JPH07305000A - Antistatic coating composition - Google Patents

Abstract

PURPOSE:To obtain the composition which can provide a coating film which is transparent and improved in antistatic properties, hardness, friction resistance, etc., by mixing a specified aminoalkylalkoxysilane compound with a specified silane compound, a specified acid, an organic solvent, water and a specified metal alkoxide compound. CONSTITUTION:This composition is obtained by mixing an aminoalkylalkoxysilane compound represented by formula I (wherein Y<1> is an organic amine group; Y<2> is a hydrocarbon group; R<1> is 1-5C alkyl; m is 1-5; and n is 0-2) with a silane compound represented by formula II (wherein Y<3> is an organic group; R<2> is R<1>; and p is 0-3), an acid (salt) having -log Ka (the logarithm of the reciprocal of the dissociation constant (Ka) in a 0.1mol/dm<3> concentration) of 3.5 or below, an organic solvent, water and at least one metal alkoxide compound selected from among a zirconium tetraalkoxide of formula III (wherein R<3> is R<1>), a titanium tetraalkoxide of formula IV (wherein R<4> is R<1>) and an aluminum trialkoxide of formula V (wherein R<5> is R<1>).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to antistatic coating compositions.

[0002]

2. Description of the Related Art Plastic products having low hygroscopicity and high electric insulation are apt to be damaged by static electricity.
For example, during the processing or use of various plastics molded products, films, etc., the adhesion of dust or dust or the occurrence of electric discharge may cause the plastics products to become dirty, or the functions of the products to deteriorate or be damaged. In order to prevent such electrostatic damage, a conductive coating is formed on the surface of the plastic to prevent charging. Also,
In many cases, the coating is required to be transparent so that the texture and color of the plastic are not lost.

The following are known as such a coating having conductivity and transparency. A product coated with a surfactant-based paint. Inorganic salts such as lithium chloride and magnesium chloride, ion conductive materials such as polymer electrolytes containing carboxylic acid groups and sulfonic acid groups,
A film formed from a composition that is dispersed in a film-forming substance such as synthetic resin or silicate. For example, Japanese Patent Publication No. 58-3586
Japanese Unexamined Patent Publication 7 discloses an antistatic coating composition in which an acrylic polymer is used as a film-forming substance and lithium nitrate is blended as an ion conductive substance, which is coated with a polyester film. Also, the Journal of the A
American Ceramic Society, 484〜486, Vol.72, No.3, (1
989), phosphomolybdic acid (H ₃ PMo ₁₂ O ₄₀・ 29
H ₂ O) is dissolved in a solution of a hydrolyzate of tetraethoxysilane, and a film is formed on a glass plate or a stainless plate. A composition is prepared by dispersing conductive fine particles such as a powder of a metal such as silver, nickel, copper, tin or an oxide thereof in a film-forming substance such as an acrylic resin, a polyester resin, or tetraethoxysilane. The filmed one. For example, in Japanese Patent Publication No. 63-33778, conductive fine powder composed of antimony-containing tin oxide and having a particle size of 0.2 micron or less is contained in a proportion of 50 to 70% by weight in the solid content of the coating material. It is disclosed that paints result in antistatic coatings for plastic products.

However, the above-mentioned coatings have the drawback that not only the surface resistance is as high as 10 ¹⁰ Ω / □ or more, but also the surface resistance value increases with time.

The above-mentioned coating has a drawback in that the conventionally used ion-conducting substance has a low electric conductivity when the humidity is low, and a sufficient antistatic property cannot be obtained.
For example, in the above-mentioned Japanese Patent Publication No. 58-35867, the surface resistance is a high value of about 10 ¹⁰ Ω / □ at a relative humidity of 50%, and the antistatic performance is insufficient. In addition, phosphomolybdic acid (H ₃ PMo ₁₂ O ₄₀
・ 29H ₂ O) dissolved in a solution of a hydrolyzate of tetraethoxysilane has a drawback that when it is applied to a plastic plate to form a film, cracks occur in the film, and it cannot be applied to plastic products. .

In the above coating, in order to obtain a sufficient antistatic property, it is necessary to increase the concentration of conductive fine particles in the film. Therefore, there is a drawback that haze is generated due to light scattering by the fine particles, and transparency is impaired.

Further, the above-mentioned coatings have poor water resistance, and there is a drawback that in a water immersion test or the like, performances such as peeling of the coating, increase of surface resistance, and loss of transparency are deteriorated.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to easily provide a transparent and highly antistatic film, which is free from cracks, and has excellent scratch resistance and hardness and abrasion resistance, especially for plastic products. An object is to provide an antistatic coating composition that can be formed.

[0009]

First, the invention according to claim 1 (hereinafter referred to as "present invention 1") will be described in detail. The aminoalkylalkoxysilane compound (A) used in the present invention 1 is represented by the following general formula [I],

[0010]

[Chemical 4]

Where Y¹Represents an organic group having an amino group
However, for example, the amino group itself, the hydrogen atom of the amino group
Examples thereof include a substituted amino group substituted with an alkyl group.
Y²Represents a hydrocarbon group such as an alkyl group or a substituted group.
Examples thereof include a rukyl group. R¹Represents an alkyl group,
As the carbon number increases, the antistatic coating composition of the present invention
Since the stability decreases and the long-term storage stability deteriorates, the carbon number is
Limited to 1-5. R ¹Examples of
Cyl group, n-propyl group, iso-propyl group, n-bu
Cyl group, sec-butyl group, tert-butyl group, n-
Pentyl group, sec-pentyl group, tert-pentyl group
Groups and the like. m is an integer from 1 to 5, n is an integer from 0 to 2
Is a number.

