JPH041248A - Conductive crosslinkable material - Google Patents

Abstract

PURPOSE:To obtain the title material which, after applied as a solution, can be easily crosslinked and cured by light and/or heat and thus gives a cured conductive material resistant to water and/or an org. solvent by compounding a specific org. polymer. CONSTITUTION:The title material contains an org. polymer of formula 1 (wherein R1 is H or methyl; R2, R3, and R4 are each H or 1-4C alkyl; m and n are each an integer of 1 or higher; and X is a halogen atom). In the polymer, the ratio of m to n is pref. (20:80)-(85:15); the wt.-average mol.wt. is pref. 3000-150000; and the two kinds of repeating units in formula 1 may bonded to each other in blocks or randomly. The material may contain, in addition to the polymer, a photopolymerizable unsatd. compd. and/or a photopolymn. initiator and/or a bisazide compd. and/or other additives, fillers, etc.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a conductive crosslinkable resin composition, particularly a conductive crosslinkable resin composition that can be easily crosslinked and cured by light and/or heat to obtain water resistance and/or organic solvent resistance. It relates to conductive materials that can be made.

[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 provides general formula (1) R4 (wherein R7 represents a hydrogen atom or a methyl group, R2,
R3 and R4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m and n represent an integer of 1 or more, and X represents a halogen atom. ) is a conductive crosslinkable material characterized by containing an organic polymer represented by:

In the organic polymer represented by general formula (1), R2, R
3. Examples of the alkyl group having 1 to 4 carbon atoms for R4 include straight chain and branched alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group.

When R2-R4 are all methyl groups, the heat resistance is excellent, and R
When 2-R4 are not the same, the compatibility with the solvent and other components is excellent.

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.

The ratio of m and n is usually 10:90 to 95:5, preferably 20:80 to 85:15. If the ratio of m is less than 10, a decrease in water resistance is observed, and liquid resistance during photo and/or thermal crosslinking becomes insufficient.

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.

As a specific example of the organic polymer represented by the general formula (1), for example, the groups shown in Table 1 and the m:n ratio are A (1° (margins below this page) Table 1 (1) (When R is a hydrogen atom) Indicates a chlorine atom, and the same description will be used below.

The organic polymer represented by the general formula (2) I represents a methyl group, Et represents an ethyl group, and CI represents (where R2, m% n and X are The same as in case 1)) is mixed with the corresponding amine in water, an organic solvent (benzene, toluene, 1,2-dichloroethane, chlorobenzene, acetone, etc.), and a mixed solvent of these solvents. 0.1-3 at 0-100℃
It is obtained by reacting with stirring for 0 hours and quaternizing it. The end point of the reaction is easily confirmed by titration using a 1/ION aqueous hydrochloric acid solution. The concentration of the reaction solution at this time is usually 1
0 to 50% by weight, preferably 15 to 45% by weight.

The organic polymer of general formula (2) can be obtained, for example, by polymerization of corresponding monomers (chloromethylstyrene, fluoromethylstyrene, bromomethylstyrene, etc.). For polymerization, a radical polymerization method using azobisisobutyronitrile, benzoyl peroxide, dicumyl peroxide, etc., a Lewis acid (BF3-Et20.AI
C13, etc.) and protonic acids (H2SO4, HClO4,
cationic polymerization method using (p-) luenesulfonic acid, etc.),
An anionic polymerization method using butyllithium or the like can be used.

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-methylolacrylamide, N-methylolmethacrylamide, acrylamide, methacrylamide, N,N-monotrimethylenebisacrylamide, N.

