JP2005272835A - Silicon-containing liquid composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition improving function of coating such as resistance to pollution, weather resistance, etc., only by coating to the substrate such as the surface of a structure like an architectural structure, a civil engineering structure, etc., directly or on an existing coating without necessitating under coating. <P>SOLUTION: The invention relates to the silicon-containing liquid composition having ≥50 wt.% of water content and ≥70% of light transmittance, wherein the liquid composition containing silicon is a composition capable of forming a coating on a substrate having ≥60° of contact angle to water. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention prevents dirt and oily components from adhering to surfaces of building structures, civil engineering structures, industrial equipment, traffic signs, etc., and easily removes adhering dirt by rain or wiping. It is related with the liquid composition used suitably for forming the coating film which can be formed.

In recent years, landscapes such as building structures and civil engineering structures have been regarded as important, and various low-contamination paint finishes have been performed for the purpose of improving the contamination resistance of the surfaces of these structures. As a method for finishing a low-contamination paint, a highly weather-resistant organic paint such as a fluorine resin paint, an acrylic silicon resin paint, or a urethane resin paint has been conventionally used for the finish paint.
Also, in recent years, by adding a small amount of alkyl silicate to these paints to make the coating surface hydrophilic, it is difficult for dust and oily contaminants to adhere, and even if they adhere, it can be washed away by rain or the like. Has been done. In addition, inorganic paints based on organopolysiloxane, which are generally superior in weather resistance, durability, chemical resistance, heat resistance, etc. compared to organic paints, are also being actively developed, and some of them are put into practical use. Has been.

  However, when performing these finish coatings, in order to improve the adhesion between the structure and the coating film, generally, undercoating is applied between the structure and the finish coating, and in some cases intermediate coating is applied. This is a problem common to organic paints and inorganic paints. In particular, the coating film of organic paint is easily contaminated by the influence of sand dust, metal powder, rain (acid rain, etc.) and exhaust gas, and the scenery is likely to deteriorate.

  In addition, top coatings with a small amount of alkyl silicate added to organic coatings tend to increase in viscosity during storage, and the coating film is susceptible to problems such as cracks. Need. As with organic paints with a small amount of alkyl silicate added, inorganic paints also have problems with the storage stability of the paint, and many of them require heat-curing during painting. At present, it has various problems in handling and painting because it is easy.

In addition, these paints contain many volatile organic solvents, so they are classified as dangerous materials under the Fire Service Act of Japan, and care must be taken when handling them safely. As described above, the existing topcoat paint is desired to be improved in terms of storage stability, coating film function, workability during coating, safety, environmental load, and the like.
Furthermore, a method for imparting low contamination by applying a hydrolyzate of organosilicate to make the surface of the coating film hydrophilic has been proposed (for example, see Patent Document 1, etc.), but the solvent component is a water / alcohol system. And the concentration of contained SiO ₂ is so dilute that there is a problem that repelling is likely to occur on the organic coating film.

Although the addition of a surface tension adjusting agent or the like has been proposed as a countermeasure against this repellency, it cannot actually be sufficiently prevented. Further, when a large amount of the surface tension adjusting agent is added so as not to cause cissing, the contact angle of the coating film with water becomes large, and it becomes difficult to exhibit low contamination.
JP 2000-327996 A

  An object of this invention is to provide the coating composition which can form a hydrophilic coating film, without causing repellency irrespective of the presence or absence of the existing coating film.

As a result of intensive studies in view of the above problems, the present inventors have obtained a coating film that has a silicon-containing liquid composition having the following composition that is rich in contamination resistance and that can be easily removed even if contaminants adhere to it. The present invention has been completed.
That is, the present invention is a silicon-containing liquid composition having a water concentration of 50% by weight or more and a light transmittance of 70% or more, wherein the silicon-containing liquid composition has a water contact angle of 60 degrees or more. The present invention resides in a silicon-containing liquid composition characterized by being a composition capable of forming a film on a substrate. Further, it is formed by blending the following components (A) to (E), the concentration of the component (A) is 6% by weight or less in terms of SiO ₂ , and the concentration of the component (C) is 50% by weight or more. A silicon-containing liquid composition characterized by

Component (A) Organosilicate or oligomer thereof
100 parts by weight in terms of SiO ₂ Component (B) Hydrolysis condensation catalyst 0.1 to 10 parts by weight Component (C) Water 100 to 50000 parts by weight Component (D) Organic solvent 100 to 50000 parts by weight Component (E) Aqueous resin component 10 to 1000 parts by weight as solid content

  ADVANTAGE OF THE INVENTION According to this invention, regardless of the presence or absence of the existing coating film on the structure surface, it is hydrophilic and can form the coating film excellent in stain resistance, a weather resistance, etc.

Hereinafter, the present invention will be described in detail.
The silicon-containing liquid composition according to the present invention is a silicon-containing liquid composition having a water concentration of 50% by weight or more and a light transmittance of 70% or more. Furthermore, this silicon-containing liquid composition is a composition capable of forming a film on a substrate having a water contact angle of 60 degrees or more.
In addition, the silicon-containing liquid composition according to the present invention is not particularly limited as long as it satisfies the above performance, but for example, components (A) to (E) described below are essential components. This can be further blended with component (F) and the like, if necessary.

Component (A);
Component (A) is an organosilicate or an oligomer thereof (hereinafter collectively referred to as 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 organoxysilane in which four organic groups are bonded to one silicon atom through an oxygen atom, and an organoxysiloxane in which silicon forms a siloxane main chain (Si—O) n). .

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

From the aspect of solubility in the case of the silicon-containing liquid composition according to the present invention and the expression of the low-fouling function of the resulting coating film, the organic group bonded to silicon via an oxygen atom in the component (A) is , A methyl group and / or an ethyl group are preferable, and a methyl group is most preferable.
In the case where the organic group is an alkyl group having more than 4 carbon atoms, since the solubility is low, a large amount of an organic solvent is required to obtain the liquid composition according to the present invention. In many cases, handling problems such as falling under the category of dangerous goods occur. In addition, alkyl groups having more than 4 carbon atoms are poorly hydrolyzable, and even when the resulting coating film is exposed outdoors, the formation of SiOH groups is remarkably slow, and there is a tendency for low fouling function to be poor.

  Examples of the organoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, and dimethoxydiethoxysilane. Examples of the organoxysiloxane include hydrolyzed condensates of these organoxysilanes. The degree of condensation is not particularly limited, but a preferred range includes those in which the following formulas showing the degree of condensation are shown below.

SiOx (OR) y
(In the formula, 0 ≦ x ≦ 1.2, 1.6 ≦ y ≦ 4, and 2x + y = 4. R is an organic group, preferably an alkyl group having 1 to 4 carbon atoms.)
The coefficient x indicates the degree of condensation of the siloxane, but when the siloxane has a molecular weight distribution, it means the average degree of condensation. x = 0 represents an organoxysilane which is a monomer, and 0 <x <2 corresponds to an oligomer which is a condensate obtained by partial hydrolysis condensation of the monomer. x = 2 corresponds to SiO ₂ (silica). The degree of condensation x of the organosilicate used in the present invention is:
The range of 0 ≦ x ≦ 1.2 is preferable, and more preferably 0 ≦ x ≦ 1.0. The siloxane main chain may be linear, branched or cyclic, or a mixture thereof.

  Organosilicates with x> 1.2 are difficult to use because they have a high degree of condensation, a high molecular weight, a high viscosity, are easily gelled during storage and have poor stability. In addition, since the solubility in organic solvents is low, a large amount of organic solvent is required when preparing the silicon-containing liquid composition according to the present invention, and the resulting composition falls under the category of dangerous materials under the Japanese Fire Service Act. It is easy to cause problems in handling such as.

The characteristic formula SiOx (OR) can be obtained by the following method. Degree of condensation: x can be easily known by measuring Si-NMR. Tetramethylsilane (reference substance) has a chemical shift value of 0 ppm, and in the case of organosilicate, 5 groups of peaks are given between the chemical shift value and -75 to -120 ppm, and Q0, Q1, Q2 respectively.
, Q3, Q4. Each peak is derived from the number of siloxane bonds of silicon atoms, Q0 is a monomer having zero siloxane bonds, Q1 is one siloxane bond, Q2 is two siloxane bonds, and Q3 is siloxane. The number of bonds is 3, and Q4 represents the number of siloxane bonds is 4. The degree of condensation: x is obtained by calculating the area ratio of each peak and calculating according to the following formula. 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 Q0, Q1, Q2, Q3, and Q4 is A: B: C: D: E. However, A + B +
C + D + E = 1. The coefficient y in the equation is obtained from 2x + y = 4. In addition, when it has two or more different groups as an organic group and calculates | requires the bonding amount of each organic group, it can obtain | require easily from H-NMR or ¹³ C-NMR. In this case, a method that allows easy identification of chemical shifts may be selected as appropriate.

  Preferable specific examples of the organosilicate used in the present invention include, for example, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetra sec-butoxysilane, Examples thereof include tetra-t-butoxysilane and partial hydrolysis condensates thereof. A combination of two or more of these can also be used. Among these organosilicates, tetramethoxysilane and its partially hydrolyzed condensate have high hydrolytic reactivity and easily generate silanol groups, so the amount of organic solvent used to prepare a uniform liquid composition is small. This is preferable because a liquid composition that does not require a small amount, does not correspond to a dangerous substance, and has a high anti-contamination effect can be easily obtained.

  In the organosilicate, the organic group is bonded to silicon through oxygen. However, in the silicon-containing liquid composition according to the present invention, an organic silicon compound other than the organosilicate, for example, an organic bonded directly to silicon. A silicon compound having a group may be contained. Examples of such compounds include various silane coupling agents. Specific examples thereof include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane. Methoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri Propoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 3-glycidoxypropyl Methoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2- Examples thereof include trialkoxysilane compounds such as aminoethyl) -3-aminopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane, and partial hydrolysis condensates thereof.

  Further, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- Examples thereof include dialkoxysilane compounds such as mercaptopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and partial hydrolysis condensates thereof.

  Further, chlorosilane compounds such as methyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, dimethylchlorosilane, methylvinyldichlorosilane, 3-chloropropylmethyldichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane , And these partially hydrolyzed condensates.

  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] phenethyltrimethoxy Silane etc. And the like.

When these organosilicon compounds are contained in the silicon-containing liquid composition according to the present invention, the amount thereof is usually in terms of Si with respect to 100 parts by weight (in terms of SiO ₂ ) of organosilicate as component (A). And 50 parts by weight or less. The amount is preferably 30 parts by weight or less, and more preferably 20 parts by weight or less. This is because these organosilicon compounds have a smaller amount of hydrolyzable functional groups than organosilicate, and the degree of contribution to the prevention of contamination in the coating film is extremely low. In addition, since a silicon compound containing a halogen element may generate a difficult-to-handle substance such as hydrochloric acid by hydrolysis, it is not environmentally desirable. At most, Si is contained in 100 parts by weight of organosilicate (in terms of SiO ₂ ). In terms of conversion, it is 20 parts by weight or less, preferably 10 parts by weight or less.

Component (B);
Component (B) is a hydrolysis-condensation catalyst as long as it has a hydrolytic condensation action of organosilicate. More specifically, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Organic acids such as acetic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, benzoic acid, phthalic acid, maleic acid, formic acid, and oxalic acid. Basic compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia and organic amine compounds. Organotin compounds such as dibutyltin dilaurate, dibutyltin dioctiate, dibutyltin diacetate, aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (ethylacetoacetate), ethylacetoacetate aluminum di Organic aluminum compounds such as isopropylate, organic titanium compounds such as titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium tetra-n-butoxide, zirconium tetrakis (acetylacetonate), zirconium bis ( Butoxy) bis (acetylacetonate) and zirconium (isopropoxy) bis (acetylacetonate), zir Tetra n- such as organic zirconium compounds such butoxide, organometallic compounds other than organosilicate or a metal alkoxide compound. Examples thereof include boron compounds such as boron trinormal butoxide and boric acid.

These catalysts can also be used in combination of two or more. In the case where the silicon-containing liquid composition according to the present invention is applied to a building structure, a civil engineering structure, an industrial device, a transportation device, a traffic sign, or the like, an organic metal chelate compound or a metal is used from the viewpoint of preventing corrosion of the substrate by a catalyst. It is preferable to use an alkoxide compound.
The amount of the catalyst added is 0.1 with respect to 100 parts by weight of the organosilicate (in terms of SiO ₂ ).
-10 parts by weight, more preferably 0.5-5 parts by weight. When the amount of catalyst is less than 0.1 parts by weight, the storage stability of the silicon-containing liquid composition is lowered, or the resulting coating film is poor in the low-fouling function. Moreover, 0.1-10 weight part is sufficient for the addition amount of a catalyst from the storage stability of a silicon-containing liquid composition, and the expression property of a coating film function, and the excessive addition exceeding 10 weight part is unnecessary. The method for adding the catalyst is arbitrary, and it may be used by dissolving in advance in an organosilicate, or may be used by dissolving in water or a solvent. The catalyst usually dissolves easily at room temperature only by mixing with an organosilicate, water or solvent, but may be heated if it is difficult to dissolve.

Component (C);
The amount of water as component (C) is 100 to 50000 parts by weight, preferably 500 to 25000 parts by weight, with respect to 100 parts by weight of the organosilicate (in terms of SiO ₂ ). This generally means that an excessive amount of water is added in excess of the theoretical amount of water that can hydrolyze the organoxy group of the organosilicate. Thereby, the silanol group produced | generated by the hydrolysis of the organosilicate coexists with a large amount of water, the condensation reaction of the silanol group is suppressed, and the storage stability of the hydrolyzed solution is considered to be improved. Moreover, this can reduce the blending ratio of an organic solvent such as alcohol. Furthermore, by making water 50% by weight or more, the flash point can be raised and it can be made non-hazardous.

When the amount of water added is less than 100 parts by weight based on 100 parts by weight of the organosilicate (in terms of SiO ₂ ), the Si content in the resulting silicon-containing liquid composition becomes too high and is easily gelled during storage. In addition to the problem of stability, the effect of preventing contamination of the coating film is low. On the other hand, if it exceeds 50000 parts by weight, the Si content in the resulting silicon-containing liquid composition is too small, and the film-forming property is liable to cause repellency, resulting in the formation of a coating film with excellent low-fouling function. Have difficulty.

  The water used in the present invention is not particularly limited and may be tap water. However, depending on the application of the silicon-containing liquid composition, it may be desirable to use deionized water or ultrapure water. For example, when the object of painting is mild steel, copper, aluminum, etc., which are particularly susceptible to corrosion by acids, and the formation of heat resistant coating, moisture resistant coating, chemical resistant coating, barrier resistant coating, electrical insulating coating, etc. is required When used for electrical and electronic materials, it is preferable to use demineralized water. Further, when it is not desirable to mix impurities such as semiconductors, it is preferable to use ultrapure water.

Component (D);
Any solvent can be used as the solvent for component (D) as long as it provides a uniform liquid composition. In general, water-soluble organic solvents such as alcohols and glycol derivatives are used, but esters, ketones, ethers and the like can also be used. Further, if the amount is small, hydrocarbons can be used in combination with other organic solvents. Examples of alcohols include lower alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4- And lower alkylene glycols such as butanediol.

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

  Examples of hydrocarbons include benzene, toluene, xylene, kerosene, n-hexane, and examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, acetoacetate. Butyl acetate or the like can be used. Examples of ketones that can be used include acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetyl acetone. Examples of ethers that can be used include ethyl ether, butyl ether, methoxyethanol, ethoxyethanol, dioxane, furan, and tetrahydrofuran. Among these solvents, alcohols, particularly monohydric alcohols having 1 to 3 carbon atoms such as methanol, ethanol and isopropanol, and glycol derivatives such as propylene glycol monomethyl ether and diethylene glycol monoethyl ether are easy to handle. In addition to good storage stability in the case of a silicon-containing liquid composition, it is preferable from the standpoint of expression of a low-fouling function of the resulting coating film.

The blending amount of the solvent is 100 with respect to 100 parts by weight of the organosilicate (in terms of SiO ₂ ).
It is -50000 weight part, Preferably it is the range of 200-10000 weight part. When the blending amount of the organic solvent is less than 100 parts by weight with respect to 100 parts by weight of the organosilicate (in terms of SiO ₂ ), it becomes difficult to uniformly dissolve the organosilicate, the catalyst, and water. On the contrary, if it exceeds 50000 parts by weight, the Si content in the resulting silicon-containing liquid composition is too small, the film-forming property is lowered, and it becomes difficult to form a coating film having a low contamination function. At the same time, the possibility of falling under the dangerous goods of the Japanese Fire Service Act increases. The solvent of component (D) also includes alcohol produced by hydrolysis of organosilicate.

Component (E);
Component (E) is an aqueous resin component. Specific examples include water-dispersible resins, that is, aqueous emulsions and water-soluble resins.
Examples of the aqueous emulsion include (meth) acrylic resin emulsions, styrene-acrylic resin emulsions, acrylic silicon resin emulsions, fluororesin emulsions, urethane resin emulsions, urethane-acrylic resin emulsions, and the like. Examples of the water-soluble resin include polyvinyl alcohol (PVA), ethylene vinyl alcohol copolymer resin (EvOH), polyethylene oxide, polyvinyl acetal, and water-soluble acrylic resin.

(Meth) acrylic resin emulsions include (meth) acrylic monomer homopolymer emulsions and copolymer emulsions, (meth) acrylic monomers and other monomers copolymerizable therewith. And a copolymer emulsion.
(Meth) acrylic monomer means acrylic acid, methacrylic acid and ester compounds thereof, (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having cycloalkyl group, (meth) acrylic acid alkoxyalkyl Examples include esters and cross-linkable (meth) acrylic acid esters, and two or more of these may be used in combination.

Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, (meth) Examples include lauryl acrylate and stearyl (meth) acrylate.
Examples of the (meth) acrylic acid ester having a cycloalkyl group include (meth) acrylcyclohexyl and isobornyl (meth) acrylate.

Examples of the (meth) acrylic acid-based alkoxyalkyl ester include 2 methoxyethyl (meth) acrylate, 2 ethoxyethyl (meth) acrylate, and 2 butoxyethyl (meth) acrylate.
Examples of the (meth) acrylic acid alkyl ester having crosslinkability include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like.

In the present specification, “(meth) acryl” means “acryl or methacryl”.
Other monomers copolymerizable with (meth) acrylic monomers include aromatic hydrocarbon vinyl monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene, maleic acid, itaconic acid, croton Α, β-ethylenically unsaturated carboxylic acids such as acids, fumaric acid, citraconic acid and the like, acid anhydrides thereof, sulfonic acid-containing vinyl monomers such as styrene sulfonic acid, vinyl sulfonic acid, vinyl chloride, vinylidene chloride, chloroprene, etc. Chlorine-containing unsaturated compounds, hydroxyl-containing alkyl vinyl ethers such as hydroxyethyl vinyl ether and hydroxypropyl vinyl ether, alkylene glycol monoallyl ethers such as ethylene glycol monoallyl ether, propylene glycol monoallyl ether and diethylene glycol monoallyl ether, ethylene, Α-olefins such as lopyrene and isobutylene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl pivalate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, ethyl allyl ether, butyl allyl ether, etc. Examples include allyl ether.

Acrylic silicone resin emulsions include homopolymer emulsions or copolymer emulsions of silicon-containing acrylic monomers, silicon-containing acrylic monomers, and radical polymerization with other monomers copolymerizable therewith. And a copolymer emulsion obtained by the following.
Silicon-containing acrylic monomers include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth ) Hydrolyzable silyl group-containing vinyl monomers such as acryloxypropylmethyldiethoxysilane.

As the other monomer copolymerizable with the silicon-containing acrylic monomer, monomers exemplified as being usable in the above-mentioned acrylic resin emulsion can be used.
Fluororesin emulsions include homopolymer emulsions or copolymer emulsions of fluorine-containing monomers, copolymers obtained by radical copolymerization of fluorine-containing monomers and other monomers copolymerizable therewith. A combined emulsion or the like can be used.

  Fluorine-containing monomers include fluoroolefins such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, pentafluoroethylene, hexafluoropropylene, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, And fluorine-containing (meth) acrylates such as perfluorocyclohexyl (meth) acrylate.

The urethane resin-based emulsion is a generic term for emulsions that give urethane bonds in the coating film formed from the silicon-containing liquid composition according to the present invention, and may be those already having urethane bonds in the liquid composition. The thing which forms urethane bridge | crosslinking by reaction after formation may be sufficient.
Specifically, a method of copolymerizing a polymerizable monomer having a urethane bond with another copolymerizable monomer, a method of polymerizing a polymerizable unsaturated monomer in the presence of an aqueous resin having a urethane bond And an emulsion obtained by a method of mixing an aqueous urethane resin having a reactive group and an emulsion containing a group capable of reacting with the reactive group.

  Examples of water-dispersible resins that can be obtained on the market include acrylic resin emulsions such as Aquabrid 903, Aquabrid TT-103, Aquabrid CS-175, and Aquabrid 4790 from Daicel Chemical Industries, and urethanes such as Aquabrid 950. An acrylic resin emulsion is mentioned. Among these, an acrylic resin type is preferable to a urethane resin type, and particularly Aquabrid CS-175 and 4790 are preferable.

In the urethane resin emulsion, precipitation may occur when a certain amount or more of alcohol is present in the system.
The water-dispersible resin available on the market usually contains a film-forming aid, but the component (E) may or may not contain a film-forming aid. The film forming aid has the following functions. That is, the water-dispersible resin forms a continuous film in the drying process, but if the minimum film-forming temperature (MFT) of the water-dispersible resin is equal to or higher than the coating operation temperature, the water-dispersible resin forms a continuous film due to poor film formation. It cannot be formed. In order to enable film formation in a low temperature range, it is necessary to lower the Tg of the base resin and adjust the MFT to a low temperature range. It is necessary to use a high base resin. In such a case, the target film can be formed by adding a volatile organic compound as a film-forming aid, even if a base resin having a high Tg is used.

Further, since the water-dispersed resin composition is an aqueous medium, it freezes in a low temperature (0 ° C. or lower) region.
In cold regions, there are long-term storage at 0 ° C or below and painting operations. Therefore, low-volatile organic compounds such as ethylene glycol and propylene glycol are used for the purpose of preventing freezing at low temperatures and improving freeze-thaw stability. The method of intentionally adding is common. As the film-forming aid used for such purposes, those having a high boiling point and low volatility are preferable, for example, ethyl carbitol, butyl carbitol, butyl carbitol acetate, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, benzyl acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name: Texanol CS-12, manufactured by Chisso Corporation), glycols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, and benzyl alcohol It is done.

  Examples of the water-soluble resin of component (E) include polyvinyl alcohol, polyethylene oxide, ethylene-vinyl alcohol, polyvinyl acetal, and the like, specifically, Soarnol D2908, Goseifamer Z, Gohsenol N, Gohsenol from Nippon Synthetic Chemical Industry Co., Ltd. A, Gohsenol G, Sreck KX-5, Sreck KW-10 from Sekisui Chemical Co., Ltd. and the like.

  The silicon-containing liquid composition according to the present invention is a homogeneous solution and is not usually gelled. The light transmittance is 70% or more. The light transmittance is measured as follows. Using a U-1000 type Hitachi ratio beam spectrophotometer manufactured by Hitachi, Ltd., a 1 cm quartz cell is filled with a sample at a wavelength of 550 nm, and the transmittance is measured. At this time, the transmittance in distilled water is corrected to 100%.

The silicon-containing liquid composition according to the present invention is characterized in that the coating film obtained by applying the liquid composition has low contamination, and when an exposure test is conducted according to the JIS Z2381 direct exposure test method for 3 months. In addition, a low-contamination transparent coating film having a whiteness change (ΔL) of 5 or less, and further 4 or less can be formed.
The exposure angle in the exposure test in the present invention is 60 degrees from the horizontal plane. Moreover, the measuring method of a whiteness change ((DELTA) L) is as follows. As a measuring device, Color Checker NR-1 manufactured by Nippon Denshoku is used. Standard white plate (Nippon Denshoku Calibration Board C / 2 ° X = 85.32, Y = 87.08, Z = 99.35D65 / 10 ° X = 82.50, Y = 87.07, Z = 90 17), the L value of the coating film before being subjected to the actual exposure test is measured, and the brightness difference (L0) from the standard white plate is obtained. Then, the L value is measured again after the exposure test to determine the brightness difference (L) from the standard white plate, and ΔL = | L ₀ −L | is calculated.

The silicon-containing liquid composition according to the present invention forms a hydrophilic coating film. The hydrophilicity of the coating film can be displayed using the contact angle of water as an index. The contact angle of water is the contact angle formed between the water droplet and the coating film when the water droplet is placed on the coating film surface.
In general, when the contact angle between the coating film and water is larger than 60 °, when rainwater flows on the surface of the coating film, it flows only in specific places, making it difficult to clean the entire coating film, and rain streak stains are likely to adhere. The silicon-containing liquid composition according to the present invention can easily form a coating film having a contact angle with water of 60 ° or less, and 50 ° by adjusting the composition. It is also easy to form the following coating film.
Moreover, the coating film obtained with the silicon-containing liquid composition according to the present invention is usually colorless and transparent.

The silicon-containing liquid composition according to the present invention can be produced by uniformly mixing the components (A), (B), (C), (D) and (E) described above within the composition range of the present invention. it can. For example, using an appropriate mixing container such as a mixing tank or a mixer, components (A) to (E) are sequentially charged at room temperature, and a mixing operation such as stirring, rotation, and vibration is performed to obtain a uniform silicon-containing liquid composition. do it.
The hydrophilicity of the coating film formed by the liquid composition according to the present invention is due to silanol groups, and since the coating film is hydrophilic, it exhibits stain resistance. It is preferable that it is a form which has many. For this purpose, the component (A) itself of the liquid composition preferably has a large amount of silanol groups. In such a liquid composition, for example, components (A), (B), (C), and in some cases, (D) component are also mixed in advance and heated to promote hydrolysis condensation of component (A). Thereafter, it can be obtained by adding the component (E) to obtain a final composition. In this case, the components (A) and (B) are mixed with only a part of the components (C) and (D) to carry out hydrolysis condensation of the component (A), and then the components (C) and ( The remainder of D) may be added.

In one preferred method for producing the liquid composition according to the present invention, the components (A) to (D) are first added so that the concentration of the component (A) is ₂ to 6% by weight in terms of SiO _2. Component (A) is hydrolyzed and condensed by blending leaving (C) and a part of component (D). Next, the remaining component (C) and component (D) are added to the mixture to dilute the mixture by 2 times or more, and the components (E) and (F) are further added to obtain a desired silicon-containing liquid composition.

  A surface tension reducing agent (hereinafter sometimes referred to as component (F)) can also be added to the silicon-containing liquid composition according to the present invention. There are many types of surface tension reducing agents, which can be classified into four types: (1) acrylic, (2) vinyl, (3) silicone, and (4) fluorine. Any of these can be used in the present invention. The compounding amount of the component (F) is 0.1 to 2% by weight, preferably 0.3 to 1% by weight in the silicon-containing liquid composition. Among the components (F), the ability to lower the surface tension is generally strong in the silicone system and the fluorine system, and the acrylic and vinyl systems have the advantage that they can be used in both top / intermediate coatings with very few problems such as recoatability. Examples of the component (F) that can be obtained on the market include Dapro W77, Dapro U-99, and Dapro W95HS manufactured by ELEMENTIS JAPAN.

  In the silicon-containing liquid composition according to the present invention, a pigment dispersant, an anti-settling agent, an anti-sagging agent, a matting agent, a reversing agent, an antifoaming agent, an adhesion improver that is an auxiliary agent added to a conventional paint, Preservatives, algae inhibitors, antibacterial agents, deodorants, UV absorbers and the like can be added. The amount of these additives is not particularly limited as long as the effect of the target additive is manifested, but is 0.01 to 10.0% by weight in the silicon-containing liquid composition according to the present invention. The addition amount of 0.01 to 1.0% by weight is sufficient.

The blending method of component (F) is not limited, and it may be added to a silicon-containing liquid composition prepared by blending all components (A) to (E), and component (F) is easily dissolved or dispersed. You may add and use for each component, such as an alkyl silicate, water, and an organic solvent.
The concentration of organosilicate in the silicon-containing liquid composition according to the present invention is preferably 6% by weight or less, more preferably 0.2 to 5% by weight in terms of SiO ₂ . The lower limit of the concentration of the organosilicate is 0.1 wt% in terms of SiO ₂ concentration. If it is less than this concentration, the low contamination property of the coating film formed using this is hardly exhibited. On the contrary, when the concentration of organosilicate exceeds 6% by weight in terms of SiO ₂ , since the concentration is high, it tends to gel during storage and storage stability tends to be a problem.

  In the silicon-containing liquid composition according to the present invention, the concentration of the component (C) is 50% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more. This reduces organic solvent components, suppresses volatile components during coating, promotes hydrolysis of organosilicates as much as possible, ensures a sufficient amount of silanol groups during coating formation, Is to keep the surface hydrophilic. If the surface of the coating film is hydrophilic, the attached dirt is easily washed away by rainfall, and self-cleaning properties can be imparted to the surface. In addition, since the quantity of the water consumed by hydrolysis of an organosilicate is very small, the preparation amount of the water which is a component (C) and the moisture content in a silicon-containing liquid composition are substantially the same.

On the other hand, the organic solvent of component (D) is less than 50% by weight, preferably less than 20% by weight, more preferably less than 10% by weight.
The silicon-containing liquid composition according to the present invention preferably has a silicon concentration of 40 to 90% by weight in terms of SiO ₂ when coated and dried. This concentration is 45 to 85% by weight, in particular 50
More preferably, it is ˜80% by weight. The silicon concentration in the dry film is determined as follows.

Silicon concentration in dry film (%) = Si amount in terms of SiO ₂ in the silicon-containing liquid composition (g)
/ (Si amount in terms of SiO ₂ in silicon-containing liquid composition + solid content (g) of component (E)) × 100
When the silicon concentration in the dry film is 90% or more, the adhesion to the glass substrate is not particularly problematic, but repelling on the organic coating film (for example, on the coating film of a general paint, on the resin substrate, etc.) It becomes difficult to obtain a large and uniform coating film. On the other hand, if it is less than 40%, the paintability is good, but the hydrolyzed condensate of organosilicate, that is, the concentration of silica fine particles having a large amount of silanol groups is low, and hydrophilicity is not exhibited.

The silicon-containing liquid composition according to the present invention is excellent in storage stability, for example, it does not lead to gelation even in a storage stability test at 50 ° C. for 40 days in a sealed state, and maintains the coating film performance at the initial stage of preparation. Can do.
The silicon-containing liquid composition according to the present invention can be applied to the surface of a substrate such as a building structure, a civil engineering structure, an industrial device, a transportation device, or a traffic sign regardless of the presence or absence of an existing coating film. . In particular, it is characterized in that a film can be formed on a substrate having a water contact angle of 60 ° or more on the surface of the substrate, preferably, a film can be formed on a substrate having a water contact angle of 70 ° or more, more preferably, It is characterized in that the film can be formed on a substrate having a water contact angle of 85 ° or more, and more preferably, the film can be formed on a substrate having a water contact angle of 80 ° or more. The substrate is not particularly limited as long as the contact angle of water is 60 degrees or more, and examples thereof include an organic substrate or a substrate covered with an organic film.

In the present invention, “being able to form a film” means the following. It is possible to form a coating film having an area of 85% or more on the coated surface by dipping the substrate to a depth of 7 cm in a substrate having a width of 7 cm, a length of 15 cm, and a thickness of 2 mm, and dipping at a lifting speed of 2 mm / sec. . The dipping conditions are as follows. It is applied at a lifting speed of 2 mm / second in a room at a temperature of 25 ± 10 ° C. (humidity 65 ± 30%) and dried at room temperature as it is until the sticky feeling disappears.
As a coating method of the silicon-containing liquid composition of the present invention, there is a method of coating on the surface of a substrate and drying to form a coating film, but the coating method is a simple method such as aerosolization and spray coating. Can do. Of course, it can also be applied by various methods such as ordinary brush coating, roller coating, spray coating, roll coater, flow coater and the like.

  For example, tunnels, dams, bridges, tanks, civil engineering structures such as chimneys, houses, buildings, and other building structures, temples, shrines, stone statues, and the like are structures to which the silicon-containing liquid composition according to the present invention is applied. It is an outdoor structure such as cultural assets such as ruins, transportation equipment such as automobiles, airplanes, rail cars, ships, industrial equipment, traffic signs, guardrails. In addition to outdoor structures, bathrooms, wall surfaces of cooking rooms, furniture, refrigerators, televisions, outer box surfaces of air conditioners and the like, and window glass that are easily soiled can also be applied.

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

(Preparation Example 1)
Tetramethoxysilane (manufactured by Mitsubishi Chemical Co., Ltd .: hereinafter referred to as TMOS) was mixed at the following blending ratio, and then heated for 4 hours in the reflux state to cause hydrolytic condensation.
253.3 parts by weight of TMOS (100 parts by weight in terms of SiO ₂ )
Hydrolysis condensation catalyst (5% methanol solution of acetylacetone aluminum)
38.4 parts by weight Ethanol 1407.7 parts by weight Ion exchanged water 1657.6 parts by weight The silicon content in terms of SiO _{2 in} this liquid is 3.0%.
This composition was diluted with the following aqueous ethanol solution to prepare a colorless and transparent silicon-containing composition-1.
Ion-exchanged water 5594.6 parts by weight Ethanol 3543.9 parts by weight

The silicon content in terms of SiO _{2 in} this liquid is 0.8%, methanol concentration 2.0%, ethanol concentration 39.6%, and water content 57.6%.
Dangerous goods judgment of this silicon-containing composition-1 is a test method for dangerous goods judgment prescribed in the Fire Service Act of Japan (Articles 1-3 to 1-8 of the Cabinet Order on the regulation of dangerous goods) (Ministerial Ordinance on Testing and Properties of Dangerous Goods). The alcohol component in this silicon-containing composition-1 is less than 60%. At the Mitsubishi Chemical Safety Science Laboratory, Kitakyushu Laboratory, the flash point (closed tag type) and the combustion point (open tag type) As a result of measurement, the flash point was 26 ° C. and the combustion point was 29 ° C. The flash point of 60% ethanol water is 23 ° C. and the combustion point is 23 ° C. From these results, it can be seen that this silicon-containing composition-1 does not fall under the dangerous materials of the Japanese Fire Service Act.
The light transmittance was measured and found to be 100%.

(Preparation Example 2)
After mixing at the following blending ratio using TMOS, the mixture was heated for 4 hours in the reflux state to cause hydrolysis and condensation.
253.3 parts by weight of TMOS (100 parts by weight in terms of SiO ₂ )
Hydrolysis condensation catalyst (5% methanol solution of acetylacetone aluminum)
38.4 parts by weight Ethanol 1407.7 parts by weight Ion exchanged water 1657.6 parts by weight The silicon content in terms of SiO _{2 in} this liquid is 3.0%.

This composition was diluted with 9138.5 parts by weight of ion-exchanged water to prepare a colorless and transparent silicon-containing composition-2.
The silicon content in terms of SiO _{2 in} this liquid is 0.8%, methanol concentration 2.0%, ethanol concentration 11.3%, and water content 85.9%.
The light transmittance was measured and found to be 100%.

(Preparation Example 3)
The silicon-containing composition-1 obtained previously and the acrylic silicone resin cationic emulsion “CS-175” manufactured by Daicel Chemical Industries, Ltd. were mixed at the following ratio to obtain “silicon-containing liquid composition-A”.
Silicon-containing composition-1 1000 parts by weight CS-175 2.7 parts by weight (as solids)
The light transmittance of this silicon-containing liquid composition-A was 73.5%.

(Preparation Example 4)
The silicon-containing composition-2 obtained previously and the acrylic silicone resin cationic emulsion “CS-175” manufactured by Daicel Chemical Industries, Ltd. and the surface tension reducing agent “Dapro W77” manufactured by ELEMENTIS JAPAN were mixed at the following ratio. As a result, a silicon-containing liquid composition-B was obtained.
Silicon-containing composition-2 1000 parts by weight CS-175 2.7 parts by weight (as solid content)
Dapro W77 5 parts by weight The light transmittance of this silicon-containing liquid composition-B was 73.5%.

(Preparation Example 5)
After mixing at the following blending ratio using TMOS, the mixture was heated for 4 hours in the reflux state to cause hydrolysis and condensation.
253.3 parts by weight of TMOS (100 parts by weight in terms of SiO ₂ )
Hydrolysis condensation catalyst (5% methanol solution of acetylacetone aluminum)
38.4 parts by weight Deionized water 4704.2 parts by weight The silicon content in terms of SiO _{2 in} this liquid is 2.0%.
This composition was diluted with 7491.1 parts by weight of ion-exchanged water to prepare a colorless and transparent silicon-containing composition-5.
The silicon content in terms of SiO _{2 in} this liquid is 0.8%, the methanol concentration is 2.0%, and the water content is 97.2%.

(Preparation Example 6)
The silicon-containing composition-5 obtained previously and the acrylic silicone resin cationic emulsion “CS-175” manufactured by Daicel Chemical Industries, Ltd. and the surface tension reducing agent “Dapro W77” manufactured by ELEMENTIS JAPAN, in the following ratio: By mixing, a silicon-containing liquid composition-C was obtained.
Silicon-containing composition-5 1000 parts by weight CS-175 2.7 parts by weight (as solid content)
Dapro W77 5 parts by weight The light transmittance of this silicon-containing liquid composition-C was 73.5%.

(Example 1)
About 350 ml of the silicon-containing liquid composition-A obtained in Preparation Example 3 is placed in a wide-mouthed plastic container, and Substrate-0, Substrate-1, Substrate-2, and Substrate-3 described later are immersed therein. And pulled up at a speed of 2 mm / sec. Then, it was made to dry at room temperature for 24 hours, and the coating film was formed on the base material. Coating was possible without cissing except for the base material-3, and almost 100% of the surface of the coated base material could be covered with the silicon-containing liquid composition, thereby forming a film. The contact angle between the coating film and water was 48 ° when using the base material-0, 40 ° when using the base material-1, and 45 ° when using the base material-2. In addition, since the coating film was not formed on the base material-3 due to repelling, the area where the silicon-containing liquid composition covered the base material was 20% or less, and film formation was not possible. The ΔL of the exposure test was very good at 1.6 when the substrate-1 was used and 1.3 when the substrate-2 was used. Moreover, the tape peeling test of the coating film at the time of using base material-0, 1, and 2 was favorable.

In addition, the following were used as a base material.
Substrate-0;
Substrate-0 was obtained by thoroughly washing and degreasing crusty glass (150 × 70 × 2 mm: JIS R3202) manufactured by Nippon Test Panel.
It was 10 degrees or less when the contact angle of water of this base material was measured.

Base material-1:
After thoroughly cleaning and degreasing the edged glass (150x70x2mm: JIS R3202) made by Nippon Test Panel, the Nichiban double-sided tape "Nystack" width 10mm, including release paper on both ends of the long side of the glass Duplicated. The tape thickness is about 300 μm.
About 5 ml of water-based acrylic silicone paint “SK Component Silicone (White)” made by SK Kaken Co., Ltd., diluted with 15% water added to the outer frame, is placed on this glass and stretched with a glass rod so that it is flat. Coated. The film thickness of the undried coating film is about 300 μm.

This was dried and cured at room temperature for 7 days or more to obtain a substrate-1.
It was 90 degree | times when the contact angle of water of this base material-1 was measured.
Substrate-2;
In the preparation of the substrate-1, instead of “SK Component Silicone (White)”, 20% of toluene is added to the solvent-based acrylic paint “SK Acrylic Color (White)” manufactured by SK Kaken Co. The diluted one was coated and dried by the same method to obtain Substrate-2.

It was 90 degree | times when the contact angle of water of this base material-2 was measured.
Substrate-3;
In the preparation of the base material-1, 20% of toluene was added to the solvent-based acrylic paint “elastic color enamel (white)” manufactured by SK Kaken Co., Ltd. instead of “SK component silicon (white)”. The diluted one was coated and dried by the same method to obtain Substrate-3.

It was 92 degree | times when the contact angle of water of this base material-3 was measured.
The exposure test was conducted by the direct exposure test method specified in JIS Z2381. That is, like the above-mentioned base material 1-3, a commercially available white paint was applied to a test piece (glass) having a thickness of 2 mm, a width of 7 cm, and a length of 15 cm to prepare a sufficiently dried substrate. Then, the silicon-containing liquid composition according to the present invention was applied onto the substrate, dried, and placed directly on the exposure table, and the change in whiteness (ΔL value) was followed over time. The exposure table was 932 mm from the installation surface, and the height of the portion closest to the installation surface was 500 mm or more.

The exposure angle was set to 60 degrees from the horizontal plane, and 1-1 Shiroishi, Yahatani-ku, Kitakyushu City. It was installed on the roof of the R & D department building (5 stories) at the Kurosaki Plant for three months facing south. The exposure table was installed in a place where it was not affected by the shade or drops of water.
A color checker NR-1 manufactured by Nippon Denshoku Co., Ltd. was used for measurement of the change in whiteness (ΔL). Standard white plate (Nippon Denshoku Calibration Board C / 2 ° X = 85.32, Y = 87.08, Z = 99.35D65 / 10 ° X = 82.50, Y = 87.07, Z = 90 17), the L value of the coating film before being subjected to the actual exposure test was measured, and the brightness difference (L0) from the standard white plate was determined. After the exposure test, the L value was measured again to determine the brightness difference (L) from the standard white plate, and ΔL = | L ₀ −L | was calculated.

  The tape peeling test, which is an index of the adhesion of the coating film, was made by attaching a cellophane tape according to JIS Z1522 to the surface of the coating film, rubbing it with an eraser (JIS S6050), and then attaching the tape after 1-2 minutes. It was done by holding one end and pulling it away in the vertical direction. The peeling state of the coating film at this time was visually observed, and the film in which no peeling was observed was regarded as good.

(Example 2)
About 350 ml of the silicon-containing liquid composition-B obtained in Preparation Example 4 was placed in a wide-mouthed plastic container, and Substrate-0, Substrate-1, Substrate-2 and Substrate-3 were immersed in this, and the speed was Pulled up at 2 mm / sec. Then, it was dried at room temperature for 24 hours. Almost 100% of the surface of the coated substrate could be covered with the silicon-containing liquid composition, and a film was formed. The contact angle of water is 13 degrees when the base material-0 is used, 20 degrees when the base material-1 is used, 24 degrees when the base material-2 is used, and the base material-3 is used. It was 30 degrees. The ΔL of the exposure test was 1.6, when the base material-1 was used, 1.1 when the base material-2 was used, and 1.5 when the base material-3 was used. . The tape peeling test of the coating film was also good.

(Example 3)
About 350 ml of the silicon-containing liquid composition-C obtained in Preparation Example 6 was placed in a wide-mouthed plastic container, and the base material-1, the base material-2, and the base material-3 were immersed in this, and pulled up at a speed of 2 mm / sec. And dried at room temperature for 24 hours. In Base-1 and Base-2, almost 100% of the surface of the coated base material could be covered with the silicon-containing liquid composition, and film formation was possible. The contact angle of water was 20 degrees when the base material-1 was used, and 20 degrees when the base material-2 was used. In addition, since the coating film was not formed for the base material-3 due to repelling, the area where the silicon-containing liquid composition covered the base material was 20% or less, and film formation was not possible. The ΔL of the exposure test was very good at 3.2 when the base material-1 was used and 2.5 when the base material-2 was used. The tape peeling test when using base materials-1 and 2 was also good.

Example 4
The silicon-containing liquid composition-B was placed in a glass container that can be sealed, and stored in a thermostatic bath at 50 ° C. for 40 days. Then, using this silicon-containing liquid composition-B, the substrate-0, the substrate-1, the substrate-2, and the substrate-3 were each applied by dipping-pulling in the same manner as in Example 3. Then, it was dried at room temperature for 24 hours. Almost 100% of the surface of the coated substrate could be covered with the silicon-containing liquid composition, and a film was formed. The contact angle of water is 15 degrees when the base material-0 is used, 18 degrees when the base material-1 is used, 20 degrees when the base material-2 is used, and sometimes the base material-3 is used. It was 27 degrees. The tape peeling test of the coating film was good.

(Example 5)
The silicon-containing liquid composition-C was placed in a glass container that could be sealed, and stored in a thermostatic bath at 50 ° C. for 40 days. Then, using this silicon-containing liquid composition-C, the substrate-1, the substrate-2, and the substrate-3 were respectively applied by dipping-pulling up in the same manner as in Example 3, and the coating was performed at room temperature for 24 hours. Dried. In Base-1 and Base-2, almost 100% of the surface of the coated base material could be covered with the silicon-containing liquid composition, and film formation was possible. The contact angle of water was 18 degrees when the base material-1 was used, and 17 degrees when the base material-2 was used. In addition, since the coating film was not formed for the base material-3 due to repelling, the area where the silicon-containing liquid composition covered the base material was 20% or less, and film formation was not possible. The tape peeling test when using base materials-1 and 2 was also good.

(Comparative Example 1)
About 350 ml of the silicon-containing composition-1 obtained in Preparation Example 1 was placed in a wide-mouthed plastic container, and the base material-1, the base material-2, and the base material-3 were immersed in this, and pulled up at 2 mm / sec. For 24 hours. Since neither base material was repelled, no coating film was obtained, and the area where the silicon-containing liquid composition covered the base material was 20% or less, and film formation was not possible.

(Comparative Example 2)
The substrate-1, the substrate-2, and the substrate-3 were subjected to an exposure test without any coating. The contact angle of water was 90 degrees for the base material-1, 90 degrees for the base material-2, and 92 degrees for the base material-3. The ΔL of the exposure test was a result in which the base material-1 was 8.2, the base material-2 was 9.2, and the base material-3 was 10.

Claims (19)

  A silicon-containing liquid composition having a water concentration of 50% by weight or more and a light transmittance of 70% or more, wherein the silicon-containing liquid composition is formed on a substrate having a water contact angle of 60 degrees or more. A silicon-containing liquid composition, which is a composition capable of forming a film. The silicon-containing liquid composition according to claim 1, wherein the substrate is an organic substrate or a substrate covered with an organic film. It is formed by blending the following components (A) to (E), the concentration of the component (A) is 6% by weight or less in terms of SiO ₂ , and the concentration of the component (C) is 50% by weight or more. The silicon-containing liquid composition according to claim 1 or 2.
Component (A) Organosilicate or oligomer thereof
100 parts by weight in terms of SiO ₂ Component (B) Hydrolysis condensation catalyst 0.1 to 10 parts by weight Component (C) Water 100 to 50000 parts by weight Component (D) Organic solvent 100 to 50000 parts by weight Component (E) Aqueous resin component 10 to 1000 parts by weight as solid content It is formed by blending the following components (A) to (E), the concentration of the component (A) is 6% by weight or less in terms of SiO ₂ , and the concentration of the component (C) is 50% by weight or more. The silicon-containing liquid composition according to claim 1 or 2.
Component (A) Organosilicate or oligomer thereof
100 parts by weight in terms of SiO ₂ Component (B) Hydrolysis condensation catalyst 0.5-5 parts by weight Component (C) Water 500-25000 parts by weight Component (D) Organic solvent 200-10000 parts by weight Component (E) Aqueous resin component 10 to 1000 parts by weight as solid content   The silicon-containing liquid composition according to any one of claims 1 to 4, wherein a surface tension reducing agent is contained as a component (F) in a concentration of 0.1 to 2.0% by weight.   The silicon-containing liquid composition according to any one of claims 1 to 5, wherein the component (E) is an aqueous emulsion.   Component (E) is an aqueous emulsion selected from a (meth) acrylic resin system, a styrene-acrylic resin system, an acrylic silicone resin system, a fluororesin system, a urethane resin system, and a urethane-acrylic resin system. The silicon-containing liquid composition according to claim 6.   The silicon-containing liquid composition according to any one of claims 1 to 7, wherein the component (A) is methyl silicate or an oligomer thereof. The silicon-containing liquid composition according to any one of claims 1 to 8, wherein the component (A) is represented by the following sexual formula.
SiOx (OR) y
(However, 0 ≦ x ≦ 1.2, 1.6 ≦ y ≦ 4, 2x + y = 4) It is formed by blending the following components (A) to (E), the concentration of the component (A) is 6% by weight or less in terms of SiO ₂ , and the concentration of the component (C) is 50% by weight or more. A silicon-containing liquid composition.
Component (A) Organosilicate or oligomer thereof
100 parts by weight in terms of SiO ₂ Component (B) Hydrolysis condensation catalyst 0.1 to 10 parts by weight Component (C) Water 100 to 50000 parts by weight Component (D) Organic solvent 100 to 50000 parts by weight Component (E) Aqueous resin component 10 to 1000 parts by weight as solid content It is formed by blending the following components (A) to (E), the concentration of the component (A) is 6% by weight or less in terms of SiO ₂ , and the concentration of the component (C) is 50% by weight or more. A silicon-containing liquid composition.
Component (A) Organosilicate or oligomer thereof
100 parts by weight in terms of SiO ₂ Component (B) Hydrolysis condensation catalyst 0.5-5 parts by weight Component (C) Water 500-25000 parts by weight Component (D) Organic solvent 200-10000 parts by weight Component (E) Aqueous resin component 10 to 1000 parts by weight as solid content   The silicon-containing liquid composition according to claim 10 or 11, which contains a surface tension reducing agent as a component (F) at a concentration of 0.1 to 2.0% by weight. The silicon-containing liquid composition according to any one of claims 10 to 12, wherein the component (A) is represented by the following formula.
SiOx (OR) y
(However, 0 ≦ x ≦ 1.2, 1.6 ≦ y ≦ 4, 2x + y = 4) After component (A) to component (D) are blended so that the concentration of component (A) is ₂ to 6% by weight in terms of SiO2, component (A) is hydrolyzed and condensed, and then component (C) And / or component (D) is added to dilute to 2 times or more and component (E) or component (E) and component (F) are added thereto. 2. A method for producing a silicon-containing liquid composition according to item 1.   14. A coating method comprising applying the silicon-containing liquid composition according to any one of claims 1 to 13 to a surface of a substrate and drying to form a coating film.   A coating film formed by applying the silicon-containing liquid composition according to any one of claims 1 to 13 to a substrate.   The coating film according to claim 16, which is colorless and transparent.   The coating film according to claim 16 or 17, wherein the contact angle of water is 60 ° or less. The coating film according to any one of claims 16 to 18, wherein a change in whiteness (ΔL) of the coating film subjected to the exposure test by the following exposure test method is 5 or less.
(Exposure test method) An outdoor exposure test is conducted for 3 months in accordance with the JIS Z2381 direct exposure test method. However, the exposure angle is 60 degrees from the horizontal plane.