JPH09272859A - Production of composition for water-repellent and antistatic coating film and production of base material bearing the coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of giving coating film of excellent water repellency and antistaticity, and useful for precision equipment and optical equipment, etc., in the information/electronics industry, comprising a specific compound, fatty acid compound, catalyst, hydrosilicofluoric acid compound and hydrous organic solvent. SOLUTION: This composition comprises (A) an inorganic alkoxide A1 such as a compound of the formula M(OR)n (X)a-n [M is Si, Al, Ti, Zr, Ca, Fe, V, Sn, Li, Y, Be, B or P; R is an alkyl; X is a (functional group-bearing) hydrocarbon group or halogen; (a) is the valence of M; (n) is (0-a)] or a polymer produced by hydrolysis and polymondensation of the compound A1 , (B) a fatty acid compound such as oleic acid (salt), (C) a catalyst such as N,N- dimethylbenzylamine, (D) a hydrosilicofluoric acid compound, and (E) a hydrous organic solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is used in the field of precision equipment, optical equipment, etc.
A method for producing a water-repellent / antistatic coating composition and a coated substrate capable of forming a film having antistatic properties as well as high water repellency / insolubility and high surface hardness by coating glass or other various materials Regarding

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Originally,
As for the antistatic property, most of the charged charges are leaked quickly by making the surface of the base material conductive, and in addition, the generated charges may be reduced as much as possible by the surface contact.
Particularly important charge leakage methods are: Method of applying antistatic agent to the surface of substrate (surface application method) 1. There are methods such as kneading an antistatic agent into a polymer material and transferring a part of it to the surface (internal kneading method). In both cases, the surface is covered with a thin layer of antistatic agent to conduct electricity. I have sex. Most of the antistatic agents are surfactants, and metal thin films are also used.

Various attempts have hitherto been made as a surface coating method. When a surfactant solution is used as an antistatic agent, the lipophilic portion of the surfactant is applied to the surface of a base material (for example, a polymer material). Are adsorbed and the hydrophilic polar parts are arranged toward the outside (in the room air), the conductive layer is formed by the adsorption of moisture in the air and the polarization of the surfactant and the polarization effect of moisture, and the antistatic effect is obtained. Occurs.

In this case, the surfactant and the like easily fall off from the surface and are scattered from the surface or migrate to the inside of the film layer to reduce the effect.

Despite the ease of processing, the surface coating method of the base material has a limit in its durability. Therefore, by the internal kneading method, the structure or ionic polymer obtained by polymerizing the polymeric surfactant into a monomer containing a quaternary ammonium salt such as acrylic acid or methacrylic acid or a tertiary amine, or containing an ionic polymer in the vehicle, A material containing inorganic conductive fine particles is used as a conductive paint.

Further, as a method of utilizing an inorganic polymer,
A thin film having polysiloxane as a main chain is formed to make it electrically conductive by interaction with adsorbed water as a hygroscopic surface, or an antistatic coating film is formed by combining polysiloxane and a surfactant. These have both advantages and disadvantages, but even if the water-absorbent coating film essentially becomes an antistatic coating film, the surfactant is washed away by water and the conductive layer disappears, and contaminants in the air are absorbed by water. There is a great obstacle because it is absorbed inside.

Regarding water repellency, wax, oil, silicone resin, metallic soap, etc. have been used as the base of the water repellent at present.
There is a problem with weather resistance, and there is no satisfactory water-repellent coating.

[0008] For example, during exposure to the external environment, there is little resistance to adhered contaminants such as dust and iron powder, and the durability of the water repellent effect is impaired by acid rain and sunlight.

The contact angle of water is often used as a measurement standard for water repellency. PTF developed by US DUPONT
E (Teflon) is a polymer having the chemical formula: —CF ₂ —CF ₂ — and has a low surface energy and water repellency is known as a contact angle of water of 110 °.

Further, in a recent research, graphite fluoride was discovered and shows strong water repellency (contact angle of 80 °) and excellent lubricity. Smaller than surface energy −
CH ₃ is 3. -CF ₃ is 1.9 for l × 10 ^-4 N / cm
It is said to show × 10 ^-4 N / cm and is considered to be the smallest among the substances,
If the polarizability is small, the water repellency is large.

Since both PTFE and graphite fluoride have an organic polymer material as a matrix, they are susceptible to heat and abrasion, and metal plating incorporating fluoride particles for complexing with a metal has been considered. However, this method also produces a so-called anodic effect in the electrolytic solution for the metal complex having a high fluorine concentration,
The electrolysis is stopped and fluoride precipitates, which is far from practical use.

Metal soap is water repellent with calcium stearate at 110 ° and aluminum stearate.
It has a contact angle of 120 ° and 135 ° with zinc stearate, which is the largest among general organic substances. However, most metal soaps are fine powders, and in order to form a molecular film,
After adhering these fine powders to the surface of the substrate, it is heated to a temperature above its melting point to form a water-repellent film. However, it is weak against heat and abrasion.

In general, water repellency and antistatic property are in conflict with each other. Most conventional antistatic agents are hydrophilic, and water repellent or hydrophobic polymers have problems in antistatic property. is there.

Therefore, an object of the present invention is to provide a coating composition excellent in both water repellency and antistatic property.

Another object of the present invention is to provide a method for producing a coated substrate excellent in both water repellency and antistatic property.

[Means for Solving the Problems]

As a result of earnest research in view of the above-mentioned object, the present inventors have found that a tertiary polymer of a polymer obtained by reacting an inorganic alkoxide with a fatty acid in an organic solvent to produce a metallic soap, hydrolyzing the inorganic alkoxide and then polycondensing the same. By providing a coating composition in which the above-mentioned metal soap is cross-linked to the original skeleton, the water repellency unique to metal soap (contact angle with water: 120 °)
A film having water repellency and antistatic property which is insoluble and has high surface hardness when an antistatic molecule is formed due to the surface activity of polar soap and nonpolar property unique to metal soap as well as retaining the surface of It was discovered that, when the coating composition was applied and heat-treated at a predetermined temperature after coating, a coated substrate having water repellency and antistatic property was obtained.

That is, the water-repellent / antistatic coating composition of the present invention comprises (A) (a) an inorganic alkoxide and / or (b) a polymer obtained by hydrolyzing and polycondensing the (a) inorganic alkoxide. , (B) a fatty acid, (C) a catalyst, (D) a hydrosilicofluoric acid, and (E) a water-containing organic solvent.

Further, a method for producing a coated substrate having a water repellent / antistatic film includes a step of applying a film formed of the above-mentioned coating composition on at least one surface of the substrate, and 80
The method is characterized by including a step of forming a water repellent / antistatic coating by heat treatment at a temperature of not less than ° C.

The present invention will be described in detail below. [1] Component of composition (A) (a) Inorganic alkoxide and / or (b) OH group-containing polymer (a) Inorganic alkoxide (1) General formula The inorganic alkoxide used in the present invention is represented by the following formula (I): M (OR) _n (X) _an (I) (where M is Si, Al, Ti, Zr, Ca, Fe,
An inorganic atom selected from the group consisting of V, Sn, Li, Be, Y, B and P, R is an alkyl group, and X is
Is a hydrocarbon group, a hydrocarbon group having a functional group or halogen, a is a valence of M, and n is an integer from 0 to a. At least one compound represented by the formula (1) is preferable.

(2) In the case of n = a Among the compounds of the above formula (I), generally used is n = a, that is, a compound in which only an alkoxide group is bonded to M.

(I) Alkoxysilane When the above M is Si, the above a is 4. Such an alkoxide is represented by Si (OR ¹ ) ₄ . Here, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms (hereinafter referred to as a lower alkyl group). Such alkoxysilanes include Si (OCH ₃ ) ₄ and Si (OC
₂ H ₅ ) _{4 and the} like.

(Ii) Aluminum alkoxide When the above M is Al, the above a is 3. Such an alkoxide is represented by Al (OR ² ) ₃ . Here, R ² is preferably a lower alkyl group. Such aluminum alkoxides include Al (OC
_{H 3) 3, Al (OC} 2 H 5) 3, Al (O-n-C 3
_{H 7) 3, Al (O} -i-C 3 H 7) 3, Al (OC 4
H ₉ ) _{3 and the} like. The aluminum alkoxide is usually used as a mixture with the alkoxysilane, and by using the aluminum alkoxide, the surface hardness and heat resistance of the obtained coating film are improved.

The amount of aluminum alkoxide used is preferably 40 parts by weight or less, more preferably about 30 parts by weight, based on 100 parts by weight of the above-mentioned alkoxysilane. If it exceeds 40 parts by weight, the polymer formed tends to gel, and the resulting coating may crack.

(Iii) Titanium alkoxide When M is Ti, a is 4. Such an alkoxide is represented by Ti (OR ³ ) ₄ . Here, R ³ is preferably a lower alkyl group. As such a titanium alkoxide, Ti (OC
_{H 3) 4, Ti (OC} 2 H 5) 4, Ti (OC 3 H 7)
_{4, Ti (OC 4 H 9} ) 4, Ti (O-i-C 3 H 7)
_{4 and the} like.

(Iv) Zirconium alkoxide When the above M is Zr, the above a is 4. Such an alkoxide is represented by Zr (OR ⁴ ) ₄ . Here, R ⁴ is preferably a lower alkyl group. As such a zirconium alkoxide, Zr (OCH ₃ )
_{4, Zr (OC 2 H 5} ) 4, Zr (O-i-C 3 H 7)
_{4, Zr (O-t-} C 4 H 9) 4, Zr (O-n-C 4
H ₉ ) _{4 and the} like.

(V) Other alkoxides Examples of alkoxides other than the above include, for example, Ca (OC
₂ H ₅ ) ₂ , Fe (OC ₂ H ₅ ) ₃ , V (O-i-C _{4
H 9) 3, Sn (O} -i-C 4 H 9) 4, Li (OC 2
_{H 5), Be (OC 2} H 5) 2, B (OC 2 H 5) 3,
Y (OCH ₃ ) ₃ , Y (OC ₂ H ₅ ) ₃ , P (OC
_{H 3) 3, P (OC} 2 H 5) 3 and the like.

(3) In the case of n ≦ a−1 Among the inorganic alkoxides represented by the formula (I), in the case of n ≦ a-1, that is, a compound in which a group X other than an alkoxy group is bonded to M is: For example, there are compounds in which X is a halogen such as Cl and Br. A compound in which X is a halogen is hydrolyzed to generate an OH group in the same manner as an alkoxy group as described later, and a polycondensation reaction occurs. X may also be a hydrocarbon group or a hydrocarbon group having a functional group, and the hydrocarbon group usually has 1 to 15 carbon atoms. Such groups remain as organic moieties in the polymer resulting from the polycondensation reaction after hydrolysis. As the functional group, a carboxyl group,
Carbonyl group, amino group, vinyl group, epoxy group and the like are preferable. Such groups are suitable for increasing the insolubility of the coating.

Examples of the compound of the formula (I) having X include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoquinsilane, γ-glycidoxypropyltrimethoxysilane and γ-. Aminopropyl methoxysilane etc. are mentioned.

(B) OH Group-Containing Polymer Instead of the above-mentioned inorganic alkoxide, or at the same time, a polymer having an OH group in which the inorganic alkoxide is previously hydrolyzed and polycondensed can be used. This polymer is produced by hydrolysis and polycondensation of an inorganic alkoxide in the presence of an acid and a base catalyst as described later. This polymer is an oligomer having a relatively low molecular weight, and for example, a molecular weight of 700 to 900 is preferable. The hydrolysis and polycondensation reaction of the inorganic alcoside is generally carried out at a temperature of 25 ° C for 2 hours.

(B) Fatty Acids The fatty acids used in the present invention include fatty acids and salts thereof, and the fatty acids include saturated fatty acids and unsaturated fatty acids.

(1) Saturated Fatty Acids The saturated fatty acids used in the present invention include capric acid,
Examples include lauric acid, myristic acid, palmitic acid, and stearic acid, with stearic acid being particularly preferred. As the salt of the saturated fatty acid, metal soap produced by combining with the inorganic alkoxide is preferable. This metal soap is
It mainly contributes to the water repellency of the coating film of the present invention.

The amount of saturated fatty acid used is 10 for the inorganic alkoxide.
It is preferably 8 to 13 parts by weight with respect to 0 parts by weight. When it is less than 8 parts by weight, the water repellency of the coating becomes poor, and when it exceeds 13 parts by weight, the surface hardness decreases.

As the saturated fatty acid used in the present invention, for example, stearic acid is combined with aluminum in an organic solvent of aluminum isopropoxide to form aluminum stearate disorpate. Aluminum stearate disoap has high water repellency and a contact angle with water of 12
The surface repellency of the film obtained by this is remarkably improved and the polarity of the metallic soap is
Due to the non-polar surface activity, it exhibits antistatic performance. The amount of stearic acid used is preferably 20 to 70 parts by weight with respect to 100 parts by weight of aluminum isopropoxide,
More preferably 45 parts by weight. When it is less than 20 parts by weight, the water repellency of the coating becomes poor, and when it exceeds 70 parts by weight, the surface hardness decreases.

(2) Unsaturated Fatty Acids Examples of the unsaturated fatty acids used in the present invention include oleic acid, linoleic acid and linolenic acid, with oleic acid being particularly preferred. As the salts of unsaturated fatty acids, metal soap formed by combining with the above-mentioned inorganic alkoxide is preferable. Since this metallic soap has excellent conductivity, it mainly contributes to the antistatic property of the coating film of the coating composition of the present invention.

The amount of unsaturated fatty acid used is an inorganic alkoxide
4 to 10 parts by weight is preferable with respect to 100 parts by weight. When it is less than 4 parts by weight, the conductivity is lost, and when it exceeds 10 parts by weight, the surface hardness is lowered.

As the unsaturated fatty acid used in the present invention,
For example, oleic acid reacts with calcium ethoxide in organic solvents to produce calcium oleate. Calcium oleate is originally an ionic bond and exhibits an antistatic function by performing ionic conduction, but its water repellency is second only to aluminum stearate. The coating film thus obtained is ionic-bonding, so that it has conductivity, has good antistatic properties, conductivity (surface resistance of 10 ⁴ Ω), and water-repellent property of having a water contact angle of 180 °. The amount of oleic acid used is 30 to 60 parts by weight based on 100 parts by weight of calcium ethoxide. It is preferably 50 parts by weight. When it is less than 30 parts by weight, the conductivity is lost, and when it is 60 parts by weight or more, the surface hardness is lowered.

(C) Catalyst The catalyst used in the present invention includes an acid catalyst and a base catalyst.

(1) Acid catalyst The acid catalyst is used for the hydrolysis reaction of the inorganic alkoxide. Therefore, when a polymer having an OH group in which the inorganic alkoxide is hydrolyzed to some extent and polycondensed in advance is used, the acid catalyst is unnecessary.

Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, anhydrides of mineral acids such as hydrogen chloride gas, tartaric acid, phthalic acid, maleic acid, dodecylsuccinic acid, hexahydrophthalic acid and methyl nadic acid. , Pyromellitic acid, benzophenonetetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, phthalic anhydride, maleic anhydride, dodecylsuccinic anhydride, hexahydrophthalic anhydride, methylnadic acid anhydride, pyromellitic anhydride, benzophenone anhydride Examples thereof include organic acids such as tetracarboxylic acid, dichlorosuccinic anhydride, and chlorendic anhydride, and anhydrides thereof.

The above-mentioned acid catalyst is used in an amount of inorganic alkoxide.
0.01 to 0.5 parts by weight per 100 parts by weight is preferred, 0.01
Particularly preferred is 5 to 0.3 parts by weight. If the amount is less than 0.01 part by weight, the hydrolysis may be insufficient, and if it exceeds 0.5 part by weight, the polycondensation reaction may proceed to increase the viscosity.

(2) Base catalyst The base catalyst is mainly used as a catalyst for the polycondensation reaction of the above-mentioned inorganic alkoxide hydrolyzate, and as a catalyst for its rapid crosslinking reaction and three-dimensional network structure formation. As a result, the metal portion of the metallic soap produced from the inorganic alkoxide and the fatty acid crosslinks into the three-dimensional network structure and is included in the three-dimensional network structure.

As the base catalyst, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is preferable. Preferred base catalysts include N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like, with N, N-dimethylbenzylamine being particularly preferred.

The amount of the base catalyst used is preferably 0.01 to 1 part by weight, and 0.05 to 100 parts by weight of the coating composition of the present invention.
Part by weight is particularly preferred. If the amount is less than 0.01 parts by weight, the polycondensation reaction proceeds slowly, and if the amount exceeds 1 part by weight, the polycondensation reaction proceeds rapidly, which makes it difficult to dissolve in the organic solvent described later and the resulting coating film becomes non-uniform. It may decrease.

(D) Hydrosilicofluoric acid Examples of the hydrosilicofluoric acid used in the present invention include hydrosilicofluoric acid and salts thereof. As the salts of hydrosilicofluoric acid, metal fluoride salts formed by combining with the above-mentioned inorganic alkoxide are preferable. Further, hydrosilicofluoric acid preferably deposits high-density SiO ₂ in the presence of the mineral acid as the acid catalyst, the saturated and unsaturated fatty acids, and the SiO ₂ and the metal fluoride salt of the present invention Contributes to the water repellency and antistatic property of the coating composition.

The amount of hydrosilicofluoric acid used is preferably 0.1 to 3 parts by weight in 100 parts by weight of the coating composition of the present invention.

(E) Water-Containing Organic Solvent Examples of the organic solvent used in the present invention include water-miscible solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol. This organic solvent is used with water. The amount of the organic solvent used is 100 parts by weight in total of (A) to (D).
100 to 5000 parts by weight are preferred and about 3000 parts by weight are particularly preferred. The amount of water used is preferably 3 to 5 parts by weight with respect to 100 parts by weight of the organic solvent.

(F) Other Components The coating composition of the present invention may further contain at least one polyacrylic acid. Examples of the polyacrylic acids include polyacrylic acid, polymethacrylic acid and salts thereof. The amount of the polyacrylic acid used is 0.3 to 1 with respect to 100 parts by weight of the above (A) to (E).
Parts by weight are preferred.

[2] Coated Substrate [A] Substrate The substrate used in the present invention is preferably glass, plastic, metal or the like.

[B] Method for producing coating film (1) Application of coating composition The respective components of the above water-repellent / antistatic coating composition are mixed to obtain a transparent coating liquid. This coating liquid is applied to at least one surface of the above base material. The coating method is not particularly limited,
Spray coating, dip coating, brush coating, roll coater coating and the like can be used.

(2) Heating / drying The above coated substrate is heated to a temperature of 80 ° C. or higher, preferably 80 ° C.
The water repellent / antistatic coating of the present invention can be obtained by heating and drying in the range of up to 150 ° C. If necessary, the heating / drying treatment may be carried out after the coating liquid has been applied several times.

[C] Characteristics of Coating The thickness of the coating obtained above is preferably 0.05 to 1.0 μm, and particularly preferably 0.08 to 0.1 μm. The film thickness of the coating film can be appropriately adjusted by coating the coating liquid thickly or by coating the coating liquid several times.

The coating film thus obtained imparts water repellency and antistatic property to the surface of the substrate. The formed film is insoluble in water and organic solvents, and has high surface hardness,
Has abrasion resistance and weather resistance.

[0053]

In the water-repellent / antistatic coating composition of the present invention, the inorganic alkoxide is hydrolyzed by the action of the acid catalyst in the organic solvent solution, and mainly the alkoxy group is changed to the OH group to start the polycondensation action. To do. The action of the base catalyst added thereto causes deprotonation of the OH group, and as a result, the hydrolyzate advances polycondensation to form an inorganic alkoxide three-dimensional network structure. On the other hand, a salt of a fatty acid, preferably a metal soap as a reaction product with an inorganic alkoxide and a fatty acid, is crosslinked into the inorganic alkoxide three-dimensional network structure, and is excellent in water repellency and antistatic coating composition of the present invention. The thing is obtained.

Specifically, aluminum isopropoxide as an inorganic alkoxide and a fatty acid such as stearic acid are reacted in an organic solvent solution to produce metal soap such as aluminum stearate trisoap, and aluminum stearate trisoapate. Is easily hydrolyzed by moisture in the air to form aluminum stearate aluminum aluminum disorp and fatty acid. The same applies to the case of reacting oleic acid with calcium ethoxide to form calcium oleate, if necessary.

An inorganic alkoxide in which X is a hydrocarbon group having an epoxy group in the chemical formula (I) is added to an organic solvent solution containing the above-mentioned aluminum isopropoxide, aluminum stearate disoap, and optionally calcium oleate. And hydrolyze with a mineral acid in an organic solvent solution. Then add a base catalyst to this solution,
O generated from an alkoxide group by ring-opening and polycondensation reaction and hydrolysis with respect to the epoxy group in the presence of a base catalyst.
For the H group, polycondensation reaction is initiated, and aluminum stearate disoap and calcium oleate are sol-
By cross-linking the inorganic alkoxide three-dimensional network structure by the gel method, and at the same time mixing and stirring hydrofluoric acid, a coating liquid having good transparency and adhesion is obtained. The surface hardness of the coating film formed by this coating solution is 4H to 5H, and a transparent film having insolubility and good adhesion can be obtained.

As the antistatic coating, a metal soap such as calcium oleate having a large ionic bond or aluminum stearate disoap having a large dipole moment is partially cross-linked to the inorganic alkoxide three-dimensional network structure obtained by the sol-gel method. However, through the surface micropores in the porous part of the three-dimensional network structure, it becomes a surface activity consisting of polar-non-polarity peculiar to metal soap, forming an antistatic molecule, and drying shrinkage of the inorganic alkoxide three-dimensional network structure part. Accordingly, the antistatic molecule migrates from the inside of the hole to the back surface, and the minimum antistatic effect of the monomolecular film appears.

Originally, it has been clarified that metallic soap has an ionic bond between fatty acid and metal and has a considerable conductivity even in an organic solvent. In particular, in the case of calcium oleate, charge transfer occurs due to ionic conduction. Aluminum stearate disoap has a large dipole moment, its solubility is improved in the presence of alcohol and amine, its molecular structure becomes chain or network, and the mechanism of charge transfer is combined with the presence of calcium oleate. Make up.
If necessary, an In or Sn acetylacetonate solution may be prepared and used by mixing with the above coating solution.

This antistatic coating has a surface resistance of 10 ⁴ to 10 ^4.
It is as low as ^7, and the antistatic effect is excellent. It can be used for electronic parts.

The water-repellent coating was formed from aluminum isopropoxide and stearic acid in a solution of aluminum isopropoxide and an inorganic alkoxide in which X in formula (I) is a hydrocarbon group having an epoxy group. Presence of aluminum stearate disorpate, calcium oleate formed by optionally reacting calcium ethoxide and oleic acid, and aluminum fluoride formed by hydrosilicofluoric acid and aluminum isopropoxide As a result, the water repellency is large and the contact angle with water is almost 120 °.

Originally, CH ₃ having a small surface energy is regularly arranged in the metallic soap, so that the surface cohesive energy is very small as a whole and has a good slip property. Its cohesive energy is considered to be the second lowest after CF ₃ .

Since the water repellency, the lubricant property and the antistatic property operate in parallel, contaminants in the air (cigarette smoke, various oxides, dusts, etc.) are not adsorbed on the surface of the base material, and rainwater is not absorbed. , Moisture and the like drop off without adhering to the surface of the substrate due to self-surface tension and gravity difference.

[0062]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

Example 1 1. Preparation and coating of coating composition A coating composition of the present invention was prepared by the following procedure using each component (unit:% by weight) shown in Table 1 and applied.

Aluminum isopropoxide hydrolyzed liquid (aluminum isopropoxide was added to the mineral acid catalyst (HCl 3
5%), and the reaction is carried out only with the water content of the mineral acid catalyst, and the water content is converted to isopropanol, which has an Al ₂ O ₃ content of 4%) (A-2) Stearic acid (B) was added to the mixed solution with ethanol (E-1), and the mixture was heated with stirring at 80 ° C for 20 minutes.

After aluminum stearate disoap was formed in the above solution, it was allowed to stand at room temperature (25 ° C.) for 40 to 60 minutes. To this, γ-glycidoxypropylmethoxysilane (trade name “SH6040”, manufactured by Toray Dow Corning) (A-
When 1) was added, the methoxy group of γ-glycidoxypropylmethoxysilane started to hydrolyze due to the action of the mineral acid in the solution. Furthermore, hydrosilicofluoric acid aqueous solution (40%)
(D) and ethanol (E-1), n-butanol (E-2),
N, N-Dimethylbenzylamine (C) was added and stirred for 10 minutes to prepare a coating solution as the coating composition of the present invention. In the coating solution, SiO ₂ was precipitated and a metal fluoride salt was formed, and the epoxy group of SH6040 was ring-opening polymerized. Apply this transparent coating solution to one side of the glass plate,
It was heated and dried at 0 ° C for 10 minutes.

2. Evaluation As a result of measuring the above coated glass plate by a droplet method using an automatic contact angle measuring system (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle is
It was 110 °. Moreover, after rubbing with paper or cloth, the distance and the amount of suction of carbon black were examined using carbon black. As a result, there was almost no suction or adhesion. Further, the electric resistance value of the coated glass plate was 10 ⁷ Ω or less.

Table 1 Ingredients Used (A-1) SH6040 29.54 (A-2) Aluminum Isopropoxide Hydrolyzed Solution 28.14 (B) Stearic Acid 1.91 (C) N, N-Dimethylbenzylamine 0.01 (D) Silica Fluoride Aqueous hydrogen acid solution 0.62 (E-1) Ethanol 27.82 (E-2) n-Butanol 11.96 Total 100.00

Example 2 As in Example 1, stearic acid (B-1) was added to a mixed solution of aluminum isopropoxide hydrolyzed solution (A-2) and ethanol (E-1), and aluminum stearate diester was added. Soap was produced to prepare a mixed solution of aluminum stearate disoap and aluminum isopropoxide hydrolysis solution. Separately, a mixed solution of calcium ethoxide hydrolyzed solution (A-3), oleic acid (B-2) and ethanol (E-1) was prepared and heated and stirred at 80 ° C for 10 minutes. This is mixed with the aluminum stearate disoap and aluminum isopropoxide hydrolyzed liquid mixed solution, stirred for 10 minutes, and SH
6040 (A-1), hydrosilicofluoric acid aqueous solution (40%) (D), ethanol (E-1), n-butanol (E-2), N, N-dimethylbenzylamine (C) were added, and 10 The coating liquid was prepared by stirring for 1 minute. Table 2 shows the amount of each component used. Dip a piece of polycarbonate into the coating solution and apply at 120 ℃ ~
It was dried at 150 ° C for 5 minutes. The coated polycarbonate piece was evaluated in the same manner as in Example 1, and as a result, the contact angle was
The electrical resistance was 106 ° and the resistance was 10 ⁵ Ω.

Table 2 Component Usage (A-1) SH6040 29.54 (A-2) Aluminum Isopropoxide Hydrolyzed Solution 14.00 (A-3) Calcium Ethoxide Hydrolyzed Solution 14.14 (B-1) Stearic Acid 0.95 (B -2) Oleic acid 0.96 (C) N, N-dimethylbenzylamine 0.01 (D) Aqueous hydrofluoric acid solution 0.62 (E-1) Ethanol 27.82 (E-2) n-Butanol 11.96 Total 100.00

Comparative Example 1 As in Example 1, the uncoated glass slide plate was measured by the droplet method using an automatic contact angle measuring system. As a result, the contact angle was 26.
°. Further, as a result of investigating the suction distance and the suction amount of the carbon black as in Example 1, the carbon black was suction-adhered.

From the results of the above Examples and Comparative Examples, the coating films of the coating compositions of the Examples are superior to the Comparative Examples in water repellency and antistatic property.

[0072]

As described in detail above, the coating composition of the present invention can provide a coating excellent in water repellency and antistatic property. Moreover, the method for producing a coated substrate coated with the coating composition of the present invention can provide a coated substrate having excellent water repellency and antistatic properties. This coated substrate is extremely useful in precision equipment and optical equipment in the information / electronic industry.

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[Procedure amendment]

[Submission date] September 10, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Claims (9)

[Claims] 1. (A) (a) an inorganic alkoxide and / or (b)
(A) a polymer obtained by subjecting an inorganic alkoxide to hydrolysis and polycondensation, (B) a fatty acid, (C) a catalyst, (D) a hydrosilicofluoric acid, and (E) a water-containing organic solvent. Water repellency characterized by
Antistatic coating composition. 2. The water repellent / antistatic coating composition according to claim 1, wherein the inorganic alkoxide (A) (a) has the chemical formula (I): M (OR) _n (X) _an (I). (Where M is Si, Al, Ti, Zr, Ca, Fe,
An inorganic atom selected from the group consisting of V, Sn, Li, Be, Y, B and P, R is an alkyl group, and X is
Is a hydrocarbon group, a hydrocarbon group having a functional group or halogen, a is a valence of M, and n is 0 to a.
Is an integer up to. ) A water-repellent / antistatic coating composition, which is at least one compound selected from the group consisting of: 3. The water repellent / antistatic coating composition according to claim 2, wherein X in the chemical formula (I) has a carbonyl group, a carboxyl group, an amino group, a vinyl group, or an epoxy group. A water-repellent / antistatic coating composition characterized by having a hydrogen group. 4. The water-repellent / antistatic coating composition according to claim 1, wherein the inorganic alkoxide (A) (a) is S.
_{i (OC 3 H 7) 4} , Al (O-i-C 3 H 7) 3, T
_{i (O-i-C 3} H 7) 4, Zr (O-i-C 3 H 7)
_{4, Zr (O-n-} C 4 H 9) 4, Ca (OC 2 H 5)
₂ , Fe (OC ₂ H ₅ ) ₃ , V (O-i-C
_{4 H 9) 4, Sn (} OC 2 H 5) 4, Sn (O-i-C
_{4 H 9) 4, Li (} OC 2 H 5), Be (OC 2 H 5)
₂ , B (OC ₂ H ₅ ) ₃ , Y (OCH ₃ ) ₃ , Y (OC
₂ H ₅ ) ₃ , P (OCH ₃ ) ₃ and P (OC ₂ H ₅ ) ₃
A water-repellent / antistatic coating composition, which is at least one selected from the group consisting of: 5. The water-repellent / antistatic coating composition according to any one of claims 1 to 4, wherein the (B) fatty acid is capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and salts thereof. A water-repellent / antistatic coating composition, which is at least one selected from the group consisting of: 6. The water repellent / antistatic coating composition according to claim 1, wherein the (B) fatty acid is at least one selected from the group consisting of oleic acid and salts thereof. A water-repellent / antistatic coating composition characterized by: 7. The water repellent / antistatic coating composition according to claim 1, wherein the (D) hydrosilicofluoric acid is at least selected from the group consisting of hydrosilicofluoric acid and salts thereof. A water-repellent / antistatic coating composition, which is one kind. 8. The water-repellent / antistatic film composition according to claim 1, wherein the (C) catalyst is N, N-dimethylbenzylamine. Coating composition. 9. A method for producing a coated substrate having a water-repellent / antistatic coating, wherein the film is formed on at least one surface of the substrate by the water-repellent / antistatic coating composition according to claim 1. A method for producing a coated substrate having a water-repellent / antistatic coating, comprising the steps of: applying a water-repellent / antistatic coating by heat treatment at 80 ° C. or higher to form a water-repellent / antistatic coating.