Examples of the aminoalkylalkoxysilane compound (A) include aminomethyltriethoxysilane, γ-aminopropyltrimethoxysilane and γ-
Aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N
-(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis [3
Examples include-(methyldimethoxysilyl) propyl] ethylenediamine and the like. Of these, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane is particularly preferable. These may be used alone or 2
You may use together more than one kind.

The silane compound (B ¹ ) used in the present invention 1 is represented by the following general formula [II]:

[0014]

[Chemical 5]

In the formula, P represents an integer of 0 to 3. R
² represents an alkyl group, but when the number of carbon atoms increases, the stability of the coating composition decreases and the long-term storage stability deteriorates.
The carbon number is limited to 1-5. Examples of R ² are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, tert.
-Pentyl group and the like. Y ³ represents an organic group,
Examples of the organic group include a hydrocarbon group, a glycidoxyalkyl group, an epoxycyclohexylalkyl group, a (meth) acryloyloxyalkyl group, a mercaptoalkyl group, and the like. Examples of the hydrocarbon group include an alkyl group, a substituted alkyl group, an allyl group, a vinyl group, a phenyl group and a naphthyl group. Note that P
When is 2 or 3, Y ³ may be the same or different from each other.

As the silane compound (B ¹ ), when P is 0, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-
iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-ter
Examples thereof include t-butoxysilane. Of these, tetraethoxysilane is particularly preferable.

When P is 1, for example, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-propoxysilane, monomethyltri-i.
so-propoxysilane, monomethyltri-n-butoxysilane, monomethyltri-sec-butoxysilane,
Monomethyltri-tert-butoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, methacryloxypropyl Examples thereof include trimethoxysilane and mercaptopropyltrimethoxysilane. Among these, especially monomethyltrimethoxysilane, monomethyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane is preferred.

When P is 2, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n
-Propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, diethyldiethoxysilane, ethylvinyldiethoxysilane, ethylphenyldiethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, methylaminodiethoxysilane, methylacryloxydiethoxysilane and the like. Of these, dimethyldimethoxysilane is particularly preferable.

When P is 3, for example, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-i.
so-propoxysilane, trimethylmono-n-butoxysilane, trimethylmono-sec-butoxysilane,
Examples include trimethyl mono-tert-butoxy silane, triethyl ethoxy silane, diethyl vinyl ethoxy silane, diethyl phenyl ethoxy silane, and γ-glycidoxy propyl ethyl methyl ethoxy silane.

Examples of the silane compound (B ¹ ) include those mentioned above, and these may be used alone or in combination of two or more kinds.

When the amount of the silane compound (B ¹ ) increases,
When the antistatic coating composition obtained in the present invention 1 is prepared, white precipitates or gelation occurs and the composition cannot be used as a coating solution. Therefore, the aminoalkylalkoxysilane compound (A) and the silane are not used. The molar ratio of the compound (B ¹ ) is 100 to 50:50 to 0, preferably 93 to 53:35 to 5.

In the present invention 1, pKa (= -logK
a) is the logarithm of the reciprocal of the acid dissociation constant (Ka) at a concentration of 0.1 mol / dm ³ at 25 ° C. (hereinafter, simply referred to as “pKa”), and pKa is 3.5 or less. Examples of the acid include perchloric acid (pKa = −∞), trifluoromethanesulfonic acid (pKa = −∞), fluorosulfonic acid (pKa = −∞) and nitric acid (pKa = −1.8), and Examples of salts include perchlorates and trifluoromethanesulfonates.

The perchloric acid or its salt (hereinafter referred to as "perchloric acid compound") is represented by the general formula X ¹ ClO ₄ ,
In the formula, X ¹ is a hydrogen atom, a monovalent metal atom, NH
₄ and quaternary ammonium represented by the following general formula [IV].

[0024]

[Chemical 6]

Examples of the monovalent metal atom include lithium, sodium and potassium. The above quaternary ammonium substituents, M ¹ , M ² , M ³ and M
⁴ represents an alkyl group having 1 to 20 carbon atoms. Examples of the perchloric acid compound include perchloric acid, lithium perchlorate, ammonium perchlorate, tetramethylammonium perchlorate, tetraethylammonium perchlorate and the like, and these may be used alone. However, two or more kinds may be used in combination.

If the amount of the above-mentioned perchloric acid compound added is too small, the film does not have sufficient conductivity to prevent electrification, and if it is too large, the film becomes cloudy and opaque. ) 0.005 to 0.64 mol, preferably 0.
It is 01 to 0.5.

The above-mentioned trifluoromethanesulfonic acid or a salt thereof (hereinafter referred to as "trifluoromethanesulfonic acid compound")
Is represented by the general formula CF ₃ SO ₃ X ^2, where:
X ² represents a hydrogen atom or a monovalent metal atom. Examples of the monovalent metal atom include lithium, sodium and potassium. Examples of the trifluoromethanesulfonic acid compound include trifluoromethanesulfonic acid, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, and the like. These may be used alone or in combination of two or more kinds. Good.

