JP2696415B2 - Film production method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a film that is soluble in an organic solvent, has electrical conductivity, optical transparency, and has no hygroscopicity.

(Prior Art and Problems to be Solved by the Invention) In recent years, various plastics have been widely used for electric and electronic components, and there has been a demand for preventing their charging.

Conventionally, as means for imparting antistatic properties to polymer substances, polyethylene glycol, non-ionic surfactants such as alcohol ethoxylates, anionic surfactants such as sodium salts of sulfonated alkylphenol condensates, Alternatively, a method of adding an inorganic conductive substance such as a conductive carbon material, a metal flake, a metal fiber, and a sintered metal oxide has been developed.

However, in the method of adding the surfactants, the surfactant moves from the inside of the polymer substance to the surface,
By absorbing the moisture in the air, it increases the ionic conductivity of the surface of the polymer substance and exerts an antistatic effect, so that the surfactant is easily dropped off by washing, and the whole substance has a hygroscopic property. In addition, there is a disadvantage that the antistatic effect is reduced in an environment under low humidity.

In addition, the method of adding the inorganic conductive substance to the polymer substance has a drawback that the inorganic conductive substance is liable to be removed, and further has an adverse effect on the entire light transmittance and clouding characteristics.

As described above, in this technical field, an antistatic agent that has excellent light transmittance, has no hygroscopicity, maintains a good antistatic effect even in a low humidity environment, and does not lose its antistatic effect even by washing. Was sought.

On the other hand, the present inventors have previously made various proposals as an electroactive polymer soluble in an organic solvent (Japanese Patent Application Laid-Open No.
308019, Japanese Patent Application No. 1-222839).

The present inventors have conducted intensive studies, and as a result, it has been found that a compound obtained by doping the above polymer with an electron acceptor in a specific concentration range has high conductivity and excellent light transmittance. Even at the point of the above, it was found that it was easy to form a film with an organic solvent, and it was found that the above-mentioned disadvantages could be overcome by using a film-like molded product of the compound as an antistatic agent, leading to the present invention.

That is, the present invention provides a compound represented by the general formula (I) (Wherein, R ¹ is H or a hydrocarbon residue having 1 to 20 carbon atoms,
R ² represents H, a hydrocarbon residue having 1 to 20 carbon atoms, a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, or a methoxyphenyl group; l is an integer of 2 or more;
The above integer and n each represent an integer of 2 or more) are formed into a film after being dissolved in a solvent, and then doped with an electron acceptor before and / or after the formation, The present invention also relates to a method for producing a film, wherein the doping concentration is in the range of 0.1 to 5 mol% with respect to the doping site.

 Hereinafter, the present invention will be described in detail.

The film produced by the production method of the present invention contains, as an essential component, a compound obtained by doping the copolymer represented by the general formula (I) with an electron acceptor.

The copolymer represented by the general formula (I) used in the present invention is obtained by polycondensing a compound represented by the following general formula (II) with an aldehyde represented by the following general formula (III) or a polymer thereof. Can be manufactured.

R ² CHO (III) In the compound represented by the general formula (II), R ¹ represents hydrogen or a hydrocarbon residue having usually 1 to 20, preferably 1 to 8 carbon atoms. Methyl group,
An alkyl group such as an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an n-hexyl group or an allyl group, and various aryl groups such as a phenyl group, a tolyl group, and an ethylphenyl group. Groups, aralkyl groups and derivatives thereof.

l is 2 or more, usually 2 to 50, preferably 2 to 10, and more preferably 2 to 5. m is 1 or more, usually 1
To 50, preferably 1 to 30, and more preferably 1 to 10. Although both ends of the formula are not particularly specified, they are usually the substituted hydrogens.

As the compound represented by the general formula (II), specifically,
N, N'-diphenyl-p-phenylenediamine compounds, N-phenyl-N '-(4-phenylamino) phenyl-p-phenylenediamine compounds and the like are exemplified.

In addition, among the compounds represented by the general formula (II), those in which m is 2 or more usually have m = 1 represented by the general formula (II).
Is produced by using a method such as an oxidative coupling reaction using an oxidizing agent such as a manganese compound or a ferric salt or electrolytic oxidation polymerization. For example, when the compound represented by the general formula (II) is N, N'-diphenyl-p-
In the case of a phenylenediamine compound, N, N'-diphenyl-p-phenylenediamine is produced by an oxidative coupling reaction in a solvent such as ethanol, acetone, acetonitrile, ether, or benzene using ferric chloride as a catalyst. Can be.

The reaction temperature at this time is usually from -50 ° C to 100 ° C, preferably from -20 ° C to the boiling point of the solvent used, and the reaction time is usually 10 ° C.
The reaction can be carried out in minutes to 100 hours, preferably 1 hour to 50 hours.

Representative of these N, N'-diphenyl-p-phenylenediamines include, for example, N, N'-
Dimethyl-N, N'-diphenyl-p-phenylenediamine, N, N'-diethyl-N, N'-diphenyl-p-phenylenediamine, N, N'-dipropyl-N, N'-diphenyl-p-phenylene Diamines and the like can be mentioned.

Compounds represented by the general formula (II) other than the N, N'-diphenyl-p-phenylenediamine compound are also produced by a conventional method. For example, in the presence of a transition metal catalyst, an aromatic amine is used. A method in which an aromatic hydroxy compound is reacted in an organic solvent, a method in which a phthalic acid ester is used as a raw material, and the like. Specific examples of these methods include JP-A-55-38311, Journal of Polymer Scie
nce Part C22, p.451 (1968).

As the aldehyde represented by the general formula (III), R ² is hydrogen or a hydrocarbon residue having 1 to 20, preferably 1 to 8 carbon atoms, or a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, A compound of a methoxyphenyl group is used, and examples of the hydrocarbon residue include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-
An alkyl group or an allyl group such as a butyl group, an i-butyl group, and an n-hexyl group, various aryl groups such as a phenyl group, a tolyl group, and an ethylphenyl group, an aralkyl group, and derivatives thereof can be used. Representative examples of these aldehydes include, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, acrylaldehyde, cinnamaldehyde, anisaldehyde, nicotinaldehyde, nitrobenzaldehyde, chlorobenzaldehyde, furfural and the like. .

The aldehyde polymer refers to a polymer obtained by subjecting the aldehyde represented by the general formula (III) to a concentrated solution and self-condensing, or condensing in the presence of an acid catalyst. Represents an aldehyde monomer which is easily hydrolyzed under the reaction conditions for the synthesis of the copolymer of Representative examples include paraformaldehyde, which is a polymer of formaldehyde, and paraaldehyde, which is a trimer of acetaldehyde.

The polycondensation of the compound represented by the general formula (II) with the aldehyde represented by the general formula (III) or a polymer thereof is as follows:
The reaction can be carried out in an organic solvent in which both are soluble, usually at a temperature of 0 to 200 ° C. using an acid or an alkali catalyst. Examples of the acid catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid, and diphosphorus pentoxide, and organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, and p-toluenesulfonic acid. Can be. These acid catalysts may be used alone or in combination of two or more. Further, as the organic solvent, for example, ethers such as ethyl ether, tetrahydrofuran, dioxane, chloroform, dichloromethane, halogenated hydrocarbons such as chlorobenzene,
Examples include nitro compounds such as nitrobenzene, acetonitrile, propylene carbonate, dimethylformamide, and N-methylpyrrolidone. The reaction time can be appropriately selected in the range of usually 1 minute to 500 hours, preferably 5 minutes to 200 hours.

N of the copolymer represented by the general formula (I) thus obtained is desirably 2 or more, usually 2 to 1000, preferably 5 to 200, and has a substantially linear structure.

The copolymer represented by the general formula (I) is usually chloroform, benzene, tetrahydrofuran (THF), C
Since it is soluble in organic solvents such as H ₂ Cl ₂ , N-methylpyrrolidone, nitrobenzene, etc., it can be made into various shaped articles of any shape.

Further, since the copolymer represented by the general formula (I) is soluble as described above, impurities can be usually removed by purification or the like for the purpose of further improving performance and the like.

For example, GPC (Gel Permeation Chromatography), chromatography using an ion exchange resin, etc., reprecipitation method and washing method using an insoluble solvent such as ethanol and hexane, extraction method using the above-mentioned soluble solvent and the like can be mentioned.

Next, the copolymer represented by the general formula (I) is doped with an electron acceptor.

The dope comprises (a) after producing the copolymer represented by the general formula (I) and before dissolving in a solvent, (b) when dissolving in a solvent, and (c) after forming a film. This can be performed in any case.

The doping method can be a known method, for example, a method of directly mixing when the copolymer is dissolved in a solvent, an electron acceptor from the gas phase after producing or molding the copolymer. Method of infiltrating, an electrochemical method of performing electrolytic oxidation in a solvent containing an anion serving as an electron acceptor,
Any method such as an ion implantation method in which ions serving as electron acceptors are accelerated and implanted into a substance can be used.

Among the electron acceptors, those which can be used in a method of mixing when dissolved in a solvent or a method of invading from a gas phase include, for example, halogen compounds such as iodine, bromine and hydrogen iodide, and pentafluoride. Metal halides such as arsenic, phosphorus pentafluoride, phosphorus pentachloride, antimony pentafluoride, silicon tetrafluoride, aluminum chloride, aluminum bromide, aluminum fluoride, ferric chloride, sulfuric acid, nitric acid, chlorosulfonic acid And oxidizing agents such as sulfur trioxide and difluorosulfonyl peroxide, and organic substances such as tetracyanodimethane.

Electron acceptors that can be electrochemically doped include, for example, halide anions of Va group elements such as PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , and halides of IIIa group elements such as BF ₄ ⁻ Examples include anions, halogen anions such as I ⁻ (I ₈ ⁻ ), Br ⁻ and Cl ⁻ , and perchlorate anions such as ClO ₄ ⁻ .

Further, electron acceptors that can be doped by ion implantation include, for example, Br ⁺ , Cl ⁺ , and I ⁺ .

The doping concentration is determined based on the dopeable portion of the copolymer, that is, the doping site, that is, the formula (I) Of 0.1 to 5 when expressed as mol% based on the repeating unit
%, Preferably within a range of 0.3 to 3%, depending on the type of electron acceptor or copolymer used.

If the doping concentration is less than the above range, sufficient conductivity cannot be obtained, and if the doping concentration exceeds the above range, problems such as solubility in a solvent and color tone may occur, which is not preferable.

As a method of doping mixed when dissolved in the above-mentioned solvent, specifically, usually, an organic solvent such as chloroform, benzene, tetrahydrofuran (THF), CH ₂ Cl ₂ , N-methylpyrrolidone, nitrobenzene or the like is added to the general formula (I) A method of mixing the above-mentioned electron acceptor in a solution in which the copolymer represented by the formula (1) is dissolved is used.

As a method for allowing the electron acceptor to penetrate from the gas phase, specifically, a copolymer represented by the general formula (I) is molded by a method described later, and then the volatility of the electron acceptor is determined. The method of holding in a sealed container with the thing to be used is used. At this time, the temperature can be appropriately selected as long as it is higher than the temperature at which the electron acceptor to be used is volatilized and usually lower than 400 ° C., and the holding time can be selected according to the desired doping concentration and the above temperature.

In the present invention, the copolymer represented by the general formula (I) or the copolymer doped with the copolymer is formed into a film.

The film here includes not only a thin film but also a protective film.

In the molding, first, a copolymer represented by the general formula (I) or a product obtained by doping the copolymer is usually subjected to chloroform, benzene, tetrahydrofuran (THF), CH ₂ C
The film can be formed into a film by dissolving in an organic solvent such as l ₂ , N-methylpyrrolidone, nitrobenzene, and the like, and then performing a method such as spin coating, casting, or dipping.

The temperature during the dissolution, the shaping, and the removal of the solvent,
At least the melting point of the solvent used, less than the boiling point, usually-
The temperature is from 20 to 80 ° C., but it is particularly desirable to carry out at room temperature.

Further, the above-mentioned molding and the removal of the solvent can be carried out in the air or in an inert atmosphere.

The film obtained by the above-mentioned production method may contain additives such as an antioxidant and an ultraviolet inhibitor as long as the object of the present invention is not impaired.

A film is manufactured by the manufacturing method of the present invention described above.

(Effect of the Invention) The film produced by the present invention is a tough film having conductivity, light transmission, and solubility in a solvent,
Further, since it does not have hygroscopicity or water solubility, when used as a protective film, it has excellent antistatic effects, excellent durability and washing resistance, and does not lose its effect even in low humidity conditions.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 N, N'-methyl-N, N'-diphenyl-p-phenylenediamine (1.0 g) was placed in a 100 ml three-necked flask purged with nitrogen, and 15 ml of nitrobenzene was added to dissolve the mixture. Add 80 ml
For 5 hours. The reaction solution was poured into 300 ml of ethanol containing 30 ml of a 1N aqueous solution of NaOH, and an off-white precipitate was filtered.
After washing with ethanol and distilled water, it was dried to obtain 0.95 g of an off-white powder. ¹ H-NMR, ¹³ C-NMR, I
When R (FIG. 1) was measured, N, N 'having the following structure was obtained.
-Dimethyl-N, N'-diphenyl-p-phenylenediamine-paraaldehyde copolymer (degree of polymerization: about 110).

2.0 g of the copolymer obtained in the above operation was mixed with 100 ml of chloroform.
Dissolved in, further I ₂ was added 32 mg, was a homogeneous solution.
The doping concentration at this time was equivalent to about 1%. The solution is poured on a glass plate and dried at room temperature to a thickness of 2
A μm transparent film was obtained.

The conductivity of the above film was measured by the four-point probe method and found to be 6 × 10 ⁻¹⁰ S / cm. This film was not hygroscopic and was extremely stable in air.

In Example 1, except that the I ₂ was added 60mg Operations in the same manner as in Example 1, the doping concentration of about 2%, the thickness
A 1.7 μm transparent film was obtained.

The conductivity of the film was measured by a four-point needle method and found to be 3 × 10 ⁻⁸ S / cm. This film was not hygroscopic and was extremely stable in air.

Example 3 The film obtained in Example 1 was kept under I ₂ atmosphere for 1 hour, then washed with ethanol and dried, and the dope concentration was about
A 1.5%, 1.5 μm thick transparent film was obtained.

The conductivity of the film was measured by a four-point needle method and found to be 7 × 10 ⁻⁹ S / cm. This film was not hygroscopic and was extremely stable in air.

The conductivity of the film was measured by a four-point needle method and found to be 6 × 10 ⁻¹⁰ S / cm. This film was not hygroscopic and was extremely stable in air.

Comparative Example 1 In Example, except that no addition of I ₂ The same procedure as in Example 1 to obtain a transparent film having a thickness of 1.5 [mu] m. When the conductivity of the film was measured, it was 5 × 10
^It showed ^-15 S / cm and was an insulator.

Example 4 N, N'-dimethyl-N, N'-diphenyl-p-phenylenediamine 1.0 was placed in a 100 ml three-necked flask purged with nitrogen.
After adding 0 g and dissolving by adding 15 ml of nitrobenzene and 6 ml of acetic acid, sulfuric acid 120 μl, propionaldehyde 250 μl
1 was added and reacted at 50 ° C. with stirring for 140 hours. Ethanol containing 30 ml of 1N NaOH aqueous solution
The precipitate was filtered off, washed with ethanol and distilled water, and dried to obtain 0.85 g of an off-white powder.
When the ¹ N-NMR and ¹³ C-NMR of the obtained powder were measured, an N, N′-dimethyl-N, N′-diphenyl-p-phenylenediamine-propionaldehyde copolymer having the following structure ( The degree of polymerization was found to be about 20).

_{^{1 N-NMR (C 6 D}} 6) :( ppm) 6.82~7.20 (m), 3.65 (m), 2.97 (m), 2.02
(M), 0.92 (t) ¹³ C-NMR (CDCl ₃ ): (ppm) 147.4,143.7,137.4,128.4,122.6,118.6,51.8,40.4,2
8.9,12.9 2.0 g of the copolymer obtained in the above operation was chloroform 100m.
was dissolved in l, further I ₂ was added 60mg, was a homogeneous solution. The solution was poured on a glass plate and dried at room temperature to obtain a transparent film having a dope concentration of about 2% and a thickness of 1.8 μm.

The conductivity of the film was measured by a four-point needle method, and was 1.8 × 10 ⁻⁹ S / cm. This film was not hygroscopic and was extremely stable in air.

[Brief description of the drawings]

FIG. 1 shows the IR (infrared absorption spectrum) of the copolymer obtained in Example 1 of the present invention.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Kazuo Matsuura 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Pref. Japan Petroleum Co., Ltd. Central Technology Research Institute (56) Reference JP-A-52-60613 (JP, A) JP-A-63-308019 (JP, A) JP-A-2-167335 (JP, A) JP-A-52-108133 (JP, A) JP-A-51-135538 (JP, A) JP-A-50-1735 (JP, A) JP-A-2-282263 (JP, A) JP-A-3-240270 (JP, A) JP-A-3-241322 (JP, A)

Claims (1)

(57) [Claims] 1. The compound of the general formula (I) (Wherein, R ¹ is H or a hydrocarbon residue having 1 to 20 carbon atoms, R ²
Represents H, a hydrocarbon residue having 1 to 20 carbon atoms, a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, or a methoxyphenyl group, l is an integer of 2 or more, m is an integer of 1 or more, and n is A copolymer represented by the following formula (2) is dissolved in a solvent and then molded into a film, and before and / or after the molding, the electron acceptor is doped. Formula (I)
In A method for producing a film, wherein the molar% is in the range of 0.1 to 5% with respect to the repeating unit.