JPH06200185A - Antistatic coating composition for plastic - Google Patents

Abstract

PURPOSE:To provide the subject composition capable of giving coating films having antistatic effect at low humidities and excellent in transparency, hardness and friction resistance, useful for molded products, etc., comprising a specific silane compound mixture, heteropoly-acid (salt), organic solvent and acid-contg. water at specified proportion. CONSTITUTION:The objective composition comprising (A) a silane compound mixture composed of (1) a silane compound of formula I (R<4> is 1-5C alkyl) and (2) a second silane compound of formula II, III or IV (R<2>-R<4> are each the same as R<1>; Y<1>-Y<6> are each organic group) at the molar ratio (l)/(2) of (80:20) to (20:80), (B) a heteropoly-acid (salt) such as phosphotungstic acid, (C) an organic solvent such as methanol, and (D) water containing 0.01-5wt.% of an acid such as hydrochloric acid, at the molar ratio A/B/C/D of 1:(0.001-0.15):(10-100):(1-30).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antistatic coating composition for plastics.

[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・ 29H
₂ O) is dissolved in a solution of a hydrolyzate of tetraethoxysilane to form a film 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 low 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 tetraethoxysilane hydrolyzate has a drawback that it cannot be applied to plastic products because cracks occur in the film when applied on a plastic plate to form a film. .

In the above film, 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 occurs due to the scattering of light by the fine particles and the transparency is impaired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and an object thereof is to provide a plastic product with a transparent and high antistatic effect and an antistatic effect even in low humidity. Accordingly, it is an object of the present invention to provide an antistatic coating composition capable of easily forming a crack-free coating.

[0008]

The first antistatic coating composition for plastics of the present invention comprises a specific silane compound mixture (a), a heteropolyacid or a salt thereof (b), an organic solvent (c) and It is characterized by comprising water (d) containing an acid.

The first antistatic coating composition will be described below.

The silane compound mixture (a) used in the present invention comprises a silane compound A represented by the following general formula [I]:

[Chemical 4] A silane compound B represented by the following general formula [II], [III] or [IV].

[Chemical 5]

In the formula, R ¹ , R ² , R ³ and R ⁴ represent an alkyl group having 1 to 5 carbon atoms. However, when the carbon number increases, the stability of the coating composition decreases and the long-term storage stability becomes long. Is deteriorated, the carbon number is limited to 1 to 5. R ¹ , R ² , R ³
Examples of R ⁴ and R ⁴ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec.
Examples include -butyl group and tert-butyl group. Y
¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ represent an organic group, for example, saturated hydrocarbon group (alkyl group, substituted alkyl group, etc.), unsaturated hydrocarbon group (allyl group, vinyl group, etc.) ), An aromatic hydrocarbon group (phenyl group, naphthyl group, etc.), an epoxy group, an amino group and the like.

As the compound represented by the general formula [I],
For example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-
Propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane and the like can be mentioned.

As the compound represented by the general formula [II],
For example, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-propoxysilane, monomethyltri-iso-propoxysilane, monomethyltri-n-butoxysilane, monomethyltri-
sec-Butoxysilane, monomethyltri-tert-
Butoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, epoxytriethoxysilane, aminotriethoxysilane,
Examples thereof include acryloxytriethoxysilane.

Examples of the compound represented by the general formula [III] include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane and dimethyldi-n.
-Butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, diethyldiethoxysilane, ethylvinyldiethoxysilane, ethylphenyldiethoxysilane, methylepoxydiethoxysilane, methylaminodiethoxysilane, methylacryloxy Examples thereof include diethoxysilane.

As the compound represented by the general formula [IV],
For example, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-iso-propoxysilane, trimethylmono-n-butoxysilane, trimethylmono-
sec-Butoxysilane, trimethylmono-tert-
Examples include butoxysilane, triethylethoxysilane, diethylvinylethoxysilane, diethylphenylethoxysilane, and methylethylepoxytriethoxysilane.

As the silane compound A and the silane compound B, compounds within the range defined above may be used alone or in combination of two or more kinds. Among many combinations of the silane compound A and the silane compound B constituting the silane compound mixture of the present invention, a combination of tetraethoxysilane as the silane compound A and methyltrimethoxysilane as the silane compound B is particularly preferable.

In the present invention, the molar ratio of silane compound A: silane compound B is limited to 80:20 to 20:80. If the molar ratio is greater than 80:20, cracks tend to occur in the coating, and if it is less than 20:80, the coating becomes opaque.

The heteropolyacid or salt (b) thereof used in the present invention is boron, aluminum, gallium, silicon, germanium, cesium, titanium, zirconium,
Antimony, bismuth, rhodium, copper, platinum, phosphorus,
Consists of 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. Examples of the salt include sodium salt and ammonium salt.

Examples of the heteropolyacid include linthanum.
Gustonic acid (H₃PW₁₂O₄₀・ NH ₂O), phosphorus morib
Denic acid (H₃PMo₁₂O₄₀・ NH₂O), Katangs
Tenic acid (H₃SiW₁₂O₄₀・ NH₂O) etc.
It Heteropolyacid salts include, for example, phosphorus molybdate.
Sodium vanadate acid (Na_3-XPMo_12-XV_XO
₄₀・ NH₂O). These heteropolyacids
Or the salts thereof may be used alone or in combination of two or more kinds.
May be done

The heteropolyacid or its salt (b) used in the present invention is 0.001 to 0 with respect to 1 mole of the total moles of the silane compound A and the silane compound B constituting the silane compound mixture (a). 0.15 mol is added.
If it is added in an amount of less than 0.001 mol, the film will not be provided with sufficient conductivity to prevent electrification. If it is added in an amount of more than 0.15 mol, the film will be opaque. The preferred addition amount is 0.01 to 1 mol with respect to the total mol number of the silane compound mixture.
It is in the range of 0.10 mol.

The organic solvent (c) used in the present invention is compatible with the silane compound mixture (a) and the acid-containing water (d), and dissolves the heteropolyacid or its salt (b). It is not particularly limited as long as it is, for example, methyl alcohol, ethyl alcohol,
Alcohols such as isopropyl alcohol and butyl alcohol, ketones such as acetone and methyl ethyl ketone,
Tetrahydrofuran etc. are mentioned, Especially methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferable. These may be used alone or in combination of two or more.

The organic solvent (c) is used in an amount of 10 to 10 with respect to 1 mole of the total moles of the silane compound mixture (a).
It is added in a proportion of 0 mol. With less than 10 moles added,
It is difficult to mix the coating composition uniformly, resulting in a heterogeneous composition, and when it is added in excess of 100 mol, the solid content concentration of the coating composition becomes too low, and sufficient charging is obtained when a coating film is formed. You cannot get preventive power. The preferable addition amount is 20 to 50 with respect to 1 mol of the total mol number of the silane compound mixture.
It is in the molar range.

Water (d) containing the acid used in the present invention
In the above, since the acid is added as a catalyst for the hydrolysis of the silane compound, the acid may be contained in the water to be added in a proportion of 0.01 to 5% by weight. If it is less than this proportion, the effect as a catalyst cannot be expected, and if it is more than this proportion, the coating becomes inhomogeneous. The acid is not particularly limited, and either an inorganic acid or an organic acid can be used. Examples of the acid include hydrochloric acid and sulfuric acid. In addition, since water (d) is also added for the above hydrolysis, 1 is used for 1 mol of the total number of moles of the silane compound mixture (a).
It is added in a proportion of -30 mol. If the amount is less than 1 mol, sufficient hydrolysis is unlikely to occur, and if the amount exceeds 30 mol, the compatibility with the coating composition is poor. The preferable addition amount is 3 to 10 mol per mol of the silane compound.

The method for producing the antistatic coating composition for plastics of the present invention is not particularly limited, and examples thereof include a method of mixing the above-mentioned constituent materials at once and a method of dividing a specific constituent material. After mixing, there may be mentioned a method of adding and mixing the remaining constituent materials. For example, the silane compound A and the silane compound B are mixed, an organic solvent is added to this mixture, and the mixture is stirred. For the decomposition, water containing an acid is added as a catalyst to obtain a hydrolyzate of the silane compound. To this solution, a mixture of one or more heteropolyacids or salts thereof is added and mixed by stirring to obtain the coating composition.

The second antistatic coating composition for plastics of the present invention comprises a specific silane compound mixture (a), a perchloric acid compound (b), an organic solvent (c) and water (d) containing an acid. ) Consists of.

The second antistatic coating composition will be described below.

The silane compound mixture (a) used in the present invention is the same as that used in the first composition.

Perchloric acid compound (b) used in the present invention
Is a compound represented by the general formula XClO ₄ (wherein X is a hydrogen atom, a monovalent metal atom, NH ₄ or a fourth group represented by the following general formula [V]).
It is a compound represented by ammonium).

[Chemical 6] Examples of the monovalent metal atom include lithium, sodium and potassium. Quaternary ammonium substituent, M
¹ , M ² , M ³ and M ⁴ are alkyl groups having 1 to 20 carbon atoms. Examples of the perchloric acid compound (b) include perchloric acid, lithium perchlorate, ammonium perchlorate, tetramethylammonium perchlorate, and tetraethylammonium perchlorate.

Perchloric acid compound (b) used in the present invention
Is added in a proportion of 0.005 to 0.32 mol per 1 mol of the total number of mols of the silane compound mixture (a). If it is added in an amount of less than 0.005 mol, sufficient electrical conductivity for antistatic cannot be imparted to the coating. If it is added in excess of 0.32 mol, the coating becomes cloudy and opaque.

The organic solvent (c) used in the present invention is compatible with the silane compound mixture (a) and the acid-containing water (d) and dissolves the perchloric acid compound (b). If there is no particular limitation, for example,
It is similar to that used in the first composition.

The ratio of the organic solvent (c) added to the silane compound mixture (a) is also the same as in the first composition. The water (d) containing an acid used in the present invention has the same purpose and concentration as those of the first composition.

The method for producing the antistatic coating composition of the present invention is not particularly limited, except that the heteropolyacid or salt thereof in the first composition is used in place of the perchloric acid compound. Similar to the first composition.

By the way, the transparent antistatic coating has high hardness and abrasion resistance in addition to transparency and conductivity.
A film having high scratch resistance may be required. The third and fourth antistatic coating compositions for plastics of the present invention are antistatic coating compositions capable of easily forming a coating having high scratch resistance in addition to transparency and conductivity on a plastic product. It is to provide things.

The third antistatic coating composition for plastics of the present invention comprises a specific silane compound mixture (a), a heteropolyacid or a salt thereof (b), an organic solvent (c), and water containing an acid ( d) and a metal alkoxide (e).

The third antistatic coating composition will be described below.

The silane compound mixture (a) used in the present invention is the same as that used in the first composition.

The metal alkoxide (e) used in the present invention includes a zirconium tetraalkoxide represented by the general formula Zr (OR ⁵ ) ₄ , a titanium tetraalkoxide represented by the general formula Ti (OR ⁶ ) ₄ and a general formula. Al
It is at least one metal alkoxide selected from the group consisting of aluminum trialkoxides represented by (OR ⁷ ) ₃ .

Zr (OR ⁵ ) ₄ zirconium tetraalkoxide, Ti (OR ⁶ ) ₄ titanium tetraalkoxide and Al (OR ⁷ ) ₃ aluminum trialkoxide R ⁵ , R ⁶ And R ⁷ represents an alkyl group having 1 to 5 carbon atoms. However, when the carbon number 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. To be done. R
Examples of ⁵ , R ⁶ and R ⁷ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group.

Examples of zirconium tetraalkoxides include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetra-iso-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide. , Zirconium tetra-
tert-butoxide and the like, particularly zirconium tetra-n-butoxide, zirconium tetra-is.
O-propoxide is preferred.

As the titanium tetraalkoxide,
For example, titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide,
Titanium tetra-iso-propoxide, titanium tetra-n-butoxide, titanium tetra-sec-
Examples thereof include butoxide and titanium tetra-tert-butoxide, and titanium tetra-n-butoxide and titanium tetra-iso-propoxide are particularly preferable.

As aluminum trialkoxide,
For example, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide,
Aluminum tri-iso-propoxide, aluminum tri-n-butoxide, aluminum tri-sec-
Examples thereof include butoxide and aluminum tri-tert-butoxide, and aluminum tri-sec-butoxide and aluminum tri-iso-propoxide are particularly preferable.

The ratio of the total number of moles of the silane compound mixture (a) of the present invention to the number of moles of the metal alkoxide (e) is 50:
50-99: 1. When the ratio is less than 50:50, the film-forming property of the composition is deteriorated and the resulting coating film is apt to crack, and when it exceeds 99: 1, the effect of adding the metal alkoxide is not obtained. In the case of zirconium tetraalkoxide as the metal alkoxide, this molar ratio is preferably 60:40 to 99: 1,
Particularly preferred is 0:30 to 95: 5. When titanium tetraalkoxide is used as the metal alkoxide, the molar ratio is particularly preferably 70:30 to 95: 5. When aluminum trialkoxide is used as the metal alkoxide, this molar ratio is preferably 70:30 to 99: 1, and particularly preferably 75:25 to 95: 5.

The heteropolyacid or salt (b) thereof used in the present invention is the same as that used in the first composition,
It is the same.

The heteropolyacid or its salt (b) used in the present invention is 0.001 with respect to 1 mole of the total number of moles of the silane compound mixture (a) and the number of moles of the metal alkoxide (e). It is added in a proportion of 0.15 mol.
If it is added in an amount of less than 0.001 mol, the film will not be provided with sufficient conductivity to prevent electrification. If it is added in an amount of more than 0.15 mol, the film will be opaque. The preferable addition amount is 0.01 to 0. 0, based on 1 mole of the total number of moles of the silane compound mixture (a) and the number of moles of the metal alkoxide (e).
It is in the range of 10 moles.

The organic solvent (c) used in the present invention is compatible with the silane compound mixture (a), the acid-containing water (d) and the metal alkoxide (e), and the heteropolyacid or its salt ( It is not particularly limited as long as b) shows solubility, 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. Especially, methyl alcohol, ethyl alcohol and isopropyl alcohol are preferable. These may be used alone or in combination of two or more.

The organic solvent (c) is added in a proportion of 10 to 100 moles based on 1 mole of the total number of moles of the silane compound mixture (a) and the number of moles of the metal alkoxide (e). If it is added in an amount of less than 10 mol, the coating composition is difficult to mix uniformly, resulting in a heterogeneous composition.
If it is added in excess of the molar amount, the solid content concentration of the coating composition becomes too small, and a sufficient antistatic ability cannot be obtained when formed into a film. The preferable addition amount is in the range of 20 to 50 mol with respect to 1 mol as the sum of the total number of mols of the silane compound mixture and the number of mols of the metal alkoxide.

Water (d) containing the acid used in the present invention
In the above, since the acid is added as a catalyst for the hydrolysis of the silane compound and the metal alkoxide, it may be contained in the water to be added in a proportion of 0.001 to 5% by weight. If it is less than this proportion, the effect as a catalyst cannot be expected, and if it is more than this proportion, the coating becomes inhomogeneous. The acid is the same as that used in the first composition.
Further, since water (d) is also added for the above-mentioned hydrolysis, it is not possible to adjust the total number of moles of the silane compound mixture (a) and the number of moles of the metal alkoxide (e) to 1 mole to 0.
It is added at a ratio of 1 to 5 mol. When less than 0.1 mol is added, sufficient hydrolysis is unlikely to occur, and when more than 5 mol is added, the hydrolysis rate is too fast, and the storage stability of the obtained coating composition decreases, Cracks may occur when the coating is cured. The preferable addition amount is 1 to 3 mol with respect to 1 mol of the total number of mols of the silane compound mixture and the number of mols of the metal alkoxide. In particular, in the case of aluminum trialkoxide as the metal alkoxide, 0.1 to 3 mol is preferable, and 1 to 2 mol is particularly preferable, relative to 1 mol of the total number of moles of the silane compound mixture and the number of moles of the metal alkoxide. .

The method for producing the antistatic coating composition for plastics of the present invention is not particularly limited, and examples thereof include a method of mixing the above-mentioned constituent materials at once and a method of dividing a specific constituent material. After mixing, there may be mentioned a method of adding and mixing the remaining constituent materials. For example, the silane compound A and the silane compound B are mixed, an organic solvent is added to this mixture, and the mixture is stirred. For the decomposition, water containing an acid is added as a catalyst to obtain a hydrolyzate of the silane compound. A metal alkoxide is added to this solution to obtain a Si-metal hydrolyzate. In this solution,
A mixture of one or more of heteropolyacids or salts thereof is added and mixed by stirring to obtain the coating composition.

The fourth antistatic coating composition for plastics of the present invention comprises a specific silane compound mixture (a), a perchloric acid compound (b), an organic solvent (c) and an acid-containing water (d). ) And a metal alkoxide (e).

The fourth antistatic coating composition will be described below.

The silane compound mixture (a) used in the present invention is the same as that used in the first composition.

The metal alkoxide (e) used in the present invention is the zirconium tetraalkoxide represented by the general formula Zr (OR ⁵ ) ₄ and the general formula Ti, similar to those used in the third composition. Titanium tetraalkoxide represented by (OR ⁶ ) ₄ and the general formula Al (OR
⁷ ) At least one metal alkoxide selected from the group consisting of aluminum trialkoxides represented by ₃ .

Zr (OR ⁵ ) ₄ zirconium tetraalkoxides, Ti (OR ⁶ ) ₄ titanium tetraalkoxides and Al (OR ⁷ ) ₃ aluminum trialkoxides R ⁵ and R ⁶ And R ⁷ represent an alkyl group having 1 to 5 carbon atoms, like the one used in the third composition, but when the number of carbon atoms increases, the stability of the coating composition decreases and the long-term Since the storability deteriorates, the carbon number is limited to 1-5. R ⁵ , R
Examples of ⁶ and R ⁷ include a methyl group, an ethyl group, n-
Propyl group, iso-propyl group, n-butyl group, se
Examples thereof include c-butyl group and tert-butyl group.

Examples of the zirconium tetraalkoxide, titanium tetraalkoxide and aluminum trialkoxide include those similar to those used in the third composition.

The ratio of the total number of moles of the silane compound mixture (a) of the present invention to the number of moles of the metal alkoxide (e) is 50:
50-99: 1. When the ratio is less than 50:50, the film-forming property of the composition is deteriorated and the resulting coating film is apt to crack, and when it exceeds 99: 1, the effect of adding the metal alkoxide is not obtained. In the case of zirconium tetraalkoxide as the metal alkoxide, this molar ratio is preferably 60:40 to 99: 1,
Particularly preferred is 0:30 to 95: 5. When titanium tetraalkoxide is used as the metal alkoxide, the molar ratio is particularly preferably 70:30 to 95: 5. When aluminum trialkoxide is used as the metal alkoxide, this molar ratio is preferably 70:30 to 99: 1, and particularly preferably 75:25 to 95: 5.

Perchloric acid compound (b) used in the present invention
Are similar to those used in the second composition.

Perchloric acid compound (b) used in the present invention
Is 0.0 with respect to 1 mole of the total number of moles of the silane compound mixture (a) and the number of moles of the metal alkoxide (e).
It is added in a proportion of 05 to 0.32 mol. If it is added in an amount of less than 0.005 mol, sufficient electrical conductivity for antistatic cannot be imparted to the coating, and if it is added in excess of 0.32 mol, the coating becomes opaque.

The organic solvent (c) used in the present invention is compatible with the silane compound mixture (a), the acid-containing water (d) and the metal alkoxide (e), and the perchloric acid compound (b). Is not particularly limited as long as it dissolves a), and examples thereof include those similar to those used in the third composition.

The ratio of the above organic solvent (c) added to 1 mole of the total number of moles of the silane compound mixture (a) and the number of moles of the metal alkoxide (e) is also the third composition. Is the same as.

Water (d) containing the acid used in the present invention
Also, the purpose and concentration of use are the same as those of the third composition.

The method for producing the antistatic coating composition for plastics of the present invention is not particularly limited, and the heteropolyacid or salt thereof in the third composition is used in place of the perchloric acid compound. Except for this, it is the same as the third composition.

The constitutions of the first to fourth antistatic coating compositions for plastics of the present invention are as described above, but a hydrophilic polymer such as polyethylene glycol is added to further improve the conductivity. Good. In addition, in order to improve the film forming property, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose,
A cellulose derivative such as hydroxyethyl cellulose or 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 for plastics of the present invention 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 for plastics of the present invention is applied to a plastic product and dried to form an antistatic coating. The coating method is not particularly limited, for example, brush, spray coating, dip coating, spin coating, roll coating,
A coating method such as flow coating may be used.

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, and examples thereof include a molded product and a film.

The film obtained from the antistatic coating composition of the present invention has a transparency because the heteropolyacid or its salt or the perchloric acid compound is present in the film in a uniform ionic state. High and conductive. Further, even if it is rubbed strongly with a hard material such as steel wool, it is difficult to be scratched, and it is difficult for the scratches to deteriorate the appearance. In particular,
The coating films obtained from the third and fourth antistatic coating compositions have high hardness and abrasion resistance and excellent abrasion resistance.

[0068]

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 are as follows.

(1) Crack test The obtained antistatic coating composition was added with 50 × 100 mm (thickness 2 m
m) Polycarbonate substrate (Lexan sheet 9034 manufactured by Asahi Glass Co., Ltd.) was dipped and pulled up at a speed of 300 mm / min.
After drying at room temperature for 60 minutes, it was cured at 110 ° C. for 60 minutes to form an antistatic coating on the substrate to prepare an evaluation sample, and the presence or absence of cracks was examined by visual observation. (Judgment Criteria) O: No cracks are observed. X: A crack is observed.

(2) Surface Resistance An evaluation sample prepared in the same manner as the above-mentioned crack test was performed using the obtained antistatic coating composition,
Using STACK TR-3 manufactured by Tokyo Electronics Co., Ltd., surface resistance was measured and evaluated by a two-terminal method in an atmosphere of relative humidity of 30% or 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 an evaluation, a spectrophotometer UV-3101PC manufactured by Shimadzu Corporation 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-mentioned crack test was rubbed with a woolen fabric and cut into 1 × 3 mm PET film ( A thickness of 100 μm) and a distance of about 1 cm, P
The adherence of the ET film was evaluated according to the following criteria. (Judgment Criteria) A: No adhesion to the surface. Δ: A little adhered to the surface. X: Many adhere 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: No scratch is given to the surface even with strong rubbing. Δ: The surface is slightly scratched when strongly rubbed. X: The surface is markedly damaged even with weak friction.

(Examples 1 to 9) The predetermined amount of ethyl alcohol shown in Table 1 was supplied to a glass beaker, the predetermined amounts of silane compound A and silane compound B shown in Table 1 were added, and Table 1 was further added. After adding a predetermined amount of water containing hydrochloric acid having a predetermined concentration shown in Table 1, the mixture was stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an alcohol solution of a silane compound.

A predetermined amount of the heteropolyacid shown in Table 1 was added to the obtained alcohol solution, and the mixture was further stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an antistatic coating composition. Since the heteropolyacid contains water of hydration, water of hydration is inevitably added to this composition as the heteropolyacid is added. Therefore, the predetermined amount of water shown in Table 1 and Tables 2 and 4 described later is a value including the amount of hydration water.

Using the resulting antistatic coating composition,
Each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 1.

Example 10 0.36 g of sodium vanadate (manufactured by Wako Pure Chemical Industries, Ltd.) and 7 g of phosphomolybdic acid hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 10 g of distilled water at 3 ° C. at 25 ° C. Sodium vanadate phosphomolybdate was prepared by time mixing, dried at 80 ° C. and water evaporated. The antistatic coating composition was prepared in the same manner as in Example 1 except that the obtained sodium vanadate phosphomolybdate was used in place of the heteropolyacid of Example 1 in the proportions shown in Table 1. Got Using the obtained antistatic coating composition, each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 1.
It was shown to.

[0079]

[Table 1]

Comparative Examples 1 to 6 Using the silane compound A and silane compound B shown in Table 2, ethyl alcohol, water containing hydrochloric acid and heteropolyacid, an antistatic coating composition was prepared in the same manner as in Example 1. Obtained. Using the obtained antistatic coating composition, based on the above measurement method, each physical property was measured,
The results are shown in Table 2.

Comparative Example 7 An antistatic coating was prepared in the same manner as in Comparative Example 5 except that the inorganic salt LiNO ₃ was used in the prescribed amount ratio shown in Table 2 instead of the heteropolyacid of Comparative Example 5. A composition was obtained. Using the obtained antistatic coating composition, each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 2.
It was shown to.

[0082]

[Table 2]

(Examples 11 to 15) A predetermined amount of ethyl alcohol shown in Table 3 was supplied to a glass beaker, the predetermined amounts of silane compound A and silane compound B shown in Table 3 were added, and further, Table 3 After adding a predetermined amount of water containing hydrochloric acid of the specified concentration shown in Table 3, the mixture was stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an alcohol solution of a silane compound.

A predetermined amount of perchloric acid compound shown in Table 3 was added to the obtained alcohol solution, and the mixture was further stirred at room temperature for 3 hours.
The mixture was stirred at a stirring speed of 800 rpm to obtain an antistatic coating composition.

Using the obtained antistatic coating composition,
Each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 3.

Comparative Examples 8 to 11 Using the silane compound A and silane compound B shown in Table 3, water containing ethyl alcohol and hydrochloric acid, and a perchloric acid compound, an antistatic coating composition was prepared in the same manner as in Example 11. I got a thing. Using the obtained antistatic coating composition, each physical property was measured based on the above-mentioned measurement methods, and the results are shown in Table 3.

[0087]

[Table 3]

(Examples 16 to 18) The predetermined amount of ethyl alcohol shown in Table 4 was supplied to a glass beaker, the predetermined amounts of silane compound A and silane compound B shown in Table 4 were added, and Table 4 was further added. After adding a predetermined amount of water containing hydrochloric acid having the specified concentration shown in Table 4, the mixture was stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an alcohol solution of a silane compound.

A predetermined amount of zirconium tetra-n-butoxide shown in Table 4 was added to the obtained alcohol solution, and the mixture was further stirred at room temperature for 3 hours at a stirring speed of 800 rpm.
A predetermined amount of the heteropolyacid shown in Table 4 was added to this solution, and the mixture was further stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an antistatic coating composition.

Using the obtained antistatic coating composition,
Each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 4.

Examples 19 to 21 Similar to Example 16 except that a predetermined amount of titanium tetra-n-butoxide shown in Table 4 was used instead of the zirconium tetra-n-butoxide of Example 16. To obtain an antistatic coating composition.

Using the resulting antistatic coating composition,
Each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 4.

(Examples 22-24) Example 16 was repeated except that the zirconium tetra-n-butoxide of Example 16 was replaced with the predetermined amount of aluminum tri-iso-propoxide shown in Table 4. Similarly, an antistatic coating composition was obtained.

Using the resulting antistatic coating composition,
Each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 4.

[0095]

[Table 4]

(Examples 25 to 27) The predetermined amount of ethyl alcohol shown in Table 5 was supplied to a glass beaker, the predetermined amount of silane compound A and silane compound B shown in Table 5 were added, and further, Table 5 was added. After adding a predetermined amount of water containing hydrochloric acid of the specified concentration shown in Table 5, the mixture was stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an alcohol solution of a silane compound.

A predetermined amount of zirconium tetra-n-butoxide shown in Table 5 was added to the obtained alcohol solution, and the mixture was further stirred at room temperature for 3 hours at a stirring speed of 800 rpm.
A predetermined amount of the perchloric acid compound shown in Table 5 was added to this solution, and the mixture was further stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an antistatic coating composition.

Using the obtained antistatic coating composition,
Each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 5.

(Examples 28 to 30) The same as Example 25 except that a predetermined amount of titanium tetra-n-butoxide shown in Table 5 was used in place of the zirconium tetra-n-butoxide of Example 25. To obtain an antistatic coating composition.

Using the resulting antistatic coating composition,
Each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 5.

(Examples 31 to 33) The same procedures as in Example 25 except that a predetermined amount of aluminum tri-iso-propoxide shown in Table 5 was used in place of the zirconium tetra-n-butoxide of Example 25. Similarly, an antistatic coating composition was obtained.

Using the obtained antistatic coating composition,
Each physical property was measured based on the above-mentioned measuring method, and the results are shown in Table 5.

[0103]

[Table 5]

[0104]

The composition of the first antistatic coating composition for plastics of the present invention is as described above, and the specific silane compound mixture, the heteropolyacid or its salt, the organic solvent, and the water containing the acid are used. Since a specific amount of is added, it is possible to easily form a transparent coating having a high antistatic effect and an antistatic effect even in low humidity on a plastic product without cracks.

The composition of the second antistatic coating composition for plastics of the present invention is as described above, and a specific silane compound mixture, a perchloric acid compound, an organic solvent and water containing an acid are contained in specific amounts. Since it is blended, it is possible to easily form a transparent coating having a high antistatic effect and an antistatic effect even at low humidity, which is free from cracks.

The composition of the third antistatic coating composition for plastics of the present invention is as described above, and the specific silane compound mixture, heteropolyacid or salt thereof, organic solvent, water containing acid, and metal. Since a specific amount of alkoxide is blended, the plastic product is transparent and has a high antistatic effect, and also has an antistatic effect even in low humidity, and it has no cracks and is excellent in hardness and abrasion resistance. A coating having high properties can be easily formed.

The composition of the fourth antistatic coating composition for plastics of the present invention is as described above, and the specific silane compound mixture, perchloric acid compound, organic solvent, water containing acid, and metal alkoxide are used. Since it is blended in a specific amount, plastic products are transparent and have a high antistatic effect, have an antistatic effect even at low humidity, and have no cracks, and have excellent scratch resistance and hardness and abrasion resistance. A high-quality coating can be easily formed.

Claims (4)

[Claims] 1. A silane compound A represented by the following general formula [I]: (Wherein R ¹ is an alkyl group having 1 to 5 carbon atoms) and a silane compound B represented by the following general formula [II], [III] or [IV]: (In the formula, R ² , R ³ , and R ⁴ are alkyl groups having 1 to 5 carbon atoms, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are organic groups) Silane compound A: Silane compound B The molar ratio of 80: 20-2
Silane compound mixture of (a) consisting of 0:80 silane compound mixture (b) heteropolyacid or salt thereof (c) organic solvent, and (d) water containing acid in a proportion of 0.01 to 5% by weight Total moles of mixture:
The molar ratio of (b) :( c) :( d) is 1: 0.001.
The composition for antistatic coating for plastics is characterized in that the proportion is from 0.15: 10 to 100: 1 to 30. 2. A silane compound A represented by the general formula [I] according to claim 1, and a general formula [II] according to claim 1.
A silane compound B represented by [III] or [IV], and the molar ratio of silane compound A: silane compound B is 8
Silane compound mixture of 0:20 to 20:80 (b) Perchloric acid compound represented by the general formula XClO ₄ (wherein, X is a hydrogen atom, a monovalent metal atom, NH ₄ or the following general formula [V ] Quaternary ammonium represented by the following] (In the formula, M ¹ , M ² , M ³ and M ⁴ are alkyl groups having 1 to 20 carbon atoms) (c) Organic solvent, and (d) Water containing 0.01 to 5% by weight of acid And the total number of moles of the silane compound mixture of (a):
The molar ratio of (b) :( c) :( d) is 1: 0.005.
The antistatic coating composition for plastics is characterized in that the proportion is from 0.32: 10 to 100: 1 to 30. 3. A silane compound A represented by the general formula [I] according to claim 1, and a general formula [II] according to claim 1.
A silane compound B represented by [III] or [IV], and the molar ratio of silane compound A: silane compound B is 8
Silane compound mixture of 0:20 to 20:80 (b) Heteropoly acid or salt thereof, (c) Organic solvent, (d) Water containing 0.001 to 5% by weight of acid,
And (e) a zirconium tetraalkoxide represented by the general formula Zr (OR ⁵ ) ₄ , a titanium tetraalkoxide represented by the general formula Ti (OR ⁶ ) ₄ and a general formula Al (O
An aluminum trialkoxide represented by R ⁷ ) ₃ (in the formula, R ⁵ , R ⁶ , and R ⁷ are alkyl groups having 1 to 5 carbon atoms) and at least one metal alkoxide selected from the group consisting of (a The ratio of the total number of moles of the silane compound mixture of (4) to the number of moles of the metal alkoxide of (e) is 50: 50-9.
9: 1 and the sum of the total number of moles of the silane compound mixture of (a) and the number of moles of the metal alkoxide of (e):
The molar ratio of (b) :( c) :( d) is 1: 0.001.
The composition for antistatic coating for plastics is characterized in that the ratio is from 0.15: 10 to 100: 0.1-5. (A) A silane compound A represented by the general formula [I] according to claim 1, and a general formula [II] according to claim 1.
A silane compound B represented by [III] or [IV], and the molar ratio of silane compound A: silane compound B is 8
A silane compound mixture of 0:20 to 20:80 (b) A perchloric acid compound represented by the general formula XClO ₄ (wherein, X is a hydrogen atom, a monovalent metal atom, NH ₄ or the compound of claim 2). Quaternary ammonium represented by the general formula [V]) (c) Organic solvent, (d) Water containing acid in a proportion of 0.001 to 5% by weight,
And (e) a zirconium tetraalkoxide represented by the general formula Zr (OR ⁵ ) ₄ , a titanium tetraalkoxide represented by the general formula Ti (OR ⁶ ) ₄ and a general formula Al (O
An aluminum trialkoxide represented by R ⁷ ) ₃ (in the formula, R ⁵ , R ⁶ , and R ⁷ are alkyl groups having 1 to 5 carbon atoms) and at least one metal alkoxide selected from the group consisting of (a The ratio of the total number of moles of the silane compound mixture of (4) to the number of moles of the metal alkoxide of (e) is 50: 50-9.
9: 1 and the sum of the total number of moles of the silane compound mixture of (a) and the number of moles of the metal alkoxide of (e):
The molar ratio of (b) :( c) :( d) is 1: 0.005.
The composition for antistatic coating for plastics is characterized in that the proportion is from 0.32: 10 to 100: 0.1 to 5.