When the amount of the trifluoromethanesulfonic acid compound added is small, the film does not have sufficient conductivity to prevent static electricity, and when it is too large, the film becomes cloudy and opaque. Therefore, the aminoalkylalkoxysilane compound ( A) 0.001 to 0.6 mol, preferably 0.01 to 0.5 mol, per 1 mol.

The above fluorosulfonic acid has the general formula FSO
Represented by ₃ H, if the amount added is too small, the film does not have sufficient conductivity to prevent electrification, and if the amount is too large, the film becomes cloudy and opaque. Therefore, the above aminoalkylalkoxysilane compound (A) 1 0.000 per mole
1 to 0.2 mol, preferably 0.001 to 0.1
It is 5 mol.

The nitric acid may be added as it is, or may be added as a nitric acid aqueous solution. When the amount of the nitric acid added is small, the conductivity is not imparted to the film sufficiently to prevent electrification, and when it is large, the film becomes cloudy and opaque. Therefore, relative to 1 mol of the aminoalkylalkoxysilane compound (A). , 0.001 to 0.5 mol, preferably 0.01 to 0.2 mol.

The organic solvent (D) used in the present invention 1 is
Compatible with the above aminoalkylalkoxysilane compound (A), water (E) and metal alkoxide (F),
It is not particularly limited as long as it can dissolve an acid having a pKa of 3.5 or less or a salt thereof (C ¹ ), and examples thereof include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and acetone. , Ketones such as methyl ethyl ketone, tetrahydrofuran, and the like, and methyl alcohol, ethyl alcohol, and isopropyl alcohol are particularly preferable in terms of good film-forming property. These may be used alone or in combination of two or more.

When the amount of the organic solvent (D) added is small, the antistatic coating composition of the present invention 1 is difficult to mix uniformly, resulting in a heterogeneous composition, and when the amount is large, the antistatic coating composition is added. Since the solid content concentration of the above becomes too low and a sufficient antistatic ability cannot be obtained when formed into a film, it is 10 to 200 mol, preferably 20 to 20 mol, relative to 1 mol of the aminoalkylalkoxysilane compound (A). 10
It is 0.

The water (E) used in the present invention 1 is the aminoalkylalkoxysilane compound (A) or the silane compound (B ¹ ) and the metal alkoxide (F).
Added as a catalyst for the hydrolysis of When the amount of the water (E) added is small, sufficient hydrolysis is unlikely to occur, and when the amount is large, the compatibility with the coating composition is poor, so that 1 mol of the aminoalkylalkoxysilane compound (A) is used. It is preferably 0.1 to 10 mol, more preferably 0.5 to 6 mol.

An inorganic or organic acid such as hydrochloric acid or sulfuric acid may be added to the water (E) as a catalyst for hydrolysis, and the content in the water (E) is small. If so, the effect as a catalyst cannot be expected, and if it increases, the coating becomes inhomogeneous, so 0.001 is preferable.
~ 5% by weight.

The metal alkoxide (F) used in the present invention 1 is a zirconium tetraalkoxide represented by the general formula Zr (OR ³ ) ₄ , a titanium tetraalkoxide represented by the general formula Ti (OR ⁴ ) ₄ and a general formula. Al
It is at least one metal alkoxide selected from the group consisting of aluminum trialkoxides represented by (OR ⁵ ) ₃ . However, in the formula, R ³ , R ⁴ and R ⁵ represent an alkyl group, but if the number of carbon atoms increases, the stability of the coating composition decreases and the long-term storage stability deteriorates. Limited to 5. Examples of R ³ , R ⁴ and R ⁵ are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert.
A butyl group and the like.

Examples of the zirconium tetraalkoxide include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetra-iso-propoxide, zirconium tetra-n-butoxide and zirconium tetra-sec-. Butoxide, zirconium tetra-
tert-butoxide and the like, particularly zirconium tetra-n-butoxide, zirconium tetra-iso.
-Propoxide is preferred.

Examples of the titanium tetraalkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-iso-propoxide, titanium tetra-n-butoxide, titanium tetra-se.
Examples thereof include c-butoxide and titanium tetra-tert-butoxide, and titanium tetra-n-butoxide and titanium tetra-iso-propoxide are particularly preferable.

Examples of the aluminum trialkoxide include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-iso-propoxide, aluminum tri-n-butoxide and aluminum tri-se.
Examples thereof include c-butoxide and aluminum tri-tert-butoxide, and aluminum tri-sec-butoxide and aluminum tri-iso-propoxide are particularly preferable.

The amount of the metal alkoxide (F) added is
When the amount is small, sufficient film strength cannot be obtained and the film is easily scratched, and when the amount is large, the film-forming property of the coating composition is deteriorated and cracks are easily generated in the obtained film, and thus the aminoalkylalkoxysilane compound (A) is used. And the metal alkoxide (F) has a molar ratio of 70:30 to 99 :.
1, but when the above zirconium tetraalkoxide is used as the metal alkoxide (F), the above molar ratio is preferably 80:20 to 99: 1, more preferably 8:20 to 99: 1.
In the case of titanium tetraalkoxide, the above molar ratio is preferably 80: 2.
In the case of aluminum trialkoxide, the above molar ratio is preferably 85: 15-9.
It is 9: 1, more preferably 85:15 to 95: 5.

The method for producing the antistatic coating composition of the present invention 1 is not particularly limited, and, for example, a method of mixing the above-mentioned constituent materials at once or a specific constituent material is divided and mixed. After that, a method of adding and mixing the remaining constituent materials can be mentioned. As a method of dividing and mixing, for example, the aminoalkylalkoxysilane compound (A) and the silane compound (B) are mixed, the organic solvent (D) is added to the mixture, and the mixture is stirred.
Water (E) is added as a catalyst for hydrolysis to obtain a hydrolyzate of the silane compound. The metal alkoxide (F) is added to this solution and mixed with stirring to obtain a solution of a hydrolyzate of the silane compound and the metal alkoxide. To this solution, pKa
Of 3.5 or less, or a mixture of one or more kinds of salts thereof is added and mixed by stirring to obtain the antistatic coating composition.

The composition of the antistatic coating composition of the present invention 1 is as described above, but a hydrophilic polymer such as polyethylene glycol may be added to further improve the conductivity. Further, in order to improve the film forming property, a cellulose derivative such as methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose may be contained. Further, for the same purpose, an oxide colloid such as silica sol, alumina sol, zirconia sol may be contained.

The antistatic coating composition of the present invention 1 can be produced by the usual simple method as described above, and can be used in the same manner as the conventional silicone coating composition.

The antistatic coating composition of the present invention 1 is applied to a plastic product, a glass plate, a metal plate or the like and dried to form an antistatic coating. The coating method is not particularly limited, and examples thereof include brush, spray coating, dip coating, spin coating, roll coating, and flow coating.

The drying method is not particularly limited, and may be naturally dried at room temperature or may be dried by heating. Further, after drying, high temperature heat treatment may be carried out, if necessary. For example, when the antistatic coating composition is coated on the surface of a plastic product by the above method, naturally dried at room temperature, and then cured at a temperature of 60 ° C to 150 ° C, an antistatic coating is formed. A plastic product is obtained.

The plastics coated with the above antistatic coating composition are not particularly limited,
Examples thereof include plastics such as polycarbonate, acrylic resin, polyvinyl chloride, polystyrene, polyester and polyurethane. Also, the shape of the product is not particularly limited.

The coating obtained from the antistatic coating composition of the present invention 1 is transparent because the acid having a pKa of 3.5 or less or a salt thereof is uniformly present in an ionic state. And high conductivity. Further, since the obtained coating contains oxides of zirconium, titanium, or aluminum, scratches are less likely to occur even when strongly rubbed with a hard material such as steel wool, and a deterioration in appearance due to scratches is less likely to occur.

Next, the invention according to claim 2 (hereinafter referred to as "present invention 2") will be described in detail. In the present invention 2, from the same components as in the present invention 1, except that sulfuric acid (C ² ) is used in place of the acid having a pKa of 3.5 or less or its salt (C ¹ ) used in the present invention 1. The detailed description is the same as in the first aspect of the invention.

When the added amount of the above sulfuric acid (C ² ) is small, the film does not have sufficient conductivity to prevent electrification, and when it is too large, the film becomes cloudy and opaque. Therefore, the above aminoalkylalkoxysilane compound ( A) 0.001 to 0.8 mol, preferably 0.01 to 1 mol
It is 0.5 mol.

The organic solvent (D) used in the present invention 2 is
There is no particular limitation as long as it is compatible with the aminoalkylalkoxysilane compound (A), the silane compound (B ¹ ), water (E) and the metal alkoxide (F) and can dissolve the sulfuric acid (C ² ). Not something, for example,
Examples thereof include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran and the like, with methyl alcohol, ethyl alcohol and isopropyl alcohol being particularly preferable. These may be used alone or in combination of two or more.

When the amount of the organic solvent (D) added is small, the antistatic coating composition of the present invention 2 is difficult to mix uniformly, resulting in a heterogeneous composition, and when it is large, the solid content of the coating composition is solid. Since the concentration of the component becomes too low and a sufficient antistatic ability cannot be obtained when it is formed into a film, it is 10 per mol of the aminoalkylalkoxysilane compound (A).
˜200 mol, preferably 20˜100.

The water (E) used in the present invention 2 is the aminoalkylalkoxysilane compound (A) or the silane compound (B ¹ ) and the metal alkoxide (F).
Added as a catalyst for the hydrolysis of When the amount of the water (E) added is small, sufficient hydrolysis is unlikely to occur, and when the amount is large, the compatibility with the coating composition is poor, so that 1 mol of the aminoalkylalkoxysilane compound (A) is used. It is preferably 0.1 to 10 mol, more preferably 0.5 to 6 mol.

Further, an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid may be added to the water (E) as a catalyst for hydrolysis, and the content in the water (E) is small. If so, the effect as a catalyst cannot be expected, and if it increases, the coating becomes inhomogeneous, so 0.001 is preferable.
~ 5% by weight.

The coating film obtained from the antistatic coating composition of the present invention 2 has a high transparency and a high conductivity because sulfuric acid is uniformly present in the coating film in an ionic state. In addition, since the obtained coating contains oxides of zirconium, titanium or aluminum, scratches are unlikely to occur even when strongly rubbed with a hard material such as steel wool, and deterioration in appearance due to scratches is less likely to occur.

Next, the invention according to claim 3 (hereinafter referred to as "present invention 3") will be described in detail. The present invention 3 has the same constitution as that of the present invention 1 except that a heteropolyacid compound (C ³ ) is used in place of the acid having a pKa of 3.5 or less or the salt thereof (C ¹ ) used in the present invention 1. It is composed of components, and its detailed description is the same as that of the first invention.

Examples of the above-mentioned heteropolyacid compound (C ³ ) include heteropolyacids and salts thereof, including boron, aluminum, gallium, silicon, germanium, cesium, titanium, zirconium, antimony, bismuth, rhodium, copper, platinum and phosphorus. At least one element selected from the group consisting of iron, cobalt, nickel, arsenic, chromium, sulfur, selenium, tellurium, and thorium, and molybdenum, tungsten, vanadium, niobium, and tantalum as adjacent metal atoms forming a heteropolyacid. It is a complex oxygen acid or a salt thereof comprising at least one element selected from the group consisting of: Examples of the salt include sodium salt and ammonium salt.

Examples of the heteropolyacid include phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ .nH ₂ O), phosphomolybdic acid (H ₃ PMo ₁₂ O ₄₀ .nH ₂ O), silicotungstic acid (H ₃ SiW). ₁₂ O ₄₀ · nH ₂ O) and the like. Examples of the salt of the heteropoly acid include sodium phosphomolybdate vanadate (Na _3-X PMo _{12 -X}
V _X O ₄₀ · nH ₂ O). These may be used alone or in combination of two or more.

If the amount of the above-mentioned heteropolyacid compound (C ³ ) added is small, the film does not have sufficient conductivity for antistatic treatment, and if it is too large, the film becomes cloudy and opaque. Compound (A)
With respect to 1 mol, preferably 0.01 to 0.35 mol,
More preferably, it is 0.01 to 0.3 mol.

The organic solvent (D) used in the present invention 3 is
In particular, if it is compatible with the aminoalkylalkoxysilane compound (A), the silane compound (B ¹ ), water (E) and the metal alkoxide (F) and can dissolve the heteropolyacid compound (C ³ ). The present invention is not limited, and examples thereof include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, ketones such as acetone and methyl ethyl ketone, and tetrahydrofuran. Particularly, methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferable. . These may be used alone or in combination of two or more.

When the amount of the organic solvent (D) added is small, the antistatic coating composition of the present invention 3 is hardly mixed uniformly, resulting in a heterogeneous composition, and when the amount is large, the solid content of the coating composition is solid. Since the concentration of the component becomes too low and a sufficient antistatic ability cannot be obtained when it is formed into a film, it is 1 mol per mol of the aminoalkylalkoxysilane compound (A).
It is 0 to 200 mol, preferably 20 to 100 mol.

The water (E) used in the present invention 3 is the aminoalkylalkoxysilane compound (A) or the silane compound (B ¹ ) and the metal alkoxide (F).
Added as a catalyst for the hydrolysis of When the amount of the water (E) added is small, sufficient hydrolysis is unlikely to occur, and when the amount is large, the compatibility with the coating composition is poor, so that 1 mol of the aminoalkylalkoxysilane compound (A) is used. It is preferably 0.1 to 10 mol, more preferably 0.5 to 3 mol.

An inorganic or organic acid such as hydrochloric acid or sulfuric acid may be added to the water (E) as a catalyst for hydrolysis, and the content in the water (E) is small. If so, the effect as a catalyst cannot be expected, and if it increases, the coating becomes inhomogeneous, so 0.001 is preferable.
~ 5% by weight.

The coating obtained from the antistatic coating composition of the present invention 3 has a high transparency because the heteropolyacid compound (C ³ ) is present in the coating in a uniform ionic state.
Highly conductive. In addition, zirconium in the obtained coating,
Since it contains an oxide of titanium or aluminum, even if it is rubbed hard with a hard material such as steel wool, it is less likely to be scratched, and the appearance is less likely to be deteriorated due to scratches.

Next, the invention according to claim 4 (hereinafter referred to as "present invention 4") will be described in detail. In the present invention 4, in place of the silane compound (B ¹ ) used in the present inventions 1 to 3, an epoxyalkylalkoxysilane compound (B ¹ ) is used.
By using ² ) and limiting the metal alkoxide (F) to zirconium tetraalkoxide or titanium tetraalkoxide, an antistatic coating composition with improved water resistance can be obtained. Except for being limited to the above, it is composed of the same components as in the first aspect of the invention, and the detailed description thereof is the same.

The epoxyalkylalkoxysilane compound (B ² ) is represented by the following general formula [III],

[0065]

[Chemical 7]

In the formula, Z represents a glycidoxy group or an epoxycyclohexyl group. Y ⁴ represents a hydrocarbon group, and examples thereof include an alkyl group and a substituted alkyl group. R ⁶
Represents an alkyl group having 1 to 5 carbon atoms. However, when the number of carbon atoms increases, the stability of the coating composition decreases and the long-term storage stability deteriorates, so the carbon number is limited to 1 to 5. Examples of R ¹ are methyl group, ethyl group, n-propyl group, iso
-Propyl group, n-butyl group, sec-butyl group, te
Examples include rt-butyl group. q is an integer of 1 to 5, t
Is an integer of 0 to 2.

