TW201536867A - Polysiloxane copolymer and antistatic agent containing the same - Google Patents

Abstract

The present invention provides a novel polysiloxane copolymer and an antistatic agent containing the same, which imparts a high antistatic property to the resin. The polysiloxane copolymer is prepared by the copolymerization of onium salt represented by formula (1) and dialkoxy silane represented by formula (2). (wherein, Q+ represents a nitrogen cation or a phosphorus cation, R1 represents an alkyl group having 1 to 3 carbon atoms, R2 to R4 each individually represent an alkyl group having 1 to 8 carbon atoms, X represents an anion, m and n are independently an integer of 1 to 3); (wherein, R5 represents an alkyl group having 1 to 3 carbon atoms or phenyl group, and R6 represents an alkyl group having 1 to 3 carbon atoms).

Description

Polyoxyalkylene copolymer and antistatic agent containing the above polyoxyalkylene copolymer

The present invention relates to a polyoxyalkylene copolymer and an antistatic agent containing the aforementioned polyoxyalkylene copolymer.

The polyoxyalkylene compounds described in Patent Documents 1 and 2 are known. Patent Document 1 describes the use of a polyoxyalkylene compound for a tackifier such as a hydrophobic polyoxygenated oil. Gelling agent. However, there is no description about the antistatic property of the aforementioned polyoxyalkylene compound. Patent Document 2 describes that a film-like composition containing a polyoxyalkylene compound exhibits high antistatic property. However, in the present invention, the film-like composition described in Patent Document 2 was used as an antistatic agent and stirred into a resin, and as a result, it was found that the antistatic property was insufficient (see a comparative example described later).

In addition, it has been reported that the cation is an ammonium salt or a ruthenium having a trialkoxyalkylalkyl group, and the anion is a perfluoroalkyl sulfonyl ruthenium imine salt, which can be used as a low molecular type antistatic for acrylic resin. (see Patent Document 3). However, the present invention will belong to one of the aforementioned sulfonium salts of 1-{(3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium=double As a result of using (trifluoromethanesulfonyl) quinone imine as an antistatic agent for a polyoxyxylene resin, it was found that although the antistatic property can be imparted to the polyoxyxene resin, the hardening of the polyoxyxylene resin is reversed. In the case of the optical adhesive, it is not possible to obtain a polyoxyxylene resin composition having practical strength characteristics (see the comparative example described later).

Prior technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-199918

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-286815

[Patent Document 3] Japanese Patent Publication No. 2013-28586

An object of the present invention is to provide a novel polyoxyalkylene copolymer which can impart high antistatic property to a resin, an antistatic agent containing the above polyoxyalkylene copolymer, and a resin composition containing the above antistatic agent. Further, an object of the present invention is to provide a polyoxyxylene resin composition which has high antistatic property and has practical strength properties for an optical adhesive.

In order to solve the above problems, the present invention has been specifically studied, and has found a polyoxyalkylene copolymer obtained by copolymerizing an onium salt represented by the formula (1) with a dialkoxysilane of the formula (2). Further, it has been found that when the polyoxyalkylene copolymer is used as an antistatic agent for a polycarbonate resin, a polyacrylic resin, and a polyoxyxylene resin, it is possible to impart antistatic properties to each of the resins. Further, the polyoxyxylene resin composition of the present invention in which a polyoxyalkylene copolymer has been blended with a polyoxyxylene resin has high antistatic property and is known as an optical adhesive. The present invention has been completed with practical strength characteristics.

That is, the present invention relates to a polyoxyalkylene copolymer, A method of copolymerizing an onium salt represented by the formula (1) (hereinafter referred to as a phosphonium salt (1)) with a dialkoxysilane (hereinafter referred to as a dialkoxysilane (2)) represented by the formula (2), and Regarding an antistatic agent containing the aforementioned polyoxyalkylene copolymer.

A polyoxyalkylene copolymer obtained by copolymerizing an onium salt represented by the formula (1) with a dialkoxysilane of the formula (2):

(wherein, Q ⁺ represents a nitrogen cation or a phosphorus cation, R ₁ represents an alkyl group having 1 to 3 carbon atoms, R ₂ to R ₄ are each independently, and represents an alkyl group having 1 to 8 carbon atoms; X ^- represents an anion, m and n are independent, an integer from 1 to 3);

(wherein R ₅ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ₆ represents an alkyl group having 1 to 3 carbon atoms).

The polyoxyalkylene copolymer of the present invention is used as a polycarbonate Antistatic agents for ester resins, polyacrylic resins, and polyoxyxylene resins impart higher antistatic properties than known polyoxyalkylene compounds. Further, the polyfluorene oxide resin composition containing the polyoxyalkylene copolymer of the present invention has high antistatic property and has practical strength properties as an optical adhesive.

Hereinafter, the present invention will be specifically described. In the formula (1), Q ⁺ represents a nitrogen cation or a phosphorus cation. R ₁ is an alkyl group having 1 to 3 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group, and a methyl group and an ethyl group are preferred. R ₂ to R _{4 each} represent an alkyl group having 1 to 8 carbon atoms, and may be any of a linear chain and a branched chain, and a linear alkyl group is preferred. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group, and a methyl group, an ethyl group, a propyl group, and a butyl group are preferred. X ^- represents an anion. Specifically, X ^- may be exemplified by a chloride anion, a bromide anion, a trifluoromethanesulfonate anion, a bis(perfluoroalkylsulfonyl) quinone imine anion, a tetrafluoroborate anion, a hexafluorophosphate anion, or the like. Preferably, a chloride anion and a bis(trifluoromethanesulfonyl) quinone imide are preferred, and a bis(trifluoromethanesulfonyl) quinone imine is preferred.

In the formula (2), R ₅ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group. Specific examples of R ₅ include a methyl group, an ethyl group, a propyl group, and a phenyl group, and a methyl group and a phenyl group are preferable. R ₆ represents an alkyl group having 1 to 3 carbon atoms. Specifically, R ₆ may, for example, be a methyl group, an ethyl group or a propyl group, and preferably a methyl group or an ethyl group.

