JPH041213A - Conductive crosslinkable material - Google Patents

Abstract

PURPOSE:To obtain a conductive crosslinkable material which can be easily crosslinked and cured by the application of light and/or heat and is improved in the light resistance and organic solvent resistance of a cured film by using a specified organic polymer. CONSTITUTION:An organic polymer of formula I (wherein R1 and R5 are each H or CH3; X is halogen; and p, q and n are each 1 or greater) is reacted with an amine at 0-100 deg.C for 0.1-30 hr in an organic solvent to obtain an organic polymer having a weight-average mol. wt. of 500-500000 and represented by formula II (wherein Z is formula III; R2 to R4 are each H or 1-4C alkyl; and m is 1 or greater). This polymer is optionally mixed with a photopolymerizable unsaturated compound, a photopolymerization initiator, a bisazide compound, a filler and other additives to obtain the title material. 5-60wt.% this material is dissolved in water and/or an organic solvent and applied to a substrate, and the material is crosslinked and cured by the application of light and/or heat to obtain a cured film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to conductive crosslinkable resin compositions, particularly those easily crosslinked and cured by light and/or heat to obtain water resistance and/or organic solvent resistance. The present invention relates to conductive materials that can be used.

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

[Problems to be Solved by the Invention] Since these antistatic 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, so that the desired antistatic effect cannot be achieved. There are problems such as not being able to

[Means for Solving the Problems] The present inventors aim to obtain a conductive material that can be easily crosslinked and cured by light and/or heat after application, and can have water resistance and/or organic solvent resistance. As a result of intensive studies aimed at this purpose, the present invention was arrived at. That is, the present invention is based on the general formula (1) (wherein Z is represented by the general formula (2), R7 represents a hydrogen atom or a methyl group, and R2, R3, and R4 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m1n represents an integer of 1 or more, and X represents a halogen atom.

(In the formula, R7 and X are the same as in general formula (1),
R5 represents a hydrogen atom or a methyl group, and p and q represent an integer of 1 or more. ) is a conductive crosslinkable material characterized by containing an organic polymer represented by:

In the organic polymers represented by the general formulas (1) and -Funazo (2), the alkyl groups having 1 to 4 carbon atoms in R2, R3, and RJ include methyl group, ethyl group, n-propyl group, isopropyl group, Mention may be made of straight chain and branched alkyl groups such as n-butyl groups. When R2-R4 are all methyl groups, it has excellent heat resistance, and when R2-R4 are not the same, it has excellent compatibility with solvents and other components.

Examples of the halogen atom for X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of raw material availability, chlorine atoms are preferred.

plqSn is usually p/(p+q+n)=o, os ~0
．． 9, q/ (p+q+n) ~ 0.05 ~ 0.9, n/
(p+q+n) ~0.05-0.9, preferably q/(p + q + n) ~0.1-0.85, n
/ (p+q+n)~0.1~0.85. q/(
If p+q+n) is less than 0.05, a decrease in crosslinking properties will be observed, resulting in insufficient liquid resistance after photo and/or thermal crosslinking, and if n/(p+q+n) is less than 0.05, conductivity will be poor. It becomes insufficient. The n, p, and q constituent units may be connected in blocks or randomly.

The weight average molecular weight is usually 500 to 500,000, preferably 3,000 to 150,000. If the weight average molecular weight is less than 500, the liquid resistance of the cured product will be insufficient, and if it exceeds 500,000, for example, when the material of the present invention is used as a solution, the viscosity will increase and the coating properties will decrease.

Specific examples of the organic polymers represented by the general formulas (1) and -Funezo (2) include the groups shown in Table 1 and p
Examples include organic polymers having a ratio of :q:n.

Table-1 (1) (When R1 and R5 are hydrogen atoms and X is chlorine atom) (Left space below this page) (When R1 and R5 are hydrogen atoms and X is chlorine atom) - Onboard (1) The organic polymer represented by and - Funazou (2) has the general formula (3). In Table 1, Mw represents the weight average molecular weight, Me represents a methyl group, Et represents an ethyl group, and nPr represents - represents a propyl group and the same description will be used below.

