JPH04175388A - Coating composition, coated inorganic cured body, and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain the title compsn. which can be cured even at ordinary temp. and provides a film with a high hardness, excellent weatherability and good smoothness by incorporating a silica-dispersed oligomer soln. of a specified organosilane, a silanol group-contg. polyorganosiloxane and a catalyst. CONSTITUTION:A coating compsn. is obtd. by incorporating a silica-dispersed oligomer soln. of an organosilane (A) prepd. by hydrolyzing partially a partially hydrolyzable organosilane of formula I [wherein R<1> is a 1-8C monovalent (substd.)hydrocarbon group; n is 0-3 ; X is a hydrolyzable group 1 in a colloidal silica dispersed in an org. solvent or water, a silanol group-contg. polyorganosiloxane (B) of formula II [ wherein R<2> is a 1-8C monovalent (substd.) hydrocarbon group; 0.2<=a<=2; 0.0001<=b<=3; a+b<=4] and a catalyst (C) as the essential ingredients. This compsn. can be cured and dried at ordinary temp. and is curable at a relatively low temp. by thermal accerelation and the obtd. film has high hardness, excellent weatherability and good smoothness.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a coating composition, and more specifically, to coating compositions for coating compositions for coatings on non-ferrous metals such as steel plates such as stainless steel, aluminum, etc.; inorganic building materials such as concrete and slate; The present invention relates to a coating composition that can be coated onto the surface of a substrate, left at room temperature or heat-treated at a low temperature to form a coating that is hard, has high hardness, and has excellent heat resistance and weather resistance. Furthermore, the present invention relates to a coated inorganic cured body having a cured layer of a coating composition that has high hardness and excellent weather resistance, and a method for producing the same.

[Prior art] Conventionally, hydration has been used as a coating agent that can form a durable film for the purpose of protecting the surface of steel plates such as stainless steel; non-ferrous metals such as aluminum; inorganic building materials such as concrete and slate; or plastic substrates. Coating agents obtained by hydrolyzing or partially hydrolyzing degradable organosilane, or coating agents obtained by mixing colloidal silica with the coating composition are known.

For example, JP-A-51-2736, JP-A-51-
No. 2737, JP-A-53-130732, and JP-A-63-168470 disclose organoalkoxysilane, a hydrolyzate of the organoalkoxysilane and/or a partial condensate thereof, and colloidal silica, A coating agent has been proposed in which an alkoxy group is converted to a silanol using excess water. However, although the films obtained with these coating agents have high hardness, good weather resistance, and are excellent for protecting substrates, they require high-temperature or long-term heat treatment of approximately 100°C or higher to obtain the desired film properties. However, there are disadvantages in that it may not be applicable depending on the molding method, dimensions, heat resistance, or location of the base material, such as outdoors. In addition, these coating compositions have a problem in that the silanol obtained by hydrolyzing alkoxysilane has high activity, and their condensation reaction gradually occurs even at room temperature, resulting in easy gelation and poor stability. especially,
When trying to make paints by adding pigments to these coating compositions as vehicles, the stability becomes even worse.
It had drawbacks such as not being able to be made into paint.

In addition, as in JP-A-61168, a coating agent has been proposed in which alkoxysilane is partially hydrolyzed and water and a catalyst are added as a curing agent to a partially condensed product to convert alkoxy groups into silanol before coating. has been done. However, the coating agent obtained in this way has good storage stability and is relatively stable even when pigments are added to make it into a paint. It is necessary to bake by heat treatment,
It cannot be applied depending on the molding method, size, heat resistance, or location of the base material, such as outdoors.

In order to eliminate such drawbacks, Japanese Patent Application Laid-Open No. 63-268
Publication No. 772 proposes a coating agent that is composed of a prepolymer mainly composed of silicon alkoxide, a curing catalyst, and water and that cures at around room temperature, but the coating agent has poor paintability; However, there were disadvantages such as its properties being easily affected by humidity.

On the other hand, silicone resins are known as vehicles for heat-resistant paints or weather-resistant paints. Many of these are composed of polysiloxanes containing silanol groups, and these organopolysiloxanes containing silanol groups are often made by hydrolyzing organochlorosilanes to form a toluene or xylene solution, and they are also made using organoalkoxysilanes. However, the silanol groups are subjected to a condensation reaction until the hydrolyzate is dissolved in toluene or xylene. Although the silicone resin solution obtained in this way has good stability even when mixed with pigment and made into a paint, it has the disadvantage that it must be treated at high temperatures for a long time to form a heat-cured film. Moreover, there is a limit to increasing the hardness of the coating even if it is heated for a long time, and the properties are insufficient for a durable coating.

By the way, the above-mentioned inorganic hardened materials such as concrete and cement base materials are materials with excellent heat resistance and durability, but if the surface is left unpainted, moisture will penetrate, and on the other hand, it will not be resistant to staining. It has the disadvantage of poor strength and acid resistance. Moreover, the unpainted appearance is often not aesthetically pleasing.

In order to solve these problems, coating the surface with an organic paint has been carried out.

However, organic paints have disadvantages in that they have poor weather resistance and are easily scratched due to their low coating hardness.

Therefore, attempts were made to use inorganic coating agents such as water glass instead of organic paints, but satisfactory results were not obtained in terms of efflorescence and porosity.

Silicon alkoxide-based coating agents are being considered as inorganic coating agents that do not have the above drawbacks. However, when silicon alkoxide-based coating agents are used, there are problems with alkali generation from the cement-based base material, relatively large dimensional changes in the base material, and the adhesion of the coating agent to the base material. Due to insufficient coverage, there is a problem in that cracks and peeling are likely to occur due to the effects of rainwater and temperature changes. Therefore, an example of applying a silicon alkoxide coating agent through a primer was published in JP-A-63
As shown in Japanese Patent Publication No. 262203 and Japanese Patent Application Laid-Open No. 1-83580, the silicon alkoxide coating agent applied on the primer layer requires heat treatment at 100°C or higher and the time required for that is quite long. is the reality.

Therefore, when painting at construction sites, painting on base materials with low heat resistance, and when painting on cement-based base materials that have patterns such as rabbets or unevenness, use thinner areas. Those with this type were more likely to generate cranks during processing.

[Problems to be solved by the invention] This invention has the following features: (1) It is possible to cure and dry at room temperature and at the same time to accelerate curing by heating at a relatively low temperature, and the obtained film has high hardness, excellent weather resistance, and smoothness. A good coating composition, ■ A coating composition that can be used as a stable vehicle when adding pigments to form a paint, and therefore can be colored as desired, and has excellent weather resistance, smoothness, and gloss; ■ Storage stability. The object of the present invention is to provide a coating composition that has good properties and can stably obtain the performance (2) over a long period of time.

Furthermore, this invention enables a cured layer of a silicon alkoxide-based inorganic coating agent with high hardness and excellent weather resistance to be applied to the surface of an inorganic hardened material such as concrete or cement over a long period of time without cracking or peeling. It is a treatment that does not cause the risk of cranking, even on substrates that have been painted with paint or have low heat resistance, or substrates with tongue or grooved patterns that have thin areas. An object of the present invention is to provide a painted inorganic cured body having an inorganic coating layer and a method for producing the same.

[Means for Solving the Problems] As a result of intensive research into solutions to the problems of the conventional coating agents described above, the present inventors have developed a method for partially hydrolyzing alkoxysilanes in colloidal silica dispersed in an organic solvent or water. The inventors have discovered that a parabolic coating composition consisting of a silica-dispersed oligomer, a silanol group-containing organopolysiloxane, and a catalyst solves all of the problems of the conventional coating agents, and has completed the present invention. That is, in order to obtain the above-mentioned performance (2), the coating composition of the present invention has the following characteristics: 8 represents a monovalent hydrocarbon group, n is an integer of O to 3, and X represents a hydrolyzable group). A silica-dispersed oligomer solution of organosilane obtained by hydrolysis; Represents a hydrogen group, a and b are each 0.2≦a≦2.0.0001≦b≦3.a+b
This is a number that satisfies the relationship of ≦4. ) A polyorganosiloxane containing a silanol group in the molecule and (C) a catalyst are essential components.

In the coating composition of the present invention, in order to obtain the above-mentioned performance (1), the weight average molecular weight of the component (B) in terms of polystyrene is 700 or more and 20,000 or less.

In the coating composition of the present invention, in order to obtain the above-mentioned performance (1), the pH of the component (A) may be from 2.0 to 7.0.

In addition, the present inventors have conducted intensive studies to find solutions to the problems of the conventional coated inorganic cured product, and have developed a silica-dispersed oligomer containing a silanol group containing partially hydrolyzed alkoxysilane in solvent-dispersible colloidal silica. We have discovered that all of the above problems can be solved by applying a coating composition consisting of an organopolysiloxane and a catalyst to a substrate such as cement via a primer layer to form a cured film, and have completed the present invention. It's arrived.

That is, the painted inorganic cured body of the present invention has a primer layer on the surface of the inorganic cured body, and has a film formed of the cured body of the coating composition of the present invention on the primer layer.

Furthermore, the method for producing a coated inorganic cured body of the present invention includes a first step in which a primer layer is formed on the surface of the inorganic cured body.
and a second step of coating the coating composition of the present invention on the primer layer and drying it by heating at room temperature or low temperature to form an inorganic coating layer.

The silica-dispersed oligomer as component (A) used in this invention is the main component of a base polymer having a hydrolyzable group (X) as a functional group that undergoes a curing reaction when forming a film. This involves adding one or more hydrolyzable organosilanes represented by the general formula (1) to colloidal silica dispersed in an organic solvent or water (including a mixed solvent of an organic solvent and water). It is obtained by partially hydrolyzing the hydrolyzable organosilane with water in colloidal silica or water added separately.

The group R1 in the hydrolyzable organosilane represented by the general formula (1) represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Butyl group, pentyl group, hexyl group, heptyl group,
Alkyl groups such as octyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aralkyl groups such as 2-phenylethyl, 2-phenylpropyl and 3-phenylpropyl groups; aryl groups such as phenyl and tolyl groups : Alkenyl group such as vinyl group, allyl group: Chloromethyl group, r-chloropropyl group, 3,3.
．． 3-) halogen-substituted hydrocarbon groups such as lifluoropropyl group and T-methacryloxypropyl group, γ-
Examples include substituted hydrocarbon groups such as a glycidoxypropyl group, a 3,4-epoxycyclohexylethyl group, and a T-mercaptopropyl group. Among these, those with 1 to 4 carbon atoms are preferred due to ease of synthesis or availability.
The alkyl group and phenyl group are preferred.

The hydrolyzable group X is an alkoxy group, an acetoxy group, an oxime group (-0-N=(,-R), an amino group, an aminoxy group (-0-N-R'), an amide group (-N- C-R) R' 0 [Here, R, R' and R'' are, for example, each independently hydrogen or a monovalent hydrocarbon group.] Ease of availability and silica dispersion An alkoxy group is preferred since it is easy to prepare an oligomer solution.

Such hydrolyzable organosilanes include mono-, di-, tri-, and tetra-functional alkoxysilanes, acetoxysilanes, and oxime Silanes, enoxysilanes,
Examples include aminosilanes, aminoxysilanes, amidosilanes, and the like. Alkoxysilanes are preferred because of their ease of availability and ease of preparing a silica-dispersed organosilane oligomer solution.

In particular, examples of the tetraalkoxysilane where n=o include tetramethoxysilane and tetraethoxysilane, and examples of the organotrialkoxysilane where n=1 include methyltrimethoxysilane, methyltriethoxysilane,
Methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3.3-
) Lifluoropropyltrimethquine silane and the like can be exemplified.

Further, examples of the diorganodialkoxysilane with n=2 include dimethyldimethoxysilane, dimethyljethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, and methylphenyldimethoxysilane, and triorganodialkoxysilane with n=3. Examples include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylbutylmethoxysilane. Furthermore, organonlan compounds, which are generally called silane coupling agents, are also included in the alkoxysilanes.

It is preferable that 50 mol% or more of these hydrolyzable organosilanes represented by general formula (I) be trifunctional compounds represented by n=1, more preferably 60 mol%
or more, most preferably 70 mol% or more.

If it is less than 50 mol%, sufficient coating film hardness may not be obtained and dry curability may tend to be poor.

Colloidal silica in component (A) is essential for increasing the hardness of the cured film of the coating composition of the present invention. As such colloidal silica, water-dispersible colloidal silica or colloidal silica dispersible in non-aqueous organic solvents such as alcohol can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content.
The content of silica can be determined from this value.

Furthermore, when water-dispersible colloidal silica is used, water present as a component other than the solid content can be used for hydrolysis of the organosilicon compound of component (A). These are usually made from water glass, and such colloidal silica is readily available commercially. Furthermore, organic solvent-dispersed colloidal silica can be easily prepared by replacing the water in the water-dispersible colloidal silica with an organic solvent. Such organic solvent-dispersed colloidal silica can also be easily obtained as a commercial product like water-dispersed colloidal silica. The types of organic solvents in which colloidal silica is dispersed include, for example, methanol, ethanol, isopropanol (also referred to as IPA), n-butanol,
Lower aliphatic alcohols such as isobutanol; ethylene glycol, ethylene glycol monobutyl ether,
Ethylene glycol derivatives such as acetic acid ethylene glycol monoethyl ether; diethylene glycol, diethylene glycol monobutyl ether, etc. (7) Derivatives of ethylene glycol, diacetone alcohol, etc. can be mentioned, and one or two selected from the group consisting of these More than one species can be used. Toluene, xylene, ethyl acetate, 9-butyl acid, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can also be used in combination with these hydrophilic organic solvents.

In component (A), colloidal silica is preferably contained in a range of 5 to 95% by weight as silica. More preferably 10-90% by weight, most preferably 20-8%
It is in the range of 5% by weight. If the content is less than 5% by weight, the desired film hardness cannot be obtained, and if it exceeds 95% by weight, uniform dispersion of silica becomes difficult, and component (A) may cause problems such as gelation. .

The silica-dispersed oligomer of component (A) can usually be obtained by partially hydrolyzing a hydrolyzable organosilane in water-dispersed colloidal silica or organic solvent-dispersed colloidal silica. The amount of water used for the hydrolyzable organosilane is 0.001 water per 1 mole of the hydrolyzable group (X).
~0.5 mol is preferred. If the ratio is less than o or ooi moles, a sufficient partial hydrolyzate cannot be obtained, and if it exceeds 0.5 mole, the stability of the partial hydrolyzate may deteriorate. The method of partial hydrolysis is not particularly limited, and it is sufficient to mix the hydrolyzable organosilane and colloidal silica, and add and blend the required amount of water, at which time the partial hydrolysis reaction proceeds at room temperature.

You may heat to 60-100 degreeC in order to promote a partial hydrolysis reaction. Furthermore, for the purpose of promoting the partial hydrolysis reaction, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluene Organic and inorganic acids such as sulfonic acid and oxalic acid may be used as catalysts.

In order to obtain stable performance over the long term, component (A) should have a pH of 2.0 to 7.0, more preferably a pH of 2.5 to 7.0.
6.5, and even more preferably pH 3.0 to 6.0. If the pH is outside this range, the long-term performance of component (A) may deteriorate significantly, especially when the amount of water used is 0.3 mol or more per 1 mol of water. (A) pH of component
If it is outside this range, it can be adjusted by adding basic reagents such as ammonia, ethylenediamine, etc. if it is more acidic than this range.
It may be adjusted using an acidic reagent such as acetic acid. However, the adjustment method is not particularly limited.

Component (B), a silanol group-containing polyorganosiloxane, is an important component that characterizes the present invention. C like this
Component B) has an average compositional formula (%) (in the formula, R2 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are each 0.2≦ a≦2.0.0001≦b≦3.a+b
This is a number that satisfies the relationship of ≦4. ) can be expressed as In the formula, R2 is exemplified by the same as R1 in (■) above, but preferably has 1 carbon number.
~4 alkyl group, phenyl group, vinyl group, T-glycidoxypropyl group, γ-methacryloxypropyl group, T
Substituted hydrocarbon groups such as -aminopropyl group, 3.3.3-)lifluoropropyl group, more preferably methyl group and phenyl group. In addition, a and b in the formula are numbers that satisfy the above relationship, and if a is less than 0.2 or b exceeds 3, there will be problems such as cracking in the cured film, and if a exceeds 2, 4 or less or b
If it is less than 0.0001, curing will not proceed well.

Such a silanol group-containing polyorganosiloxane can be produced by, for example, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or a mixture of one or more alkoxysilanes corresponding to these, by a known method. 9 can be obtained by hydrolysis with a large amount of water. When hydrolyzing an alkoxysilane by a known method to obtain a silanol group-containing polyorganosiloxane,
Trace amounts of alkoxy groups that are not hydrolyzed may remain. In other words, a polyorganosiloxane in which a ranol group and a very small amount of alkoxy group coexist may be obtained, but in this invention, such a polyorganosiloxane may be used without any problem.

The curing catalyst which is component (C) of the present invention is the above-mentioned (A).
It promotes the condensation reaction between the component and the component (B) and hardens the film. Such catalysts include alkyl titanates, metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate, dioctyltin dimaleate, amine salts such as nidibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate;
i [Carboxylic acid quaternary ammonium salts such as tetramethylammonium: amines such as tetraethylpentamine@-N-β-aminoethyl-T-aminopropyltrimethoxysilane, N-β-aminoethyl-T-aminopropyl Amine-based silane coupling agents such as methyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid, and hydrochloric acid; aluminum compounds such as nialium alkoxide and aluminum chelate; alkaline catalysts such as potassium hydroxide; tetraisopropyl titanate, tetrabutyl There are titanium compounds such as titanate and titanium tetraacetylacetonate, and halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane. In addition to the above catalysts, (A)
There is no particular restriction as long as it is effective for the condensation reaction with the component and component (B).

The mixing ratio of component (A) and component (B) is preferably 99 to 1 part by weight of component (B) to 1 to 99 parts by weight of component (A), more preferably 5 to 95 parts by weight of component (A). 95 to 5 parts by weight of component (B), most preferably (A)
The amount of component (B) is 90 to 10 parts by weight relative to 10 to 90 parts by weight of component (however, the total of component (A) and component (B) is 100 parts by weight). If component (A) is less than 1 part by weight, room temperature curability will be poor and sufficient film hardness will not be obtained; on the other hand, if it exceeds 99 parts by weight, curability will be unstable and a good coating film will not be obtained. Sometimes there isn't.

Further, the amount of component (C) added is preferably 0.0001 to 10 parts by weight per 100 parts by weight of the total of components (A) and (B). More preferably 0.0005~
8 parts by weight, most preferably 0.0007 to 5 parts by weight. If it is less than 0.0001 parts by weight, it may not harden at room temperature, and if it exceeds 10 parts by weight, heat resistance and weather resistance may deteriorate.

The hydrolyzable groups contained in the silica-dispersed oligomer of component (A) and the silanol groups of component (B) are heated at room temperature or low temperature (for example, at a temperature of 100°C or less) in the presence of a curing catalyst of component (C). This causes a condensation reaction to form a cured film. Therefore, like a moisture-curing type coating composition, the coating composition of the present invention is hardly affected even when cured at room temperature. Further, a cured film can be formed by promoting the condensation reaction by heat treatment.

When a pigment is added to the coating composition of the present invention to form a paint, the molecular weight of the polyorganosiloxane as component (B) is preferably 700 to 20,000. In addition, the molecular weight here is a weight average molecular weight measured in terms of standard polystyrene by GPC (gel permeation chromatography) measurement. When the molecular weight is less than 700, the curing of the finished coating film is slow and cracks are likely to occur. Moreover, if it exceeds 20,000, the coating film made from the paint to which the pigment is added lacks gloss and has poor smoothness. however,
Weight average molecular weight is greater than 10,000 and 20,000
In the following cases, it is necessary to devise pigment dispersion conditions and/or additives in order to give the coating film gloss or improve smoothness. For example, pigment dispersion conditions include increasing the rotational speed during dispersion and lengthening the processing time for dispersion. Further, as additives, for example, coupling agents, dispersion aids, etc. are used in a weight ratio of 0.3% or more to the pigment, although it depends on the type of additives.

The pigment types to be added are carbon blank, quinacridone,
WAB pigments such as naphthol red, cyanine green running green, and Hansa yellow, inorganic pigments such as titanium oxide, barium sulfate, Bengara, and composite metal oxides are preferred, and one or a combination of two or more selected from these groups are preferred. There is no problem in using it. There is no particular limit to the amount of pigment added, as the hiding power depends on the type of pigment (A)
It is preferably 5 to 80 parts by weight based on 100 parts by weight of the solid content of the mixture of component (B). If it is less than 5 parts by weight, the hiding property is poor, and if it exceeds 80 parts by weight, the smoothness of the coating may deteriorate.

Pigments may be dispersed by a conventional method. Further, at that time, it is possible to use a dispersant, a dispersion aid, a thickener, a coupling agent, etc. Furthermore, leveling agents, dyes, metal powders, glass powders, antioxidants, ultraviolet absorbers, etc. can be added.

The coating composition of the present invention can be used after being diluted with various organic solvents for ease of handling. The type of organic solvent can be selected depending on the type or molecular weight of the monovalent hydrocarbon group of component (A) or component (B). Examples of such organic solvents include those shown as dispersion solvents for colloidal silica, and one or more solvents selected from the group consisting of these can be used. Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can also be used in combination with these hydrophilic @solvents.

As a method for preserving the coating composition of the present invention, (
Generally, three packages are used to store components A), (B), and (C), respectively;
It is also possible to separate the mixed component and component (B) into two packages and mix them at the time of use, or to mix all the components and store them in one container. . However, when storing the (A) component and (C) component together, adjust the pH of the (A) component to 2 to 7 before storing the (C) component.
It is preferable to add a component, and more preferably, the amount of water used per mole of hydrolyzable group X of the organosilane of component (A) is 0.3 mole or less.

The coating composition of the present invention can be applied to plastics such as polycarbonate resin, acrylic resin, ABS resin,
Wall materials made of metals such as aluminum, stainless steel, copper, iron, and duralumin, paper, wood, glass, cement, and plaster, as well as acrylic, alkyd, polyester, epoxy, and urethane paints, etc. It can also be applied to surface protection.

Furthermore, the thickness of the coating is not particularly limited, and is 0.1 to 100 μm.
m is fine, but in order for the paint film to stick and hold stably over a long period of time and to prevent cranking and peeling, it is necessary to
It is more preferably μm, and even more preferably 1 to 50 μm.

The coating composition of the present invention can be coated by a conventional coating method, such as brushing, spraying,
Various application methods can be selected, such as dipping, flow, roll, curtain, and knife coating. Further, there is no particular restriction on the dilution ratio with the organic solvent, and the dilution ratio may be determined as necessary.

In addition, the coating composition of this invention may contain leveling agents, thickeners, pigments, dyes, aluminum paste, glass frit, metal powder, antioxidants, ultraviolet absorbers, etc. as necessary. It can be added within a certain range.

An example of the inorganic cured material used in this invention is as follows.

The hydraulic inorganic adhesive material used as the raw material for the inorganic hardened material is not particularly limited, and for example, one or more types selected from Portland cement, blast furnace cement, blast furnace slag, calcium silicate, gypsum, etc. are used. can.

The adhesive material usually contains an inorganic filler, a fibrous material, and the like. Although not particularly limited, examples of inorganic fillers include fly ash, micro silica, silica sand, etc., and examples of fibrous materials include valves, synthetic fibers, inorganic fibers such as asbestos, and metal fibers such as steel fibers. selected and used alone or in combination.

The inorganic cured material raw material constructed in this manner is formed by extrusion molding, casting molding, paper molding, press molding, etc., and then is subjected to autoclave curing, steam curing, room temperature curing, etc., although there is no particular limitation. Are suitable.

The obtained inorganic cured product preferably has a bulk density of 0.5 g/d or more and a dimensional change of 0.5% or less from the time of saturated water absorption to absolute dryness, and more preferably has a bulk density of 0. A value of .7g/C11 or more and a dimensional change of 0.4% or less are selected. If the bulk density is less than 0.5 g/ci, the primer and the coating composition of the present invention (silicon alkoxide coating agent) will be strongly absorbed, making it difficult to exhibit adhesion performance, and the appearance of the coating film will also be poor. There is a risk that it will happen. Furthermore, if the dimensional change exceeds 0.5%, even if the primer layer can follow the movement of the base material, the silicon alkoxide coating layer will not be able to follow it sufficiently, which tends to cause cracking and peeling. .

In addition, before applying the primer composition to the base material, sealing is performed with a solvent-based, water-soluble, or emulsion-based sealer depending on the type of base material, and the unevenness of suction on the surface of the base material is adjusted and the sealer is sealed. You can. The sealer to be used is not particularly limited, and acrylic, Latinx, etc. can be used.The coating layer can be coated on a primer layer formed by adding a coloring component such as a pigment to a primer composition. A clear inorganic coating layer may be provided, or an inorganic coating layer containing a coloring component such as a pigment may be provided on a primer layer that does not contain a coloring component such as a pigment. Moreover, it is also possible to further provide a clear inorganic coating layer thereon. The method to be used is selected depending on the purpose of use. In addition, in the above, when an inorganic coating layer to which a coloring component such as a pigment is added is used as a top coat, if a glossy coating film is desired, as described above,
The weight average molecular weight of the component (B) in terms of polystyrene is preferably 700 or more and 20,000 or less.

Next, the primer layer will be explained. The primer layer includes, for example, (a) 100 parts by weight of an isocyanate prepolymer containing two or more isocyanate groups in the molecule but no urethane bonds; (b) one or more mercapto groups and two or more mercapto groups in the molecule; Organosilicon compounds containing an alkoxy group of 1 to 100
Part by weight (C) 100 parts by weight or less of epoxy resin-modified silicone resin (as solid content) (d) Organotin compound and/or organic acid salt of tin 0.
It is formed from a primer composition containing 01 to 30 parts by weight of each component. Preferably, component ('a) contains two or more isocyanate groups in the molecule, but the incyanate groups of the isocyanate prepolymer that does not contain urethane bonds are not directly bonded to the benzene ring. Further, the primer composition may contain the pigment described above.

In general, isocyanate groups are reactive groups that react with hydroxyl groups, water, etc. to form urethane type, urea type, etc. chemical bonds, so the isocyanate prepolymer (a) having such incyanate groups It can react with hydroxyl groups on the surface of the material and form a strong film through chemical bonding. Examples of such isocyanate prepolymers include partial hydrolysis products and trimers of isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, m-xylylene diisocyanate, and tris(2-hydroxyethyl) isocyanate;
Further examples include reaction products of mixtures of these incyanates.

Among the above-mentioned isocyanate prepolymers, the isocyanate prepolymers constituting the primer composition used in this invention contain two or more isocyanate groups in the molecule from the viewpoint of weather resistance, but do not contain urethane bonds. It is necessary that it does not contain. Specifically, such isocyanate prepolymers include those having a biuret bond as shown in (1) or (2) below, and those having isocyanurate rings as shown in (3) to (6) below. Can be mentioned.

-NH-X/X-N
...(1)\ -NH-X (However, X = (CH2)6 NC0)CN HCH
z A r / A r CHz X N
-(2)\CN HCHz Ar (However, X is the same group as the TI formula) J Ar These are used alone or in combination of multiple types. In addition, especially when it is required that the polymer not be discolored by light, it is preferable that the isocyanate group in the prepolymer is not directly bonded to the benzene ring.

The organosilicon compound (b) containing one or more mercapto groups and two or more alkoxy groups in the molecule has a mercapto group as an organic functional group that binds to an organic material, and a hydrolyzable compound that reacts with an inorganic material. It is a neutralizing agent that has an alkoxy group as a group in the same molecule, and acts as an adhesion improver. Further, it is a component that forms a tough and weather-resistant film by reacting with the isocyanate prepolymer (a) mentioned above and the epoxy resin-modified silicone resin (C) described below in the primer composition. Examples of such organic silica compounds include, for example, HS −(−CH2):l Si (OCH:+)
i, R3(CH2)3 S i (OC2R5)3
, R5(CHz)z S i (OCH3)3
, HS (CHz)z S i (OCz
Hs)+ , R3(CH2)3 S i (C
Silanes such as H3) (OCH3)Z and their hydrolyzed condensates can be mentioned. These may be used alone or in combination.

The amount of the organosilicon compound (b) blended is 1 to 100 parts by weight, preferably 3 to 50 parts by weight, based on 100 parts by weight of the prepolymer (a), although it depends on the viscosity of the prepolymer (a). If the above proportion is less than 1 part by weight, the adhesive properties may not be sufficiently exhibited and the strength of the coating may be poor.
If the amount exceeds 0.00 parts by weight, the adhesive function tends to deteriorate.Even if the epoxy resin-modified silicone resin (C) is not added, the purpose of the present invention can be fully achieved, but the adhesion of the primer and It is a component that contributes to improving UV resistance.

The ratio of the silicone resin component and the epoxy resin component in the modified resin (c) above is arbitrary and is not particularly limited. %, epoxy resin 30-85
Preferably, it is % by weight. The silicone resin component is
Usually, average formula;% formula%([[) (wherein, R3 is a monovalent hydrocarbon group, R4 is a hydrogen atom or a monovalent hydrocarbon group, h is a number from 1.0 to 1.7, i is a number from 0.05 to 0.2, and j is (4-h −i ) /
The polyorganosiloxane is preferably a polyorganosiloxane consisting of a polyfunctional siloxane unit represented by the number 4 (k is a number of 2 or more).

The hydrocarbon group for R3 in the above Cm> formula includes an ethyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
Alkyl groups such as octyl groups: alkenyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups are examples. From the viewpoint of ease of use, it is preferable to use a hybrid of a methyl group and a phenyl group, that is, polymethylphenylsiloxane.

Examples of R4 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and the like.

The numerical value in the above formula (III) is 1.0 to 1. 7,
It is preferable that i is 0.05 to 0.2.

When h is less than 1.0, the compatibility of polyorganosiloxane with an appropriate degree of polymerization with the epoxy resin tends to be poor, and when it exceeds 1.7, the toughness of the resin coating may decrease. . Even if i is less than 0.05, the toughness of the resin coating decreases, and if it exceeds 0°2, there is a tendency for viscosity increase and gelation to occur during storage. Further, from the viewpoint of film forming properties and stability during storage, the numerical value is preferably 2 or more.

The epoxy resin component is a low-mer or polymer containing a compound with an oxirane oxygen such as a glycidyl group or a 3,4-oxycyclohexyl group, and various acid anhydrides, amines, etc. are used as a curing agent. Good too. These curing agent components are not particularly limited and can be used as general curing agents for epoxy resins, but they coexist stably with other components in solution,
In addition, in order to form a film by curing at around room temperature, it is recommended to use an acid anhydride curing agent.

Examples of such acid anhydrides include phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, dodecylsuccinic anhydride, etc. They can be used alone or in combination.

The above-mentioned silicone resin component and epoxy resin component may be used by simply mixing them within a range in which they are compatible with each other, or may be used by being chemically bonded by heating. It is usually used as a solution in an organic solvent such as toluene or xylene.

The amount of the epoxy resin-modified silicone resin (C) obtained as described above is 100 parts by weight or less as a solid component, and 3 to 50 parts by weight, based on 100 parts by weight of the isocyanate prepolymer (a). is preferred. If the above ratio exceeds 100 parts by weight, not only may weather resistance and adhesiveness be impaired, but also it is unfavorable from the viewpoint of system stability.

The organic tin compound and/or tin organic acid salt of (d) has a catalytic effect on the reaction of isocyanate groups, alkoxysilyl groups, silanol groups, etc. contained in other primer components, and is formed. It is an important component that strengthens the adhesion of the cured primer film to the substrate and the adhesion of the coating composition of the present invention to the cured primer film, and imparts weather resistance, water resistance, etc. Such tin compounds are not particularly limited, and include tin carboxylates such as tin octylate, organic tin carboxylates such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin simalate, and dibutyltin siphthalate, and these compounds and tetramethoxy Examples include deesterification reaction products with alkoxysilanes such as silane and tetraethoxysilane, and reaction products with organic tin oxides and esters thereof such as dibutyltin oxide.

The amount of the tin compound (d) is 0.01 to 30 parts by weight based on 100 parts by weight of the prepolymer (a),
Preferably it is 0.05 to 10 parts by weight. If the amount is less than 0.01 part by weight, the adhesive properties, especially the water resistance of the adhesion, may deteriorate, and if it exceeds 30 parts by weight, the curing speed of the primer composition will be too high (too much). This tends to cause problems in coating workability.

The primer composition composed of the above-mentioned components may be diluted with an organic solvent as appropriate for the purpose of facilitating the coating operation and imparting storage stability. Examples of such solvents include carboxylic acid esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic compounds such as toluene, xylene, and benzene; ethers such as diethyl ether, tetrahydrofuran, and dioxane, and oxygen. Compounds such as heterocyclic compound systems including the following can be used. These solvents may be used alone or in combination.

Furthermore, the primer composition of the present invention may contain other additives such as titanium oxide, carbon blank, color pigments such as iron oxide, and the like.

These additives are used within an amount that does not impair the effects of this invention.

The method for storing the primer composition includes a mixed component consisting of (a) an isocyanate prepolymer, (b) an organosilicon compound, and (c) an epoxy resin-modified silicone resin added as necessary; and (d) Generally, the tin compound and the tin compound are separated into two packages and both are mixed before use, but it is also possible to mix all the components and store them in one container. It is.

Next, as a first step, a step of coating and curing the primer on the inorganic cured body will be explained.

In principle, the surface of the inorganic cured material used should be free of dirt and oil. Further, it is desirable that the moisture content of the substrate is less than 80%, preferably less than 70% of the saturated moisture content of each substrate. Adhesion will decrease if there is dirt or oil on the substrate, or if the moisture content of the substrate is high.

The method of applying the primer is not particularly limited, and spray, roll, flow coater, etc. may be used depending on the use and purpose. Further, the coating film thickness is preferably 0.5 μm or more and less than AIm above the knee. If it is less than 0.5 μm, it is difficult to obtain a uniform coating, and if it is 50 μm or more, there is a risk of foaming. If you really want to obtain a coating thickness of 50 μm or more, it is best to perform a drying step and apply multiple coats.

Further, the drying conditions for the primer are preferably 5°C or more and 150°C or less, more preferably 10°C or more and 100°C or less. If the temperature is less than 5°C, curing will be slow, and if it exceeds 150°C, there is a risk of foaming. Although the processing time varies depending on the temperature and amount of coating, the processing time is generally in the range of 3 minutes to 24 hours.

If it is carried out in a process such as a factory, 1. 3 when productivity is taken into account
Minutes to 60 minutes is best. For example, when using a hot air dryer, if the set temperature is 80℃ and the wind speed is 4m/s in vertical flow, 1
It can be processed from 0 to 20 minutes.

It is also possible to add a pigment to the primer, but the amount of pigment added should be 6 parts by weight per 100 parts by weight of the solid vehicle component.
It is desirable that the content be less than 0 parts by weight. If it exceeds 60 parts by weight, the adhesion may decrease and the crack resistance of the silicon alkoxide coating may decrease.

Next, as a second step, the coating composition of the present invention is applied onto the primer layer, but a clear coating may be applied directly, or a colored paint containing pigments may be applied.
A colored layer may or may not be coated on top of the colored layer multiple times, depending on the purpose. For example, when using a base material with a brick pattern or tile pattern, the concave portions and convex portions may be painted in a wing color, and then a clear coat may be applied thereon. As an example of painting the concave portions and convex portions separately, first, the entire surface can be painted with a spray, and the convex portions can be painted with a roll. In addition, to create a spotted pattern on the entire surface, the pattern can be applied either by spraying or by using a brush-like roll.

When applying the coating composition of the present invention, the coating method is not particularly limited, and any of the above-mentioned coating methods may be used depending on the purpose. The coating film thickness is 0.1 to 100μm, preferably 1 to 80μm.
m, more preferably 1 to 50 μm, and even more preferably 3
A range of from 25 μm to 25 μm is preferable. If the thickness is less than a predetermined thickness, the coating may not be continuous, and if it exceeds the predetermined thickness, there is a risk of cracking or foaming. Further, the drying conditions are preferably 5°C or more and 200°C or less, preferably 10°C or more and 150°C or less. If the temperature is less than 5°C, curing will be slow, and if it exceeds 200°C, there is a risk of cracking or foaming. Although the processing time varies depending on the temperature and amount of coating, the processing time is generally in the range of 3 minutes to 24 hours.

If it is carried out in a process such as a factory, 3 minutes to 60 minutes is recommended, taking into account productivity. For example, when using a hot air dryer, if the set temperature is 80 degrees Celsius and the wind speed is 4 m/s in vertical flow, then 10
It can be processed within 20 minutes.

Additionally, in the case of conventional hardening type (dehydration condensation reaction type) silicon alkoxide coating agents, baking may occur during processing on substrates with uneven or rabbeted processing.
Since cracks form in the base material, there are restrictions on the pattern and tongue shape of the base material. Also, in the case of plastics that are not heat resistant, they may become deformed due to processing. Such problems can be solved by using the coating composition of the present invention.

[Examples] Specific examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following implementations. In addition, in the following, all "parts" represent "parts by weight", and all "r%" represent "wt% J".

First, an example of a method for preparing component (A) will be explained.

(Preparation Example A-1) In a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer, IPA-3T (improper tool dispersed colloidal silica sol, two particle diameters 10 to 20 mμ,
Solid content 30%, H2O 0.5%, manufactured by Nissan Chemical Industries, Ltd.) 1
00 parts, 68 parts of methyltrimethoxysilane, 10.8 parts of water
A partial hydrolysis reaction was carried out at a temperature of 65° C. for about 5 hours with stirring, and the mixture was cooled to obtain component (A).

This product has a solid content of 3 when left at room temperature for 48 hours.
It was 6%. The component (A) obtained here is referred to as A-1.

Preparation conditions for A-1: - Number of moles of water per mole of hydrolyzable group.

...4 x 10 days Silica content of component (A)...47.3
%, mole % of n-1 hydrolyzable organosilane...
100 mol% (Preparation Example A-2) XBA-3T (xylene-butanol dispersed colloidal silica sol: particle size 10 to 20 m) was placed in a flask equipped with a stirrer, heating jacket, condenser, and temperature needle.
μ, solid content 30%, HzOO 02%, manufactured by Yasan Kagaku Kogyo Co., Ltd.) 100 parts, 68 parts of methyltrimethoxysilane, 49.5 parts of phenyltrimethoxysilane, 14.4 parts of water, and 0.1 part of acetic anhydride were added. A partial hydrolysis reaction was carried out at a temperature of 80° C. for about 3 hours while stirring, and the mixture was cooled to obtain component (A). This product had a solid content of 41% when left at room temperature for 48 hours. The component (A) obtained here is A-
It is called 2.

Preparation conditions for A-2: Number of moles of water per mole of hydrolyzable group...4X1
0-' Silica content of component (A)...31.3
%・n=1 mole% of hydrolyzable organosilane...
100 mol% (Preparation Example A-3) NBA-3T (n-butanol colloidal silica sol, 2 particles with a diameter of 10 to 20 mg,
Solid content 20%, H2O 0.5%, manufactured by Yasan Kagaku Kogyo Co., Ltd.) 1
50 parts methyltriethoxysilane 178 parts, 3.3.3
-21.4 parts of trifluoropropyltrimethoxysilane, 12 parts of dimethyldimethoxysilane, 26 parts of water, 0.0 parts of acetic anhydride. 2 parts of the solution were added, a partial hydrolysis reaction was carried out at a temperature of 80° C. for about 8 hours with stirring, and the mixture was cooled to obtain component (A). This product had a solid content of 31% when left at room temperature for 48 hours. The component (A) obtained here is A-
It is called 3.

Preparation conditions for A-3: Number of moles of water per mole of hydrolyzable group...4X1
0-' Silica content of component (A)...25.2
%, mole % of hydrolyzable organosilane with n=1...
92 mol% (Preparation Example A-4) In a flask equipped with a stirrer, heating jacket, condenser and thermometer, 100 parts of methyltris(methylethylketoxime)silane was added, followed by NBA-3T (n
-Butanol silica sol: particle size 10-20 mtt, solid content 20%, H2O0.

A mixture of 100 parts of 5% (manufactured by Yasan Kagaku Kogyo Co., Ltd.) and 9 parts of water was added with stirring, a partial hydrolysis reaction was carried out at room temperature for about 8 hours, and the mixture was cooled to obtain component (A). This product had a solid content of 31% when left at room temperature for 48 hours. The component (A) obtained here is referred to as A-4.

Preparation conditions for A-4: -Number of cups of water per mole of hydrolyzable group...5X1
0-' Silica content of component (A)...47.3
%・n=1 mole% of hydrolyzable organosilane...
100 mol% (Preparation Example A-5) XBA-3T (xylene n
Butanol dispersed colloidal silica sol 2 particle size 10-2
0 mμ, solid content 30%, H2O 0.2% (manufactured by Nissan Chemical Industries, Ltd.) 100 parts and 68 parts of methyltrimethoxysilane were added, and a partial hydrolysis reaction was carried out at a temperature of 65°C for about 5 hours with stirring, followed by cooling. Component (A) was obtained. This product had a solid content of 36% when left at room temperature for 48 hours. The component (A) obtained here is called A-5.

Preparation conditions for A-5: Number of moles of water per mole of hydrolyzable group...7X1
0-3 Silica content of component (A)...47.2%
Mol% of hydrolyzable organosilane with n=1...10
0 mol% (Preparation Example A-6) In a flask equipped with a stirrer, a heating jacket, a condenser, and a temperature needle, IPA-ST (isopropyl alcohol-dispersed colloidal silica sol: particle size 10-20
mμ, solid content 30%, H2C 0.5% (manufactured by Nissan Chemical Industries, Ltd.) 100 parts, methyltrimethoxysilane 68 parts, dimethyldimethoxysilane 18 parts, water 2.7 parts, acetic anhydride 0.
18 was added, a partial hydrolysis reaction was carried out at a temperature of 80° C. for about 3 hours with stirring, and the mixture was cooled to obtain component (A). This product had a solid content of 36% when left at room temperature for 48 hours. The component (A) obtained here is called A-6.

Preparation conditions for A-6: -Number of moles of water per mole of hydrolyzable group...1 ×1
0-' ・(A) Silica content of component...40.2%
・Mole% of n-1 hydrolyzable organosilane...7
7 mol% (1 part Preparation Example A-7) In a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer, add IPA-3T (Impropatol dispersed colloidal silica sol: particle size 10 to 20 mμ).
, solid content 30%, H2C 0.5% (manufactured by Nissan Chemical Industries, Ltd.) 1
00B, 68 parts of methyltrimethoxysilane, 49.5 parts of phenyltrimethoxysilane, and 7.7 parts of water were charged, and a partial hydrolysis reaction was carried out at a temperature of 65° C. for about 5 hours with stirring, followed by cooling. A) Component was obtained. This product had a solid content of 36% when left at room temperature for 48 hours.

The component (A) obtained here is called A-7.

Preparation conditions for A-7: -Number of moles of water per mole of hydrolyzable group...2
10-' Silica content of component (A)...31.3%.
Mol% of hydrolyzable organosilane with n=1...10
0 mol% (Preparation Example A-8) In a flask equipped with a stirrer/heating jacket, condenser, and thermometer, IPA-3T (isopropyl alcohol-dispersed colloidal silica sol with two particle diameters of 10 to 2
0 mμ, solid content 30%, H2C 0.5% (manufactured by Nissan Chemical Industries, Ltd.) 100 parts, methyltrimethoxysilane 68 parts, trimethylmethoxysilane 5 parts, water 2.3 parts, anhydride trace r! i
0.1 part was added, a partial hydrolysis reaction was carried out at a temperature of 80° C. for about 3 hours with stirring, and the mixture was cooled to obtain component (A). This product had a solid content of 36% when left at room temperature for 48 hours. The component (A) obtained here is called A-8.

Preparation conditions for A-8: -Number of moles of water per mole of hydrolyzable group...I
10-' Silica content of component (A)...44.5%.
Mol% of n-1 hydrolyzable organosilane...91
．． 2 mol% Note that room temperature is 25 parts at 2°C and 60 parts at 5% RH.

Next, an example of a method for preparing component (B) will be explained.

(Preparation Example B-1) Weigh out a mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene into a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, and thermometer, and add 1% 108 parts of an aqueous hydrochloric acid solution was added dropwise to the above mixture over 20 minutes to hydrolyze methyltripropoxysilane.

After 40 minutes of dropping, the stirring was stopped, and the mixture of water and isopropyl alcohol in the lower layer containing a small amount of hydrochloric acid was separated into two layers, and then the remaining hydrochloric acid in the toluene resin solution was removed by water washing, and then After removing toluene under reduced pressure, the mixture was diluted with isopropyl alcohol to obtain a 40% isopropyl alcohol solution of a silanol group-containing organopolysiloxane having an average molecular weight of about 2,000. This is called B=1. The molecular weight was measured by GPC (Gel Permini-Sicon Chromatography) using a measurement model HLC-802UR (manufactured by Tosoh Corporation) by creating a calibration curve with standard polystyrene. Subsequent molecular weights were also measured in the same manner.

(Preparation Example B-2) Weigh out 1000 parts of water and 50 parts of acetone into a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, and thermometer, and add 44.8 parts of methyltrichlorosilane ( 0.3 mol), dimethyldichlorosilane 38. '1 (0.3 mol) and 84.6 parts (0.4 mol) of phenyltrichlorosilane dissolved in 200 parts of toluene were hydrolyzed while being added dropwise with stirring.

After 40 minutes of dropping, the stirring was stopped, and the reaction solution was transferred to a branch funnel and allowed to stand. The lower layer of hydrochloric acid water separated into two layers was separated and removed, and then the upper layer of organopolysiloxane remained in the toluene solution. Water and hydrochloric acid were distilled off along with excess toluene by vacuum stripping to obtain a 60% toluene solution of a silanol group-containing organopolysiloxane having an average molecular weight of 3,000. This is called B-2.

(Preparation Example B-3) Silanol group-containing organomethane obtained in the same manner as B-2 except that 19.4 parts (0.15 mol) of dimethyldichlorosilane was modified to odiphenyldichlorosilane and toluene was replaced with xylene. A xylene solution of polysiloxane was obtained. Further, a dehydration condensation reaction of the silanol group-containing organopolysiloxane was carried out at a temperature of 150° C. for 16 hours to obtain B-3 containing 50% xylene and an average molecular weight of about 300,000.

(Preparation Example B-4) Water and hydrochloric acid remaining in the toluene solution of organopolysiloxane in the upper layer were removed under reduced pressure along with excess toluene to make the resin concentration 80%, and the resin concentration was further made 60% with isopropyl alcohol. Other than that, same as B-1, 60% toluene/isopropyl alcohol of silanol group-containing organopolysiloxane with an average molecular weight of 3000.
Solution B-4 was obtained.

First, Examples and Comparative Examples in which the coating composition of the present invention is a clear type paint will be shown.

Examples 1 to 9 and Comparative Example 1.2 - A coating composition was obtained by mixing the components shown in Table 1 in the proportions shown in the table. In addition, in Comparative Example 1.2, IPA was used as a diluting solvent to facilitate spray painting.

The coating compositions obtained in Examples and Comparative Examples were spray-painted on aluminum bombarded test pieces (Ulstar: trade name, manufactured by Nippon Test Panel) to a cured film thickness of approximately 10/Im. , curing temperature 14
A film (coating film) was formed by curing at 0° C. for 30 minutes, and the film properties were tested.

In addition, the test of film characteristics was based on the following evaluation method.

・Adhesion: Adhesion to two substrates: Peeling test using adhesive tape (using cellophane tape) ・Coating hardness: Pencil hardness test method (according to JIS K5400) ・Solvent resistance: Using gauze impregnated with toluene The coating film was lightly pressed and rubbed back and forth 100 times, and the condition of the coating film at that time was observed, and those with no change were evaluated as having good curing properties.

- Boiling water resistance: After boiling tap water and testing for 16 hours, the test piece was left for 1 hour and the state of the coating film was observed, and those with no change were rated as good.

・Weather resistance: Sunshine Weather-Ometer (JIS
Compatible with K5400. ) The state of the coating film was observed after irradiation for 2500 hours, and those with no change were rated as good.

The formulation conditions of the coating compositions of Examples 1 to 9 and Comparative Example 1.2 and the evaluation results of coating hardness were summarized in Table 1.
Shown in the table.

Comparative Example 3 - 100 parts of A-6 and 0.0 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane. A coating composition of Comparative Example 3 was obtained by adding 3 parts of water to this mixture before coating. A test piece was prepared in the same manner as in Example 1, except that IPA was used as the diluting solvent to facilitate spray painting, and the film properties were tested. The results are shown in Table 1.

As shown in Table 1, the coating composition of the present invention has better adhesion, film hardness, and solvent resistance (
Curability), boiling water resistance, and weather resistance were all good.

Next, Examples and Comparative Examples in which the coating composition of the present invention contains a pigment and other optional components will be shown.

Examples 10 to 14 - A white paint was prepared by dispersing a mixture of component (B) shown in Table 2 and a white pigment titanium oxide (rR-820J manufactured by Ishiya Sangyo) using a sand grinder. Then, component (A) and component (C) (catalyst) shown in Table 2 were further added to obtain a coating composition.

Example 15.16 - A white paint was prepared by dispersing a mixture of A-3 in the amount shown in Table 2 and a white pigment titanium oxide (rR-820J manufactured by Ishiya Sangyo) using a sand grinder. Furthermore, component (C) shown in Table 2 was added and combined with component (B) shown in the same table to obtain a coating composition.

- Comparative Example 4 - Example 10-1, in which a coating composition was prepared in the same manner as in Example 10, except that no curing catalyst was used.
The coating compositions of 6 and Comparative Example 4 were applied to a slate board by spray painting so that the cured film (coating film) had a thickness of about 20 μm, and was left at room temperature for one week to form a cured film that dried at room temperature. , was used as a test piece. The properties of these coatings are shown in Table 2.

The curing and drying properties of the film at room temperature were determined by drying to the touch and measuring the curing and drying time in accordance with JIS-5400. Further, each test piece was immersed in hot water at 60° C. for 200 hours continuously, and the state of the coating film was observed. Other than that, the coating film properties were tested in the same manner as in Example 1. The results are shown in Table 2.

As shown in Table 2, the coating films formed with the coating compositions of the Examples have better curing and drying properties at room temperature than those of the Comparative Examples, and have good film hardness, curing properties, and weather resistance. Everything was excellent.

Examples 17 to 20 - The coating compositions of Examples 17 to 20 were obtained using the formulations shown in Table 3, and the coating compositions were spray-painted on the substrates shown in Table 3, and cured as shown in Table 3. A cured film was formed under the following conditions and used as a test piece. Table 3 shows the evaluation results of coating film properties in the same manner as described above. In Table 3, Tinuvin P is the trade name of a benzotriazole ultraviolet absorber manufactured by Ciba Geigy.

As shown in Table 3, the adhesion, coating hardness, curability, and weather resistance were good.

Next, Examples, Reference Examples, and Comparative Examples will be shown in which the coating composition of the present invention also contains a pigment and forms a coating with good gloss.

Examples 21 to 28 and Reference Examples 1 to 4 - First, (
A) An example of a method for preparing the component will be explained.

(Aim Example GA-1) In a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer, IPA-3T (isopropanol-dispersed colloidal silica sol, two particle diameters of 10 to 20 mμ,
Solid content 30%, H, 0.5%, manufactured by 8 San Kagaku Kogyo Co., Ltd.) 1
00 parts, 68 parts of methyltrimethoxysilane, 5.4 g of water
was added, a partial hydrolysis reaction was carried out at a temperature of 65° C. for about 5 hours with stirring, and the mixture was cooled to obtain component (A). This product has 36 pieces when left at room temperature for 48 hours.
%Met. The component (A) obtained here is called GA-1.

Preparation of GA~1: ・Number of moles of water per mole of hydrolyzable group...2 X
10-' Silica content of component (A')...47.
2%・mol% of hydrolyzable organosilane with n=1...
・100 mol% (Preparation Example GA-2) ME-5T (methanol-dispersed colloidal silica sol, 2 particle diameters 10-20 mμ, solid content 3) was placed in a flask equipped with a stirrer, heating jacket, condenser, and thermometer.
0%, H2O0.5%, manufactured by Yasan Kagaku Kogyo Co., Ltd.) 150 copies,
136 parts of methyltrimethoxysilane, 36 parts of dimethyldimethoxysilane, 75 parts of IPA, and 19.4 parts of water were added, and a partial hydrolysis reaction was carried out at a temperature of 60°C for about 6 hours with stirring, followed by cooling (A). Got the ingredients. This product had a solid content of 32% when left at room temperature for 48 hours. The component (A) obtained here is called GA-2.

・Number of moles of water per mole of hydrolyzable group...3X1
0-' Silica content of component (A) - 33.5
%・n=1 mole% of hydrolyzable organosilane...
76.9 mol% (1s!!!Example GA-3) IPA-3T (isopropanol dispersed colloidal silica sol: particle size 10-20 mμ, solid content) was placed in a flask equipped with a stirrer, heating jacket, condenser and thermometer. 30%, H2O0.5%, manufactured by 8 San Kagaku Kogyo Co., Ltd.) 10
0 parts, methyl) IJ methoxysilane 68 parts, dimethyldimethoxysilane 18 parts, water 2.7 parts, acetic anhydride 0.1
A partial hydrolysis reaction was carried out at a temperature of 80° C. for about 3 hours with stirring, and the mixture was cooled to obtain component (A).

This product has a solid content of 3 when left at room temperature for 48 hours.
It was 6%. The component (A) obtained here is called GA-3.

Preparation conditions for GA-3: Number of moles of water per mole of hydrolyzable group...I
X 1 0-' Silica content of component (A)...40.2
%・n=1 mole% of hydrolyzable organosilane...
77 mol% Next, an example of a method for preparing component (B) will be explained.

(Preparation Example CB-1) Weigh out a mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene into a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, and thermometer, and add 1% 108 parts of an aqueous hydrochloric acid solution was added dropwise to the above mixture over 20 minutes to hydrolyze methyltriisopropoxysilane. After 30 minutes of dropping, stop stirring, separate the lower layer mixture of water and isopropyl alcohol containing a small amount of hydrochloric acid, and then remove the remaining hydrochloric acid in the toluene resin solution by washing with water. After removing toluene under reduced pressure, dilute with isopropyl alcohol to reduce the average molecular weight to 10.
A 40% solution of 00 silanol group-containing organopolysiloxane in isopropyl alcohol was obtained. This is GB-1
It is called. The molecule i was measured by GPC (gel permeation chromatography) using HLC802A and HLC8020 (manufactured by Tosoh Corporation) by creating a calibration curve with standard polystyrene. Subsequent molecular weights were also measured in the same manner.

(Part a side GB-2) A mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene was weighed into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer. 108 parts of .5% aqueous hydrochloric acid solution was added dropwise to the above mixture over 20 minutes to hydrolyze methyltriisopropoxysilane. After 60 minutes of dropping, stop stirring, separate the lower layer mixture of water and isopropyl alcohol that contains a small amount of hydrochloric acid, and then remove the hydrochloric acid in the remaining toluene resin solution by washing with water. After removing toluene under reduced pressure, the mixture was diluted with isopropyl alcohol to obtain a 40% solution of silanol group-containing organopolysiloxane with an average molecular weight of 3000 in isopropyl alcohol. CB this
-2.

(Preparation Example GB-3) Weigh out a mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene into a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, and temperature needle, and add 2% 108 parts of an aqueous hydrochloric acid solution was added dropwise to the above mixture over 20 minutes to hydrolyze methyltriisopropoxysilane. After 120 minutes of dropping, the stirring was stopped, and the mixture of water and isopropyl alcohol in the lower layer containing a small amount of hydrochloric acid was separated into two layers, and then the hydrochloric acid in the remaining toluene resin solution was removed by water washing, and then After removing toluene under reduced pressure, dilute with isopropyl alcohol to reduce the average molecular weight to 7.
A 40% solution of 000 silanol group-containing organopolysiloxane in isopropyl alcohol was obtained. CB-
It is called 3.

(Preparation Example GB-4) Weigh out 1000 parts of water and 50B of acetone into a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, and thermometer, and add 44.9 parts of methyltrichlorosilane (0.0 , 3 moles), 38.7 parts (0.3 moles) of dimethyldichlorosilane, and 84.6 parts (0.4 moles) of phenyltrichlorosilane dissolved in 200 parts of toluene were hydrolyzed while being added dropwise with stirring. .

After 40 minutes of dropping, the stirring was stopped, and the reaction solution was transferred to a branch funnel and allowed to stand. The lower layer of hydrochloric acid water separated into two layers was separated and removed, and then the upper layer of organopolysiloxane remained in the toluene solution. Water and hydrochloric acid were distilled off along with excess toluene by vacuum stripping to obtain a 60% toluene solution of a silanol group-containing organopolysiloxane having an average molecular weight of 3,000. This is called GB-4.

(To Preparation Example CB 5) A mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene was weighed into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer. 108 parts of a 2% aqueous hydrochloric acid solution was added dropwise to the above mixture over 20 minutes to hydrolyze methyltriisopropoxysilane. After 30 minutes of dropping, stirring was stopped, and the mixture of water and isopropyl alcohol in the lower layer containing a small amount of hydrochloric acid was separated into two layers, and then the hydrochloric acid in the remaining toluene resin solution was removed by water washing, and then the toluene solution was removed. was removed under reduced pressure, and diluted with isopropyl alcohol to obtain a 40% solution of silanol group-containing organopolysiloxane with an average molecular weight of 500 in isopropyl alcohol. This is GB
-5.

(Preparation Example GB-6) Into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer, a mixed solution of 220 parts (1 mole) of methyltriisopropoxysilane and 150 parts of toluene was weighed, and 5% 108 parts of an aqueous hydrochloric acid solution was added dropwise to the above mixture over 20 minutes to hydrolyze methyltriisopropoxysilane. After 150 minutes of dropping, the stirring was stopped, and the mixture of water and isopropyl alcohol in the lower layer containing a small amount of hydrochloric acid was separated into two layers, and then the remaining hydrochloric acid in the toluene resin solution was removed by water washing, and then After removing toluene under reduced pressure, dilute with isopropyl alcohol to reduce the average molecular weight to 1.
A 40% solution of 3000 silanol group-containing organopolysiloxane in isopropyl alcohol was obtained. This is C,
It is called B-6.

(Preparation Example CB-7) Weigh out 1000 parts of water and 50 parts of acetone into a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, and temperature needle, and add 44.8 parts of methyltrichlorosilane ( 0.3 mol), dimethyldichlorosilane 19.4B (0.15 mol), diphenyldichlorosilane 38.088 (0.15 mol), phenyltrichlorosilane 84.6 parts (0.4 mol) in toluene 2
00 parts was hydrolyzed while being added dropwise with stirring. After 40 minutes of dropping, the stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand. The lower layer of hydrochloric acid water separated into two layers was separated and removed, and then added to the toluene solution of organopolysiloxane in the upper layer. The remaining water and hydrochloric acid were distilled off together with excess toluene by vacuum stripping to obtain a xylene solution of the silanol group-containing organopolysiloxane. This was further subjected to a dehydration condensation reaction at 150° C. for 8 hours to obtain a 50% xylene solution of a silanol group-containing organopolysiloxane having an average molecular weight of about 100,000. This is called GB-1.

(Dispersion of pigment) Titanium oxide, a white pigment ("R-820J" manufactured by Ishihara Sangyo Co., Ltd.)
A mixture (pigment) consisting of 99 parts, 1 part of Bengara (manufactured by Toda Kogyo Co., Ltd.) and 0.1 part of carbon blank (HCC) was dispersed in a grain mill. Furthermore, after dispersing the pigment and leaving it at room temperature for 24 hours, N was added as a catalyst to 100 parts of liquid A.
-β-aminoethyl-γ-aminopropyltrimethoxysilane 5B and 1 part of dibutyltin dilaurate were added to prepare a liquid A' in which a pigment was dispersed. The amount of pigment added is the fourth
, the changes were made as shown in Table 5.

Furthermore, in Example 28 and Reference Example 3.4, GA-
When dispersing the above pigment in one liquid, use a sand mill to
minute treatment (Example 28 and Reference Example 4) and 20 min.
The same conditions were used except that the treatment was carried out for a minute (Reference Example 3).

Thereafter, liquid A' and liquid B were combined so that the ratio of liquid A and liquid B was 50 parts: 50 parts, and the coatings of Examples 21 to 28 and Reference Examples 1 to 4 shown in Table 4.5 were applied. A composition for use was obtained. When used, liquid A' and liquid B were mixed together.

The obtained coating composition was spray-coated onto an aluminum spray-sprayed test piece (Ulstar, trade name, manufactured by Nippon Test Panel Co., Ltd.) to a cured film thickness of approximately 10 μm, and cured at a curing temperature of 100°C for 20 minutes. The film properties were tested.

The adhesion to the base material was determined by peeling test using adhesive tape (cellophane tape), and the hardness of the film was determined by pencil hardness (JIS K5).
400), measure the gloss with a gloss meter (60 degrees gloss),
Curing properties are improved by toluene resistance (solvent resistance) and boiling water resistance (
Boiling resistant. Observation was made using boiling tap water for 1 hour).

In addition, weather resistance is due cycle test (500 hours)
Judgment was made based on the subsequent gloss retention rate.

The test was conducted after being left at room temperature for one week after the curing treatment.

The solvent resistance was determined by lightly pressing the coating film with gauze impregnated with toluene and rubbing it back and forth 100 times, observing the condition of the coating film at that time, and rating it as good if there was no change.

Boiling water resistance is determined after being immersed in boiling tap water for 1 hour.
The test piece (test piece) was left for 1 hour and the state of the coating film was observed, and those with no change were evaluated as good.

The results are shown in Tables 4 and 5.

Comparative Example 5 - 10 parts of tetraethoxysilane, 100 parts of methyltrimethoxysilane, 35 parts of dimethyldimethoxysilane, IPA
80 parts of silica sol (manufactured by Catalysts Kasei Kogyo, 0.5% H2O, 30% solids), 50 parts of isopropanol, 0.4 part of IN-hydrochloric acid, and 6 parts of water at 500 rpm in an atmosphere of 25°C.
After stirring for 0 minutes, it was stored at room temperature for 3 days. Furthermore, r
Titanium oxide (manufactured by Ishiya Sangyo) relative to the solid content of IIj liquid
50 parts, 1.0 part of silicon oxide was added to Aerosil (Nippon Aerosil Co., Ltd.!!), and 110 parts of silicon oxide was added using a sand mill.
00 rpm for 20 minutes. The obtained liquid is called C-A liquid. When using, 100 parts of C-A solution, 30 parts of water, IP
30 parts of A and 0.2 parts of IN-hydrochloric acid were added to obtain coating liquid C-1.

Preparation conditions for liquid C-1: - Number of moles of water per mole of hydrolyzable group...before use 1 x 10-weight...when used 2 x 10' - Solid content of colloidal silica in component (A) -・・24
．． 4% ・Mole% of hydrolyzable organosilane with n=1...6
8.5 mol% This liquid C-1 was tested in the same manner as in Examples 21 to 28 above, and the results are shown in Table 6. As shown in Table 4.5, The composition has excellent weather resistance and adhesion, high hardness, and good gloss. It also has good solvent resistance and boiling water resistance. In contrast, the coating composition of Reference Example 1 formed a film with poor weather resistance, adhesion, hardness, and boiling water resistance.

The coating compositions of Reference Examples 2 to 4 formed coating films with poor gloss (other performances were equivalent to Examples 21 to 28). The coating composition of Comparative Example 5 was
Because it does not contain component (B) and water, hydrochloric acid, etc. are added instead, it is a baking type coating material and forms a coating film with poor weather resistance, adhesion, and hardness. Example 29 - Color black (HC) was added to 700 parts of the above GA-2 solution.
A black paint was prepared by mixing 17.2 parts of C) and dispersing carbon blank in a grain mill, and further adding 6 parts of N-β-aminoethyl-T-aminopropyltrimethoxysilane and 1.2 parts of dibutyltin dilaurate. In addition, a solution A' was prepared.

Next, add 15 parts of GB-1 liquid to 356.8 parts of this A' liquid.
0 parts were mixed to obtain a coating composition.

This was spray-painted on a cement base material [manufactured by Ask Co., Ltd., hard slate board (bulk density 1.7 g/ad, dimensional change from saturated water absorption to bone dry is 0.1 to 0.15%)]. 1 at room temperature so that the cured film has a thickness of about 20 μm.
After curing for a week, coating properties were tested as described above. The results are shown in Table 7.

Comparative Example 6-Snowtic O (water-dispersed silica vine, particle size 10-20 mμ, solid content (S i O□) 20%: 8 in a flask
150 parts of Sankagaku Kogyo fil and 136 parts of methyltrimethoxysilane were mixed and heated at 65°C for hydrolysis over about 5 hours to obtain a silanol solution in which methyltrimethoxysilane was partially condensed. This material was diluted with isopropyl alcohol to a solid content of 20%. Furthermore, add 500 parts of this solution to 500 parts of color black (HCC).
A black paint was prepared by dispersing carbon black in a grain mill, and then N-β-aminoethyl-γ
A comparative coating material was obtained by adding 3 parts of amylpropyltrimethoxysilane and 0.6 parts of dibutyltin dilaurate.

- Number of moles of water per mole of hydrolyzable group...2.2 - Solid content of colloidal silica in component (A)...30
．． 9% ・In the hydrolyzable organosilane represented by the formula (1),
Mol% of hydrolyzable organosilane when n=1
...100 mol% This comparative coating material was tested for film properties in the same manner as in Example 29, and the results are shown in Table 7.

The coating material of Example 29 was cured at room temperature to form a coating film with excellent weather resistance, adhesion, high hardness, good gloss, and good solvent resistance and boiling water resistance. On the other hand, since the coating material of Comparative Example 6 did not contain the component (B), it was a baking type coating material and formed a coating film with poor weather resistance, adhesion, and hardness.

The paints obtained in Examples 21 to 29 (Liquid A') and the paint obtained in Comparative Example 6 were placed in a sealed container, and their stability was evaluated by an accelerated heating test at 50°C. As a result, the paint of Comparative Example 6 gelled in one day, whereas the paint of Examples 21 to 2
Sample No. 9 only slightly thickened even after 7 days.

Next, Examples and Reference Examples in which the coating composition of the present invention has good storage stability will be shown.

(Preparation Example A-9) Component (A) shown in Table 8 was stored in a tightly closed polyethylene container for 48 hours, and ethylenediamine (anhydrous) diluted to 10% with IPA was added to the solution to adjust the pH of component (A). The solution was added dropwise while being monitored to adjust the pH to various values. Hereinafter, these will be referred to as A-9.

In addition, a similarly prepared product was stored in a tightly sealed polyethylene container for 3 months.

Examples 30 to 34 and Reference Examples 5 and 6 - 160 parts of A-9 prepared at various pHs shown in Table 8, B-1
and 40 parts of N-β-aminoethyl- as a curing catalyst.
A coating composition of the present invention was obtained by mixing with 0.5 part of γ-aminopropylmethyldimethoxysilane. Hereinafter, a test piece was prepared in the same manner as in Example 1 using this coating composition immediately after production (initial stage), and a film hardness test was conducted. Similarly, test pieces were prepared for the coating composition stored for 3 months, and a film hardness test was conducted. Table 8 shows the evaluation results of the coating hardness.

Example 35-! Component (A) obtained in Part A of Preparation Example 1 was stored for 48 hours in a tightly closed polyethylene container, and ethylenediamine (anhydrous) diluted to 10% with IPA was added to (A).
) While monitoring the pH of the components, add them dropwise until pH = 5.
2. Hereinafter, this liquid will be referred to as A-10. This A
-60 parts of
After mixing 40 parts of component B-1 with C-2, a test piece was immediately prepared in the same manner as in Example 1, and a film hardness test was conducted. Further, C-2 was stored for 3 months, test pieces were prepared in the same manner, and a film hardness test was conducted. The test results are shown in Table 9. Reference Example 7 - pH to 1.6g! ! [Other than that, a test piece was prepared in the same manner as in Example 35, and a film hardness test was conducted.

The test results are shown in Table 9.

As shown in Table 8.9 of Table 9, good storage stability was obtained by adjusting the pH of component (A) to 2 to 7.

The coating composition of this invention has a pH of component (A)
By adjusting the value in the range of 2 to 7, good storage stability and long-term stable performance can be obtained.

The following are examples and comparative examples of the coated inorganic cured body of the present invention and its manufacturing method.

Examples 36 to 41 and Comparative Example 7- (Solution 5-1) 7 parts of dimethyldichlorosilane, 40 g of methyltrichlorosilane (+, 48 parts of diphenyldichlorosilane and 78 parts of phenyltrichlorosilane were mixed with 95 parts of toluene, - 350 parts of water in a container with a reflux condenser
The mixture was added dropwise to a mixed solution of 50 parts of methanol while stirring while maintaining the temperature at 50° C. or lower to perform hydrolysis and condensation.

Wash the generated polymethylphenylsiloxane with water,
Hydrogen chloride produced as a by-product was removed. This was heated under reduced pressure to remove water remaining as a part of the solvent to obtain a silicone resin toluene solution with a concentration of 50%.

Next, 70 parts of bisphenol A epichlorohydrin type epoxy resin with an epoxy equivalent of 250, 5 parts of phthalic anhydride
1 part, 10 parts of linseed oil fatty acid, and 75 parts of toluene was prepared, and the temperature was gradually raised while stirring while removing toluene, and when the temperature reached 230°C, the temperature was maintained and further heated for 5 hours. continued. Here, 50 parts of the silicone resin toluene solution and the entire solid content of 50% are added.
Add an amount of toluene and stir until the solution becomes clear.
-1 was obtained.

(Solution $-2) Mix 51 parts of dimethyldichlorosilane, 15 parts of methyltrichlorosilane, 44 parts of diphenyldichlorosilane, and 52 parts of phenyltrichlorosilane with 50 parts of xylene, maintain the temperature between 40°C and 60°C, and add 320 parts of water. The solution was added dropwise while stirring, and then the solution was prepared in the same manner as solution S-1 until the concentration was 6.
A 0% silicone resin xylene solution was obtained.

Next, 54 parts of bisphenol A epichlorohydrin type epoxy resin having an epoxy equivalent of 500 and 25 parts of dodecylsuccinic anhydride were dissolved in 23 parts of xylene, and therein,
51 parts of the above silicone resin xylene solution was added and heated and stirred at reflux temperature for 3 hours to cause the epoxy resin and silicone resin to react. Furthermore, a required amount of xylene was added to obtain a 50% xylene solution S-2 of epoxy resin-modified silicone resin.

(Solution 5-3) 498 parts of dimethyldichlorosilane, 84 parts of phenyltrichlorosilane and 103 parts of diphenyldichlorosilane were mixed, and a mixed solution of 40 parts of methanol and 159 parts of water was added thereto for 2 hours while keeping the temperature below 25°C. I poured it on and slowly dripped it. Next, the temperature was raised to 70° C. to 75° C. while stirring, and the mixture was heated under reflux for 1 hour, and then cooled, 40 parts of methanol was added, and the mixture was separated.

Calcium carbonate 2 is added to the collected polyorganosiloxane layer.
After neutralizing by-product hydrogen chloride, methanol and low-boiling compounds were removed by heating under reduced pressure to obtain a liquid polyorganosiloxane.

50 parts of this polyorganosiloxane, 100 parts of xylene, and 45 parts of novolac type epoxy resin with an epoxy equivalent of 180.
1 part and 3.5 parts of phthalic anhydride were added, and the mixture was heated under xylene reflux for 3 hours. After cooling and filtration, a 50% xylene solution S-3 of epoxy resin-modified silicone resin was obtained.

■ Preparation of primer composition 75% butyl acetate solution I-1 of an isocyanate prepolymer mixture whose main component is represented by the above chemical formula (3), 75% butyl acetate solution I-1 of an isocyanate prepolymer mixture whose main component is represented by the above chemical formula (1) % butyl acetate solution 1-2, and
First, add a 50% ethyl acetate solution 1-3 of an isocyanate prepolymer mixture whose main component is represented by the chemical formula (5) above.
Primer compositions P-1 to P-5 were prepared by adding an epoxy resin-modified silicone resin, a mercapto group-containing silicon compound, an organic tin compound, and a solvent in the proportions shown in Table 0.

Preparation of coating composition As component (A), the above A-5 and A-6 were used.

(B) As the component, the above B-1, B-2 and CB-1
was used, and the following B-6 was used (Preparation Example B-6
) Isopropyl alcohol of a silanol group-containing organopolysiloxane with an average molecular weight of 3000 was prepared in the same manner as in GB-1 above, except that a 1.5% aqueous hydrochloric acid solution was used and the time until stirring was stopped after dropping was 40 minutes. A 40% solution was obtained. This is called B-6.

(Addition of pigment) A mixture of the component (A) shown in Table 11 and the white pigment titanium oxide ("R~820" manufactured by Ishihara Sangyo Co., Ltd.) was put through a sand grinder to disperse the titanium oxide, A paint was prepared. To this, add the component (C) shown in Table 11, and then add the component (B) shown in the same table.
The ingredients were blended to obtain a coating composition.

(Preparation Example Coating Liquid C-3) 100 parts of methyltrimethoxysilane, 20 parts of tetraethoxysilane, IPA silica sol (0S manufactured by Catalysts & Chemical Industry Co., Ltd.)
CAL 1432, SiO□ content 30%), 105 parts of dimethyldimethoxysilane, and 100 parts of JPA were mixed. Add 1 part of catalyst IN-hydrochloric acid and 4 parts of water to this mixed solution.
．． 5 parts were added to prepare solution A. In addition, the formulation is at 25℃,
The stirring was carried out at 500 rpm for 30 minutes.

The prepared solution A is stored in a tightly stoppered state at 25°C for more than a week, and when used, 42 parts of water and 4 parts of water are added to 100 parts of solution A.
Two parts of IPA were added and stirred at 500 rpm for 10 minutes at 25°C to obtain coating liquid C-3.

Preparation conditions for C-3!・Number of moles of water per mole of hydrolyzable group...before use 0. 1...When used 3.3 - Solid content of colloidal silica in component (A)...35
．． 1% ・Mole% of hydrolyzable organosilane with n=1...8
4.2 mol% The inorganic cured product is "Multi Siding" manufactured by Matsushita Electric Works (acrylic emulsion sealer with a bulk density of 1.0 g/cffl and a dimensional change of 0.3% from saturated water absorption to bone dry). Painted cement-based board) was used. This item has a shape as shown in Figures 1 to 3,
Grooves 21 in the longitudinal direction (vertical direction in FIG. 1) and grooves 22 in the width direction (horizontal direction in FIG. 1) are formed on the surface to have an uneven pattern. The right and left ends of the board shown in Figures 1 and 2 are rabbeted (Japanese-shape and chestnut-shaped).
is applied. The plates 1 of the inorganic cured material are joined together in the width direction at the portions where the mating process has been applied. The dimensions are a=465u, b=1511.
c=511, d=7m, e=7m, f=3w, g=
5w, h=311, 1=211, j=3mm. In FIG. 2, a hole 22 is formed at the eave-like protruding portion 32 at the right end of the inorganic cured plate 1, and the thickness is the thinnest (thickness j in the figure).

Regarding the primer and coating composition used,
It is shown in Tables 10 and 11. In addition, as for the processing conditions, the primer was applied with "multi-siding" to a film thickness of 10 μm using air spray, and the primer was applied at room temperature (25±
A primer layer was formed by leaving it at 2°C, 60 ± 5% RH for 30 minutes. On top of the primer layer, the coating composition was air-sprayed to a thickness of 10 μm for intermediate coating and 8 μm for top coating. Painted and kept at room temperature (25±2℃
, 60±5% RH) for one week to cure. After that, each test was conducted.

The film properties were tested according to the following evaluation methods: Adhesion: Adhesion to the substrate was tested using adhesive tape (using cellophane tape) Peeling H test: Hot water resistance: immersed in warm water at 60°C for 8 hours. After that, leave it at room temperature (
One cycle consisted of air drying at 25±2° C., 60±5% RH for 16 hours, and the condition of the coating film was observed.

・Weather resistance: Sunshine Weather-Ometer (JIS
After 2500 hours of irradiation, the condition of the coating film was observed using a coating (based on K5400), and those with no change were rated as good.

The results are shown in Table 12.

Table 12 - Example 42 - Primer P-1 was applied to the Multi Siding J by air spray to a film thickness of 60 lopm.
It was treated at ℃×30 minutes.

Thereafter, coating composition M-4 was applied by air spray to a film thickness of 10 μm, and treated at 60° C. for 30 minutes. Furthermore, coating composition M-1 was applied on top of it by air spraying to a film thickness of 8 μm.
℃ × 30 minutes - Comparative Example 8 - Primer P-1 was applied to the above-mentioned "Multi Siding". The conditions were to apply air spray to a film thickness of 10 μm and to process at 60° C. for 30 minutes.

Thereafter, coating composition C-1 was applied with air spray to a film thickness of 10 μm, and 130'CX
Processed for 30 minutes. Further, coating composition C-3 was applied thereon by air spraying to a film thickness of 8 μm, and treated at 130° C. for 30 minutes.

When observing the area circled in Figure 3 for each of the painted inorganic cured bodies of Example 42 and Comparative Example 8, it was found that cracks had occurred in the base material in Comparative Example 8;
In Example 42, there was no abnormality.

The following examples are examples in which a high-class appearance is imparted to the inorganic cured product by overcoating.

Example 43.44 - 60 parts of the following pigment N081 or NO12 was added to 100 parts of component (A) (A-6) shown in Table 11 to prepare a coating composition M-6 and a color pigment-containing coating composition. M-7 was prepared. Dispersion was performed using a sand mill for 60 minutes.

Pigment No. 1: White pigment (manufactured by Ishiya Sangyo@)...61 parts Yellow pigment (manufactured by Inu Nissin Kakogyo Jin)...22% black pigment (manufactured by Dainichisin Kakogyo@) )...17% Pigment No. 2: White pigment (manufactured by Ishiya Sangyo ■)...77 parts Yellow pigment (manufactured by Tennichi IN Kakogyo ■)...13% black pigment (
Brown pigment (manufactured by Dainichishin Kakogyo ■)... 5% Brown pigment (manufactured by Dainichishin Kakogyo ■)... 5% In addition, the above pigment N001 was added to Primer P-1 shown in Table 10. A primer composition containing color pigments was prepared. Dispersion was performed using a sand mill for 60 minutes. Pigment N011 was added to S-1. The amount of pigment added is P-1 vehicle solid content 100
It was made to be 25B for the department. This primer composition is designated as PG.

Example 45 - The above-mentioned "Multi-Iding" was used as the inorganic cured product. Air spray primer P-G to a film thickness of 2
It was coated to a thickness of 0 μm and treated with 50”CX for 30 minutes.

Thereafter, Coating Composition M-7 was applied by air spray to a film thickness of 10 μm, and treated at 50"CX for 30 minutes. Furthermore, Coating Composition M-1
Painted with air spray to a film thickness of 10 μm,
As a result of treatment at 60° C. for 30 minutes, the convex portions and concave portions had different colors and a glossy appearance was obtained. Furthermore, no cracks or the like were observed in the base material. Furthermore, the above series of performance evaluations also showed good results.

Example 46 - The above-mentioned "Multi Siding" was used as the inorganic cured body. Air spray primer P-1 to a film thickness of 1.
It was coated to a thickness of 0 μm and treated at 50° C. for 30 minutes.

Thereafter, coating composition M-6 was applied by air spray to a film thickness of 10 μm, and treated at 50° C. for 30 minutes. Furthermore, coating composition M-7 was applied on top of it by air spraying to a film thickness of 10 μm.
After processing for 15 minutes at °C, coating composition M-1 was applied with air spray to a film thickness of 10 μm.
It was treated at 0°C for 30 minutes.

As a result, the colors of the convex portions and concave portions were different, and a glossy appearance was obtained. Furthermore, no cracks or scratches were observed on the base material. Furthermore, the above series of performance evaluations also showed good results.

[Effects of the Invention] Since the coating composition of the present invention comprises at least the above-mentioned specific components (A), (B), and (C), it dries quickly, and the cured film thereof has high hardness and has excellent adhesion and
It has excellent solvent resistance (curability), boiling water resistance, and weather resistance. Furthermore, since the coating composition of the present invention can be cured at room temperature or by heating, it can be used in a wide range of drying conditions (environments) and temperature ranges. Therefore, since it can be applied to substrates that are not heat resistant and can be applied at work sites where no heat is applied, its industrial value is extremely high.

The coating composition of this invention can be colored arbitrarily by dispersing pigments, and by limiting the average molecular weight of component (B) as described above, it has excellent smoothness, adhesion, solvent resistance (curability), Boiling water resistance and weather resistance can be obtained.

As mentioned above, the coated inorganic cured body of the present invention is
A cured layer of the coating composition of the present invention is provided on the surface of an inorganic cured body such as cement. This hardened layer is
It has high hardness and excellent weather resistance, and will not crack or peel over a long period of time.

According to the method for producing a painted inorganic cured body of the present invention, the above-mentioned cured layer can be formed even at construction sites, etc., and can be applied to substrates with low heat resistance or substrates with rabbeted or uneven patterns. A hardened layer can be formed without cracking even on base materials that have thin parts. For these reasons, the industrial value of this invention is extremely large.

Furthermore, the cured layer can impart a high-grade appearance to the inorganic cured product.

[Brief explanation of the drawing]

FIG. 1 is a plan view of a portion of the inorganic cured product used in Examples 36 to 46 and Comparative Example 7°8, and FIG.
A sectional view and FIG. 3 are views showing a part of the BB cross section. ■・・・Inorganic hardened plate

Claims (1)

[Claims] (1) (A) General formula R^1_nSiX_4_-_n...(I) (wherein, R^1 is the same or different substituted or unsubstituted monovalent group having 1 to 8 carbon atoms; (represents a hydrocarbon group, n is an integer of 0 to 3, and X represents a hydrolyzable group) is partially hydrolyzed in colloidal silica dispersed in an organic solvent or water. A silica-dispersed oligomer solution of organosilane and (B) average compositional formula R^2_aSi(OH)_bO_(_4_-_a_-_
b_)_/_2...(II) (In the formula, R^2 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are each 0.2 ≦a≦2, 0.0001≦b≦3, a+
This is a number that satisfies the relationship b≦4. ) A coating composition containing as essential components a polyorganosiloxane containing a silanol group in the molecule and (C) a catalyst. (2) Component (A) is a silica-dispersed oligomer solution of organosilane obtained by partially hydrolyzing the hydrolyzable organosilane under the conditions of using 0.001 to 0.5 mol of water per 1 mol of X. A coating composition according to claim 1. (3) The coating composition according to claim 1, wherein component (A) contains 5 to 95% by weight of silica as a solid content. (4) The coating composition according to claim 1, wherein at least 50 mol% of the hydrolyzable organosilane is an organosilane in which n=1. (5) 9 parts by weight of component (B) for 1 to 99 parts by weight of component (A)
The coating composition according to claim 1, which contains 9 to 1 parts by weight (however, a total of 100 parts by weight of components (A) and (B)). (6) The coating composition according to claim 1, which also contains (D) a pigment as an essential component. (7) The coating composition according to claim 6, wherein the weight average molecular weight of component (B) in terms of polystyrene is 700 to 20,000. (8) The coating composition according to claim 1, wherein the pH of component (A) is 2.0 to 7.0. (9) A primer layer is provided as the first layer on the surface of the inorganic cured product, and a second
A painted inorganic cured body comprising a cured layer of the coating composition according to any one of claims 1 to 8 as a layer. (10) The inorganic cured product has a bulk density of 0.5 g/cm^3 or more, and the dimensional change from the time of saturated water absorption to absolute dryness is 0.5
10. The coated inorganic cured product according to claim 9, wherein the cured inorganic material has a content of at most %. (11) The painted inorganic cured body according to claim 9, wherein the inorganic cured body has a rabbeted finish and/or an uneven lateral pattern. (12) The first primer layer is (a) 100 parts by weight of an isocyanate prepolymer containing two or more isocyanate groups per molecule but no urethane bonds (b) One or more isocyanate groups per molecule Organosilicon compounds 1 to 10 containing a mercapto group and two or more alkoxy groups
0 parts by weight (c) 100 parts by weight or less of epoxy resin-modified silicone resin (as solid content) (d) Organotin compound and/or organic acid salt of tin 0.0
The coated inorganic cured product according to claim 9, comprising a cured product of a primer composition containing 1 to 30 parts by weight of each component. (13) The painted inorganic cured product according to claim 12, wherein the primer composition contains a pigment. (14) The coated inorganic cured product according to claim 12, wherein the isocyanate group contained in component (a) is not directly bonded to a benzene ring. (15) The coated inorganic cured product according to claim 13, wherein the isocyanate group contained in component (a) is not directly bonded to a benzene ring. (16) Claim 9, wherein the second layer is a cured layer having a pattern formed by dividing and/or overcoating at least two types of coating compositions containing pigments.
Painted inorganic hardened body as described. (17) A claim in which the second layer comprises at least one cured layer of a coating composition containing a pigment, and further a cured layer of a coating composition not containing a pigment formed thereon. Item 9. The coated inorganic cured product according to item 9. (18) A first step of forming a primer layer on the surface of the inorganic cured product, applying the coating composition according to any one of claims 1 to 8 on the primer layer, and drying by heating at room temperature or low temperature. and a second step of forming an inorganic coating layer. (19) The formation of the primer layer consists of: (a) 100 parts by weight of an isocyanate prepolymer containing two or more isocyanate groups in one molecule but no urethane bonds; (b) one or more mercapto groups in one molecule; Organosilicon compounds 1 to 10 containing a group and two or more alkoxy groups
0 parts by weight (c) 100 parts by weight or less of epoxy resin-modified silicone resin (as solid content) (d) Organotin compound and/or organic acid salt of tin 0.0
Applying a primer composition containing 1 to 30 parts by weight of each component,
The method for producing a coated cured inorganic material according to claim 18, which is carried out by drying by heating at room temperature to low temperature. (20) Claim 18 wherein the primer layer contains a pigment.
The method for manufacturing the painted inorganic cured body described above. (21) The method for producing a coated cured inorganic body according to claim 18, wherein in the second step, a pigment-free coating composition is applied as a final top coat. (22) The primer layer contains a pigment, and in the second step, the primer layer is formed by overcoating a coating composition containing at least one pigment of a wing color on the primer layer to create a pattern. 19. The method for producing a coated cured inorganic body according to claim 18, wherein a coating composition containing no pigment is applied as an overcoat. (23) At least two types of different colors in the second step,
19. The method for producing a painted inorganic cured body according to claim 18, wherein a pattern is formed by dividing and/or overcoating the pigment-containing coating composition.