Specific examples of the strontium salt (1) can be enumerated as follows: 1-{(3-Third A) Oxalyl propyl)amine methyl decyloxyethyl}-1,1,1-trimethylammonium = chloride, 1-{(3-triethoxydecylpropyl)amine carbhydryloxy Ethyl}-1,1,1-trimethylammonium=chloride, 1-{(3-tripropoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethyl Alkyl ammonium = chloride, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-triethylammonium = chloride, 1-{(3-three Ethoxypropyl propyl)amine methyl decyloxyethyl}-1,1,1-triethylammonium = chloride, 1-{(3-tripropoxydecylpropyl)amine methyl hydrazide Ethylethyl}-1,1,1-triethylammonium=chloride, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-tripropyl Alkyl ammonium = chloride, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tripropylammonium = chloride, 1-{(3- Tripropoxydecyl propyl)amine methyl decyloxyethyl}-1,1,1-tripropylammonium = chloride, 1-{(3-trimethoxydecylpropyl)amine methyl hydrazino Ethylethyl}-1,1,1-tributylammonium=chloride, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-three Butylammonium = chloride, 1-{(3-tripropoxydecylpropyl)amine methyl methoxyethyl}-1,1,1-tributylammonium = chlorine , 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylhydrazine=chloride, 1-{(3-triethoxyindolyl) Propyl)amine-methylmethyloxyethyl}-1,1,1-trimethylhydrazine=chloride, 1-{(3-tripropoxydecylpropyl)amine-methylcarbonyloxyethyl} -1,1,1-trimethylhydrazine=chloride, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-triethylhydrazine=chlorine Compound, 1-{(3-triethoxydecylpropyl)amine,carboxyoxyethyl}-1,1,1-triethylhydrazine=chloride, 1-{(3-tripropoxyfluoride) Propyl)aminomethane oxyethyl}-1,1,1-triethylhydrazine=chloride, 1-{(3-trimethoxydecylpropyl)amine-methyl methoxyethyl} -1,1,1-Tripropyl hydrazine=chloride, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-tripropyl hydrazine= Chloride, 1-{(3-tripropoxydecylpropyl)amine,carboxyoxyethyl}-1,1,1- Tripropyl hydrazine = chloride, 1-{(3-trimethoxydecyl propyl)amine methyl decyloxyethyl}-1,1,1-tributylphosphonium chloride, 1-{(3 -triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-tributylphosphonium chloride, 1-{(3-tripropoxydecylpropyl)amine formazan Benzyloxyethyl}-1,1,1-tributylphosphonium chloride; 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1- Trimethylammonium = trifluoromethanesulfonate, 1-{(3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium = trifluoromethyl Sulfonic acid salt, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-trimethylammonium = trifluoromethanesulfonate, 1-{( 3-trimethoxydecyl propyl)amine methyl decyloxyethyl}-1,1,1-triethylammonium = trifluoromethanesulfonate, 1-{(3-triethoxydecylpropyl) Aminomethyl methoxyethyl}-1,1,1-triethylammonium = trifluoromethanesulfonate, 1-{(3-tripropoxydecylpropyl)amine methyl hydrazide }}-1,1,1-triethylammonium = trifluoromethanesulfonate, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1- Tripropylammonium = trifluoromethanesulfonate, 1-{(3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1- Propyl ammonium = trifluoromethanesulfonate, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tripropylammonium = trifluoromethanesulfonate Acid salt, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tributylammonium = trifluoromethanesulfonate, 1-{(3- Triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-tributylammonium = trifluoromethanesulfonate, 1-{(3-tripropoxydecylpropyl) Aminomethyl methoxyethyl}-1,1,1-tributylammonium = trifluoromethanesulfonate, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl} -1,1,1-trimethylhydrazine=trifluoromethanesulfonate, 1-{(3-triethoxydecylpropyl)amine-methyldecyloxyethyl}-1,1,1-three Methyl hydrazine = trifluoromethanesulfonate, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-trimethylhydrazine=trifluoro Methanesulfonate, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-triethylhydrazine=trifluoromethanesulfonate, 1-{( 3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-triethylhydrazine=trifluoromethanesulfonate, 1-{(3-tripropoxydecylpropane) Aminomethylaminoethyl}-1,1,1-triethylhydrazine=trifluoromethanesulfonate, 1-{(3-trimethoxydecylpropyl)amine-methylcarbonyloxy }}-1,1,1-tripropyl hydrazine=trifluoromethanesulfonate, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1 -Tripropyl hydrazine = trifluoromethanesulfonate, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tripropyl fluorene = trifluoro Methanesulfonate, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tributylphosphonium = trifluoromethanesulfonate, 1-{( 3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-tributylphosphonium = trifluoromethanesulfonate, 1-{(3-tripropoxydecylpropane) Aminomethyl methoxyethyl}-1,1,1-tributylphosphonium = trifluoromethanesulfonate; 1-{(3-trimethoxydecylpropyl)amine methyl hydrazide +1,1,1-trimethylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine Methyl methoxyethyl}-1,1,1-trimethylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine formazan Hydroxyethyl}-1,1,1-trimethylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine carbhydryloxy Ethyl}-1,1,1-triethylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl }-1,1,1-Triethylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine carbhydryloxyethyl}- 1,1,1-triethylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1 , 1-tripropylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-tri-B Oxalyl propyl)amine methyl decyloxyethyl}-1,1,1-tripropylammonium=bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-tripropoxyfluoride) Alkyl)amine-methylmethyloxyethyl}-1,1,1-tripropylammonium=bis(trifluoromethanesulfonyl)indolide, 1-{(3-trimethoxydecylpropyl) Aminomethyl methoxyethyl}-1,1,1-tributylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine Methyl methoxyethyl}-1,1,1-tributylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine formazan Ethoxyethyl}-1,1,1-tributylammonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxy Ethyl}-1,1,1-trimethylhydrazine=bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl }-1,1,1-trimethyl hydrazine=bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine carbhydryloxyethyl}- 1,1,1-trimethylsulfonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1 , 1-triethyl hydrazine = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine carbhydryl Oxyethyl}-1,1,1-triethylhydrazine=bis(trifluoromethanesulfonyl)indolide, 1-{(3-tripropoxydecylpropyl)aminecarboxyloxy Ethyl}-1,1,1-triethyl hydrazine=bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-trimethoxydecyl propyl)amine methyl decyloxyethyl} -1,1,1-Tripropyl hydrazine = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-triethoxydecyl propyl)amine methionyloxyethyl}-1 1,1,1-Tripropyl hydrazine = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1,1 , 1-tripropyl hydrazine = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-trimethoxydecyl propyl)amine methyl decyloxyethyl}-1,1,1- Tributylphosphonium = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tributyl Base 鏻 = bis(trifluoromethanesulfonyl) quinone imine, 1-{(3-tripropyl) Oxalyl propyl)amine methionyloxyethyl}-1,1,1-tributylphosphonium = bis(trifluoromethanesulfonyl) quinone imine; 