HK1083858B - Polysilazane-containing coating solution - Google Patents

Description

Coating solution comprising polysilazane

Technical Field

The present invention relates to a coating solution capable of forming a coating excellent in characteristics such as corrosion resistance, scratch resistance, abrasion resistance, water wettability, easy-to-clean property, sealing property, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, fire resistance, antistatic property and antifouling property, which is formed by applying the coating solution to the surface of a body and wheels of an automobile, train, airplane and the like, dentures, tombstones, the interior and exterior of a house, products used with water in a toilet, kitchen, washing room, bathtub and the like, base materials of signboards, signs, plastic products and glass products such as metal, plastic, wood, ceramic, cement, mortar, brick, clay and the like.

Prior Art

Conventionally, various measures have been taken to prevent surface contamination of articles. For example, automobile bodies are easily soiled with dust, combustion products such as exhaust gas, and the like. Thus, these bodies are coated with wax to form a wax coating, thereby preventing contamination of the bodies. By making the surface of the body water repellent, water upon contact with the surface of the body forms water droplets to roll off from the surface of the body, whereby the adhesion and retention of the stain components in the water on the surface of the body can be prevented, while the wax coating makes it difficult for the stain components to adhere to the surface of the body, and even if the stain components adhere to the surface, they can be easily washed off with water.

In addition, products used with water, such as bathtubs, kitchen sinks, washstands, etc., come into contact with various materials, such as soap solutions containing oils and oily components, face washes, shampoos, etc., in addition to water during use. At this time, the oily substance and calcium salt of soap (i.e., soap scum) are considered to adhere to the surface of the product together with dust and the like to form dirt. In order to prevent scale formation on products, a glazed surface constituting a glassy surface formed on the products is sometimes subjected to a water repellent treatment with wax, a fluorine-containing material, or the like to prevent dirt from being left on the glazed surface. By this waterproofing treatment, it is also attempted to prevent dirt from adhering to the inside and outside of houses, toilets, products used with water, signboards, signs, gravestones, and the like.

On the other hand, it has been known for a long time to modify the surface of a substrate by coating the surface with a surfactant to make it hydrophilic, and it is described in JP-A52-101680 and the like that a water-soluble organic polymer (such as polyacrylic acid or polyvinyl alcohol) is added and introduced to the surfactant to further improve the durability of this hydrophilicity. Further, as described in JP-B5-67330 and the like, there is known a method of applying and fixing a hydrophilic material (such as cellulose, glycol and glycerin) by coating a polyvinyl alcohol-vinyl acetate copolymer on the surface and inside of a porous film made of a hydrophobic polymer.

However, the water-repellent effect of the water-repellent treatment with the conventional water-repellent wax cannot be said to be satisfactory, or even if a sufficient water-repellent treatment is initially carried out, the effect cannot be said to be durable, and thus a long and sufficient antifouling effect cannot be exhibited. Further, the hydrophilicity imparted by the conventional hydrophilic coating is only temporary or short time, so sufficient durability of the hydrophilic effect is hardly expected, and the water film on the hydrophilic coating hardly becomes uniform, which causes distortion of the transmission image or the reflection image and causes problems in practical application thereof to products.

Further, regarding the prevention of the staining of the denture and the generation of odor, fluorine treatment and the like have been studied, but it cannot be said that sufficient effects are achieved for a long time by treating the denture once.

Further, there is a demand for a coating solution capable of forming a coating excellent in characteristics such as corrosion resistance, scratch resistance, abrasion resistance, easy-to-clean property, water wettability, sealing property, chemical resistance, oxidation resistance, physical barrier effect, low shrinkage rate, UV-blocking effect, smoothing effect, durability effect, heat resistance, fire resistance and antistatic property, and there is a strong demand for improvement particularly in corrosion resistance and scratch resistance.

The present invention is to solve the aforementioned problems. Accordingly, it is an object of the present invention to provide a coating solution which, after application, can form a hard and dense coating excellent in adhesion to a substrate, and which can form a coating excellent in corrosion resistance and scratch resistance and at the same time excellent in characteristics such as a long-lasting hydrophilic and antifouling effect, abrasion resistance, easy-to-clean property, scratch resistance, corrosion resistance, sealing property, chemical resistance, oxidation resistance, physical barrier effect, low shrinkage rate, UV-blocking effect, smoothing effect, long-lasting effect, heat resistance, fire resistance and antistatic property on the surface of various substrates. Thus, the aforementioned various effects, including corrosion resistance and scratch resistance, can be imparted to the surfaces of various products or articles (e.g., automobile bodies, automobile wheels, dentures, gravestones, interiors and exteriors of houses, products used with water in bathrooms, kitchens, washrooms, bathtubs, etc., toilets, signboards, signs, plastic products, glass products, ceramic products, wood products, etc.).

The desired characteristics of the coating solution, for example, appearance such as uniform transparency after coating, drying characteristics, odor, safety, less damage to the substrate, and the like, vary depending on the substrate of the product or article to be coated with the coating solution, the conditioning conditions and the application mode, and the necessity of considering the surrounding environment when the coating solution is applied. Therefore, it is another object of the present invention to provide a coating solution which can easily prepare a suitable coating solution suitable for various applications.

Disclosure of Invention

The invention relates to a coating solution having the following properties:

(1) a coating solution includes polysilazane having Si-H bonds, a diluting solvent, and a catalyst.

(2) The coating solution according to item 1 above, wherein a petroleum solvent, an aromatic or alicyclic solvent, an ether, a halogenated hydrocarbon or a terpene mixture or a mixture of these solvents is used as the diluting solvent.

(3) The coating solution as described in item 1, wherein a paraffin type solvent, mineral spirits (mineralspirit), a terpene mixture or an ether or a mixture thereof is used as a diluting solvent.