(In the formula, R7, R5, p, q, n and
1) and - Same as in the case of shipyard (2). ) with water, an organic solvent (benzene, toluene, 1.2
-dichloroethane, chlorobenzene, acetone, etc.) and the corresponding amines in a mixed solvent of these solvents, usually by stirring and reacting with the corresponding amine at 0 to 100°C for 0.1 to 30 hours, and quaternizing. The end point of the reaction is 1/I
It is easily confirmed by titration using ON aqueous hydrochloric acid solution. The concentration of the reaction solution at this time is usually 10 to 50% by weight, preferably 15 to 45% by weight.

- Organic polymers in stock (4) are, for example, copolymerization of corresponding monomers (styrene, α-methylstyrene, chloromethylstyrene, fluoromethylstyrene, bromomethylstyrene, etc.), homopolymerization of styrene or α-methylstyrene, etc. It can be obtained by halomethylation of a combination.

For copolymerization, a radical polymerization method using azobisisobutyronitrile, benzoyl peroxide, dicumyl peroxide, etc., a Lewis acid (BF3-Et20, AlCl3
etc.) and protonic acids (H2SO4, HClO4, p-)
A cationic polymerization method using luenesulfonic acid, etc., and an anionic polymerization method using butyllithium, etc. can be used. For halomethylation, 1,2-ethylene dichloride is used as a solvent, and each homopolymer is reacted with paraform and hydrogen halide in the presence of zinc chloride.