1-{(3-trimethoxyindolyl) Propyl)amine-methylmethyloxyethyl}-1,1,1-trimethylammonium=bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl) Aminomethyl methoxyethyl}-1,1,1-trimethylammonium=bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine Methyl methoxyethyl}-1,1,1-trimethylammonium=bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine carbhydryl Oxyethyl}-1,1,1-triethylammonium=bis(nonafluorobutyrylsulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)aminecarboxyloxy Ethyl}-1,1,1-triethylammonium=bis(nonafluorobutyrylsulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl }-1,1,1-Triethylammonium = bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine-methyl methoxyethyl}-1 1,1,1-Tripropylammonium = bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1 , 1-tripropylammonium = bis(nonafluorobutyrylsulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine carbenyl Oxyethyl}-1,1,1-tripropylammonium=bis(nonafluorobutyrylsulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine methyl hydrazide -1}-1,1,1-tributylammonium=bis(nonafluorobutyrylsulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl} -1,1,1-Tributylammonium = bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1 , 1,1-Tributylammonium = bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1, 1-trimethylhydrazine=bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1- Trimethyl hydrazine = bis(nonafluorobutylsulfonyl) quinone imine, 1-{(3-tripropoxydecyl propyl)amine methyl hydrazide }}-1,1,1-trimethylhydrazine=bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine-methyl methoxyethyl}- 1,1,1-triethylsulfonium = bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1, 1,1-triethylhydrazine=bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine-mercaptooxyethyl}-1,1, 1-triethylhydrazine=bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-three Propyl 鏻 = bis(nonafluorobutylsulfonyl) quinone imine, 1-{(3-triethoxydecyl propyl)amine methyl decyloxyethyl}-1,1,1-tripropyl鏻=bis(nonafluorobutylsulfonyl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tripropyl hydrazine= Bis(nonafluorobutsulfonyl) quinone imine, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tributyl fluorene=double (nine Fluorosulfonyl) quinone imine, 1-{(3-triethoxydecylpropyl)amine, decyloxyethyl}-1,1,1-tributylphosphonium=bis(nonafluorobutene) Sulfhydryl) quinone imine, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tributyl fluorene=double Nonafluorobutyrylsulfonyl)imine; 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium = tetrafluoroborate, 1-{(3-triethoxydecylpropyl)amine-methyl methoxyethyl}-1,1,1-trimethylammonium = tetrafluoroborate, 1-{(3-tripropoxyfluoride) Alkyl propyl)amine methionyloxyethyl}-1,1,1-trimethylammonium = tetrafluoroborate, 1-{(3-trimethoxydecylpropyl)amine carbhydryloxy }}-1,1,1-triethylammonium = tetrafluoroborate, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-three Ethylammonium = tetrafluoroborate, 1-{(3-tripropoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-triethylammonium = tetrafluoroborate, 1 -{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-tripropylammonium=tetrafluoroboron Acid salt, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tripropylammonium = tetrafluoroborate, 1-{(3-three Propionyl propyl)amine methyl decyloxyethyl}-1,1,1-tripropylammonium = tetrafluoroborate, 1-{(3-trimethoxydecylpropyl)amine carbhydryl Oxyethyl}-1,1,1-tributylammonium = tetrafluoroborate, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl}-1,1, 1-tributylammonium = tetrafluoroborate, 1-{(3-tripropoxydecylpropyl)amine-methyl methoxyethyl}-1,1,1-tributylammonium = tetrafluoroboric acid Salt, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylhydrazine=tetrafluoroborate, 1-{(3-triethoxy) Mercaptopropyl)amine mercaptooxyethyl}-1,1,1-trimethylhydrazine=tetrafluoroborate, 1-{(3-tripropoxydecylpropyl)aminecarboxyloxy Ethylethyl}-1,1,1-trimethylhydrazine=tetrafluoroborate, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1- Triethyl hydrazine = tetrafluoroborate, 1-{(3-triethoxydecyl propyl)amine methyl decyloxyethyl}-1,1,1-triethyl hydrazine = tetrafluoroborate, 1-{(3-tripropoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-triethylhydrazine=tetrafluoro Acid salt, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tripropyl hydrazine=tetrafluoroborate, 1-{(3-triethyl) Oxyl propyl)amine methyl decyloxyethyl}-1,1,1-tripropyl hydrazine = tetrafluoroborate, 1-{(3-tripropoxydecylpropyl)amine carbhydryl Oxyethyl}-1,1,1-tripropylhydrazine=tetrafluoroborate, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1 -tributyl hydrazine = tetrafluoroborate, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tributylphosphonium = tetrafluoroborate , 1-{(3-tripropoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-tributylphosphonium=tetrafluoroborate; 1-{(3-trimethoxyoxanium) Propyl)amine methylmercaptooxyethyl}-1,1,1-trimethylammonium=hexafluorophosphate, 1-{(3-triethoxydecylpropyl) Aminomethyl methoxyethyl}-1,1,1-trimethylammonium = hexafluorophosphate, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}- 1,1,1-trimethylammonium = hexafluorophosphate, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-triethylammonium = Hexafluorophosphate, 1-{(3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-triethylammonium=hexafluorophosphate, 1-{(3 -tripropoxydecylpropyl)amine-methylmethyloxyethyl}-1,1,1-triethylammonium = hexafluorophosphate, 1-{(3-trimethoxydecylpropyl)amine A Mercaptooxyethyl}-1,1,1-tripropylammonium=hexafluorophosphate, 1-{(3-triethoxymercaptopropyl)amine-methyldecyloxyethyl}-1, 1,1-Tripropylammonium = hexafluorophosphate, 1-{(3-tripropoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-tripropylammonium=six Fluorophosphate, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-tributylammonium=hexafluorophosphate, 1-{(3-three Ethoxypropyl propyl)amine methyl decyloxyethyl}-1,1,1-tributylammonium = hexafluorophosphate, 1-{(3-tripropoxydecylpropyl)amine formazan Ethoxyethyl}-1,1,1-tributylammonium = hexafluorophosphate, 1-{(3-trimethoxydecylpropyl) Aminomethyl methoxyethyl}-1,1,1-trimethyl hydrazine = hexafluorophosphate, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl} -1,1,1-trimethylsulfonium = hexafluorophosphate, 1-{(3-tripropoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethyl鏻=hexafluorophosphate, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-triethylhydrazine=hexafluorophosphate, 1-{( 3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-triethylhydrazine=hexafluorophosphate, 1-{(3-tripropoxydecylpropyl) Aminomethyl methoxyethyl}-1,1,1-triethyl hydrazine = hexafluorophosphate, 1-{(3-trimethoxydecyl propyl)amine methyl decyloxyethyl}-1 1,1-Tripropyl hydrazine=hexafluorophosphate, 1-{(3-triethoxydecylpropyl)amine-methyl methoxyethyl}-1,1,1-tripropyl hydrazine= Hexafluorophosphate, 1-{(3-tripropoxydecylpropyl)amine,carboxamoxy Ethyl}-1,1,1-tripropyl hydrazine=hexafluorophosphate, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-three Butyl hydrazine = hexafluorophosphate, 1-{(3-triethoxymercaptopropyl)amine methyl decyloxyethyl}-1,1,1-tributylphosphonium = hexafluorophosphate, 1 -{(3-Tripropoxydecylpropyl)amine-methyldecyloxyethyl}-1,1,1-tributylphosphonium = hexafluorophosphate. However, the invention is not limited by the terms.

The onium salt (1) used in the present invention can be produced by various methods. A representative method is an ion exchange reaction of an onium salt represented by the formula (3) (hereinafter referred to as a phosphonium salt (3)) with an alkali metal salt represented by the formula (4) (hereinafter referred to as an alkali metal salt (4)). method.

(wherein, Q ⁺ , R ₁ to R ₄ , m and n are the same as defined above. Y ^- represents a halogen ion.)

Equation (4): M ⁺ . X ^- (4)

(wherein M ⁺ represents an alkali metal ion. X ^{- is the} same as described above.)

As the onium salt (3), for example, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium = chloride, 1 -{(3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium = chloride, 1-{(3-tripropoxydecylpropyl) Aminomethyl methoxyethyl}-1,1,1-trimethylammonium = chloride, 1-{(3-trimethoxydecylpropyl)amine-methyl methoxyethyl}-1, 1,1-triethylammonium = chloride, 1-{(3-triethoxydecylpropyl)amine formazan Benzyloxyethyl}-1,1,1-triethylammonium=chloride, 1-{(3-tripropoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1 -Triethylammonium = chloride, 1-{(3-trimethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tripropylammonium = chloride, 1-{( 3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-tripropylammonium = chloride, 1-{(3-tripropoxydecylpropyl)amine A Mercaptooxyethyl}-1,1,1-tripropylammonium=chloride, 1-{(3-trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1 -tributylammonium = chloride, 1-{(3-triethoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tributylammonium = chloride, 1-{ (3-tripropoxydecylpropyl)amine methyl methoxyethyl}-1,1,1-tributylammonium = chloride, 1-{(3-trimethoxydecylpropyl)amine A Mercaptooxyethyl}-1,1,1-trimethylhydrazine=chloride, 1-{(3-triethoxydecylpropyl)amine-methylcarbonyloxyethyl}-1,1, 1-trimethylhydrazine=chloride, 1-{(3-tripropoxydecylpropyl)amine-methyldecyloxyethyl}-1,1,1-trimethylhydrazine=chloride, 1- {(3-Trimethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-triethylhydrazine=chloride, 1-{(3-triethoxy) Alkyl)amine-methylmethyloxyethyl}-1,1,1-triethylhydrazine=chloride, 1-{(3-tripropoxydecylpropyl)amine-methylcarbonyloxyethyl }-1,1,1-Triethyl hydrazine=chloride, 1-{(3-trimethoxydecyl propyl)amine methyl decyloxyethyl}-1,1,1-tripropyl hydrazine= Chloride, 1-{(3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-tripropylhydrazine=chloride, 1-{(3-tripropoxygen) Mercaptopropyl)amine mercaptooxyethyl}-1,1,1-tripropylhydrazine=chloride, 1-{(3-trimethoxydecylpropyl)amine-methylcarbonyloxyethyl }-1,1,1-Tributylphosphonium = chloride, 1-{(3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-tributylphosphonium = chloride, 1-{(3-tripropoxydecylpropyl)amine methyl decyloxyethyl}-1,1,1-tributylphosphonium chloride, and the like.

As the alkali metal salt (4), for example, trifluoromethanesulfonic acid can be cited. Lithium, sodium triflate, potassium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonyl quinone, sodium bistrifluoromethanesulfonyl sulfoximine, bistrifluoromethanesulfonyl ruthenium Potassium, lithium hexafluorobutasulfonyl phthalimide, sodium bis-nonafluorobutasulfonyl sulphonide, potassium hexa-hexafluorobutanesulfonyl phthalimide, lithium tetrafluoroborate, sodium tetrafluoroborate, tetrafluoro Potassium borate, lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, and the like. The amount of the alkali metal salt (4) used is usually from 0.8 mol to 0.9 mol per mol of the bismuth salt (3), preferably from 0.9 to 1.5 mol.

The ion exchange reaction is usually carried out in an aqueous solvent. The amount of water used is usually 20 parts by weight or less, preferably 0.5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, per part by weight of the cerium salt (3). Further, an organic solvent such as toluene, ethyl acetate or dichloromethane may be coexisted in the aqueous solvent.

The order of mixing the onium salt (3), the alkali metal salt (4), and water is not particularly limited, and the alkali metal salt (4) may be added after mixing the onium salt (3) with water, or the alkali metal salt may be mixed ( 4) Add barium salt (3) with water.

The reaction temperature of the ion exchange reaction is preferably a temperature higher than the melting point of the produced cerium salt (1), usually 10 to 80 ° C, preferably 20 to 40 ° C. The reaction time is usually 15 minutes or more, preferably 45 minutes to 3 hours.

The method of removing the onium salt (1) from the reaction mixture after the completion of the reaction includes the following methods. (i) If the reaction liquid is separated into an organic layer and an aqueous layer, the organic layer is separated from the reaction liquid, and the obtained organic layer is washed with water, and then the organic layer after water washing is concentrated to obtain hydrazine. Salt (1). (ii) if the reaction solution is uniform, the cerium salt (1) is extracted into an organic solvent using an organic solvent insoluble in water and the cerium salt (1) is soluble, and the obtained organic layer is washed with water as desired. The organic solvent is distilled off, and the obtained Barium salt (1).

Next, the copolymerization of the onium salt (1) and the dialkoxysilane (2) will be described. Copolymerization of cerium salt (1) with dialkoxy decane (2), usually by adding a soluble cerium salt (1) and a dialkoxy group in a mixture of cerium salt (1) and dialkoxy decane (2) An acid (hereinafter referred to as an acid (5)) or a base (hereinafter referred to as a base (6)) which can be a hydrolysis catalyst after the solution of the ketone (2) is dissolved in an organic solvent such as methanol, ethanol, isopropanol or acetone. And water drops to the solution to proceed. The acid (5) or the base (6) may also be dropped in an aqueous solution.

Examples of the dialkoxy decane (2) include dimethyl dimethoxy decane, diethyl dimethoxy decane, dipropyl dimethoxy decane, diphenyl dimethoxy decane, and dimethyl. Diethoxy decane, diethyl diethoxy decane, dipropyl diethoxy decane, diphenyl diethoxy decane, dimethyl dipropoxy decane, diethyl dibutoxy Decane, dipropyldibutoxydecane, diphenyldibutoxydecane, etc., preferably dimethyldimethoxydecane and dimethyldiethoxydecane, dimethyldimethoxydecane Preferably.

The molar ratio of the cerium salt (1) to the dialkoxy decane (2) in the copolymerization, relative to the cerium salt (1) 1 mole, the dialkoxy decane (2) in the range of 4 to 49 moles The dialkoxy decane (2) is preferably 4 to 16 moles, and the dialkoxy decane (2) is preferably 4 to 8 moles.

The amount of the organic solvent to be used in the copolymerization is usually 20 parts by weight or less, preferably 0.5 to 10 parts by weight, and preferably 1 to 5 parts by weight, based on 1 part by weight of the onium salt (1).

Examples of the acid (5) used in the copolymerization include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, p-toluenesulfonic acid monohydrate, and the like. Use of acid (5) The amount is usually 0.001 to 1 mol, preferably 0.1 to 0.2 mol, relative to the strontium salt (1) or (2) 1 mol.

Examples of the base (6) used in the copolymerization include sodium hydroxide, potassium hydroxide, and lithium hydroxide. The base (6) is usually used in an amount of 0.001 to 1 mol, preferably 0.1 to 0.2 mol, relative to 1 mol of the barium salt (1).

The amount of water used in the copolymerization is usually from 1 to 10 moles per mole of the strontium salt (1).

The reaction temperature in the copolymerization of the onium salt (1) and the dialkoxysilane (2) is usually 10 to 80 ° C, preferably 20 to 40 ° C. The reaction time is usually 3 hours or more, preferably 3 to 72 hours.

The polyoxyalkylene copolymer of the present invention can be obtained by concentrating the reaction mixture. The concentration of the reaction mixture is usually from 10 to 120 ° C, preferably from 30 to 100 ° C, and preferably from 60 to 80 ° C. The polyoxyalkylene copolymer of the present invention thus obtained can be washed with an organic solvent such as hexane, heptane, benzene or toluene which is not mixed with the polyoxyalkylene copolymer of the present invention as needed.

The amount of the organic solvent used when the polyoxyalkylene copolymer of the present invention is washed is usually 1 to 20 parts by weight, preferably 3 to 9 parts by weight, per part by weight of the polyoxyalkylene copolymer of the present invention. .

The polyoxyalkylene copolymer of the present invention thus obtained can be imparted with antistatic property to the resin by stirring into the resin. Examples of the resin include a polycarbonate resin, a polyacryl resin, a polyoxymethylene resin, and the like.

The method of stirring the polyoxyalkylene copolymer of the present invention into the resin can be exemplified by the following methods. (i) A method in which the polyoxyalkylene copolymer of the present invention is heated and melted with a resin to be stirred. (ii) dissolved in dichloromethane, ethyl acetate, toluene, etc. After the solution is prepared in a solvent, the solution is applied and the solvent is removed. (iii) In the case of a photocurable resin, a method in which a resin or a solution containing the polyoxyalkylene copolymer of the present invention is applied and then cured by ultraviolet irradiation.

The amount of the polyoxyalkylene copolymer of the present invention to be added to the resin is usually 0.01 to 5% by weight based on the resin, preferably 0.05 to 1% by weight, and preferably 0.1 to 0.5% by weight.

[Examples]

Next, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In the examples, ¹ H-NMR was measured by AL-400 manufactured by JEOL Ltd DATUM, and the chemical shift was calculated based on tetramethyl decane at 400 MHz. Further, the surface resistivity was measured using a Hiresta UP (MCP-HT450) manufactured by Mitsubishi Chemical Corporation under the conditions of 23 ± 3 ° C and a humidity of 45 ± 5%. Further, in the examples, the room temperature means 20 to 25 °C.

Example 1 Production of Polyoxane Copolymer [A]

In a 100 mL glass reactor, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-tributylphosphonium=bis(trifluoromethanesulfonate) was weighed. Sulfhydryl iodide 7.16 g (0.01 mol), dimethyl dimethoxydecane 10.00 g (0.08 mol) and dehydrated isopropanol 17.16 g, and titrated 0.1 equivalent of hydrochloric acid 1.65 in the obtained mixture g, stirred at room temperature overnight. The concentrated polyoxane copolymer [A] 17.17 g which was a transparent liquid at room temperature was obtained by concentrating the obtained reaction mixture. The results of ¹ H-NMR analysis of the obtained polyoxyalkylene copolymer [A] are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 5.40-5.20 (m, 1H), 4.20-4. 00 (m, 2H), 3.20-3.00 (m, 2H), 2.75-2.45 (m, 2H), 2.20-2.00(m,6H),1.70-1.30(m,12H),1.20-1.05(m,9H),1.00-0.80(m,9H),1.65-1.45(m,2H),0.30-0.00(m , 28H)

Example 2 Production of Polyoxane Copolymer [B]

In a 100 mL glass reactor, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium = chloride 0.66 g (0.002) was weighed. 1 part g (0.08 mol) of dimethyl dimethoxy decane and 10.66 g of dehydrated isopropanol, and 1.53 g of 0.1 equivalent hydrochloric acid was titrated in the obtained mixture, and stirred at room temperature for 2 hours. By concentrating the obtained reaction mixture, a polyaluminoxane copolymer [B] of 3.68 g which was a thin yellow liquid at 25 ° C was obtained. The results of ¹ H-NMR analysis of the obtained polyoxyalkylene copolymer [B] are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 4.60 (brs, 1H), 4.40-3.90 (m, 3H), 3.65-3.40 (m, 9H), 3.30-3.10 (m, 2H), 1.20-1.05 ( m, 27H), 0.70-0.45 (m, 2H), 0.30-0.00 (m, 145H)

Example 3 Production of Polyoxane Copolymer [C]

In a 500 mL glass reactor, weigh 1-{(3-triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium=bis(trifluoromethanesulfonate)醯 醯 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Stir at room temperature overnight. The polyoxyalkylene copolymer [C] 45.26 g which was a thin yellow liquid at room temperature was obtained by concentrating the obtained reaction mixture. The results of ¹ H-NMR analysis of the obtained polyoxyalkylene copolymer [C] are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 5.80-5.20 (s, 1H), 4.50-4.3 0 (s, 2H), 4.20-4.00 (m, 2H), 3.75-3.50 (m, 2H), 3.25 -2.95 (m, 11H), 1.60-1.40 (m, 2H), 1.25-1.05 (m, 10H), 0.60-0.40 (m, 2H), 0.30-0.00 (m, 33H)

Example 4 Production of Polyoxane Copolymer [D]

In a 100 mL glass reactor, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium chloride 3.58 g (0.01) was weighed. 1 part g (0.08 mol) of dimethyl dimethoxy decane and 14.00 g of dehydrated isopropanol, and 1.66 g of 0.1 equivalent hydrochloric acid was titrated in the obtained mixture, and stirred at room temperature for 2 hours. By concentrating the obtained reaction mixture, a polyaluminoxane copolymer [D] 5.42 g which was a thin yellow waxy solid at room temperature was obtained. The results of ¹ H-NMR analysis of the obtained polyoxyalkylene copolymer [D] are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 4.60 (brs, 1H), 4.40-3.90 (m, 3H), 3.65-3.40 (m, 9H), 3.30-3.10 (m, 2H), 1.35-1.10 ( m, 5H), 0.70-0.45 (m, 2H), 0.30-0.00 (m, 23H)

Example 5 Production of Polyoxane Copolymer [E]

In a 100 mL glass reactor, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium chloride 3.58 g (0.01) was weighed. 1 part g (0.08 mol) of dimethyl dimethoxy decane and 14.00 g of dehydrated isopropanol, and 1.51 g of 0.1 equivalent hydrochloric acid was titrated in the obtained mixture, and stirred at room temperature for 2 hours. The polyoxyalkylene copolymer [E] 5.42 g which was a thin yellow waxy solid at room temperature was obtained by concentrating the obtained reaction mixture. The results of ¹ H-NMR analysis of the obtained polyoxyalkylene copolymer [E] are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 4.43 (1H, brs), 4.00-3.80 (4H, m), 3.39 (9H, s), 3.03 (2H, brs), 1.50 (2H, brs), 1.13 -1.05 (34H, m), 0.50-0.45 (2H, m), 0.05-0.00 (26H, m)

Example 6 Production of Polyoxane Copolymer [F]

In a 50 mL glass reactor, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium = bis(trifluoromethanesulfonate) was weighed.醯 醯 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 After stirring at room temperature for 3 hours, it was concentrated at 80 ° C for 3 hours. The obtained concentrated residue was washed three times with 15.00 g of toluene, and then concentrated at 80 ° C for 3 hours, whereby a polyaluminoxane copolymer [F] of 6.53 g which was a thin yellow liquid at room temperature was obtained. The results of ¹ H-NMR analysis of the obtained polyoxyalkylene copolymer [F] are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 5.89-5.43 (0.9H, brm), 4.45 (2H, s), 4.24 - 4.13 (1.1H, brm), 4.83-4.71 (0.4H, brm), 3.64 (2H, s), 3.54-3.46 (0.5H, brm), 3.28-3.08 (11.8H, brm), 1.59 (2H, brs), 1.25-1.12 (7.0H, brm), 0.63-0.50 (2H, m ), 0.24-0.02 (17.6H, brm)

Example 7 Production of Polyoxane Copolymer [G]

In a 50 mL glass reactor, 1-{(3-triethoxydecylpropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium = bis(trifluoromethanesulfonate) was weighed.醯 醯 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 After stirring at room temperature for 3 hours, it was concentrated at 80 ° C for 3 hours. The obtained concentrated residue was washed three times with 15.00 g of toluene, and then concentrated at 80 ° C for 3 hours to obtain a polyoxyalkylene copolymer [G] of 6.91 g which was a thin yellow liquid at room temperature. The results of ¹ H-NMR analysis of the obtained polyoxyalkylene copolymer [G] are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 5.89-5.43 (0.9H, brm), 4.45 (2H, s), 4.24 - 4.13 (1.3H, brm), 4.83-4.71 (0.5H, brm), 3.64 (2H, s), 3.54-3.46 (1.1H, brm), 3.28-3.08 (11.5H, brm), 1.59 (2H, brs), 1.25-1.12 (8.5H, brm), 0.63-0.50 (2H, m ), 0.24-0.02 (13.1H, brm)

Example 8 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

In a 50 mL sample bottle, 3.2 g of polycarbonate resin (Calibre (registered trademark) 200-13 NAT) manufactured by Sumitomo Dow Co., Ltd. and 20 mL of dichloromethane were weighed to prepare a dichloromethane solution of a polycarbonate resin. To the obtained solution, 0.0016 g of the polyoxyalkylene copolymer [A] of Example 1 was added as an antistatic agent and completely dissolved, and then poured into a mold (12 cm × 20 cm × 2 cm) to make it at room temperature. The mixture was dried for 1 hour and further dried at 40 ° C for 1 hour to prepare a polycarbonate resin composition sample (film thickness: 0.1 ± 0.02 mm). The surface resistivity of the sample of the polycarbonate resin composition which had been prepared was measured. The results are shown in Table 1.

Example 9 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

A polycarbonate resin composition sample was prepared and measured in the same manner as in Example 8 except that the polyoxyalkylene copolymer [B] of Example 2 was used instead of the polyoxyalkylene copolymer [A]. Surface resistivity. The results are shown in Table 1.

Example 10 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

A polycarbonate resin composition sample was prepared and measured in the same manner as in Example 8 except that the polyoxyalkylene copolymer [C] of Example 3 was used instead of the polyoxyalkylene copolymer [A]. Surface resistivity. The results are shown in Table 1.

Example 11 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

A polycarbonate resin composition sample was prepared and measured in the same manner as in Example 8 except that the polyoxyalkylene copolymer [D] of Example 4 was used instead of the polyoxyalkylene copolymer [A]. Surface resistivity. The results are shown in Table 1.

Example 12 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

A polycarbonate resin composition sample was prepared and measured in the same manner as in Example 8 except that the polyoxyalkylene copolymer [E] of Example 5 was used instead of the polyoxyalkylene copolymer [A]. Surface resistivity. The results are shown in Table 1.

Example 13 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

A polycarbonate resin composition sample was prepared and measured in the same manner as in Example 8 except that the polyoxyalkylene copolymer [F] of Example 6 was used instead of the polyoxyalkylene copolymer [A]. Surface resistivity. The results are shown in Table 1.

Comparative Example 1 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

The same as in the eighth embodiment except that the polyoxyalkylene copolymer [A] was not used. A sample of the polycarbonate resin composition was prepared, and the surface resistivity thereof was measured. The results are shown in Table 1.

Comparative Example 2 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

1-{(3-Triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-trimethylammonium = bis(trifluoromethanesulfonyl) quinone imine (hereinafter A polycarbonate resin composition sample was prepared in the same manner as in Example 8 except that the sulfonium salt [A]) was used in place of the polyoxyalkylene copolymer [A], and the surface resistivity thereof was measured. The results are shown in Table 1.

Comparative Example 3 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

1-{(3-Triethoxymercaptopropyl)amine-mercaptooxyethyl}-1,1,1-tributylphosphonium = bis(trifluoromethanesulfonyl) quinone imine (hereinafter A polycarbonate resin composition sample was prepared in the same manner as in Example 8 except that the sulfonium salt [B] was used in place of the polyoxyalkylene copolymer [A], and the surface resistivity thereof was measured. The results are shown in Table 1.

Comparative Example 4 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

The polyazepine copolymer [A] was replaced with tributyl lauryl hydrazine = bis(trifluoromethanesulfonyl) quinone imine (hereinafter referred to as hydrazine salt [C]), and the examples were 8 was also carried out, and a polycarbonate resin composition sample was prepared, and the surface resistivity thereof was measured. The results are shown in Table 1.

Comparative Example 5 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

A polycarbonate resin composition sample was prepared in the same manner as in Example 8 except that 0.032 g of the onium salt [C] was used instead of the polyoxyalkylene copolymer [A], and the surface resistivity thereof was measured. The results are shown in Table 1.

Comparative Example 6 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

A film-like composition obtained by hydrolyzing a polymer of 1-methyl-3-(3-trimethoxydecylpropyl)imidazolium=tetrafluoroborate polymer was prepared by referring to Patent Document 2 (JP-A-2009-286815). A polycarbonate resin composition sample was prepared in the same manner as in Example 8 except that the sulfonium salt [D] was used instead of the polyoxyalkylene copolymer [A]. And measure its surface resistivity. The results are shown in Table 1.

Example 14 Preparation of a sample of a polyacrylic resin composition and measurement of its surface resistivity

Dioxonicol hexaacrylate (A-DPH: manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.50 g, pentaerythritol triacrylate (A-TMM-3LM-N: manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.50 g, trimethylolpropane triacrylate (A-TMPT: manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.50 g, isopropanol 1.75 g, colloidal ceria IPA dispersion (IPA-ST: 3 wt% of cerium oxide solids, manufactured by Nissan Chemical Industry Co., Ltd., 3.60 g of polyoxyalkylene copolymer [E] as an antistatic agent, and 2-hydroxy-2-methyl as a photopolymerization initiator 0.15 g of acetophenone was mixed.

The obtained mixture was applied to one side of a polyethylene terephthalate film having a thickness of 100 μm by a bar coater to have a dry film thickness of about 5 μm, and a coating film was formed. A sample of the polyacrylic resin composition was prepared by irradiating ultraviolet light of a high-pressure mercury UV lamp (120 W/cm) on the surface of the coating film with an integrated light amount of about 400 mJ/cm ² to cure it. The surface resistivity of the prepared sample of the polyacrylic resin composition was measured. The results are shown in Table 2.

Example 15 Preparation of a sample of a polyacrylic resin composition and measurement of its surface resistivity

A sample of the polyacrylic resin composition was prepared in the same manner as in Example 14 except that the polyoxyalkylene copolymer [F] was used instead of the polyoxyalkylene copolymer [E], and the surface resistivity thereof was measured. The results are shown in Table 2.

Example 16 Preparation of a sample of a polyacrylic resin composition and determination of its surface resistivity

A sample of the polyacrylic resin composition was prepared in the same manner as in Example 14 except that the polyoxyalkylene copolymer [G] was used instead of the polyoxyalkylene copolymer [E], and the surface resistivity thereof was measured. The results are shown in Table 2.

Comparative Example 7 Preparation of a sample of a polyacrylic resin composition and measurement of its surface resistivity

A sample of the polyacrylic resin composition was prepared in the same manner as in Example 14 except that the polyoxyalkylene copolymer [E] was not added, and the surface resistivity thereof was measured. The results are shown in Table 2.

Comparative Example 8 Preparation of a sample of a polyacrylic resin composition and measurement of its surface resistivity

A sample of the polyacrylic resin composition was prepared in the same manner as in Example 14 except that 0.54 g of the onium salt [A] was used instead of the polyoxyalkylene copolymer [E], and the surface resistivity thereof was measured. The results are shown in Table 2.

Example 17 Preparation of a sample of polymethyl methacrylate resin composition and determination of its surface resistivity

5.00 g of methyl methacrylate, 0.20 g of azobisisobutyronitrile, and a polyoxyalkylene copolymer [E] as an antistatic agent were mixed in an amount of 0.005 g. The obtained mixture was poured into a plastic container (cylindrical shape having an inner diameter of 5 cm and a height of 1.5 cm), and allowed to harden at 50 ° C for 10 hours to prepare a sample of a polymethyl methacrylate resin having a thickness of about 2 mm. The surface resistivity of the prepared sample of the polymethyl methacrylate resin resin composition was measured. The results are shown in Table 3.

Example 18 Preparation of a sample of a polymethyl methacrylate resin resin composition and measurement of its surface resistivity

A sample of a polymethyl methacrylate resin resin composition was prepared and measured in the same manner as in Example 17 except that the polyoxyalkylene copolymer [F] was used instead of the polyoxyalkylene copolymer [E]. Surface resistivity. The results are shown in Table 3.

Comparative Example 9 Preparation of a sample of a polymethyl methacrylate resin resin composition and measurement of its surface resistivity

A sample of a polymethyl methacrylate resin resin composition was prepared in the same manner as in Example 17 except that the polyoxyalkylene copolymer [E] was not added, and the surface resistivity thereof was measured. The results are shown in Table 3.

Comparative Example 10 Preparation of a sample of a polymethyl methacrylate resin resin composition and measurement of its surface resistivity

The same procedure as in Example 17 except that 0.50 g of tributylmethylammonium = bis(trifluoromethanesulfonyl) quinone imine (hereinafter referred to as sulfonium salt [E]) was used instead of the polyoxyalkylene copolymer [E]. A sample of a polymethyl methacrylate resin resin composition was prepared, and the surface resistivity thereof was measured. The results are shown in Table 3.

Example 19 Preparation of a sample of a polyoxyxene resin composition and determination of its surface resistivity

The peroxide-curable polyadhesive adhesive KR-101-10 (solid content 60%, manufactured by Shin-Etsu Chemical Co., Ltd.) 4.0 g, hardener BPO (benzophenone peroxide) 0.08 g, ethyl acetate 6.2 g and 0.049 g of a polyoxyalkylene copolymer [A] as an antistatic agent were mixed to obtain a polyoxyxylene resin adhesive.

The polyoxyethylene resin adhesive was applied to one side of a polyethylene terephthalate film (release paper) by a bar coater so that the dried and dried film thickness became about 8 μm, and it was dried by heating at 90 ° C. The layer was heated and dried at 160 ° C for 2 minutes to form a polyoxymethylene resin adhesive layer, and the surface resistivity thereof was measured. The results are shown in Table 4.

A triethylene fluorene cellulose film (TAC film) was bonded to the surface having the above-mentioned pressure-sensitive adhesive layer, and aged at 25 ° C and 50% RH for 1 hour to prepare a test film. The state of adhesion of the adhesive to the release paper when the release paper was peeled off from the test film was visually evaluated. The results are shown in Table 4.

○: Adhesion of the adhesive to the release paper was not observed.

△: It was observed that some of the adhesive adhered to the release paper.

×: The adhesion of most of the adhesive to the release paper was observed.

Comparative Example 11 Preparation of a sample of a polyoxyxene resin composition and measurement of its surface resistivity

A polyoxyxylene resin adhesive layer and a test film were prepared in the same manner as in Example 19 except that the polyoxyalkylene copolymer was not used, and the surface resistivity was measured, and the adhesion of the adhesive to the release paper was visually evaluated. status. The results are shown in Table 4.

Comparative Example 12 Preparation of a sample of a polyoxyxene resin composition and measurement of its surface resistivity

A polyoxyxylene resin adhesive layer and a test film were prepared in the same manner as in Example 19 except that the sulfonium salt [A] was used instead of the polyoxyalkylene copolymer [A], and the surface resistivity thereof was measured, and visually measured. The adhesion state of the adhesive to the release paper was evaluated. The results are shown in Table 4.

Claims (9)

A polyoxyalkylene copolymer obtained by copolymerizing an onium salt represented by the formula (1) with a dialkoxysilane of the formula (2): (wherein, Q ⁺ represents a nitrogen cation or a phosphorus cation, R ₁ represents an alkyl group having 1 to 3 carbon atoms, R ₂ to R ₄ are each independently, and represents an alkyl group having 1 to 8 carbon atoms; X ^- represents an anion, m and n are independent, an integer from 1 to 3); (wherein R ₅ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ₆ represents an alkyl group having 1 to 3 carbon atoms). The polyoxyalkylene copolymer of claim 1, wherein in the above formula (1), X ^- is a halogen anion. The polyoxyalkylene copolymer of claim 1, wherein in the above formula (1), X ^- is a fluorine-containing anion. The polyoxyalkylene copolymer of claim 3, wherein the fluorine-containing anion is It is selected from at least one anion selected from the group consisting of an anion of a trifluoromethanesulfonate anion, a bis(perfluoroalkylsulfonyl)phosphonium anion, a tetrafluoroborate anion, and a hexafluorophosphate anion. The polyoxyalkylene copolymer of claim 1, which is obtained by copolymerizing a sulfonium salt 1 mol represented by the above formula (1) with a dialkoxy decane 4 to 49 represented by the above formula (2). . An antistatic agent comprising the polyoxyalkylene copolymer according to any one of claims 1 to 5. A resin composition containing the antistatic agent of claim 6. The resin composition of claim 7, wherein the resin composition is at least one resin composition selected from the group consisting of a polycarbonate resin composition, a polyacryl resin composition, and a polyoxymethylene resin composition. A method for producing a polyoxyalkylene copolymer, which is used for producing the polyoxyalkylene copolymer of claim 1, which is characterized by the above formula (1) in the presence of water and an acid or a base The onium salt shown is copolymerized with the dialkoxysilane of the above formula (2).