, repelling agents,
By blending various paint additives such as an adhesion improver, an algicide, an antibacterial agent, a deodorant, and an ultraviolet absorber, the coating film function can be further improved.

[0014]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a liquid composition is prepared by blending the components (A) to (D) described below or the component (E). First, the component (A) is an organosilicate, that is, a compound in which an organic group is bonded to a silicon atom via an oxygen atom. Examples of the organosilicate include an organooxysilane in which four organic groups are bonded to one silicon atom via an oxygen atom, and an organooxysiloxane in which silicon forms a siloxane main chain ((Si—O) n). Can be

The organic group bonded to silicon via an oxygen atom is not particularly limited. For example, a linear, branched or cyclic alkyl group, more specifically, methyl, ethyl, n
-Propyl, i-propyl, n-butyl, i-butyl,
Examples thereof include t-butyl, n-pentyl, i-pentyl, neopentyl, hexyl, and octyl groups. Particularly, an alkyl group having 1 to 4 carbon atoms is preferable. Other organic groups include an aryl group, a xylyl group, and a naphthyl group. Further, the organic group may have two or more different groups.

The alkyl group is preferably one having 1 to 4 carbon atoms, but may be linear or branched, such as methyl, ethyl, n-propyl, i-alkyl.
Examples thereof include a propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a t-butyl group, and a complex and / or a mixture of these groups can also be used. The alkyl group may have two or more different alkyl groups. Among these alkyl groups, a methyl group and / or an ethyl group are preferred from the viewpoints of solubility when the silicon-containing composition of the present invention is used and the low contamination function of the obtained coating film, and the most preferred is It is a methyl group.

In the case of an alkyl group having more than 4 carbon atoms, a large amount of an organic solvent is required due to low solubility when the silicon-containing composition of the present invention is used. The above problems often occur. Also,
Alkyl groups having more than 4 carbon atoms are poorly hydrolyzable,
The formation of SiOH groups during outdoor exposure of the resulting coating film tends to be extremely slow, and the expression of the low stain function tends to be poor.

Examples of the organooxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, dimethoxydiethoxysilane and the like. Examples of the organoxysiloxane include condensates of the above-mentioned organoxysilanes. Although the degree of condensation is not particularly limited, preferred ranges include those represented by the following descriptive formulas.

SiOx (OR) y (where 0 ≦ x ≦ 1.2, 1.4 ≦ y ≦ 4, and R is an organic group. Preferably, R is an alkyl group having 1 to 4 carbon atoms.) (However, 2x + y = 4.)

The coefficient x indicates the degree of condensation of siloxane,
When the siloxane has a molecular weight distribution, it means the average degree of condensation. x = 0 represents a monomer, organoxysilane, and 0 <x <2 corresponds to an oligomer which is a condensate exceeding a monomer obtained by partially hydrolyzing and condensing it. x = 2 corresponds to SiO ₂ (silica). The condensation degree x of the organosilicate used in the present invention is 0 ≦ x
≦ 1.2, more preferably 0 ≦ x ≦
1.0. The siloxane main chain is linear, branched,
Regardless of the ring shape, a mixture thereof may be used.

The organosilicate having x> 1.2 has a high degree of condensation and a high molecular weight, has a high viscosity and easily gels upon storage, and has poor stability, so that it is difficult to use. In addition, since the solubility in organic solvents is low, a large amount of organic solvents are required when preparing the silicon-containing composition of the present invention, and the resulting composition falls under dangerous goods under the Fire Service Law. Problems are easy to occur.

