KR20160148511A - Polysiloxane copolymer and antistatic agent comprising same - Google Patents

Abstract

The present invention relates to a polysiloxane copolymer which is capable of imparting high antistatic property to a resin and capable of producing a silicone resin having practical strength properties as an optical pressure-sensitive adhesive. According to the present invention, it is possible to provide a polysiloxane copolymer which is capable of imparting high antistatic properties to a polycarbonate resin, an acrylic resin and a silicone resin, and capable of producing a silicone resin having practical strength characteristics as an optical pressure- It is possible to provide an antistatic agent containing a coagent.

Description

TECHNICAL FIELD The present invention relates to a polysiloxane copolymer and an antistatic agent containing the polysiloxane copolymer and antistatic agent containing the polysiloxane copolymer.

[Cross reference of related application]

This application claims priority from Japanese Patent Application No. 2014-086978, filed April 21, 2014, the disclosure of which is incorporated herein by reference in its entirety.

The present invention relates to a polysiloxane copolymer and an antistatic agent containing the same.

It has been reported that an onium salt in which cation is ammonium or phosphonium having a trialkoxysilylalkyl group and anion is perfluoroalkylsulfonylimide can be used as a low molecular weight antistatic agent for fluorine resin ( Patent Document 1). However, the present inventors have found that when 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) imide, which is one of the above onium salts, is reacted with a polycarbonate resin, As a result of using them as an antistatic agent for a resin and a silicone resin, antistatic properties could be imparted to the silicone resin, but practical antistatic properties could not be imparted to the polycarbonate resin and the acrylic resin. As to the silicone resin, it was found that the curing reaction of the silicone resin did not sufficiently proceed and a silicone resin composition having practical strength properties as an optical adhesive was not obtained (see comparative examples described later).

Japanese Patent Application Laid-Open No. 2010-248165

The present invention relates to a polysiloxane copolymer which is capable of imparting high antistatic properties to a polycarbonate resin, an acrylic resin and a silicone resin and capable of producing a silicone resin having practical strength characteristics as an optical pressure-sensitive adhesive, and a polysiloxane copolymer And an antistatic agent containing the antistatic agent.

The inventors of the present invention have conducted intensive studies in order to solve the above problems and have found out a polysiloxane copolymer obtained by copolymerizing an onium salt represented by the formula (1) and a dialkoxysilane represented by the formula (2), and further to obtain the polysiloxane copolymer As a result of using them as polycarbonate resin, acrylic resin and silicone resin as an antistatic agent, it was found that high antistatic properties can be imparted to each resin. It has also been found that a curing reaction of a silicone resin progresses smoothly, and a silicone resin composition having practical strength characteristics as an optical pressure-sensitive adhesive can be obtained, thereby completing the present invention.

That is, the present invention relates to a process for producing a polyalkoxysilane composition by copolymerizing an onium salt represented by the formula (1) (hereinafter referred to as an onium salt (1)) with a dialkoxysilane represented by the formula (2) Polysiloxane copolymer (hereinafter referred to as polysiloxane copolymer).

Equation (1):

[Chemical Formula 1]

(Represents the formula, Q ⁺ is a nitrogen cation or a cation. R ₁ represents an alkyl group having a carbon number of _{1 ~ 3, R 2 ~ R} 4 represents an alkyl group having 1 ~ 8. R ₂ and R ₃ is A pyrrolidine ring, a piperidine ring, a pyridine ring, a phosphorane ring, a phospholane ring, or a phospholine ring may be formed, provided that when a pyridine ring or a phospholine ring is formed, R ₄ is absent, X ^- represents anion, n is an integer of 0 to 3,

Equation (2):

(2)

(Wherein R ₅ represents an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an aralkyl group of 7 to 10 carbon atoms, and R ₆ represents an alkyl group of 1 to 3 carbon atoms.)

The polysiloxane copolymer of the present invention can be used as an antistatic agent, and a resin composition having high antistatic properties can be produced by using the antistatic agent for a polycarbonate resin, an acrylic resin and a silicone resin. In addition, when the polysiloxane copolymer of the present invention is used, a silicone resin composition having practical strength properties as an optical pressure-sensitive adhesive can be produced.

Hereinafter, the present invention will be described in detail.

In the formula (1), Q ^{< +} & gt ^; represents a nitrogen cation or an incat ion, and an incat ion is preferable. R ₁ is an alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group and an isopropyl group, and a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable. R ₂ to R _{4 each} represent an alkyl group having 1 to 8 carbon atoms, which may be linear or branched, and is preferably a linear alkyl group. Specific examples include methyl, ethyl, propyl, butyl, hexyl and octyl. Methyl, ethyl, propyl and butyl are preferred, and butyl is particularly preferred. R ₂ and R ₃ may combine with each other at the ends to form a pyrrolidine ring, a piperidine ring, a pyridine ring, a phosphorane ring, a phospholane ring, or a phospholine ring. However, when R ₂ and R ₃ are bonded to each other at the ends to form a pyridine ring or a morpholine ring phosphine, R ₄ is not present. X ^- represents anion. X ^{- represents} halogen anion or fluorine anion, and halogen anion is preferably chloro anion, bromo anion or iodide anion, more preferably chloro anion. As the fluorine anion, trifluoromethanesulfonic anion, bis (trifluoromethanesulfonyl) imide anion, tetrafluoroborate anion and hexafluorophosphate anion are preferable, and bis (trifluoromethanesulfonyl) imide anion, tetrafluoroborate anion and hexafluorophosphate anion are preferable, Methanesulfonyl) imide anion are more preferable.

Specific examples of the onium salt (1) include 1,1,1-trimethyl-1 - [(trimethoxysilyl) methyl] ammonium = bis (trifluoromethanesulfonyl) imide, Trimethyl-1- [3- (trimethoxysilyl) ethyl] ammonium] bis (trifluoromethanesulfonyl) imide, 1,1,1- (Trifluoromethanesulfonyl) imide, 1,1,1-trimethyl-1- [4- (trimethoxysilyl) butyl] ammonium = bis (trifluoromethanesulfonyl) , 1,1-triethyl-1 - [(trimethoxysilyl) methyl] ammonium = bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1,1,1-triethyl-1- [3- (trimethoxysilyl) propyl] ammonium = bis (trifluoromethanesulfonyl) imide 1,1,1-triethyl-1- [4- (trimethoxysilyl) butyl] ammonium = bis (trifluoromethanesulfonyl) imide, 1,1,1-tributyl- 1 - [(trimethoxy) Bis (trifluoromethanesulfonyl) imide, 1,1,1-tributyl-1- [2- (trimethoxysilyl) ethyl] ammonium = bis (trifluoromethanesulfonyl) imide (Trifluoromethanesulfonyl) imide, 1,1,1-tributyl-imide, 1,1,1-tributyl-1- [3- (trimethoxysilyl) 1 - [(trimethoxysilyl) methyl] ammonium] bis (trifluoromethanesulfonyl) imide, 1,1,1-trihexyl- (Trifluoromethanesulfonyl) imide, 1,1,1-trihexyl-1- [2- (trimethoxysilyl) ethyl] ammonium = bis (trifluoromethanesulfonyl) (Triphenylmethanesulfonyl) imide, 1,1,1-trihexyl-1- [4- (trimethoxysilyl) propyl] (Triphenylmethanesulfonyl) imide, 1,1,1-trioctyl-1 - [(trimethoxysilyl) methyl] ammonium = bis (trifluoromethanesulfonyl) Amide, 1,1,1-trioctyl-1- [2- (trimethoxysilyl) ethyl] ammonium = bis (trifluoromethanesulfonyl) imide, (Trimethoxysilyl) propyl] ammonium = bis (trifluoromethanesulfonyl) imide, 1,1,1-trioctyl-1- [4- (trimethoxysilyl) butyl] ammonium = bis Trifluoromethanesulfonyl) imide,

1,1,1-trimethyl-1 - [(trimethoxysilyl) methyl] phosphonium = bis (trifluoromethanesulfonyl) imide, 1,1,1-trimethyl-1- [2- (Trimethoxysilyl) propylphosphonium bis (trifluoromethanesulfonyl) imide, 1,1,1-trimethyl-1- [3- (trimethoxysilyl) (Trifluoromethanesulfonyl) imide, 1,1,1-trimethyl-1- [4- (trimethoxysilyl) butyl] phosphonium = bis (Trimethoxysilyl) methyl] phosphonium = bis (trifluoromethanesulfonyl) imide, 1,1,1-triethyl-1- [2- (trimethoxysilyl) ethyl] (Trifluoromethanesulfonyl) imide, 1,1,1-triethyl-1- [3- (trimethoxysilyl) propyl] phosphonium = bis (trifluoromethanesulfonyl) imide , 1,1,1-triethyl-1- [4- (trimethoxysilyl) butyl] phosphonium = bis (trifluoromethanesulfonyl) imide, (Trimethoxysilyl) (Triphenylmethanesulfonyl) imide, 1,1,1-tributyl-1- [2- (trimethoxysilyl) ethyl] phosphonium = bis (trifluoromethanesulfonyl) imide ) Imide, 1,1,1-tributyl-1- [3- (trimethoxysilyl) propyl] phosphonium = bis (trifluoromethanesulfonyl) imide, 1 - [(trimethoxysilyl) butyl] phosphonium bis (trifluoromethanesulfonyl) imide, 1,1,1-trihexyl-1 - [(trimethoxysilyl) methyl] phosphonium Bis (trifluoromethanesulfonyl) imide, 1,1,1-trihexyl-1- [2- (trimethoxysilyl) ethyl] phosphonium = bis (trifluoromethanesulfonyl) imide, 1,1,1-trihexyl-1- [3- (trimethoxysilyl) propyl] phosphonium = bis (trifluoromethanesulfonyl) imide, 1,1,1- - (trimethoxysilyl) butyl] phosphonium = bis (trifluoromethanesulfonyl) imide, 1,1,1-trioctyl-1 - [(trimethoxysilyl) methyl] phosphonium = bis Fluoro 1,1,1-trioctyl-1- [2- (trimethoxysilyl) ethyl] phosphonium = bis (trifluoromethanesulfonyl) imide, 1,1,1-tri Octyl-1- [3- (trimethoxysilyl) propyl] phosphonium bis (trifluoromethanesulfonyl) imide, 1,1,1-trioctyl-1- [4- (trimethoxysilyl) Butyl] phosphonium = bis (trifluoromethanesulfonyl) imide,

Methyl-1 - [(trimethoxysilyl) methyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-propyl-1 - [(trimethoxysilyl) methyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-hexyl-1 - [(trimethoxysilyl) methyl] pyrrolidinium = bis (trifluoromethanesulfonyl) (Trifluoromethanesulfonyl) imide, 1-methyl-1- [2- (trimethoxysilyl) methyl] pyrrolidinium imide, ) Ethyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- [2- (trimethoxysilyl) ethyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide Propyl-1- [2- (trimethoxysilyl) ethyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide 1-butyl-1- [2- (trimethoxysilyl) ethyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, 1-hexyl- (Trifluoromethanesulfonyl) imide, 1-octyl-1- [2- (trimethoxysilyl) ethyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, Ethyl-1- [3- (trimethoxysilyl) propyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-propyl-1- [3- (trimethoxysilyl) propyl] pyrrolidinium = bis (trifluoromethanesulfonyl) 1-hexyl-1- [3- (trimethoxysilyl) propyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, 1-octyl-1- [3- (trimethoxysilyl) propyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, 1-methyl-1- [4- (trimethoxysilyl) butyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-propyl-1- [4- (trimethoxysilyl) butyl] pyrrolidinium = bis (trifluoromethanesulfonyl) 1-butyl-1- [4- (trimethoxysilyl) butyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide, 1-hexyl- (Trifluoromethanesulfonyl) imide, 1-octyl-1- [4- (trimethoxysilyl) butyl] pyrrolidinium = bis (trifluoromethanesulfonyl) imide Phenyl) imide,

Methyl-1 - [(trimethoxysilyl) methyl] piperidinium = bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-propyl-1 - [(trimethoxysilyl) methyl] piperidinium = bis (trifluoromethanesulfonyl) imide, (Trimethoxysilyl) methyl] piperidinium = bis (trifluoromethanesulfonyl) imide, 1-hexyl-1 - [(trimethoxysilyl) methyl] piperidinium = bis (Trifluoromethanesulfonyl) imide, 1-methyl-1- [2- (trimethoxysilyl) methyl] piperidinium iodide, ) Ethyl] piperidinium = bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (trifluoromethanesulfonyl) imide Propyl-1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (trifluoromethanesulfonyl) imide 1-butyl-1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (trifluoromethanesulfonyl) imide, 1-hexyl- (Triphenylmethanesulfonyl) imide, 1-octyl-1- [2- (trimethoxysilyl) ethyl] piperidinium = bis (trifluoromethanesulfonyl) imide, Ethyl-1- [3- (trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-propyl-1- [3- (trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) 1-hexyl-1- [3- (trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) imide, 1-octyl-1- [3- (trimethoxysilyl) propyl] piperidinium = bis (trifluoromethanesulfonyl) imide, Methyl-1- [4- (trimethoxysilyl) butyl] piperidinium = bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- [4- (Trimethoxysilyl) butyl] piperidinium = bis (trifluoromethanesulfonyl) imide, 1-propyl-1- [4- (trimethoxysilyl) butyl] piperidinium = bis 1-butyl-1- [4- (trimethoxysilyl) butyl] piperidinium = bis (trifluoromethanesulfonyl) imide, 1-hexyl- (Trifluoromethanesulfonyl) imide, 1-octyl-1- [4- (trimethoxysilyl) butyl] piperidinium = bis (trifluoromethanesulfonyl) imide Phenyl) imide,

(Trifluoromethanesulfonyl) imide, 1- [2- (trimethoxysilyl) ethyl] pyridinium = bis (trifluoromethanesulfonyl) imide (Trimethoxysilyl) propyl] pyridinium = bis (trifluoromethanesulfonyl) imide, 1- [4- (trimethoxysilyl) butyl] pyridinium = bis (Trifluoromethanesulfonyl) imide, 1- [2- (trimethoxysilyl) methyl] -2-methylpyridinium = bis (trifluoromethanesulfonyl) (Trifluoromethanesulfonyl) imide, 1- [3- (trimethoxysilyl) propyl] -2-methylpyridinium = bis (trifluoromethanesulfonyl) Imide, 1 - [(trimethoxysilyl) methyl] -3- (trimethoxysilyl) butyl] -2-methylpyridinium = bis (trifluoromethanesulfonyl) Methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- [2- (trimethoxysilyl) ethyl] -3-methylpyridine (Trifluoromethanesulfonyl) imide, 1- [3- (trimethoxysilyl) propyl] -3-methylpyridinium = bis (trifluoromethanesulfonyl) (Trifluoromethanesulfonyl) imide, 1 - [(trimethoxysilyl) methyl] -4-methylpyridinium = bis (trifluoromethanesulfonyl) Methanesulfonyl) imide, 1- [2- (trimethoxysilyl) ethyl] -4-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- [3- (trimethoxysilyl) (Trifluoromethanesulfonyl) imide, 1- [4- (trimethoxysilyl) butyl] -4-methylpyridinium = bis (trifluoromethanesulfonyl) Imide, and the like.

The onium salt (1) used in the present invention can be produced in accordance with the method described in JP-A-2010-248165. Representative methods thereof will be described in the following Reaction Scheme 1. R ¹ , R ² , R ³ , R ⁴ , Q, X and n are as defined above, Z represents a halogen atom, and M represents an alkali metal.

(3)

(Hereinafter referred to as amines 5a) or phosphines (hereinafter referred to as phosphines 5b) with alkyl halides represented by the formula (6) (hereinafter referred to as alkyl halides (Hereinafter referred to as Onium = halide (7)) represented by the formula (7) is produced. When X ^- is halogen anion, onium = halide (7) can be used as the onium salt (1).

Next, the onium salt (1) can be produced by an ion exchange reaction of the onium = halide (7) and the alkyl metal salt represented by the formula (8).

Examples of the amine (5a) include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine,

Methylpiperidine, 1-ethylpiperidine, 1-ethylpiperidine, 1-propylpyrrolidine, 1-propylpiperidine, 1-isopropylpyrrolidine, Butylpiperidine, 1-pentylpyrrolidine, 1-pentylpiperidine, 1-hexylpyrrolidine, 1-hexylpiperidine, Methyl-2-methylpyrrolidine, 1-methyl-3-methylpiperidine, 1-methyl-4- Methyl-2-propylpyrrolidine, 1-methyl-2-isopropylpyrrolidine, 1-methyl-2-butylpyrrolidine, Methyl-2-sec-butylpyrrolidine, 1-methyl-2-tert-butylpyrrolidine,

Examples of the amines include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, Examples of the pyridine compounds include pyridine, 3-propylpyridine, 4-propylpyridine, 2-isopropylpyridine, 3-isopropylpyridine, 4-isopropylpyridine, 2-butylpyridine, 3-butylpyridine, Butylpyridine, 3-tert-butylpyridine, 4-tert-butylpyridine, 4-tert-butylpyridine, 3- tert-butylpyridine and the like.

Examples of the phosphine (5b) include, but are not limited to, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, tripentylphosphine, trihexylphosphine, triheptylphosphine, trioctylphosphine,

Ethylphosphorane, 1-ethylphosphorane, 1-propylphosphorane, 1-propylphosphorane, 1-isopropylphosphorane, 1-isopropylphosphorane, 1-pentylphosphorane, 1-hexylphosphorane, 1-hexylphosphorane, 1-methyl-2-methyl Methylphosphorane, 1-methyl-3-methylphosphorane, 1-methyl-3-methylphospholane, 1-methyl- Methyl-2-isopropylphosphorane, 1-methyl-2-butylphosphorane, 1-methyl-2-isobutylphosphorane, 1- Methyl-2-sec-butylphosphorane, 1-methyl-2-tert-butylphosphorane,

Methylphosphorine, 4-methylphosphorine, 2-ethylphosphorine, 3-ethylphosphorine, 4-ethylphosphorine, 2-propylphosphorine, 3-propylphosphorine , 4-propylphosphorine, 2-propylphosphorine, 3-propylphosphorine, 4-propylphosphorine, 2-isopropylphosphorine, 3-isopropylphosphorine, Butylphosphorine, 2-sec-butylphosphorine, 2-sec-butylphosphorine, 3-butylphosphorine, , 4-sec-butylphosphorine, 2-tert-butylphosphorine, 3-tert-butylphosphorine, 4-tert-butylphosphorine and the like.

The alkyl halide (6) includes, for example, chloromethyltrimethoxysilane, 2-chloroethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorobutyltrimethoxysilane, chloromethyltri 2-chloroethyltriethoxysilane, 3-chloropropyltriethoxysilane, 4-chlorobutyltriethoxysilane, chloromethyltripropoxysilane, 2-chloroethyltripropoxysilane, 3-chloropropyltriethoxysilane, But are not limited to, tripropoxysilane, tripropoxysilane, 4-chlorobutyltripropoxysilane, chloromethyltributoxysilane, 2-chloroethyltributoxysilane, 3-chloropropyltributoxysilane, 4- Methyltrimethoxysilane, 2-bromoethyltrimethoxysilane, 3-bromopropyltrimethoxysilane, 4-bromobutyltrimethoxysilane, bromomethyltriethoxysilane, 2-bromoethyltris 3-bromopropyltriethoxysilane, 4-bromo Tributyltriethoxysilane, bromomethyltripropoxysilane, 2-bromoethyltripropyloxysilane, 3-bromopropyltripropoxysilane, 4-bromobutyltripropoxysilane, bromomethyltributoxysilane , 2-bromoethyltributoxysilane, 3-bromopropyltributoxysilane, 4-bromobutyltributoxysilane, iodomethyltrimethoxysilane, 2-iodoethyltrimethoxysilane, 3- Iodomethyltriethoxysilane, 3-iodopropyltriethoxysilane, 4-iodobutyltriethoxysilane, iodomethyltriethoxysilane, iodomethyltriethoxysilane, 3-iodopropyltriethoxysilane, 4-iodobutyltrimethoxysilane, Iodomethyltributoxysilane, 3-iodopropyltripropoxysilane, 3-iodopropyltripropoxysilane, 4-iodobutyltripropoxysilane, iodomethyltributoxysilane, 2-iodethyltributoxysilane, 3 - iodopropyltributoxysilane, 4-iodobutyltri Butoxysilane and the like.

The quaternization reaction of the amines or phosphines represented by the formula (5) with the alkyl halides (6) may or may not use a solvent. Examples of the solvent when the solvent is used include alcohols such as methanol, ethanol and 2-propanol, acetonitrile, ethyl acetate, tetrahydrofuran, dimethylformamide and the like.

The alkyl halide (6) is used in an amount of 0.7 mol or more, preferably 0.9 to 1.5 mol based on 1 mol of the amine or phosphine represented by the formula (5).

Examples of the alkali metal salt (8) include lithium bis (trifluoromethanesulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, potassium bis (trifluoromethanesulfonyl) imide, tetrafluoro Alkali metal salts of fluorinated anions such as borate lithium, sodium tetrafluoroborate, potassium tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate and potassium hexafluorophosphate.

Examples of the alkali metal forming the counter cation of anion include lithium, sodium and potassium.

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

The ion exchange reaction is usually carried out 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. The amount to be used is not particularly limited, but is usually 10 parts by weight or less, preferably 1 to 10 parts by weight, and particularly preferably 2 to 6 parts by weight based on 1 part by weight of onium = halide (5).

The order of mixing the onium halide 5, the alkali metal salt 6 and the solvent is not particularly limited and the alkali metal salt 6 may be added after mixing the onium halide 5 and the solvent, 6) and a solvent may be mixed and then the onium = halide (5) may be added.

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

In order to separate the onium salt (1) from the reaction solution after completion of the reaction, the solvent and the resulting inorganic salt are removed from the reaction solution. If the inorganic salt is precipitated in the obtained reaction solution, the reaction solution is filtered to remove the precipitated inorganic salt, and then the unit operation such as concentration, filtration and extraction is appropriately combined to isolate the onium salt (1). When the inorganic salt is not precipitated in the obtained reaction liquid, the inorganic salt is precipitated by concentrating the reaction liquid, the inorganic salt is removed by filtration, and the unit operations such as concentration, filtration and extraction are appropriately combined, The onium salt (1) is isolated.

In the formula (2), R ₅ 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 ₅ may be the same or different and R ₅ is specifically exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, A methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. R ₆ represents an alkyl group having 1 to 3 carbon atoms, and specific examples thereof include a methyl group, an ethyl group and a propyl group, and a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

Specific examples of the dialkoxysilane (2) include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, methylethyldimethoxysilane, methylpropyldimethoxysilane, methylbutyldimethoxysilane, methylpentyldimetate Methylhexyldimethoxysilane, methylhexyldimethoxysilane, methylhexyldimethoxysilane, methylhexyldimethoxysilane, methylhexyldimethoxysilane, methylhexyldimethoxysilane, methylhexyldimethoxysilane, methylhexyldimethoxysilane, methylhexyldimethoxysilane, , Dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, methylethyldiethoxysilane, methylpropyldiethoxysilane, methylbutyldiethoxysilane, methylpentyldiethoxysilane, methylhexyldiethoxysilane, methylheptyl Diethoxy silane, methyl octyl diethoxy silane, methyl nonyl diethoxy silane, methyldecyl diethoxy silane, methyl phenyl diethoxy silane, methyl benzyl diethoxy silane, methyl naphthyl diethoxy silane , Dimethyldipropoxysilane, diethyldipropoxysilane, dipropyldipropoxysilane, methylethyldipropoxysilane, methylpropyldipropoxysilane, methylbutyldipropoxysilane, methylpentyldipropoxysilane, methyl But are not limited to, hexyldipropoxysilane, methylheptyldipropoxysilane, methyloctyldipropoxysilane, methylnonyldipropoxysilane, methyldecyldipropoxysilane, methylphenyldipropoxysilane, methylbenzyldipropoxysilane, methylnaphthyl Dipropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, and the like, and dimethyldimethoxysilane is preferable.

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

The copolymerization of the onium salt (1) and the dialkoxy silane (2) usually involves dissolving both the onium salt (1) and the dialkoxy silane (2) in a mixture of the onium salt (1) and the dialkoxy silane (2) (Hereinafter referred to as acid (3)) or a base (hereinafter referred to as acid (3)) which is a catalyst for the hydrolysis reaction is added to an organic solvent (for example, methanol, ethanol, isopropyl alcohol, acetone, (Hereinafter referred to as base (4)) and water. The acid (3) or the base (4) may be dropped into an aqueous solution. The stoichiometric ratio of the onium salt (1) to the dialkoxy silane (2) is usually in the range of 4 to 49 mol, preferably 1 mol of the dialkoxysilane (2), per mol of the onium salt (1) 4 to 16 mol of dialkoxysilane (2), and more preferably 4 to 8 mol of dialkoxysilane (2) per mol of onium salt (1). Further, in the copolymerization of the onium salt (1) and the dialkoxy silane (2), the copolymer obtained by containing a trialkoxy silane such as methyltrimethoxysilane or vinyltrimethoxysilane can be obtained by adding the trialkoxysilane , The antistatic performance of the resin tends to be lowered. Therefore, the copolymer of the onium salt (1) and the dialkoxy silane (2) does not contain the trialkoxysilane. As other arbitrary components, monoalkoxysilane and tetraalkoxysilane may be mixed and copolymerized in such a range that the effect of the antistatic property is not impaired. Specific examples of the monoalkoxysilane include trimethylmethoxysilane, vinyldimethylmethoxysilane, trimethylethoxysilane, vinyldimethylethoxysilane, trimethylpropoxysilane, and vinyldimethylpropoxysilane, and tetraalkoxysilane Specific examples of the silane coupling agent include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

The amount of the organic solvent which dissolves the onium salt (1) and the dialkoxy silane (2) is not particularly limited, but is usually 20 parts by weight or less, preferably 0.5 to 10 parts by weight per 1 part by weight of the onium salt (1) By weight, particularly preferably 1 to 5 parts by weight.

Examples of the acid (3) include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, paratoluenesulfonic acid monohydrate, and the like, with hydrochloric acid being particularly preferred. The amount of the acid (3) to be used is usually 0.001 to 1 mol, preferably 0.01 to 0.2 mol, per 1 mol of the onium salt (1).

Examples of the base (4) include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The amount of the base (4) to be used is usually 0.001 to 1 mol, preferably 0.01 to 0.2 mol, per 1 mol of the onium salt (1).

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

The reaction temperature for the copolymerization of the onium salt (1) and the dialkoxy silane (2) is not particularly limited, but 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 polysiloxane copolymer is obtained by concentrating the reaction mixture obtained by the above reaction, and the resulting polysiloxane copolymer may be washed with an organic solvent (hexane, heptane, benzene, toluene, etc.) which is not miscible, if necessary.

The amount of the organic solvent used for the copolymerization is not particularly limited, but is usually 20 parts by weight or less, preferably 2 to 9 parts by weight, per 1 part by weight of the onium salt (1).

The concentration temperature of the reaction mixture is not particularly limited, but is usually from 10 to 120 캜, preferably from 60 to 80 캜.

The thus obtained polysiloxane copolymer can impart antistatic properties to the resin by kneading with the resin. Examples of the resin include a polycarbonate resin, an acrylic resin and a silicone resin. Accordingly, the present invention also provides a method for imparting an antistatic property to a resin, which comprises the step of adding (for example, kneading) the polysiloxane copolymer to the resin. The present invention also provides use of the polysiloxane copolymer as an antistatic agent, particularly for imparting an antistatic property to a resin.

When the polysiloxane copolymer is kneaded in a resin, it may be heated and melted and kneaded. After the solution is prepared by mixing with a suitable solvent (for example, dichloromethane, ethyl acetate or toluene), the solution is applied, The resin may be formed by a method of removing the resin. In the case of a photocurable resin, the resin containing the polysiloxane copolymer or its solution may be coated, and then the coated surface may be cured by ultraviolet irradiation.

