CN100375769C - Coating solution containing polysilazane - Google Patents

Abstract

A coating solution comprising 0.1 to 35% by weight of an inorganic or organic polysilazane having repeating units represented by the general formula below and soluble in a solvent and 0.1 to 10% by weight of catalyst such as 4,4'-trimethylenebis(1-methylpiperidine) based on a pure polysilazane content. By applying the coating solution onto the surface of base materials such as metals, plastics, glass, ceramic, wood, cement, mortar, bricks, etc., a silica coating strongly adhered to the base materials can be formed excellent in corrosion resistance and anti-scratch properties and simultaneously excellent in characteristics such as abrasion resistant, long-lasting anti-fouling properties, wetting properties to water, sealing properties, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, fire resistance and antistatic properties.

Description

Coating solution containing polysilazane

technical field

The present invention relates to properties such as corrosion resistance, scratch resistance, abrasion resistance, water wettability, easy cleaning, sealing performance, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, Coating solution for a coating excellent in fire resistance, antistatic property and antifouling property, which is formed by applying the coating solution to the main bodies and wheels of automobiles, trains, airplanes, etc., dentures, tombstones, interiors of houses and Exterior, products used with water in bathrooms, kitchens, washrooms, bathtubs, etc. Substrates for signs, signs, plastic products and glass products such as metal, plastic, wood, ceramics, cement, mortar, brick, Formed on the surface of clay etc.

current technology

Traditionally, various measures have been taken to prevent surface contamination of items. For example, the main body of an automobile is easily soiled by dust, combustion products such as exhaust gas, and the like. Accordingly, these bodies are coated with wax to form a wax coating, thereby preventing contamination of the body. By making the surface of the body repellent, water in contact with the surface of the body forms water droplets to roll off the surface of the body, thereby preventing the dirt components in the water from adhering and remaining on the surface of the body, while the wax coating makes the dirt components It is difficult to adhere to the surface of the main body, and even if the dirt 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., are in contact with various materials other than water during use, such as soaps, facial cleansers, shampoos, etc. containing oil and oily components . At this time, oily substances and calcium salts of soap (ie, soap scum) are considered to adhere to the surface of the product together with dust and the like to form stains. In order to prevent scaling on the product, the glazed surface constituting the glass-like surface formed on the product is sometimes subjected to a water repellent treatment with wax, fluorine-containing material, etc. to prevent stains from being left on the glazed surface. By means of the waterproofing treatment, an attempt is also made to prevent dirt from adhering to the inside and outside of the house, toilet stools, products used with water, sign boards, signs, tombstones, and the like.

On the other hand, it has long been known to modify the surface of a substrate by coating the surface with a surfactant to make it hydrophilic, and it is described in JP-A 52-101680 etc. that adding and Water-soluble organic polymers such as polyacrylic acid or polyvinyl alcohol are introduced to further improve the persistence of this hydrophilicity. In addition, as described in JP-B5-67330 and the like, it is known to apply and fix hydrophilic materials such as cellulose, glycols, and glycerol.

However, the water-repellent effect of water-repellent treatment with conventional water-repellent wax cannot be said to be satisfactory, or the effect cannot be said to be long-lasting even if sufficient water-repellent treatment is initially performed, and thus cannot show long-term and sufficient repellency. dirty effect. In addition, the hydrophilicity imparted by conventional hydrophilic coatings is only temporary or for a short time, so that sufficient durability of the hydrophilic effect can hardly be expected, and the water film on the hydrophilic coating can hardly become uniform, which leads to transmission The image or reflected image is distorted and makes it problematic to actually apply it to the product.

In addition, regarding the prevention of staining and odor of dentures, fluorine treatment and the like have been studied, but it cannot be said that a sufficient effect can be achieved for a long time by a single treatment of dentures.

In addition, it is also required to be able to form properties such as corrosion resistance, scratch resistance, abrasion resistance, easy cleaning, water wettability, sealing performance, chemical resistance, oxidation resistance, physical barrier effect, low shrinkage Coating solutions for coatings excellent in efficiency, UV-blocking effect, smoothing effect, long-lasting effect, heat resistance, fire resistance and antistatic properties, and are strongly demanded for improvement especially in corrosion resistance and scratch resistance .

The present invention is to solve the aforementioned problems. Accordingly, an object of the present invention is to provide a coating solution which, after application, forms a hard and dense coating excellent in adhesion to substrates, and which can be applied on the surface of various substrates. Form excellent corrosion resistance and scratch resistance and at the same time in the characteristics (such as long-lasting hydrophilic and antifouling effect, wear resistance, easy cleaning, scratch resistance, corrosion resistance, sealing performance, chemical resistance, anti-corrosion Oxidation resistance, physical barrier effect, low shrinkage, UV-blocking effect, smoothing effect, long-lasting effect, heat resistance, fire resistance and antistatic property). Thus, it can be applied to various products or items such as car bodies, car wheels, dentures, tombstones, house interiors and exteriors, products used with water in bathrooms, kitchens, washrooms, bathtubs, etc., toilets, signs, Signs, plastic products, glass products, ceramic products, wood products, etc.) impart the aforementioned various effects, including corrosion resistance and scratch resistance.