The characteristic formula SiOx (OR) can be obtained by the following method. Degree of condensation: x is Si-NMR
Can be easily known by measuring Chemical shift value of tetramethylsilane (reference substance) is 0p
As pm, in the case of organosilicate, chemical shift values, giving a peak of 5 groups between -75 to-120 ppm, referred to as _{Q 0, Q 1, Q 2} , Q 3, Q 4 , respectively. Each peak is derived from the number of siloxane bonds possessed by the silicon atom, Q ₀ is a monomer having 0 siloxane bonds, Q ₁ is _one siloxane bond, Q ₂ is two siloxane bonds, Q _{2 3} has _three siloxane bonds and Q ₄
Represents a compound having four siloxane bonds. By calculating the area ratio of each of these peaks and calculating according to the following formula, the degree of condensation: x is obtained. In the case of silica (SiO ₂ ), x = 2. x = A × 0 + B × 0.5 + C × 1.0 + D × 1.5 + E
× 2 Each area ratio of Q ₀ , Q ₁ , Q ₂ , Q ₃ , Q ₄ is A: B:
C: D: E. However, A + B + C + D + E = 1. The coefficient y in the expression is obtained from 2x + y = 4. Note that the organic group has two or more different groups,
The amount of each organic group bonded can be easily determined from H-NMR or ¹³ C-NMR. In this case, a method for easily identifying the chemical shift may be appropriately selected.

Preferred examples of the organosilicate used in the present invention include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetraisobutoxysilane, Examples thereof include sec-butoxysilane, tetra-t-butoxysilane and / or partially hydrolyzed condensates thereof. These may be used alone or in combination of two or more. Of these organosilicates, tetramethoxysilane and / or its partially hydrolyzed condensate have high hydrolysis reactivity and are apt to form silanol groups, so that an organic solvent used to prepare a uniform liquid composition is used. It is preferable to improve the safety, because it is possible to easily obtain a composition which does not correspond to a dangerous substance and has a high effect of preventing contamination.

In the organosilicate, the organic group is bonded to silicon via oxygen, but in the silicon-containing composition of the present invention, an organic silicon compound other than the organosilicate, for example, silicon is directly bonded via silicon. It may contain a silicon compound having an organic group. Such compounds include, for example, various silane coupling agents, and more specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane,
Methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane,
Butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane Benzyltrimethoxysilane, benzyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane,
-Trialkoxysilane compounds such as mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and parts thereof Hydrolysis condensate is mentioned.

Further, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane , 3-mercaptopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, dialkoxysilane compounds such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and partially hydrolyzed condensates thereof No.

Further, methyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, dimethylchlorosilane, methylvinyldichlorosilane, 3-chloropropylmethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, etc. And partially hydrolyzed condensates thereof.

Further, 3, -mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-3-trimethoxysilylpropyl-m-phenylenediamine, N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N-bis [3- (trimethoxysilyl)
Propyl] ethylenediamine, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, P- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane and the like.

These organosilicon compounds may be included in the silicon-containing composition of the present invention.
The organosilicate as the component (A) is used in an amount of 25 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of SiO ₂ . This is because such an organosilicon compound other than the organosilicate has a smaller amount of hydrolyzable functional groups than the organosilicate, and has a remarkably low degree of contributing to the prevention of contamination. Of course, such a compound need not be contained at all. Further, a hydrolyzable functional group other than the organooxy group, for example, a silicon compound in which various halogen elements or the like are present may be present, but a substance which is difficult to handle such as hydrochloric acid may be generated by hydrolysis. Therefore, it is not desirable from the viewpoint of environment. At most, the content of the organosilicate is 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of SiO ₂ . Of course, such a compound need not be contained at all.

The component (B) is a catalyst, and may be one having an action of hydrolyzing an organosilicate. More specifically, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Acetic acid, benzenesulfonic acid, toluenesulfonic acid,
Organic acids such as xylenesulfonic acid, ethylbenzenesulfonic acid, benzoic acid, phthalic acid, maleic acid, formic acid, and oxalic acid. Alkaline catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, and organic amine compounds. Organotin compounds such as dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (ethylacetoacetate), ethylacetoacetate aluminum Organic aluminum compounds such as isopropylate, titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), and organic titanium compounds such as titanium tetra-n-butoxide;
Organics other than organosilicates, such as organic zirconium compounds such as zirconium tetrakis (cetylacetonate), zirconium bis (butoxy) bis (acetylacetonate) and zirconium (isopropoxy) bis (acetylacetonate), and zirconium tetra-n-butoxide Metal compounds or metal alkoxide compounds.
And boron compounds such as boron tri-n-butoxide and boric acid.

These catalysts can be used alone or in combination of two or more. The silicon-containing composition of the present invention, building structures, civil engineering structures, industrial equipment, transportation equipment,
When applied to the surface of a painted or unpainted structure such as a traffic sign, it is preferable to use an organic metal chelate compound or a metal alkoxide compound from the viewpoint of preventing corrosion of the substrate by these catalysts.

The amount of the catalyst to be added is determined by converting the amount of Si in the organosilicate to 100 parts by weight in terms of SiO ₂ .
0.1 to 10 parts by weight. More preferably 0.5 to 5
Parts by weight. When the amount of the catalyst is less than 0.1 part by weight, when the silicon-containing composition of the present invention is used, the storage stability of the composition is reduced, and the obtained coating film is poor in exhibiting a low stain function. Further, from the storage stability of the silicon-containing composition and the development of the function of the coating film, the amount of the catalyst to be added is sufficient to be 0.1 to 10 parts by weight, and excessive addition exceeding 10 parts by weight is not required. Regarding the method of adding the catalyst, the catalyst may be dissolved in an organosilicate and used as a mixed solution, or may be used after being dissolved in water or a solvent. Upon dissolution, it may be mixed with an organosilicate and / or water or a solvent at room temperature and dissolved, and may be heated if it is difficult to dissolve at room temperature.

The compounding amount of water as the component C) is 100 to 50,000 parts by weight based on 100 parts by weight of the amount of Si in the organosilicate converted to SiO ₂ . Preferably, it is in the range of 500 to 10000 parts by weight. This means that a large excess of water is added, which is generally larger than the theoretical amount of water that can hydrolyze the organooxy group of the organosilicate, and thereby the silanol groups generated by the hydrolysis of the organosilicate are combined with a large amount of water. It is considered that the coexistence suppresses the condensation reaction of the silanol group, thereby improving the storage stability of the hydrolyzed solution. At the same time, the blending ratio of an organic solvent such as alcohol as a composition can be reduced, and the flash point and the burning point can be suppressed low, so that the safety in use is greatly improved.

The amount of water added is determined by the amount of S in the organosilicate.
i amount is converted to SiO ₂ and 100 parts by weight to 100 parts by weight.
When the amount is less than parts by weight, Si in the obtained silicon-containing composition
The content is so high that it is easily gelled during storage, which causes a problem in storage stability from the practicality point of view and also has a low effect of preventing contamination. On the other hand, if it exceeds 50,000 parts by weight, the silicon content in the obtained silicon-containing composition is too small, and the low-staining function when formed into a coating film is poor.

There is no particular limitation on the water used in the present invention, and tap water may be used. However, depending on the purpose and use, it is desirable to use deionized water or ultrapure water. For example, when used in electrical or electronic materials such as mild steel, copper, aluminum, etc., heat-resistant coatings, moisture-resistant coatings, chemical-resistant coatings, barrier-resistant coatings, electrically insulating coatings, etc. For example, demineralized water can be used, or ultrapure water can be used when contamination of impurities is not desired, such as in applications such as semiconductors.

The solvent of component D) is not particularly limited. Generally, various organic solvents such as alcohols, or glycol derivatives, hydrocarbons, esters, ketones,
One of the ethers or a mixture of two or more thereof can be used. Examples of the alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and acetylacetone alcohol.

Examples of the glycol derivative include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and ethylene glycol monomethyl ether. Examples include acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.

As hydrocarbons, for example, benzene, toluene, xylene, kerosene, n-hexane and the like can be used, and as esters, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl acetoacetate, acetoacetic acid Ethyl, butyl acetoacetate and the like can be used. As ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and the like can be used, and as ethers, ethyl ether, butyl ether, methoxyethanol, ethoxyethanol, dioxane, furan, tetrahydrofuran and the like can be used. Among these solvents, alcohols, especially C1
~ C3 methanol, ethanol, isopropanol,
The glycol derivatives propylene glycol monomethyl ether and diethylene glycol monoethyl ether are easy to handle, and have good storage stability when the silicon-containing composition of the present invention is used, and also exhibit a low contamination function of the obtained coating film. Is preferred.

The amount of the solvent to be added is 1 to 100 parts by weight in terms of the amount of Si in the organosilicate converted to SiO _2.
It should be 00 to 50,000 parts by weight. More preferably 500
It is set in the range of 1 to 10,000 parts by weight. When the amount of the organic solvent added is less than 100 parts by weight based on 100 parts by weight of the amount of Si in the organosilicate converted to SiO ₂ , it becomes difficult to uniformly dissolve the organosilicate, the catalyst and water. On the other hand, if it exceeds 50,000 parts by weight, the silicon content in the obtained silicon-containing composition is too low, and the low contamination function when formed into a coating film is poor. This results in handling problems. In the above, the amount is indicated by the amount of the solvent including the alcohol produced by hydrolysis of the organosilicate.

(Method of Compounding Silicon-Containing Composition) The method of compounding the silicon-containing composition of the present invention is as follows.
What is necessary is just to mix (B), (C), and (D) uniformly within the composition range of the present invention, and it is preferable to form a transparent liquid. The temperature and the mixing method at the time of mixing are not particularly limited. Room temperature is sufficient and there is no particular need for heating. For example, components (A) to (D) are sequentially charged at room temperature using a mixing vessel, a mixing vessel or a mixing machine, a drum can, a petroleum can or the like, and a mixing operation such as stirring or rotation, inversion, or vibration is performed. It is good also as a uniform and transparent one-part type silicon-containing composition. Also,
It may be a silicon-containing composition used as a two-part type compounding form in which the main agent and the curing agent are mixed before use, divided into the main agent and the curing agent.For example, the main agent is an alkyl silicate, the curing agent is a catalyst, water, organic The mixture may be a mixture of solvents, or the main agent may be a mixture of an alkyl silicate and a catalyst, and the curing agent may be a mixture of water and an organic solvent. The form of these two-part types is not limited to those described above.

In the present invention, as the component (E), pigments such as coloring pigments and extenders, fillers, and other various additives which can be blended into ordinary paints can be blended. The amount of addition is not particularly limited, and may be generally selected appropriately so as not to affect the effects of the present invention. Examples of the additive of the component (E) include titanium oxide, zinc oxide, carbon black, ferric oxide (bengara), lead chromate, graphite, yellow iron oxide, ocher, ultramarine, cobalt green, and the like for coloring pigments. And organic pigments such as azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine and quinophthalone. It is also possible to use extenders such as heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, and diatomaceous earth.

Further, various additives include a pigment dispersant,
Anti-settling agent, anti-sag agent, matting agent, plasticizer, defoamer,
Leveling agent, anti-cissing agent, adhesion improver, preservative,
Anti-algal agents, antibacterial agents, deodorants, ultraviolet absorbers and the like,
It is possible to use it by adding a small amount. The amount of these additives is not particularly limited as long as the effect of the intended additive is exhibited, but is, for example, 0.01 to 10 parts by weight based on 100 parts by weight of the silicon-containing composition of the present invention. An addition amount of 0 parts by weight, preferably 0.01 to 1.0 parts by weight is sufficient.

The method of blending the component (E) is not limited, and all the components (A) to (D) may be blended and added to the one-part silicon-containing composition, or an alkyl silicate which is easily dissolved or dispersed. , Water, an organic solvent and the like. In addition, in the case of a silicon-containing composition used as a two-pack type compounding form in which the main agent and the curing agent are mixed before use, which is divided into the main agent and the curing agent, the component (E) is either the main agent or the curing agent. What is necessary is just to mix and use it.