The conductive crosslinkable material of the present invention contains a photopolymerizable unsaturated compound (
A) and/or a photopolymerization initiator (B) and/or a bisazide compound (C) and/or other additives and fillers can be added. Examples of the photopolymerizable unsaturated compound as component (A) include 2-hydroxyethyl methacrylate, 1,1,2.2-tetraallyloxyethane, amides (N,N'-methylenebisacrylamide, N,N '-methylenebismethacrylamide, N
-Methylol acrylamide, N-methylol methacrylamide, acrylamide, methacrylamide, N, N
'-trimethylenebisacrylamide, N,N'-hexamethylenebisacrylamide, etc.), polyhydric alcohols (triethylene glycol, tetraethylene glycol, ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, neopentyl glycol, dipenta esters of acrylates such as erythritol, methacrylates of polyhydric alcohols (such as triethylene glycol, tetraethylene glycol, ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, neopentyl glycol, dipentaerythritol, etc.) Can be mentioned. These photopolymerizable unsaturated compounds can be used alone or in combination of two or more. As the photoinitiator component (B), any initiator that initiates the polymerization of unsaturated compounds by active energy rays such as ultraviolet rays and deep ultraviolet rays can be used. For example, benzoin alkyl ethers (benzoin, benzoin isobutyl ether, benzoin isopropyl ether, etc.), benzophenones (benzophenone, Michler's ketone, 4-benzoylbenzyltrimethylammonium chloride, etc.), acetophenones (2,2-dimethoxy-2-phenylacetophenone, 2,2-jethoxyacetophenone, 2
, 2-dichloro-4'-phenoxyacetophenone, p
-t-butyltrichloroacetophenone, etc.), anthraquinones (2-ethylanthraquinone, etc.), thioxanthones [2-(carboxymethoxy)thioxanthone, 2-(3-sulfopropoxy)thioxanthone,
-(2-sulfoethoxyethoxy)thioxanthone, 3
．． 4-dimethyl-2-(3-sulfopropoxy)thioxanthone, 2-(3-dimethylamino-2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthine-9-one methochloride, 2-(carboxymethoxy) ) Sodium salt of thioxanthone, ammonium salt of 2-(3-sulfopropoxy)thioxanthone, diethylthioxanthone, diisopropylthioxanthone,
2-chlorothioxanthone, etc.]. Further, as a sensitizer, triethanolamine, methylgetanolamine, ethylgetanolamine, 2-(dimethylamino)ethyl methacrylate, etc. can be made to coexist. As the bisazide compound which is the component (C), a water-soluble bisazide compound [4,4-monodiazidostilbene-2,2-disodium sulfate, 4.4
--Diazidostilbene-2,2-disulfonic acid diammonium salt, 4,4--diazidostilbene-2゜2
--Disulfonic acid di(tetramethylammonium salt),
4,4-Diazidostilbene-2,2-disulfonic acid di(tetraethylammonium salt), 4,4-diazidostilbene-2,2-disulfonic acid di(trimethylammonium salt), 4,4- -Diazidostilbene-
2,2-Disulfonic acid di(dimethylammonium salt)
, etc.], organic solvent-soluble bisazide compound [2,6-
Di(p-azidobenzal)cyclohexanone, 2,6-
Examples include di(ρ-azidobenzal)-4-methylcyclohexanone, 2,6-di(ρ-azidobenzal)-4-(t-amyl)cyclohexanone, and 4,4-diazidochalcone. When containing these photopolymerizable unsaturated compounds (A) and/or photopolymerization initiators (B), the amounts of the components are usually: - 30 to 99% by weight of the organic polymer in the ship's inventory (1); Photopolymerizable unsaturated compound 0-70
% by weight, 0 to 25% by weight of photopolymerization initiator, preferably 40 to 99% by weight of the organic polymer of general formula (1), 5 to 60% by weight of photopolymerizable unsaturated compound, and 0.1% by weight of photopolymerization initiator. ~1
It is 0% by weight. In addition, when the bisazide compound (C) is contained, the blending ratio of the constituent components is usually - 70 to 99% by weight of the organic polymer of shipyard (1), 1 to 30% by weight of the bisazide compound (C);
% by weight, preferably organic polymer of general formula (1) 85
-99% by weight, bisazide compound 1-20% by weight. This crosslinkable conductive material can be mixed with water, organic solvents (dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, γ-butyrolactone, butyl alcohol, ethyl alcohol, isopropyl alcohol, methyl alcohol, ethyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, etc.). ) or a mixed solvent of these solvents, it becomes a coatable solution and can be used for various antistatic purposes. The concentration of the solution is usually 5 to 60% by weight, preferably 10 to 50% by weight.

The method of using the conductive crosslinkable material of the present invention is to apply the solution to paper, various recording papers, organic resin films, organic resin molded bodies, etc.
A coating film thickness of 1 is applied onto a base material such as an inorganic molded body by spin cord coating, screen printing coating, spray coating, roll coating coating, dipping coating, bar coater coating, etc.
It is coated to a thickness of 0.3 mm or less, and then crosslinked by irradiation with ultraviolet rays, deep ultraviolet rays, etc., resulting in water resistance and/or solvent resistance. At this time, as a light source, a high pressure mercury lamp,
An ultra-high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, a far ultraviolet lamp, an excimer laser, etc. can be used. Crosslinking also proceeds by heating at 50 to 150°C, and heating can be done using a circulating oven, hot plate,
An infrared furnace, a far-infrared furnace, 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 10 g of styrene-chloromethylstyrene copolymer (chloromethylstyrene content 50%, Mw = 10000) was dissolved in 30 g of 1,2-dichloroethane, and 4.60 g of a 30% by weight aqueous solution of trimethylamine and 20 g of water were added. After stirring and reacting at room temperature for 3 hours, the mixture was added to 1 liter of acetone. The precipitated polymer was dried under reduced pressure to obtain 10.5 g of partially quaternized styrene-chloromethylstyrene, which is the conductive crosslinkable material of the present invention.

Example 2 10 g of styrene-chloromethylstyrene copolymer (chloromethylstyrene content 60%, Mw = 20000) was dissolved in 30 g of 1,2-dichloroethane, and 4.44 g of a 30% by weight aqueous solution of trimethylamine and 20 g of water were added. After stirring and reacting at room temperature for 3 hours, the mixture was added to 1 liter of acetone. The precipitated polymer was dried under reduced pressure to obtain 11 g of partially quaternized styrene-chloromethylstyrene, which is the conductive crosslinkable material of the present invention.

Example 3 10 g of styrene-crocomethylstyrene copolymer (chloromethylstyrene content 55%, Mw = 50000) was dissolved in 30 g of 1,2-dichloroethane, and 5.27 g of a 30% by weight aqueous solution of trimethylamine and 20 g of water were added. After stirring and reacting at room temperature for 3 hours, the mixture was added to 1 liter of acetone. The precipitated polymer was dried under reduced pressure to obtain 10.5 g of partially quaternized styrene-chloromethylstyrene, which is the conductive crosslinkable material of the present invention.

Example 4 Styrene-chloromethylstyrene copolymer (chloromethylstyrene content 65%, Mw = 20000) 10g
was dissolved in 30 g of 1,2-dichloroethane, and 6.54 g of a 30% by weight aqueous solution of trimethylamine and 20 g of water were added.
After stirring and reacting at room temperature for 3 hours, the mixture was added to 1 liter of acetone. The precipitated polymer was dried under reduced pressure to obtain 10 g of partially quaternized styrene-chloromethylstyrene, which is the conductive crosslinkable material of the present invention.

Usage Example 1 5 g of the polymer obtained in Example 1 was mixed with DMF-water mixed solvent 2
A conductive crosslinkable material solution, which is a solution of the material of the present invention, was prepared by dissolving 0g of the material. This solution was spin-coated onto a glass substrate to obtain a uniform coating film of 1.5 μm. This coating film was heated to 500mj/cm2 using a high-pressure mercury lamp.
UV irradiation was performed. Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Usage Example 2 The solution prepared in Usage Example 1 was spin-coated onto a glass substrate to obtain a uniform coating film of 1.5 μm.

This substrate was baked at 150° C. for 2 hours under nitrogen using a circulating oven. Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Use example 3 5 g of the polymer obtained in Example 2 was mixed with DMF-water mixed solvent 2
A conductive crosslinkable material solution, which is a solution of the material of the present invention, was prepared by dissolving 0g of the material. This solution was spin-coated onto a glass substrate to obtain a uniform coating film of 1.5 μm. A metal halide lamp was applied to this coated film for 500 m j /
Ultraviolet irradiation was performed at cm2.

Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Usage Example 4 The solution prepared in Usage Example 3 was spin coated onto a glass substrate to obtain a uniform coating film of 1.5 μm.

This substrate was baked at 150° C. for 2 hours under nitrogen using a circulating oven. Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Use Example 5 5 g of the polymer obtained in Example 3 was dissolved in 20 g of water to prepare a conductive crosslinkable material solution, which is a solution of the material of the present invention. This solution was spin-coated onto a glass substrate, and 1.
A uniform coating film of 5 μm was obtained. This coated film was irradiated with ultraviolet light at 500 mj/cm2 using a high-pressure mercury lamp. Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Usage Example 6 The solution prepared in Usage Example 5 was spin coated onto a glass substrate to obtain a uniform coating film of 1.5 μm.

This substrate was baked at 150° C. for 2 hours under nitrogen using a circulating oven. Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Use Example 7 5 g of the polymer obtained in Example 4 was dissolved in 20 g of water to prepare a conductive crosslinkable material solution, which is a solution of the material of the present invention. This solution was spin-coated onto a glass substrate, and 1.
A uniform coating film of 5 μm was obtained. This coated film was irradiated with ultraviolet light at 500 m j /Cm2 using a metal halide lamp. Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Use Example 8 The solution prepared in Use Example 7 was spin coated onto a glass substrate to obtain a uniform coating film of 1.5 μm.