N-hexamethylene bisacrylamide, etc.), polyhydric alcohols (triethylene glycol, tetraethylene glycol, ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol,
esters of acrylates (neopentyl glycol, dipentaerythritol, etc.), polyhydric alcohols (triethylene glycol, tetraethylene glycol, ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, neopentyl glycol, dipentaerythritol, etc.) Examples include methacrylic acid esters. 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, pt-butyltrichloroacetophenone, etc.), anthraquinones (such as 2-ethylanthraquinone), thioxanthone [2-(carboxylated) methoxy)thioxanthone, 2-(3-sulfopropoxy)thioxanthone, 2-(2-sulfoethoxyethoxy)thioxanthone, 3,4-dimethyl-2-(3-sulfopropoxy)thioxanthone, 2-(3-dimethylamino-2 −
hydroxypropoxy) -3,4-dimethyl-9H-
Thioxanthin-9-one methochloride, 2-(carboxymethoxy)thioxanthone sodium salt, 2-
(3-sulfopropoxy)thioxanthone ammonium salt, diethylthioxanthone, diisopropylthioxanthone, 2-chlorothioxanthone, etc.). In addition, triethanolamine, methyljetanolamine, ethyljetanolamine,
2-(dimethylamino)ethyl methacrylate and the like can be present together. As the bisazide compound which is component (C), water-soluble bisazide compound [4゜4--
Diazidostilbene-2,2-disodium sulfate, 4,4-diazidostilbene-2,2-disulfonic acid diammonium salt, 4,4-diazidostilbene-2,2-disulfonic acid diammonium salt (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 compounds [2,6-di(p-azidobenzal)cyclohexanone, clohexanone, 4,4-diazide chalcone, etc.]
Examples include. These photopolymerizable unsaturated compounds (A
) and/or a photopolymerization initiator (B), the blending ratio of the components is usually 30 to 99% by weight of the organic polymer of general formula (1) and 0 to 70% by weight of the photopolymerizable unsaturated compound. , 0 to 25% by weight of a photopolymerization initiator, preferably 40 to 99% by weight of an organic polymer of general formula (1), 5 to 60% by weight of a photopolymerizable unsaturated compound, and 0.1 to 10% by weight of a photopolymerization initiator. 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 (1) and 1 to 30% by weight of the bisazide compound, preferably the general formula (1). ) organic polymers 85-9
9% by weight, and 1 to 20% by weight of the bisazide compound. This crosslinkable conductive material is mixed with water, organic solvents (dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, γ-butyrolactone, butyl alcohol, ethyl alcohol, isopropyl alcohol, methyl alcohol,
By dissolving it in a solvent such as 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% by weight.
~50% by weight solution.

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 p-chloromethylstyrene polymer (Mw=10000)
Dissolve Log in 30 g of 1,2-dichloroethane, 5.16 g of a 30% by weight aqueous solution of trimethylamine, and 20 g of water.
After stirring and reacting at room temperature for 3 hours, acetone 1
Added to Little. The precipitated polymer was dried under reduced pressure to obtain 10 g of partially quaternized chloromethylstyrene, which is the conductive crosslinkable material of the present invention.

Example 2 p-chloromethylstyrene polymer (Mw=50000)
Dissolve 10g in 30g of 1,2-dichloroethane, 3.87g of 30% by weight aqueous solution of trimethylamine, and 20g of water.
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 9.5 g of partially quaternized chloromethylstyrene, which is the conductive crosslinkable material of the present invention.

Example 3 p-chloromethylstyrene polymer (Mw=50000)
Dissolve 10g in 30g of 1,2-dichloroethane, 7.75g of 30% by weight aqueous solution of trimethylamine, and 20g of water.
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 chloromethylstyrene, which is the conductive crosslinkable material of the present invention.

Example 4 p-chloromethylstyrene polymer (Mw=50000)
Dissolve 10g in 30g of 1,2-dichloroethane, 10.33g of a 30% by weight aqueous solution of trimethylamine, and 20g of water.
After stirring and reacting at room temperature for 3 hours, acetone 1
Added to Little. The precipitated polymer was dried under reduced pressure to obtain 11.5 g of partially quaternized 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 coated on 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 2 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 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 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 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.

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 3, 0.5 g of N,N-methylenebisacrylamide, and 0.2 g of benzoin isopropyl ether were dissolved in 20 g of a DMF-water mixed solvent,
A conductive crosslinkable material solution, which is a solution of the material of the present invention, was prepared. Apply this solution on a glass substrate with a spin cord,
A uniform coating film of 1.5 μm was obtained. This coated film was irradiated with ultraviolet rays at 200 m j /Cm 2 using a high-pressure mercury lamp. Table 2 shows the surface resistance values after immersion in methanol for 60 seconds.
Shown below.

Usage Example 10 5 g of the polymer obtained in Example 4, 0.5 g of N,N--methylenebisacrylamide, and 0.2 g of 2-(3-sulfopropoxy)thioxanthone were mixed in a DMF-water mixed solvent of 20 g.
A conductive crosslinkable material solution, which is a solution of the material of the present invention, was prepared by dissolving the material in g. 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 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 coated film was irradiated with ultraviolet rays of 500 m j /cm 2 using a high-pressure mercury lamp. Table 2 shows the surface resistance values after being immersed 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.

Table 2 In Table 2, 3.4E7 indicates 3.4X107, and the same description will be used hereinafter.

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 conductive crosslinkable materials, and these conductive crosslinkable materials have the following remarkable characteristics.

(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 can cause 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 be suppressed.

(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.

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 R_
2, R_3 and R_4 are hydrogen atoms or have 1 to 4 carbon atoms
represents an alkyl group, m and n represent integers of 1 or more, and
indicates a halogen atom. ) A conductive crosslinkable material characterized by containing an organic polymer represented by: