TWI657102B - Polysiloxane copolymer and antistatic agent and resin composition containing the same - Google Patents

Abstract

The present invention provides a silicone resin that can impart high antistatic properties to resins, has good heat resistance that can withstand high temperatures during melt-kneading of resins, and can be used as an optical adhesive with practical strength characteristics. Polysiloxane copolymer.

The present invention provides a polysiloxane copolymer which copolymerizes an onium salt represented by formula (1), a trialkoxysilane represented by formula (2), and a compound represented by formula (3) as an optional component. The obtained dialkoxysilane is obtained.

R ⁵ -Si (OR ⁶ ) ₃ (2)

Description

Polysiloxane copolymer and antistatic agent and resin composition containing the same

The present invention relates to a polysiloxane copolymer, an antistatic agent containing the copolymer, and a resin composition incorporating the antistatic agent.

It is reported that the cation is ammonium or phosphonium having a trialkoxysilylalkyl group, and the anion is a perfluoroalkylsulfonylsulfoniumimine salt, which can be used as a low molecular antistatic agent for fluororesins. (Refer to Patent Document 1: Japanese Patent Application Laid-Open No. 2010-248165). However, the inventors have learned that 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonium), which is one of the aforementioned onium salts, Base) When used as an antistatic agent for polycarbonate resins, acrylic resins, and silicone resins, although antistatic properties can be imparted to silicone resins, practical antistatic properties cannot be imparted to polycarbonate resins and acrylic resins. performance. Furthermore, when an antistatic agent is heated and melted in a polycarbonate resin for kneading, the heat resistance of the antistatic agent itself is required. However, the ammonium-type onium salt or a polysiloxane copolymer containing the same does not have sufficient heat resistance that can withstand the high temperature during melt-kneading. Moreover, it was understood that silicone resin cannot be sufficiently used for silicone resin. Silicone resin composition (see Comparative Example to be described later) cannot be obtained as a hardening reaction of the optical fiber as a practical strength characteristic.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-248165

Accordingly, the present invention is to provide a polycarbonate resin, an acrylic resin, and a silicone resin with high antistatic properties. In particular, the invention can be used as an antistatic agent to heat-melt a polycarbonate resin and provide excellent heat resistance during kneading. In addition, it is possible to produce a polysiloxane copolymer of a siloxane resin having practical strength characteristics as an optical adhesive and an antistatic agent containing the polysiloxane copolymer. Further, another object is to provide a resin composition incorporating the antistatic agent.

In order to solve the above-mentioned object, the present inventors have conducted research and found that the onium salt represented by the formula (1), the trialkoxysilane represented by the formula (2), and the formula ( 3) At the same time as the polysiloxane copolymer obtained from the dialkoxysilane shown in the figure, when the polysiloxane copolymer was used as an antistatic agent in polycarbonate resin, acrylic resin, and silicone resin, Provides high antistatic properties to various resins. Furthermore, the polysiloxane copolymer was found to have good heat resistance which can withstand the high temperature during melt-kneading of the polycarbonate resin. In addition, it was found that the hardening reaction of the siloxane resin progresses smoothly, and a siloxane resin composition having practical strength characteristics can be obtained as an optical adhesive, and the present invention has been completed.

That is, this invention provides the following polysiloxane copolymer, its manufacturing method, an antistatic agent, and a resin composition.

〔1〕

A polysiloxane obtained by copolymerizing an onium salt represented by the formula (1), a trialkoxysilane represented by the formula (2), and a dialkoxysilane represented by the formula (3) as an optional component. Copolymer, formula (1): (In the formula, 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 represents an alkyl group having 1 to 8 carbon atoms; R ² and R ³ are bonded to each other at the ends; Can form a pyridine ring, a piperidine ring, a pyridine ring, a phosphorane ring, a phosphocyclohexane ring, or a triphosphine ring; however, R ² and R ³ are bonded to each other at the ends to form a pyridine ring or a triphosphorus ring In the heterobenzene ring, R ⁴ does not exist; X ^- represents an anion; n is an integer of 0 to 3); Formula (2): [Chem. 2] R ⁵ -Si (OR ⁶ ) ₃ (2) (where, R ⁵ represents an alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms, or alkenyl group having 2 to 8 carbon atoms, and R ⁶ represents an alkyl group having 1 to 3 carbon atoms Base); formula (3): (In the formula, R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R ⁸ represents an alkyl group having 1 to 3 carbon atoms).

〔2〕

The polysiloxane copolymer according to [1], wherein in the formula (1), Q ⁺ is a phosphorus cation.

[3]

The polysiloxane copolymer according to [1] or [2], wherein in the formula (1), X ^- is a halogen anion or a fluorine-containing anion.

[4]

The polysiloxane copolymer according to [3], wherein the fluorine-containing anion is a trifluoromethanesulfonic acid anion, a bis (trifluoromethanesulfonyl) sulfonimide anion, a tetrafluoroborate anion, or hexafluorophosphate Ester anion.

[5]

The polysiloxane copolymer according to any one of [1] to [4], which copolymerizes a trioxane represented by the aforementioned formula (2) with respect to 1 mole of the onium salt represented by the aforementioned formula (1). It is obtained from 0.5 to 95 moles of oxysilane and 0 to 49 moles of the dialkoxysilane represented by the formula (3).

[6]

The polysiloxane copolymer according to any one of [1] to [4], which copolymerizes a trioxane represented by the aforementioned formula (2) with respect to 1 mole of the onium salt represented by the aforementioned formula (1). It is obtained from 0.5 to 95 moles of oxysilane and 4 to 49 moles of dialkoxysilane represented by the formula (3).

[7]

An antistatic agent containing a polysiloxane copolymer according to any one of [1] to [6].

〔8〕

A resin composition containing an antistatic agent such as [7].

〔9〕

The resin composition according to [8], wherein the resin composition is a polycarbonate resin composition, an acrylic resin composition, or a silicone resin composition.

[10]

A method for producing a polysiloxane copolymer according to any one of [1] to [6], which is characterized by copolymerizing an onium salt represented by the aforementioned formula (1) and the aforementioned formula (2) in the presence of hydrochloric acid. A trialkoxysilane represented by) and a dialkoxysilane represented by the aforementioned formula (3) as an optional component.

The polysiloxane copolymer of the present invention can be used as an antistatic agent. By using the antistatic agent in polycarbonate resin, acrylic resin, and silicone resin, a resin composition having high antistatic properties can be produced, especially It is excellent in heat resistance necessary for melt-kneading polycarbonate resins, In addition, when the polysiloxane copolymer of the present invention is used, a silicone resin composition having practical strength characteristics as an optical adhesive can be produced.

The present invention will be specifically described below.

As described above, the polysiloxane copolymer of the present invention is obtained by copolymerizing an onium salt represented by formula (1) (hereinafter referred to as an onium salt (1)) and a trialkoxysilane represented by formula (2). (Hereinafter referred to as trialkoxysilane (2)) and a dialkoxysilane (hereinafter referred to as dialkoxysilane (3)) represented by formula (3) as an optional component.

Formula 1): (In the formula, Q ⁺ represents a nitrogen cation or a phosphorus cation. R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² to R ⁴ represent an alkyl group having 1 to 8 carbon atoms. R ² and R ³ are bonded to each other at the terminals. It can form a pyridine ring, a piperidine ring, a pyridine ring, a phosphorane ring, a phosphocyclohexane ring or a triphosphine ring. However, R ² and R ³ are bonded to each other at the ends to form a pyridine ring or a triphosphorus ring. In the case of a heterobenzene ring, R ⁴ does not exist. X ^- represents an anion. N is an integer of 0 to 3).

Formula (2): [Chem 5] R ⁵ -Si (OR ⁶ ) ₃ (2) (where R ⁵ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 10 carbon atoms) An aralkyl group of 10 or an alkenyl group of 2 to 8 carbons, and R ⁶ represents an alkyl group of 1 to 3 carbons).

Equation (3): (In the formula, R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R ⁸ represents an alkyl group having 1 to 3 carbon atoms).

Hereinafter, when the above-mentioned components are further described in detail, the onium salt (1) used in the present invention can be produced by a method described in Japanese Patent Application Laid-Open No. 2010-248165.

In the formula (1), Q ⁺ represents a nitrogen cation or a phosphorus cation, and is preferably a phosphorus cation. R ¹ is an alkyl group having 1 to 3 carbon atoms, and specifically, methyl, ethyl, propyl, and isopropyl are mentioned, methyl and ethyl are preferred, and methyl is particularly preferred. R ² to R ⁴ represent an alkyl group having 1 to 8 carbon atoms, and may be any of a linear and branched chain, and a linear alkyl group is preferred. Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl, and the like, methyl, ethyl, propyl, and butyl are preferred, and butyl is particularly preferred. R ² and R ³ are bonded to each other at the ends, and can form a pyridine ring, a piperidine ring, a pyridine ring, a phosphine ring, a phosphocyclohexane ring, or a triphosphine ring. However, when R ² and R ³ are bonded to each other at the ends to form a pyridine ring or a triphosphine ring, R ⁴ does not exist. X ^- represents an anion. Examples of X ⁻ include a halogen anion or a fluorine-containing anion. As the halogen anion, a chloride anion, a bromine anion, and an iodine anion are preferable, and a chloride anion is more preferable. As the fluorine-containing anion, a trifluoromethanesulfonic acid anion, a bis (trifluoromethanesulfonyl) fluorenimide anion, a tetrafluoroborate anion, and a hexafluorophosphate anion are preferable, and a bis (trifluoromethane) is more preferable. Sulfonyl) fluorenimide anion.

Specific examples of the onium salt (1) include 1,1,1-trimethyl-1-[(trimethoxysilyl) methyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trimethyl-1- [2- (trimethoxysilyl) ethyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trimethyl- 1- [3- (trimethoxysilyl) propyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trimethyl-1- [4- (trimethoxysilane ) Butyl) ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-triethyl-1-[(trimethoxysilyl) methyl] ammonium = bis (trifluoromethane Sulfonyl) fluorenimine, 1,1,1-triethyl-1- [2- (trimethoxysilyl) ethyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1, 1,1-triethyl-1- [3- (trimethoxysilyl) propyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-triethyl-1- [4- (trimethoxysilyl) butyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-tributyl-1-[(trimethoxysilyl) methyl ] Ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-tributyl-1- [2- (trimethoxysilyl) ethyl] ammonium = bis (trifluoromethanesulfonyl) Amidyl) imine 1,1,1-tributyl-1- [3- (trimethoxysilyl) propyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-tributyl -1- [4- (trimethoxysilyl) butyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trihexyl-1-[(trimethoxysilyl) Methyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trihexyl-1- [2- (trimethoxysilyl) ethyl] ammonium = bis (trifluoromethanesulfonyl) Fluorenyl) fluorenimine, 1,1,1-trihexyl-1- [3- (trimethoxysilyl) Propyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trihexyl-1- [4- (trimethoxysilyl) butyl] ammonium = bis (trifluoromethanesulfonyl) Fluorenyl) fluorenimine, 1,1,1-trioctyl-1-[(trimethoxysilyl) methyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1 -Trioctyl-1- [2- (trimethoxysilyl) ethyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trioctyl-1- [3- (Trimethoxysilyl) propyl] ammonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trioctyl-1- [4- (trimethoxysilyl) butyl] Ammonium = bis (trifluoromethanesulfonyl) phosphonium imine, 1,1,1-trimethyl-1-[(trimethoxysilyl) methyl] phosphonium = bis (trifluoromethanesulfonyl) Fluorenimine, 1,1,1-trimethyl-1- [2- (trimethoxysilyl) ethyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1 -Trimethyl-1- [3- (trimethoxysilyl) propyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trimethyl-1- [4 -(Trimethoxysilyl) butyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-triethyl-1-[(trimethoxysilyl) methyl] Phosphonium = double (three Methanesulfonyl) fluorenimine, 1,1,1-triethyl-1- [2- (trimethoxysilyl) ethyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-triethyl-1- [3- (trimethoxysilyl) propyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-triethyl -1- [4- (trimethoxysilyl) butyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-tributyl-1-[(trimethoxysilane (Methyl) methyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-tributyl-1- [2- (trimethoxysilyl) ethyl] phosphonium = bis (Trifluoromethanesulfonyl) Fluorenimine, 1,1,1-tributyl-1- [3- (trimethoxysilyl) propyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1 -Tributyl-1- [4- (trimethoxysilyl) butyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trihexyl-1-[(trimethyl Oxysilyl) methyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trihexyl-1- [2- (trimethoxysilyl) ethyl] phosphonium = Bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trihexyl-1- [3- (trimethoxysilyl) propyl] phosphonium = bis (trifluoromethanesulfonyl) Fluorenimine, 1,1,1-trihexyl-1- [4- (trimethoxysilyl) butyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1- Trioctyl-1-[(trimethoxysilyl) methyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trioctyl-1- [2- (trimethyl Oxysilyl) ethyl] phosphonium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trioctyl-1- [3- (trimethoxysilyl) propyl] phosphonium Onium = bis (trifluoromethanesulfonyl) fluorenimine, 1,1,1-trioctyl-1- [4- (trimethoxysilyl) butyl] phosphonium = bis (trifluoromethanesulfonyl) Base) Amine, 1-methyl-1-[(trimethoxysilyl) methyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-ethyl-1-[(trimethoxysilyl ) Methyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-propyl-1-[(trimethoxysilyl) methyl] pyrrolium = bis (trifluoromethanesulfonyl) Fluorenimine, 1-butyl-1-[(trimethoxysilyl) methyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-hexyl-1-[(trimethoxysilane (Methyl) methyl] pyrrolidium = bis (trifluoromethanesulfonyl) fluorenimine, 1-octyl-1-[(trimethoxysilyl) methyl] pyrrole Onium = bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1- [2- (trimethoxysilyl) ethyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimide 1-ethyl-1- [2- (trimethoxysilyl) ethyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-propyl-1- [2- (trimethoxy Silyl) ethyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-butyl-1- [2- (trimethoxysilyl) ethyl] pyrrolium = bis (trifluoro Methanesulfonyl) fluorenimine, 1-hexyl-1- [2- (trimethoxysilyl) ethyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-octyl-1 -[2- (trimethoxysilyl) ethyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1- [3- (trimethoxysilyl) propyl] Pyrrolidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-ethyl-1- [3- (trimethoxysilyl) propyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorene Amine, 1-propyl-1- [3- (trimethoxysilyl) propyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-butyl-1- [3- (trimethyl Oxysilyl) propyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine 1-hexyl-1- [3- (trimethoxysilyl) propyl] pyrrolidium = bis (trifluoromethanesulfonyl) fluorenimine, 1-octyl-1- [3- (trimethoxysilane Propyl) propyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1- [4- (trimethoxysilyl) butyl] pyrrolium = bis (trifluoromethanesulfonyl) Fluorenyl) fluorenimine, 1-ethyl-1- [4- (trimethoxysilyl) butyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-propyl-1- [4- (trimethoxysilyl) butyl] pyrrolidium = bis (trifluoromethanesulfonyl) fluorenimine, 1-butyl-1- [4- (trimethoxysilyl) butyl] pyrrole Onium = bis (trifluoromethanesulfonyl) fluorenimine, 1-hexyl-1- [ 4- (trimethoxysilyl) butyl] pyrrolium = bis (trifluoromethanesulfonyl) fluorenimine, 1-octyl-1- [4- (trimethoxysilyl) butyl] pyrrolium = Bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1-[(trimethoxysilyl) methyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1 -Ethyl-1-[(trimethoxysilyl) methyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-propyl-1-[(trimethoxysilyl) methyl Group] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-butyl-1-[(trimethoxysilyl) methyl] piperidinium = bis (trifluoromethanesulfonyl) Fluorenimine, 1-hexyl-1-[(trimethoxysilyl) methyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-octyl-1-[(trimethoxy Silyl) methyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (tri Fluoromethanesulfonyl) fluorenimine, 1-ethyl-1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-propane Yl-1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (tri Methanesulfonyl) fluorenimine, 1-butyl-1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-hexyl- 1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-octyl-1- [2- (trimethoxysilyl) ethyl Yl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1- [3- (trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) Yl) fluorenimine, 1-ethyl-1- [3- (trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-propyl-1- [3- (trimethoxysilyl) propyl] piper Pyridinium = bis (trifluoromethanesulfonyl) fluorenimide, 1-butyl-1- [3- (trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) fluorene Imine, 1-hexyl-1- [3- (trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-octyl-1- [3- ( Trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1- [4- (trimethoxysilyl) butyl] piperidinium = Bis (trifluoromethanesulfonyl) fluorenimine, 1-ethyl-1- [4- (trimethoxysilyl) butyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-propyl-1- [4- (trimethoxysilyl) butyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-butyl-1- [4- (trimethoxy Silyl) butyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-hexyl-1- [4- (trimethoxysilyl) butyl] piperidinium = bis (tri Fluoromethanesulfonyl) fluorenimine, 1-octyl-1- [4- (trimethoxysilyl) butyl] piperidinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [ (Trimethoxysilyl) methyl] pyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [2 -(Trimethoxysilyl) ethyl] pyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [3- (trimethoxysilyl) propyl] pyridinium = bis (trifluoromethane Sulfonyl) fluorenimine, 1- [4- (trimethoxysilyl) butyl] pyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-[(trimethoxysilyl) methyl Group] -2-methylpyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [2- (trimethoxysilyl) ethyl] -2-methylpyridinium = bis (trifluoro Methanesulfonyl) fluorenimine, 1- [3- (trimethoxysilyl) propyl] -2-methylpyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [4- (three Methoxysilyl) butyl] -2-methylpyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-[(trimethoxysilyl) methyl] -3-methylpyridinium = Bis (trifluoromethanesulfonyl) fluorenimine, 1- [2- (trimethoxysilyl) ethyl] -3-methylpyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [3- (trimethoxysilyl) propyl] -3-methylpyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [4- (trimethoxysilyl) butyl ] -3-methylpyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1-[(trimethoxysilyl) methyl] -4-methylpyridinium = bis (trifluoromethanesulfonyl) Yl) fluorenimine, 1- [2- (trimethoxysilyl) ethyl] -4-methylpyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [3- (trimethoxy Silyl) propyl] -4-methylpyridinium = bis (trifluoromethanesulfonyl) fluorenimine, 1- [4- (trimethoxysilyl) butyl] -4-methylpyridinium = Bis (trifluoromethanesulfonyl) fluorenimine and the like.

The onium salt (1) used in the present invention can be produced by a method described in Japanese Patent Application Laid-Open No. 2010-248165. A typical method will be described by the following reaction formula 1. In this reaction formula, R ¹ , R ² , R ³ , R ⁴ , Q, X, and n are the same as described above, Z represents a halogen atom, and M represents an alkali metal.

An amine (hereinafter referred to as an amine (4a)) or a phosphine (hereinafter referred to as a phosphine (4b)) represented by the formula (4) and an alkyl halide (hereinafter referred to as an alkane) represented by the formula (5) Base halides (5)) are subjected to a quaternary reaction to produce onium = halides (hereinafter referred to as onium = halides (6)) represented by the formula (6). X ^- is a halogen anion time, may be an onium halides = (6) (1) is used as a salt.

Next, an onium salt (1) can be produced by an ion exchange reaction with an onium = halide (6) and an alkyl metal salt represented by the formula (7).

Examples of the amines (4a) include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, 1- Methylpyrrolidine, 1-methylpiperidine, 1-ethylpyrrolidine, 1-ethylpiperidine, 1-propylpyrrolidine, 1-propylpiperidine, 1-isopropylpyrrolidine, 1- Isopropylpiperidine, 1-butylpyrrolidine, 1-butylpiperidine, 1-pentyl Pyrrolidine, 1-pentylpiperidine, 1-hexylpyridine, 1-hexylpiperidine, 1-methyl-2-methylpyridine, 1-methyl-2-methylpiperidine, 1-methyl -3-methylpyrrolidine, 1-methyl-3-methylpiperidine, 1-methyl-4-methylpiperidine, 1-methyl-2-ethylpyridine, 1-methyl-2 -Propylpyrrolidine, 1-methyl-2-isopropylpyrrolidine, 1-methyl-2-butylpyrrolidine, 1-methyl-2-isobutylpyrrolidine, 1-methyl-2 -sec-butyl pyrrolidine, 1-methyl-2-tert-butyl pyrrolidine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3- Ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, 2-isopropyl Pyridine, 3-isopropylpyridine, 4-isopropylpyridine, 2-butylpyridine, 3-butylpyridine, 4-butylpyridine, 2-isobutylpyridine, 3-isobutylpyridine, 4 -Isobutylpyridine, 2-sec-butylpyridine, 3-sec-butylpyridine, 4-sec-butylpyridine, 2-tert-butylpyridine, 3-tert-butylpyridine, 4-tert- Butyl pyridine and the like.

Examples of the phosphines (4b) include trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, tripentylphosphine, trihexylphosphine, triheptylphosphine, trioctylphosphine, 1- Methylphosphane, 1-methylphosphaline, 1-ethylphosphane, 1-ethylphosphane, 1-propylphosphane, 1-propylphosphone Alkanes, 1-isopropylphosphorane, 1-isopropylphosphorane, 1-butylphosphorane, 1-butylphosphorane, 1-pentylphosphorane, 1-pentylphosphorane Hexane, 1-hexylphosphane, 1-hexylphosphacyclohexane, 1-methyl-2-methylphosphane, 1-methyl-2-methylphosphacyclohexane, 1-methyl 3-methylphosphorane, 1-methyl-3-methylphosphane, 1-methyl-4-methyl Phosphocyclohexane, 1-methyl-2-ethylphosphane, 1-methyl-2-propylphosphane, 1-methyl-2-isopropylphosphorane, 1-methyl-2 -Butylphosphorane, 1-methyl-2-isobutylphosphorane, 1-methyl-2-sec-butylphosphorane, 1-methyl-2-tert-butylphosphorane, triphosphine Benzene (Phosphorine), 2-methyltriphosphazene, 3-methyltriphosphazene, 4-methyltriphosphazene, 2-ethyltriphosphazene, 3-ethyltriphosphazene, 4-ethyltriphosphazene, 2-propyltriphosphazene, 3-propyltriphosphazene, 4-propyltriphosphazene, 2-propyltriphosphazene, 3-propyltrisphazene Phosphabenzene, 4-propyltriphosphane, 2-isopropyltriphosphane, 3-isopropyltriphosphane, 4-isopropyltriphosphane, 2-butyltriphosphane Benzene, 3-butyltriphosphane, 4-butyltriphosphane, 2-isobutyltriphosphane, 3-isobutyltriphosphane, 4-isobutyltriphosphane, 2-sec-butyltriphosphane, 3-sec-butyltriphosphane, 4-sec-butyltriphosphane, 2-tert-butyltriphosphane, 3-tert-butyl Triphosphene, 4-tert-butyltriphosphane, etc.

Examples of the alkyl halide (5) include chloromethyltrimethoxysilane, 2-chloroethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and 4-chlorobutyltrimethoxysilane. , Chloromethyltriethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltriethoxysilane, 4-chlorobutyltriethoxysilane, chloromethyltripropoxy Silane, 2-chloroethyltripropoxysilane, 3-chloropropyltripropoxysilane, 4-chlorobutyltripropoxysilane, chloromethyltributoxysilane, 2-chloroethyltrisiloxane Butoxysilane, 3-chloropropyltributoxysilane, 4-chlorobutyltributoxysilane, bromomethyltrimethoxysilane, 2-bromoethyltrimethoxysilane, 3-bromopropyl Trimethoxysilicon Alkane, 4-bromobutyltrimethoxysilane, bromomethyltriethoxysilane, 2-bromoethyltriethoxysilane, 3-bromopropyltriethoxysilane, 4-bromobutyltriethane Oxysilane, bromomethyltripropoxysilane, 2-bromoethyltripropoxysilane, 3-bromopropyltripropoxysilane, 4-bromobutyltripropoxysilane, bromomethyltrisilane Butoxysilane, 2-bromoethyltributoxysilane, 3-bromopropyltributoxysilane, 4-bromobutyltributoxysilane, iodomethyltrimethoxysilane, 2-iodoethyl Trimethoxysilane, 3-iodopropyltrimethoxysilane, 4-iodobutyltrimethoxysilane, iodomethyltriethoxysilane, 2-iodoethyltriethoxysilane, 3-iodopropane Triethoxysilane, 4-iodobutyltriethoxysilane, iodomethyltripropoxysilane, 2-iodoethyltripropoxysilane, 3-iodopropyltripropoxysilane, 4 -Iodobutyltripropoxysilane, iodomethyltributoxysilane, 2-iodoethyltributoxysilane, 3-iodopropyltributoxysilane, 4-iodobutyltributoxy Silane, etc.

The quaternary reaction of the amines or phosphines represented by the formula (4) and the alkyl halides (5) may be performed with or without a solvent. Examples of the solvent used in the solvent include alcohols such as methanol, ethanol, and 2-propanol, acetonitrile, ethyl acetate, tetrahydrofuran, and dimethylformamide.

The amount of the alkyl halide (5) to be used is 0.7 mol or more with respect to 1 mol of the amine or phosphine represented by the formula (4), and preferably 0.9 to 1.5 mol.

Examples of the alkali metal salt (7) include lithium bis (trifluoromethanesulfonyl) fluorenimide, sodium bis (trifluoromethanesulfonyl) fluorenimide, and bis (trifluoromethanesulfonyl) fluorenimide. Potassium, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate, six An alkali metal salt of a fluorine-containing anion such as potassium fluorophosphate.

Examples of the alkali metal that forms a counter cation of the anion include lithium, sodium, and potassium.

The amount of alkali metal salt (5) used in the ion exchange reaction is usually 0.8 mol or more, preferably 0.9 to 1.2 mol, and more preferably 1 to mol relative to 1 mol of onium = halide (6). 1.05 moles.

The ion exchange reaction is usually performed in a solvent. Examples of the solvent include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, and 2-propanol, acetonitrile, ethyl acetate, tetrahydrofuran, and dimethylformamide. Although the amount used is not particularly limited, it is usually 10 parts by mass or less, preferably 1 to 10 parts by mass, and particularly preferably 2 to 6 parts by mass, based on 1 part by mass of onium = halide (6).

The mixing order of onium = halide (6), alkali metal salt (5) and solvent is not particularly limited, and after the onium = halide (6) and solvent are mixed, the alkali metal salt (5) can be added, or After the alkali metal salt (5) and the solvent are mixed, onium = halides (6) are added.

The reaction temperature in the ion exchange reaction is usually 10 ° C or higher, preferably 10 to 60 ° C, and particularly preferably 10 to 30 ° C.

The onium salt (1) is separated from the reaction liquid after the reaction is completed, and the solvent and the generated inorganic salt are removed from the reaction liquid. If an inorganic salt can be precipitated from the obtained reaction solution, the precipitated inorganic salt can be removed by filtering the reaction solution, and then unit operations such as concentration, filtration, and extraction are appropriately combined to separate the onium salt (1). When an inorganic salt cannot be precipitated from the obtained reaction solution, the reaction solution is concentrated to precipitate the inorganic salt, and the inorganic salt is removed by filtration. Unit operations such as shrinking, filtering, extraction, etc., separate the onium salt (1).

In formula (2), R ⁵ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. Specific examples of R ⁵ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, naphthyl, benzyl, and vinyl. , Allyl, butenyl, hexenyl, octenyl, etc., methyl, phenyl and vinyl are preferred, and methyl and vinyl are particularly preferred. R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and specifically, methyl, ethyl, propyl, and the like are preferred, methyl and ethyl are preferred, and methyl is particularly preferred.

Specific examples of the trialkoxysilane (2) include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, Hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, naphthyltrimethoxysilane, benzyl Trimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, butenyltrimethoxysilane, hexenyltrimethoxysilane, octenyltrimethoxysilane, methyltriethoxy Silane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyl Triethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, benzyltriethoxysilane, vinyltriethoxysilane Ethoxysilane, allyltriethoxysilane, butenyltriethoxysilane, hexene Silane triethoxysilane, octenyl triethoxy Silane, methyl tripropoxy Silane, ethyl tripropoxy Oxysilane, propyltripropoxysilane, butyltripropoxysilane, pentyltripropoxysilane, hexyltripropoxysilane, heptyltripropoxysilane, octyltripropoxysilane , Nonyltripropoxysilane, decyltripropoxysilane, phenyltripropoxysilane, naphthyltripropoxysilane, benzyltripropoxysilane, vinyltripropoxysilane, olefin Propyltripropoxysilane, butenyltripropoxysilane, hexenyltripropoxysilane, octenyltripropoxysilane, etc., preferably methyltrimethoxysilane, vinyltrimethoxy Silane.

As the trialkoxysilane (2), a commercially available product may be used, or a product produced by a known production method may be used.

In the formula (3), R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. R ⁷ may be the same or different. Specific examples of R ⁷ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and phenyl. , Naphthyl, benzyl and the like, methyl and phenyl are preferred, and methyl is particularly preferred. R ⁸ represents an alkyl group having 1 to 3 carbon atoms. Specific examples thereof include methyl, ethyl, and propyl. Methyl and ethyl are preferred, and methyl is particularly preferred.

Specific examples of the dialkoxysilane (3) include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, and methylethyldimethoxy. Silane, methylpropyldimethoxysilane, methylbutyldimethoxysilane, methylpentyldimethoxysilane, methylhexyldimethoxysilane, methylheptyldimethoxysilane , Methyloctyldimethoxysilane, methylnonyldimethoxysilane, methyldecyldimethoxysilane, methylphenyldimethoxysilane, methylnaphthyldimethoxysilane Alkane, methylbenzyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, methylethyldiethoxysilane, methyl Propyldiethoxysilane, methylbutyldiethoxysilane, methylpentyldiethoxysilane, methylhexyldiethoxysilane, methylheptyldiethoxysilane, methyl Octyldiethoxysilane, methylnonyldiethoxysilane, methyldecyldiethoxysilane, methylphenyldiethoxysilane, methylnaphthyldiethoxysilane, methyl Benzyldiethoxysilane, dimethyldipropoxysilane, diethyldipropoxysilane, dipropyldipropoxysilane, methylethyldipropoxysilane, methylpropyldisilane Propoxysilane, methylbutyldipropoxysilane, methylpentyldipropoxysilane, methylhexyldipropoxysilane, methylheptyldipropoxysilane, methyloctyldipropyl Oxysilane, methylnonyldipropoxysilane, methyldecyldipropoxysilane, methylphenyldipropoxysilane, methylnaphthyldipropoxysilane, methylbenzyldipropyl oxygen Silane, Silane diphenyl dimethoxysilane, diphenyl diethoxy Silane, diphenyl-dipropoxy Silane like, preferably dimethyl dimethoxysilane Silane.

As the dialkoxysilane (3), a commercially available product may be used, or a product produced by a known production method may be used.

The copolymerization of onium salt (1) with trialkoxysilane (2) and dialkoxysilane (3), which is an optional component, is usually based on onium salt (1) and trialkoxysilane (2) and A mixture of an optional alkoxysilane (3) is dissolved when an onium salt (1), trialkoxy silane (2), and an optional alkoxy silane (3) are added. Dialkoxysilane (3) all organic solvents (e.g. methanol, ethanol, isopropyl Alcohol, acetone, and the like) to form a solution, and an acid (hereinafter referred to as an acid (8)) or a base (hereinafter referred to as a base (9)) and water serving as a hydrolysis reaction catalyst are dropped into the solution and carried out. The acid (8) or base (9) can be dropped in an aqueous solution. The stoichiometric ratio of the onium salt (1) and the trialkoxysilane (2) to the dialkoxysilane (3), which is an optional component, is preferably 1 mol relative to the onium salt (1), and the trialkoxy Silane (2) 0.5 to 95 moles, dialkoxysilane (3) 0 to 49 moles, more preferably 0.5 to 10 moles relative to onium salt (1), and trialkoxysilane (2) Ear, dialkoxysilane (3) 4 to 16 moles, the best is 0.5 to 4 moles, trialkoxysilane (2) 0.5 to 4 moles, compared to onium salt (1), 3) 4 ~ 8 moles. When the stoichiometric ratio of trialkoxysilane (2) is less than the above range, the heat resistance of the obtained polysiloxane copolymer may be impaired. In addition, the stoichiometric ratio of trialkoxysilane (2) is larger than the above. In the range, the surface mobility of the polysiloxane copolymer is decreased, and when the polysiloxane copolymer is used as an antistatic agent, there is a possibility that good antistatic properties may not be exhibited. When the stoichiometric ratio of dialkoxysilane (3) is larger than the above range, there is a possibility that the heat resistance of the obtained polysiloxane copolymer may be lowered. Moreover, as another arbitrary component, a monoalkoxysilane and a tetraalkoxysilane can be mixed and copolymerized within the range which does not impair the effect which exhibits antistatic property and heat resistance. Specific examples of the monoalkoxysilane include trimethylmethoxysilane, vinyldimethylmethoxysilane, trimethylethoxysilane, vinyldimethylethoxysilane, and trimethyl Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and the like.

Although the amount of the organic solvent used to dissolve the onium salt (1) and trialkoxysilane (2) and the dialkoxysilane (3) which is an optional component is not particularly limited, it is usually relative to the onium salt (1) The mass part is usually 20 parts by mass or less, preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass.

Examples of the acid (8) include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and p-toluenesulfonic acid monohydrate. Particularly preferred is hydrochloric acid. The amount of the acid (8) to be used is usually 0.001 to 1 mol, preferably 0.01 to 0.2 mol relative to 1 mol of the onium salt (1).

Examples of the base (9) include sodium hydroxide, potassium hydroxide, and lithium hydroxide. The amount of the base (9) to be used is usually 0.001 to 1 mol, preferably 0.01 to 0.2 mol relative to 1 mol of the onium salt (1).

The amount of water used for copolymerization is usually 4 to 49 moles relative to 1 mole of the onium salt (1).

Although the reaction temperature for the copolymerization of the onium salt (1) with trialkoxysilane (2) and the dialkoxysilane (3) which is an arbitrary component is not particularly limited, it is usually 10 to 80 ° C, preferably 20 ~ 40 ℃. The reaction time is usually 3 hours or more, and preferably 3 to 72 hours.

The polysiloxane copolymer is obtained by concentrating the reaction mixture obtained through the aforementioned reaction, and the obtained polysiloxane copolymer can be carried out with an unmixed organic solvent (hexane, heptane, benzene, toluene, etc.) if necessary. Wash.

Although the concentration temperature of the reaction mixture is not particularly limited, it is usually 10 to 120 ° C, preferably 60 to 80 ° C.

The obtained polysiloxane copolymer is kneaded with a resin, and can provide antistatic performance to the resin. Examples of the resin include polycarbonate resin, acrylic resin, and silicone resin. Accordingly, the present invention also provides a method including adding (for example, kneading) the above-mentioned polysiloxane copolymer to a resin to impart antistatic properties to the resin. Furthermore, the present invention also provides the above-mentioned polysiloxane copolymer as an antistatic agent, especially for imparting antistatic properties to a resin.

In addition, when the polysiloxane copolymer is kneaded to a resin, it may be heated and melted for kneading, or it may be prepared by mixing with a suitable solvent (for example, dichloromethane, ethyl acetate, toluene, etc.), and then applied. This solution is formed by removing a solvent and the like. In the case of a photocurable resin, a resin containing a polysiloxane copolymer or a solution thereof may be applied, and then the coated surface may be cured by irradiation with ultraviolet rays.

Although the amount of the resin added to the polysiloxane copolymer is not particularly limited, it is preferably 0.01 to 1% by mass, and particularly preferably 0.05 to 0.5% by mass based on 1 part by mass of the resin.

[Example]

Next, although the present invention will be specifically described based on examples, the present invention is not limited to any one.

In the examples, the surface resistivity was measured using HirestaUP (MCP-HT450) manufactured by Mitsubishi Chemical Corporation, under conditions of 23 ± 3 ° C and humidity 45 ± 5%.

For evaluation of heat resistance, Seiko Instruments Co., Ltd. has TG / DTA 220, manufactured by Tokushima Co., Ltd. In the measurement result of TG-DTA measured under a nitrogen atmosphere and a heating condition of 10 ° C / min, the temperature at which the mass was reduced by 5% was taken as the decomposition temperature. When the decomposition temperature is 300 ° C or higher, the heat resistance with melt-kneading of the polycarbonate resin is evaluated as "A", and when the decomposition temperature is less than 300 ° C, the heat resistance is insufficiently evaluated as "C".

[Manufacturing example 1]

In a 500 mL glass reactor equipped with a stirring device and under a nitrogen atmosphere, 130.3 g (1.1 mol) of dimethyldimethoxysilane, 42.20 g (0.31 mol) of methyltrimethoxysilane, and isopropyl alcohol were placed. 136.3 g and 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethane) manufactured by the method described in Japanese Patent Application Laid-Open No. 2010-248165 Sulfonyl) fluorenimine 100.0 g (0.15 mole). About 30.00 g of 0.1 predetermined hydrochloric acid was dripped at the obtained mixture at room temperature, and further, the reaction mixture obtained by stirring at room temperature for 16 hours was concentrated on a rotary evaporator at 80 ° C for 4 hours. The obtained concentrated residue was separated and washed twice with 272.5 g of n-hexane, and further concentrated at 80 ° C. for 5 hours by using a rotary evaporator to obtain a polysilicone copolymer A120.2 g of a white suspension liquid. .

[Manufacture example 2]

The same procedure as in Production Example 1 was performed except that 45.90 g (0.31 mole) of vinyltrimethoxysilane was used in place of methyltrimethoxysilane to obtain a white suspension liquid polysiloxane copolymer B123.10 g.

[Manufacture example 3]

In a 500 mL glass reactor equipped with a stirring device, in a nitrogen atmosphere, 190.0 g (1.40 mol) of methyltrimethoxysilane, 145.0 g of isopropyl alcohol, and the method described in Japanese Patent Application Laid-Open No. 2010-248165 The produced 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = 100.0 g (0.15 mole) of bis (trifluoromethanesulfonyl) fluorenimide. About 39.20 g of 0.1 predetermined hydrochloric acid was dripped at the obtained mixture at room temperature, and then the reaction mixture obtained by stirring at room temperature for 16 hours was concentrated on a rotary evaporator at 80 ° C for 4 hours. The obtained concentrated residue was separated and washed twice with 290.0 g of n-hexane, and further concentrated at 80 ° C for 5 hours by using a rotary evaporator to obtain a polysilicone copolymer C139.2 g of a white suspension liquid. .

[Comparative Manufacturing Example 1]

In a 500 mL glass reactor equipped with a stirring device, under a nitrogen atmosphere, 171.3 g (1.4 mol) of dimethyldimethoxysilane, 135.7 g of isopropyl alcohol, and N-{(3-triethoxysilane) Propyl) carbamoyloxyethyl} -N, N, N-trimethylammonium = bis (trifluoromethanesulfonyl) fluorenimine 100.0 g (0.16 mole). The resulting mixture was dropped at room temperature with 28.00 g of 0.1 prescribed hydrochloric acid, and then the reaction mixture obtained by stirring at room temperature for 16 hours was concentrated on a rotary evaporator at 80 ° C. for 4 hours. The obtained concentrated residue was separated and washed twice with 271.3 g of n-hexane, and further concentrated at 80 ° C. for 5 hours by using a rotary evaporator to obtain a polysilicone copolymer D127.1 g of a pale yellow transparent liquid. .

[Example 1]

In a 50 mL sample bottle, 3.2 g of polycarbonate resin (made by Sumitomo Dow Co., Ltd., Caliber (registered trademark) 200-13 NAT) and 20 mL of dichloromethane were added to dissolve the polycarbonate resin to prepare the polycarbonate resin. Dichloromethane solution. To this solution, 3.2 mg of the polysiloxane copolymer A obtained in Production Example 1 as an antistatic agent was added to completely dissolve, and then poured into a mold (12 cm in height × 20 cm in width × 2 cm in depth), and the mixture was left at room temperature for 1 hour Then, it was made to dry at 40 degreeC for 1 hour, and the test piece (film thickness 0.1 ± 0.02 mm) of a polycarbonate resin composition was produced. Table 1 shows the measurement results of the surface resistivity of the obtained test pieces.

[Example 2]

A test piece of a polycarbonate resin composition was produced in the same manner as in Example 1 except that 16 mg of the polysiloxane copolymer A was used instead, and the surface resistivity was measured. The results are shown in Table 1.

[Example 3]

A test piece of a polycarbonate resin composition was prepared in the same manner as in Example 1 except that 32 mg of the polysiloxane copolymer A was used instead, and the surface resistivity was measured. The results are shown in Table 1.

[Example 4]

Instead of using 3.2 mg of the polysiloxane copolymer obtained in Manufacturing Example 2 Other than B, it carried out similarly to Example 1, and produced the test piece of the polycarbonate resin composition, and measured the surface resistivity. The results are shown in Table 1.

[Example 5]

A test piece of a polycarbonate resin composition was prepared in the same manner as in Example 1 except that 16 mg of the polysiloxane copolymer B was used instead, and the surface resistivity was measured. The results are shown in Table 1.

[Example 6]

A test piece of a polycarbonate resin composition was produced in the same manner as in Example 1 except that 32 mg of the polysiloxane copolymer B was used instead, and the surface resistivity was measured. The results are shown in Table 1.

[Example 7]

A test piece of a polycarbonate resin composition was produced in the same manner as in Example 1 except that 32 mg of the polysiloxane copolymer C obtained in Production Example 3 was used, and the surface resistivity was measured. The results are shown in Table 1.

[Comparative Example 1]

A test piece of a polycarbonate resin composition was produced in the same manner as in Example 1 except that the polysiloxane copolymer A, B, or C was not added, and the surface resistivity was measured. The results are shown in Table 1.

[Comparative Example 2]

Instead of replacing polysiloxane copolymers A, B or C, use 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) A test piece of a polycarbonate resin composition was prepared in the same manner as in Example 1 except for fluoreneimine, and the surface resistivity was measured. The results are shown in Table 1.

[Comparative Example 3]

A test for producing a polycarbonate resin composition was performed in the same manner as in Example 1 except that the polysiloxane copolymer A, B, or C was used instead of the polysiloxane copolymer D obtained in Comparative Production Example 1. Sheet, and the surface resistivity was measured. The results are shown in Table 1.

[Example 8]

Mixed dipentaerythritol hexaacrylate (A-DPH: manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 0.50 g, pentaerythritol triacrylate (A-TMN-3LM-N: manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 1.50 g, trihydroxy 0.50 g of methylpropane triacrylate (A-TMPT: manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 0.54 g of polysiloxane copolymer A obtained in Production Example 1 as an antistatic agent, and 1.75 g of isopropyl alcohol 3.60 g of colloidal silica's IPA dispersion (IPA-ST: 30% by mass of silica solid content, manufactured by Nissan Chemical Industries, Ltd.) and 2-hydroxy-2-methyl as a photopolymerization initiator 0.15 g of phenylacetone. The obtained mixture was applied to one side of a polyethylene terephthalate film having a thickness of 100 μm by using a bar coater so that the dry film thickness was approximately 5 μm, and the total light amount was approximately 400 mJ / cm ² Under the conditions, ultraviolet rays of a high-pressure mercury UV lamp (120 W / cm ² ) were irradiated to the coating film side to harden the coating film, thereby preparing a test piece hard-coated with an acrylic resin. Table 2 shows the measurement results of the surface resistivity of the hard coated surface of the obtained test piece.

[Example 9]

A test piece hard-coated with an acrylic resin was produced in the same manner as in Example 8 except that 0.54 g of the polysiloxane copolymer B obtained in Production Example 2 was used instead. Table 2 shows the measurement results of the surface resistivity of the hard coated surface of the obtained test piece.

[Example 10]

A test piece hard-coated with an acrylic resin was produced in the same manner as in Example 8 except that 0.54 g of the polysiloxane copolymer C obtained in Production Example 3 was used instead. Table 2 shows the measurement results of the surface resistivity of the hard coated surface of the obtained test piece.

[Comparative Example 4]

A test piece hard-coated with an acrylic resin was produced in the same manner as in Example 8 except that the polysiloxane copolymer A, B, or C was not added. Table 2 shows the measurement results of the surface resistivity of the hard coated surface of the obtained test piece.

[Comparative Example 5]

Instead of replacing polysiloxane copolymer A or B, use 0.54g of 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) Except for fluorene imine, the same procedure as in Example 8 was performed to prepare a test piece hard-coated with an acrylic resin. Table 2 shows the measurement results of the surface resistivity of the hard coated surface of the obtained test piece.

[Example 11]

5.00 g of methyl methacrylate, 0.20 g of azobisisobutyronitrile, and 5 mg of the polysiloxane copolymer A obtained in Production Example 1 as an antistatic agent were mixed, and the resulting mixture was poured into a plastic container (inner diameter 5 cm × A cylindrical shape having a depth of 1.5 cm) was cured at 50 ° C. for 10 hours to prepare a test piece of polymethyl methacrylate resin having a thickness of about 2 mm. Table 3 shows the measurement results of the surface resistivity of the obtained test pieces.

[Comparative Example 6]

A test was performed in the same manner as in Example 11 except that the polysiloxane copolymer A, B, or C was not added to prepare a polymethyl methacrylate resin, and the surface resistivity was measured. The results are shown in Table 3.

[Comparative Example 7]

Instead of using polysiloxane copolymers A, B or C, use 5 mg 1- Except for (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) fluorenimine, the same procedure as in Example 11 was performed to prepare a polyformyl Based on a test piece of a methyl acrylate resin, the surface resistivity was measured. The results are shown in Table 3.

[Example 12]

Mixed peroxide hardened silicone adhesive KR-101-10 (60% solids, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 4.0 g, 0.08 g of hardener BPO (benzidine peroxide), and 6.2 g of ethyl acetate And as an antistatic agent, 48 mg of the polysiloxane copolymer A obtained in Example 1 was used to obtain a silicone resin adhesive. The above-mentioned silicone resin adhesive was applied to one side of a polyethylene terephthalate film (release film) by using a bar coater so that the dry film thickness became about 8 μm, at 90 ° C. 3 It was dried by heating at 160 ° C for 2 minutes for 2 minutes to prepare a silicone resin adhesive layer, and the surface resistivity was measured. The results are shown in Table 4.

A triethyl cellulose cellulose film (TAC film) was laminated on the surface having the adhesive layer, and aged at 25 ° C and 50% RH for 1 hour to prepare a test film. When peeling the release paper from the test film, The adhesion state of the adhesive was evaluated visually. The results are shown in Table 4.

A: Adhesion to the adhesive of the release paper cannot be confirmed.

B: Adhesion of the adhesive to the part of the release paper was confirmed.

C: Adhesion to most of the adhesive of the release paper was confirmed.

[Comparative Example 8]

Except that no polysiloxane copolymer A, B, or C was added, it was performed in the same manner as in Example 12. A silicone resin adhesive layer and a test film were produced, and the surface resistivity was measured. The adhesion state of the paper adhesive was evaluated visually. The results are shown in Table 4.

[Comparative Example 9]

Instead of replacing polysiloxane copolymers A, B or C, use 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) Except for fluorene imine, it was carried out in the same manner as in Example 12. A silicone resin adhesive layer and a test film were produced, and the surface resistivity was measured. At the same time, the state of adhesion to the release paper adhesive was visually checked. Evaluation. The results are shown in Table 4.

Claims (9)

A polysiloxane copolymer copolymerized with an onium salt represented by formula (1), a trialkoxysilane represented by formula (2), and a dioxane represented by formula (3) as an optional component Obtained from oxysilane, formula (1): (In the formula, 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 represents an alkyl group having 1 to 8 carbon atoms; R ² and R ³ are bonded to each other at the ends; Can form a pyridine ring, a piperidine ring, a pyridine ring, a phosphorane ring, a phosphocyclohexane ring, or a triphosphine ring; however, R ² and R ³ are bonded to each other at the ends to form a pyridine ring or a triphosphorus ring When a heterobenzene ring is present, R ⁴ does not exist; X ^- represents a fluorine-containing anion; n is an integer of 0 to 3); Formula (2): [Chem 2] R ⁵ -Si (OR ⁶ ) ₃ (2) (wherein , R ⁵ represents an alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms, or alkenyl group having 2 to 8 carbon atoms, and R ⁶ represents 1 to 3 carbon atoms (Alkyl); formula (3): (In the formula, R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R ⁸ represents an alkyl group having 1 to 3 carbon atoms). The polysiloxane copolymer according to claim 1, wherein in the formula (1), Q ⁺ is a phosphorus cation. The polysiloxane copolymer according to claim 1, wherein the foregoing fluorine-containing anion is a trifluoromethanesulfonic acid anion, a bis (trifluoromethanesulfonyl) fluorenimide anion, a tetrafluoroborate anion, or hexafluorophosphate Ester anion. The polysiloxane copolymer according to claim 1 or 2 copolymerizes 0.5 to 95 of the trialkoxysilane represented by the aforementioned formula (2) with respect to 1 mol of the onium salt represented by the aforementioned formula (1). Mohr is obtained from 0 to 49 moles of the dialkoxysilane represented by the formula (3). The polysiloxane copolymer according to claim 1 or 2 copolymerizes 0.5 to 95 of the trialkoxysilane represented by the aforementioned formula (2) with respect to 1 mol of the onium salt represented by the aforementioned formula (1). Mohr is obtained from 4 to 49 moles of the dialkoxysilane represented by the formula (3). An antistatic agent comprising the polysiloxane copolymer according to any one of claims 1 to 5. A resin composition containing the antistatic agent according to claim 6. The resin composition according to claim 7, wherein the resin composition is a polycarbonate resin composition, an acrylic resin composition, or a silicone resin composition. A method for producing a polysiloxane copolymer according to any one of claims 1 to 5, which is characterized by copolymerizing an onium salt represented by the aforementioned formula (1) and the compound represented by the aforementioned formula (2) in the presence of hydrochloric acid. And a dialkoxysilane represented by the aforementioned formula (3) as optional components.