JP4526068B2 - Conductivity imparting agent and conductive resin composition - Google Patents

Description

  The present invention relates to a conductivity imparting agent for imparting conductivity to a thermoplastic resin or rubber and a conductive resin composition to which the conductivity imparting agent is added.

  Conductive resin compositions such as thermoplastic resins, ultraviolet curable resins or rubbers with added conductivity-imparting agents are used for conductive sheets such as dustproof sheets, antistatic films, static elimination mats, antistatic flooring, and electrophotographic printers. It is used as a conductive roll (charging roll, developing roll, transfer roll, etc.), a substrate for magnetic recording media, a semiconductor material, etc.

  Conventionally, a conductivity imparting agent using lithium perchlorate as an ionic conductive agent has been proposed (see, for example, Patent Document 1). Lithium perchlorate is an anti-static property, that is, an electrical conductivity imparting agent that is excellent in electrical conductivity, is inexpensive and advantageous in terms of cost, but the compound is an oxidizable solid belonging to the first class of dangerous substances stipulated in the Fire Service Law. When mixed with combustible materials, there is a risk of heat generation and ignition. Therefore, special care is required for handling, and the amount added to the resin or the like is limited from the viewpoint of safety.

  In recent years, conductivity imparting agents using fluorine-containing organic anion salts such as lithium bis (trifluoromethanesulfonyl) imidoate and lithium tris (trifluoromethanesulfonyl) methanoate have been proposed as ionic conductive agents (for example, Patent Document 2). reference). Although the compound has a relatively high conductivity, further improvement in performance has been desired with respect to compatibility when kneaded into a thermoplastic resin or rubber or the like, or heat resistance and bleed resistance during or after processing. .

Japanese Patent Laid-Open No. 08-176255 JP 2002-146178 A

  The purpose of the present invention is, when kneaded into a thermoplastic resin or rubber, etc., has good compatibility, excellent heat resistance, improved bleeding to the surface of the resin or rubber, and reduced risk of heat generation and ignition, It is in providing the conductive resin composition formed by adding the conductivity imparting agent excellent in safety | security, and this conductivity imparting agent.

  As a result of intensive studies, the present inventors have dealt with a cyclic perfluoroalkylene disulfonimide compound or a conductivity imparting agent containing the cyclic perfluoroalkylene disulfonimide compound and perchlorates as an ionic conductive agent. It has been found that the above problems can be solved easily, and the present invention has been completed.

  That is, the present invention is a conductivity-imparting agent comprising at least one selected from cyclic perfluoroalkylene disulfonimide compounds represented by the general formula [1] as an ionic conductive agent. .

一般式〔１〕中、ｍは２〜８の正整数、ｎは１または２の正整数、Ｍはアルカリ金属またはアルカリ土類金属を表す。

In the general formula [1], m represents a positive integer of 2 to 8, n represents a positive integer of 1 or 2, and M represents an alkali metal or an alkaline earth metal.

  The cyclic perfluoroalkylene disulfonimide compound is a cyclohexafluoropropane-1,3-bis (sulfonyl) imide compound represented by the general formula [2].

一般式〔２〕中、ｎは１または２の正整数、Ｍはアルカリ金属またはアルカリ土類金属を表す。

In general formula [2], n represents a positive integer of 1 or 2, and M represents an alkali metal or an alkaline earth metal.

  Further, the present invention provides at least one selected from cyclic perfluoroalkylene disulfonimide compounds represented by the general formula [1] or the general formula [2] and perchlorates as the ionic conductive agent. 1 type is contained, It is an electroconductivity imparting agent characterized by the above-mentioned.

  In the present invention, a cyclic perfluoroalkylene disulfonimide compound, or an ionic conductive agent comprising the imide compound and perchlorates is a polyethylene oxide, a polypropylene oxide, a polyethylene oxide-polypropylene oxide copolymer, a polyethylene-polyalkylene glycol graft. It is added to at least one selected from polyether polyols made of a copolymer, and less than 20 parts by weight of perchlorates are added to 100 parts by weight of the polyether polyols. It is a conductivity-imparting agent.

  Furthermore, this invention is a conductive resin composition characterized by adding 0.1-30 mass parts of electroconductivity imparting agents of this invention to 100 mass parts of thermoplastic resins or rubber | gum.

  The conductivity-imparting agent of the present invention comprises a cyclic perfluoroalkylene disulfonimide compound, or a cyclic perfluoroalkylene disulfonimide compound and perchlorates as an ionic conductive agent. , Good compatibility with resins, etc., excellent heat resistance, has the effect of reducing contamination by bleed on the resin or rubber surface, and, in combination with perchlorates, has high conductivity, An electroconductivity imparting agent that is also excellent in economic efficiency can be obtained. In addition, when the amount of perchlorate added is less than 20 parts by mass, the risk of heat generation and ignition is reduced and handling is easy.

  In addition, the conductive resin composition using the conductivity-imparting agent of the present invention is excellent in bleed resistance, heat resistance and antistatic properties, and can maintain stable characteristics for a long period of time.

  Hereinafter, the conductivity imparting agent of the present invention will be described in detail.

  The conductivity-imparting agent of the present invention contains at least one selected from cyclic perfluoroalkylene disulfonimide compounds represented by the general formula [1] as an ionic conductive agent.

  As said cyclic perfluoroalkylene disulfonimide compound, in general formula [1], m is represented by the positive integer of 2-8, M is an alkali metal (lithium, sodium, potassium) or alkaline-earth metal (magnesium, calcium) In the present invention, at least one compound obtained by combining these two components is used. Among these compounds, the cyclohexafluoropropane-1,3-bis (sulfonyl) imide compound represented by the general formula [2] is preferable from the viewpoint of being easily available industrially and economically excellent.

  The cyclic perfluoroalkylene disulfonimide compound has good compatibility with resins, etc., excellent heat resistance, and reduced contamination due to bleeding on the resin or rubber surface. Alone, it may be economically disadvantageous.

  In the conductivity-imparting agent of the present invention, perchlorates can be used in combination with the above-mentioned cyclic perfluoroalkylene disulfonimide compound from the viewpoint of enhancing economy and conductivity.

  Examples of perchlorates used in the present invention include alkali metal salts such as lithium perchlorate, sodium perchlorate and potassium perchlorate, and alkaline earth metal salts such as magnesium perchlorate and calcium perchlorate. Among these, lithium perchlorate is more preferable because of its high conductivity.

  That is, the conductivity-imparting agent of the present invention contains at least one selected from cyclic perfluoroalkylene disulfonimide compounds and at least one selected from perchlorates as an ionic conductive agent. Increasing the proportion of acid salts increases the risk of heat generation, ignition, etc., making handling difficult.On the other hand, increasing the proportion of fluorine-containing organic anion salts is economically disadvantageous. In general, the mass ratio of the cyclic perfluoroalkylene disulfonimide compound and the perchlorates is in the range of 1:10 to 10: 1, preferably 1: 5 to 5: 1.

  The conductivity-imparting agent of the present invention is selected from the group consisting of polyethylene oxide, polypropylene oxide, polyethylene oxide-polypropylene oxide copolymer and polyethylene-polyalkylene glycol graft copolymer which are polyether polyols as the ionic conductive agent. By adding at least one kind, the conductivity can be increased and the compatibility with the thermoplastic resin and rubber can be further improved. Preferably, the polyether polyol is added to 1 part by mass of the ionic conductive agent. In the range of 2 to 100 parts by mass.

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

  The conductive resin composition of the present invention is one in which the conductivity imparting agent of the present invention is contained in a thermoplastic resin or rubber.

  Examples of the thermoplastic resin used in the present invention include polyolefin resins such as polyethylene, polypropylene, and polystyrene, polyacetal, acrylic resin, polyphenylene ether, polystyrene, polyether ketone, polyethylene terephthalate, polycarbonate, polyurethane, polyvinyl chloride, and poly Examples include vinylidene chloride, polyimide, polyetherimide, polyamideimide, polyphenylene sulfide, and polysulfone. Among these, polyacrylic resin, polyester resin, polyamide resin, polyurethane resin, polyvinyl chloride resin, Epoxy resins or at least one of these resins is preferred.

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and a block copolymer of polyethylene glycol and polypropylene glycol. Diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate and the like. Examples of the acrylate include trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylolmethane triacrylate, butanediol diacrylate, polyethylene glycol diacrylate, and the like.

  Examples of the rubber used in the present invention 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. Examples thereof include at least one selected from rubber and foams thereof.

  The conductive resin composition of the present invention is used by adding a predetermined amount of the conductivity imparting agent of the present invention to the above thermoplastic resin or rubber, kneading, and forming into a film, sheet or roll.

  Moreover, the electroconductivity imparting agent of the present invention and the thermoplastic resin or rubber can be used as a coating liquid composition by dissolving them in a soluble solvent, and the coating liquid composition can be used as a resin film, glass or the like. After applying to a base material, it is possible to form a conductive coating film on the surface of the base material by drying and curing.

  When the conductivity-imparting agent of the present invention is added to the thermoplastic resin or rubber, the cyclic perfluoroalkylene disulfonimide compound or cyclic perfluoroalkylene that is an ionic conductive agent is usually added to 100 parts by mass of the thermoplastic resin or rubber. The total amount of the disulfonimide compound and perchlorates is added within a range of 0.1 to 30 parts by mass. When the addition amount of the ionic conductive agent is less than 0.1 parts by mass, the conductivity of the resulting conductive resin composition may be insufficient, and when it exceeds 30 parts by mass, the conductivity is sufficient. However, bleed is likely to occur.

  Hereinafter, the present invention will be described based on examples. In addition, this invention is not limited at all by the Example. In the examples, “part” represents “part by mass”.

Reference example 1
85 parts of polyethylene-polyethylene glycol graft copolymer (Sumitomo Chemical Co., Ltd., registered trademark: Sumiade 300G, hereinafter abbreviated as “PE-PEG copolymer”), cyclic perfluoroalkylene disulfonimide as an ionic conductive agent After adding 15 parts of cyclohexafluoropropane-1,3-bis (sulfonyl) imide potassium (hereinafter abbreviated as “CFPSI-K”) as a compound (hereinafter abbreviated as “CFASI”), a temperature of 70 ° C. The mixture was heated and kneaded to obtain a conductivity imparting agent.

  Next, 100 parts of a methacrylic resin (Mitsubishi Rayon Co., Ltd. registered trademark: Acrypet IR H-70, hereinafter abbreviated as “PMMA”), which is a thermoplastic resin, is added with 5 parts of the conductivity imparting agent obtained above. It was added and heated and kneaded at a temperature of 180 ° C. in a test roll machine (HR-2 type manufactured by Nisshin Kagaku Co., Ltd.) to obtain a 1 mm thick conductive sheet.

As a result of measuring the surface resistance of the obtained conductive sheet at a temperature of 25 ° C. and a humidity of 40% using a surface resistance measuring machine (HT-210 manufactured by Mitsubishi Chemical Corporation), 5.0 × 10 ⁷ Ω / □ And showed sufficient conductivity for antistatic. Further, the occurrence of bleeding on the surface was observed by visually observing whether or not the conductivity-imparting agent oozed out after the conductive sheet was folded in two and left for 100 days in an environment of a temperature of 40 ° C. and a humidity of 80%. As a result, no bleed was observed. Table 1 shows the composition of the conductive sheet and the evaluation results.

Example 1
80 parts of PE-PEG copolymer (Sumiade 300G), 10 parts of cyclohexafluoropropane-1,3-bis (sulfonyl) imidolithium (hereinafter abbreviated as “CPPSI-Li”), which is an ionic conductive agent, and perchlorine After adding 10 parts of lithium acid, it was heat-kneaded at a temperature of 70 ° C. to obtain a conductivity imparting agent.

  Next, 100 parts of polyurethane resin (Dainippon Ink Chemical Co., Ltd., Pandex T-8190N, hereinafter abbreviated as “PU”), which is a thermoplastic resin, is added with 10 parts of the previously obtained conductivity imparting agent. It was added and heated and kneaded at a temperature of 180 ° C. in a test roll machine to obtain a conductive sheet having a thickness of 1 mm.

About the obtained conductive sheet, the surface resistance value was measured in the same manner as in Reference Example 1. As a result, it was 0.9 × 10 ⁷ Ω / □, showing sufficient conductivity for antistatic, Not observed. The results are shown in Table 1.

Reference example 2
10 parts of a conductivity-imparting agent obtained in the same manner as in Reference Example 1 were added to 100 parts of urethane (Nippon Polyurethane Industry Co., Ltd., trade name: NIPPOLAN 5119, hereinafter abbreviated as “UR”), which is a foaming rubber. It was added, heated and kneaded at a temperature of 110 ° C., fired and crosslinked, and then poured into a molding die to obtain a conductive rubber molded body having a thickness of 12 mm.

About the obtained conductive rubber molding, the surface resistance value was measured in the same manner as in Reference Example 1. As a result, it was 1.5 × 10 ⁷ Ω / □, showing sufficient conductivity for antistatic, Development was not observed. The results are shown in Table 1.

Example 2
To 100 parts of epichlorohydrin (Daiso registered trademark: Epichroma CG-102, hereinafter abbreviated as “EP”) which is a foaming rubber, 5 parts of a conductivity imparting agent obtained in the same manner as in Example 1 was added. Then, after heating and kneading at a temperature of 100 ° C., firing and crosslinking, the mixture was poured into a molding die to obtain a conductive rubber molded body having a thickness of 12 mm.

As a result of measuring the surface resistance value of the obtained conductive rubber molded body in the same manner as in Reference Example 1 , it was 4.0 × 10 ⁷ Ω / □, and showed sufficient conductivity for antistatic, Development was not observed. The results are shown in Table 1.

Reference example 3
Polyethylene oxide-polypropylene oxide copolymer (registered trademark of Nippon Oil & Fats Co., Ltd .: Pronon 201, hereinafter abbreviated as “PEO-PPO copolymer”), which is a polyether polyol, is added to CFPSI— K20 parts and 10 parts of lithium chlorate were dissolved to obtain a conductivity imparting agent.

  To 100 parts of the resulting conductivity imparting agent, 30 parts of tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., hereinafter abbreviated as “TDI”) is added as a curing agent, and 100 parts of methyl ethyl ketone as an organic solvent. The coating liquid composition was obtained by adding and dissolving.

  The coating liquid composition is applied onto a polyethylene terephthalate (hereinafter abbreviated as “PET”) film using a bar coater (# 20 coating rod), dried and cured, and then a urethane resin having a thickness of 5 μm. A conductive coating film was formed.

As a result of measuring the surface resistance value of the obtained conductive coating film in the same manner as in Reference Example 1 , it was 3.5 × 10 ⁷ Ω / □, showing sufficient conductivity for antistatic, and generation of bleeding. Was not observed. Table 2 shows the main components of the coating film and the evaluation results.

Reference example 4
25 parts of COPSI-Li, which is an ionic conductive agent, was added to and dissolved in 75 parts of a PEO-PPO copolymer (Sanyo Kasei Kogyo Co., Ltd .: New Pole PE-62) to obtain a conductivity imparting agent.

  To 100 parts of the resulting conductivity imparting agent, 32 parts of TDI was added, and 100 parts of methyl ethyl ketone was further added and dissolved as a solvent to obtain a coating liquid composition.

Using the coating liquid composition, a conductive coating film made of a urethane resin having a thickness of 5 μm was formed on a PET film in the same manner as in Reference Example 3 .

The surface resistance of the conductive coating film was measured in the same manner as in Reference Example 1. As a result, it was 5.3 × 10 ⁷ Ω / □, and it showed sufficient conductivity for antistatic, and the occurrence of bleeding was observed. There wasn't. The results are shown in Table 2.

Reference Example 5
In 70 parts of a PEO-PPO copolymer (Pronon 201), 20 parts of CPPSI-K and 10 parts of lithium perchlorate were dissolved as an ionic conductive agent to obtain a conductivity-imparting agent.

  26 parts of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., hereinafter abbreviated as “HDI”) and 0.01 part of dibutyltin dilaurate are added to 100 parts of the resulting conductivity imparting agent, and urethanized at 85 ° C. for 3 hours. Reaction was performed. Subsequently, 45 parts of trimethylolpropane triacrylate (hereinafter abbreviated as “TPT”) and 0.1 part of a polymerization inhibitor hydroquinone were added and reacted at 80 ° C. for 4 hours.

  To 100 parts of the reaction product, 4 parts of photopolymerization initiator (registered trademark of Nagase Sangyo Co., Ltd .: Darocur 1173) and 100 parts of methyl ethyl ketone were added and dissolved to obtain a coating liquid composition.

The coating liquid composition is applied onto a PET film using a bar coater (# 5 coating rod), and then cured by irradiating with 100 mJ / cm ² ultraviolet rays to form a 10 μm-thick polyurethane acrylate conductive coating film. Formed.

As a result of measuring the surface resistance value of the conductive coating film in the same manner as in Reference Example 1 , it was 7.5 × 10 ⁸ Ω / □, and showed sufficient conductivity for antistatic, and generation of bleeding. Was not observed. The results are shown in Table 2.

Reference Example 6
20 parts of CPPSI-Li, which is an ionic conductive agent, was added to and dissolved in 80 parts of a PEO-PPO copolymer (New Pole PE-62) to obtain a conductivity imparting agent.

  30 parts of methacrylic acid (hereinafter abbreviated as “MAA”), 7 parts of sulfuric acid, 100 ml of n-hexane and 0.1 part of phenothiazine are added to 100 parts of the obtained conductivity imparting agent, and dehydrated ester at 60 ° C. for 12 hours. And water and hexane were distilled off under reduced pressure.

  To 100 parts of the reaction product, 4 parts of photopolymerization initiator (Darocur 1173) and 100 parts of methyl ethyl ketone were added and dissolved to obtain a coating liquid composition.

Using the coating liquid composition, a conductive coating film made of polyester acrylate having a thickness of 8 μm was formed on a PET film by the same operation as in Reference Example 5 .

With respect to the conductive coating film, the surface resistance value was measured in the same manner as in Reference Example 1. As a result, it was 9.7 × 10 ⁸ Ω / □, showing sufficient conductivity for antistatic, and occurrence of bleeding was observed. Was not. The results are shown in Table 2.

<Dangerous goods confirmation test>
Reference Example 7
In 80 parts of a PEO-PPO copolymer (New Pole PE-62), 20 parts of CFPSI-Li as an ionic conductive agent was dissolved to obtain a conductivity-imparting agent.

  About the obtained electroconductivity imparting agent, the thermal analysis test (differential scanning calorimetry) was done according to the 5th class dangerous goods judgment test of the Fire Service Act. In this test, the exothermic starting temperature and calorific value of a standard substance (2,4-dinitrotoluene, benzoyl peroxide) are measured with a differential scanning calorimeter, and the exothermic starting temperature and calorific value of the test sample are obtained from the standard substance. It is determined that there is a risk if it exceeds the specified risk standard. Table 3 shows the composition ratio of the conductivity imparting agent and the dangerous substance confirmation test.

Reference Example 8
In 80 parts of the PEO-PPO copolymer, 10 parts of CPPSI-Li as an ionic conductive agent and 10 parts of lithium perchlorate were dissolved to obtain a conductivity-imparting agent.

About the obtained electroconductivity imparting agent, it carried out similarly to the reference example 7, and performed the dangerous substance confirmation test. The results are shown in Table 3.

Comparative Example 1
The PEO-PPO copolymer 90 parts, was dissolved in 10 parts of lithium perchlorate which is an ion conductive agent, to obtain a conductive agent, for the conductive agent, confirmed hazardous materials tested in the same manner as in Reference Example 7 Table 3 shows the results of the test.

Comparative Example 2
The PEO-PPO copolymer 80 parts, was dissolved lithium perchlorate 20 parts is an ionic conductive agent to obtain a conductive agent, for the conductive agent, confirmed hazardous materials tested in the same manner as in Reference Example 7 Table 3 shows the results of the test.

From the dangerous substance confirmation test results in Table 3, when only 10 parts of lithium perchlorate was added as an ionic conductive agent (Comparative Example 1), it was judged that there was no danger, but 20 parts of the same was added (Comparative Example 2). The calorific value was high and it was judged that there was danger. On the other hand, the conductivity-imparting agent of the present invention ( Reference Example 8 ) added by mixing 10 parts of lithium perchlorate and 10 parts of CPPSI-Li was judged as no danger, and 20 parts of CPPSI-Li was added. It can be seen that the conductivity imparting agent of the present invention ( Reference Example 7 ) is further excellent in safety.

  The conductivity-imparting agent of the present invention contains a cyclic perfluoroalkylene disulfonimide compound, or a cyclic perfluoroalkylene disulfonimide compound and perchlorates as an ionic conductive agent. Good compatibility with resins, etc., excellent heat resistance, and the effect of reducing contamination by bleed on the resin or rubber surface. Furthermore, when used in combination with perchlorates, it is highly conductive and economical. In addition, an excellent conductivity imparting agent can be obtained. Moreover, when the addition amount of perchlorates is less than 20 parts by mass, the risk of heat generation and ignition is reduced and handling is easy.

  In addition, the conductive resin composition using the conductivity-imparting agent of the present invention is excellent in bleed resistance, heat resistance and antistatic properties, can maintain stable characteristics for a long period of time, and has excellent transparency. So conductive sheets such as dustproof sheets, static elimination mats and antistatic flooring materials, antistatic films, antistatic release films, antistatic agents for various displays, conductive paints, conductive coating agents, electrophotographic printers and copiers It can be applied to electroconductive rolls (charging rolls, cleaning rolls, developing rolls, etc.), electrolytes for electrochemical devices such as polymer secondary batteries, substrates for magnetic recording media, and materials for semiconductors.

Claims (5)

An electrical conductivity imparting agent contained in a thermoplastic resin or rubber, an ionic conductive agent comprising a cyclic perfluoroalkylene disulfonimide compound represented by the following general formula [1] and perchlorates, polyethylene oxide, It is added to at least one selected from polyether polyols consisting of polypropylene oxide, polyethylene oxide-polypropylene oxide copolymer, polyethylene-polyalkylene glycol graft copolymer, and 100 parts by mass of the polyether polyols. On the other hand, the electroconductivity imparting agent characterized by adding less than 20 mass parts perchlorates.

(In the formula, m represents a positive integer of 2 to 8, n represents a positive integer of 1 or 2, and M represents an alkali metal or an alkaline earth metal.) A conductive resin composition comprising 0.1 to 30 parts by mass of the conductivity imparting agent according to claim 1 added to 100 parts by mass of a thermoplastic resin. A conductive resin composition comprising 0.1 to 30 parts by mass of the conductivity-imparting agent according to claim 1 added to 100 parts by mass of rubber . A conductive resin film produced using the conductive resin composition according to claim 2 . A coating liquid composition produced using the conductive resin composition according to claim 2 .