(4) The coating solution according to item 3, wherein dibutyl ether, dimethyl ether, diethyl ether, polyglycol ether or tetrahydrofuran or a mixture thereof is used as the diluting solvent.

(5) The coating solution as claimed in any one of claims 2 to 4, wherein the diluting solvent further comprises one or more solvents selected from the group consisting of xylene, methylcyclohexane and ethylcyclohexane.

(6) The coating solution as described in any one of items 1 to 5, wherein the concentration of the polysilazane having Si-H bonds is 0.1 to 35% by weight.

(7) The coating solution as described in any one of items 1 to 5, wherein the concentration of the polysilazane having Si-H bonds is 0.5 to 10% by weight.

(8) The coating solution as claimed in any of claims 1 to 7, wherein the catalyst content is from 0.01 to 30% by weight, based on the content of pure polysilazane having Si-H bonds.

(9) The coating solution as described in any one of items 1 to 8, wherein the catalyst is an N-heterocyclic compound, an organic or inorganic acid, a metal carboxylate, an acetylacetone complex, a metal fine particle, a peroxide, a metal chloride, or an organometallic compound.

(10) The coating solution as described in any one of items 1 to 9, wherein the polysilazane having Si-H bond is prepared by reacting SiH₂Cl₂Reaction with alkali to form SiH₂Cl₂And then SiH₂Cl₂The adduct of (a) is reacted with ammonia to synthesize the resulting inorganic polysilazane.

(11) The coating solution as described in any one of items 1 to 9, wherein the polysilazane having Si-H bond is prepared by reacting SiH₂Cl₂And CH₃SiHCl₂Reaction with alkali to form SiH₂Cl₂And CH₃SiHCl₂And then SiH₂Cl₂And CH₃SiHCl₂The adduct of (a) is reacted with ammonia to synthesize the resulting polysilazane.

(12) Use of the coating solution according to any one of items 1 to 11 for coating a surface of a substrate to enhance corrosion resistance, abrasion resistance, stain resistance, easy cleaning, water wettability, sealing effect, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, fire resistance, low shrinkage, UV-barrier effect, smoothing effect, lasting effect, antistatic property and scratch resistance of the surface of the substrate of a product or article.

(13) The use according to item 12, wherein the coating solution is applied to the surface of the substrate in combination with a primer.

(14) Use according to claim 12 and/or 13, wherein the surface has been coated with a varnish, varnish or lacquer before the application of the coating solution.

Preferred mode of the invention

Hereinafter, the present invention will be described in more detail.

The coating solution of the present invention contains polysilazane having Si — H bonds, a diluent, and a catalyst as essential components. Polysilazanes having Si — H bonds used in the coating solution of the present invention include inorganic polysilazanes soluble in a solvent and having a repeating unit represented by the following general formula:

the inorganic polysilazane used in the present invention, which has a repeating unit represented by the above general formula and is soluble in a solvent, may be any inorganic polysilazane prepared by a method known in the art.

As a method for preparing an inorganic polysilazane having a repeating unit represented by the general formula and being soluble in a solvent, as described above, any one of methods including a method known in the art may be used. One method is, for example, by reacting a compound of the formula SiH₂X₂(X is a halogen atom) with a base to form a dihalosilane adduct and then reacting the dihalosilane adduct with ammonia to synthesize an inorganic polysilazane. The halosilane is generally acidic and can react with a base to form an adduct. Since the rate of formation and stability of the adduct depend on the acidity of the halosilane and the basicity or steric factor of the basic substance, they may be appropriately selectedThe type of halosilane and the type of base to form a stable adduct capable of reacting with ammonia to readily prepare an inorganic polysilazane. In this case, the stability of the adduct does not necessarily mean the stability as it can be isolated in the form of an adduct, but all possible cases in which, for example, the adduct is stably present in a solvent and also serves substantially as a reaction intermediate.

As the halosilane, the general formula SiH is preferably selected from the viewpoint of handling and reactivity thereof₂X₂The dihalosilane represented by (X ═ F, Cl, Br, or I) is preferably dichlorosilane, particularly in view of reactivity, raw material price thereof, and the like.

The base used to form the adduct may be a base which does not cause other reactions than the reaction to form an adduct with the halosilane, and preferable examples thereof include lewis bases, tertiary amines (trialkylamines), pyridine, picoline and derivatives thereof, secondary amines having a sterically hindered group, phosphine, arsine and derivatives thereof (such as trimethylphosphine, dimethylethylphosphine, methyldiethylphosphine, trimethylarsine, trimethylstilbene, trimethylamine, triethylamine, thiophene, furan, dioxane, selenophene, and the like), wherein pyridine and picoline are particularly preferable for handling and from an economical point of view. The amount of base used is not particularly limited and may be present in excess of the stoichiometric ratio of base (including amine in the adduct) to silane, i.e., in excess of the amine to silane ratio of 2: 1. The reaction to form the adduct is carried out in a solvent.

In the synthesis of the inorganic polysilazane via the adduct, the adduct is reacted with ammonia in an inert solution to form the inorganic polysilazane, wherein the amount of ammonia may exceed that of silane, and the reaction conditions are that the reaction temperature is usually-78 ℃ to 100 ℃, preferably-40 ℃ to 80 ℃, and the reaction time and the reaction pressure are not particularly limited. The polymerization of the inorganic polysilazane is preferably carried out in an inert gas atmosphere, and the inert gas is preferably nitrogen or argon.

In the present invention, the inorganic polysilazane may be an inorganic polysilazane which is soluble in a solvent and has a repeating unit represented by the general formula above, but it is generally preferred to use an inorganic polysilazane having a number average molecular weight in the range of 600 to 3000. Further, the inorganic polysilazane is preferably used in an amount of 0.1 to 35 wt%, preferably 0.5 to 10 wt%, with respect to the total weight of the coating solution.

Further, the organic polysilazanes having an Si-H bond suitable as the polysilazane used in the present invention include a polysilazane prepared by reacting a dihalosilane (preferably dichlorosilane) with R¹R²SiX₂(R¹And R²Represents a hydrogen atom or an alkyl group (preferably methyl), with the proviso that R¹And R²Not simultaneously represents a hydrogen atom; x represents F, Cl, Br or I, preferably Cl) with a base to form their corresponding adducts, and then reacting the adducts with ammonia. The base and reaction conditions used to form the adduct and the conditions for reacting the adduct with ammonia may be the same as those described previously for preparing the inorganic polysilazane.

On the other hand, the catalyst used in the present invention may be any catalyst having a function of converting polysilazane into silica at a general temperature. Preferred examples of the catalyst in the present invention include N-heterocyclic compounds such as 1-methylpiperazine, 1-methylpiperidine, 4 ' -trimethylene-dipiperidine, 4 ' -trimethylene bis (1-methylpiperidine), diazabicyclo [2.2.2] octane, cis-2, 6-dimethylpiperazine, 4- (4-methylpiperidine) pyridine, bipyridine (diperidine), α -methylpyridine, β -methylpyridine, γ -methylpyridine, piperidine, dimethylpyridine, pyrimidine, pyridazine, 4 ' -trimethylene bipyridine, 2- (methylamino) pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole, tetrazole and 1-methylpyrrolidine; amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, dihexylamine, trihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, trioctylamine, aniline, diphenylamine and triphenylamine; DBU (1, 8-diazabicyclo [5.4.0] 7-undecene), DBN (1, 5-diazabicyclo [4.3.0] 5-nonene), 1, 5, 9-triazacyclododecane, 1, 4, 7-triazacyclononane, and the like.

Further, organic acids, inorganic acids, metal carboxylates, acetylacetone complexes, and metal fine particles can also be cited as examples of preferred catalysts. The organic acids include acetic acid, propionic acid, butyric acid, valeric acid, maleic acid and stearic acid, and the inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid and hypochlorous acid. The metal carboxylate is of the formula (RCOO)_nM, wherein R represents C_1-22An aliphatic or alicyclic group; m represents at least one metal selected from the group consisting of Ni, Ti, Pt, Rh, Co, Fe, Ru, Os, Pd, Ir and Al; n is the valence of M. The metal carboxylate may be an anhydride or a hydrate. The acetylacetone complex is a complex comprising an anion acac^-The complex of the coordinated metal atom, the anion acac-being formed from acetylacetone (2, 4-pentanedione) via acid dissociation and is generally of the formula (CH)₃COCHCOCH₃)_nM represents, wherein M is an n-valent metal. Preferred examples of the metal M include nickel, platinum, palladium, aluminum and rhodium. The metal fine particles are preferably fine particles of Au, Ag, Pd, or Ni, and particularly preferably Ag. The particle diameter of the metal fine particles is preferably less than 0.5 micrometer, more preferably 0.1 micrometer or less, and even more preferably less than 0.05 micrometer. In addition to these materials, peroxides, metal chlorides or organometallic compounds (such as ferrocene or zirconocene) can also be used. These catalysts are incorporated in amounts of from 0.01 to 30%, preferably from 0.1 to 10%, particularly preferably from 0.5 to 7%, based on the pure polysilazane content.

The diluting solvent used in the coating solution of the present invention may be any diluting solvent capable of dissolving polysilazane having Si — H bonds and a catalyst. In view of storage stability, this diluting solvent is preferably a solvent having a lasting ability to dissolve polysilazane and a catalyst, and is preferably stable even over a long period of use without giving off gas such as silane, hydrogen, ammonia, and the like. The diluting solvent used in the coating solution of the present invention includes petroleum solvents (such as mineral spirits), paraffin-type solvents, aromatic solvents, alicyclic solvents, ethers, and halogenated hydrocarbons. Examples of such solvents or solvent components include paraffinic typesA solvent or solvent component (e.g., octane and 2, 2, 3-trimethylpentane having 8 carbons, nonane and 2, 2, 5-trimethylhexane having 9 carbons, decane having 10 carbons, n-undecane having 11 carbons, etc.), an aromatic solvent or solvent component (e.g., xylene having 8 carbons, cumene and lee having 9 carbons, naphthalene having 10 carbons, tetrahydronaphthalene, butylbenzene, p-cymene, diethylbenzene and tetramethylbenzene, pentylbenzene having 11 carbons, etc.), an alicyclic solvent or solvent component (e.g., methylcyclohexane having 7 carbons, ethylcyclohexane having 8 carbons, terpene having 10 carbons, α (monopinene, dipentene and decalin, etc.), an ether (e.g., dimethyl ether, diethyl ether, dibutyl ether, polyglycol ether, tetrahydrofuran, etc.) and a halogenated hydrocarbon (e.g., chlorinated hydrocarbons of methylene chloride, dichloroethane, chloroform, etc., or fluorinated, respectively, Brominated or iodinated hydrocarbons, and chlorinated aromatics of chlorobenzene, and the like). Furthermore, it has been shown that terpene mixtures, such as Depanol, can be used^®As a solvent. However, these solvents are merely illustrative examples, and the solvent or solvent component is not limited to these specifically exemplified solvents. Furthermore, these solvents or solvent components are used individually or in the form of mixtures thereof. Among these solvents, mineral spirits, paraffin type solvents and dibutyl ethers are particularly preferred.

The coating solution of the present invention may be applied to the surfaces of automobile bodies, automobile wheels, dentures, gravestones, interiors and exteriors of houses, products used with water in toilets, kitchens, laundry rooms, bathtubs, etc., toilets, signboards, signs, plastic products, glass products, ceramic products, wood products, etc., or to the surfaces of various articles to form dense and hydrophilic coatings on these products or article surfaces. The substrate to which the coating solution of the present invention is applied includes various materials such as metals (e.g., iron, steel, zinc, aluminum, nickel, titanium, vanadium, chromium, cobalt, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, boron, tin, lead or manganese or alloys thereof, with the proviso that an oxide film or a plated film is necessary), various types of plastics (e.g., polymethyl methacrylate (PMMA), polyurethane, polyester (e.g., PET), polyallyl diglycol carbonate (PADC), polycarbonate, polyimide, polyamide, epoxy resin, ABS resin, polyvinyl chloride, polyethylene, polypropylene, polysulfide, POM and polytetrafluoroethylene), if necessary, in combination with a primer to enhance adhesion to the materials. Such primers as silanes, siloxanes, silazanes, to name only a few. Other substrates to which the coating solution of the present invention may be applied include glass, wood, ceramic, concrete, mortar, brick, clay, or fiber, among others. If desired, these substrates may be coated with lacquers, varnishes or paints (e.g., polyurethane lacquers, acrylic lacquers and dispersion paints).

The method of applying the coating solutions of the present invention may be any known method of applying liquids. Specifically, the method of applying the coating solution of the present invention includes, for example, a method of coating with cloth, a method of coating with sponge, spray coating, flow coating, roll coating, dip coating, etc., but the coating method is not limited to these methods as examples. The preferred method of applying the coating solution of the present invention varies depending on various conditions such as the shape, size and number of products to which the coating solution is applied, for example, in the case of automobile bodies and gravestones, the cloth-coating method, the sponge-coating method and the spray method are operationally preferred, and in the case of interiors and exteriors of houses, roll coating and spray coating are preferred. In the case of dentures, spray coating and dip coating are preferred. Preferably, the coating solution is applied in an amount such that the formed coating has a thickness of about 0.1 to 2 microns after drying.

By applying the coating solution of the present invention, a dense coating layer can be formed on the surface of a product, and thus the surface of a base material of the product or article is provided with corrosion resistance, abrasion resistance, stain resistance, easy-to-clean property, water wettability, sealing effect, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, fire resistance, low shrinkage rate, UV-barrier effect, smoothing effect, lasting effect, antistatic property, and scratch resistance. The reason why the aforementioned characteristics can be provided to the products and articles is that polysilazane contained in the coating solution is converted into a dense silica coating due to the action of the catalyst. In addition, by forming a silica coating, the surface of a product or article exhibits strong hydrophilicity based on a silica film. The coating solution of the present invention readily forms a hard and dense coating made of silica when dried at ordinary temperatures. The formation of this silica coating varies depending on the polysilazane type, catalyst type, etc., but the coating will form in a period of about 1 to 2 weeks. The coating solution of the present invention is in the form of a solution at the time of application, and thus can be very easily applied to form a coating layer. This coating will convert to a dense and hard hydrophilic coating after application, thereby providing the aforementioned properties to various surfaces of products and articles. The surface of the formed coating is hard and dense so that it is excellent as a corrosion-resistant coating and a scratch-resistant coating and at the same time the coating is excellent in wear resistance, antifouling effect and easy-to-clean property after being stained. Further, the coating solution of the present invention can be used not only as a corrosion-resistant coating, a scratch-resistant coating, an abrasion-resistant coating, an antifouling coating or a coating excellent in easy-to-clean property, but also as a film-forming coating solution for forming a hydrophilic coating, a sealing material, a chemical-resistant coating, an oxidation-resistant coating, a physical barrier coating, a coating imparting heat resistance, a fire-resistant coating, an antistatic coating, a low-shrinkage coating, a UV-barrier coating, a smooth coating, a durable coating, or the like.

When the coating solution of the present invention is used to form a hydrophilic and dense silica coating on a surface such as an automobile, a tombstone, an exterior wall of a house, etc. by using an inorganic polysilazane, the resulting hydrophilic surface comes to be in a water-like coating state without forming water droplets thereon when it comes into contact with rainwater. In addition, the affinity of this hydrophilic surface for water is higher than that for hydrophobic substances (such as combustion products including dust and the like), thereby making these contaminants easy to wash away with rainwater. Further, since a dense surface is formed, the amount of smoke and dust adhering thereto can be made small. Therefore, the scale visible to the naked eye hardly appears, and the amount of adhered scale decreases. And is difficult to scratch and achieve corrosion protection because a dense coating is formed.

In the case of dentures, acrylic resins, which are the material of dentures, absorb water, from which dirt enters the resin or dirt is absorbed or adhered to the resin, and these dirt is a source of the denture odor. Since the coating solution of the present invention forms a hydrophilic and dense silica coating which adheres well to a denture at a temperature at which an acrylic resin as a denture material does not deform or deteriorate, water can be prevented from being absorbed into the resin, thereby preventing dirt from invading the denture material, and even if dirt adheres to the silica coating, they are easily washed away with water, and thus odor can be prevented from being emitted. Furthermore, the dental prosthesis is coated with the coating solution of the present invention so that even if irregularities occur on the dental prosthesis in the manicure, the silica coating smoothes the irregularities to make dirt adhesion more difficult. Further, the formed silica coating has high surface hardness and high durability, and thus is not abraded by food or at the time of biting, is stable in a living body, and is not eluted. Even if the silica is released, it is not toxic.

The desired properties of the coating solutions of the present invention (such as appearance, drying characteristics, odor, safety, damage to substrates, and storage stability of the coating solution) vary somewhat depending on the use of the product to which the coating solution is applied. To cope with this problem, it is possible to easily provide the most suitable coating solution for the intended use by changing not only the type and amount of polysilazane and catalyst used but also the type of solvent and compounding ratio.

For example, heavy solvents such as mineral spirits are suitable as solvents for substrates whose appearance is considered important (e.g. dark-coated cars, dentures, polished granite, mirror-finished metal or plated substrates, transparent resins and glass) which are stained with ease to observe. Mineral terpenes, Pegasol AN45 and Pegasol 3040 from Mobil Sekiyu corp. By using mineral spirits as a solvent, a substrate whose mottle, interference color, whiteness and grittiness can be easily observed can be perfectly coated with the coating solution. Mineral spirits have the aforementioned advantages, but are poor in solubilizing ability, so that mixed aromatic solvents (such as Solvesso100 and Solvesso150 of Esso Sekiyu Co., and Pegasol R-100 and Pegasol R-150 of Mobil Sekiyu Corp., etc.) can be compounded in addition to mineral spirits to compensate for the solubilizing ability. Further, a paraffin type solvent having no aromatic component may also be used as the solvent. Specifically, low-odor solvents, Exxol DSP100/140, Exxol D30, Exxol D40, and the like, by Tonen Chemical co.

Furthermore, it is also important that products used with water, such as those in toilets, kitchens, washing rooms, bathrooms, etc., and dentures, are odorless. If desired, by adding a low odor solvent (such as methylcyclohexane or ethylcyclohexane as part of the solvent), a less odorous coating solution can be provided for such products that require no odor.

The coating solutions of the present invention can be applied to newly manufactured products and articles or to products during use.

Examples of compositions of inorganic polysilazanes, catalysts and dilution solvents intended for use in the respective application coating solutions are shown below. These examples are shown for illustrative purposes only, and the composition and compounding ratio of the coating solution can be adapted to the use of the product coated therewith, and the composition and compounding ratio of the coating solution of the present invention are not limited to those shown below.

A. Automobile main body and wheel

This solution should not damage the underlying layer of the coating and should be stable so that it is not whitened in the cup gun, particularly when the solution is applied by the cup gun.

(examples of compounding ratios)

Inorganic polysilazane: 0.3 to 2% by weight

DMPP: 0.01 to 0.1% by weight

Xylene: 0.5 to 10% by weight

Pegasol AN 45: balance of

DMPP is 4, 4' -trimethylenebis (1-methylpiperidine) (hereinafter this abbreviation is used).

(preferred embodiment of compounding ratio)

Inorganic polysilazane: 0.4 to 1% by weight

DMPP: 0.01 to 0.05% by weight

Xylene: 1 to 4% by weight

Pegasol AN 45: balance of

B. Artificial tooth

The solution should be stable for a long period of time without whitening and be complete to the human body, and have less odor without deforming or deteriorating acrylic resin as a material for dental prosthesis.

(compounding ratio example)

Inorganic polysilazane: 0.5 to 5% by weight

DMPP: 0.02 to 0.2% by weight

Pega sol AN 45: balance of

(preferred embodiment of compounding ratio)

Inorganic polysilazane: 1 to 2% by weight

DMPP: 0.04 to 0.08% by weight

Pegasol AN 45: balance of

C. Gravestone

This solution should exhibit less interference color when applied on granite or the like and be stable for a long time so as not to be whitened.

(compounding ratio example)

Inorganic polysilazane: 0.5 to 4% by weight

DMPP: 0.01 to 0.2% by weight

Xylene: 5 to 50% by weight

Pegasol 3040: balance of

(preferred embodiment of compounding ratio)

Inorganic polysilazane: 1 to 3% by weight

DMPP: 0.01 to 0.1% by weight

Xylene: 5 to 15% by weight

Pegasol 3040: balance of

D. Inside and outside of houses, bathtubs, kitchens, etc

The solution should be almost odorless, safe to the human body and have high drying characteristics.

(compounding ratio example)

Inorganic polysilazane: 0.3 to 2% by weight

DMPP: 0.01 to 0.2% by weight

Xylene: 1 to 10% by weight

Pegasol AN 45: 5 to 88% by weight

Ethyl cyclohexane: 5 to 88% by weight

Methylcyclohexane: 5 to 88% by weight

(preferred embodiment of compounding ratio)

Inorganic polysilazane: 0.5 to 2% by weight

DMPP: 0.01 to 0.1% by weight

Xylene: 1 to 5% by weight

Pegasol AN 45: 20 to 50% by weight

Ethyl cyclohexane: 20 to 50% by weight

Methylcyclohexane: 20 to 50% by weight

E. Polycarbonate plate

The solution should not corrode polycarbonate sheets as substrates.

(compounding ratio example)

Inorganic polysilazane: 0.5 to 5% by weight

DMPP: 0.01 to 0.4% by weight

Xylene: 1 to 10% by weight

Pegasol 3040: balance of

(preferred embodiment of compounding ratio)

Inorganic polysilazane: 0.5 to 4% by weight

DMPP: 0.03 to 0.2% by weight

Xylene: 3 to 10% by weight

Pegasol 3040: balance of

Solvents Pegasol AN45 and Pegasol 3040(Mobil Sekiyu Corp.), which are fractions obtained by hydrogenation and refining of distilled oils obtained by distilling crude oils at atmospheric pressure, are mainly hydrocarbons of the C8 to C11 petroleum type and their aniline points are 43 ℃ and 54 ℃, respectively, and Pegasol AN45 contains higher contents of aromatic components than Pegasol 3040.

Best mode for carrying out the invention

Hereinafter, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to the production examples and examples described below.

Preparation example 1 (preparation of inorganic polysilazane)

The gas line, mechanical stirrer and Dewar condenser were fitted into a four-necked flask having an internal volume of 300 ml. The interior of the reactor was replaced by deoxygenated dry nitrogen, and then 150 ml of degassed dry pyridine was introduced into a four-necked flask and cooled on ice. Then, 16.1 g of dichlorosilane was added thereto over 50 minutes to form a white solid adduct (SiH)₂Cl₂2 Py). The reaction mixture was cooled on ice with vigorous stirring and bubbled with a mixture of nitrogen and 10.9 g of ammonia (previously purified by means of an alkali lime tube and carbon activated tubes) for 1 hour. After the reaction was complete, the solid product was removed by centrifugation and subsequent filtration. The solvent was removed from the filtrate under reduced pressure (50 ℃, 5 mm hg, 2 hours) to give 5.52 g of a glassy solid polysilazane. The polysilazane has a molecular weight of 2000 as measured by the vapor pressure lowering method. The yield was 77%.

Preparation example 2 (preparation of organic polysilazane)

A gas inlet tube, a mechanical stirrer and a Dewar condenser were fitted into a four-necked flask having an internal volume of 300 ml. The interior of the reactor was replaced by deoxygenated dry nitrogen, and then 150 ml of degassed dry pyridine was introduced into a four-necked flask and cooled on ice. Then, 9.2 g of methyldichlorosilane and 8.1 g of dichlorosilane were added thereto to form a white solid adduct. The reaction mixture was cooled on ice with vigorous stirring and bubbled with a mixture of nitrogen and 12.0g of ammonia (previously purified by means of an alkali lime tube and carbon activated tubes). After the reaction was complete, the solid product was removed by centrifugation and subsequent filtration. The solvent was removed from the filtrate under reduced pressure (50 ℃, 5 mm hg, 2 h) to give 5.2 g of viscous liquid polysilazane. The molecular weight as measured by vapor pressure reduction was 1600. The yield was 72%.

Example 1

0.5 part by weight of the inorganic polysilazane obtained in preparation example 1 and 0.02 part by weight of DMPP (catalyst) were dissolved in a solvent consisting of 1.98 parts by weight of xylene and 97.5 parts by weight of Pegasol AN45(Mobil Sekiyu Corp.) to obtain a repellent for automobile bodies and wheels

The coating solution is soiled.

The coating solution was sprayed onto the coated steel sheet by means of a spray gun in such an amount that a coating having a thickness of 0.2 μm after conversion to silica was obtained. After drying, the coatings were tested in an outdoor exposure test and observed for changes in contact angle, the results of which are shown in table 1.

TABLE 1

Outdoor exposure days (heaven)	0	7	14	21	28	3 months old	6 months old	1 year
									Contact angle (degree)	65	41	23	16	11	10	9	10

As can be seen from table 1, the silica coating layer was gradually formed, and after 2 weeks, a hydrophilic coating layer was almost formed, whereby the hydrophilic silica coating layer, the coated steel sheet was maintained in a stably coated state for a long period of time. This coated steel sheet, observed after 6 months and 1 year respectively, was not considered to be stained.

The coating solution was sealed in a nitrogen atmosphere and stored at a usual temperature, and the production of monosilane was examined after 1 month, 3 months and 6 months, respectively, with the result that the amount of monosilane produced after 1 month was 43ppm, 61ppm after 3 months and 75ppm after 6 months, indicating good storage stability.

When the coating solution in example 1 was placed in the cup of a spray gun and left in the air at normal temperature for 30 minutes, the solution maintained its transparent state. Separately, a coating solution was prepared from the same composition as previously described, but Pegasol AN45 was replaced with Pegasol 3040(Mobil Sekiyu Corp.) having a lower aromatics content than Pegasol AN45, which became cloudy after 20 minutes. From this result, it was found that, when the automotive antifouling coating solution having the aforementioned composition is applied with a spray gun, it is preferable to use a solvent containing a high aromatic component content in the coating solution in a range that does not affect the lower layer of the coating layer from the viewpoint of the stability of the coating solution.

Example 2

1 part by weight of the inorganic polysilazane obtained in preparation example 1 and 0.04 part by weight of DMPP (catalyst) were dissolved in a solvent consisting of 98.96 parts by weight of Pegasol AN45(Mobil Sekiyu Corp.) to obtain AN antifouling coating solution for dentures.

This coating solution was applied to the entire set of dentures with a spray gun to form a 0.3 μm thick silica coating thereon. This coating was completely converted to silica by drying in an oven at 45 ℃ for 60 minutes and then treating at 40 ℃ and 90% relative humidity for 12 hours. A hydrophilic and dense silica coating is formed on the surface of the dental prosthesis, and when this dental prosthesis is used, the coating is not damaged, dirt can be easily washed away with water, and no odor is generated.

Example 3

1 part by weight of the inorganic polysilazane obtained in preparation example 1 and 0.04 part by weight of DMPP (catalyst) were dissolved in a solvent consisting of 11.46 parts by weight of xylene and 87.5 parts by weight of Pegasol 3040(Mobil Sekiyu Corp.) to obtain an antifouling coating solution for a tombstone.

This coating solution was applied to the polished granite by aerosol spraying. Thereby forming a uniform coating of 0.4 microns thick. After 2 weeks, a hydrophilic and dense silica coating was formed on the surface, and when left for one year outdoors, the coating was not damaged, and no fouling was observed.

Example 4

0.5 part by weight of the inorganic polysilazane obtained in preparation example 1 and 0.02 part by weight of DMPP (catalyst) were dissolved in a solvent consisting of 1.98 parts by weight of xylene, 32.5 parts by weight of Pegasol AN45(Mobil Sekiyu Corp.), 32.5 parts by weight of ethyl cyclohexane and 32.5 parts by weight of methyl cyclohexane to obtain AN antifouling coating solution for coating products (such as bathtubs, wash stands, etc.) used with water. The coating solution was applied to the surfaces of ceramic ware wash stands and enamel bathtubs. Respectively, a uniform coating of 0.2 microns was formed. The soil hardly adheres, and if adhered, the soil can be easily removed.

Example 5

1 part by weight of the inorganic polysilazane obtained in preparation example 1 and 0.04 part by weight of DMPP (catalyst) were dissolved in a solvent consisting of 3.96 parts by weight of xylene, 31.7 parts by weight of Pegasol AN45(Mobil Sekiyu Corp.), 31.7 parts by weight of ethyl cyclohexane and 31.7 parts by weight of methyl cyclohexane to obtain AN antifouling coating solution for the interior and exterior of houses. The coating solution is applied to the surface of the exterior wall of a house by roll coating. The outer wall is not soiled for a long time. Dirt such as dust can be easily removed by spraying water.

Example 6

2 parts by weight of the inorganic polysilazane obtained in preparation example 1 and 0.08 part by weight of DMPP (catalyst) were dissolved in a solvent consisting of 7.92 parts by weight of xylene and 90 parts by weight of Pegasol 3040(Mobil Sekiyu Corp.) to obtain an antifouling coating solution for polycarbonate sheet. The coating solution was applied by hand to a polycarbonate plate using a cloth impregnated with the coating solution. A hydrophilic and dense silica coating can be formed on the surface without the coating solution corroding the substrate.

Example 7

5 parts by weight of the inorganic polysilazane obtained in preparation example 1 and 0.035 part by weight of palladium propionate (catalyst) were dissolved in a solvent composed of 25 parts by weight of xylene and 69.97 parts by weight of Solvesso150(Esso Sekiyu Co.) to obtain a coating solution. The aluminum plates were coated with this coating solution by flow coating in such an amount that after conversion to silica a coating with a thickness of 0.3 μm was obtained. After drying, the aluminum plate was calcined in air at 120 ℃ for 1 hour to obtain a sample for corrosion resistance test. Separately, a PET film was coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating having a thickness of 0.3 μm was obtained. After drying, the aluminum plate and the PET film were treated at 90 ℃ and 90% RH for 3 hours to obtain a sample for a scratch test. The coating properties were evaluated in the following manner, and the obtained corrosion resistance results are shown in table 2, and the results of the scratch resistance properties are shown in table 3.

Evaluation of coating Properties

(1) Corrosion resistance

A coating was formed on an aluminum plate, and then the substrate was examined for the degree of corrosion in the CASS test in which a sample was sprayed with a solution prepared by adding acetic acid and copper (II) chloride to an aqueous sodium chloride solution for 96 hours.

Very good: very good corrosion resistance

O: excellent in corrosion resistance

And (delta): slightly poor corrosion resistance

X: poor corrosion resistance

CASS test method

The specimens were sprayed with a mixture of 4% brine and 0.027% copper chloride (dihydrate) in a test bath set at 50 ℃ and evaluated for corrosion and corrosion resistance.

The term CASS is an abbreviation for "copper accelerated acetate spray".

(2) Scratch resistance

A coating layer was formed on polyethylene terephthalate (PET film), and then tested with steel wool #000 under a load of 500 g (area: 2 cm square) reciprocating 300 times, and the haze was measured with a haze meter.

Example 8

0.2 part by weight of the inorganic polysilazane obtained in preparation example 1 and 0.002 part by weight of palladium propionate (catalyst) were dissolved in a solvent consisting of 1 part by weight of xylene and 98.80 parts by weight of Solvesso150(Esso Sekiyu Co.) to obtain a coating solution. The aluminum plates were coated with this coating solution by flow coating in such an amount that after conversion to silica a coating with a thickness of 0.03 μm was obtained. After drying, the aluminum plate was calcined in air at 120 ℃ for 1 hour to obtain a sample for corrosion resistance test. Separately, a PET film was coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating having a thickness of 0.03 μm was obtained. After drying, the PET film was treated at 90 ℃ and 90% RH for 3 hours to obtain a sample for a scratch test. The coatings were evaluated in the same manner as in example 7, and the obtained corrosion resistance results are shown in table 2, and the results of the scratch resistance properties are shown in table 3.

Example 9

20 parts by weight of the inorganic polysilazane obtained in preparation example 1 and 0.14 part by weight of palladium propionate (catalyst) were dissolved in a solvent consisting of 25 parts by weight of xylene and 54.86 parts by weight of Solvesso150(Esso Sekiyu Co.) to obtain a coating solution. The aluminum plates were coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating with a thickness of 1.2 μm was obtained. After drying, the aluminum plate was calcined in air at 120 ℃ for 1 hour to obtain a sample for corrosion resistance test. Separately, a PET film was coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating having a thickness of 1.2 μm was obtained. After drying, the PET film was treated at 90 ℃ and 90% RH for 3 hours to obtain a sample for a scratch test. The coatings were evaluated in the same manner as in example 7, and the corrosion resistance results obtained are shown in table 2 and the scratch resistance results are shown in table 3.

Example 10

5 parts by weight of the organic polysilazane obtained in preparation example 2 and 0.035 part by weight of palladium propionate (catalyst) were dissolved in a solvent consisting of 94.97 parts by weight of dibutyl ether to obtain a coating solution. The aluminum plates were coated with this coating solution by flow coating in such an amount that after conversion to silica a coating with a thickness of 0.3 μm was obtained. After drying, the aluminum plate was calcined in air at 120 ℃ for 1 hour to obtain a sample for corrosion resistance test. Separately, a PET film was coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating having a thickness of 0.3 μm was obtained. After drying, the PET film was treated at 90 ℃ and 90% RH for 3 hours to obtain a sample for a scratch test. The coatings were evaluated in the same manner as in example 7, and the corrosion resistance results obtained are shown in table 2 and the scratch resistance results are shown in table 3.

Example 11

20 parts by weight of the organopolysilazane obtained in preparation example 2 and 0.14 part by weight of palladium propionate (catalyst) were dissolved in a solvent consisting of 79.86 parts by weight of dibutyl ether to obtain a coating solution. The aluminum plates were coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating with a thickness of 1.2 μm was obtained. After drying, the aluminum plate was calcined in air at 120 ℃ for 1 hour to obtain a sample for corrosion resistance test. Separately, a PET film was coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating having a thickness of 1.2 μm was obtained. After drying, the PET film was treated at 90 ℃ and 90% RH for 3 hours to obtain a sample for a scratch test. The coatings were evaluated in the same manner as in example 7, and the corrosion resistance results obtained are shown in table 2 and the scratch resistance results are shown in table 3.

Example 12

5 parts by weight of the inorganic polysilazane obtained in preparation example 1 and 0.2 part by weight of DMPP (catalyst) were dissolved in a solvent consisting of 25 parts by weight of xylene and 69.8 parts by weight of Pegasol AN45(Mobil Sekiyu Corp.) to obtain a coating solution. The aluminum plates were coated with this coating solution by flow coating in such an amount that after conversion to silica a coating with a thickness of 0.3 μm was obtained. After drying, the aluminum plate was calcined in air at 120 ℃ for 1 hour to obtain a sample for corrosion resistance test. Separately, a PET film was coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating having a thickness of 0.3 μm was obtained. After drying, the PET film was treated at 90 ℃ and 90% RH for 3 hours to obtain a sample for a scratch test. The coatings were evaluated in the same manner as in example 7, and the corrosion resistance results obtained are shown in table 2 and the scratch resistance results are shown in table 3.

Example 13

15 parts by weight of the inorganic polysilazane obtained in preparation example 1 and 0.6 part by weight of DMPP (catalyst) were dissolved in a solvent consisting of 25 parts by weight of xylene and 59.4 parts by weight of Pegasol AN45(Mobil Sekiyu Corp.) to obtain a coating solution. The aluminum plates were coated with this coating solution by flow coating in such an amount that after conversion to silica a coating with a thickness of 1.0 μm was obtained. After drying, the aluminum plate was calcined in air at 120 ℃ for 1 hour to obtain a sample for corrosion resistance test. Separately, a PET film was coated with this coating solution by flow coating in such an amount that, after conversion to silica, a coating having a thickness of 1.0 μm was obtained. After drying, the PET film was treated at 90 ℃ and 90% RH for 3 hours to obtain a sample for a scratch test. The characteristics of the coating layer were evaluated in the same manner as in example 7, and the obtained corrosion resistance results are shown in table 2 and the anti-scratch property results are shown in table 3.

Table 2: results of corrosion resistance test

Examples	7	8	9	10	11	12	13	Aluminium plate
									Evaluation results	○	△	◎	○	◎	○	◎	×

Table 3: results of the scratch test

Examples	7	8	9	10	11	12	13	PET
									Haze (%)	2	5	1	3	1	2	1	20

Effects of the invention

As described above, the coating solution of the present invention is in a liquid form at the time of application, and thus the coating solution can be easily applied to a substrate by spraying, a method of coating with cloth or sponge, or the like. After application, polysilazane in liquid form can be converted into a hard and dense coating layer, whereby a coating film excellent in corrosion resistance and scratch resistance is easily formed. Further, the hydrophilicity of the coating film thus formed is durable and its effective hydrophilicity can be maintained for usually 1 to 2 years. In addition to hydrophilicity, the coating may provide the product or article with properties such as abrasion resistance, stain resistance, water wettability, scratch resistance, corrosion resistance, sealing effect, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, fire resistance, and antistatic property. Further, by merely adjusting the type of solvent, the amount of compounding material, and the like, it is possible to apply this coating solution to a very wide range of uses.

Claims (13)

1. A coating solution comprising polysilazane having Si — H bonds, a diluting solvent and a catalyst, wherein the catalyst is an N-heterocyclic compound, an organic or inorganic acid, a metal carboxylate, an acetylacetone complex, a metal fine particle, a peroxide, a metal chloride or an organometallic compound.

2. The coating solution of claim 1, wherein a petroleum solvent, an aromatic or alicyclic solvent, an ether, a halogenated hydrocarbon or a terpene mixture or a mixture of these solvents is used as the diluting solvent.

3. The coating solution according to claim 2, wherein a paraffin-type solvent, mineral spirits, terpene mixtures or ethers or mixtures thereof are used as the diluting solvent.

4. The coating solution according to claim 3, wherein dibutyl ether, dimethyl ether, diethyl ether, polyglycol ether or tetrahydrofuran or a mixture thereof is used as the diluting solvent.

5. The coating solution of any one of claims 2 to 4, wherein the diluting solvent additionally comprises one or more solvents selected from the group consisting of xylene, methylcyclohexane, and ethylcyclohexane.

6. The coating solution of any one of claims 1 to 4, wherein the concentration of the polysilazane having Si-H bonds is from 0.1 to 35% by weight.

7. The coating solution of any one of claims 1 to 4, wherein the concentration of the polysilazane having Si-H bonds is from 0.5 to 10% by weight.

8. The coating solution of any one of claims 1 to 4, wherein the catalyst content is from 0.01 to 30% by weight, based on the content of pure polysilazane having Si-H bonds.

9. The coating solution of any one of claims 1 to 4, wherein the polysilazane having Si-H bonds is prepared by reacting SiH₂Cl₂Reaction with alkali to form SiH₂Cl₂Adduct then SiH₂Cl₂The adduct is reacted with ammonia to synthesize the resulting inorganic polysilazane.

10. RightsThe coating solution of any one of claims 1 to 4, wherein the polysilazane having Si-H bonds is prepared by reacting SiH₂Cl₂And CH₃SiHCl₂Reaction with alkali to form SiH₂Cl₂And CH₃SiHCl₂And then SiH₂Cl₂And CH₃SiHCl₂The adduct of (a) is reacted with ammonia to synthesize the resulting polysilazane.

11. Use of a coating solution according to any one of claims 1 to 10 for coating a substrate surface to enhance corrosion resistance, wear resistance, stain resistance, easy-to-clean property, water wettability, sealing effect, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, fire resistance, low shrinkage rate, UV-barrier effect, smoothing effect, lasting effect, antistatic property and scratch resistance of the substrate surface of a product or article.

12. Use according to claim 11, wherein the coating solution is applied to the substrate surface in combination with a primer.

13. Use according to claim 11 or 12, wherein the surface has been coated with a varnish, varnish or lacquer prior to application of the coating solution.