This substrate was baked at 150° C. for 2 hours under nitrogen using a circulating oven. Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Use Example 9 5 g of the polymer obtained in Example 2, 0.5 g of N,N-methylenebisacrylamide, and 0.25 g of benzoin isopropyl ether were dissolved in 20 g of a DMF-water mixed solvent to form a solution of the material of the present invention. A conductive crosslinkable material solution was prepared. This solution was spin-coated onto a glass substrate to obtain a uniform coating film of 1.5 μm. This coated film was irradiated with ultraviolet light at 200 m j /cm 2 using a high-pressure mercury lamp. Table of surface resistance values after immersion in methanol for 60 seconds.
Shown in 2.

Usage example: 0 5 g of the polymer obtained in Example 4, 0.5 g of triethylene glycol diacrylate, and 0.2 g of 2-(3-sulfopropoxy)thioxanthone were mixed in a DMF-water mixed solvent 2
A conductive crosslinkable material solution, which is a solution of the material of the present invention, was prepared by dissolving 0g of the material. This solution was spin-coated onto a glass substrate to obtain a uniform coating film of 1.5 μm. This coated film was heated to 200mj/cm” using a high-pressure mercury lamp.
UV irradiation was performed. Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

Comparative Example 1 10 g of completely quaternized trimethylamine of styrene-chloromethylstyrene copolymer (chloromethylstyrene content 50%, Mw = 10000) was dissolved in 40 g of water, and this solution was spin-coated on a glass substrate, 1.
A coating film of 5 μm was obtained. This coating film was irradiated with ultraviolet rays of 500 mj/cm'' using a high-pressure mercury lamp.Table 2 shows the surface resistance values after immersion in methanol for 60 seconds.

Comparative Example 2 10 g of completely quaternized trimethylamine of styrene-chloromethylstyrene copolymer (chloromethylstyrene content 70%, Mw = 30000) was dissolved in 40 g of water, and this solution was coated on a glass substrate with a bar coater. 1.5μ
A coating film of m was obtained. This substrate was heated under nitrogen using a circulating oven.
Baking was performed at 50°C for 2 hours.

Table 2 shows the surface resistance values after being immersed in methanol for 60 seconds.

(Margins below this page) Table 2 In Table 2, 2. OF2 indicates 2.0X107, and the same description will be used below.

Changes in the coating film were evaluated by measuring the surface resistance value by immersion in a solvent. From a comparison with a comparative example in which crosslinking does not proceed,
Good conductivity was confirmed even after immersion in the solvent, demonstrating the effect of imparting water resistance and/or organic solvent resistance to the conductive crosslinkable material of the present invention. Moreover, no stickiness was observed in any of the cured films prepared in Usage Examples 1 to 10 after being left in the air for one week.

[Effects of the Invention] The present invention provides electrically conductive crosslinkable materials, and these electrically conductive crosslinkable materials have the following notable features.

(1) It is a conductive material that can be crosslinked and cured by light and/or heat. The use of this conductive cross-linked material prevents problems such as stickiness due to moisture absorption after application, and the fact that it is easily removed by contact with water or organic solvents after application, making it impossible to obtain the desired antistatic effect. can do.

(2) By changing the content ratio of ionic components and/or the alkyl group of the amine used for quaternization, the solvent solubility before crosslinking can be freely changed and the use conditions are highly acceptable.

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

(4) Since it can be photocured, it can be applied and used on materials with poor heat resistance.

(5) Since photocuring is possible, compositions with poor conductivity and heat resistance can also be used.

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

(7) A pattern can be formed by utilizing the difference in solubility between exposed and unexposed areas.

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Claims (1)

[Claims] 1. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, Z is represented by the general formula (2), and R_1 represents a hydrogen atom or a methyl group. , R_2, R_3 and R_4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m,
n represents an integer of 1 or more, and X represents a halogen atom. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, R_1 and X are the same as in general formula (1), R_5 represents a hydrogen atom or a methyl group, and p and q are 1
Indicates an integer greater than or equal to ) A conductive crosslinkable material characterized by containing an organic polymer represented by: