JP2008127483A - Electrically conductive resin composition and electrically conductive resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrically conductive resin composition which is free from metal corrosiveness or hygroscopicity and has good compatibility with various resins and thus imparts high electrical conductivity even in the case of small amounts of an ionically conductive agent incorporated into a thermoplastic resin, ultraviolet-curable resin, rubber, adhesive, or the like, by kneading the ionically conductive agent in high compatibility. <P>SOLUTION: The electrically conductive resin composition is provided, being such as to be incorporated, as the ionically conductive agent, with a fluoroalkyl group-substituted boron complex salt. Electrically conductive materials made from the above composition are also provided, being useful as dustproof sheets, antistatic films, electricity-removing mats, electrically conductive sheets for e.g. antistatic flooring materials, electrically conductive rolls for electrophotographic printers and copiers (e.g. antistatic rolls, developing rolls, transfer rolls), magnetic recording medium bases, semiconductor materials, etc. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a conductive resin composition in which an ionic conductive agent for imparting conductivity is contained in a resin such as a thermoplastic resin, an ultraviolet curable resin, rubber or an adhesive, and more specifically, a novel ionic conductive. The present invention relates to a conductive resin composition containing a boron complex salt substituted with a fluoroalkyl group, which is an agent, and a conductive resin molding.

  Conductive resin compositions such as thermoplastic resins, ultraviolet curable resins, rubbers or pressure-sensitive adhesives to which ionic conductive agents are added are conductive sheets such as dustproof sheets, antistatic films, static elimination mats, antistatic flooring, It is used as a conductive roll (charging roll, developing roll, transfer roll, etc.), base material for magnetic recording medium, semiconductor material, etc. for electrophotographic printers and copying machines.

  Conventionally, a conductive resin composition using lithium perchlorate as an ionic conductive agent has been proposed (see Patent Document 1). Lithium perchlorate is an ionic conductive agent that has excellent antistatic properties, that is, electrical conductivity, is inexpensive and advantageous in terms of cost, but the compound is an oxidizable solid and requires special care in handling. Furthermore, since the ionic conductive agent has metal corrosivity and hygroscopicity, it has a drawback that its substrate surface and electrical characteristics are easily affected by moisture.

  Patent Documents 2 to 4 disclose conductive resin compositions using boron complex salts as ionic conductive agents. In general, a boron complex salt has no metal corrosiveness and can further reduce hygroscopicity compared to lithium perchlorate. However, the conventionally known boron complex salt compound has a defect that it is necessary to add a large amount of the boron complex salt in order to obtain high electrical characteristics because the conductivity imparting ability to the resin is insufficient. .

Japanese Patent Laid-Open No. 08-176255 Japanese Patent Laid-Open No. 10-046023 (Japanese Patent No. 3772402) Japanese Patent Laid-Open No. 10-048912 (Japanese Patent No. 3451845) JP-A-10-207182

  The object of the present invention is that there is no metal corrosiveness and hygroscopicity, and when the ionic conductive agent is kneaded into a thermoplastic resin, an ultraviolet curable resin, rubber or an adhesive, etc., the compatibility is good and uniform mixing is possible, and a small addition amount However, it is to provide a conductive resin composition that provides high conductivity.

  In view of the above problems, the present inventors have intensively studied. As a result, a conductive resin composition containing an ion conductive agent composed of a boron complex salt substituted with a fluoroalkyl group in the resin monomer body solves the above problems. As a result, the present invention has been completed.

  That is, the present invention is a conductive resin composition characterized in that the resin monomer body contains at least a boron complex salt represented by the following general formula (A) or (B).

R ₁ represents a fluorine atom or a fluoroalkyl group, R ₂ , R ₃ and R ₄ represent a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group or an aryl group, and R ₁ , R ₂ , R ₃ and R 4 ₄ may be the same as or different from each other. X represents an alkali metal.

In the formula, R ₅ represents a fluorine atom or a fluoroalkyl group, R ₆ , R ₇ and R ₈ represent a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group or an aryl group, and R ₅ , R ₆ , R ₇ and R ₈ may be the same as or different from each other. X represents an alkali metal.

  In the present invention, the ionic conductive agent is added to at least one resin monomer selected from the group consisting of thermoplastic resins, ultraviolet curable resins, rubbers or elastomers, and pressure-sensitive adhesives. It is an adhesive resin composition.

  The present invention also provides the conductive resin composition, wherein a mass mixing ratio of the resin monomer body and the ionic conductive agent is 99: 1 to 50:50.

  Furthermore, the present invention is a conductive resin molded body obtained by molding the conductive resin composition into a film shape, a sheet shape, or a roll shape.

  Moreover, this invention is a coating agent containing the said conductive resin composition.

  Moreover, this invention is a conductive film in which the said coating agent was coated on the base film, and the conductive layer was formed.

  Since the conductive resin composition of the present invention uses a boron complex salt substituted with a fluoroalkyl group as an ionic conductive agent, the ionic conductive agent is converted into a thermoplastic resin, an ultraviolet curable resin, a rubber, an adhesive, or the like. When kneading, it has good compatibility and can be mixed uniformly. Moreover, even if it adds a small amount of ionic conductive agents, since the conductive resin composition of this invention is excellent in electroconductivity provision ability, the conductive resin molding excellent in the electrical property can be provided.

  Hereinafter, the conductive resin composition of the present invention will be described in detail.

  The present invention is a conductive resin composition characterized in that the resin monomer body contains at least one boron complex salt represented by the general formula (A) or (B) as an ionic conductive agent.

In the general formula (A), R ₁ represents a fluorine atom or a fluoroalkyl group, R ₂ , R ₃ and R ₄ represent a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group or an aryl group, and R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. As the fluoroalkyl group, a fluorine-substituted alkyl group having 1 to 8 carbon atoms in which at least one hydrogen is substituted with fluorine is preferable, and a fluorine-substituted alkyl group having 1 to 4 carbon atoms is more preferable from the viewpoint of molecular weight. More specifically, a fluoromethyl group is preferable, and a perfluoromethyl group is particularly preferable. X represents an alkali metal, preferably Na or K.

  Specific examples of the compound represented by the general formula (A) include the following compounds (a) and (b).

In the general formula (B), R ₅ represents a fluorine atom or a fluoroalkyl group, R ₆ , R ₇ and R ₈ represent a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group or an aryl group, and R ₅ , R ₆ , R ₇ and R ₈ may be the same or different. As the fluoroalkyl group, a fluorine-substituted alkyl group having 1 to 8 carbon atoms in which at least one hydrogen is substituted with fluorine is preferable, and a fluorine-substituted alkyl group having 1 to 4 carbon atoms is more preferable from the viewpoint of molecular weight. More specifically, a fluoromethyl group is preferable, and a perfluoromethyl group is particularly preferable. X represents an alkali metal, preferably Na or K.

  Specific examples of the compound represented by the general formula (B) include the following compounds (c) and (d).

  The boron complex salt substituted with the fluoroalkyl group used in the present invention can be produced, for example, by the following method.

  For example, compound (a) is prepared by adding equimolar amounts of boric acid and potassium hydroxide to water, and adding 3,3,3-trifluoro-2-hydroxy-2-methylpropionic acid to boric acid and potassium hydroxide. It can be obtained by adding a 2-fold molar amount to the reaction.

  In addition, compound (c) is added by adding equimolar amounts of boric acid and potassium hydroxide to water, and adding 4- (trifluoromethyl) salicylic acid to this in an amount twice as much as boric acid and potassium hydroxide. You can get it by doing.

  The resin monomer body is preferably at least one resin monomer body selected from the group consisting of thermoplastic resins, ultraviolet curable resins, rubbers or elastomers, and pressure-sensitive adhesives.

  Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, and polystyrene, polyacetal, polyacrylate, polyacrylic resin, polyphenylene ether, polystyrene, polyetherketone, polyethylene terephthalate, polyester resin, polycarbonate, polyurethane resin, and polyamide resin. , Polyvinyl chloride resin, polyvinylidene chloride, polyimide, polyetherimide, polyamideimide, polyphenylene sulfide, polysulfone, epoxy resin and the like. In particular, at least one of polyacrylic resin, polyvinyl chloride resin, and epoxy resin is preferable from the viewpoint of excellent conductivity of the obtained conductive resin composition.

  Examples of the ultraviolet curable resin include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate having two functional groups. And pentaerythritol triacrylate, pentaerythritol tetraacrylate having three or more functional groups, and ethoxylated trimethanolpropane triacrylate. In particular, at least one acrylate having two functional groups is preferable from the viewpoint of excellent viscosity adjustment of the obtained conductive resin composition.

  Examples of rubber or elastomer include urethane rubber, acrylic rubber, acrylonitrile / butadiene rubber, epichlorohydrin rubber, epichlorohydrin / ethylene oxide copolymer rubber, silicon rubber, fluoroolefin / vinyl ether copolymer urethane rubber, styrene / butadiene copolymer rubber, and The at least 1 sort (s) chosen from the group which consists of those foams is mentioned.

  Examples of the pressure sensitive adhesive include rubber pressure sensitive adhesive, acrylic pressure sensitive adhesive, and silicon pressure sensitive adhesive. Examples of rubber-based pressure-sensitive adhesives include pressure-sensitive adhesives made of natural rubber, SBR, or block copolymers such as polybutadiene, polyisoprene, and polystyrene. Examples of the acrylic pressure-sensitive adhesive include butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, acrylic acid, and the like, and lauryl acrylate and 2-ethylhexyl acrylate as raw materials for the energy ray-curable solvent-free acrylic pressure-sensitive adhesive. , Glycidyl acrylate, ethyl acrylate and the like.

  In the present invention, the mixing ratio of the ionic conductive agent is such that the sum of the ionic conductive agent is 1 to 50 masses with respect to 99 to 50 mass parts of the resin monomer body such as thermoplastic resin, ultraviolet curable resin, rubber or elastomer and adhesive. It is preferable that a part is added. That is, the mass mixing ratio of the resin monomer body and the ionic conductive agent is preferably 99: 1 to 50:50, more preferably 90:10 to 70:30.

  As a method of dissolving the fluoroalkylboron complex salt in the thermoplastic resin, ultraviolet curable resin, rubber or elastomer, adhesive, etc., the resin monomer body is heated and the complex salt is added and dissolved, or the resin A method in which the complex salt is once dissolved in a solvent and added to and mixed with the monomer body, and then the solvent is removed. A method in which the polyether polyol incorporated into the resin by reacting with the resin monomer body is substituted with the solvent. Can be prepared.

  In addition to the specific fluoroalkyl boron complex salt, various additives can be appropriately added to the conductive resin composition of the present invention. These additives include conductive aids such as metal oxides, reinforcing agents such as carbon black, graphite, calcium carbonate, mica and silica, fillers, stabilizers, ultraviolet absorbers, antistatic agents, lubricants, release agents. Examples include molds, dyes, pigments and flame retardants. These can be used alone or in combination of two or more.

  By kneading the conductive resin composition of the present invention and molding it into a film, sheet, roll, or the like, a conductive resin molded article having excellent antistatic properties and electrostatic properties can be obtained.

  Moreover, it is also possible to add a solvent suitably to the conductive resin composition of the present invention to form a coating agent. By coating the base film with a coating agent containing the conductive resin composition of the present invention, a conductive film in which a conductive layer is formed on the film is obtained.

  The coating method is not particularly limited, and a bar coating method, a roll coating method, a gravure coating method, a die coating method, or the like can be used as appropriate. Moreover, there is no restriction | limiting in particular also about the solvent when setting it as the said coating agent.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not restrict | limited at all by the Example. In the examples, “part” represents “part by mass”.

Example 1
Polyurethane resin (Dainippon Ink Chemical Co., Ltd., Pandex T-8190N) (hereinafter abbreviated as “PU”) (70 parts) as a thermoplastic resin is added 30 parts of compound (A) as an ionic conductive agent. After the addition, it was dissolved by heating at a temperature of 70 ° C., and heated and kneaded at a temperature of 100 ° C. in a test roll machine (manufactured by Nisshin Kagaku Co., Ltd., HR-2 type) to obtain a conductive sheet having a thickness of 1 mm. .

  The surface resistance of the obtained conductive sheet at a temperature of 25 ° C. and a humidity of 40% was measured using a surface resistance measuring machine (manufactured by Mitsubishi Chemical Corporation, HT-210).

Example 2
To 70 parts of a methacrylic resin (Mitsubishi Rayon Co., Ltd., Acrypet IRH-70) (hereinafter abbreviated as “PMMA”) which is a thermoplastic resin, 30 parts of a compound (c) which is an ionic conductive agent is added. It was heated and melted at a temperature of 70 ° C., and heated and kneaded in a test roll machine at a temperature of 180 ° C. to obtain a conductive sheet having a thickness of 1 mm.

  The obtained conductive sheet was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
To 70 parts of urethane (Nippon Polyurethane Industry Co., Ltd., Nipponporan 5119) (hereinafter abbreviated as “U”), which is an expandable rubber, is added 30 parts of the compound (A) which is an ionic conductive agent, and the temperature is 110 ° C. The mixture was heated and kneaded to foam and crosslink, and then poured into a molding die to obtain a conductive rubber molded body having a thickness of 12 mm.

  The obtained conductive rubber molding was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
To 70 parts of epichlorohydrin (Daiso Co., Ltd., Epichromer CG-102) (hereinafter abbreviated as “EP”), which is a foaming rubber, 30 parts of compound (U) as an ionic conductive agent was added, and the temperature was 110 ° C. After heating and kneading to foam and crosslink, it was poured into a molding die to obtain a conductive rubber molded body having a thickness of 12 mm.

  The obtained conductive rubber molding was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
A conductive sheet was obtained in the same manner as in Example 1 except that 30 parts of the following compound (e) as an ionic conductive agent was used. The obtained conductive sheet was evaluated in the same manner as in the example. The results are shown in Table 1.

  The obtained conductive sheet was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
A conductive sheet was obtained in the same manner as in Example 1 except that 30 parts of the following compound (f) as an ionic conductive agent was used. The obtained conductive sheet was evaluated in the same manner as in the example. The results are shown in Table 1.

  The obtained conductive sheet was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3
A conductive sheet was obtained in the same manner as in Example 1 except that 30 parts of the following compound (ki) as an ionic conductive agent was used. The obtained conductive sheet was evaluated in the same manner as in the example. The results are shown in Table 1.

  The obtained conductive sheet was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4
A conductive sheet was obtained in the same manner as in Example 1 except that 30 parts of the following compound (K), which is an ionic conductive agent, was used. The obtained conductive sheet was evaluated in the same manner as in the example. The results are shown in Table 1.

  The obtained conductive sheet was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5
A conductive rubber molding was obtained in the same manner as in Example 3 except that 30 parts of the following compound (I), which was an ionic conductive agent, was used. The obtained conductive rubber molding was evaluated in the same manner as in the examples. The results are shown in Table 1.

  The obtained conductive rubber molding was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  From the results of Table 1, conductive resin molded bodies formed from conductive resin compositions to which boron complex salts substituted with fluoroalkyl groups of Examples 1 to 4 are added are those of Comparative Examples 1 to 5. The surface resistance value was excellent by about one digit as compared with.

Example 5
In 80 parts of a polyoxyethylene glycol-polyoxypropylene glycol block copolymer (Nippon Yushi Co., Ltd., Pronon 201) (hereinafter abbreviated as “PEO-PPO copolymer”) which is a polyether polyol. 20 parts of the compound (A) is added and dissolved as a conductive agent, 30 parts of tolylene diisocyanate (Nippon Polyurethane Industry Co., Ltd.) is added as a curing agent, and 100 parts of methyl ethyl ketone is added and dissolved as an organic solvent. To obtain a coating agent.

  The coating composition is applied onto a polyethylene terephthalate (hereinafter abbreviated as “PET”) film using a bar coater (# 20 coating rod), dried and cured, and is made of a 5 μm thick urethane resin. An adhesive film was formed.

  The obtained conductive film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 6
As an ionic conductive agent, 20 parts of the compound (c) is added and dissolved in 80 parts of a polyether polyol PEO-PPO copolymer (Sanyo Kasei Kogyo Co., Ltd., New Pole PE-62) as a curing agent. 30 parts of tolylene diisocyanate (Nippon Polyurethane Industry Co., Ltd.) was added, and 100 parts of methyl ethyl ketone was further added and dissolved as an organic solvent to obtain a coating agent.

  In the same manner as in Example 5 using the coating composition, a conductive film made of 5 μm urethane resin was formed on a PET film, and the obtained conductive film was evaluated. The results are shown in Table 2.

Comparative Example 6
A conductive film made of a urethane resin was formed in the same manner as in Example 5 except that 20 parts of the compound (e) was used as the ionic conductive agent, and the obtained conductive film was evaluated. The results are shown in Table 2.

Comparative Example 7
A conductive film made of a urethane resin was formed in the same manner as in Example 5 except that 20 parts of the compound (f) was used as the ionic conductive agent, and the obtained conductive film was evaluated. The results are shown in Table 2.

Comparative Example 8
A conductive film made of a urethane resin was formed in the same manner as in Example 6 except that 20 parts of the compound (ki) was used as the ionic conductive agent, and the obtained conductive film was evaluated. The results are shown in Table 2.

  From the results of Table 2, the conductive film formed from the conductive resin composition to which the boron complex salt substituted with the fluoroalkyl group of Examples 5 and 6 was added was compared with those of Comparative Examples 6-8. The surface resistance value was excellent by about one digit.

  The conductive resin composition of the present invention includes a conductive sheet such as a dustproof sheet, an antistatic film, a static elimination mat, an antistatic flooring, a conductive roll (electrostatic roll, developing roll, transfer roll) of an electrophotographic printer or copying machine. Etc.), and can be suitably used as a formed material that requires electrical conductivity, such as a magnetic recording medium substrate and a semiconductor material.

Claims (6)

In the conductive resin composition formed by adding an ionic conductive agent to the resin monomer body,
The conductive resin composition, wherein the ionic conductive agent contains at least a boron complex salt represented by the following general formula (A) or (B).

(In Formula A, R ₁ represents a fluorine atom or a fluoroalkyl group, and R ₂ , R ₃ and R ₄ may be the same or different from each other, hydrogen atom, fluorine atom, alkyl group, fluoroalkyl group, aryl group. X represents an alkali metal.)

(In the formula B, R ₅ represents a fluorine atom or a fluoroalkyl group, and R ₆ , R ₇ and R ₈ may be the same or different from each other, hydrogen atom, fluorine atom, alkyl group, fluoroalkyl group, aryl group. X represents an alkali metal.)   The conductive resin composition according to claim 1, wherein the resin monomer body is at least one resin monomer body selected from the group consisting of a thermoplastic resin, an ultraviolet curable resin, a rubber or an elastomer, and an adhesive. object.   The conductive resin composition according to claim 1, wherein a mass mixing ratio of the resin monomer body and the ionic conductive agent is 99: 1 to 50:50.   The electroconductive resin molding formed by shape | molding the electroconductive resin composition in any one of Claim 1 to 3 in the shape of a film, a sheet, or a roll.   The coating agent containing the conductive resin composition in any one of Claim 1 to 3.   A conductive film having a conductive layer formed by coating the coating agent according to claim 5 on a base film.