KR102170994B1 - Polysiloxane copolymer and antistatic agent comprising said polysiloxane copolymer - Google Patents

Polysiloxane copolymer and antistatic agent comprising said polysiloxane copolymer Download PDF

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KR102170994B1
KR102170994B1 KR1020140065536A KR20140065536A KR102170994B1 KR 102170994 B1 KR102170994 B1 KR 102170994B1 KR 1020140065536 A KR1020140065536 A KR 1020140065536A KR 20140065536 A KR20140065536 A KR 20140065536A KR 102170994 B1 KR102170994 B1 KR 102170994B1
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carbamoyloxyethyl
polysiloxane copolymer
resin composition
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다케히데 가와미치
유우스케 이시이
리카 오카다
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고에이 가가쿠 고교 가부시키가이샤
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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
    • 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
    • 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
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Abstract

높은 대전 방지성을 수지에 부여할 수 있는 신규의 폴리실록산 공중합체 및 상기 폴리실록산 공중합체를 함유하는 대전 방지제를 제공하는 것.
식(1)로 나타내어지는 오늄염과 식(2)로 나타내어지는 디알콕시실란을 공중합하여 얻어지는 폴리실록산 공중합체 및 상기 폴리실록산 공중합체를 함유하는 대전 방지제.
식(1):

Figure 112014051289330-pat00006

(식 중, Q＋는 질소 카티온 또는 인 카티온을 나타낸다. R1은 탄소수 1~3의 알킬기를 나타내고, R2~R4는 각각 독립적으로 탄소수 1~8의 알킬기를 나타낸다. X－는 어니온을 나타낸다. m 및 n은 각각 독립적으로 1~3의 정수이다.),
식(2):
Figure 112014051289330-pat00007

(식 중, R5는 탄소수 1~3의 알킬기 또는 페닐기를 나타내고, R6는 탄소수 1~3의 알킬기를 나타낸다.)To provide a novel polysiloxane copolymer capable of imparting high antistatic properties to a resin and an antistatic agent containing the polysiloxane copolymer.
A polysiloxane copolymer obtained by copolymerizing an onium salt represented by formula (1) and a dialkoxysilane represented by formula (2), and an antistatic agent containing the polysiloxane copolymer.
Equation (1):
Figure 112014051289330-pat00006

(In the formula, Q + represents a nitrogen cation or a phosphorus cation. R 1 represents an alkyl group having 1 to 3 carbon atoms, and R 2 to R 4 each independently represent an alkyl group having 1 to 8 carbon atoms. X − Represents anion. m and n are each independently an integer of 1 to 3.),
Equation (2):
Figure 112014051289330-pat00007

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

Description

폴리실록산 공중합체 및 상기 폴리실록산 공중합체를 함유하는 대전 방지제{POLYSILOXANE COPOLYMER AND ANTISTATIC AGENT COMPRISING SAID POLYSILOXANE COPOLYMER}A polysiloxane copolymer and an antistatic agent containing the polysiloxane copolymer TECHNICAL FIELD [0001]

본 발명은 폴리실록산 공중합체 및 상기 폴리실록산 공중합체를 함유하는 대전 방지제에 관한 것이다.
The present invention relates to a polysiloxane copolymer and an antistatic agent containing the polysiloxane copolymer.

특허 문헌 1 및 2에 기재된 폴리실록산 화합물이 알려져 있다. 특허 문헌 1에는 폴리실록산 화합물을 소수성 실리콘 오일 등의 증점제ㆍ겔화제에 사용한 것이 기재되어 있다. 그러나 상기 폴리실록산 화합물의 대전 방지성에 대해서는 기재가 없다. 특허 문헌 2에는 폴리실록산 화합물을 포함하는 막형상 조성물이, 높은 대전 방지성을 나타낸 것이 기재되어 있다. 그러나 본 발명자들이 특허 문헌 2에 기재된 막형상 조성물을 대전 방지제로서 수지에 혼합 사용한 결과, 대전 방지성이 불충분한 것을 알았다(후술하는 비교예 참조).Polysiloxane compounds described in Patent Documents 1 and 2 are known. Patent Document 1 describes that a polysiloxane compound is used as a thickener or gelling agent such as a hydrophobic silicone oil. However, there is no description of the antistatic properties of the polysiloxane compound. Patent Document 2 describes that a film-like composition containing a polysiloxane compound exhibits high antistatic properties. However, as a result of mixing and using the film-like composition described in Patent Document 2 with a resin as an antistatic agent by the present inventors, it was found that the antistatic property was insufficient (see Comparative Example to be described later).

또, 카티온이 트리알콕시시릴알킬기를 갖는 암모늄 또는 포스포늄이고, 어니온이 퍼플루오로알킬설포닐이미드인 오늄염은 아크릴 수지용의 저분자형 대전 방지제로서의 보고가 되어 있다(특허 문헌 3 참조). 그러나 본 발명자들이 상기 오늄염의 1종인 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(트리플루오로메탄설포닐)이미드를 실리콘 수지의 대전 방지제로서 사용한 결과, 실리콘 수지에 대하여 대전 방지성을 부여할 수는 있었지만, 실리콘 수지의 경화 반응이 충분히 진행되지 않아서, 광학용 점착제로서 실용적인 강도 특성을 갖는 실리콘 수지 조성물을 얻을 수 없는 것을 알았다(후술하는 비교예 참조).
In addition, an onium salt in which the cation is ammonium or phosphonium having a trialkoxysilylalkyl group and the anion is perfluoroalkylsulfonylimide has been reported as a low-molecular antistatic agent for acrylic resins (see Patent Document 3). ). However, the present inventors used 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=bis(trifluoromethanesulfonyl)imide as silicon As a result of using it as an antistatic agent for the resin, it was possible to impart antistatic properties to the silicone resin, but the curing reaction of the silicone resin did not proceed sufficiently, so that a silicone resin composition having practical strength characteristics as an optical adhesive could not be obtained OK (refer to the comparative example mentioned later).

특허 문헌 1: 일본국 특개2006-199918호 공보Patent Document 1: Japanese Unexamined Patent Publication No. 2006-199918 특허 문헌 2: 일본국 특개2009-286815호 공보Patent document 2: Japanese Unexamined Patent Publication No. 2009-286815 특허 문헌 3: 일본국 특개2013-28586호 공보Patent document 3: Japanese Unexamined Patent Publication No. 2013-28586

본 발명은 높은 대전 방지성을 수지에 부여할 수 있는 신규의 폴리실록산 공중합체, 상기 폴리실록산 공중합체를 함유하는 대전 방지제 및 상기 대전 방지제를 함유하는 수지 조성물을 제공하는 것을 과제로 한다. 또, 높은 대전 방지성을 갖고, 또한 광학용 점착제로서 실용적인 강도 특성을 갖는 실리콘 수지 조성물을 제공하는 것을 과제로 한다.
An object of the present invention is to provide a novel polysiloxane copolymer capable of imparting high antistatic properties to a resin, an antistatic agent containing the polysiloxane copolymer, and a resin composition containing the antistatic agent. Further, it is an object to provide a silicone resin composition having high antistatic properties and having practical strength characteristics as an optical pressure-sensitive adhesive.

본 발명자들이 상기 과제를 해결하기 위해 예의 검토를 실시한 바, 식(1)로 나타내어지는 오늄염과 식(2)로 나타내어지는 디알콕시실란을 공중합하여 얻어지는 폴리실록산 공중합체를 발견했다. 또, 상기 폴리실록산 공중합체를 대전 방지제로 하여 폴리카보네이트 수지, 폴리아크릴 수지 및 실리콘 수지에 사용한 바, 각각의 수지에 대하여 대전 방지성을 부여할 수 있는 것을 발견했다. 또한, 본 발명의 폴리실록산 공중합체를 실리콘 수지에 배합한 실리콘 수지 조성물은 높은 대전 방지성을 갖고, 또한 광학용 점착제로서 실용적인 강도 특성을 갖는 것을 발견하고, 본 발명을 완성하기에 이르렀다.When the present inventors conducted intensive examination in order to solve the above problems, a polysiloxane copolymer obtained by copolymerizing an onium salt represented by formula (1) and a dialkoxysilane represented by formula (2) was discovered. Further, the polysiloxane copolymer was used as an antistatic agent for polycarbonate resins, polyacrylic resins and silicone resins, and found that antistatic properties could be imparted to each resin. Further, it was found that the silicone resin composition in which the polysiloxane copolymer of the present invention was blended with a silicone resin had high antistatic properties and also had practical strength characteristics as an optical pressure-sensitive adhesive, and the present invention was completed.

즉, 본 발명은 식(1)로 나타내어지는 오늄염(이하, 오늄염(1)이라 한다)과 식(2)로 나타내어지는 디알콕시실란(이하, 디알콕시실란(2)이라 한다)을 공중합하여 얻어지는 폴리실록산 공중합체(이하, 본 발명의 폴리실록산 공중합체라 한다) 및 상기 폴리실록산 공중합체를 함유하는 대전 방지제에 관한 것이다.That is, the present invention copolymerizes an onium salt represented by formula (1) (hereinafter referred to as an onium salt (1)) and a dialkoxysilane represented by formula (2) (hereinafter referred to as a dialkoxysilane (2)). The resulting polysiloxane copolymer (hereinafter referred to as the polysiloxane copolymer of the present invention) and an antistatic agent containing the polysiloxane copolymer.

식(1):Equation (1):

Figure 112014051289330-pat00001
Figure 112014051289330-pat00001

(식 중, Q＋는 질소 카티온 또는 인 카티온을 나타낸다. R1은 탄소수 1~3의 알킬기를 나타내고, R2~R4는 각각 독립적으로 탄소수 1~8의 알킬기를 나타내고, X－는 어니온을 나타낸다. m 및 n은 각각 독립적으로 1~3의 정수이다.),(In the formula, Q + represents a nitrogen cation or a phosphorus cation. R 1 represents an alkyl group having 1 to 3 carbon atoms, R 2 to R 4 each independently represent an alkyl group having 1 to 8 carbon atoms, and X − represents Represents anion. m and n are each independently an integer of 1 to 3.),

식(2):Equation (2):

Figure 112014051289330-pat00002
Figure 112014051289330-pat00002

(식 중, R5는 탄소수 1~3의 알킬기 또는 페닐기를 나타내고, R6는 탄소수 1~3의 알킬기를 나타낸다.)
(In the formula, R 5 represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, and R 6 represents an alkyl group having 1 to 3 carbon atoms.)

본 발명의 폴리실록산 공중합체는 폴리카보네이트 수지, 폴리아크릴 수지 및 실리콘 수지의 대전 방지제로서 사용하는 것으로, 공지의 폴리실록산 화합물에 비하여 높은 대전 방지성을 부여할 수 있다. 또, 상기 본 발명의 폴리실록산 공중합체를 함유하는 실리콘 수지 조성물은 높은 대전 방지성을 갖고, 또한 광학용 점착제로서 실용적인 강도 특성을 갖는다.
The polysiloxane copolymer of the present invention is used as an antistatic agent for polycarbonate resins, polyacrylic resins and silicone resins, and can impart high antistatic properties compared to known polysiloxane compounds. Further, the silicone resin composition containing the polysiloxane copolymer of the present invention has high antistatic properties, and also has practical strength properties as an optical pressure-sensitive adhesive.

이하, 본 발명을 구체적으로 설명한다. 식(1) 중, Q＋는 질소 카티온 또는 인 카티온을 나타낸다. R1은 탄소수 1~3의 알킬기이고, 구체적으로는, 메틸기, 에틸기, 프로필기 및 이소프로필기를 들 수 있고, 메틸기 및 에틸기가 바람직하다. R2~R4는 탄소수 1~8의 알킬기를 나타내고, 직쇄상 및 분지쇄상의 어느 하나이어도 좋고, 바람직하게는 직쇄상의 알킬기이다. 구체적으로는, 메틸기, 에틸기, 프로필기, 부틸기, 헥실기, 옥틸기 등을 들 수 있고, 메틸기, 에틸기, 프로필기 및 부틸기가 바람직하다. X－는 어니온을 나타낸다. X－는 구체적으로는, 클로라이드 어니온, 브로마이드 어니온, 트리플루오로메탄설폰산 어니온, 비스(퍼플루오로알킬설포닐)이미드 어니온, 테트라플루오로보레이트 어니온, 헥사플루오로포스페이트 어니온 등을 들 수 있고, 클로라이드 어니온 및 비스(트리플루오로메탄설포닐)이미드 어니온이 바람직하고, 비스(트리플루오로메탄설포닐)이미드 어니온이 보다 바람직하다.Hereinafter, the present invention will be described in detail. In formula (1), Q + represents a nitrogen cation or a phosphorus cation. R 1 is an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group and an isopropyl group are exemplified, and a methyl group and an ethyl group are preferable. R 2 to R 4 represents an alkyl group having 1 to 8 carbon atoms, and may be either a linear or branched chain, and preferably a linear alkyl group. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, etc. are mentioned, and a methyl group, an ethyl group, a propyl group, and a butyl group are preferable. X - represents anion. X − is specifically, chloride anion, bromide anion, trifluoromethanesulfonic acid anion, bis(perfluoroalkylsulfonyl)imide anion, tetrafluoroborate anion, hexafluorophosphate anion. On, and the like, chloride anion and bis(trifluoromethanesulfonyl)imide anion are preferable, and bis(trifluoromethanesulfonyl)imide anion is more preferable.

식(2) 중, R5는 탄소수 1~3의 알킬기 또는 페닐기를 나타낸다. R5의 구체예로서, 메틸기, 에틸기, 프로필기 및 페닐기를 들 수 있고, 바람직하게는 메틸기 및 페닐기이다. R6는 탄소수 1~3의 알킬기를 나타낸다. R6는 구체적으로는, 메틸기, 에틸기 및 프로필기를 들 수 있고, 메틸기 및 에틸기가 바람직하다.In formula (2), R 5 represents a C1-C3 alkyl group or a phenyl group. Specific examples of R 5 include a methyl group, an ethyl group, a propyl group and a phenyl group, and preferably a methyl group and a phenyl group. R 6 represents an alkyl group having 1 to 3 carbon atoms. R 6 specifically includes a methyl group, an ethyl group and a propyl group, and a methyl group and an ethyl group are preferable.

오늄염(1)의 구체예로서는, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암노늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=클로라이드,As a specific example of the onium salt (1), 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium = chloride, 1-{(3-triethoxysilylpropyl )Carbamoyloxyethyl}-1, 1, 1-trimethylamnonium=chloride, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=chloride, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}- 1, 1, 1-triethylammonium=chloride, 1-{(3-tripropoxycyrylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=chloride, 1-{(3-tri Methoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=chloride, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tri Propylammonium=chloride, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=chloride, 1-{(3-trimethoxysilylpropyl)carba Moyloxyethyl}-1, 1, 1-tributylammonium=chloride, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=chloride, 1- {(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=chloride, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=chloride, 1-{(3-tripropoxy Silylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphos Phonium = chloride, 1-{(3-triethoxysilylpropyl) carbamoyloxyethyl}-1, 1, 1-triethylphosphonium = chloride, 1-{(3-tripropoxysilylpropyl) carba Moyloxyethyl}-1, 1, 1-triethylphosphonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=chloride , 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=chloride, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl }-1, 1, 1-tripropylphosphonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=chloride, 1-{ (3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=chloride, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=chloride,

1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=트리플루오로메탄설포네이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=트리플루오로메탄설포네이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=트리플루오로메탄설포네이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=트리플루오로메탄설포네이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=트리플루오로메탄설포네이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=트리플루오로메탄설포네이트,1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=trifluoromethanesulfonate, 1-{(3-triethoxysilylpropyl)carbamoyl Oxyethyl}-1, 1, 1-trimethylammonium=trifluoromethanesulfonate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=trifluoro Romethanesulfonate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium = trifluoromethanesulfonate, 1-{(3-triethoxy Silylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=trifluoromethanesulfonate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=trifluoromethanesulfonate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=trifluoromethanesulfonate, 1 -{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=trifluoromethanesulfonate, 1-{(3-tripropoxysilylpropyl)carbamoyl Oxyethyl}-1, 1, 1-tripropylammonium=trifluoromethanesulfonate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium= Trifluoromethanesulfonate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium = trifluoromethanesulfonate, 1-{(3-tri Propoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium = trifluoromethanesulfonate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=trifluoromethanesulfonate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=trifluoromethanesulfonate , 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=trifluoromethanesulfonate, 1-{(3-trimethoxysilylpropyl)car Barmoyloxyethyl}-1, 1, 1-triethylphosphonium=trifluoromethanesulfonate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tri Ethylphosphonium =Trifluoromethanesulfonate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphosphonium = trifluoromethanesulfonate, 1-{(3 -Trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium = trifluoromethanesulfonate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl} -1, 1, 1-tripropylphosphonium=trifluoromethanesulfonate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=tri Fluoromethanesulfonate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium = trifluoromethanesulfonate, 1-{(3-tri Ethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=trifluoromethanesulfonate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1 , 1, 1-tributylphosphonium=trifluoromethanesulfonate,

1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸-1, 1, 1-트리에틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=비스(트리플루오로메탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=비스(트리플루오로메탄설포닐)이미드,1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-triethoxysilyl Propyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium = bis(trifluoromethanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1 , 1, 1-trimethylammonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=bis (Trifluoromethanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium = bis(trifluoromethanesulfonyl) already De, 1-{(3-tripropoxyrylpropyl)carbamoyloxyethyl-1,1,1-triethylammonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-trime) Oxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl }-1, 1, 1-tripropylammonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tri Propylammonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=bis(trifluoromethane Sulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=bis(trifluoromethanesulfonyl)imide, 1-{ (3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl) Carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=bis (Trifluoromethanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphosphonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphosphonium =bis(trifluoromethanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphosphonium = bis(trifluoromethanesulfur Phonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=bis(trifluoromethanesulfonyl)imide, 1-{ (3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl ) Carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}- 1, 1, 1-tributylphosphonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributyl Phosphonium=bis(trifluoromethanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=bis(trifluoro Methanesulfonyl)imide,

1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=비스(노나플루오로부탄설포닐}이미드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=비스(노나플루오로부탄설포닐)이미드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=비스(노나플루오로부탄설포닐)이미드,1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-triethoxysilyl Propyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1 , 1, 1-trimethylammonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=bis (Nonafluorobutanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=bis(nonafluorobutanesulfonyl)imide De, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-tri Methoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxy Ethyl}-1, 1, 1-tripropylammonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1- Tripropylammonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=bis(nonafluoro Butanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=bis(nonafluorobutanesulfonyl)imide, 1- {(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl ) Carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1 , 1, 1-trimethylphosphonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium= Bis(nonafluorobutanesulfonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1 , 1, 1-triethylphosphonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphos Phonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-tripropoxycyrylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphosphonium=bis(nonafluorobutane Sulfonyl)imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=bis(nonafluorobutanesulfonyl)imide, 1- {(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-tripropoxyryl Propyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=bis(nonafluorobutanesulfonyl}imide, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl} -1, 1, 1-tributylphosphonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tri Butylphosphonium=bis(nonafluorobutanesulfonyl)imide, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=bis(nonafluoro Lobutanesulfonyl)imide,

1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=테트라플루오로보레이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=테트라플루오로보레이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=테트라플루오로보레이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=테트라플루오로보레이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=테트라플루오로보레이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=테트라플루오로보레이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=테트라플루오로보레이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=테트라플루오로보레이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=테트라플루오로보레이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=테트라플루오로보레이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=테트라플루오로보레이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=테트라플루오로보레이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=테트라플루오로보레이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=테트라플루오로보레이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=테트라플루오로보레이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=테트라플루오로보레이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=테트라플루오로보레이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=테트라플루오로보레이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=테트라플루오로보레이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=테트라플루오로보레이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=테트라플루오로보레이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=테트라플루오로보레이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=테트라플루오로보레이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=테트라플루오로보레이트,1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=tetrafluoroborate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl }-1, 1, 1-trimethylammonium=tetrafluoroborate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=tetrafluoroborate, 1 -{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=tetrafluoroborate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl }-1, 1, 1-triethylammonium=tetrafluoroborate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=tetrafluoroborate , 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=tetrafluoroborate, 1-{(3-triethoxysilylpropyl)carbamoyl Oxyethyl}-1, 1, 1-tripropylammonium=tetrafluoroborate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=tetrafluoro Roborate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=tetrafluoroborate, 1-{(3-triethoxysilylpropyl)car Barmoyloxyethyl}-1, 1, 1-tributylammonium=tetrafluoroborate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium= Tetrafluoroborate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium = tetrafluoroborate, 1-{(3-triethoxysilylpropyl ) Carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=tetrafluoroborate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphos Phonium=tetrafluoroborate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphosphonium=tetrafluoroborate, 1-{(3-trier) Oxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphosphonium = tetrafluoroborate, 1-{(3-tripropoxysilylpropyl) Carbamoyloxyethyl}-1, 1, 1-triethylphosphonium=tetrafluoroborate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropyl Phosphonium=tetrafluoroborate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=tetrafluoroborate, 1-{(3-tri Propoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=tetrafluoroborate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1 , 1-tributylphosphonium=tetrafluoroborate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=tetrafluoroborate, 1- {(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium = tetrafluoroborate,

1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=헥사플루오로포스페이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=헥사플루오로포스페이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=헥사플루오로포스페이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=헥사플루오로포스페이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=헥사플루오로포스페이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=헥사플루오로포스페이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=헥사플루오로포스페이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=헥사플루오로포스페이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=헥사플루오로포스페이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=헥사플루오로포스페이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=헥사플루오로포스페이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=헥사플루오로포스페이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=헥사플루오로포스페이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=헥사플루오로포스페이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=헥사플루오로포스페이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=헥사플루오로포스페이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=헥사플루오로포스페이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=헥사플루오로포스페이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=헥사플루오로포스페이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=헥사플루오로포스페이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=헥사플루오로포스페이트, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=헥사플루오로포스페이트, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=헥사플루오로포스페이트, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=헥사플루오로포스페이트 등을 들 수 있는데, 본 발명은 이들에 한정되는 것은 아니다.1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=hexafluorophosphate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl }-1, 1, 1-trimethylammonium=hexafluorophosphate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=hexafluorophosphate, 1 -{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=hexafluorophosphate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl }-1, 1, 1-triethylammonium=hexafluorophosphate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=hexafluorophosphate , 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=hexafluorophosphate, 1-{(3-triethoxysilylpropyl)carbamoyl Oxyethyl}-1, 1, 1-tripropylammonium=hexafluorophosphate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=hexafluoro Lophosphate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=hexafluorophosphate, 1-{(3-triethoxysilylpropyl)car Barmoyloxyethyl}-1, 1, 1-tributylammonium=hexafluorophosphate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium= Hexafluorophosphate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium = hexafluorophosphate, 1-{(3-triethoxysilylpropyl ) Carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=hexafluorophosphate, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphos Phonium = hexafluorophosphate, 1-{(3-trimethoxysilylpropyl) carbamoyloxyethyl}-1, 1, 1-triethylphosphonium = hexafluorophosphate, 1-{(3-trier Oxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphosphonium = hexafluorophosphate, 1-{(3-tripropoxysilylpropyl) Carbamoyloxyethyl}-1, 1, 1-triethylphosphonium=hexafluorophosphate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropyl Phosphonium = hexafluorophosphate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium = hexafluorophosphate, 1-{(3-tri Propoxycyrylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=hexafluorophosphate, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1 , 1-tributylphosphonium=hexafluorophosphate, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=hexafluorophosphate, 1- {(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=hexafluorophosphate, etc. are mentioned, but the present invention is not limited thereto.

본 발명에 사용하는 오늄염(1)은 여러 가지 방법으로 제조할 수 있다. 그 대표적인 방법으로서는, 식(3)으로 나타내어지는 오늄염(이하, 오늄염(3)이라 한다)을 식(4)로 나타내어지는 알칼리 금속염(이하, 알칼리 금속염(4)라 한다)으로 이온 교환 반응을 하는 방법을 들 수 있다.The onium salt (1) used in the present invention can be produced by various methods. As a typical method, an onium salt represented by formula (3) (hereinafter referred to as an onium salt (3)) is converted to an alkali metal salt represented by formula (4) (hereinafter referred to as an alkali metal salt (4)). How to do it.

식(3):Equation (3):

Figure 112014051289330-pat00003
Figure 112014051289330-pat00003

(식 중, Q＋, R1~R4, m 및 n은 상기와 같음. Y－는 할로겐 이온을 나타낸다.)(In the formula, Q + , R 1 to R 4 , m and n are the same as described above. Y − represents a halogen ion.)

식(4):Equation (4):

M＋·X－ (4)M + · X - (4)

(식 중, M＋는 알칼리 금속 이온을 나타낸다. X－는 상기와 같음)(In the formula, M + represents an alkali metal ion. X − is the same as above)

오늄염(3)으로서는 예를 들면, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸암모늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필암모늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸암모늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸포스포늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리에틸포스포늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리프로필포스포늄=클로라이드, 1-{(3-트리메톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=클로라이드, 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=클로라이드, 1-{(3-트리프로폭시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=클로라이드 등을 들 수 있다.As the onium salt (3), for example, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium = chloride, 1-{(3-triethoxysilyl Propyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=chloride, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=chloride, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}- 1, 1, 1-triethylammonium=chloride, 1-{(3-tripropoxycyrylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylammonium=chloride, 1-{(3-tri Methoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=chloride, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tri Propylammonium=chloride, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylammonium=chloride, 1-{(3-trimethoxysilylpropyl)carba Moyloxyethyl}-1, 1, 1-tributylammonium=chloride, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=chloride, 1- {(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylammonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=chloride, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=chloride, 1-{(3-tripropoxy Silylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylphosphonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-triethylphos Phonium = chloride, 1-{(3-triethoxysilylpropyl) carbamoyloxyethyl}-1, 1, 1-triethylphosphonium = chloride, 1-{(3-tripropoxysilylpropyl) carba Moyloxyethyl}-1, 1, 1-triethylphosphonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium=chlora Id, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tripropylphosphonium = chloride, 1-{(3-tripropoxysilylpropyl)carbamoyloxy Ethyl}-1, 1, 1-tripropylphosphonium=chloride, 1-{(3-trimethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=chloride, 1- {(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=chloride, 1-{(3-tripropoxysilylpropyl)carbamoyloxyethyl}-1 , 1, 1-tributylphosphonium=chloride, etc. are mentioned.

알칼리 금속염(4)로서는 예를 들면, 트리플루오로메탄설폰산리튬, 트리플루오로메탄설폰산나트륨, 트리플루오로메탄설폰산칼륨, 비스트리플루오로메탄설포닐이미드리튬, 비스트리플루오로메탄설포닐이미드나트륨, 비스트리플루오로메탄설포닐이미드칼륨, 비스노나플루오로부탄설포닐이미드리튬, 비스노나플루오로부탄설포닐이미드나트륨, 비스노나플루오로부탄설포닐이미드칼륨, 리튬테트라플루오로보레이트, 나트륨테트라플루오로보레이트, 칼륨테트라플루오로보레이트, 리튬헥사플루오로포스페이트, 나트륨헥사플루오로포스페이트, 칼륨헥사플루오로포스페이트 등을 들 수 있다. 알칼리 금속염(4)의 사용량은 오늄염(3) 1몰에 대하여 통상 0.8몰 이상, 바람직하게는 0.9~1.5몰이다.As the alkali metal salt (4), for example, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide, bistrifluoromethane Sodium sulfonylimide, potassium bistrifluoromethanesulfonylimide, lithium bisnonafluorobutanesulfonylimide, sodium bisnonafluorobutanesulfonylimide, potassium bisnonafluorobutanesulfonylimide, Lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, and the like. The amount of the alkali metal salt (4) used is usually 0.8 mol or more, preferably 0.9 to 1.5 mol, per 1 mol of the onium salt (3).

이온 교환 반응은 통상 수용매 중에서 실시된다. 물의 사용량은 오늄염(3) 1중량부에 대하여 통상 20중량부 이하, 바람직하게는 0.5~10중량부, 특히 바람직하게는 1~5중량부이다. 또, 상기 수용매에는 톨루엔, 초산에틸, 디클로로메탄 등의 유기 용매를 공존시킬 수도 있다.The ion exchange reaction is usually carried out in an aqueous medium. The amount of water used is usually 20 parts by weight or less, preferably 0.5 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight, based on 1 part by weight of the onium salt (3). In addition, an organic solvent such as toluene, ethyl acetate, and dichloromethane may coexist in the aqueous medium.

오늄염(3), 알칼리 금속염(4) 및 물의 혼합 순서는 특별히 한정되지 않고, 오늄염(3)과 물을 혼합한 후에 알칼리 금속염(4)를 첨가해도 좋고, 알칼리 금속염(4)와 물을 혼합한 후에 오늄염(3)을 첨가해도 좋다.The order of mixing the onium salt (3), the alkali metal salt (4) and water is not particularly limited, and the alkali metal salt (4) may be added after the onium salt (3) and water are mixed, or the alkali metal salt (4) and water are mixed. After mixing, you may add the onium salt (3).

이온 교환 반응의 반응 온도는, 생성하는 오늄염(1)의 융점보다 높은 온도인 것이 바람직하고, 통상 10~80℃, 바람직하게는 20~40℃이다. 반응 시간으로서는, 통상 15분 이상, 바람직하게는 45분~3시간이다.The reaction temperature of the ion exchange reaction is preferably a temperature higher than the melting point of the onium salt (1) to be produced, and is usually 10 to 80°C, preferably 20 to 40°C. The reaction time is usually 15 minutes or more, and preferably 45 minutes to 3 hours.

반응 종료 후의 반응 혼합물로부터 오늄염(1)을 꺼내는 방법으로서는, 이하의 방법을 들 수 있다. (ⅰ) 반응액이 유기층과 수층으로 분액하고 있는 경우, 반응액으로부터 유기층을 분리하여, 얻어진 유기층을 원하는 바에 따라 수세한 후, 수세 후의 유기층을 농축함으로써 오늄염(1)을 얻는다. (ⅱ) 반응액이 균일한 경우, 물에 불용이거나, 또는 오늄염(1)이 가용인 유기 용매를 사용하여 오늄염(1)을 유기 용매에 추출, 얻어진 유기층을 원하는 바에 따라 수세한 후, 유기 용매를 증류 제거함으로써 오늄염(1)을 얻는다.The following method is mentioned as a method of taking out the onium salt (1) from the reaction mixture after completion|finish of reaction. (I) When the reaction solution is separated into an organic layer and an aqueous layer, the organic layer is separated from the reaction solution, the obtained organic layer is washed with water as desired, and the organic layer after washing is concentrated to obtain an onium salt (1). (Ii) When the reaction solution is uniform, the onium salt (1) is extracted with an organic solvent using an organic solvent insoluble in water or the onium salt (1) is soluble, and the obtained organic layer is washed with water as desired, The onium salt (1) is obtained by distilling off the organic solvent.

다음으로, 오늄염(1)과 디알콕시실란(2)의 공중합에 대하여 설명한다. 오늄염(1)과 디알콕시실란(2)의 공중합은 통상 오늄염(1)과 디알콕시실란(2)의 혼합물에 오늄염(1) 및 디알콕시실란(2)의 양쪽을 용해하는 메탄올, 에탄올, 이소프로필알코올, 아세톤 등의 유기 용매를 첨가하여 용액으로 한 후, 그 용액에 가수 분해의 촉매로 되는 산(이하, 산(5)라 한다.) 또는 염기(이하, 염기(6)이라 한다.)와 물을 적하하여 실시한다. 산(5) 또는 염기(6)은 수용액으로 적하해도 좋다.Next, the copolymerization of the onium salt (1) and the dialkoxysilane (2) will be described. The copolymerization of the onium salt (1) and the dialkoxysilane (2) is usually carried out by dissolving both the onium salt (1) and the dialkoxysilane (2) in a mixture of the onium salt (1) and the dialkoxysilane (2), An organic solvent such as ethanol, isopropyl alcohol, or acetone is added to form a solution, and then an acid (hereinafter referred to as acid (5)) or a base (hereinafter referred to as a base (6)) as a catalyst for hydrolysis to the solution. It is carried out by dripping) and water. Acid (5) or base (6) may be added dropwise as an aqueous solution.

디알콕시실란(2)로서는 예를 들면, 디메틸디메톡시실란, 디에틸디메톡시실란, 디프로필디메톡시실란, 디페닐디메톡시실란, 디메틸디에톡시실란, 디에틸디에톡시실란, 디프로필디에톡시실란, 디페닐디에톡시실란, 디메틸디프로폭시실란, 디에틸디프로폭시실란, 디프로필디프로폭시실란, 디페닐디프로폭시실란 등을 들 수 있고, 바람직하게는 디메틸디메톡시실란 및 디메틸디에톡시실란, 보다 바람직하게는 디메틸디메톡시실란이다.As dialkoxysilane (2), for example, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane , Diphenyldiethoxysilane, dimethyldipropoxysilane, diethyldipropoxysilane, dipropyldipropoxysilane, diphenyldipropoxysilane, and the like, preferably dimethyldimethoxysilane and dimethyldiethoxy Silane, more preferably dimethyldimethoxysilane.

공중합에 있어서의 오늄염(1)과 디알콕시실란(2)의 몰비는 오늄염(1) 1몰에 대하여 디알콕시실란(2) 4~49몰, 바람직하게는 디알콕시실란(2) 4~16몰, 보다 바람직하게는 디알콕시실란(2) 4~8몰이다.The molar ratio of the onium salt (1) and the dialkoxysilane (2) in the copolymerization is 4 to 49 moles of dialkoxysilane (2), preferably 4 to 4 moles of dialkoxysilane (2) per 1 mole of the onium salt (1). It is 16 mol, more preferably 4 to 8 mol of dialkoxysilane (2).

공중합에서 사용하는 유기 용매의 사용량은 오늄염(1) 1중량부에 대하여 통상 20중량부 이하, 바람직하게는 0.5~10중량부, 특히 바람직하게는 1~5중량부이다.The amount of the organic solvent used in the copolymerization is usually 20 parts by weight or less, preferably 0.5 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight, based on 1 part by weight of the onium salt (1).

공중합에서 사용하는 산(5)로서는 예를 들면, 염산, 황산, 질산, 초산, 파라톨루엔설폰산1수화물 등을 들 수 있다. 산(5)의 사용량은 통상 오늄염(1) 또는 (2) 1몰에 대하여 0.001~1몰, 바람직하게는 0.1~0.2몰이다.Examples of the acid (5) used in the copolymerization include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and paratoluenesulfonic acid monohydrate. The amount of acid (5) to be used is usually 0.001 to 1 mole, preferably 0.1 to 0.2 mole per 1 mole of the onium salt (1) or (2).

공중합에서 사용하는 염기(6)으로서는 예를 들면, 수산화나트륨, 수산화칼륨, 수산화리튬 등을 들 수 있다. 염기(6)의 사용량은 통상 오늄염(1) 1몰에 대하여 0.001~1몰, 바람직하게는 0.1~0.2몰이다.Examples of the base 6 used in the copolymerization include sodium hydroxide, potassium hydroxide, and lithium hydroxide. The amount of base (6) to be used is usually 0.001 to 1 mol, preferably 0.1 to 0.2 mol, per 1 mol of the onium salt (1).

공중합에서 사용하는 물의 양은 통상 오늄염(1) 1몰에 대하여 1~10몰이다.The amount of water used in the copolymerization is usually 1 to 10 moles per 1 mole of the onium salt (1).

오늄염(1)과 디알콕시실란(2)의 공중합에 있어서의 반응 온도는 통상 10~80℃, 바람직하게는 20~40℃이다. 반응 시간은 통상 3시간 이상, 바람직하게는 3~72시간이다.The reaction temperature in the copolymerization of the onium salt (1) and the dialkoxysilane (2) is usually 10 to 80°C, preferably 20 to 40°C. The reaction time is usually 3 hours or more, and preferably 3 to 72 hours.

본 발명의 폴리실록산 공중합체는 반응 혼합물을 농축하는 것으로 얻어진다. 반응 혼합물의 농축 온도는 통상 10~120℃, 바람직하게는 30~100℃, 보다 바람직하게는 60~80℃이다. 이와 같이 하여 얻어진 본 발명의 폴리실록산 공중합체는 필요에 따라서 본 발명의 폴리실록산 공중합체와 혼화(混和)하지 않는 헥산, 헵탄, 벤젠, 톨루엔 등의 유기 용매로 세정해도 좋다.The polysiloxane copolymer of the present invention is obtained by concentrating the reaction mixture. The concentration temperature of the reaction mixture is usually 10 to 120°C, preferably 30 to 100°C, and more preferably 60 to 80°C. The polysiloxane copolymer of the present invention thus obtained may be washed with an organic solvent such as hexane, heptane, benzene, or toluene that is not miscible with the polysiloxane copolymer of the present invention, if necessary.

본 발명의 폴리실록산 공중합체를 세정할 때의 유기 용매의 사용량은 본 발명의 폴리실록산 공중합체 1중량부에 대하여 통상 1~20중량부, 바람직하게는 3~9중량부이다.The amount of the organic solvent used when washing the polysiloxane copolymer of the present invention is usually 1 to 20 parts by weight, preferably 3 to 9 parts by weight, based on 1 part by weight of the polysiloxane copolymer of the present invention.

이와 같이 하여 얻어진 본 발명의 폴리실록산 공중합체는 수지에 혼합되는 것으로 수지에 대전 방지성을 부여한다. 이와 같은 수지로서는 예를 들면, 폴리카보네이트 수지, 폴리아크릴 수지, 실리콘 수지 등을 들 수 있다.The polysiloxane copolymer of the present invention thus obtained is mixed with a resin to impart antistatic properties to the resin. Examples of such resins include polycarbonate resins, polyacrylic resins, and silicone resins.

본 발명의 폴리실록산 공중합체를 수지에 교반하는 방법으로서는, 이하의 방법을 들 수 있다. (ⅰ) 본 발명의 폴리실록산 공중합체와 수지를 가열 용융하여 혼련(混練)하는 방법. (ⅱ) 디클로로메탄, 초산에틸, 톨루엔 등의 용매에 용해하여 용액을 조제한 후, 상기 용액을 도포하여 용매를 제거하는 방법. (ⅲ) 광경화성 수지의 경우, 본 발명의 폴리실록산 공중합체를 포함하는 수지 또는 그 용액을 도포 후, 자외선 조사에 의해 경화하는 방법.The following methods are mentioned as a method of stirring the polysiloxane copolymer of this invention with resin. (I) A method of kneading by heating and melting the polysiloxane copolymer of the present invention and a resin. (Ii) A method of preparing a solution by dissolving in a solvent such as dichloromethane, ethyl acetate, and toluene, and then applying the solution to remove the solvent. (Iii) In the case of a photocurable resin, a method of curing by irradiation with ultraviolet rays after applying the resin or a solution thereof containing the polysiloxane copolymer of the present invention.

수지에 대한 본 발명의 폴리실록산 공중합체의 첨가량에 대해서는, 수지에 대하여 통상 0.01~5중량％, 바람직하게는 0.05~1중량％, 특히 바람직하게는 0.1~0.5중량％이다.
The amount of the polysiloxane copolymer of the present invention added to the resin is usually 0.01 to 5% by weight, preferably 0.05 to 1% by weight, and particularly preferably 0.1 to 0.5% by weight, based on the resin.

(실시예)(Example)

다음으로, 본 발명을 실시예에 기초하여 구체적으로 설명하는데, 본 발명은 전혀 이들에 한정되는 것은 아니다. 실시예 중, 1H-NMR은 일본 전자 데이텀 주식회사제 AL-400으로 측정하고, 400MHz로 테트라메틸실란을 기준으로 하여 케미컬 시프트를 산출했다. 또, 표면 저항률은 미츠비시 화학 주식회사제 하이 레스터UP(MCP-HT450)를 사용하여 23±3℃, 습도 45±5％의 조건으로 측정했다. 또한, 실시예 중, 실온이란, 20~25℃를 나타낸다.
Next, the present invention will be specifically described based on examples, but the present invention is not limited to these at all. Examples of, on the basis of tetramethylsilane in 1 H-NMR was measured by Japan Datum Co., Ltd. E-AL-400, 400MHz was calculated chemical shift. In addition, the surface resistivity was measured using Mitsubishi Chemical Co., Ltd. Hi Lester UP (MCP-HT450) under conditions of 23±3°C and humidity of 45±5%. In addition, in Examples, room temperature represents 20 to 25°C.

실시예 1 폴리실록산 공중합체[A]의 제조Example 1 Preparation of polysiloxane copolymer [A]

100mL의 유리 반응기에 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=비스(트리플루오로메탄설포닐)이미드 7.16g(0.01몰), 디메틸디메톡시실란 10.00g(0.08몰) 및 탈수 이소프로필알코올 17.16g을 재고, 얻어진 혼합물에 0.1규정의 염산 1.65g을 적하하여 실온에서 하룻밤 교반했다. 얻어진 반응 혼합물을 농축함으로써 실온에서 투명 액체의 폴리실록산 공중합체[A] 17.17g을 얻었다. 얻어진 폴리실록산 공중합체[A]의 1H-NMR분석 결과를 이하에 나타낸다.In a 100 mL glass reactor, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=bis(trifluoromethanesulfonyl)imide 7.16 g (0.01 Mol), 10.00 g (0.08 mol) of dimethyldimethoxysilane and 17.16 g of dehydrated isopropyl alcohol were stocked, 1.65 g of 0.1 N hydrochloric acid was added dropwise to the obtained mixture, followed by stirring at room temperature overnight. The obtained reaction mixture was concentrated to obtain 17.17 g of a transparent liquid polysiloxane copolymer [A] at room temperature. Shows a 1 H-NMR analysis of the resulting polysiloxane copolymer [A] below.

1H-NMR(CDCl3)δ(ppm) 5.40-5.20(m, 1H), 4.20-4.00(m, 2H), 3.20-3.00(m, 2H), 2.75-2.45(m, 2H), 2.20-2.00(m, 6H), 1.70-1.30(m, 12H), 1.20-1.05(m, 9H), 1.00-0.80(m, 9H), 1.65-1.45(m, 2H), 0.30-0.00(m, 28H)
 1 H-NMR(CDCl 3 )δ(ppm) 5.40-5.20(m, 1H), 4.20-4.00(m, 2H), 3.20-3.00(m, 2H), 2.75-2.45(m, 2H), 2.20- 2.00(m, 6H), 1.70-1.30(m, 12H), 1.20-1.05(m, 9H), 1.00-0.80(m, 9H), 1.65-1.45(m, 2H), 0.30-0.00(m, 28H) )

실시예 2 폴리실록산 공중합체[B]의 제조Example 2 Preparation of polysiloxane copolymer [B]

100mL의 유리 반응기에 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=클로라이드 0.66g(0.02몰), 디메틸디메톡시실란 10.01g(0.08몰) 및 탈수 이소프로필알코올 10.66g을 재고, 얻어진 혼합물에 0.1규정 염산 1.53g을 적하하여 실온에서 2시간 교반했다. 얻어진 반응 혼합물을 농축함으로써 25℃에서 박황색 액체의 폴리실록산 공중합체[B] 3.68g을 얻었다. 얻어진 폴리실록산 공중합체[B]의 1H-NMR분석 결과를 이하에 나타낸다.In a 100 mL glass reactor, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium = chloride 0.66 g (0.02 mol), dimethyldimethoxysilane 10.01 g (0.08 mol) ) And 10.66 g of dehydrated isopropyl alcohol were stocked, 1.53 g of 0.1 N hydrochloric acid was added dropwise to the obtained mixture, followed by stirring at room temperature for 2 hours. The obtained reaction mixture was concentrated to obtain 3.68 g of a light yellow liquid polysiloxane copolymer [B] at 25°C. Shows a 1 H-NMR analysis of the resulting polysiloxane copolymer [B] below.

1H-NMR(CDCl3)δ(ppm) 4.60(brs, 1H), 4.40-3.90(m, 3H), 3.65-3.40(m, 9H), 3.30-3.10(m, 2H), 1.20-1.05(m, 27H), 0.70-0.45(m, 2H), 0.30-0.00(m, 145H)
 1 H-NMR(CDCl 3 )δ(ppm) 4.60(brs, 1H), 4.40-3.90(m, 3H), 3.65-3.40(m, 9H), 3.30-3.10(m, 2H), 1.20-1.05( m, 27H), 0.70-0.45 (m, 2H), 0.30-0.00 (m, 145H)

실시예 3 폴리실록산 공중합체[C]의 제조Example 3 Preparation of polysiloxane copolymer [C]

500mL의 유리 반응기에 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(트리플루오로메탄설포닐)이미드 35.03g(0.06몰), 디메틸디메톡시실란 60.00g(0.5몰) 및 탈수 이소프로필알코올 95.03g을 재고, 얻어진 혼합물에 0.1규정 염산 9.99g을 적하하여 실온에서 하룻밤 교반했다. 얻어진 반응 혼합물을 농축함으로써 실온에서 박황색 액체의 폴리실록산 공중합체[C] 45.26g을 얻었다. 얻어진 폴리실록산 공중합체[C]의 1H-NMR분석 결과를 이하에 나타낸다.In a 500 mL glass reactor, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=bis(trifluoromethanesulfonyl)imide 35.03 g (0.06 mol) , 60.00 g (0.5 mol) of dimethyldimethoxysilane and 95.03 g of dehydrated isopropyl alcohol were stocked, 9.99 g of 0.1 N hydrochloric acid was added dropwise to the obtained mixture, followed by stirring at room temperature overnight. The obtained reaction mixture was concentrated to obtain 45.26 g of a light yellow liquid polysiloxane copolymer [C] at room temperature. Shows a 1 H-NMR analysis of the resulting polysiloxane copolymer [C] below.

1H-NMR(CDCl3)δ(ppm) 5.80-5.20(s, 1H), 4.50-4.30(s, 2H), 4.20-4.40(m, 2H), 3.75-3.50(m, 2H), 3.25-2.95(m, 11H), 1.60-1.40(m, 2H), 1.25-1.05(m, 10H). 0.60g-0.40(m, 2H), 0.30-0.00(m, 33H)
 1 H-NMR(CDCl 3 )δ(ppm) 5.80-5.20(s, 1H), 4.50-4.30(s, 2H), 4.20-4.40(m, 2H), 3.75-3.50(m, 2H), 3.25- 2.95 (m, 11H), 1.60-1.40 (m, 2H), 1.25-1.05 (m, 10H). 0.60g-0.40(m, 2H), 0.30-0.00(m, 33H)

실시예 4 폴리실록산 공중합체[D]의 제조Example 4 Preparation of polysiloxane copolymer [D]

100mL의 유리 반응기에 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=클로라이드 3.58g(0.01몰), 디메틸디메톡시실란 10.01g(0.08몰) 및 탈수 이소프로필알코올 14.00g을 재고, 얻어진 혼합물에 0.1규정 염산 1.66g을 적하하여 실온에서 2시간 교반했다. 얻어진 반응 혼합물을 농축함으로써 실온에서 박황색 왁스상 고체의 폴리실록산 공중합체[D] 5.42g을 얻었다. 얻어진 폴리실록산 공중합체[D]의 1H-NMR분석 결과를 이하에 나타낸다.In a 100 mL glass reactor, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium = chloride 3.58 g (0.01 mol), dimethyldimethoxysilane 10.01 g (0.08 mol) ) And 14.00 g of dehydrated isopropyl alcohol were stocked, 1.66 g of 0.1 N hydrochloric acid was added dropwise to the obtained mixture, followed by stirring at room temperature for 2 hours. The obtained reaction mixture was concentrated to obtain 5.42 g of a light yellow waxy solid polysiloxane copolymer [D] at room temperature. Shows a 1 H-NMR analysis of the resulting polysiloxane copolymer [D] in the following.

1H-NMR(CDCl3)δ(ppm) 4.60(brs, 1H), 4.40-3.90(m, 3H), 3.65-3.40(m, 9H), 3.30-3.10(m, 2H), 1.35-1.10(m, 5H), 0.70-0.45(m, 2H), 0.30-0.00(m, 23H)
 1 H-NMR(CDCl 3 )δ(ppm) 4.60(brs, 1H), 4.40-3.90(m, 3H), 3.65-3.40(m, 9H), 3.30-3.10(m, 2H), 1.35-1.10( m, 5H), 0.70-0.45(m, 2H), 0.30-0.00(m, 23H)

실시예 5 폴리실록산 공중합체[E]의 제조Example 5 Preparation of polysiloxane copolymer [E]

100mL의 유리 반응기에 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=클로라이드 3.58g(0.01몰), 디메틸디메톡시실란 10.01g(0.08몰) 및 탈수 이소프로필알코올 14.00g을 재고, 얻어진 혼합물에 0.1규정 염산 1.51g을 적하하여 실온에서 2시간 교반했다. 얻어진 반응 혼합물을 농축함으로써 실온에서 박황색 왁스상 고체의 폴리실록산 공중합체[E] 5.42g을 얻었다. 얻어진 폴리실록산 공중합체[E]의 1H-NMR분석 결과를 이하에 나타낸다.In a 100 mL glass reactor, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium = chloride 3.58 g (0.01 mol), dimethyldimethoxysilane 10.01 g (0.08 mol) ) And 14.00 g of dehydrated isopropyl alcohol were stocked, 1.51 g of 0.1 N hydrochloric acid was added dropwise to the obtained mixture, followed by stirring at room temperature for 2 hours. The obtained reaction mixture was concentrated to obtain 5.42 g of a light yellow waxy solid polysiloxane copolymer [E] at room temperature. Shows a 1 H-NMR analysis of the resulting polysiloxane copolymer [E] shown below.

1H-NMR(CDCl3)δ(ppm) 4.43(1H, brs), 4.00-3.80(4H, m), 3.39(9H, s), 3.03(2H, brs), 1.50(2H, brs), 1.13-1.05(34H, m), 0.50-0.45(2H, m), 0.05-0.00(26H, m)
 1 H-NMR(CDCl 3 )δ(ppm) 4.43(1H, brs), 4.00-3.80(4H, m), 3.39(9H, s), 3.03(2H, brs), 1.50(2H, brs), 1.13 -1.05(34H, m), 0.50-0.45(2H, m), 0.05-0.00(26H, m)

실시예 6 폴리실록산 공중합체[F]의 제조Example 6 Preparation of polysiloxane copolymer [F]

50mL의 유리 반응기에 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(트리플루오로메탄설포닐)이미드 5.86g(0.01몰), 디메틸디메톡시실란 10.00g(0.08몰) 및 탈수 이소프로필알코올 15.00g을 재고, 얻어진 혼합물에 0.1규정 염산 1.65g을 적하하여 실온에서 3시간 교반 후, 80℃에서 3시간 농축했다. 얻어진 농축 잔사를 톨루엔 15.00g으로 3회 세정한 후, 80℃에서 3시간 농축함으로써 실온에서 박황색 액체의 폴리실록산 공중합체[F] 6.53g을 얻었다. 얻어진 폴리실록산 공중합체[F]의 1H-NMR분석 결과를 이하에 나타낸다.In a 50 mL glass reactor, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium = bis (trifluoromethanesulfonyl) imide 5.86 g (0.01 mol) , 10.00 g (0.08 mol) of dimethyldimethoxysilane and 15.00 g of dehydrated isopropyl alcohol were stocked, 1.65 g of 0.1 N hydrochloric acid was added dropwise to the obtained mixture, stirred at room temperature for 3 hours, and then concentrated at 80°C for 3 hours. The obtained concentrated residue was washed three times with 15.00 g of toluene, and then concentrated at 80° C. for 3 hours to obtain 6.53 g of a light yellow liquid polysiloxane copolymer [F] at room temperature. Shows a 1 H-NMR analysis of the resulting polysiloxane copolymer [F] are shown below.

1H-NMR(CDCl3)δ(ppm) 5.89-5.43(0.9H, brm), 4.45(2H, s), 4.24-4.13(1.1H, brm), 4.83-4.71(0.4H, brm), 3.64(2H, s), 3.54-3.46(0.5H, brm), 3.28-3.08(11.8H, brm). 1.59(2H, brs), 1.25-1.12(7.0H, brm), 0.63-0.50(2H, m), 0.24-0.02(17.6H, brm)
 1 H-NMR(CDCl 3 )δ(ppm) 5.89-5.43 (0.9H, brm), 4.45 (2H, s), 4.24-4.13 (1.1H, brm), 4.83-4.71 (0.4H, brm), 3.64 (2H, s), 3.54-3.46 (0.5H, brm), 3.28-3.08 (11.8H, brm). 1.59 (2H, brs), 1.25-1.12 (7.0H, brm), 0.63-0.50 (2H, m), 0.24-0.02 (17.6H, brm)

실시예 7 폴리실록산 공중합체[G]의 제조Example 7 Preparation of polysiloxane copolymer [G]

50mL의 유리 반응기에 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(트리플루오로메탄설포닐)이미드 5.91g(0.01몰), 디메틸디메톡시실란 10.00g(0.08몰) 및 탈수 이소프로필알코올 15.00g을 재고, 얻어진 혼합물에 0.1규정 염산 1.50g을 적하하여 실온에서 3시간 교반 후, 80℃에서 3시간 농축했다. 얻어진 농축 잔사를 톨루엔 15.00g으로 3회 세정한 후, 80℃에서 3시간 농축함으로써 실온에서 박황색 액체의 폴리실록산 공중합체[G] 6.91g을 얻었다. 얻어진 폴리실록산 공중합체[G]의 1H-NMR분석 결과를 이하에 나타낸다.In a 50 mL glass reactor, 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium=bis(trifluoromethanesulfonyl)imide 5.91 g (0.01 mol) , 10.00 g (0.08 mol) of dimethyldimethoxysilane and 15.00 g of dehydrated isopropyl alcohol were stocked, 1.50 g of 0.1 N hydrochloric acid was added dropwise to the obtained mixture, stirred at room temperature for 3 hours, and then concentrated at 80°C for 3 hours. The obtained concentrated residue was washed three times with 15.00 g of toluene and then concentrated at 80°C for 3 hours to obtain 6.91 g of a light yellow liquid polysiloxane copolymer [G] at room temperature. Shows a 1 H-NMR analysis of the resulting polysiloxane copolymer [G] below.

1H-NMR(CDCl3)δ(ppm) 5.89-5.43(0.9H, brm), 4.45(2H, s), 4.24-4.13(1.3H, brm), 4.83-4.71(0.5H, brm), 3.64(2H, s), 3.54-3.46(1.1H, brm), 3.28-3.08(11.5H, brm). 1.59(2H, brs), 1.25-1.12(8.5H, brm), 0.63-0.50(2H, m), 0.24-0.02(13.1H, brm)
 1 H-NMR(CDCl 3 )δ(ppm) 5.89-5.43 (0.9H, brm), 4.45 (2H, s), 4.24-4.13 (1.3H, brm), 4.83-4.71 (0.5H, brm), 3.64 (2H, s), 3.54-3.46 (1.1H, brm), 3.28-3.08 (11.5H, brm). 1.59 (2H, brs), 1.25-1.12 (8.5H, brm), 0.63-0.50 (2H, m), 0.24-0.02 (13.1H, brm)

실시예Example 8 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정 8 Preparation of polycarbonate resin composition sample and measurement of its surface resistivity

50mL의 샘플병에 폴리카보네이트 수지(스미토모 다우 주식회사제, 캘리버(등록 상표) 200-13 NAT) 3.2g과 디클로로메탄 20mL을 재고, 폴리카보네이트 수지의 디클로로메탄 용액을 조제했다. 얻어진 용액에 대전 방지제로서 실시예 1의 폴리실록산 공중합체[A] 0.0016g을 첨가하고, 용해 완료시킨 후, 금형(12㎝×20㎝×2㎝)에 흘려 넣고, 실온에서 1시간, 또한 40℃에서 1시간 건조시켜서 폴리카보네이트 수지 조성물 샘플(막두께 0.1±0.02㎜)을 작성했다. 작성한 폴리카보네이트 수지 조성물 샘플의 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
In a 50 mL sample bottle, 3.2 g of polycarbonate resin (manufactured by Sumitomo Dow, Caliber (registered trademark) 200-13 NAT) and 20 mL of dichloromethane were stocked to prepare a dichloromethane solution of polycarbonate resin. To the obtained solution, 0.0016 g of the polysiloxane copolymer [A] of Example 1 was added as an antistatic agent, and after dissolution was completed, it was poured into a mold (12 cm x 20 cm x 2 cm), and at room temperature for 1 hour and further 40°C. It dried for 1 hour at the same time, and produced the polycarbonate resin composition sample (film thickness 0.1±0.02 mm). The surface resistivity of the prepared polycarbonate resin composition sample was measured. The results are shown in Table 1.

실시예 9 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 9 Preparation of polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 실시예 2의 폴리실록산 공중합체[B]를 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
A sample of a polycarbonate resin composition was prepared in the same manner as in Example 8 except that the polysiloxane copolymer [B] of Example 2 was used in place of the polysiloxane copolymer [A], and the surface resistivity was measured. The results are shown in Table 1.

실시예 10 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 10 Preparation of polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 실시예 3의 폴리실록산 공중합체[C]를 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
Except using the polysiloxane copolymer [C] of Example 3 in place of the polysiloxane copolymer [A], a polycarbonate resin composition sample was prepared in the same manner as in Example 8, and the surface resistivity was measured. The results are shown in Table 1.

실시예 11 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 11 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 실시예 4의 폴리실록산 공중합체[D]를 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
Except for using the polysiloxane copolymer [D] of Example 4 in place of the polysiloxane copolymer [A], a polycarbonate resin composition sample was prepared in the same manner as in Example 8, and the surface resistivity was measured. The results are shown in Table 1.

실시예 12 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 12 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 실시예 5의 폴리실록산 공중합체[E]를 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
Except for using the polysiloxane copolymer [E] of Example 5 in place of the polysiloxane copolymer [A], a polycarbonate resin composition sample was prepared in the same manner as in Example 8, and the surface resistivity was measured. The results are shown in Table 1.

실시예 13 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 13 Preparation of polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 실시예 6의 폴리실록산 공중합체[F]를 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
Except for using the polysiloxane copolymer [F] of Example 6 in place of the polysiloxane copolymer [A], a polycarbonate resin composition sample was prepared in the same manner as in Example 8, and the surface resistivity was measured. The results are shown in Table 1.

비교예 1 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 1 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]를 사용하지 않는 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
A polycarbonate resin composition sample was prepared in the same manner as in Example 8, except that the polysiloxane copolymer [A] was not used, and the surface resistivity was measured. The results are shown in Table 1.

비교예 2 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 2 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리메틸암모늄=비스(트리플루오로메탄설포닐)이미드(이하, 오늄염[A]라 한다)를 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
In place of the polysiloxane copolymer [A], 1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-trimethylammonium = bis(trifluoromethanesulfonyl)imide (hereinafter , Except using the onium salt [A]), a polycarbonate resin composition sample was prepared in the same manner as in Example 8, and the surface resistivity was measured. The results are shown in Table 1.

비교예 3 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 3 Preparation of polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 1-{(3-트리에톡시시릴프로필)카르바모일옥시에틸}-1, 1, 1-트리부틸포스포늄=비스(트리플루오로메탄설포닐)이미드(이하, 오늄염[B]라 한다)를 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
1-{(3-triethoxysilylpropyl)carbamoyloxyethyl}-1, 1, 1-tributylphosphonium=bis(trifluoromethanesulfonyl)imide in place of the polysiloxane copolymer [A] Except for using (hereinafter referred to as onium salt [B]), a polycarbonate resin composition sample was prepared in the same manner as in Example 8, and the surface resistivity was measured. The results are shown in Table 1.

비교예 4 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 4 Preparation of a polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 트리부틸도데실포스포늄=비스(트리플루오로메탄설포닐)이미드(이하, 오늄염[C]라 한다)를 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.
In the same manner as in Example 8, except that tributyldodecylphosphonium=bis(trifluoromethanesulfonyl)imide (hereinafter referred to as onium salt [C]) was used in place of the polysiloxane copolymer [A]. A sample of the polycarbonate resin composition was prepared and the surface resistivity was measured. The results are shown in Table 1.

비교예 5 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 5 Preparation of polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 오늄염[C] 0.032g을 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.A polycarbonate resin composition sample was prepared in the same manner as in Example 8, except that 0.032 g of the onium salt [C] was used in place of the polysiloxane copolymer [A], and the surface resistivity was measured. The results are shown in Table 1.

비교예 6 폴리카보네이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 6 Preparation of polycarbonate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 특허 문헌 2(특개2009-286815호 공보)를 참고로 하여 얻은, 1-메틸-3-(3-트리메톡시시릴프로필)이미다졸륨=테트라플루오로보레이트 중합물을 가수 분해 중합한 막형상 조성물(이하, 오늄염[D]라 한다)을 사용한 이외는, 실시예 8과 동일하게 하여 폴리카보네이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 1에 나타낸다.1-methyl-3-(3-trimethoxysilylpropyl)imidazolium = tetrafluoroborate polymer obtained by referring to Patent Document 2 (Patent Publication No. 2009-286815) in place of the polysiloxane copolymer [A] A polycarbonate resin composition sample was prepared in the same manner as in Example 8, except that the film-like composition (hereinafter referred to as onium salt [D]) obtained by hydrolysis polymerization was used, and the surface resistivity was measured. The results are shown in Table 1.

대전 방지제Antistatic agent 표면 저항률(Ω／□)Surface resistivity (Ω/□) 실시예 8Example 8 폴리실록산 공중합체[A]Polysiloxane copolymer [A] 3.46×1013 3.46×10 13 실시예 9Example 9 폴리실록산 공중합체[B]Polysiloxane copolymer [B] 1.17×1012 1.17×10 12 실시예 10Example 10 폴리실록산 공중합체[C]Polysiloxane copolymer [C] 2.36×1012 2.36×10 12 실시예 11Example 11 폴리실록산 공중합체[D]Polysiloxane copolymer [D] 2.88×1011 2.88×10 11 실시예 12Example 12 폴리실록산 공중합체[E]Polysiloxane copolymer [E] 1.32×1011 1.32×10 11 실시예 13Example 13 폴리실록산 공중합체[F]Polysiloxane copolymer [F] 3.17×1010 3.17×10 10 비교예 1Comparative Example 1 없음none ＞1015 ＞10 15 비교예 2Comparative Example 2 오늄염[A]Onium salt [A] ＞1015 ＞10 15 비교예 3Comparative Example 3 오늄염[B]Onium salt [B] ＞1015 ＞10 15 비교예 4Comparative Example 4 오늄염[C]Onium salt [C] ＞1015 ＞10 15 비교예 5Comparative Example 5 오늄염[C]Onium salt [C] 2.75×1011 2.75×10 11 비교예 6Comparative Example 6 오늄염[D]Onium salt [D] ＞1015 ＞10 15

실시예 14 폴리아크릴 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 14 Preparation of polyacrylic resin composition sample and measurement of its surface resistivity

디펜타에리스리톨헥사아크릴레이트(A-DPH: 신나카무라 화학 공업 주식회사제) 0.50g, 펜타에리스리톨트리아크릴레이트(A-TMM-3LM-N: 신나카무라 화학 공업 주식회사제) 1.50g, 트리메틸올프로판트리아크릴레이트(A-TMPT: 신나카무라 화학 공업 주식회사제) 0.50g, 이소프로필알코올 1.75g, 콜로이달 실리카의 IPA분산액(IPA-ST: 실리카 고형분 30wt％, 닛산 화학 공업 주식회사제) 3.60g, 대전 방지제로서 폴리실록산 공중합체[E] 0.54g 및 광중합 개시제로서 2-히드록시-2-메틸프로피오페논 0.15g을 혼합했다.Dipentaerythritol hexaacrylate (A-DPH: manufactured by Shinnakamura Chemical Industries, Ltd.) 0.50g, pentaerythritol triacrylate (A-TMM-3LM-N: manufactured by Shinnakamura Chemical Industries, Ltd.) 1.50g, trimethylolpropanetriacrylic Rate (A-TMPT: manufactured by Shin-Nakamura Chemical Industries, Ltd.) 0.50 g, isopropyl alcohol 1.75 g, IPA dispersion of colloidal silica (IPA-ST: 30 wt% silica solid content, manufactured by Nissan Chemical Industries, Ltd.) 3.60 g, as an antistatic agent 0.54 g of polysiloxane copolymer [E] and 0.15 g of 2-hydroxy-2-methylpropiophenone as a photopolymerization initiator were mixed.

얻어진 혼합물을 두께 100㎛의 폴리에틸렌테레프탈레이트 필름의 편면에 바코터를 사용하여 건조 막두께가 약 5㎛로 되도록 도포하여 도막을 작성했다. 상기 도막면에 고압 수은 UV램프(120W／㎝)의 자외선을 적산 광량 약 400mJ／㎠로 조사하여 경화시킴으로써 폴리아크릴 수지 조성물 샘플을 작성했다. 작성한 폴리아크릴 수지 조성물 샘플의 표면 저항률을 측정했다. 그 결과를 표 2에 나타낸다.
The obtained mixture was applied onto one side of a 100 µm-thick polyethylene terephthalate film using a bar coater so that the dry film thickness was about 5 µm to prepare a coating film. A polyacrylic resin composition sample was prepared by irradiating the surface of the coating film with ultraviolet rays of a high-pressure mercury UV lamp (120 W/cm) at a cumulative amount of about 400 mJ/cm 2 and curing. The surface resistivity of the prepared polyacrylic resin composition sample was measured. The results are shown in Table 2.

실시예 15 폴리아크릴 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 15 Preparation of polyacrylic resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[E]에 대신하여 폴리실록산 공중합체[F]를 사용한 이외는, 실시예 14와 동일하게 하여 폴리아크릴 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 2에 나타낸다.
Except using the polysiloxane copolymer [F] in place of the polysiloxane copolymer [E], a polyacrylic resin composition sample was prepared in the same manner as in Example 14, and the surface resistivity was measured. The results are shown in Table 2.

실시예 16 폴리아크릴 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 16 Preparation of polyacrylic resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[E]에 대신하여 폴리실록산 공중합체[G]를 사용한 이외는, 실시예 14와 동일하게 하여 폴리아크릴 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 2에 나타낸다.
Except using the polysiloxane copolymer [G] in place of the polysiloxane copolymer [E], it carried out similarly to Example 14, and produced the polyacrylic resin composition sample, and the surface resistivity was measured. The results are shown in Table 2.

비교예 7 폴리아크릴 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 7 Preparation of polyacrylic resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[E]를 첨가하지 않는 이외는, 실시예 14와 동일하게 하여 폴리아크릴 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 2에 나타낸다.
Except not adding the polysiloxane copolymer [E], it carried out similarly to Example 14, and produced the polyacrylic resin composition sample, and the surface resistivity was measured. The results are shown in Table 2.

비교예 8 폴리아크릴 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 8 Preparation of polyacrylic resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[E]에 대신하여 오늄염[A] 0.54g을 사용한 이외는, 실시예 14와 동일하게 하여 폴리아크릴 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 2에 나타낸다.A polyacrylic resin composition sample was prepared in the same manner as in Example 14, except that 0.54 g of the onium salt [A] was used in place of the polysiloxane copolymer [E], and the surface resistivity was measured. The results are shown in Table 2.

대전 방지제Antistatic agent 표면 저항률(Ω／□)Surface resistivity (Ω/□) 실시예 14Example 14 폴리실록산 공중합체[E]Polysiloxane copolymer [E] 2.76×1012 2.76×10 12 실시예 15Example 15 폴리실록산 공중합체[F]Polysiloxane copolymer [F] 4.70×1012 4.70×10 12 실시예 16Example 16 폴리실록산 공중합체[G]Polysiloxane copolymer [G] 4.42×1012 4.42×10 12 비교예 7Comparative Example 7 없음none ＞1015 ＞10 15 비교예 8Comparative Example 8 오늄염[A]Onium salt [A] 4.12×1014 4.12×10 14

실시예 17 폴리메틸메타크릴레이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 17 Preparation of polymethylmethacrylate resin composition sample and measurement of its surface resistivity

메타크릴산메틸 5.00g, 아조비스이소부티로니트릴 0.20g 및 대전 방지제로서 폴리실록산 공중합체[E] 0.005g을 혼합했다. 얻어진 혼합물을 플라스틱 용기(내경 5㎝×높이 1.5㎝의 원통형)에 흘려 넣고, 50℃에서 10시간 경화시켜서 두께 약 2㎜의 폴리메틸메타크릴레이트 수지의 샘플을 작성했다. 작성한 폴리메틸메타크릴레이트 수지 조성물 샘플의 표면 저항률을 측정했다. 그 결과를 표 3에 나타낸다.
5.00 g of methyl methacrylate, 0.20 g of azobisisobutyronitrile, and 0.005 g of polysiloxane copolymer [E] as an antistatic agent were mixed. The obtained mixture was poured into a plastic container (a cylinder having an inner diameter of 5 cm x a height of 1.5 cm), and cured at 50° C. for 10 hours to prepare a sample of a polymethyl methacrylate resin having a thickness of about 2 mm. The surface resistivity of the prepared polymethyl methacrylate resin composition sample was measured. The results are shown in Table 3.

실시예 18 폴리메틸메타크릴레이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 18 Preparation of polymethylmethacrylate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[E]에 대신하여 폴리실록산 공중합체[F]를 사용한 이외는, 실시예 17와 동일하게 하여 폴리메틸메타크릴레이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 3에 나타낸다.
Except for using the polysiloxane copolymer [F] in place of the polysiloxane copolymer [E], a polymethyl methacrylate resin composition sample was prepared in the same manner as in Example 17, and the surface resistivity was measured. The results are shown in Table 3.

비교예 9 폴리메틸메타크릴레이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 9 Preparation of polymethylmethacrylate resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[E]를 첨가하지 않는 이외는, 실시예 17과 동일하게 하여 폴리메틸메타크릴레이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 3에 나타낸다.
Except not adding the polysiloxane copolymer [E], it carried out similarly to Example 17, and produced the sample of a polymethyl methacrylate resin composition, and the surface resistivity was measured. The results are shown in Table 3.

비교예 10 폴리메틸메타크릴레이트 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 10 Preparation of a sample of a polymethyl methacrylate resin composition and measurement of its surface resistivity

폴리실록산 공중합체[E]에 대신하여 트리부틸메틸암모늄=비스(트리플루오로메탄설포닐)이미드(이하, 오늄염[E]라 한다) 0.50g을 사용한 이외는, 실시예 17과 동일하게 하여 폴리메틸메타크릴레이트 수지 조성물 샘플을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 3에 나타낸다.In the same manner as in Example 17 except that 0.50 g of tributylmethylammonium = bis (trifluoromethanesulfonyl) imide (hereinafter referred to as onium salt [E]) was used instead of the polysiloxane copolymer [E]. A sample of the polymethyl methacrylate resin composition was prepared, and the surface resistivity was measured. The results are shown in Table 3.

대전 방지제Antistatic agent 표면 저항률(Ω／□)Surface resistivity (Ω/□) 실시예 17Example 17 폴리실록산 공중합체[E]Polysiloxane copolymer [E] 1.20×109 1.20×10 9 실시예 18Example 18 폴리실록산 공중합체[F]Polysiloxane copolymer [F] 2.48×109 2.48×10 9 비교예 9Comparative Example 9 없음none ＞1015 ＞10 15 비교예 10Comparative Example 10 오늄염[E]Onium salt [E] ＞1015 ＞10 15

실시예 19 실리콘 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Example 19 Preparation of silicone resin composition sample and measurement of its surface resistivity

과산화물 경화형 실리콘 점착제 KR-101-10(고형분 60％, 신에츠 화학 공업 주식회사제) 4.0g, 경화제 BPO(과산화벤조일) 0.08g, 초산에틸 6.2g 및 대전 방지제로서 폴리실록산 공중합체[A] 0.049g을 혼합하여 실리콘 수지 점착제를 얻었다. 상기 실리콘 수지 점착제를 폴리에틸렌테레프탈레이트 필름(이형지)의 편면에 바코터를 사용하여 건조 막두께가 약 8㎛로 되도록 도포하고, 90℃에서 4분간, 160℃에서 2분간 가열 건조시켜서 실리콘 수지 점착제층을 작성하고, 그 표면 저항률을 측정했다. 그 결과를 표 4에 나타낸다.Mixing peroxide curable silicone adhesive KR-101-10 (solid content 60%, manufactured by Shin-Etsu Chemical Co., Ltd.) 4.0 g, curing agent BPO (benzoyl peroxide) 0.08 g, ethyl acetate 6.2 g, and polysiloxane copolymer [A] 0.049 g as an antistatic agent Thus, a silicone resin adhesive was obtained. The silicone resin adhesive was applied to one side of a polyethylene terephthalate film (release paper) using a bar coater to a dry film thickness of about 8 μm, and heated and dried at 90° C. for 4 minutes and 160° C. for 2 minutes. Was created and the surface resistivity was measured. The results are shown in Table 4.

상기 점착제층을 갖는 면에 트리아세틸셀룰로오스 필름(TAC필름)을 부착하고, 25℃, 50％RH로 1시간 에이징하여 시험용 필름을 작성했다. 시험용 필름으로부터 이형지를 박리했을 때의 이형지로의 점착제의 부착 상태를 육안으로 평가했다. 그 결과를 표 4에 나타낸다.A triacetyl cellulose film (TAC film) was attached to the surface having the pressure-sensitive adhesive layer, and aged at 25°C and 50% RH for 1 hour to prepare a test film. When the release paper was peeled from the test film, the state of adhesion of the pressure-sensitive adhesive to the release paper was visually evaluated. The results are shown in Table 4.

○: 이형지로의 점착제의 부착이 인정되지 않는다.○: The adhesion of the adhesive to the release paper was not recognized.

△: 이형지로의 부분적인 점착제의 부착이 인정된다.?: A partial adhesion of the adhesive to the release paper is recognized.

×: 이형지로의 대부분의 점착제의 부착이 인정된다.
×: adhesion of most of the adhesive to the release paper is recognized.

비교예 11 실리콘 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 11 Preparation of silicone resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체를 사용하지 않는 이외는, 실시예 19와 동일하게 하여 실리콘 수지 점착제층 및 시험용 필름을 작성하고, 그 표면 저항률을 측정하는 것과 함께, 이형지로의 점착제의 부착 상태를 육안으로 평가했다. 그 결과를 표 4에 나타낸다.
Except for not using the polysiloxane copolymer, in the same manner as in Example 19, a silicone resin pressure-sensitive adhesive layer and a test film were prepared, and 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.

비교예 12 실리콘 수지 조성물 샘플의 작성 및 그 표면 저항률의 측정Comparative Example 12 Preparation of silicone resin composition sample and measurement of its surface resistivity

폴리실록산 공중합체[A]에 대신하여 오늄염[A]를 사용한 이외는, 실시예 19와 동일하게 하여 실리콘 수지 점착제층 및 시험용 필름을 작성하고, 그 표면 저항률을 측정하는 것과 함께, 이형지로의 점착제의 부착 상태를 육안으로 평가했다. 그 결과를 표 4에 나타낸다.Except for using the onium salt [A] in place of the polysiloxane copolymer [A], in the same manner as in Example 19, a silicone resin pressure-sensitive adhesive layer and a test film were prepared, and the surface resistivity thereof was measured, and the pressure-sensitive adhesive as a release paper The adhesion state of was evaluated visually. The results are shown in Table 4.

대전 방지제Antistatic agent 표면 저항률(Ω／□)Surface resistivity (Ω/□) 이형지로의 점착제 부착Adhesive adhesion to release paper 실시예 19Example 19 폴리실록산 공중합체[A]Polysiloxane copolymer [A] 9.06×1011 9.06×10 11 ○○ 비교예 11Comparative Example 11 없음none ＞1015 ＞10 15 ○○ 비교예 12Comparative Example 12 오늄염[A]Onium salt [A] 2.11×1011 2.11×10 11 △△

Claims (9)

식(1)로 나타내어지는 오늄염과 식(2)로 나타내어지는 디알콕시실란을 공중합하여 얻어지는 폴리실록산 공중합체.
식(1):
Figure 112014051289330-pat00004

(식 중, Q＋는 질소 카티온 또는 인 카티온을 나타낸다. R1은 탄소수 1~3의 알킬기를 나타내고, R2~R4는 각각 독립적으로 탄소수 1~8의 알킬기를 나타낸다. X－는 어니온을 나타낸다. m 및 n은 각각 독립적으로 1~3의 정수이다.),
식(2):
Figure 112014051289330-pat00005

(식 중, R5는 탄소수 1~3의 알킬기 또는 페닐기를 나타내고, R6는 탄소수 1~3의 알킬기를 나타낸다.)
A polysiloxane copolymer obtained by copolymerizing an onium salt represented by formula (1) and a dialkoxysilane represented by formula (2).
Equation (1):
Figure 112014051289330-pat00004

(In the formula, Q + represents a nitrogen cation or a phosphorus cation. R 1 represents an alkyl group having 1 to 3 carbon atoms, and R 2 to R 4 each independently represent an alkyl group having 1 to 8 carbon atoms. X − Represents anion. m and n are each independently an integer of 1 to 3.),
Equation (2):
Figure 112014051289330-pat00005

(In the formula, R 5 represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, and R 6 represents an alkyl group having 1 to 3 carbon atoms.)
 제1항에 있어서,
상기 식(1)에 있어서, X－가 할로겐 어니온인
폴리실록산 공중합체.
The method of claim 1,
In the above formula (1), X − is a halogen anion
Polysiloxane copolymer.
 제1항에 있어서,
상기 식(1)에 있어서, X－가 함불소 어니온인
폴리실록산 공중합체.
The method of claim 1,
In the above formula (1), X − is a fluorinated onion
Polysiloxane copolymer.
 제3항에 있어서,
상기 함불소 어니온이 트리플루오로메탄설폰산 어니온, 비스(퍼플루오로알킬설포닐)이미드 어니온, 테트라플루오로 보레이트 어니온 및 헥사플루오로포스페이트 어니온으로 이루어지는 군으로부터 선택되는 적어도 1종의 어니온인
폴리실록산 공중합체.
The method of claim 3,
The fluorinated anion is at least 1 selected from the group consisting of trifluoromethanesulfonic acid anion, bis(perfluoroalkylsulfonyl)imide anion, tetrafluoro borate anion, and hexafluorophosphate anion. Servant of the onion man
Polysiloxane copolymer.
 제1항에 있어서,
상기 식(1)로 나타내어지는 오늄염 1몰과 상기 식(2)로 나타내어지는 디알콕시실란 4~49몰을 공중합하여 얻어지는
폴리실록산 공중합체.
The method of claim 1,
Obtained by copolymerizing 1 mol of the onium salt represented by the formula (1) and 4 to 49 mol of the dialkoxysilane represented by the formula (2)
Polysiloxane copolymer.
 제1항 내지 제5항 중 어느 한 항에 기재된 폴리실록산 공중합체를 함유하는
대전 방지제.
Containing the polysiloxane copolymer according to any one of claims 1 to 5
Antistatic agent.
 제6항에 기재된 대전 방지제를 함유하는
수지 조성물.
Containing the antistatic agent according to claim 6
Resin composition.
 제7항에 있어서,
상기 수지 조성물이 폴리카보네이트 수지 조성물, 폴리아크릴 수지 조성물 및 실리콘 수지 조성물로 이루어지는 군으로부터 선택되는 적어도 1종의 수지 조성물인
수지 조성물.The method of claim 7,
The resin composition is at least one resin composition selected from the group consisting of a polycarbonate resin composition, a polyacrylic resin composition, and a silicone resin composition.
Resin composition. 물 및 산의 존재 하, 또는 물 및 염기의 존재 하, 상기 식(1)로 나타내어지는 오늄염과 상기 식(2)로 나타내어지는 디알콕시실란을 공중합시키는 것을 특징으로 하는 제1항에 기재된 폴리실록산 공중합체의 제조 방법.The polysiloxane according to claim 1, wherein the onium salt represented by formula (1) and the dialkoxysilane represented by formula (2) are copolymerized in the presence of water and acid, or in the presence of water and a base. Method for producing a copolymer.
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