Examples of the epoxyalkylalkoxysilane compound (B ² ) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltri. Methoxysilane, β- (3,4-
Epoxycyclohexyl) ethylmethyldimethoxysilane and the like.

Further, in the present invention 4, the above-mentioned zirconium tetraalkoxide and titanium tetraalkoxide are particularly used as the metal alkoxide (F),
All the specific examples mentioned above are included.

The molar ratio of the above-mentioned aminoalkylalkoxysilane compound (A) to the epoxyalkylalkoxysilane compound (B ² ) and zirconium tetraalkoxide used in the present invention 4 is based on the above aminoalkylalkoxysilane compound (A). When the amount of the epoxyalkylalkoxysilane compound (B ² ) is small, sufficient film strength cannot be obtained and the film is easily scratched, and when it is large, the film-forming property of the coating composition is deteriorated and cracks are easily generated in the film obtained. Further, if the amount of the zirconium tetraalkoxide added is small, the film does not have sufficient conductivity to prevent electrification, and if it is large, the film becomes cloudy and opaque. Therefore, 93 to 53:35 is preferable.
5: 12-2, more preferably 90-70: 26-6:
It is 10-4.

When the above titanium tetraalkoxide is used as the metal alkoxide, for the same reason as in the case of the above zirconium tetraalkoxide,
The molar ratio of the above three components is preferably 93 to 55:35.
5:10 to 2, more preferably 90 to 70:26.
˜6: 10 to 4

The coating film obtained from the antistatic coating composition of the present invention 4 comprises an acid having a pKa of 3.5 or less, a salt thereof (C ¹ ), sulfuric acid (C ² ), or a heteropolyacid described above. Since (C ³ ) is uniformly present in an ionic state, it has high transparency and high conductivity. In addition, since the obtained coating contains zirconium or titanium alkoxide, scratches are less likely to occur even when strongly rubbed with a hard material such as steel wool, the appearance is less likely to be scratched, and water resistance is particularly improved. is doing.

[0072]

The coatings obtained from the antistatic coating compositions of the present inventions 1 to 3 are those in which the acid having a pKa of 3.5 or less, a salt thereof, sulfuric acid or a heteropolyacid compound is uniformly present in an ionic state. Therefore, it has high transparency and high conductivity. In addition, the aminoalkylalkoxysilane compound, the silane compound and the metal alkoxide are the coatings obtained from the composition blended in a specific amount, so even if they are hard rubbed with a hard material such as steel wool, they are hard to be scratched and scratched. It is difficult for the appearance to deteriorate.

The coating obtained from the antistatic coating composition of the present invention 4 has an acid having a pKa of 3.5 or less, a salt thereof, sulfuric acid or a heteropolyacid compound, which is uniformly present in an ionic state. Therefore, it has high transparency and high conductivity. Further, since the aminoalkylalkoxysilane compound, the epoxyalkylalkoxysilane compound and the zirconium tetraalkoxide or the titanium tetraalkoxide are the coatings obtained from the composition blended in a specific amount, they should be rubbed strongly with a hard material such as steel wool. It is difficult to be scratched, the appearance is not deteriorated due to scratches, and the water resistance is particularly improved.

[0074]

EXAMPLES Examples of the present invention will be described below. The methods for evaluating the physical properties of the antistatic coating composition shown in the results were as follows.

(1) Crack test The obtained antistatic coating composition was added with 50 × 100 mm
(Thickness 2 mm) polycarbonate substrate (manufactured by Asahi Glass Co., Ltd.,
Immerse the product name "Lexan sheet 9034") in
After pulling up at a speed of mm / min, it was dried at room temperature for 60 minutes and then cured at 110 ° C. for 60 minutes to form an antistatic coating on the substrate to prepare an evaluation sample, and to make a crack by visual observation. Existence was checked. (Judgment Criteria) O: No crack was observed. X: A crack was observed.

(2) Surface Resistance An evaluation sample was prepared in the same manner as the above-mentioned crack test using the obtained antistatic coating composition.
Using "STACK TR-3" manufactured by Tokyo Electronics Co., Ltd., the surface resistance was measured and evaluated by a two-terminal method in an atmosphere with a relative humidity of 50%.

(3) Light Transmittance The light transmittance of an evaluation sample prepared in the same manner as the above-mentioned crack test using the obtained antistatic coating composition was compared with that of an untreated polycarbonate substrate. As a spectrophotometer "UV-3101" manufactured by Shimadzu Corporation
"PC" was used to measure and evaluate in the range of 400 to 700 nm.

(4) Pencil Hardness An evaluation sample prepared in the same manner as the above-mentioned crack test was prepared by using the obtained antistatic coating composition.
It was measured and evaluated according to IS K 5400.

(5) Polyethylene terephthalate (PE
T) Film Adhesion Test Using the obtained antistatic coating composition, the surface of an evaluation sample prepared in the same manner as the above-described crack test was rubbed with a woolen fabric and cut into 1 × 3 mm pieces of PET.
The film (100 μm in thickness) was brought close to a distance of about 1 cm, and the adhered state of the PET film was evaluated according to the following criteria. (Judgment Criteria) ◯: No adhesion to the surface. Δ: A little adhered to the surface. X: Many adhered to the surface.