The silicon-containing composition of the present invention can be obtained by blending the above components. The concentration of organosilicate the silicon-containing composition, in terms of Si content in the organosilicate to SiO _2, 0.05 to 15 wt%
And more preferably 0.1 to 10% by weight. When the concentration of the organosilicate is less than 0.05% by weight in terms of SiO ₂ , the concentration is low, and the concentration is low on the surface of painted or unpainted structures such as architectural structures, civil engineering structures, industrial equipment, transportation equipment, and traffic signs. Poor expression of low stain function when applied. On the other hand, when the concentration of the alkyl silicate exceeds 15% by weight in terms of SiO ₂ , the silicon-containing composition tends to gel during storage due to its high concentration, and storage stability tends to be a problem from the viewpoint of practicality. is there.

(Coating method) Paper, cloth, non-woven fabric, etc. are impregnated with the silicon-containing composition of the present invention on the painted surface or unpainted surface of building structures, civil engineering structures, industrial equipment, transportation equipment, traffic signs, etc. It can be applied by a simple method such as wiping or aerosolizing and spraying. Of course, it is also possible to apply by various methods such as ordinary brush coating, roller coating, spray coating, roll coater and flow coater.

The structures to which the silicon-containing composition of the present invention is applied include, for example, tunnels, dams, bridges, tanks,
Civil engineering structures such as chimneys, architectural structures such as houses and buildings, cultural properties such as temples, shrines, stone statues and archeological sites, transportation equipment such as automobiles, aircraft, railway vehicles, ships, industrial equipment, traffic signs, guardrails, etc. Outdoor structures, which are structures that have been pre-painted or unpainted. Specific application surfaces include, for example, the outer and inner surfaces (outer walls and inner walls) of the above-mentioned structures, bathrooms of building structures, walls of cooking rooms, outer cabinet surfaces of furniture, refrigerators, televisions, air conditioners, and windows. Places that are easily contaminated, such as glass. The place where the silicon-containing composition of the present invention can be applied is not limited to the place described above, and can be used in various places for preventing contamination.

The first method of the simple coating method of the present invention is as follows.
The silicon-containing composition of the present invention is impregnated with a medium capable of impregnating the silicon-containing liquid composition of the present invention, such as paper, cloth, non-woven fabric, and the like. Is the way. The second method is a method in which the silicon-containing composition of the present invention is aerosolized and sprayed and applied to the surface of a structure.

In the first method, the silicon-containing composition of the present invention is impregnated in paper, cloth, non-woven fabric or the like in advance and stored in a closed container. Either a coating method or a method in which paper, cloth, nonwoven fabric, or the like is dipped in the silicon-containing composition of the present invention at the time of use, and is appropriately squeezed to wipe the surface of the structure. According to this method, it is possible to easily apply the surface of the structure regardless of whether it is a new coating film, an existing coating film, or non-painting, and there is no sagging due to wiping. In addition, since dirt already attached can be wiped off simultaneously with the wiping, the coating can be performed without previously cleaning the surface of the structure.

In the second method, the silicon-containing composition of the present invention is filled into an aerosol container together with a propellant to form an aerosol. As the propellant, a known propellant can be used. For example, dimethyl ether, LP gas, or the like can be used alone or in combination. This aerosolized product can be used on the same structure surface as in the first method, and the coating method can be easily applied by directly spraying the aerosolized product on the structure surface. In the case where the aerosol is spray-coated on the surface of a coating or the surface of a non-coated material of an existing structure to which dirt has already adhered, pretreatment such as cleaning the surface in advance and removing dirt is preferable. On the other hand, when there is no adhesion of dirt such as the surface of a structure such as a new coating film, a repair coating film, or an unpainted new structure, it is possible to spray-apply the aerosol directly without washing. In this case, it is possible to spray-apply the aerosolized product even if the new coating film, the repair coating film, or the surface of the unpainted new structure is not dried.

As described above, by a simple coating method using the silicon-containing composition of the present invention, the surface of various structures exhibits a good coating finish without coating unevenness, sagging, cracks, etc., stain resistance and weather resistance. It becomes possible to form a thin film capable of improving the coating function such as the property. The silicon-containing liquid composition of the present invention described above can be stably stored in a liquid state, and can be reduced to a dangerous substance under the Fire Services Act by suppressing the amount of an organic solvent such as alcohol. This is also preferable from the viewpoint of safety in use. It is considered that this is because the balance of the quantitative ratios of the components is well maintained.

[0050]

The present invention will be described in more detail with reference to the following examples. In addition,% shows weight% unless there is particular notice.

(Preparation Example 1) Partially hydrolyzed condensate of methyl silicate (manufactured by Mitsubishi Chemical Corporation: trade name "MKC silicate MS51", denotation formula: SiO _0.8 (OC
Using H ₃ ) _2.4 ), the mixture was mixed at the following mixing ratio at room temperature for 20 minutes to prepare a colorless transparent liquid “silicon-containing composition-1”. MS 51 100 parts by weight (in terms of SiO ₂ ) Aluminum catalyst 8% solution 1.8 parts by weight Industrial ethanol 5385 parts by weight Deionized water 7500 parts by weight The content in terms of SiO _{2 in} this liquid is 0.8 wt%.

The dangerous substance determination of the “silicon-containing composition-1” was performed according to the test method for dangerous substance determination prescribed by the Fire Service Law (Article 1-3 to Article 1 of the Cabinet Order on Regulation of Dangerous Goods). 8, Ministry of Ordinance on Testing and Properties of Dangerous Goods). The alcohol component in the “silicon-containing composition-1” is less than 60 wt% (water content: about 57 wt%), and the flash point (tag closed type) and the burning point are measured at the Kitakyushu Fire and Science Research Institute. As a result of measuring (open tag type), the flash point was 25.5 ° C and the burning point was 31.5 ° C. In addition,
Flash point of 60 wt% ethanol water 22.6 ° C, combustion point 2
4.7 ° C. From these results, it can be seen that this "silicon-containing composition-1" does not fall under the category of dangerous substances under the Fire Service Law (the alcohol content is less than 60 wt%, the burning point and the flash point of a 60 wt% aqueous ethanol solution are as follows: Those exceeding the flash point are not considered to be dangerous goods under the Fire Service Act).

(Preparation Example 2) With respect to 1000 parts by weight of the “silicon-containing composition-1” prepared in Preparation Example 1, “BY
0.5 parts by weight of "K-301" (trade name, a repelling inhibitor manufactured by BYK Chemie KK) was added and mixed at room temperature for 20 minutes to prepare "silicon-containing composition-2".

(Preparation Example-3) "MK" used in Preparation Example-1
Instead of "C silicate MS51", use a partially hydrolyzed condensate of ethyl silicate "ES40" (manufactured by Huls Japan) so that the SiO2 content (conversion) in the liquid is 0.8 wt%. Except for adjusting the amount of ethanol, the mixture was mixed at the same mixing ratio as in Preparation Example 1 at room temperature for 20 minutes. As a result, “ES40” did not dissolve and the solution became cloudy. By adjusting the composition, industrial ethanol required for ES40 to become a colorless and transparent homogeneous solution was mixed in the minimum necessary composition at room temperature for 20 minutes to prepare “silicon-containing composition-3”. The content in terms of SiO _{2 in} this liquid is 0.8 wt%. The mixing ratio at this time is shown below. ES40 100 parts by weight (in terms of SiO ₂ ) Aluminum catalyst 8% solution 1.8 parts by weight Industrial ethanol 8531 parts by weight Ion exchange water 4296 parts by weight

The concentration of industrial ethanol in this "silicon-containing composition-3" is about 65% by weight, and the alcohol content is 60% by weight or more. From this, it can be seen that when ethyl silicate is used, the amount of alcohol for achieving a uniform liquid state corresponds to a dangerous substance, and it is understood that methyl silicate is preferably used from the viewpoint of safety.

Example 1 A rag was soaked in the “silicon-containing composition-2” obtained in Preparation Example 2, squeezed lightly by hand, and wiped on the exterior painted surface of a passenger car. The amount of diluent applied is about 16
g / m ² .

(Example 2) The "silicon-containing composition-2" obtained in Preparation Example 2 was impregnated in a paper towel and stored in a closed container. Resin paint (trade name "PF-250
B ", manufactured by Dainippon Color Materials Co., Ltd.), the surface of the heavy oil tank overcoated was washed with water, and wiped on the naturally dried surface. The coating amount of the “silicon-containing composition-2” was about 50 g /
m ² .

Example 3 The “silicon-containing composition-2” obtained in Preparation Example 2 and LPG (propellant) were mixed in a volume ratio of 10
The aerosol container was filled at a ratio of 0: 200 to obtain an aerosol composition. This was spray-coated on a heavy oil tank in the same manner as in Example 2. The applied amount of the aerosol composition is about 35 g /
m ² .

(Comparative Example 1) In Example 1, the portion not diluted with the "silicon-containing composition-2" diluted solution was left.

(Comparative Example 2) In Example 2, the portion containing "silicon-containing composition-2" was not applied by wiping. the above,
The painted surfaces of Examples 1 to 3 and Comparative Examples 1 and 2 were exposed outdoors for six months (June to December 1998, location: Miwa-cho, Sarushima-gun, Ibaraki Prefecture), and the degree of dirt was visually observed. Table 1 shows the results.

[0061]

[Table 1] (Evaluation of the dirt situation was made such that a small amount of dirt was visually observed, "low adhesion", and a case where dirt was clearly observed was "high adhesion". Was evaluated.)

Comparative Example 3 A "silicon-containing composition-4" was prepared in the same mixing ratio as in Preparation Example 2 except that the mixing amount of industrial ethanol was changed to 80 parts by weight. This composition became cloudy and could not be uniformly dissolved.

Comparative Example 4 A silicon-containing composition-5 was prepared in the same mixing ratio as in Preparation Example 2 except that the mixing amount of industrial ethanol was changed to 60000 parts by weight. As in Example 1, outdoor exposure was performed. Six months later, the degree of dirt was "adhered" in the degree of dirt adhesion, and "many" in the rain streaks.

Comparative Example 5 A silicon-containing composition-6 was prepared in the same mixing ratio as in Preparation Example 2 except that the mixing amount of water was changed to 70 parts by weight. As in Example 1, outdoor exposure was performed. Six months later, the degree of dirt was "adhered" in the degree of dirt adhesion, and "many" in the rain streaks.

Comparative Example 6 A "silicon-containing composition-7" was prepared in the same mixing ratio as in Preparation Example 2 except that the amount of water was changed to 60000 parts by weight. Outdoor exposure was performed in the same manner as in Example 1. Six months later, the degree of dirt was "adhered" in the degree of dirt adhesion, and "many" in the rain streaks.

[0066]

As described above, the silicon-containing composition of the present invention can maintain a stable liquid state while keeping the content of the solvent low, and can be regarded as one which does not correspond to a dangerous substance under the Fire Service Law. The safety during handling and painting is improved, the painting method using the same is simple, and a uniform thin film can be formed on the surface of various structures. Furthermore,
The coating film obtained therefrom has an excellent effect of exhibiting functions such as stain resistance, weather resistance and contaminant removal properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B05D 7/24 303 B05D 7/24 303A C08K 3/00 C08K 3/00 5/00 5/00 C08L 83 / 02 C08L 83/02 C09D 5/16 C09D 5/16 (72) Inventor Wakako Fukamachi 1778 Owada Sezaki, Miwa-machi, Sarushima-gun, Ibaraki Pref. Dainichi Color Materials Industry Co., Ltd. Sanwa Plant (72) Inventor Naoki Honma Tokyo (72) Inventor Nobuyuki Matsuzoe 1-1 Kurosaki Shiroishi, Yawatanishi-ku, Kitakyushu-shi Mitsubishi Chemical Corporation Kurosaki Works (72) Inventor Takeshi Sawai Kurosaki Shiroishi, Yawatanishi-ku, Kitakyushu-shi, Chiyoda-ku, Japan No. 1-1 F-term in Kurosaki Plant of Mitsubishi Chemical Corporation (reference) 4D075 AA01 AC51 CA34 DC01 EB42 EC11 EC13 4J002 CP021 DA039 DD016 DE027 DE056 DE086 DE099 DE109 DE119 DE139 DF006 DF036 DG046 DH026 DJ009 EA028 EA058 EC038 EC048 EC076 ED028 EE038 EF036 EF066 EF096 EH038 EH058 EL068 EL108 EN006 EV236 EZ006 EZ046 FD001 FD001 06

Claims (12)

[Claims] 1. The following components (A) to (1):
Applying a silicon-containing liquid composition comprising (D),
A painting method that prevents the surface of a structure from being stained. Component (A) 100 parts by weight of organosilicate in terms of SiO ₂ Component (B) catalyst 0.1 to 10 parts by weight Component (C) water 100 to 50,000 parts by weight Component (D) solvent 100 to 50,000 parts by weight 2. The following components (A) to
Applying a silicon-containing liquid composition comprising (E),
A painting method that prevents the surface of a structure from being stained. Component (A) 100 parts by weight of organosilicate in terms of SiO ₂ Component (B) catalyst 0.1 to 10 parts by weight Component (C) water 100 to 50,000 parts by weight Component (D) solvent 100 to 50,000 parts by weight Component (E) pigment , Fillers, paint additives 3. The coating method according to claim 1, wherein the silicon-containing liquid composition comprising the components (A) to (D) is aerosolized and sprayed on the surface of the structure to apply the composition. 4. The coating method according to claim 2, wherein the silicon-containing liquid composition comprising the components (A) to (E) is aerosolized and sprayed onto the surface of the structure to apply the composition. 5. The coating method according to claim 1, wherein the silicon-containing liquid composition comprising the components (A) to (D) is applied by wiping the surface of the structure. 6. The coating method according to claim 2, wherein the silicon-containing liquid composition comprising the components (A) to (E) is applied by wiping the surface of the structure. 7. The composition of claim 1, wherein the component (A) is of the formula SiOx (OR)
The coating method according to any one of claims 1 to 6, which is represented by y. (However, 0 ≦ x ≦ 1.2, 1.4 ≦ y ≦ 4
R is an alkyl group having 1 to 4 carbon atoms, and 2x +
y = 4. ) 8. The coating method according to claim 1, wherein the organosilicate is methyl silicate. 9. A silicon-containing liquid composition comprising the following components (A) to (D). Component (A) 100 parts by weight of organosilicate in terms of SiO ₂ Component (B) catalyst 0.1 to 10 parts by weight Component (C) water 100 to 50,000 parts by weight Component (D) solvent 100 to 50,000 parts by weight 10. The following components (A) to
A silicon-containing liquid composition comprising (E). Component (A) 100 parts by weight of organosilicate in terms of SiO ₂ Component (B) catalyst 0.1 to 10 parts by weight Component (C) water 100 to 50,000 parts by weight Component (D) solvent 100 to 50,000 parts by weight Component (E) pigment , Fillers, paint additives 11. Component (A) having the chemical formula SiOx (O
R) The silicon-containing liquid composition according to claim 9 or 10, which is represented by y. (However, 0 ≦ x ≦ 1.2, 1.
4 ≦ y ≦ 4, R is an alkyl group having 1 to 4 carbon atoms, and 2x + y = 4. ) 12. The silicon-containing liquid composition according to claim 9, wherein the organosilicate is methyl silicate.