Desired properties of the coating solution, such as appearance, such as uniform transparency after coating, drying characteristics, odor, safety, low damage to the substrate, etc. Depending on the product or article to be coated with the coating solution The substrate, conditioning conditions, and mode of application vary as necessary, taking into account the surrounding environment in which the coating solution is applied. It is therefore another object of the present invention to provide coating solutions which allow easy preparation of suitable coating solutions for various applications.

Contents of the invention

The present invention relates to coating solutions having the following properties:

(1) A coating solution comprising a polysilazane having an Si—H bond, a diluent solvent, and a catalyst.

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

(3) The coating solution according to item 1, wherein a paraffin type solvent, mineral spirit, terpene mixture or ether or a mixture thereof is used as the dilution 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 dilution solvent.

(5) The coating solution according to any one of items 2 to 4, wherein the diluting solvent additionally contains one or more solvents selected from xylene, methylcyclohexane, and ethylcyclohexane.

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

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

(8) The coating solution according to any one of items 1 to 7, wherein the catalyst content is 0.01 to 30% by weight based on the content of pure polysilazane having Si—H bonds.

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

(10) The coating solution according to any one of items 1 to 9, wherein the polysilazane having an Si-H bond is formed by reacting SiH ₂ Cl ₂ with a base to form an adduct of SiH ₂ Cl ₂ and Then, the obtained inorganic polysilazane was synthesized by reacting the adduct of SiH ₂ Cl ₂ with ammonia.

(11) The coating solution according to any one of items 1 to 9, wherein the polysilazane having an Si-H bond is formed by reacting SiH ₂ Cl ₂ and CH ₃ SiHCl ₂ with a base to form SiH ₂ Cl ₂ and CH ₃ SiHCl ₂ , and then reacting the SiH ₂ Cl ₂ and CH ₃ SiHCl ₂ adduct with ammonia to synthesize the resulting polysilazane.

(12) The coating solution according to any one of items 1 to 11 is used to coat the surface of the substrate to enhance the corrosion resistance, abrasion resistance, antifouling, easy cleaning, Water wettability, sealing effect, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, fire resistance, low shrinkage, UV-blocking effect, smoothing effect, long-lasting effect, antistatic and scratch resistance The purpose of the feature.

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

(14) Use according to item 12 and/or 13, wherein the surface has been coated with a lacquer, varnish or paint before applying 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 a Si—H bond, a diluent, and a catalyst as essential components. The polysilazanes having Si-H bonds used in the coating solution of the present invention include inorganic polysilazanes which are soluble in solvents and have repeating units represented by the following general formula:

The solvent-soluble inorganic polysilazane having the repeating unit represented by the above general formula used in the present invention may be any inorganic polysilazane prepared by methods known in the art.

As a method for preparing the inorganic polysilazane having a repeating unit represented by the above general formula and being soluble in a solvent, as described above, any arbitrary method including methods known in the art can be used. One of the methods is, for example, by reacting a dihalosilane of the general formula SiH ₂ X ₂ (X is a halogen atom) with a base to form a dihalosilane adduct and then reacting the dihalosilane adduct with ammonia A method for synthesizing inorganic polysilazane by reaction. The halosilanes are generally acidic and can react with bases to form adducts. Since the formation rate and stability of the adduct depends on the acidity of the halosilane and the basicity or steric factor of the basic substance, the type of halosilane and the type of base can be appropriately selected to form And easily prepare stable adducts of inorganic polysilazanes. In this case, the stability of the adduct does not necessarily mean that it can be isolated in the form of the adduct, but rather all possible situations in which, for example, the adduct is present stably in the solvent and also in the Essentially used as a reaction intermediate.

As the halosilane, it is preferable to select a dihalosilane represented by the general formula SiH ₂ X ₂ (X=F, Cl, Br or I) in view of its handling and reactivity, especially in terms of reactivity, its raw material price, etc. Considering that, dichlorosilane is preferably selected.

The base used to form the adduct may be a base that does not cause a reaction other than the reaction with the halosilane to form the adduct, and preferred examples include Lewis bases, tertiary amines (trialkylamines), pyridine, methyl Basepyridine and its derivatives, secondary amines with sterically hindered groups, phosphine, arsine and its derivatives (such as trimethylphosphine, dimethylethylphosphine, methyldiethylphosphine, trimethylarsine, Trimethylstilbene, trimethylamine, triethylamine, thiophene, furan, dioxane, selenophene, etc.), among them, 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 the base may be present in excess of the stoichiometric ratio of base (including the amine in the adduct) to silane, ie, beyond the amine:silane ratio = 2:1. The reaction to form the adduct is carried out in a solvent.

When synthesizing inorganic polysilazane via adducts, the adduct reacts with ammonia in an inert solution to form inorganic polysilazane, wherein the amount of ammonia can exceed silane, and the reaction conditions are that the reaction temperature is usually -78°C to 100°C, preferably -40°C to 80°C, the reaction time and reaction pressure are not particularly limited. The polymerization reaction 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 that is soluble in a solvent and has a repeating unit shown in the preceding general formula, but it is generally preferred to use an inorganic polysilazane with a number average molecular weight in the range of 600 to 3000 alkyl. Furthermore, the inorganic polysilazane is used in an amount of preferably 0.1 to 35% by weight, preferably 0.5 to 10% by weight, relative to the total weight of the coating solution.

Furthermore, organopolysilazanes having Si-H bonds suitable as polysilazanes used in the present invention include those obtained by combining dihalosilane (preferably dichlorosilane) and R ¹ R ² SiX ₂ (R ¹ and R ² represents a hydrogen atom or an alkyl group (preferably methyl), provided that R ^{and R} do not represent a hydrogen atom at the same time; X represents F, Cl, Br or I, preferably Cl) reacts with a base to form their corresponding adducts, And then react the adduct with ammonia to synthesize polysilazane. The base and reaction conditions used to form the adduct and the conditions for the reaction of the adduct with ammonia may be the same as previously described for the preparation of the inorganic polysilazane.

On the other hand, the catalyst used in the present invention may be any catalyst having the function of converting polysilazane to silica at ordinary temperature. Preferred examples of catalysts in the present invention include N-heterocyclic compounds such as 1-methylpiperazine, 1-methylpiperidine, 4,4'-trimethylene-dipiperidine, 4,4'-trimethylene Bis(1-methylpiperidine), diazabicyclo[2.2.2]octane, cis-2,6-dimethylpiperazine, 4-(4-methylpiperidine)pyridine, pyridine, Diperidine, α-picoline, β-picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine, 4,4'-trimethylenebipyridine, 2- (Methylamino)pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole, tetrazole and 1-methylpyrrolidine; amines such as methylamine, dimethyl Amine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, di Hexylamine, 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-triaz Heterocyclic nonane, etc.

In addition, organic acids, inorganic acids, metal carboxylates, acetylacetonate complexes, and metal fine particles are also exemplified as preferable catalysts. Organic acids include acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, and stearic acid, and inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid, and hypochlorous acid. Metal carboxylate is the compound represented by formula (RCOO) _n M, wherein R represents C _1-22 aliphatic group or alicyclic group; M represents and is selected from Ni, Ti, Pt, Rh, Co, Fe, Ru, Os, At least one metal of Pd, Ir and Al; n is the valence of M. The metal carboxylate may be an anhydride or a hydrate. An acetylacetone complex is a complex comprising a metal atom coordinated to an anion ^acac- generated from acetylacetone (2,4-pentanedione) via acid dissociation, and the complex is generally of the formula (CH ₃ COCHCOCH ₃ ) _n M represents, wherein M is an n-valent metal. Preferable 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, 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, even more preferably less than 0.05 micrometer. In addition to these materials, it is also possible to use peroxides, metal chlorides or organometallic compounds such as ferrocenes or zirconocenes. These catalysts are introduced in amounts of 0.01 to 30%, preferably 0.1 to 10%, particularly preferably 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 the polysilazane having Si—H bonds and the catalyst. In consideration of storage stability, this diluting solvent is preferably a solvent having a long-lasting ability to dissolve polysilazane and a catalyst, and even a solvent that is used for a long time is preferably stable without releasing gas such as silane, hydrogen, ammonia, etc. . Diluting solvents used in the coating solution of the present invention include 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 paraffin-type solvents or solvent components (such as octane with 8 carbons and 2,2,3-trimethylpentane, nonane with 9 carbons and 2,2 , 5-trimethylhexane, decane with 10 carbons, n-undecane with 11 carbons, etc.), aromatic solvents or solvent components (such as xylene with 8 carbons, xylene with 9 carbons cumene and radium, naphthalene with 10 carbons, tetrahydronaphthalene, butylbenzene, p-cymene, diethylbenzene and tetramethylbenzene, pentylbenzene with 11 carbons, etc.), alicyclic solvents or Solvent components (such as methylcyclohexane with 7 carbons, ethylcyclohexane with 8 carbons, terpenes with 10 carbons, α (pinene, dipentene and decalin, etc.), Ether (such as dimethyl ether, diethyl ether, dibutyl ether, polyglycol ether, tetrahydrofuran, etc.) and halogenated hydrocarbons (such as dichloromethane, dichloroethane, chloroform, etc.) or iodinated hydrocarbons, and chlorinated aromatic compounds of chlorobenzene, etc.). In addition, it has been demonstrated that terpene mixtures, such as Depanol ^(R) , can be used as solvents. But these solvents are only examples for illustration, and solvents Or the solvent component is not limited to these specific example solvents.In addition, these solvents or solvent components are used alone or as a mixture thereof. Mineral spirits, paraffin type solvents and dibutyl ether are particularly preferred among these solvents.

The coating solution of the present invention can be applied to car bodies, car wheels, dentures, tombstones, house interiors and exteriors, products used with water in bathrooms, kitchens, laundry rooms, bathtubs, etc., toilets, signs, signs, plastics products, glass products, ceramic products, wood products, etc., or applied to the surface of various items to form a dense and hydrophilic coating on the surface of these products or items. The substrates to which the coating solutions of the present invention are applied include a wide variety of materials such as metals (such as iron, steel, zinc, aluminum, nickel, titanium, vanadium, chromium, cobalt, copper, zirconium, niobium, molybdenum, ruthenium , rhodium, boron, tin, lead or manganese or their alloys, if necessary with an oxide film or coating), various types of plastics (such as polymethyl methacrylate (PMMA), polyurethane, polyester (such as PET), polyallyl diglycol carbonate (PADC), polycarbonate, polyimide, polyamide, epoxy resin, ABS resin, polyvinyl chloride, polyethylene, polypropylene, polythiocyanate , POM and PTFE), if necessary, in combination with a primer to enhance the adhesion to the material in question. Such primers as silanes, siloxanes, silazanes, to name a few. Other substrates to which the coating solutions of the present invention may be applied include glass, wood, ceramics, concrete, mortar, brick, clay, or fibers, among others. If desired, these substrates can be coated with lacquers, varnishes or paints such as polyurethane lacquers, acrylic lacquers and dispersion paints.

The method of applying these 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 a cloth, a method of coating with a sponge, spray coating, flow coating, roller coating, dip coating, etc., but the coating method is not limited to these exemplified methods . 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 this coating solution is applied, for example, in the case of automobile bodies and tombstones, the method of applying with a cloth, Sponge and spray methods are operationally preferred, while roller and spray applications are preferred in the case of interior and exterior premises. In the case of dentures, spraying and dipping are preferred. Preferably, the coating solution is applied in such an amount that the resulting 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 can be formed on the surface of a product, thereby providing the substrate surface of a product or article with corrosion resistance, abrasion resistance, stain resistance, ease of cleaning, water Wetting properties, sealing effect, chemical resistance, oxidation resistance, physical barrier effect, heat resistance, fire resistance, low shrinkage, UV-blocking effect, smoothing effect, long-lasting effect, antistatic and scratch resistance . The reason why the aforementioned characteristics can be provided to products and articles is that the polysilazane contained in the coating solution is converted into a dense silica coating due to the action of a catalyst. In addition, by forming a silica coating, the surface of a product or article exhibits strong hydrophilicity based on the silica film. The coating solutions of the present invention tend to form hard and dense coatings made of silica when dried at ordinary temperatures. Formation of this silica coating varies depending on the type of polysilazane, catalyst type, etc., but the coating will form over a period of about 1 to 2 weeks. The coating solution of the present invention is in the form of a solution when applied, and thus can be applied very easily to form a coating. This coating is transformed into a dense and hard hydrophilic coating after application, thereby providing the aforementioned properties to various surfaces of products and objects. 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 abrasion resistance, antifouling effect and ease of cleaning after being stained. In addition, the coating solution of the present invention can be used not only as corrosion-resistant paint, scratch-resistant paint, abrasion-resistant paint, anti-fouling paint, or paint excellent in easy-cleaning properties, but can also be used to form a hydrophilic coating, seal Materials, Chemical Resistant Coatings, Antioxidant Coatings, Physical Barrier Coatings, Heat Resistance Imparting Coatings, Fire Resistant Coatings, Antistatic Coatings, Low Shrinkage Coatings, UV-Blocking Coatings, Smoothing Coatings , durable coating, etc. film-forming coating solution.

When the coating solution of the present invention is used to form a hydrophilic and dense silica coating on surfaces such as automobiles, tombstones, house exterior walls, etc., by using inorganic polysilazane, the resulting hydrophilic surface is resistant to rainwater. On contact, to achieve a watery coating state without forming water droplets thereon. In addition, this hydrophilic surface has a higher affinity for water than for hydrophobic substances such as combustion products including dust and the like, thereby allowing these stains to be easily washed off with rainwater. In addition, since the dense surface is formed, the amount of smoke and dust adhering thereto can be reduced. Therefore, there is little fouling visible to the naked eye, and the amount of adhering dirt is reduced. And because it forms a dense coating, it is difficult to be scratched and achieves corrosion resistance.

In the case of dentures, acrylic resin, which is a material of the dentures, absorbs water from which dirt enters the resin or absorbs or adheres to the resin, and these dirts are a source of denture odor. Since the coating solution of the present invention forms a hydrophilic and dense silica coating that adheres well to dentures at a temperature at which acrylic resin as a denture material does not deform or deteriorate, water can be prevented. It is absorbed into the resin, thereby preventing dirt from penetrating into the denture material, and even if dirt adheres to the silica coating, they are easily washed off with water, thus preventing odor emission. In addition, dentures are coated with the coating solution of the present invention so that even if unevenness occurs on the denture in finishing polishing, the silica coating smoothes the unevenness to make it more difficult for dirt to adhere. In addition, the formed silica coating has high surface hardness and high durability, so it will not be abraded by food or when biting, is stable in the living body, and will not be eluted. Even if the silica is released, it is not toxic.

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

For example, heavy solvents such as mineral spirits are suitable for use on substrates whose appearance is considered important where fouling is easily observed (such as darkly painted cars, dentures, polished granite, mirror-finished metal or plated substrates, transparent resins and glass). Mineral terpenes, Pegasol AN45 and Pegasol 3040 from Mobil Sekiyu Corp. are also preferably usable solvents. Substrates whose mottling, interference color, whiteness and sandiness can be easily observed can be perfectly coated with the coating solution by using mineral spirits as a solvent. Mineral spirit has the aforementioned advantages, but it is poor in solubilizing ability, so that in order to make up for the solubilizing ability, in addition to mineral spirits, mixed aromatic solvents (such as Solvesso100 and Solvesso150 of Esso Sekiyu Co. and Solvesso150 and Pegasol R-100 and Pegasol R-150 from Mobil Sekiyu Corp.). In addition, paraffin-type solvents having no aromatic component can also be used as the solvent. Specifically, low-odor solvents, Exxol DSP100/140, Exxol D30, Exxol D40, etc. of Tonen Chemical Co. can be mentioned.

Furthermore, it is also important that products used with water, such as those in toilets, kitchens, washrooms, bathrooms, etc., and dentures, are odorless. By adding a low odor solvent such as methylcyclohexane or ethylcyclohexane as part of the solvent, if necessary, a less odorous coating solution can be provided for such products which are required to be odorless.

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

Examples of compositions of inorganic polysilazanes, catalysts, and diluent solvents in coating solutions intended for use in the respective applications are shown hereinafter. 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 of those.

A. Car body, wheels

The solution should not damage the underlying layer of the coating and should be stable so that it will not be bleached in the cup gun, especially when the solution is applied from the cup gun.

(Example of Compounding Ratio)

Inorganic polysilazane: 0.3 to 2% by weight

DMPP: 0.01 to 0.1% by weight

Xylene: 0.5 to 10% by weight

Pegasol AN45: Balance

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

(Preferred Example 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 AN45: Balance

B. Dentures

This solution should be stable for a long time without whitening and be safe to the human body, have less odor, and not deform or deteriorate the acrylic resin used as a denture material.

(mixing ratio embodiment)

Inorganic polysilazane: 0.5 to 5% by weight

DMPP: 0.02 to 0.2% by weight

Pega sol AN45: margin

(Preferred Example of Compounding Ratio)

Inorganic polysilazane: 1 to 2% by weight

DMPP: 0.04 to 0.08% by weight

Pegasol AN4 5: Balance

C. tombstone

This solution should show less interference color when applied on granite etc. and be stable for a long time so as not to be bleached.

(mixing ratio embodiment)

Inorganic polysilazanes: 0.5 to 4% by weight

DMPP: 0.01 to 0.2% by weight

Xylene: 5 to 50% by weight

Pegasol 3040: Balance

(Preferred Example 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

D. House interior and exterior, bathtub, kitchen, etc.

This solution should be virtually odorless, safe for humans and have high drying properties.

(mixing ratio embodiment)

Inorganic polysilazane: 0.3 to 2% by weight

DMPP: 0.01 to 0.2% by weight

Xylene: 1 to 10% by weight

Pegasol AN45: 5 to 88% by weight

Ethylcyclohexane: 5 to 88% by weight

Methylcyclohexane: 5 to 88% by weight

(Preferred Example 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 AN45: 20 to 50% by weight

Ethylcyclohexane: 20 to 50% by weight

Methylcyclohexane: 20 to 50% by weight

E. Polycarbonate sheet

This solution should not attack the polycarbonate sheet as the substrate.

(mixing ratio embodiment)

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

(Preferred Example of Compounding Ratio)

Inorganic polysilazanes: 0.5 to 4% by weight

DMPP: 0.03 to 0.2% by weight

Xylene: 3 to 10% by weight

Pegasol 3040: Balance

Solvent Pegasol AN45 and Pegasol 3040 (Mobil Sekiyu Corp.), which are fractions obtained by hydrogenation reaction and refining of distilled oil obtained by distilling crude oil under normal pressure, are mainly C8 to C11 petroleum-type hydrocarbons, and their aniline point They are 43°C and 54°C, respectively, and Pegasol AN45 contains a higher content of aromatic components than Pegasol 3040.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention is described in more detail with reference to Preparation Examples and Examples, but the present invention is not limited to the Preparation Examples and Examples described below.

Preparation Example 1 (preparation of inorganic polysilazane)

A gas line, mechanical stirrer and Dewar condenser were fitted into a four-necked flask with an internal volume of 300 ml. The interior of the reactor was replaced with deoxygenated dry nitrogen, and then 150 ml of degassed dry pyridine was introduced into the 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 ₂ Cl ₂ ·2Py). The reaction mixture was cooled on ice with vigorous stirring and bubbled for 1 hour with a mixture of nitrogen and 10.9 g of ammonia (previously purified by passage through a tube of soda lime and activated carbon). After the reaction was complete, the solid product was removed by centrifugation and subsequent filtration. By removing the solvent from the filtrate under reduced pressure (50°C, 5 mmHg, 2 hours), 5.52 g of glassy solid polysilazane was obtained. The molecular weight of the polysilazane measured by the vapor pressure drop method was 2,000. The yield is 77%.

Preparation Example 2 (preparation of organopolysilazane)

A gas introduction tube, a mechanical stirrer and a Dewar condenser were fitted into a four-necked flask with an internal volume of 300 ml. The inside of the reactor was replaced with deoxygenated dry nitrogen, and then 150 ml of degassed dry pyridine was introduced into the 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 sparged with a mixture of nitrogen and 12.0 g of ammonia (previously purified by passing through a tube of soda lime and activated carbon). After the reaction was complete, the solid product was removed by centrifugation and subsequent filtration. By removing the solvent from the filtrate under reduced pressure (50°C, 5 mmHg, 2 hours), 5.2 g of viscous liquid polysilazane was obtained. The molecular weight determined by the vapor pressure drop method was 1600. The yield is 72%.

Example 1

0.5 parts by weight of the inorganic polysilazane obtained in Preparation Example 1 and 0.02 parts 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.), Get anti-corrosion protection for car body and wheels

Dirty coating solution.

The coating solution was sprayed onto the coated steel sheet by using a spray gun in such an amount as to obtain a coating having a thickness of 0.2 microns after conversion to silica. After drying, the coating was tested in an outdoor exposure test to observe the change of contact angle, and the results are shown in Table 1.

Table 1

Days of outdoor exposure (days) 0 7 14 twenty one 28 3 months 6 months 1 year contact angle (degrees) 65 41 twenty three 16 11 10 9 10

As can be seen from Table 1, the silica coating was gradually formed, and after 2 weeks, almost a hydrophilic coating had been formed, whereby the coated steel sheet remained in a stably coated state for a long period of time with the hydrophilic silica coating. The coated panels, observed after 6 months and 1 year respectively, were not considered to be stained.

This coating solution was sealed in a nitrogen atmosphere, stored at a normal temperature, and the generation of monosilane was checked after 1 month, 3 months, and 6 months, and the result was that the amount of monosilane generated 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 the 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 before, but Pegasol AN45 was replaced by Pegasol 3040 (Mobil Sekiyu Corp.) having a lower aromatics content than Pegasol AN45, and this coating solution became cloudy after 20 minutes. From these results, 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 coating solution containing a higher content of aromatic components but not affecting the coating solution from the viewpoint of the stability of the coating solution. Solvents in the range of the underlying layer of the coating.

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 anti-aging compound for dentures. Dirty coating solution.

This coating solution was applied with a spray gun to the entire set of dentures to form a 0.3 micron thick silica coating thereon. The coating was completely converted to silica by drying in an oven at 45°C for 60 minutes and subsequent treatment at 40°C and 90% relative humidity for 12 hours. A hydrophilic and dense silica coating is formed on the surface of the denture, and when the denture is used, the coating is not damaged, dirt can be easily washed off 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 parts 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.), An antifouling coating solution for tombstones was obtained.

The coating solution was applied to polished granite by aerosol spraying. A uniform coating of 0.4 micron thickness was thereby formed. After 2 weeks, a hydrophilic and dense silica coating was formed on the surface, and when left outdoors for a year, the coating was not damaged and no scaling was observed.

Example 4

0.5 parts by weight of the inorganic polysilazane obtained in Preparation Example 1 and 0.02 parts by weight of DMPP (catalyst) were dissolved in a mixture 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 B In a solvent consisting of methylcycloethane and 32.5 parts by weight of methylcycloethane, an antifouling coating solution for coating products used with water (such as bathtubs, washstands, etc.) was obtained. This coating solution was applied to the surfaces of washstands and enamel bathtubs made of ceramic ware. A uniform coating of 0.2 microns was formed, respectively. Dirt hardly adheres, and if adhered, the dirt can be easily removed.

Example 5

1 part by weight of the inorganic polysilazane obtained in Preparation Example 1 and 0.04 parts by weight of DMPP (catalyst) were dissolved in a mixture 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 In a solvent composed of cyclohexane and 31.7 parts by weight of methylcycloethane, an antifouling coating solution for interior and exterior of houses was obtained. This coating solution was applied to the surface of the house exterior wall by roller coating. This facade has not been stained 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 parts 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.), An antifouling coating solution for polycarbonate panels was obtained. Using a cloth soaked with this coating solution, the coating solution was applied to the polycarbonate panels by hand. A hydrophilic and dense silica coating can be formed on the surface, and the coating solution will not corrode the substrate.

Example 7

5 parts by weight of the inorganic polysilazane obtained in Preparation Example 1 and 0.035 parts by weight of palladium propionate (catalyst) were dissolved in a solvent consisting of 25 parts by weight of xylene and 69.97 parts by weight of Solvesso 150 (Esso Sekiyu Co.) , to obtain a coating solution. Aluminum panels were coated with this coating solution by flow coating in such an amount that a coating thickness of 0.3 μm was obtained after conversion to silicon dioxide. After drying, the aluminum plate was calcined in air at 120° C. for 1 hour to obtain a sample for corrosion resistance test. Separately, by flow coating, a PET film was coated with this coating solution in such an amount that a coating thickness of 0.3 μm was obtained after conversion to silica. After drying, the aluminum plate and the PET film were treated at 90° C. 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 results obtained are shown in Table 2 for corrosion resistance, and in Table 3 for scratch resistance.

Evaluation of Coating Properties

(1) Corrosion resistance

Coatings were formed on aluminum panels and the substrates were examined for 96 hours of corrosion in the CASS test (in which the test specimens were sprayed with a solution prepared by adding acetic acid and copper(II) chloride to aqueous sodium chloride).

◎: Excellent corrosion resistance

○: Excellent corrosion resistance

△: Corrosion resistance is slightly inferior

×: Poor corrosion resistance

CASS test method

Corrosion and corrosion resistance were evaluated by spraying the coupons with a mixture of 4% brine and 0.027% copper chloride (dihydrate) in a test bath set at 50°C.

The term CASS is an acronym for "Copper Accelerated Acetate Spray".

(2) Anti-scratch performance

Form a coating on polyethylene terephthalate (PET film), then use steel wool #000 to test it reciprocating 300 times under a load of 500 grams (area: 2 square centimeters), and measure its haze with a haze meter .

Example 8

0.2 parts by weight of the inorganic polysilazane obtained in Preparation Example 1 and 0.002 parts 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 Solvesso 150 (Esso Sekiyu Co.) , to obtain a coating solution. Aluminum panels were coated with this coating solution by flow coating in such an amount that a coating thickness of 0.03 μm was obtained after conversion to silicon dioxide. After drying, the aluminum plate was calcined in air at 120° C. for 1 hour to obtain a sample for corrosion resistance test. Separately, by flow coating, a PET film was coated with this coating solution in such an amount that a coating thickness of 0.03 μm was obtained after conversion to silica. After drying, the PET film was treated at 90° C. 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 results obtained are shown in Table 2 for corrosion resistance, and in Table 3 for scratch resistance.

Example 9

20 parts by weight of the inorganic polysilazane obtained in Preparation Example 1 and 0.14 parts 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 Solvesso 150 (Esso Sekiyu Co.) , to obtain a coating solution. Aluminum panels were coated with this coating solution by flow coating in such an amount that a coating thickness of 1.2 μm was obtained after conversion to silicon dioxide. After drying, the aluminum plate was calcined in air at 120° C. for 1 hour to obtain a sample for corrosion resistance test. Separately, by flow coating, a PET film was coated with this coating solution in such an amount that a coating thickness of 1.2 μm was obtained after conversion to silica. After drying, the PET film was treated at 90° C. and 90% RH for 3 hours to obtain a sample for a scratch test. The coating was evaluated in the same manner as in Example 7, and the results obtained for corrosion resistance are shown in Table 2, and the results for scratch resistance are shown in Table 3.

Example 10

5 parts by weight of the organopolysilazane obtained in Production Example 2 and 0.035 parts 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. Aluminum panels were coated with this coating solution by flow coating in such an amount that a coating thickness of 0.3 μm was obtained after conversion to silicon dioxide. After drying, the aluminum plate was calcined in air at 120° C. for 1 hour to obtain a sample for corrosion resistance test. Separately, by flow coating, a PET film was coated with this coating solution in such an amount that a coating thickness of 0.3 μm was obtained after conversion to silica. After drying, the PET film was treated at 90° C. and 90% RH for 3 hours to obtain a sample for a scratch test. The coating was evaluated in the same manner as in Example 7, and the results obtained for corrosion resistance are shown in Table 2, and the results for scratch resistance are shown in Table 3.

Example 11

20 parts by weight of the organopolysilazane obtained in Production Example 2 and 0.14 parts 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. Aluminum panels were coated with this coating solution by flow coating in such an amount that a coating thickness of 1.2 μm was obtained after conversion to silicon dioxide. After drying, the aluminum plate was calcined in air at 120° C. for 1 hour to obtain a sample for corrosion resistance test. Separately, by flow coating, a PET film was coated with this coating solution in such an amount that a coating thickness of 1.2 μm was obtained after conversion to silica. After drying, the PET film was treated at 90° C. and 90% RH for 3 hours to obtain a sample for a scratch test. The coating was evaluated in the same manner as in Example 7, and the results obtained for corrosion resistance are shown in Table 2, and the results for scratch resistance are shown in Table 3.

Example 12

5 parts by weight of the inorganic polysilazane obtained in Preparation Example 1 and 0.2 parts 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.), A coating solution was obtained. Aluminum panels were coated with this coating solution by flow coating in such an amount that a coating thickness of 0.3 μm was obtained after conversion to silicon dioxide. After drying, the aluminum plate was calcined in air at 120° C. for 1 hour to obtain a sample for corrosion resistance test. Separately, by flow coating, a PET film was coated with this coating solution in such an amount that a coating thickness of 0.3 μm was obtained after conversion to silica. After drying, the PET film was treated at 90° C. and 90% RH for 3 hours to obtain a sample for a scratch test. The coating was evaluated in the same manner as in Example 7, and the results obtained for corrosion resistance are shown in Table 2, and the results for scratch resistance are shown in Table 3.

Example 13

15 parts by weight of the inorganic polysilazane obtained in Preparation Example 1 and 0.6 parts 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.), A coating solution was obtained. Aluminum panels were coated with this coating solution by flow coating in such an amount that a coating thickness of 1.0 μm was obtained after conversion to silica. After drying, the aluminum plate was calcined in air at 120° C. for 1 hour to obtain a sample for corrosion resistance test. Separately, by flow coating, a PET film was coated with this coating solution in such an amount that a coating thickness of 1.0 μm was obtained after conversion to silica. After drying, the PET film was treated at 90° C. and 90% RH for 3 hours to obtain a sample for a scratch test. The characteristics of the coating were evaluated in the same manner as in Example 7, and the results obtained for corrosion resistance are shown in Table 2, and the results for scratch resistance are shown in Table 3.

Table 2: Corrosion resistance test results

Example 7 8 9 10 11 12 13 Aluminum plate evaluation result ○ △ ◎ ○ ◎ ○ ◎ x

Table 3: Scratch test results

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

Effect of the present invention

As described above, the coating solution of the present invention is in liquid form at the time of application, so the coating solution can be easily applied to a substrate by spraying, a method of smearing with a cloth or a sponge, or the like. After application, polysilazane in liquid form can be converted into a hard and dense coating, whereby a coating film excellent in corrosion resistance and scratch resistance can be easily formed. In addition, the hydrophilicity of the coating film thus formed is long-lasting and its effective hydrophilicity can generally be maintained for 1 to 2 years. In addition to hydrophilicity, coatings can provide products or articles 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 properties. In addition, this coating solution can be applied to a very wide range of uses by merely adjusting the type of solvent, the amount of compounded materials, and the like.

Claims (13)

1. coating solution, it comprises polysilazane, diluting solvent and the catalyzer with Si-H key, and wherein catalyzer is N-heterogeneous ring compound, organic or inorganic acid, metal carboxylate, acetyl acetone complex, metallic fine particle, superoxide, metal chloride or organometallic compound.

2. the coating solution of claim 1, the mixture that wherein uses petroleum solvent, aromatics or alicyclic solvents, ether, halon or terpene blend or these solvents is as diluting solvent.

3. the coating solution of claim 2 wherein uses paraffinic hydrocarbons type solvent, mineral turpentine, terpene blend or ether or its mixture as diluting solvent.

4. the coating solution of claim 3 wherein uses dibutyl ether, dme, diethyl ether, polyglycol ether or tetrahydrofuran (THF) or their mixture as diluting solvent.

5. each coating solution in the claim 2 to 4, wherein diluting solvent comprises one or more solvents that are selected from dimethylbenzene, methylcyclohexane and the ethylcyclohexane in addition.

6. each coating solution in the claim 1 to 4, the concentration that wherein has the polysilazane of Si-H key is 0.1 to 35 weight %.

7. each coating solution in the claim 1 to 4, the concentration that wherein has the polysilazane of Si-H key is 0.5 to 10 weight %.

8. each coating solution in the claim 1 to 4, wherein catalyst content is 0.01 to 30 weight %, is benchmark in the pure polysilazane content with Si-H key.

9. each coating solution in the claim 1 to 4, the polysilazane that wherein has the Si-H key is by making SiH ₂Cl ₂Form SiH with alkali reaction ₂Cl ₂Adducts makes SiH then ₂Cl ₂Adducts and ammonia react and the synthetic inorganic polysilazane that obtains.

10. each coating solution in the claim 1 to 4, the polysilazane that wherein has the Si-H key is by making SiH ₂Cl ₂And CH ₃SiHCl ₂Form SiH with alkali reaction ₂Cl ₂And CH ₃SiHCl ₂Adducts, and make SiH then ₂Cl ₂And CH ₃SiHCl ₂Adducts and ammonia react and the synthetic polysilazane that obtains.

11. the purposes according to each coating solution in the claim 1 to 10 is used for coated substrate surface and draws a property with erosion resistance, wear resistance, didirtresistance, easy to clean, wettability, sealing effectiveness, chemical-resistant, oxidation-resistance, physical barrier effect, thermotolerance, resistivity against fire, low-shrinkage, UV-blocking effect, smooth effect, lasting effect, static resistance and anti-wiping of the substrate surface of enhancing product or article.

12. the purposes of claim 11, wherein coating solution combines with priming paint and is administered to substrate surface.

13. the purposes of claim 11 or 12, wherein before using coating solution, the surface has been used jaqan, varnish or paint application.