The amount of the polysiloxane copolymer to be added to the resin is not particularly limited, but is preferably 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight based on 1 part by weight of the resin.

Example

Next, the present invention will be described concretely with reference to examples, but the present invention is not limited to them. In the Examples, ¹ H-NMR was AL-400 manufactured by Nippon Electric Datum Co., Ltd., and the chemical shift was calculated at 400 MHz on the basis of tetramethylsilane. The surface resistivity was measured under the conditions of 23 ± 3 ° C and a humidity of 45 ± 5% by using Hirestream UP (MCP-HT450) manufactured by Mitsubishi Chemical Corporation.

Production Example 1

In a 500 ml glass reactor equipped with a stirrer, 51.64 g (0.4 mol) of dimethoxydimethylsilane, 40.34 g of isopropyl alcohol and 10.0 g of 1- (4-fluorophenyl) (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) imide was injected into the flask. To the obtained mixture, 8.47 g of 0.1 N hydrochloric acid was added dropwise at room temperature, and the mixture was further stirred at room temperature for 16 hours. The resulting reaction mixture was concentrated at 80 캜 for 4 hours using a rotary evaporator. The obtained concentrated residue was washed twice with 80 g of n-hexane and further concentrated using a rotary evaporator at 80 DEG C for 5 hours to obtain 33.14 g of a light yellow liquid polysiloxane copolymer A. [ The ¹ H-NMR analysis results are shown below.

Production Example 2

38.56 g of a white suspension liquid polysiloxane copolymer B was obtained in the same manner as in Production Example 1, except that 10.83 g of 0.1 N hydrochloric acid was used.

Example 1

3.2 g of polycarbonate resin (Caliber (registered trademark) 200-13 NAT manufactured by Sumitomo Corporation) and 20 ml of dichloromethane were placed in a 50 ml sample bottle and the polycarbonate resin was dissolved to prepare a dichloromethane solution of the polycarbonate resin Respectively. To this solution, 1.6 mg of the polysiloxane copolymer A obtained in Preparation Example 1 was added as an antistatic agent and completely dissolved. Then, the solution was poured into a mold (12 cm long × 20 cm wide × 2 cm deep) For 1 hour to prepare a test piece of a polycarbonate resin composition (film thickness: 0.1 + - 0.02 mm). 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 prepared in the same manner as in Example 1 except that 3.2 mg of the polysiloxane copolymer A was used and the surface resistivity thereof was measured. The results are shown in Table 1.

Example 3

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

Example 4

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 and the surface resistivity thereof was measured. 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 32 mg of the polysiloxane copolymer B obtained in Preparation Example 2 was used and the surface resistivity thereof was measured. The results are shown in Table 1.

Comparative Example 1

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

Comparative Example 2

Except that 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) imide was used instead of the polysiloxane copolymer A or B, 1, a test piece of a polycarbonate resin composition was prepared, and the surface resistivity thereof was measured. The results are shown in Table 1.

Example 6

0.50 g of dipentaerythritol hexaacrylate (A-DPH: Shin-Nakamura Chemical Co., Ltd.), 1.50 g of pentaerythritol triacrylate (A-TMN-3LM-N: Shin-Nakamura Chemical Co., 0.50 g of triacrylate (A-TMPT: manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.54 g of the polysiloxane copolymer A obtained in Production Example 1 as an antistatic agent, 1.75 g of isopropyl alcohol and 1.75 g of an IPA dispersion of colloidal silica (IPA- 3.60 g of silica solid content 30 wt%, manufactured by Nissan Chemical Industries, Ltd.) and 0.15 g of 2-hydroxy-2-methylpropiophenone as a photopolymerization initiator were mixed. The obtained mixture was applied on one side of a polyethylene terephthalate film having a thickness of 100 占 퐉 to a dry film thickness of about 5 占 퐉 by using a bar coater and ultraviolet rays of a high pressure mercury UV lamp (120 W / cm) And irradiated under the condition of about 400 mJ / cm < 2 > to harden the coating film, thereby preparing a test plate hard-coated with an acrylic resin. Table 2 shows the measurement results of the surface resistivity of the obtained hard coat surface.

Example 7

A test piece hard-coated with an acrylic resin was prepared in the same manner as in Example 6 except that 0.54 g of the polysiloxane copolymer B obtained in Preparation Example 2 was used. Table 2 shows the measurement results of the surface resistivity of the obtained hard coat surface.

Comparative Example 3

A test piece hard-coated with an acrylic resin was prepared in the same manner as in Example 6 except that the polysiloxane copolymer A or B was not added. Table 2 shows the measurement results of the surface resistivity of the obtained hard coat surface.

Comparative Example 4

Except that 0.54 g of 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) imide was used in place of the polysiloxane copolymer A or B, A test piece hard-coated with an acrylic resin was prepared in the same manner as in Example 6. Table 2 shows the measurement results of the surface resistivity of the obtained hard coat surface.

Example 8

5.00 g of methyl methacrylate, 0.20 g of azobisisobutyronitrile and 5 mg of the polysiloxane copolymer A obtained in Preparation Example 1 as an antistatic agent were mixed and the resulting mixture was charged into a plastic container (cylindrical with a diameter of 5 cm and a depth of 1.5 cm) And cured at 50 DEG 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 piece.

Comparative Example 5

A test piece of a polymethyl methacrylate resin was prepared in the same manner as in Example 8 except that the polysiloxane copolymer A or B was not added and the surface resistivity thereof was measured. The results are shown in Table 3.

Comparative Example 6

Except that 5 mg of 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) imide was used instead of the polysiloxane copolymer A or B, A test piece of a polymethyl methacrylate resin was prepared in the same manner as in Example 8, and the surface resistivity thereof was measured. The results are shown in Table 3.

Example 9

4.0 g of a peroxide curing type silicone pressure-sensitive adhesive KR-101-10 (solid content 60%, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.08 g of a curing agent BPO (benzoyl peroxide), 6.2 g of ethyl acetate and the polysiloxane copolymer A 48 Were mixed to obtain a silicone resin pressure-sensitive adhesive. The silicone resin pressure-sensitive adhesive was applied on one surface of a polyethylene terephthalate film (release paper) using a bar coater so as to have a dry film thickness of about 8 占 퐉 and heated and dried at 90 占 폚 for 3 minutes and at 160 占 폚 for 2 minutes to form a silicone resin pressure- And the surface resistivity thereof was measured. The results are shown in Table 4.

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

A: Adhesive adhesion to release paper is not observed.

B: Partially adherent adhesion to release paper is observed.

C: Most adhesion of adhesive to release paper is observed.

Comparative Example 7

A silicone resin pressure-sensitive adhesive layer and a test film were prepared in the same manner as in Example 9, except that the polysiloxane copolymer A or B was not added. The surface resistivity was measured, and the adhesion state of the pressure-sensitive adhesive to the release paper was visually evaluated Respectively. The results are shown in Table 4.

Comparative Example 8

Except that 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) imide was used in place of the polysiloxane copolymer A or B, , A silicone resin pressure-sensitive adhesive layer and a test film were prepared, the surface resistivity thereof was measured, and the adhesion state of the pressure-sensitive adhesive to the release paper was visually evaluated. The results are shown in Table 4.

Claims (9)

A polysiloxane copolymer obtained by copolymerizing an onium salt represented by the formula (1) and a dialkoxy silane represented by the formula (2).
Equation (1):
[Chemical Formula 1]

(Represents the formula, Q ⁺ is a nitrogen cation or a cation. R ₁ represents an alkyl group having a carbon number of _{1 ~ 3, R 2 ~ R} 4 represents an alkyl group having 1 ~ 8. R ₂ and R ₃ is A pyrrolidine ring, a piperidine ring, a pyridine ring, a phosphorane ring, a phospholane ring or a phospholine ring, provided that R ₂ and R ₃ are bonded to each other at the terminals to form pyridine When R < ₄ > is not present, X < ^- > represents an anion, and n is an integer of 0 to 3. [
Equation (2):
(2)

(Wherein R ₅ represents an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an aralkyl group of 7 to 10 carbon atoms, and R ₆ represents an alkyl group of 1 to 3 carbon atoms.) The method according to claim 1,
A polysiloxane copolymer wherein Q ^{< + &} gt ^; is cationic in the above formula (1). 3. The method according to claim 1 or 2,
A polysiloxane copolymer wherein X ^- in the formula (1) is halogen anion or fluorine anion. The method of claim 3,
Wherein the fluorinated aniline is trifluoromethanesulfonic anion, bis (trifluoromethanesulfonyl) imide anion, tetrafluoroborate anion or hexafluorophosphate anion. 5. The method according to any one of claims 1 to 4,
A polysiloxane copolymer obtained by copolymerizing 4 to 49 moles of a dialkoxysilane represented by the formula (2) per mole of the onium salt represented by the formula (1). An antistatic agent containing the polysiloxane copolymer according to any one of claims 1 to 5. A resin composition containing the antistatic agent according to claim 6. 8. The method of claim 7,
Wherein the resin composition is a polycarbonate resin composition, an acrylic resin composition, or a silicone resin composition. The process for producing a polysiloxane copolymer according to any one of claims 1 to 4, wherein the onium salt represented by the formula (1) and the dialkoxy silane represented by the formula (2) are copolymerized in the presence of hydrochloric acid .