JPH0446910A - Conductive material - Google Patents

Abstract

PURPOSE:To obtain a conductive material which can be easily cured by drying or heating, has the resistance to water or an organic solvent, and comprising an organic polymer comprising two kinds of specified structural units. CONSTITUTION:A conductive material comprising an organic polymer comprising structural units of formula I (wherein R1 is H or methyl; and X<+> is a cation) and structural units of formula II. The ratio of the structural units of formula I to the structural units of formula II is usually (10:90) to (95:5). When the content of the structural units of formula II is below 5%, the liquid resistance after crosslinking and curing by drying and/or heating is insufficient. The weight-average molecular weight of the organic polymer is usually 500-500,000. When it is below 500, the liquid resistance of the cured product is insufficient, and when it is above 500,000, the viscosity is so high that the operability such as applicability is lowered.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to conductive materials, particularly conductive materials that can be easily cured by drying and/or heat to obtain water resistance and/or organic solvent resistance. Regarding materials.

[Conventional technology] Conventionally, in order to prevent the charging of base materials such as paper, various recording papers, organic resin films, organic resin molded bodies, and inorganic molded bodies, the use of ionic or nonionic rich or low molecular weight compounds has been used. An antistatic agent is used.

[Problems to be Solved by the Invention] These); Since anti-stain agents are usually water-soluble, they do not become sticky due to moisture absorption, and are easily removed when they come into contact with water after being applied or mixed and molded, and do not have the desired antistatic effect. Problems such as not being able to obtain

[Means for Solving the Problem] The present inventors aim to obtain a conductive material that can be easily cured by drying and/or heat after application, and can have water resistance and/or organic solvent resistance. As a result of extensive Q'Q research, we have arrived at the present invention.

That is, the present invention provides a structural unit represented by the general formula (+) (wherein R+ represents a hydrogen atom or a methyl group, and X4 represents a cation) and a general formula (
2) It is a conductive material characterized by containing an organic polymer having the structural unit shown below.

In the structural unit represented by the general formula (ri), the cation of Examples include alkali metal ions (sodium ions, potassium ions, etc.).Ammonium ions, tetramethylammonium ions, and alkali metal ions have excellent heat resistance, and asymmetric tetraalkylammonium ions (methyltriethylammonium ions, dimethyldiethyl Ammonium ions (such as ammonium ions and trimethylammonium ions) have excellent compatibility with solvents and other components.Ammonium ions, which are non-metallic cations, are also suitable for applications that dislike alkali metal ions, such as electrical and electronic applications. is preferred.

The composition ratio of the structural units represented by general formula (1) and general formula (2) is usually 10:90 to 95:5, preferably 20:80 to 95:5. If the composition ratio of the structural units represented by general formula (2) is 5%, drying and/or
Alternatively, the liquid resistance becomes insufficient due to crosslinking and curing during thermal crosslinking.

Organic polymers containing the structural units represented by general formulas (1) and (2) include other structural units derived from monomers having vinyl groups (styrene units, α-methylstyrene units, vinyl acetate units, etc.). ester units, etc.). The ratio of the sum of these structural units to the sum of the structural units represented by general formula (1) and general formula (2) is usually 0:
100-80:20, preferably 0:100-7
It was 0:30. When the total ratio of the structural units represented by the general formula (1) and the general formula (2) is less than 20, the conductivity and liquid resistance will decrease.

In organic polymers containing structural units represented by general formulas (1) and (2), each structural unit may be bonded to blocks or randomly bonded. Moreover, the weight average molecular weight is usually 500 to 500,000, preferably 3,000 to +50,000. Weight average molecular weight is 5
If it is less than 00, the liquid resistance of the cured product will be insufficient, and so
If it exceeds oooo, for example, when the material of the present invention is used in the form of a solution, the viscosity becomes high, and the operability such as the applicability decreases.

Organic polymers having structural units represented by the general formula (2) and the general formula (2) can be prepared using a sulfonating agent such as sulfuric anhydride, etc. After sulfonation with alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.) or alkylammonium hydroxides (tetramethylammonium hydroxide, tetraethylammonium hydroxide, methyltetraethylammonium hydroxide, etc.) ) etc. by hydrolyzing the acetate ester moiety, X
It is possible to obtain those in which the I ion is an alkali metal ion or an alkylammonium ion. In addition, by adjusting the sulfonation rate and hydrolysis rate, other structural units derived from vinyl group-containing monomers (styrene units, α-
It is also possible to obtain a percussion polymer containing methylstyrene units, vinyl acetate units, etc.).

