JPH01236256A - Antistatic polymer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excelling in processability such as formability into films and adhesiveness and forming a transparent smooth ultra- thin film, by mixing a polymer compound mainly consisting of specified groups with a 7,7,8,8-tetracyanoquinodimethane complex. CONSTITUTION:A polymer compound mainly consisting of groups of formula I (wherein R is H, CH3 or C4H9) and 0.1-70wt.%, based on this compound, 7,7,8,8-tetracyanoquinodimethane (hereinbelow abbreviated to TCNQ) complex, i.e., a complex of D<+>.TCNQ<->.TCNQ<0> (wherein D<+> is a cation of any one of formulas II-XVII, R1, R3 and R4 are each H or a 1-12C alkyl group, R2 is H, a 1-30C alkyl group, a benzyl group or a phenylethyl group, and X is O or S) are dissolved in, for example, a solvent (e.g., acetonitrile or cyclohexanone) and applied to a base and, the solvent is evaporated from the base.

Description

[Detailed Description of the Invention] [Industrial Field of Application] A polymer compound whose main constituent is a group represented by the following formula (1) 7.
7,8.8-tetracyanoquinodimethane (hereinafter referred to as TCNQ)
This is an antistatic polymer composition containing a complex salt and having good film-forming properties.

The polymer composition of the present invention can form a thin film of 1 μm or less and exhibits a surface resistance value of 10 2 to 1 oiOΩ/mouth, so it can be used as an antistatic coating agent for various electronic components and their packaging materials, or for electronic components. It is useful as an antistatic agent during manufacturing processes.

[Prior art]

As conductive compositions, those containing a cationic polymer as a main composition and those containing metal or carbon dispersed in a polymer are widely known. However, the former has drawbacks such as a low conductivity level and high hygroscopicity, while the latter has problems with smoothness and transparency when used as a film.

On the other hand, as a conductive composition using T CN Q,
Compositions comprising a polymer having a quaternary nitrogen cationic group and TCNQ, and (2) a composition comprising a polymer compound and an organic low-molecular complex of TCNQ are known.

Among these, (■) has very poor solubility in solvents, and many are only soluble in highly polar solvents such as dimethylformamide, and when used as a coating agent, they have the disadvantage of dissolving the base material as well. Therefore, it is unsuitable for antistatic purposes.

Regarding ■, please refer to JP-B No. 44-16499,
-123750, JP-A-54-130651, JP-A-58-34841, etc., but when formed into a film, the TCNQ complex salt precipitates as crystals, so the film formability in the thin film region is poor. It is not completely satisfactory, and it is difficult to say that transparency is sufficient. That is, although these compositions can be formed into a film by increasing the film thickness, problems remain in the uniformity of the surface. This film has a rough surface and a mottled pattern, making it impractical.

[Problem to be solved by the invention]

BACKGROUND OF THE INVENTION Nowadays, antistatic is an important issue in the electronics industry, and there is a demand for antistatic agents composed only of organic substances.

However, conventionally known polymer compositions do not have sufficient electrical conductivity or film formability.

The present inventors investigated to find an antistatic polymer composition that has good film formability even when formed into an extremely thin film and maintains sufficient conductivity, and as a result, the following formula (1) % formula was found. It has been found that a composition containing a polymer compound having a group shown in %) as a main component and using a TCNQ complex salt as a conductive component achieves the object.

[Specific means to solve the problem]

The present invention relates to polymers derived from vinyl acetate and TCN.
An object of the present invention is to provide an antistatic polymer composition containing a Q complex salt and having good film-forming properties.

This will be explained in detail below.

As the polymer compound, one having a group shown in the following formula as a main component is used, and specific examples thereof include polyvinyl acetal such as polyvinyl butyral and polyvinyl formal. Of course, those in which OH groups and OAC groups remain can also be used.

+ CH2-CH-CH2-CH+.

(R: H, CH,, C4Hg) Other polymeric compounds such as poly(meth)acrylic esters, polystyrene, silicone resins, etc. can also be mixed and used.

Regarding TCNQ complex salts, see J. Am. Chem.
Soc.

843374 (1962), it is preferred in the present invention to use a complex salt represented as "Do.TCNQ-.TCNQ".

As for Dl, an organic cation shown in the following formula can be used.

he (R1, R3, R4 represent H or an alkyl group having 1 to 12 carbon atoms, R2 represents H or an alkyl group having 1 to 30 carbon atoms, a benzyl group, a phenylethyl group) Also, a quaternary nitrogen cation T of the oligomer having a functional group
CNQ salts can also be used.

As the amount of TCNQCN used increases, the conductivity of the polymer composition improves, but the processability decreases. Therefore, in order to obtain a polymer composition that exhibits conductivity in the antistatic region and has good processability, especially film formability, it is appropriate to use TCNQCN in an amount of 0.1 to 70% by weight based on the upper polymer compound. It is.

It is particularly preferable to use 0.5 to 50% by weight.

The method for obtaining a polymer composition is to use a polymer compound and TCNQ*
After kneading the salt with a solvent, the solvent may be evaporated, but in order to obtain a composition with good film-forming properties, a solvent that completely dissolves the polymer compound and TCNQCN is selected, and a uniform solution is formed. After that, it is preferable to apply it to a substrate and evaporate the solvent.

As a solvent, in addition to highly polar solvents such as dimethylformamide and acetonitrile, depending on the type of TCNQCN, alcohols such as ethanol and butanol, ketones such as cyclohexanone and methyl ethyl ketone, cellosolves such as methoxyethyl acetate and methoxyethanol, and acetic acid. Esters such as butyl and amyl acetate, ethers such as ethylene glycol dimethyl ether, aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride and trichlene can also be used. These solvents may be used alone or in combination.

The ratio of the amount of the solvent to the polymer compound to be used is 0.1 to 90% by weight, particularly preferably 0.1 to 90% by weight of the polymer compound to the solvent.
It is used in a range of 5 to 70% by weight.

〔Effect of the invention〕

The polymer composition of the present invention has a surface resistance value of 102 to 1010.
Ω/mouth, has excellent processability such as film formability, and adhesiveness, and forms a transparent and smooth extremely thin film, so the film thickness is 50 μm or less,
In particular, it is an ultra-thin film of 10 μm or less and can be used to coat various electronic parts, devices, etc. that require antistatic properties.

Example 1 2.5 g of polyvinyl butyral and 0.5 g of N-decylisoquinolinium TCNQ complex salt were stirred and dissolved in 20 g of butanol, 560 g of acetonitrile, and 20 g of methyl ethyl ketone, and the resulting green solution was applied on a glass plate. The solvent was evaporated to dryness at 100°C. 8 μm thick, surface resistance value 5. Indicates OX 107Ω/mouth,
A transparent, smooth and stable film was obtained.

Example 2 1.0 g' of polyvinyl butyral, N-butyl-α-
0.2 g of picolinium TCNQ complex salt was stirred and dissolved in 10 g of ethyl acetate, 5.0 g of acetonitrile, and 20 g of cyclohexanone, the resulting green solution was cast on a polyester film, and the solvent was evaporated at 60 °C.
Allowed to dry. Surface resistance value of 6μm thickness: 5.3 x 10
A transparent, smooth, and stable film exhibiting a resistance of Ω/m was obtained.

Example 3 0.9 g of polyvinyl butyral, 0.1 g of polyvinyl alcohol with a degree of saponification of about 88%, and 0.2 g of N-octylpyridinium/TCNQ complex salt were mixed with 2 g of ethanol.
The resulting green solution was applied to a glass plate, and the solvent was evaporated to dryness at 100°C. A transparent, smooth and stable film with a thickness of 3 μm and a surface resistance of 3.5×10” Ω/hole was obtained.

Example 4 Polyvinyl butyral 4g, polyvinyl formal Ig
, 1.5 g of N-benzylpyridinium/TCNQ complex salt was stirred and dissolved in 15 g of dimethylformamide and 30 g of methyl ethyl ketone, the resulting green solution was applied on a glass plate, and the solvent was evaporated to dryness at 100°C.

A transparent, smooth and stable film with a thickness of 10 μm and a surface resistance value of 1.6×10′Ω/hole was obtained.

Comparative Example 1 2.5 g of polycarbonate resin and 0.5 g of N-decylisoquinolinium/TCNQ complex salt were stirred and dissolved in 5.0 g of acetonitrile and 40 g of cyclohexanone, and the obtained green solution was applied on a glass plate. and 100℃
The solvent was evaporated to dryness. Surface resistance value 1 with a thickness of 8 μm
．． A film of 5 x 10'Ω/mouth was formed, but there was no T in the film.
Crystals of the CNQ complex salt had grown, and the surface of the film was extremely uneven and rough.

Comparative Example 2 1.0 g of polyacrylonitrile and 0.2 g of N-butyl-α-picolinium TCNQ complex salt were dissolved in 35 g of dimethylformamide with stirring, and the resulting green solution was cast onto a polyester film and heated at 60°C. When the solvent was evaporated, island-like repellents were observed, and no --like thin film was formed.

Claims (1)

[Claims] 1. A polymer whose main constituent is a group represented by the following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R:H, CH_3, C_4H_9) compound and 0.1 to 70% by weight of 7,7,8, based on the polymer compound.
An antistatic polymer composition with good film-forming properties, characterized by containing an 8-tetracyanoquinodimethane complex salt.