(6) Abrasion resistance test The surface of an evaluation sample prepared in the same manner as the above-mentioned crack test using the obtained antistatic coating composition was reciprocated 10 times with steel wool # 0000. Rubbing and scratch resistance of the sample surface were evaluated according to the following criteria. (Judgment Criteria) O: The surface was not scratched at all even with strong rubbing. Δ: The surface was slightly scratched when strongly rubbed. X: The surface was markedly damaged even with weak friction.

(7) Water resistance test An evaluation sample prepared in the same manner as the above-mentioned crack test using the obtained antistatic coating composition was dipped in distilled water for 30 minutes and then dried. The surface resistance was measured in the same manner as (2) above. However, this test was performed only for Examples 28 to 65 and Comparative Examples 6 to 9.

The methods for producing the antistatic coating compositions of Examples and Comparative Examples and the results of evaluation of the physical properties of the compositions are shown below. The meanings of the abbreviations used in Tables 1 to 34 below are as follows.
It is as follows. Aminoalkylalkoxysilane compound (A) (hereinafter referred to as “aminosilane compound”) S1: N- (β-aminoethyl) -γ-aminopropyltrimethoxysilanesilane compound (B ¹ ) (hereinafter referred to as “silane compound”) S2: Tetraethoxysilane Epoxyalkylalkoxysilane (B ² ) (hereinafter referred to as “epoxysilane compound”) S3: γ-glycidoxypropyltrimethoxysilane Heteropolyacid compound PM: Phosphomolybdic acid (H ₃ PMo ₁₂ O _40. 29H ₂
O) PW: Phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ / 29H ₂
O) Perchloric acid compound K1: Perchloric acid (HClO ₄ ) (pKa = -∞) K2: Ammonium perchlorate (NH ₄ ClO ₄ ) K3: Lithium perchlorate (LiClO ₄ ) Trifluoromethanesulfonic acid compound C1: Trifluoromethanesulfonic acid (pKa = -∞) C2: Lithium trifluoromethanesulfonate F1: Fluorosulfonic acid (pKa = -∞) N1: Nitric acid (pKa = -1.8) B1: Acetic acid (pKa = 4.56) H1 : Sulfuric acid Y1: Methyl alcohol metal alkoxide T1: Titanium tetra-n-butoxide Z1: Zirconium tetra-n-butoxide A1: Aluminum tri-sec-butoxide

(Examples 1-27, Comparative Examples 1-5) Table 1,
According to the compositions shown in 3 and 5, first, a predetermined amount of methyl alcohol was supplied to a glass beaker, a predetermined amount of an aminosilane compound and a silane compound were added, and further, a predetermined amount of water containing 0.36% by weight of hydrochloric acid was added. Then, the mixture was further stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an alcohol solution of a silane compound. A metal alkoxide was added to the obtained alcohol solution, and the mixture was further stirred at room temperature for 1 hour at a stirring speed of 800 rpm to obtain an alcohol solution of a hydrolyzate of a silane compound and a metal alkoxide.

A predetermined amount of any one of the heteropoly acid compound, perchloric acid compound, trifluoromethanesulfonic acid compound, sulfuric acid, fluorosulfonic acid, nitric acid and acetic acid was added to the obtained alcohol solution, and the mixture was further stirred at room temperature for 3 hours. The composition was stirred at a speed of 800 rpm to obtain an antistatic coating composition. Since the heteropolyacid compound contains water of hydration, water of hydration is necessarily added to this composition as the heteropolyacid compound is added. Therefore, the predetermined amount of water shown in the table is a value including the amount of hydration water.

Using the obtained antistatic coating composition,
Based on the test methods (1) to (6), each physical property is measured,
The results are shown in Tables 2, 4 and 6.

The antistatic coating composition of Comparative Example 4 cannot be used as an antistatic coating composition because the solution gels when the above components are mixed, and the antistatic coating composition of Comparative Example 5 is used. The coating composition could not be used as an antistatic coating composition because a white precipitate was formed in the solution when the above components were mixed.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

[Table 4]

[0091]

[Table 5]

[0092]

[Table 6]

(Examples 28 to 46, Comparative Examples 6 to 7) Table 7
According to the compositions of 9 and 9, first, a half amount of a predetermined amount of methyl alcohol was supplied to a glass beaker, and an aminoalkylalkoxysilane compound was added to obtain an alcohol solution of the aminoalkylalkoxysilane compound. Next, add an aqueous solution in which a heteropolyacid compound, a perchloric acid compound, a trifluoromethanesulfonic acid compound, sulfuric acid, fluorosulfonic acid, nitric acid and acetic acid are dissolved to 3/4 of a predetermined amount of water, and stir speed at room temperature for 3 hours. The mixture was stirred at 800 rpm to obtain an alcohol solution of hydrolyzate of aminosilane compound.

Further, an epoxyalkylalkoxysilane compound and a titanium tetraalkoxide were supplied to another glass beaker together with the remaining half amount of methyl alcohol,
After adding 1/4 of a predetermined amount of water, the mixture was stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an alcohol solution of a hydrolyzate of a silane compound or an epoxyalkylalkoxysilane compound and titanium tetraalkoxide.
An alcohol solution of each of these hydrolysates was mixed, and further stirred at room temperature for 3 hours at a stirring speed of 800 rpm,
An antistatic coating composition was obtained.

Using the resulting antistatic coating composition,
Tables 8 and 10 show the results of measuring each physical property based on the test methods (1) to (7).

[0096]

[Table 7]

[0097]

[Table 8]

[0098]

[Table 9]

[0099]

[Table 10]

(Examples 47 to 65, Comparative Examples 8 to 9) Table 7
Antistatic coating compositions were obtained according to the compositions of Tables 11 and 13 by the same procedure except that zirconium tetraalkoxide was used in place of the titanium tetraalkoxide used in Examples 9 and 10.

Using the obtained antistatic coating composition,
Physical properties were measured based on the above-mentioned test methods (1) to (7), and the results are shown in Tables 12 and 14.

[0102]

[Table 11]

[0103]

[Table 12]

[0104]

[Table 13]

[0105]

[Table 14]

[0106]

The composition of the antistatic coating composition of the present invention 1 is as described above, and the silane compound containing a specific amino group-containing silane compound as a main component has a pKa at 20 ° C. of 3.5 or less. The acid or salt thereof, organic solvent, water and metal alkoxide compound are mixed in a specific amount, so it is transparent and has a high antistatic effect, has no cracks, and has excellent hardness and abrasion resistance and scratch resistance. It is possible to easily form a coating having a high degree.

The composition of the antistatic coating composition of the present invention 2 is as described above, and a silane compound containing a specific silane compound containing an amino group as a main component, sulfuric acid, an organic solvent, water and a metal alkoxide compound is specified. Since they are mixed in a sufficient amount, it is possible to easily form a transparent, highly antistatic effect-free, crack-free coating film having excellent hardness and abrasion resistance and high scratch resistance on plastic products.

The composition of the antistatic coating composition of the present invention 3 is as described above, and a silane compound containing a specific amino group-containing silane compound as a main component, a heteropolyacid compound,
Since a specific amount of organic solvent, water and metal alkoxide compound is blended, it is easy to form a transparent, highly antistatic, crack-free coating with excellent hardness and abrasion resistance and high scratch resistance on plastic products. Can be formed.

The composition of the antistatic coating composition of the present invention 4 is as described above, and includes a silane compound containing a specific amino group, a silane compound containing a specific epoxy group, a specific acid or salt thereof, an organic solvent, Since water and zirconium tetraalkoxide or titanium tetraalkoxide are mixed in a specific amount, plastic products are transparent and have a high antistatic effect, have no cracks, have excellent hardness and abrasion resistance, and have high scratch resistance and water resistance. A coating having high properties can be easily formed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuaki Miyamoto 2-2 Kamitobaue Tonkocho Minami-ku, Kyoto City Sekisui Kagaku Kogyo Co., Ltd.

Claims (4)

[Claims] 1. (A) An aminoalkylalkoxysilane compound represented by the following general formula [I]: (In the formula, Y ¹ is an organic group having an amino group, Y ² is a hydrocarbon group, R ¹ is an alkyl group having 1 to 5 carbon atoms, m is an integer of 1 to 5, n is an integer of 0 to 2), (B ¹ ) The following general formula [II]
A silane compound represented by (In the formula, Y ³ is an organic group, R ² is an alkyl group having 1 to 5 carbon atoms, P is an integer of 0 to 3), (C ¹ ) 0.1 mol / dm
The logarithm of the reciprocal of the acid dissociation constant (Ka) at a concentration of ³ at 25 ° C, an acid having a pKa (= -logKa) of 3.5 or less, a salt thereof, (D) an organic solvent, (E) water, and (F). )
Zirconium tetraalkoxide represented by the general formula Zr (OR ³ ) ₄ , titanium tetraalkoxide represented by the general formula Ti (OR ⁴ ) ₄ , and aluminum trialkoxide represented by the general formula Al (OR ⁵ ) ₃ (in the formula: , R ³ ,
R ⁴ and R ⁵ are at least one metal alkoxide compound selected from the group consisting of C 1-5 alkyl groups), and an antistatic coating composition characterized by the above-mentioned. 2. (A) the aminoalkylalkoxysilane compound according to claim ¹ , (B ¹ ) the silane compound according to claim 1, (C ² ) sulfuric acid, (D) an organic solvent, (E) water, and ( F) An antistatic coating composition comprising the metal alkoxide compound according to claim 1. (A) Aminoalkylalkoxysilane compound according to claim ¹ , (B ¹ ) A silane compound according to claim 1, (C ³ ) Heteropolyacid compound, (D) Organic solvent,
An antistatic coating composition comprising (E) water and (F) the metal alkoxide compound according to claim 1. 4. The silane compound according to any one of claims 1 to 3 is (B ² ) an epoxyalkylalkoxysilane compound represented by the following general formula [III]: (In the formula, Z is a glycidoxy group or an epoxycyclohexyl group, Y ⁴ is a hydrocarbon group, R ⁶ is an alkyl group having 1 to 5 carbon atoms, q is an integer of 1 to 5, and t is an integer of 0 to 2.) The metal alkoxide compound (F) according to any one of claims 1 to 3 is a zirconium tetraalkoxide represented by the general formula Zr (OR ³ ) ₄ or a general formula Ti (OR ⁴ ) ₄
Titanium tetraalkoxide represented by (in the formula, R ³
And R ⁴ is an alkyl group having 1 to 5 carbon atoms) ^4. The antistatic coating composition according to claim 1, wherein