CN105916913B - Polysiloxane copolymer and antistatic agent containing it - Google Patents
Polysiloxane copolymer and antistatic agent containing it Download PDFInfo
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- CN105916913B CN105916913B CN201580004911.4A CN201580004911A CN105916913B CN 105916913 B CN105916913 B CN 105916913B CN 201580004911 A CN201580004911 A CN 201580004911A CN 105916913 B CN105916913 B CN 105916913B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/00—Materials not provided for elsewhere
- C09K3/16—Anti-static materials
Abstract
High static electricity resistance can be assigned to resin the present invention relates to one kind and can manufacture the polysiloxane copolymer of the silicone resin with practical strength characteristics as optics adhesive.According to the present invention it is possible to which high static electricity resistance can be assigned to polycarbonate resin, acrylic resin and silicone resin and can manufacture the polysiloxane copolymer of the silicone resin with practical strength characteristics as optics adhesive and containing the antistatic agent of the polysiloxane copolymer by providing.
Description
Technical field
[cross-reference to related applications]
This application claims be based on applied No. 2014-086978 explanation of Japanese Patent Application No. on April 21st, 2014
The priority of book (its disclosure is quoted in this manual entirely through reference).
The present invention relates to a kind of polysiloxane copolymer and contain its antistatic agent.
Background technique
It is perfluoroalkyl group sulfonyl that cation, which has been carried out, as An Huo Phosphonium, anion with trialkoxysilylalkyl
Imido salt may be used as the report (referring to patent document 1) of the objective of the low molecule type antistatic agent of fluororesin.But
It is that the inventors of the present invention learn: will be as the 1 of the salt kind of -1,1,1- tri- fourth of i.e. 1- (3- trimethoxy-silylpropyl)
Ji Phosphonium=bis- (trifluoromethane sulfonyl group) acid imide is used as the antistatic agent of polycarbonate resin, acrylic resin and silicone resin
When, although antistatic performance can be assigned to silicone resin, it can however not being assigned to polycarbonate resin and acrylic resin real
Antistatic performance.In addition it learns: for silicone resin, the curing reaction of silicone resin cannot be sufficiently carried out, can not be obtained
To the silicone resin component of the practical strength characteristics as optics adhesive (referring to aftermentioned comparative example).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-248165 bulletin
Summary of the invention
Problems to be solved by the invention
Problem of the present invention is that provide polycarbonate resin, acrylic resin and silicone resin can be assigned it is high
The static electricity resistance and polysiloxanes that can manufacture the silicone resin with practical strength characteristics as optics adhesive is total
Polymers and antistatic agent containing the polysiloxane copolymer.
Solution for solving the problem
The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that by will be shown in formula (1)
Polysiloxane copolymer obtained from dialkoxy silicane shown in salt and formula (2) is copolymerized, it has further been found that: by the poly- silicon
Siloxane copolymers are as antistatic agent in use, can be to each in polycarbonate resin, acrylic resin and silicone resin
Resin assigns high antistatic performance.It has further been found that: the curing reaction of silicone resin successfully carries out, and can obtain as optics
It is of the invention up to completing with the silicone resin component with practical strength characteristics of adhesive.
That is, being by formula (1) the present invention relates to a kind of polysiloxane copolymer (hereinafter referred to as polysiloxane copolymer)
Shown in dialkoxy silicane (hereinafter referred to as dialkoxy silicane shown in salt (hereinafter referred to as salt (1)) and formula (2)
(2)) obtained from being copolymerized.
Formula (1):
[chemical formula 1]
(in formula, Q+Indicate azonia or phosphorus cation.R1Indicate the alkyl of carbon number 1~3, R2~R4Indicate carbon number 1~8
Alkyl.R2And R3It is mutually bonded in end, pyrrolidine ring, piperidine ring, pyridine ring, phospholane ring, phosphorus heterocycle can be formed
Hexane ring or phospha phenyl ring.Wherein, in the case where forming pyridine ring or phospha phenyl ring, R4It is not present.X?Indicate anion.N is 0
~3 integer.)
Formula (2):
[chemical formula 2]
(in formula, R5Indicate alkyl, the aryl of carbon number 6~10 or the aralkyl of carbon number 7~10 of carbon number 1~10, R6It indicates
The alkyl of carbon number 1~3.)
Polysiloxane copolymer of the invention may be used as antistatic agent, by the way that the antistatic agent is used for polycarbonate resin
Rouge, acrylic resin and silicone resin can manufacture the resin combination with high antistatic performance.In addition, using this hair
When bright polysiloxane copolymer, the silicone resin group with practical strength characteristics as optics adhesive can be manufactured
Close object.
Specific embodiment
Hereinafter, specifically describing the present invention.
In formula (1), Q+Indicate azonia or phosphorus cation, preferably phosphorus cation.R1For the alkyl of carbon number 1~3, tool
For body, methyl, ethyl, propyl and isopropyl, preferably methyl and ethyl, particularly preferred methyl can be enumerated.R2~R4Indicate carbon number
1~8 alkyl can be any of straight chain and branched, the preferably alkyl of straight-chain.Specifically, can enumerate for example
Methyl, ethyl, propyl, butyl, hexyl, octyl etc., preferably methyl, ethyl, propyl and butyl, particularly preferred butyl.R2And R3?
End is mutually bonded, and can form pyrrolidine ring, piperidine ring, pyridine ring, phospholane ring, phospha cyclohexane ring or phospha benzene
Ring.Wherein, R2And R3In the case where end is mutually bonded and forms pyridine ring or phospha phenyl ring, R4It is not present.X?Indicate yin from
Son.As X?, halide anion or fluo anion can be enumerated, as halide anion, preferably cl anion, bromine anions,
Iodine anion, more preferable cl anion.As fluo anion, preferably trifluoromethanesulfonic acid anion, bis- (fluoroform sulphonyl
Base) imide anion, tetrafluoro boric acid salt anionic, hexafluorophosphoric acid salt anionic, more preferable bis- (trifluoromethane sulfonyl group) acyls
Imines anion.
It as the concrete example of salt (1), can enumerate: 1,1,1- trimethyl -1- [(trimethoxysilyl) methyl] ammonium
=bis- (trifluoromethane sulfonyl group) acid imides, 1,1,1- trimethyl -1- [2- (trimethoxysilyl) ethyl] ammonium=bis- (three
Fluoromethane sulfonyl) acid imide, 1,1,1- trimethyl -1- [3- (trimethoxysilyl) propyl] ammonium=bis- (fluoroforms
Sulfonyl) acid imide, 1,1,1- trimethyl -1- [4- (trimethoxysilyl) butyl] ammonium=bis- (trifluoromethane sulfonyl group)
Acid imide, 1,1,1- triethyl group -1- [(trimethoxysilyl) methyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,
1,1- triethyl group -1- [2- (trimethoxysilyl) ethyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- tri-
Ethyl -1- [3- (trimethoxysilyl) propyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- triethyl group -1-
[4- (trimethoxysilyl) butyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- tributyl -1- [(front three
Oxygroup silicyl) methyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- tributyl -1- [2- (trimethoxy first
Silylation) ethyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- tributyl -1- [3- (trimethoxysilyl)
Propyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- tributyl -1- [4- (trimethoxysilyl) butyl] ammonium
=bis- (trifluoromethane sulfonyl group) acid imides, tri- hexyl -1- of 1,1,1- [(trimethoxysilyl) methyl] ammonium=bis- (trifluoros
Methane sulfonyl) acid imide, tri- hexyl -1- of 1,1,1- [2- (trimethoxysilyl) ethyl] ammonium=bis- (fluoroform sulphur
Acyl group) acid imide, tri- hexyl -1- of 1,1,1- [3- (trimethoxysilyl) propyl] ammonium=bis- (trifluoromethane sulfonyl group) acyl
Imines, tri- hexyl -1- of 1,1,1- [4- (trimethoxysilyl) butyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,
1,1- trioctylphosphine -1- [(trimethoxysilyl) methyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- tri- are pungent
Base -1- [2- (trimethoxysilyl) ethyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- trioctylphosphine -1-
[3- (trimethoxysilyl) propyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide, 1,1,1- trioctylphosphine -1- [4- (three
Methoxysilyl) butyl] ammonium=bis- (trifluoromethane sulfonyl group) acid imide,
1,1,1- trimethyl -1- [(trimethoxysilyl) methyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide,
1,1,1- trimethyl -1- [2- (trimethoxysilyl) ethyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1-
Trimethyl -1- [3- (trimethoxysilyl) propyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- trimethyl -
1- [4- (trimethoxysilyl) butyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- triethyl group -1- [(three
Methoxysilyl) methyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- triethyl group -1- [2- (trimethoxy
Silicyl) ethyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- triethyl group -1- [3- (trimethyoxysilane
Base) propyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- triethyl group -1- [4- (trimethoxysilyl) fourth
Base] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- tributyl -1- [(trimethoxysilyl) methyl] Phosphonium=bis-
(trifluoromethane sulfonyl group) acid imide, 1,1,1- tributyl -1- [2- (trimethoxysilyl) ethyl] Phosphonium=bis- (fluoroforms
Alkane sulfonyl) acid imide, 1,1,1- tributyl -1- [3- (trimethoxysilyl) propyl] Phosphonium=bis- (fluoroform sulphonyl
Base) acid imide, 1,1,1- tributyl -1- [4- (trimethoxysilyl) butyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acyl Asia
Amine, tri- hexyl -1- of 1,1,1- [(trimethoxysilyl) methyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1-
Three hexyl -1- [2- (trimethoxysilyl) ethyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, tri- hexyl of 1,1,1- -
1- [3- (trimethoxysilyl) propyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, tri- hexyl -1- [4- of 1,1,1-
(trimethoxysilyl) butyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- trioctylphosphine -1- [(trimethoxy
Silicyl) methyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- trioctylphosphine -1- [2- (trimethyoxysilane
Base) ethyl] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- trioctylphosphine -1- [3- (trimethoxysilyl) third
Base] Phosphonium=bis- (trifluoromethane sulfonyl groups) acid imide, 1,1,1- trioctylphosphine -1- [4- (trimethoxysilyl) butyl] Phosphonium=
Bis- (trifluoromethane sulfonyl group) acid imides,
1- methyl-1-[(trimethoxysilyl) methyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide,
1- ethyl -1- [(trimethoxysilyl) methyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- propyl -1-
[(trimethoxysilyl) methyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- butyl -1- [(trimethoxy
Base silicyl) methyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- hexyl -1- [(trimethyoxysilane
Base) methyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- octyl -1- [(trimethoxysilyl) methyl]
Pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- methyl-1-[2- (trimethoxysilyl) ethyl] pyrrolidines
=bis- (trifluoromethane sulfonyl group) acid imides, 1- ethyl -1- [2- (trimethoxysilyl) ethyl] pyrrolidines=bis-
(trifluoromethane sulfonyl group) acid imide, 1- propyl -1- [2- (trimethoxysilyl) ethyl] pyrrolidines=bis- (fluoroforms
Alkane sulfonyl) acid imide, 1- butyl -1- [2- (trimethoxysilyl) ethyl] pyrrolidines=bis- (fluoroform sulphonyl
Base) acid imide, 1- hexyl -1- [2- (trimethoxysilyl) ethyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acyl Asia
Amine, 1- octyl -1- [2- (trimethoxysilyl) ethyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- first
Base -1- [3- (trimethoxysilyl) propyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- ethyl -1-
[3- (trimethoxysilyl) propyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- propyl -1- [3- (three
Methoxysilyl) propyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- butyl -1- [3- (trimethoxy
Silicyl) propyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- hexyl -1- [3- (trimethyoxysilane
Base) propyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- octyl -1- [3- (trimethoxysilyl) third
Base] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- methyl-1-[4- (trimethoxysilyl) butyl] pyrroles
Alkane=bis- (trifluoromethane sulfonyl group) acid imide, 1- ethyl -1- [4- (trimethoxysilyl) butyl] pyrrolidines=
Bis- (trifluoromethane sulfonyl group) acid imides, 1- propyl -1- [4- (trimethoxysilyl) butyl] pyrrolidines=bis- (trifluoros
Methane sulfonyl) acid imide, 1- butyl -1- [4- (trimethoxysilyl) butyl] pyrrolidines=bis- (fluoroform sulphur
Acyl group) acid imide, 1- hexyl -1- [4- (trimethoxysilyl) butyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acyl
Imines, 1- octyl -1- [4- (trimethoxysilyl) butyl] pyrrolidines=bis- (trifluoromethane sulfonyl group) acid imide,
1- methyl-1-[(trimethoxysilyl) methyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1-
Ethyl -1- [(trimethoxysilyl) methyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- propyl -1- [(three
Methoxysilyl) methyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- butyl -1- [(trimethoxy first silicon
Alkyl) methyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- hexyl -1- [(trimethoxysilyl) methyl]
Piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- octyl -1- [(trimethoxysilyl) methyl] piperidines=bis-
(trifluoromethane sulfonyl group) acid imide, 1- methyl-1-[2- (trimethoxysilyl) ethyl] piperidines=bis- (fluoroforms
Sulfonyl) acid imide, 1- ethyl -1- [2- (trimethoxysilyl) ethyl] piperidines=bis- (trifluoromethane sulfonyl group) acyl
Imines, 1- propyl -1- [2- (trimethoxysilyl) ethyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- fourth
Base -1- [2- (trimethoxysilyl) ethyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- hexyl -1- [2-
(trimethoxysilyl) ethyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- octyl -1- [2- (trimethoxy
Silicyl) ethyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- methyl-1-[3- (trimethoxysilyl)
Propyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- ethyl -1- [3- (trimethoxysilyl) propyl] piperidines
=bis- (trifluoromethane sulfonyl group) acid imides, 1- propyl -1- [3- (trimethoxysilyl) propyl] piperidines=bis- (three
Fluoromethane sulfonyl) acid imide, 1- butyl -1- [3- (trimethoxysilyl) propyl] piperidines=bis- (fluoroform sulphur
Acyl group) acid imide, 1- hexyl -1- [3- (trimethoxysilyl) propyl] piperidines=bis- (trifluoromethane sulfonyl group) acyl Asia
Amine, 1- octyl -1- [3- (trimethoxysilyl) propyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- first
Base -1- [4- (trimethoxysilyl) butyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- ethyl -1- [4-
(trimethoxysilyl) butyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- propyl -1- [4- (trimethoxy
Silicyl) butyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- butyl -1- [4- (trimethoxysilyl)
Butyl] piperidines=bis- (trifluoromethane sulfonyl group) acid imide, 1- hexyl -1- [4- (trimethoxysilyl) butyl] piperidines
=bis- (trifluoromethane sulfonyl group) acid imides, 1- octyl -1- [4- (trimethoxysilyl) butyl] piperidines=bis- (three
Fluoromethane sulfonyl) acid imide,
1- [(trimethoxysilyl) methyl] pyridine=bis- (trifluoromethane sulfonyl group) acid imide, 1- [2- (front three
Oxygroup silicyl) ethyl] pyridine=bis- (trifluoromethane sulfonyl group) acid imide, 1- [3- (trimethoxysilyl) third
Base] pyridine=bis- (trifluoromethane sulfonyl group) acid imide, 1- [4- (trimethoxysilyl) butyl] pyridine=bis- (three
Fluoromethane sulfonyl) acid imide, 1- [(trimethoxysilyl) methyl] -2- picoline=bis- (fluoroform sulphonyl
Base) acid imide, 1- [2- (trimethoxysilyl) ethyl] -2- picoline=bis- (trifluoromethane sulfonyl group) acyl Asia
Amine, 1- [3- (trimethoxysilyl) propyl] -2- picoline=bis- (trifluoromethane sulfonyl group) acid imide, 1- [4-
(trimethoxysilyl) butyl] -2- picoline=bis- (trifluoromethane sulfonyl group) acid imide, 1- [(trimethoxy first
Silylation) methyl] -3- picoline=bis- (trifluoromethane sulfonyl group) acid imide, 1- [2- (trimethoxysilyl) second
Base] -3- picoline=bis- (trifluoromethane sulfonyl group) acid imide, 1- [3- (trimethoxysilyl) propyl] -3- first
Yl pyridines=bis- (trifluoromethane sulfonyl group) acid imide, 1- [4- (trimethoxysilyl) butyl] -3- picoline
=bis- (trifluoromethane sulfonyl group) acid imides, 1- [(trimethoxysilyl) methyl] -4- picoline=bis- (fluoroforms
Alkane sulfonyl) acid imide, 1- [2- (trimethoxysilyl) ethyl] -4- picoline=bis- (trifluoromethane sulfonyl group)
Acid imide, 1- [3- (trimethoxysilyl) propyl] -4- picoline=bis- (trifluoromethane sulfonyl group) acid imide, 1-
[4- (trimethoxysilyl) butyl] -4- picoline=bis- (trifluoromethane sulfonyl group) acid imide etc..
Salt used in the present invention (1) can come according to the method recorded in Japanese Unexamined Patent Publication 2010-248165 bulletin
Manufacture.The method represented is illustrated in following reaction equations 1.It is explained, in the reaction equation, R1、R2、R3、R4、
Q, X and n are same as described above, and Z indicates that halogen atom, M indicate alkali metal.
[chemical formula 3]
Reaction equation 1
(the hereinafter referred to as amine (5a) of amine shown in formula (5).) or phosphine (hereinafter referred to as phosphine (5b).) and formula
(6) (the hereinafter referred to as alkyl halide species (6) of alkyl halide species shown in.) quaternary reaction is carried out, it manufactures shown in formula (7)
=halide (hereinafter referred to as=halogenation species (7).).X?It, can general=halide in the case where for halide anion
Class (7) is used as salt (1).
Then, it by the ion-exchange reactions of metal alkyl salt shown in=halogenation species (7) and formula (8), can make
Make salt (1).
As amine (5a), can enumerate: Trimethylamine, triethylamine, tripropylamine, tri-butylamine, three amylamines, three oneself
Base amine, three heptyl amines, trioctylphosphine amine,
1- crassitude, 1- methyl piperidine, 1- ethyl pyrrolidine, 1- ethyl piperidine, 1- propyl pyrrole alkane, 1- propyl piperazine
Pyridine, 1- isopropylpyrrolidine, 1- isopropyl phenylpiperidines, 1- butyl pyrrolidine, 1- butyl piperidine, 1- amyl pyrrolidines, 1- amyl piperazine
Pyridine, 1- hexyl pyrrolidines, 1- hexyl piperidines, 1- methyl -2- crassitude, 1- methyl-pipecoline, 1- methyl -3- first
Base pyrrolidines, 1- methyl -3- methyl piperidine, 1- methyl -4- methyl piperidine, 1- methyl -2- ethyl pyrrolidine, 1- methyl -2- third
Base pyrrolidines, 1- methyl -2- isopropylpyrrolidine, 1- methyl -2- butyl pyrrolidine, 1- methyl -2- isobutyl group pyrrolidines, 1- first
Base -2- sec-butyl pyrrolidines, 1- methyl -2- tert-butyl pyrrolidine,
Pyridine, 2- picoline, 3- picoline, 4- picoline, 2- ethylpyridine, 3-ethylpyridine, 4- ethyl pyrrole
Pyridine, 2- propyIpyridine, 3- propyIpyridine, 4- propyIpyridine, 2- propyIpyridine, 3- propyIpyridine, 4- propyIpyridine, 2- isopropyl
Pyridine, 3- isopropyl pyridine, 4- isopropyl pyridine, 2- butyl-pyridinium, 3- butyl-pyridinium, 4- butyl-pyridinium, 2- isobutyl pyridine,
3- isobutyl pyridine, 4- isobutyl pyridine, 2- sec-butyl pyridine, 3- sec-butyl pyridine, 4- sec-butyl pyridine, 2- tert-butyl pyrrole
Pyridine, 3- tert .-butylpyridine, 4- tert .-butylpyridine etc..
As phosphine (5b), can enumerate: trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tributylphosphine, three amyl phosphines, three oneself
Base phosphine, three heptyl phosphines, tri octyl phosphine,
1- methyl phospholane, 1- methyl phospha cyclohexane, 1- ethyl phospholane, 1- ethyl phosphine, 1- propyl
Phospholane, 1- propyl phospha cyclohexane, 1- isopropyl phospholane, 1- isopropyl phospha cyclohexane, 1- butyl phospha
Pentamethylene, 1- butyl phospha cyclohexane, 1- amyl phospholane, 1- amyl phospha cyclohexane, 1- hexyl phospholane, 1-
Hexyl phospha cyclohexane, 1- methyl -2- methyl phospholane, 1- methyl -2- methyl phospha cyclohexane, 1- methyl -3- methyl
Phospholane, 1- methyl -3- methyl phospha cyclohexane, 1- methyl -4- methyl phospha cyclohexane, 1- methyl -2- ethyl phospha
Pentamethylene, 1- methyl-2-propyl phospholane, 1- methyl -2- isopropyl phospholane, 1- methyl -2- butyl phosphorus heterocycle
Pentane, 1- methyl -2- isobutyl group phospholane, 1- methyl -2- sec-butyl phospholane, 1- methyl -2- tert-butyl phospha
Pentamethylene,
Phospha benzene, 2- methyl phospha benzene, 3- methyl phospha benzene, 4- methyl phospha benzene, 2- ethyl phospha benzene, 3- ethyl phospha
Benzene, 4- ethyl phospha benzene, 2- propyl phospha benzene, 3- propyl phospha benzene, 4- propyl phospha benzene, 2- propyl phospha benzene, 3- propyl phosphorus
Miscellaneous benzene, 4- propyl phospha benzene, 2- isopropyl phospha benzene, 3- isopropyl phospha benzene, 4- isopropyl phospha benzene, 2- butyl phospha benzene,
3- butyl phospha benzene, 4- butyl phospha benzene, 2- isobutyl group phospha benzene, 3- isobutyl group phospha benzene, 4- isobutyl group phospha benzene, 2- Zhong Ding
Base phospha benzene, 3- sec-butyl phospha benzene, 4- sec-butyl phospha benzene, 2- tert-butyl phospha benzene, 3- tert-butyl phospha benzene, 4- tert-butyl
Phospha benzene etc..
It as alkyl halide species (6), can enumerate for example: chloromethyl trimethoxy silane, 2- chloroethyl trimethoxy silicon
Alkane, 3- r-chloropropyl trimethoxyl silane, 4- chlorobutyl trimethoxy silane, chloromethyl triethoxysilane, three second of 2- chloroethyl
Oxysilane, 3- chloropropyl triethoxysilane, 4- chlorobutyl triethoxy silane, chloromethyl tripropoxy silane, 2- chloroethene
Base tripropoxy silane, 3- chloropropyl tripropoxy silane, 4- chlorobutyl tripropoxy silane, three butoxy silane of chloromethyl,
Three butoxy silane of 2- chloroethyl, three butoxy silane of 3- chloropropyl, three butoxy silane of 4- chlorobutyl, bromomethyl trimethoxy
Silane, 2- bromoethyl trimethoxy silane, 3- bromopropyl trimethoxy silane, 4- brombutyl trimethoxy silane, bromomethyl three
Ethoxysilane, 2- bromoethyl triethoxysilane, 3- bromopropyl triethoxysilane, 4- brombutyl triethoxysilane, bromine
Methyl tripropoxy silane, 2- bromoethyl tripropoxy silane, 3- bromopropyl tripropoxy silane, 4- brombutyl tripropoxy silicon
Alkane, three butoxy silane of bromomethyl, three butoxy silane of 2- bromoethyl, three butoxy silane of 3- bromopropyl, three fourth of 4- brombutyl
Oxysilane, iodomethyl trimethoxy silane, 2- iodine ethyl trimethoxy silane, 3- iodine propyl trimethoxy silicane, 4- iodine fourth
Base trimethoxy silane, iodomethyl triethoxysilane, 2- iodine ethyl triethoxysilane, 3- iodine propyl-triethoxysilicane,
4- iodine butyl triethoxysilane, iodomethyl tripropoxy silane, 2- iodine ethyl tripropoxy silane, 3- iodine propyl tripropoxy
Silane, 4- iodine butyl tripropoxy silane, three butoxy silane of iodomethyl, three butoxy silane of 2- iodine ethyl, 3- iodine propyl three
Butoxy silane, three butoxy silane of 4- iodine butyl etc..
Amine shown in formula (5) or phosphine and alkyl halide species (6) it is quaternary react solvent can be used can not also
Use solvent.As solvent when using solvent, can enumerate: alcohols, acetonitrile, ethyl acetate, four such as methanol, ethyl alcohol, 2- propyl alcohol
Hydrogen furans, dimethylformamide etc..
The usage amount of alkyl halide species (6) is 0.7 mole or more relative to amine shown in formula (5) or 1 mole of phosphine
, preferably 0.9~1.5 mole.
It as alkali metal salt (8), can enumerate: bis- (trifluoromethane sulfonyl group) imide lis, bis- (trifluoromethane sulfonyl groups)
Acid imide sodium, bis- (trifluoromethane sulfonyl group) acid imide potassium, LiBF4, sodium tetrafluoroborate, potassium tetrafluoroborate, hexafluorophosphoric acid
The alkali metal salt of the fluo anions such as lithium, sodium hexafluoro phosphate, Potassium Hexafluorophosphate.
As the alkali metal for the counter cation for forming anion, lithium, sodium, potassium can be enumerated.
The usage amount of alkali metal salt (6) in ion-exchange reactions relative to=(5) 1 moles of halogenation species be usually
0.8 mole or more, preferably 0.9 mole~1.2 moles, more preferably 1~1.05 mole.
Ion-exchange reactions usually carries out in a solvent.As solvent, can enumerate: the ketones such as acetone, methyl ethyl ketone, methanol,
Alcohols, acetonitrile, ethyl acetate, tetrahydrofuran, the dimethylformamides such as ethyl alcohol, 2- propyl alcohol etc..Usage amount is not particularly limited, phase
For=(5) 1 parts by weight of halogenation species, usually 10 parts by weight are hereinafter, preferably 1~10 parts by weight, particularly preferably 2~
6 parts by weight.
The order by merging of=halogenation species (5), alkali metal salt (6) and solvent is not particularly limited, and can both incite somebody to action
Alkali metal salt (6) are added after=halogenation species (5) and solvent mixing, alkali metal salt (6) and solvent can also mixed it
Addition=halogenation species (5) afterwards.
Reaction temperature in ion-exchange reactions is usually 10 DEG C or more, and preferably 10~60 DEG C, particularly preferably 10~
30℃。
In order to separate salt (1) from reaction solution after reaction, the inorganic of solvent and generation is removed from reaction solution
Salt.If inorganic in obtained reaction solution salt out, filtering reacting liquid and the inorganic salts for removing precipitation are then appropriately combined
The units operation such as concentration, filtering, extraction, salt (1) is isolated.In addition, inorganic without being precipitated in obtained reaction solution
In the case where salt, by reaction solution be concentrated and make it is inorganic salt out, inorganic salts be removed by filtration after, appropriately combined concentration, mistake
The units operation such as filter, extraction, salt (1) is isolated.
In formula (2), R5Indicate alkyl, the aryl of carbon number 6~10 or the aralkyl of carbon number 7~10 of carbon number 1~10.R5It can
With identical or different, as R5, specifically, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl can be enumerated
Base, decyl, phenyl, benzyl, naphthalene etc., preferably methyl and phenyl, particularly preferred methyl.R6Indicate the alkyl of carbon number 1~3, tool
For body, methyl, ethyl, propyl etc., preferably methyl and ethyl, particularly preferred methyl can be enumerated.
It as the concrete example of dialkoxy silicane (2), can enumerate: dimethyldimethoxysil,ne, diethyl dimethoxy
Silane, dipropyl dimethoxysilane, Methylethyl dimethoxysilane, methyl-propyl dimethoxysilane, methyl butyl two
Methoxy silane, methyl amyl dimethoxysilane, methylhexyl dimethoxysilane, methylheptyl dimethoxysilane, first
Base octyl dimethoxysilane, Nonyl dimethoxysilane, methyldecyl dimethoxysilane, aminomethyl phenyl dimethoxy
Silane, methylbenzyl dimethoxysilane, methyl naphthalene dimethoxysilane, dimethyl diethoxysilane, diethyl diethyl
Oxysilane, dipropyl diethoxy silane, Methylethyl diethoxy silane, methyl-propyl diethoxy silane, methyl fourth
Base diethoxy silane, methyl amyl diethoxy silane, methylhexyl diethoxy silane, methylheptyl diethoxy silicon
Alkane, Methyl Octyl diethoxy silane, Nonyl diethoxy silane, methyldecyl diethoxy silane, aminomethyl phenyl two
Ethoxysilane, methylbenzyl diethoxy silane, methyl naphthalene diethoxy silane, dimethyl dipropoxy silane, diethyl
Base dipropoxy silane, dipropyl dipropoxy silane, Methylethyl dipropoxy silane, methyl-propyl dipropoxy silane,
Methyl butyl dipropoxy silane, methyl amyl dipropoxy silane, methylhexyl dipropoxy silane, methylheptyl dipropyl oxygen
Base silane, Methyl Octyl dipropoxy silane, Nonyl dipropoxy silane, methyldecyl dipropoxy silane, methylbenzene
Base dipropoxy silane, methylbenzyl dipropoxy silane, methyl naphthalene dipropoxy silane, dimethoxydiphenylsilane,
Diphenyl diethoxy silane, diphenyl dipropoxy silane etc., preferably dimethyldimethoxysil,ne.
Commercially available product both can be used in dialkoxy silicane (2), also can be used by caused by well known manufacturing method system
Dialkoxy silicane.
The copolymerization of salt (1) and dialkoxy silicane (2) is usually in the mixture of salt (1) and dialkoxy silicane (2)
Organic solvent (such as the methanol, ethyl alcohol, isopropanol, acetone of middle the two that dissolving salt (1) and dialkoxy silicane (2) is added
Deng) and after being made solution, be added dropwise in the solution and become the acid (hereinafter referred to as sour (3) of the catalyst of hydrolysis.) or alkali
(hereinafter referred to as alkali (4).) and water and carry out.Sour (3) or alkali (4) can be added dropwise in aqueous solution.Salt (1) and dialkoxy
It is (2) 4~49 moles of dialkoxy silicane that the metering of silane (2), which is compared usually relative to (1) 1 mole of salt, preferably with respect to
(1) 1 mole of salt is (2) 4~16 moles of dialkoxy silicane, is more preferably dialkoxy silicane relative to (1) 1 mole of salt
(2) 4~8 moles.Be explained, in the copolymerization of salt (1) and dialkoxy silicane (2), containing methyltrimethoxysilane,
Copolymer obtained from the trialkoxy silanes such as vinyltrimethoxysilane and the poly- silicon for not containing above-mentioned trialkoxy silane
Siloxane copolymers are compared, and there is the tendency that reduced performance is assigned for the antistatic of resin.Therefore, salt (1) and dialkoxy
The copolymer of silane (2) does not contain above-mentioned trialkoxy silane.In addition, as other any ingredients, can not damage it is anti-
Monoalkoxysilane, tetraalkoxysilane are mixed and are copolymerized in the range of effect by showing for static behaviour.As single alcoxyl
The concrete example of base silane can enumerate trimethylmethoxysilane, vinyl-dimethyl methoxylsilane, front three base oxethyl silicon
Alkane, vinyl dimethylethoxysilane, trimethyl npropoxysilane, vinyl-dimethyl base npropoxysilane etc., as four alkane
The concrete example of oxysilane can enumerate tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane etc..
The usage amount of the organic solvent of dissolving salt (1) and dialkoxy silicane (2) is not particularly limited, usually relative to
(1) 1 parts by weight of salt, usually 20 parts by weight are hereinafter, preferably 0.5~10 parts by weight, particularly preferably 1~5 parts by weight.
As sour (3), can enumerate for example: hydrochloric acid, sulfuric acid, nitric acid, acetic acid, p-methyl benzenesulfonic acid monohydrate etc., it is especially excellent
Select hydrochloric acid.The usage amount of sour (3) is 0.001~1 mole, preferably 0.01~0.2 rubs usually relative to (1) 1 mole of salt
You.
As alkali (4), can enumerate such as sodium hydroxide, potassium hydroxide, lithium hydroxide.The usual phase of usage amount of alkali (4)
It is 0.001~1 mole, preferably 0.01~0.2 mole for (1) 1 mole of salt.
The usage amount of water for copolymerization is 4~49 moles usually relative to (1) 1 mole of salt.
The reaction temperature of the copolymerization of salt (1) and dialkoxy silicane (2) is not particularly limited, and usually 10~80 DEG C,
Preferably 20~40 DEG C.As reaction time, usually 3 hours or more, preferably 3~72 hours.
Polysiloxane copolymer is obtained by the way that the reaction mixture obtained by the reaction to be concentrated, and what is obtained is poly-
Silicone copolymers can be cleaned as needed with unmixed organic solvent (hexane, heptane, benzene, toluene etc.).
The usage amount of organic solvent for copolymerization is not particularly limited, usually relative to (1) 1 parts by weight of salt, usually
For 20 parts by weight hereinafter, preferably 2~9 parts by weight.
The thickening temperature of reaction mixture is not particularly limited, usually 10~120 DEG C, preferably 60~80 DEG C.
The polysiloxane copolymer obtained in this way is by that can assign antistatic performance to resin in incorporation resin.As
The resin can enumerate such as polycarbonate resin, acrylic resin and silicone resin.Therefore, the present invention also provides to resin
The method for assigning antistatic performance comprising (such as be kneaded the addition of above-mentioned polysiloxane copolymer.) in the process of resin.Into
And the present invention also provides for the antistatic agent as above-mentioned polysiloxane copolymer, particularly assigns antistatic to resin
The purposes of performance.
In addition, by polysiloxane copolymer incorporation when resin, can both carry out heating dissolve and be kneaded, can also with
Solvent (such as methylene chloride, ethyl acetate, toluene etc.) appropriate mixing and after preparing solution, by being coated with the solution and removing
The methods of solvent is gone to form resin.In the case where the resin of photo-curable, it is coated with the tree containing polysiloxane copolymer
After rouge or the solution, the coated face can be made to irradiate by ultraviolet light and solidified.
It about the additive amount of the resin relative to polysiloxane copolymer, is not particularly limited, preferably with respect to 1 weight of resin
Part is measured, is 0.01~1 weight %, particularly preferably 0.05~0.5 weight %.
[embodiment]
Then, it is based on embodiment, specifically describes the present invention, but the present invention is not by any restriction of these embodiments.It is real
It applies in example,1H-NMR uses Japan Electronics DATUM Co. Ltd. system AL-400, is calculated tetramethylsilane as benchmark using 400MHz
Chemical shift out.In addition, surface resistivity is using Mitsubishi chemical Co., Ltd Hiresta-UP (MCP-HT450), 23 ± 3
DEG C, be measured under conditions of humidity 45 ± 5%.
Production Example 1
In the glass reactor for the 500mL for having agitating device, dimethoxy dimethyl-silicon is added under nitrogen atmosphere
Alkane 51.64g (0.4 mole), isopropanol 40.34g and method system by being recorded in Japanese Unexamined Patent Publication 2010-248165 bulletin
1- (3- trimethoxy-silylpropyl) -1,1,1- San Ding Ji Phosphonium=bis- (trifluoromethane sulfonyl group) acid imides 30.77g made
(0.05 mole).It to obtained mixture, is added dropwise after 0.1 equivalent hydrochloric acid 8.47g at room temperature, further with rotary evaporation
Reaction mixture obtained from device will be stirred at room temperature 16 hours is concentrated 4 hours at 80 DEG C.It will be obtained with n-hexane 80g
Concentrated residue carries out 2 liquid separations cleaning, further uses rotary evaporator and is concentrated 5 hours at 80 DEG C, thus obtains yellowish
The polysiloxane copolymer A33.14g of color liquid.By its1H-NMR analysis result is shown in following.
1H-NMR(CDCl3) δ (ppm) 4.40-4.00 (m, 0.5H), 3.70-3.40 (m, 2H), 2.40-2.00 (m, 8H),
1.80-1.60 (m, 2H), 1.60-1.40 (m, 12H), 1.30-1.10 (m, 3H), 1.10-0.90 (m, 9H), 0.90-0.70 (m,
2H), 0.30-0.00 (m, 20H)
Production Example 2
It in addition to using 0.1 equivalent hydrochloric acid 10.83g, is operated in the same way with Production Example 1, obtains the poly- of white suspension liquid
Silicone copolymers B 38.56g.
Embodiment 1
Polycarbonate resin (Sumitomo Dow Ltd's system, Caliber (registered trademark) are put into the sample bottle of 50mL
200-13NAT) 3.2g and methylene chloride 20mL, dissolves polycarbonate resin, and the methylene chloride for preparing polycarbonate resin is molten
Liquid.The polysiloxane copolymer A 1.6mg obtained in Production Example 1 of the addition as antistatic agent in the solution, makes it completely
After dissolution, mold (vertical 12cm × horizontal 20cm × depth 2cm) is flowed in, is dried at room temperature for 1 hour, dry 1 is small at 40 DEG C
When, make the test film (0.1 ± 0.02mm of film thickness) of poly carbonate resin composition.By the surface resistivity of obtained test film
Measurement result it is shown in table 1.
Embodiment 2
It in addition to using 3.2mg polysiloxane copolymer A, operates similarly with example 1, makes polycarbonate resin group
The test film for closing object, measures its surface resistivity.It the results are shown in table 1.
Embodiment 3
It in addition to using polysiloxane copolymer A 16mg, operates similarly with example 1, makes polycarbonate resin group
The test film for closing object, measures its surface resistivity.It the results are shown in table 1.
Embodiment 4
It in addition to using polysiloxane copolymer A 32mg, operates similarly with example 1, makes polycarbonate resin group
The test film for closing object, measures its surface resistivity.It the results are shown in table 1.
Embodiment 5
It in addition to using polysiloxane copolymer B 32mg obtained in Production Example 2, operates similarly with example 1, makes
The test film for making poly carbonate resin composition measures its surface resistivity.It the results are shown in table 1.
Comparative example 1
It in addition to not adding polysiloxane copolymer A or B, operates similarly with example 1, makes polycarbonate resin group
The test film for closing object, measures its surface resistivity.It the results are shown in table 1.
Comparative example 2
Except using 1- (3- trimethoxy-silylpropyl) -1,1,1- San Ding Ji Phosphonium=bis- (trifluoromethane sulfonyl groups) acyl
Imines replaces operating similarly with example 1 other than polysiloxane copolymer A or B, making the examination of poly carbonate resin composition
Piece is tested, its surface resistivity is measured.It the results are shown in table 1.
[table 1]
| Antistatic agent | Additive amount (weight %) | Surface resistivity (Ω/) | |
| Embodiment 1 | Polysiloxane copolymer A | 0.05 | 6.30×1013 |
| Embodiment 2 | Polysiloxane copolymer A | 0.1 | 1.85×1012 |
| Embodiment 3 | Polysiloxane copolymer A | 0.5 | 2.19×1011 |
| Embodiment 4 | Polysiloxane copolymer A | 1 | 5.61×1010 |
| Embodiment 5 | Polysiloxane copolymer B | 1 | 5.46×1010 |
| Comparative example 1 | Nothing | - | > 1015 |
| Comparative example 2 | Bu3P+(CH2)3Si(OMe)3·(CF3SO2)2N- | 0.05 | > 1015 |
Embodiment 6
By dipentaerythritol hexaacrylate (A-DPH: Xin Zhong village's chemical industry Co. Ltd. system) 0.50g, pentaerythrite
Triacrylate (A-TMN-3LM-N: Xin Zhong village's chemical industry Co. Ltd. system) 1.50g, trimethylolpropane trimethacrylate
Polysiloxanes obtained in (A-TMPT: Xin Zhong village's chemical industry Co. Ltd. system) 0.50g, the Production Example 1 as antistatic agent
Copolymer A 0.54g, isopropanol 1.75g, colloidal silicon dioxide IPA dispersion liquid (IPA-ST: silica solid ingredient
30wt%, Nissan Chemical Ind Ltd's system) 3.60g and the 2- hydroxy-2-methyl propiophenone as Photoepolymerizationinitiater initiater
0.15g is mixed.100 μm of polyethylene terephthalate film of thickness one side using bar coater with dry film thickness at
After the mixture that the mode for being about 5um is coated with, in accumulated light about 400mJ/cm2Under conditions of film side is irradiated it is high
The ultraviolet light of medium pressure mercury UV lamp (120W/Cm), makes curing of coating, the test film that thus production is painted firmly with acrylic resin.It will
The measurement result of the surface resistivity of the hard coating surface of obtained test film is shown in table 2.
Embodiment 7
It in addition to using polysiloxane copolymer B 0.54g obtained in Production Example 2, operates, makes similarly to Example 6
The test film that effect acrylic resin is painted firmly.The measurement result of the surface resistivity of the hard coating surface of obtained test film is shown in
Table 2.
Comparative example 3
It in addition to not adding polysiloxane copolymer A or B, operates similarly to Example 6, production acrylic resin is hard
The test film painted.The measurement result of the surface resistivity of the hard coating surface of obtained test film is shown in table 2.
Comparative example 4
Except using -1,1,1- tri- Ding Ji Phosphonium of 1- (3- trimethoxy-silylpropyl)=bis- (trifluoromethane sulfonyl groups) acyl
Imines 0.54g replaces operating similarly to Example 6, production is applied firmly with acrylic resin other than polysiloxane copolymer A or B
At test film.The measurement result of the surface resistivity of the hard coating surface of obtained test film is shown in table 2.
[table 2]
| Antistatic agent | Surface resistivity (Ω/) | |
| Embodiment 6 | Polysiloxane copolymer A | 4.47×105 |
| Embodiment 7 | Polysiloxane copolymer B | 4.25×102 |
| Comparative example 3 | Nothing | > 1015 |
| Comparative example 4 | Bu3P+(CH2)3Si(OMe)3·(CF3SO2)2N- | > 1015 |
Embodiment 8
By methyl methacrylate 5.00g, azobis isobutyronitrile 0.20g and as being obtained in the Production Example 1 of antistatic agent
Polysiloxane copolymer A5mg mixed, obtained mixture is flowed in into plastic containers (internal diameter 5cm × depth 1.5cm
Cylindrical shape), make at 50 DEG C its solidify 10 hours, make thickness about 2mm plexiglass test film.
The measurement result of the surface resistivity of obtained test film is shown in table 3.
Comparative example 5
It in addition to not adding polysiloxane copolymer A or B, operates similarly to Example 8, makes poly-methyl methacrylate
The test film of ester resin measures its surface resistivity.It the results are shown in table 3.
Comparative example 6
Except using -1,1,1- tri- Ding Ji Phosphonium of 1- (3- trimethoxy-silylpropyl)=bis- (trifluoromethane sulfonyl groups) acyl
Imines 5mg replaces operating similarly to Example 8 other than polysiloxane copolymer A or B, makes polymethyl methacrylate tree
The test film of rouge measures its surface resistivity.It the results are shown in table 3.
[table 3]
| Antistatic agent | Surface resistivity (Ω/) | |
| Embodiment 8 | Polysiloxane copolymer A | 3.19×1010 |
| Comparative example 5 | Nothing | > 1015 |
| Comparative example 6 | Bu3P+(CH2)3Si(OMe)3·(CF3SO2)2N- | > 1015 |
Embodiment 9
By peroxide curing type silicone adhesive agent KR-101-10 (solid component 60%, Shin-Etsu Chemial Co., Ltd
System) 4.0g, curing agent BPO (benzoyl peroxide) 0.08g, ethyl acetate 6.2g and as in the embodiment 1 of antistatic agent
To polysiloxane copolymer A 48mg mixed, obtain silicone resin adhesive.In polyethylene terephthalate film
The one side of (processing release paper) is coated with the silicone resin adhesive in such a way that dry film thickness becomes about 8 μm using bar coater, 90
Heat drying 3 minutes at DEG C, heat drying 2 minutes at 160 DEG C make silicone resin adhesive layer, measure its sheet resistance
Rate.It the results are shown in table 4.
It is bonded three cellulose acetate membrane (TAC film) on the face with described adhesive layer, is cured at 25 DEG C, 50%RH
1 hour, make test film.Attachment of adhesive when removing processing release paper from test film to processing release paper is evaluated by visual observation
State.It the results are shown in table 4.
A: attachment of the adhesive to processing release paper is not seen.
B: it can be seen that attachment of some adhesive to processing release paper.
C: it can be seen that attachment of most of adhesive to processing release paper.
Comparative example 7
It in addition to not adding polysiloxane copolymer A or B, operates similarly to Example 9, makes silicone resin adhesive
Layer and test film, measure its surface resistivity, while evaluating attachment state of the adhesive to processing release paper by visual observation.It is tied
Fruit is shown in table 4.
Comparative example 8
Except using -1,1,1- tri- Ding Ji Phosphonium of 1- (3- trimethoxy-silylpropyl)=bis- (trifluoromethane sulfonyl groups) acyl
Imines replaces operating similarly to Example 9 other than polysiloxane copolymer A or B, makes silicone resin adhesive layer and test
With film, its surface resistivity is measured, while evaluating attachment state of the adhesive to processing release paper by visual observation.It the results are shown in table
4。
[table 4]
| Antistatic agent | Surface resistivity (Ω/) | Attachment of the adhesive to processing release paper | |
| Embodiment 9 | Polysiloxane copolymer A | 2.49×1011 | A |
| Comparative example 7 | Nothing | > 1015 | A |
| Comparative example 8 | Bu3P+(CH2)3Si(OMe)3·(CF3SO2)2N- | 2.50×1010 | C |
Claims (11)
1. a kind of polysiloxane copolymer is only to carry out dialkoxy silicane shown in salt shown in formula (1) and formula (2)
Obtained from copolymerization,
Formula (1):
In formula (1), Q+Indicate azonia or phosphorus cation；R1Indicate the alkyl of carbon number 1~3, R2~R4Indicate carbon number 1~8
Alkyl；R2And R3It is mutually bonded in end, pyrrolidine ring, piperidine ring, pyridine ring, phospholane ring, phospha hexamethylene can be formed
Alkane ring or phospha phenyl ring；Wherein, R2And R3In the case where end is mutually bonded and forms pyridine ring or phospha phenyl ring, R4It does not deposit
?；X?Indicate anion；The integer that n is 0~3,
Formula (2):
In formula (2), R5Indicate alkyl, the aryl of carbon number 6~10 or the aralkyl of carbon number 7~10 of carbon number 1~10, R6Indicate carbon
The alkyl of number 1~3.
2. polysiloxane copolymer according to claim 1, wherein
In the formula (1), Q+For phosphorus cation.
3. polysiloxane copolymer according to claim 1, wherein
In the formula (1), X?For halide anion or fluo anion.
4. polysiloxane copolymer according to claim 2, wherein
In the formula (1), X?For halide anion or fluo anion.
5. polysiloxane copolymer according to claim 3, wherein
The fluo anion is trifluoromethanesulfonic acid anion, bis- (trifluoromethane sulfonyl group) imide anions, tetrafluoro boric acid
Salt anionic or hexafluorophosphoric acid salt anionic.
6. polysiloxane copolymer according to claim 4, wherein
The fluo anion is trifluoromethanesulfonic acid anion, bis- (trifluoromethane sulfonyl group) imide anions, tetrafluoro boric acid
Salt anionic or hexafluorophosphoric acid salt anionic.
7. polysiloxane copolymer described according to claim 1~any one of 6, wherein
The polysiloxane copolymer is incited somebody to action relative to 1 mole of salt shown in the formula (1)
Shown in the formula (2) 4~49 moles of dialkoxy silicane be copolymerized obtained from.
8. a kind of antistatic agent contains polysiloxane copolymer according to any one of claims 1 to 7.
9. a kind of resin combination contains antistatic agent according to any one of claims 8.
10. resin combination according to claim 9, wherein
The resin combination is poly carbonate resin composition, acrylic acid resin composition or silicone resin component.
11. the manufacturing method of polysiloxane copolymer according to any one of claims 1 to 6, which is characterized in that
In presence of hydrochloric acid, it is total to dialkoxy silicane shown in salt shown in the formula (1) and the formula (2)
It is poly-.
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| PCT/JP2015/056740 WO2015163022A1 (en) | 2014-04-21 | 2015-03-06 | Polysiloxane copolymer and antistatic agent comprising same |
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| JP7009259B2 (en) * | 2018-02-28 | 2022-02-10 | 広栄化学株式会社 | Onium salt |
| CN110655670A (en) * | 2018-06-28 | 2020-01-07 | 浙江清华柔性电子技术研究院 | Antistatic silicone rubber |
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| KR102276501B1 (en) | 2021-07-12 |
| JP6177430B2 (en) | 2017-08-09 |
| TWI684617B (en) | 2020-02-11 |
| JPWO2015163022A1 (en) | 2017-04-13 |
| TW201540751A (en) | 2015-11-01 |
| KR20160148511A (en) | 2016-12-26 |
| CN105916913A (en) | 2016-08-31 |
| WO2015163022A1 (en) | 2015-10-29 |
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