When X4 is an ammonium ion, for example, after the above-mentioned sulfonation reaction, the acetate group is hydrolyzed under acidic conditions, and then reacted with ammonia to form a sulfonate, or the above-mentioned alkaline hydrolyzate After converting the sulfonic acid block into sulfonic acid under acidic conditions,
It can be obtained by converting it into a sulfonate with ammonia. Also, by this method, compounds in which X' is an alkylammonium ion can also be obtained.

Styrene sulfonic acid-vinyl alcohol copolymer and ammonium hydroxides (ammonium hydroxide, tetramethylammonium hydroxide,
For example, the reaction with a solution of styrene sulfonic acid-vinyl alcohol copolymer (water as a solvent, 2-dichloroethane, acetone, toluene, etc.) , benzene, etc.) and a mixed solvent of these solvents) and an aqueous or alcoholic solution of ammonium hydroxide are mixed, and usually □~too''c, 0.1~30
This can be carried out by stirring the reaction for a period of time. At this time, ammonia gas, ammonia aqueous solution, ammonia alcohol solution (methanol solution, ethanol solution, etc.), etc. can be used as ammonium hydroxide.

The reaction between styrene sulfonic acid-vinyl acetate copolymer and alkali metal hydroxides or alkylammonium hydroxides is usually carried out in the presence of water in a solution of styrene sulfonic acid-vinyl acetate copolymer (solvent Water, organic solvent [:1,2-dichloroethane,
Acetone, toluene, benzene, etc. or a mixed solvent of these solvents can be used) and an aqueous solution of an alkali metal hydroxide or an aqueous solution or an alcohol solution of an alkyl ammonium hydroxide.
The reaction is carried out at ~100°C with stirring for 0.1 to 30 hours.

The organic polymer having the structural units represented by the general formula (1) and the general formula (2), which is a product in each reaction, can be separated by precipitation using a poor solvent, and then made into a solution using a target solvent. It is also possible to obtain a desired solution by utilizing the difference in solubility or the difference in boiling point of the solvent.

This conductive material is mixed with water, organic solvents (dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, γ
- Butyrolactone, butyl alcohol, ethyl alcohol, isopropyl alcohol, methyl alfur, ethyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, etc.) and mixed solvents of these solvents can be used to create a solution that can be applied to various purposes. It can be used to prevent static electricity. The concentration of the solution is usually 5 to 60% by weight, preferably 1%
It is a 111% solution of 0 to 50 weight.

The method for using the conductive material of the present invention is to apply the solution to paper, various recording papers, organic resin films, punched resin moldings, etc.
A coating film thickness of 1 is applied onto a base material such as an inorganic molded body by spin foot coating, screen printing coating, spray coating, roll coating coating, dipping coating, bar coater coating, etc.
11 mm or less, then air drying and/or drying under reduced pressure, and if necessary, heating at a temperature of 300°C or less to advance crosslinking and improve water resistance and/or solvent resistance. can get. For heating, use a circulating furnace,
A hot plate, an infrared oven, a far-infrared oven, etc. can be used.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Styrene sulfonic acid-vinyl alcohol copolymer (styrene sulfonic acid content 80%, MW: 15000) l
25% aqueous ammonia G and Om I were added to a 30 ml solution of OG in dichloroethane, and the mixture was reacted with stirring at 50°C for 3ffiν, and then 30 ml of water was added. Dichloroethane and excess ammonia were removed under reduced pressure to obtain a conductive material solution, which is a solution of the material of the present invention.

Example 2 Styrene sulfonic acid-vinyl alcohol copolymer (styrene sulfonic acid content 60%, Mw-30000) I
Add 8 ml of 25% aqueous ammonia G to 30 ml of dichloroethane solution of C177, react with stirring at 50°C for 3 hours, add to 1 liter of acetone, precipitate the polymer, and quickly add 3 ml of water-dimethylformamide mixed solvent.
A conductive material solution, which is a solution of the material of the present invention, was obtained.

Example 3 Styrene sulfonic acid-styrene-vinyl alcohol copolymer (styrene sulfonic acid content 60%, vinyl alcohol content 20%, M w = 20000) 10
8.8 ml of 25% ammonia water was added to 30 ml of dichloroethane solution of g, and the reaction was stirred at 50°C for 3 hours.
In addition to 1 liter of acetone, the polymer was precipitated and then quickly dissolved in 30 ml of a water-dimethylformamide mixed solvent to obtain a conductive material solution, which is a solution of the material of the present invention.

Example 4 Styrene sulfonic acid-vinyl acetate copolymer (styrene sulfonic acid content 80%, Mw = 15000)
A solution of 2.55 g of sodium hydroxide in 20 ml of water was added to a solution of 10 g of dichloroethane in 30 ml, and the mixture was reacted with stirring at 50°C for 3 hours, then added to 1 liter of acetone to precipitate the polymer, which was quickly dissolved in water. A conductive material solution, which is a solution of the material of the invention, was obtained.

Example 5 Styrene sulfonic acid-vinyl acetate copolymer (styrene sulfonic acid content 60%, Mw = 30000)
A solution of 2.90 g of sodium hydroxide in 20 ml of water was added to a solution of IOg in 30 ml of dichloroethane, stirred and reacted at 50°C for 3 hours, and then added to IJ liter of acetone I.
After the polymer was precipitated, it was quickly dissolved in 30 ml of a water-dimethylformamide mixed solvent to obtain a conductive material solution, which is a solution of the material of the present invention.

Example 6 Styrene sulfonic acid-vinyl acetate copolymer (styrene sulfonic acid content 80%, Mw = 15000)
Add 23.3 ml of 25% tetramethylammonium hydroxide aqueous solution to 30 ml of lOH in dichloroethane.
1 and reacted with stirring at 50°C for 3 hours, then added to 2 liters of acetone to precipitate the polymer, and then quickly dissolved in 30 ml of a water-dimethylformamide mixed solvent to obtain a conductive material which is a solution of the material of the present invention. A solution was obtained.

Usage Example 1 The solution obtained in Example 1 was spin-coated onto a glass substrate to obtain a uniform coating film of 1.2 μm. This substrate was heated at 100° C. for 1 hour under nitrogen using a circulating air oven.

Table 1 shows the surface resistance values after being immersed in methanol for 60 seconds.

Use Examples 2 to 6 The solutions obtained in Examples 2 to 6 were evaluated in the same manner as in Use Example 1, and the results are shown in Table 1.

Comparative Example 1 10 g of poly(styrene sulfonic acid ammonium salt) (
MW=15000) and polyvinyl alcohol (Gohsenol NL-05, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.)2
g was dissolved in 35 ml of water, and spin coated onto a glass substrate to obtain a 1.2 μm coating film. This substrate was heated at 100° C. for 1 hour under nitrogen using a circulating oven.

Table 1 shows the surface resistance values after being immersed in methanol for 60 seconds.

Comparative Example 2 Poly(styrene sulfonic acid sodium salt) IOg(M
W = 15,000) and 2 g of Gohsenol GL-05 (manufactured by Polyvinyl Alcohol Synthetic Chemical Industry Co., Ltd.) were dissolved in 35 ml of water, and then coated on a glass substrate with a spin cord to obtain a coating film of 1.2 μm. 6) The results of the same evaluation as in Usage Example 1 using the board are shown in the table below! Shown below.

In Table 2, 3.7E7 indicates 3.7X 107, and the same description will be used below.

The liquid resistance of the coating film was evaluated by measuring the surface resistance value by immersion in a solvent. Poly(styrene sulfonate ammonium salt) or poly(styrene sulfonate sodium salt)
From a comparison with a comparative example which is a mixture of polyvinyl alcohol and polyvinyl alcohol, the present invention is characterized by comprising a polymer having structural units represented by general formula (1) and general formula (2). It is shown that this conductive material has excellent liquid resistance.

Moreover, no stickiness was observed in any of the cured films created in Usage Examples 1 to 6 after being left in the air for one week.

[Effects of the Invention] The present invention provides conductive materials, and these conductive materials have the following remarkable characteristics.

(1) It is a conductive material that can be crosslinked and cured by drying and/or heat. Due to the use of this conductive crosslinking material, for example, it becomes sticky due to moisture absorption after application, or it is easily removed by contact with water or organic solvents after application, making it impossible to obtain the desired antistatic effect or charge shielding effect. It is possible to suppress the occurrence of such problems.

(2) Water resistance and/or liquid resistance is imparted by crosslinking and curing, and other materials can be laminated onto this material.

(3) It can be applied using various coating methods, and can be applied to base materials of all shapes and materials.

(4) It has high transparency and can be used to prevent static electricity in various optical materials.

(5) It has a structure that does not contain halogen ions or metal ions when the cation component is ammonium ions, and can be used for various electrical and electronic applications.

Claims (1)

[Claims] 1. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R_1 represents a hydrogen atom or a methyl group, and
+ indicates a cation. ) and the general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) A conductive material characterized by containing an organic polymer having the structural unit shown by the following.