WO2013011822A2

WO2013011822A2 - Onium salt having trialkoxysilylalkyl group

Info

Publication number: WO2013011822A2
Application number: PCT/JP2012/066824
Authority: WO
Inventors: 洋輔田中; 卓彦神野
Original assignee: 広栄化学工業株式会社
Priority date: 2011-06-24
Filing date: 2012-06-25
Publication date: 2013-01-24
Also published as: JP2013028586A; JP6190572B2; KR101991272B1; CN103596965A; WO2013011822A3; CN103596965B; KR20140042880A

Abstract

An onium salt represented by formula (1) (In the formula: A^- represents an anion; and the remainder of the formula represents a quaternary onium cation (therein, Q⁺ represents a nitrogen cation or a phosphorous cation; R¹-R³ represent C1-6 alkyl groups, and the terminals of R¹ and R² may bond to form a pyrrolidine ring, a piperidine ring, a pyridine ring, a phosphorane ring, a phosphorinane ring or a phosphorin ring; if a pyridine ring or a phosphorin ring is formed then R³ will not be present; R⁴ represents a C1-4 alkyl group; D represents CH₂, CH(CH₃) or CH(CH₃)CH₂; E represents NH or a sulfur atom; m is an integer in the range of 0-3, and n is an integer in the range of 1-4).

Description

Onium salt having trialkoxysilylalkyl group

The present invention relates to a novel onium salt having a trialkoxysilylalkyl group.

As an onium salt having a trialkoxysilylalkyl group, one in which a cation is a nitrogen atom or a phosphorus atom and a silicon atom bonded with an alkyl group, and an anion is bis (perfluoroalkylsulfonyl) imide is known. . It is known that the onium salt can impart excellent antistatic properties to the fluororesin (see Patent Document 1).
However, when the inventor applied the onium salt described in Patent Document 1 as an antistatic agent for an acrylic resin, the surface resistivity was 10 ¹³ Ω / □ or more, which was sufficient as an antistatic agent for an acrylic resin. It was found that it has no antistatic ability.

JP 2010-248165 A

An object of the present invention is to provide a novel onium salt having a trialkoxysilylalkyl group particularly useful as an antistatic agent for acrylic resins.

As a result of intensive studies to solve the above-mentioned problems, the present inventor found an onium salt represented by the formula (1) and further used the onium salt as an antistatic agent in an acrylic resin. The inventors have found that antistatic properties can be imparted, and have completed the present invention.
That is, the present invention provides the formula (1):
Formula (1):

(In the formula, Q ⁺ represents a nitrogen cation or a phosphor cation. R ¹ to R ³ represent an alkyl group having 1 to 6 carbon atoms, and R ¹ and R ² are bonded to each other at the terminal to form a pyrrolidine ring or a piperidine ring. , A pyridine ring, a phosphorane ring, a phosphorinane ring, or a phospholine ring, provided that a pyridine ring or a phospholine ring is not present, R ³ is not present, and R ⁴ is an alkyl group having 1 to 4 carbon atoms. D represents CH ₂ , CH (CH ₃ ) or CH (CH ₃ ) CH ₂ , E represents NH or a sulfur atom, m represents an integer of 0 to 3, and n represents an integer of 1 to 4. ) Represents a quaternary onium cation, and A ⁻ represents an anion.) (Referred to below as onium salt (1)).

The onium salt (1) of the present invention is a useful compound because it can impart excellent antistatic properties to the acrylic resin.

Hereinafter, the present invention will be specifically described.
The onium salt (1) of the present invention has the formula (1):

((Where Q⁺Represents a nitrogen cation or a phosphorus cation. R¹~ R³Represents an alkyl group having 1 to 6 carbon atoms, R¹And R²May be bonded to each other at the terminal to form a pyrrolidine ring, piperidine ring, pyridine ring, phosphorane ring, phosphorinane ring or phospholine ring. However, when forming a pyridine ring or a phospholine ring, R³Does not exist. R⁴Represents an alkyl group having 1 to 4 carbon atoms. D is CH₂, CH (CH₃) Or CH (CH₃) CH₂Indicates. E represents NH or a sulfur atom. m is an integer of 0 to 3, and n is an integer of 1 to 4. ) Represents a quaternary onium cation. A⁻Represents an anion).
R in formula (1)¹~ R³Is an alkyl group having 1 to 6 carbon atoms, which may be linear or branched, and is preferably a linear alkyl group. Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like can be mentioned, and a linear alkyl group having 1 to 4 carbon atoms is preferred, and Particularly preferred. R¹And R²And may be bonded to each other at the terminal to form a pyrrolidine ring, piperidine ring, pyridine ring, phosphorane ring, phosphorinane ring or phospholine ring. However, when forming a pyridine ring or a phospholine ring, R³Does not exist. R⁴Represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. D is CH₂, CH (CH₃) Or CH (CH₃) CH₂Indicates. E represents NH or a sulfur atom. m is an integer of 0 to 3, preferably 0 to 2. n is an integer of 1 to 4, preferably 1 to 3. A⁻Represents an anion and (CF₃SO₂)₂N⁻, (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻, CH₃(CH₂)₁₀CH₂C₆H₄SO₃ ⁻, CH₃C₆H₄SO₃ ⁻Or Cl⁻Is preferred.
Specific examples of the onium salt (1) include N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}}-N, N, N, -trimethylammonium bis (trifluoromethanesulfonyl) imide, N- { (3-Trimethoxysilylpropyl) carbamoyloxyethyl)}-N-ethyl-N, N-dimethylammonium bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}- N, N-dimethyl-N-propyl-ammonium bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-butyl-N, N-dimethylammonium bis ( Trifluoromethanesulfonyl) imide, N- (3-Trimethoxysilylpropyl) carbamoyloxyethyl)}-N, N-dimethyl-N-pentyl-ammonium bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} -N-hexyl-N, N-dimethylammonium bis (trifluoromethanesulfonyl) imide, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N, -trimethylammonium bis (trifluoro) Lomethanesulfonyl) imide, N-{(3-tripropoxysilylpropyl) carbamoyloxyethyl)}-N, N, N, -trimethylammonium bis (trifluoromethanesulfonyl) imide, N-{(3-tributoxysilylpropyl) ) Carba Yloxyethyl)}-N, N, N, -trimethylammonium = bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium = Tetrafluoroborate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium = tetrafluoroborate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} -N, N, N-trimethylammonium = hexafluorophosphate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium = hexafluorophosphate, N-{(3- Trimethoxysilylpro Pyll) carbamoyloxyethyl)}-N, N, N-trimethylammonium = bisfluorosulfonylimide, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium = bisfluoro Sulfonylimide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium = p-toluenesulfonate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl) } -N, N, N-trimethylammonium = p-toluenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium = p-dodecylbenzenesulfonate, N-{(3-triethoxy Rylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium = p-dodecylbenzenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium = Chloride, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium chloride
N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl-N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-Trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N-ethyl-N, N-dimethylammonium bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-trimethoxy Silylpropylamino) -1-oxopropoxy} ethyl] -N, N-dimethyl-N-propylammonium = bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-trimethoxysilylpropylamino)- 1-oxopropoxy} ethyl] -N-butyl-N, N-dimethylammonium bis (tri Fluoromethanesulfonyl) imide, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N-dimethyl-N-pentyl-ammonium bis (trifluoromethanesulfonyl) Imido, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N-dimethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N- [ 2- {3- (3-triethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3 -Tripropoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N- Limethylammonium bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-tributoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoro) Romethanesulfonyl) imide, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = tetrafluoroborate, N- [2- { 3- (3-Triethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = tetrafluoroborate, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = hex Safluorophosphate, N- [2- {3- (3-triethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = hexafluorophosphate, N- [2- {3 -(3-Trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = bisfluorosulfonylimide, N- [2- {3- (3-triethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bisfluorosulfonylimide, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N , N, N-trimethylammonium = p-toluenesulfonate, N- [2- {3- (3-to Methoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = p-toluenesulfonate, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxo Propoxy} ethyl] -N, N, N-trimethylammonium = p-dodecylbenzenesulfonate, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N , N-trimethylammonium = p-dodecylbenzenesulfonate, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium chloride, N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} e Le] -N, N, N-trimethylammonium = chloride,
N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = bis (trifluoromethanesulfonyl) imide, N- [2- {3 -(3-Trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N-ethyl-N, N-dimethylammonium bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-tri Methoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N-dimethyl-N-propylammonium = bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N-butyl-N, N-dimethylammonium bis (trifluoro Methanesulfonyl) imide, N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N-dimethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N-dimethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-Triethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-tri Propoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammo Um = bis (trifluoromethanesulfonyl) imide, N- [2- {3- (3-tributoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = bis (trifluoromethanesulfonyl) ) Imide, N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = tetrafluoroborate, N- [2- {3- (3-Triethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = tetrafluoroborate, N- [2- {3- (3-trimethoxysilylpropylthio) -1 -Oxopropoxy} ethyl] -N, N, N-trimethylammonium = hexafluorophosphate, N- [2- {3- (3-triethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = tetrafluoroborate, N- [2- {3- (3- Trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = hexafluorophosphate, N- [2- {3- (3-triethoxysilylpropylthio) -1-oxopropoxy } Ethyl] -N, N, N-trimethylammonium = hexafluorophosphate, N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethyl Ammonium = bisfluorosulfonylimide, N- [2- {3- (3-triethoxysilylpropylthio) -1- Xoxopropoxy} ethyl] -N, N, N-trimethylammonium bisfluorosulfonylimide, N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N, -trimethylammonium = p-toluenesulfonate, N- [2- {3- (3-triethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium = p-toluene Sulfonate, N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N, -trimethylammonium = p-dodecylbenzenesulfonate, N- [2 -{3- (3-triethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethyl Ammonium = p-dodecylbenzenesulfonate, N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N, -trimethylammonium chloride, N- [ 2- {3- (3-triethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium chloride,
N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = bis (trifluoromethanesulfonyl) imide, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = bis (trifluoromethanesulfonyl) Imido, N-{(3-tripropoxysilylpropyl) carbamoyloxyethyl)} pyridinium = bis (trifluoromethanesulfonyl) imide, N-{(3-tributoxysilylpropyl) carbamoyloxyethyl)} pyridinium = bis (trifluoromethane Sulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = tetrafluoroborate, N-{(3-triethoxysilylpropyl) carbamoyl Xylethyl)} pyridinium = tetrafluoroborate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = hexafluorophosphate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = hexa Fluorophosphate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = bisfluorosulfonylimide, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = bisfluorosulfonylimide, N -{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = p-toluenesulfonate, N-{(3-triethoxysilylpropyl) carbamoyloxye )} Pyridinium = p-toluenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = p-dodecylbenzenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl) } Pyridinium = p-dodecylbenzenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} pyridinium chloride, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} pyridinium chloride,
N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N -Ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, N-{( 3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-butylpyrrolidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-pentylpyrrolidi Ni-bis Trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, N-{(3-triethoxysilylpropyl) carbamoyl Oxyethyl)}-N-methylpyrrolidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-tripropoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = bis (trifluoromethanesulfonyl) Imido, N-{(3-tributoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl )}-N-methylpyrrolidinium = tetrafluoroborate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = tetrafluoroborate, N-{(3-trimethoxy Silylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = hexafluorophosphate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = hexafluorophosphate, N- {(3-Trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = bisfluorosulfonylimide, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = Bisfluorosulfoni Luimide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = p-toluenesulfonate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N -Methylpyrrolidinium = p-toluenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = p-dodecylbenzenesulfonate, N-{(3-tri Ethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium = p-dodecylbenzenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpyrrolidinium chloride N-{(3-triethoxysilylpropyl) carba Yl oxy-ethyl)} - N-methyl-pyrrolidinium = chloride,
N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N -Ethylpiperidinium bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide, N-{( 3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-butylpiperidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-pentylpiperidi Ni-bis Trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-hexylpiperidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-triethoxysilylpropyl) carbamoyl Oxyethyl)}-N-methylpiperidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-tripropoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = bis (trifluoromethanesulfonyl) Imido, N-{(3-tributoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = bis (trifluoromethanesulfonyl) imide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl )}-N-methylpiperidinium = tetrafluoroborate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = tetrafluoroborate, N-{(3-trimethoxy Silylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = hexafluorophosphate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = hexafluorophosphate, N- {(3-Trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = bisfluorosulfonylimide, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = Bisfluorosulfoni Luimide, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = p-toluenesulfonate, N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N -Methylpiperidinium = p-toluenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = p-dodecylbenzenesulfonate, N-{(3-tri Ethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium = p-dodecylbenzenesulfonate, N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-N-methylpiperidinium chloride N-{(3-triethoxysilylpropyl) carba Yl oxy-ethyl)} - N-methyl-piperidinium = chloride,
P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = bis (trifluoromethanesulfonyl) imide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)} -P-ethyl-P, P-dimethylphosphonium bis (trifluoromethanesulfonyl) imide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P, P-dimethyl-P-propylphosphonium bis ( Trifluoromethanesulfonyl) imide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-butyl-P, P-dimethylphosphonium bis (trifluoromethanesulfonyl) imide, P-{(3-trimethoxy Silylpropyl) cal Moyloxyethyl)}-P, P-dimethyl-P-pentylphosphonium = bis (trifluoromethanesulfonyl) imide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-hexyl-P, P- Dimethylphosphonium = bis (trifluoromethanesulfonyl) imide, P-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = bis (trifluoromethanesulfonyl) imide, P-{(3 -Trimethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = tetrafluoroborate, P-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = Tetrafu Oroborate, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = hexafluorophosphate, P-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-P , P, P-trimethylphosphonium = hexafluorophosphate, P-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = hexafluorophosphate, P-{(3-trimethoxy Silylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = bisfluorosulfonylimide, P-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = bisfur Orosulfonylimide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = p-toluenesulfonate, P-{(3-triethoxysilylpropyl) carbamoyloxyethyl )}-P, P, P-tetramethylphosphonium = p-dodecylbenzenesulfonate, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium = p-dodecylbenzene Sulfonate, P-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium chloride, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P, P, P-trimethylphosphonium chloride
P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphosphoranium = bis (trifluoromethanesulfonyl) imide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P -Methylphosphoranium = tetrafluoroborate, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphosphoranium = hexafluorophosphate, P-{(3-trimethoxysilylpropyl) carbamoyl Oxyethyl)}-P-methylphosphoranium = bisfluorosulfonylimide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphosphoranium = p-toluenesulfonate, P- { (3-Trimethoxysilylop Pills) carbamoyloxy-ethyl)} - P- methyl Hosuhosu Hora hexafluorophosphate = p-dodecylbenzene sulfonate, P - {(3- trimethoxysilylpropyl) carbamoyloxy-ethyl)} - P- methyl Hosuhosu Hora hexafluorophosphate = chloride,
P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphospholinarium bis (trifluoromethanesulfonyl) imide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P -Methylphospholinarium = tetrafluoroborate, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphospholinarium = hexafluorophosphate, P-{(3-trimethoxysilylpropyl) carbamoyl Oxyethyl)}-P-methylphospholinarium = bisfluorosulfonylimide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphospholinarium = p-toluenesulfonate, P- { (3-trimetoki Silylpropyl) carbamoyloxyethyl)}-P-methylphospholinarium = p-dodecylbenzenesulfonate, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphospholinarium = p-dodecyl Benzene chloride,
P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphosphorinium bis (trifluoromethanesulfonyl) imide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P -Methylphosphorinium = tetrafluoroborate, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphosphorinium = hexafluorophosphate, P-{(3-trimethoxysilylpropyl) carbamoyl Oxyethyl)}-P-methylphosphorinium = bisfluorosulfonylimide, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphosphorinium = p-toluenesulfonate, P- { (3-Trimethoxysilylop Pill) carbamoyloxyethyl)}-P-methylphosphorinium = p-dodecylbenzenesulfonate, P-{(3-trimethoxysilylpropyl) carbamoyloxyethyl)}-P-methylphosphorinium chloride, and the like. However, the present invention is not limited to these.
The onium salt (1) of the present invention can be produced by various methods. The typical method is demonstrated in the following Reaction formula 1 and Reaction formula 2. In the reaction formula, Q⁺, R¹~ R⁴, E, n and A⁻Is the same as above, Q is a nitrogen atom or a phosphorus atom, X⁻Represents a halogen ion, and M represents a metal atom.
Reaction formula 1:

A compound represented by formula (2) (hereinafter referred to as compound (2)) and a haloalkyl alcohol represented by formula (3) (hereinafter referred to as haloalkyl alcohol (3)) are subjected to a quaternization reaction to form the formula ( 4) is produced (hereinafter referred to as onium = halides (4)). Next, the onium salt (6) can be produced by an ion exchange reaction between the onium halide (4) and the alkali metal salt represented by the formula (5) (hereinafter referred to as alkali metal salt (5)). Next, by reacting onium = halides (4) or onium salt (6) with trialkoxysilylalkyl isocyanate represented by formula (7) (hereinafter referred to as trialkoxysilylalkyl isocyanate (7)), onium Salt (1a) can be produced.
In Reaction Scheme 1, compound (2) includes N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, N-ethylpyrrolidine, N-ethylpiperidine, N-ethylmorpholine, N-propylpyrrolidine, N-propyl. Piperidine, N-propylmorpholine, N-isopropylpyrrolidine, N-isopropylpiperidine, N-isopropylmorpholine, N-butylpyrrolidine, N-butylpiperidine, N-butylmorpholine, N-pentylpyrrolidine, N-pentylpiperidine, N-pentyl Morpholine, N-hexylpyrrolidine, N-hexylpiperidine, N-hexylmorpholine, N-methyl-2-methylpyrrolidine, N-methyl-2-methylpiperidine, N-methyl-2-methylmorpholine, N-methyl-3- Methylpi Lysine, N-methyl-3-methylpiperidine, N-methyl-3-methylmorpholine, N-methyl-4-methylpiperidine, N-methyl-2-ethylpyrrolidine, N-methyl-2-propylpyrrolidine, N-methyl 2-isopropylpyrrolidine, N-methyl-2-butylpyrrolidine, N-methyl-2-isobutylpyrrolidine, N-methyl-2-sec-butylpyrrolidine, N-methyl-2-tert-butylpyrrolidine,
Pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, 2-propyl Pyridine, 3-propylpyridine, 4-propylpyridine, 2-isopropylpyridine, 3-isopropylpyridine, 4-isopropylpyridine, 2-butylpyridine, 3-butylpyridine, 4-butylpyridine, 2-isobutylpyridine, 3-isobutyl Pyridine, 4-isobutylpyridine, 2-sec-butylpyridine, 3-sec-butylpyridine, 4-sec-butylpyridine, 2-tert-butylpyridine, 3-tert-butylpyridine, 4-tert-butylpyridine, P , P, P-trimmer Ruphosphine, P, P, P-triethylphosphine, P, P, P-tripropylphosphine, P, P, P-tributylphosphine, P, P, P-tripentylphosphine, P, P, P-trihexylphosphine , P-methylphosphorane, P-ethylphosphorane, P-methylphosphorinane, P-ethylphosphorinane, P-methylphosphorin, P-ethylphosphorin and the like.
Examples of the haloalkyl alcohols (3) include 2-chloroethanol, 2-bromoethanol, 2-iodoethanol and the like.
Examples of the alkali metal salt (5) include bis (trifluoromethanesulfonyl) imide lithium, bis (trifluoromethanesulfonyl) imide sodium, bis (trifluoromethanesulfonyl) imide potassium, lithium tetrafluoroborate, sodium tetrafluoroborate, tetrafluoro Potassium borate, lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, lithium phenol sulfonate, sodium phenol sulfonate, potassium phenol sulfonate, sodium p-toluene sulfonate, sodium p-dodecylbenzene sulfonate, etc. Can be mentioned.
Examples of trialkoxysilylalkyl isocyanates (7) include trimethoxysilylmethyl isocyanate, trimethoxysilylethyl isocyanate, trimethoxysilylpropyl isocyanate, trimethoxysilylbutyl isocyanate, triethoxysilylmethyl isocyanate, triethoxysilylpropyl isocyanate, Triethoxysilylbutyl isocyanate, triethoxysilylbutyl isocyanate, tripropoxysilylmethyl isocyanate, tripropoxysilylethyl isocyanate, tripropoxysilylpropyl isocyanate, tripropoxysilylbutyl isocyanate, tributoxysilylmethyl isocyanate, tributoxysilylethyl isocyanate, tributoxy Cyril Pro Le isocyanate include tributoxysilyl butyl isocyanate.
The quaternization reaction between the compound (2) and the haloalkyl alcohol (3) may or may not use a solvent. Examples of the solvent when using the solvent include alcohols such as methanol, ethanol and 2-propanol, acetonitrile, ethyl acetate, tetrahydrofuran, dimethylformamide and the like.
The amount of the haloalkyl alcohol (3) used may be 0.7 mol or more, preferably 0.9 to 1.5 mol, relative to 1 mol of the compound (2).
The amount of the alkali metal salt (5) used in the ion exchange reaction is usually 0.8 mol or more, preferably 0.9 mol to 1.2 mol, based on 1 mol of the onium halide (4). The amount is preferably 1 to 1.05 mol.
The ion exchange reaction is usually performed in a solvent. Examples of the solvent include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol and 2-propanol, acetonitrile, ethyl acetate, tetrahydrofuran and dimethylformamide. The amount used is not particularly limited, but is usually 10 parts by weight or less, preferably 1 to 10 parts by weight, particularly preferably 2 to 6 parts by weight, based on 1 part by weight of onium halides (4).
The order of mixing the onium = halides (4), the alkali metal salt (5) and the solvent is not particularly limited, and the alkali metal salt (5) may be added after mixing the onium = halides (4) and the solvent. The onium halides (4) may be added after mixing the alkali metal salt (5) and the solvent.
The reaction temperature in the ion exchange reaction is usually 10 ° C. or higher, preferably 10 to 60 ° C., particularly preferably 10 to 30 ° C.
In order to separate the onium salt (6) from the reaction solution after completion of the reaction, the solvent and the generated inorganic salt may be removed from the reaction solution. If an inorganic salt is precipitated in the obtained reaction solution, the reaction solution is filtered or washed with water to remove the precipitated inorganic salt, and then combined with unit operations such as concentration, filtration, extraction, etc. (6) can be isolated. In addition, when the inorganic salt is not precipitated in the obtained reaction solution, the reaction solution is concentrated to precipitate the inorganic salt, filtered or washed with water to remove the inorganic salt, and then concentrated, filtered, The onium salt (6) can be isolated by appropriately combining unit operations such as extraction.
The reaction of the obtained onium salt (6) and trialkoxysilylalkyl isocyanate (7) may or may not use a solvent. Examples of the solvent when using the solvent include acetone, acetonitrile, ethyl acetate, tetrahydrofuran, dichloromethane and the like.
The amount of trialkoxysilylalkyl isocyanate (7) used may be 0.7 mol or more, preferably 0.9 to 1.5 mol, per 1 mol of onium salt (6).
As a method for separating the onium salt (1a) from the reaction solution after completion of the reaction, the same method as that for the onium salt (6) can be used.
Reaction formula 2:

An onium salt (hereinafter referred to as onium salt (9)) is obtained by an ion exchange reaction between onium = halides represented by formula (8) (hereinafter referred to as onium = halides (8)) and alkali metal salt (5). Can be manufactured. Next, the onium salt (1b) can be produced by reacting the onium salt (9) with a trialkoxysilylalkyl compound represented by the formula (10) (hereinafter referred to as trialkoxysilylalkyl compound (10)).
In Reaction Formula 2, as onium = halides (8), for example, N- (2-acryloyloxyethyl) -N, N, N-trimethylammonium chloride, N- (2-acryloyloxyethyl) -N, N , N-trimethylammonium bromide, N- (2-acryloyloxyethyl) -N, N, N-trimethylammonium iodide, N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium chloride N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium chloride, N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium bromide, N- (2- (Methacryloyloxyethyl) -N, N, N-trimethylammonium iodide and the like.
Examples of trialkoxysilylalkyl compounds (10) include trialkoxysilylalkylamines and trialkoxysilylalkylthiols. Examples of trialkoxysilylalkylamines include trimethoxysilylmethylamine, trimethoxysilylethylamine, trimethoxysilylpropylamine, trimethoxysilylbutylamine, triethoxysilylmethylamine, triethoxysilylpropylamine, triethoxysilylbutylamine, Triethoxysilylbutylamine, tripropoxysilylmethylamine, tripropoxysilylethylamine, tripropoxysilylpropylamine, tripropoxysilylbutylamine, tributoxysilylmethylamine, tributoxysilylethylamine, tributoxysilylpropylamine, tributoxysilylbutylamine, etc. Can be mentioned.
Examples of trialkoxysilylalkylthiols include trimethoxysilylmethylthiol, trimethoxysilylethylthiol, trimethoxysilylpropylthiol, trimethoxysilylbutylthiol, triethoxysilylmethylthiol, triethoxysilylpropylthiol, triethoxysilyl Butylthiol, Triethoxysilylbutylthiol, Tripropoxysilylmethylthiol, Tripropoxysilylethylthiol, Tripropoxysilylpropylthiol, Tripropoxysilylbutylthiol, Tributoxysilylmethylthiol, Tributoxysilylethylthiol, Tributoxysilylpropylthiol , Tributoxysilylbutylthiol and the like.
The amount of the alkali metal salt (5) used in the ion exchange reaction is usually 0.8 mol or more, preferably 0.9 mol to 1.2 mol, based on 1 mol of the onium halide (8). The amount is preferably 1 to 1.05 mol.
The ion exchange reaction is usually performed in a solvent. Examples of the solvent include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol and 2-propanol, acetonitrile, ethyl acetate, tetrahydrofuran and dimethylformamide. The amount used is not particularly limited, but is usually 10 parts by weight or less, preferably 1 to 10 parts by weight, particularly preferably 2 to 6 parts by weight, based on 1 part by weight of the onium halides (8).
The order of mixing the onium = halides (8), the alkali metal salt (5) and the solvent is not particularly limited, and the alkali metal salt (5) may be added after mixing the onium = halides (8) and the solvent. The onium halides (8) may be added after mixing the alkali metal salt (5) and the solvent.
The reaction temperature in the ion exchange reaction is usually 10 ° C. or higher, preferably 10 to 60 ° C., particularly preferably 10 to 30 ° C.
In order to separate the onium salt (9) from the reaction solution after completion of the reaction, the solvent and the generated inorganic salt may be removed from the reaction solution. If an inorganic salt is precipitated in the obtained reaction solution, the reaction solution is filtered or washed with water to remove the precipitated inorganic salt, and then combined with unit operations such as concentration, filtration, extraction, etc. (9) can be isolated. In addition, when the inorganic salt is not precipitated in the obtained reaction solution, the reaction solution is concentrated to precipitate the inorganic salt, filtered or washed with water to remove the inorganic salt, and then concentrated, filtered, The onium salt (9) can be isolated by appropriately combining unit operations such as extraction.
The reaction of the obtained onium salt (9) and trialkoxysilylalkyl compound (10) may or may not use a solvent. Examples of the solvent when using the solvent include acetone, acetonitrile, ethyl acetate, tetrahydrofuran, dichloromethane and the like.
The amount of trialkoxysilylalkyl compound (10) used may be 0.7 mol or more, preferably 0.9 to 1.5 mol, per 1 mol of onium salt (9).
As a method for separating the onium salt (1b) from the reaction solution after completion of the reaction, the same method as that for the onium salt (9) can be used.
The onium salt (1) thus obtained is mixed with an acrylic resin monomer and an appropriate solvent (for example, ethyl acetate, toluene, etc.) to prepare a solution, and then the solution is applied to the surface of the resin. It can be used as an antistatic agent for acrylic resins by a method such as removing the solvent. In addition, a solution in which a photopolymerization initiator is added to a solution containing an acrylic resin monomer and an onium salt (1) is prepared, and the solution is applied to the surface of the resin and irradiated with ultraviolet rays to charge the acrylic resin. It can be used as an inhibitor, and an acrylic resin composition containing the onium salt (1) can be obtained.

Next, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In the following examples, ¹ H-NMR uses “AL-400” manufactured by JEOL Datum Co., Ltd., and 400 MHz using (CD ₃ ) ₂ CO as a solvent, except when the solvent used is described. Measured with Moreover, the surface resistance value was measured at an applied voltage of 500 V using Hiresta UP (MCP-HT450) manufactured by Mitsubishi Chemical Corporation.
Example 1
Synthesis of N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide

To the reaction vessel, 503.1 g (3.60 mol) of choline chloride, 1086.2 g (3.78 mol) of lithium bis (trifluoromethanesulfonyl) imidate and 1838.9 g of ion-exchanged water were added and stirred at room temperature for 2 hours. After washing twice with ion-exchanged water, dehydration was performed to obtain 949.2 g (yield 68.5%) of 1- (2-hydroxyethyl) -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide. Obtained.
The obtained N- (2-hydroxyethyl) -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide (31.1 g, 80.9 mmol) was dissolved in acetonitrile (31.1 g) to give 3-triethoxysilyl. 20.0 g (80.9 mmol) of propyl isocyanate and 0.24 g (0.38 mmol) of dibutyltin dilaurate were added and reacted at room temperature for 5 hours. Then, it was concentrated and dried to obtain 43.6 g of N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide (yield 85.3). %)Obtained. ¹ H-NMR of the obtained 1-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N, -trimethylammonium bis (trifluoromethanesulfonyl) imide is shown below.
¹ H-NMR δ (ppm): 6.50-6.60 (br, 1H), 4.59 (t, 2H), 3.88 (t, 2H), 3.80 (q, 6H), 3 .41 (s, 9H), 3.05-3.15 (m, 2H), 1.55-1.65 (m, 2H), 1.18 (t, 9H), 1.57 (t, 2H) )
Example 2
Synthesis of N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)} pyridinium bis (trifluoromethanesulfonyl) imide

To the reaction vessel, 240.7 g (3.04 mol) of pyridine, 450.4 g (3.60 mol) of 2-bromoethanol and 1035.6 g of acetonitrile were added and stirred at 80 ° C. for 24 hours. After cooling, washing with acetonitrile, and drying, 522.6 g (yield 84.3%) of N- (2-hydroxyethyl) pyridinium bromide was obtained.
The obtained N- (2-hydroxyethyl) pyridinium bromide 522.4 g (2.56 mol), lithium bis (trifluoromethanesulfonyl) imido acid 771.7 g (2.69 mol), and ion-exchanged water 1357.8 g were added. Stir at room temperature for 2 hours. After washing twice with ion-exchanged water, dehydration was performed to obtain 743.4 g (yield 71.8%) of N- (2-hydroxyethyl) pyridinium bis (trifluoromethanesulfonyl) imide.
39.2 g (97.0 mmol) of the obtained N- (2-hydroxyethyl) pyridinium bis (trifluoromethanesulfonyl) imide was dissolved in 39.2 g of acetonitrile, and 24.0 g (97.97) of 3-triethoxysilylpropyl isocyanate was obtained. 0 mmol) and 0.31 g (0.49 mmol) of dibutyltin dilaurate were added and reacted at room temperature for 5 hours. Then, it concentrated and dried and obtained 61.0g (yield 73.7%) of N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)} pyridinium = bis (trifluoromethanesulfonyl) imide. ¹ H-NMR of the obtained N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)} pyridinium bis (trifluoromethanesulfonyl) imide is shown below.
¹ H-NMR δ (ppm): 9.21 (d, 2H), 8.82 (t, 1H), 8.34 (t, 2H), 8.40-8.55 (br, 1H), 5 .25 (t, 2H), 4.69 (t, 2H), 3.85 (q, 6H), 3.09 (q, 2H), 1.50-1.60 (m, 2H), 1. 21 (t, 9H), 0.68 (t, 2H)
Example 3
Synthesis of N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide

To the reaction vessel, add [2- (acryloyloxy) ethyl] trimethylammonium chloride 720.5 g (3.72 mol), 1090.1 g (3.40 mol) of lithium bis (trifluoromethanesulfonyl) imidate and 995.0 g of ion-exchanged water. And stirred at room temperature for 3 hours. After washing twice with ion-exchanged water, dehydration was performed to obtain 1527.0 g (yield 93.6%) of [2- (acryloyloxy) ethyl] trimethylammonium bis (trifluoromethanesulfonyl) imide.
58.7 g (133.9 mmol) of the obtained [2- (acryloyloxy) ethyl] trimethylammonium bis (trifluoromethanesulfonyl) imide was dissolved in 58.7 g of acetonitrile, and 24.0 g of 3-trimethoxysilylpropylamine (133 .9 mmol) was added and reacted at room temperature for 5 hours. Then, it was concentrated and dried to give N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide. 80.8 g (yield 97.6%) was obtained. ¹ H-NMR of the obtained N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide Is shown below.
¹ H-NMR δ (ppm): 4.65 (t, 2H), 3.95 (t, 2H), 3.51 (s, 9H), 3.45 (s, 9H), 2.83 (t , 2H), 2.50-2.60 (m, 4H), 1.45-1.55 (m, 2H), 0.60 (t, 2H)
Example 4
Synthesis of N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide

In the same manner as in Example 3, [2- (acryloyloxy) ethyl] trimethylammonium bis (trifluoromethanesulfonyl) imide was obtained.
53.6 g (122.3 mmol) of the obtained [2- (acryloyloxy) ethyl] trimethylammonium bis (trifluoromethanesulfonyl) imide was dissolved in 46.6 g of acetonitrile, and 24.0 g of 3-trimethoxysilylpropanethiol (122 .3 mmol) was added and reacted at room temperature for 5 hours. Then, it was concentrated and dried to give N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide. 74.9 g (yield 96.4%) was obtained. ¹ H-NMR of the obtained N- [2- {3- (3-trimethoxysilylpropylthio) -1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide Is shown below.
¹ H-NMR δ (ppm): 4.68 (t, 2H), 3.95 (t, 2H), 3.51 (s, 9H), 3.45 (s, 9H), 2.75-2 .80 (m, 2H), 2.65-2.75 (m, 2H), 2.55 (t, 2H), 1.60-1.70 (m, 2H), 0.70 (t, 2H) )
Example 5
Synthesis of N- [2- {3- (3-trimethoxysilylpropylthio) -2-methyl-1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide

To the reaction vessel were added 798.2 g (3.84 mol) of methacroylcholine chloride, 1125.8 g (3.92 mol) of lithium bis (trifluoromethanesulfonyl) imidoate, and 2141.4 g of ion-exchanged water, and the mixture was stirred at room temperature for 3 hours. . After washing twice with ion-exchanged water, dehydration was performed to obtain 1703.5 g (yield 96.3%) of methacryloylcholine bis (trifluoromethanesulfonyl) imide.
55.3 g (122.3 mmol) of the obtained methacryloylcholine bis (trifluoromethanesulfonyl) imide was dissolved in 47.7 g of acetonitrile, and 24.1 g (122.3 mmol) of 3-trimethoxysilylpropanethiol was added to room temperature. For 5 hours. Then, it was concentrated and dried to give N- [2- {3- (3-trimethoxysilylpropylthio) -2-methyl-1-oxopropoxy} ethyl] -trimethylammonium bis (trifluoromethanesulfonyl) imide. 8 g (yield 96.7%) was obtained. Of the resulting N- [2- {3- (3-trimethoxysilylpropylthio) -2-methyl-1-oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide ¹ H-NMR is shown below.
¹ H-NMR δ (ppm): 4.69 (t, 2H), 3.98 (t, 2H), 3.53 (s, 9H), 3.46 (s, 9H), 2.75-2 .85 (m, 2H), 2.70-2.80 (m, 1H), 2.50-2.60 (t, 2H), 1.60-1.70 (m, 2H), 1.22 (D, 3H), 0.80 (t, 2H)
Example 6
Synthesis of N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl} pyridinium = hexafluorophosphate

N- (2-hydroxyethyl) pyridinium bromide 75.9 g (0.37 mol), potassium hexafluorophosphate 69.9 g (0.38 mol), methanol 45.6 g, acetonitrile synthesized by the method described in Example 2 182.4 g was added and stirred at room temperature for 24 hours. The precipitated solid was filtered off and concentrated. After separating the precipitated solid by filtration, 68.8 g (0.37 mol) of potassium hexafluorophosphate was added and stirred at room temperature for 4 hours. The solid was separated by filtration, concentrated and dried to obtain 66.2 g of N- (2-hydroxyethyl) pyridinium = hexafluorophosphate (yield 72.7%).
The obtained N- (2-hydroxyethyl) pyridinium = hexafluorophosphate 28.4 g (0.11 mol) was dissolved in acetonitrile 28.6 g, 3-trimethoxysilylpropyl isocyanate 23.1 g (0.11 mol), and 0.35 g (0.55 mmol) of dibutyltin dilaurate was added and reacted at room temperature for 5 hours. Then, after concentration, washing with 27.3 g of toluene, and drying, 44.8 g of N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl} pyridinium = hexafluorophosphate (yield 89.6%) )Obtained. ¹ H-NMR of the obtained N-{(3-trimethoxysilylpropyl) carbamoyloxyethyl} pyridinium = hexafluorophosphate is shown below.
¹ H-NMR δ (ppm): 9.18 (d, 2H), 8.82 (t, 1H), 8.32 (t, 2H), 6.45-6.55 (br, 1H), 5 .13 (t, 2H), 4.69 (t, 2H), 3.57 (s, 9H), 3.06 (q, 2H), 1.50-1.65 (m, 2H), 1. 61 (t, 2H)
Example 7
Synthesis of P-{(3-triethoxysilylpropyl) carbamoyloxyethyl} -P, P, P-tributylphosphonium bis (trifluoromethanesulfonyl) imide

After taking 129.7 g (1.04 mol) of 2-bromoethanol in a reaction vessel and heating to 80 ° C., 200.0 g (0.99 mol) of tributylphosphine was added dropwise over 1 hour with stirring, and the mixture was stirred at 80 ° C. for 1 hour. Stirring was continued overnight. The resulting reaction solution was cooled to room temperature and washed twice with 200 ml of hexane. To the reaction solution after washing, 100 g of ion-exchanged water and 10 g of activated carbon (activated charcoal Y made by Futamura Chemical Co., Ltd.) were added and stirred at 50 ° C. for 1 hour. The activated carbon was removed by filtration, and tributyl (2-hydroxyethyl) phosphonium. = An aqueous solution of bromide was obtained.
To the obtained aqueous solution was added 447.50 g (1.19 mol) of a 76.1% aqueous solution of bis (trifluoromethanesulfonyl) imido acid, and the mixture was stirred at room temperature for 2 hours. When the obtained reaction liquid was allowed to stand, it was separated into two layers. Therefore, the oil layer was obtained by liquid separation, and the obtained oil layer was separated and washed twice with 100 g of ion-exchanged water. The obtained oil layer was concentrated and dried at 50 ° C. to obtain 287.5 g (yield 55.1%) of tributyl (2-hydroxyethyl) phosphonium = bis (trifluoromethanesulfonyl) imide. ¹ H-NMR of the obtained tributyl (2-hydroxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide is shown below.
¹ H-NMR (CDCl ₃ ) δ (ppm): 4.00 (td, 2H), 3.29 (t, 1H), 2.42 (m, 2H), 2.16 (m, 6H), 1 .51 (m, 12H), 0.97 (t, 9H)
In a reaction vessel, take 50.0 g (0.09 mol) of tributyl (2-hydroxyethyl) phosphonium = bis (trifluoromethanesulfonyl) imide, 50.0 g of acetonitrile, and 0.03 g (0.05 mmol) of dibutyltin dilaurate at room temperature. While stirring at 23.5 g (0.09 mol) of 3-triethoxysilylpropyl isocyanate was added dropwise and reacted at room temperature for 5 hours. The obtained reaction solution was washed with 150 mL of hexane, the obtained reaction solution was concentrated and dried at 50 ° C., and P-{(3-triethoxysilylpropyl) carbamoyloxyethyl} -P, P, P-tributylphosphonium. = 69.6 g of bis (trifluoromethanesulfonyl) imide (yield 94.8%). ¹ H-NMR of the obtained P-{(3-triethoxysilylpropyl) carbamoyloxyethyl} -P, P, P-tributylphosphonium bis (trifluoromethanesulfonyl) imide is shown below.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.54 (t, 1H), 4.39 (td, 2H), 3.82 (q, 6H), 3.16 (q, 2H), 2 .58 (m, 2H), 2.18 (m, 6H), 1.62 (m, 2H), 1.51 (m, 12H), 1.22 (m, 9H), 0.97 (t, 9H), 0.61 (t, 2H)
Example 8
Synthesis of N-{(3-triethoxysilylpropyl) carbamoyloxyethyl}}-N, N, N-trimethylammonium chloride

A reaction vessel was charged with 5.01 g (30 mmol) of choline chloride, 10.0 g of acetonitrile, 0.01 g (0.02 mmol) of dibutyltin dilaurate and 8.88 g (30 mmol) of 3-triethoxysilylpropyl isocyanate, and in a nitrogen atmosphere, Stir at 80 ° C. for 14 hours. The obtained reaction solution was concentrated and dried to obtain 13.68 g of N-{(3-triethoxysilylpropyl) carbamoyloxyethyl}}-N, N, N-trimethylammonium chloride (yield 98.7%). ) ¹ H-NMR of the obtained N-{(3-triethoxysilylpropyl) carbamoyloxyethyl}}-N, N, N-trimethylammonium chloride is shown below.
¹ H-NMR (DMSO-d6) δ (ppm): 7.55-7.40 (1H, brs), 4.45-4.30 (2H, brs), 3.73 (q, 6H), 3 .68-3.55 (brt, 2H), 3.14 (s, 9H), 3.00-2.90 (brt, 2H), 1.48-1.40 (m, 2H,),. 52 (t, 2H)
Application example 1
N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N obtained in Example 1 was used as an acrylic resin by using 100 parts by weight of acrylic resin adhesive SK Dyne 909A manufactured by Soken Chemical Co., Ltd. 5 parts by weight of N, N, -trimethylammonium bis (trifluoromethanesulfonyl) imide and 100 parts by weight of ethyl acetate as a diluent were added and dissolved to prepare a coating solution. This coating solution was coated on a polyester film using a bar coater so that the thickness of the pressure-sensitive adhesive when dried was about 10 μm, and heated and dried at 80 ° C. for 3 minutes to prepare a test piece. The obtained test piece was held in an atmosphere of 25 ° C. and 40% RH for 2 hours, and then the surface resistance value of the adhesive of the test piece was measured in an atmosphere of 25 ° C. and 40% RH. The results are shown in Table 1.
Application examples 2-8
Instead of N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N, -trimethylammonium bis (trifluoromethanesulfonyl) imide of Application Example 1, the onium salts of the present invention shown in Table 1 A test piece was prepared in the same manner as in Application Example 1 except that was used, and the surface resistance value of the adhesive of the test piece was measured in the same manner as in Application Example 1. The results are shown in Table 1.
Comparative application example 1
Similar to Application Example 1 except that N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N, -trimethylammonium bis (trifluoromethanesulfonyl) imide of Application Example 1 was not used. A test piece was prepared, and the surface resistance value of the adhesive of the test piece was measured in the same manner as in Application Example 1. The results are shown in Table 1.
Comparative application example 2
In place of N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N, -trimethylammonium bis (trifluoromethanesulfonyl) imide in Application Example 1, described in JP2010-248165A A test piece was prepared in the same manner as in Application Example 1 except that N- (3-trimethoxysilylpropyl) pyridinium bis (trifluoromethanesulfonyl) imide synthesized by the above-described method was used. The surface resistance was measured in the same manner as in Application Example 1. The results are shown in Table 1.

From the results shown in Table 1, it was found that the acrylic resin pressure-sensitive adhesive containing the onium salt of the present invention has a low surface resistance value.
Application examples 9 and 10
Dipentaerythritol hexaacrylate (A-DPH: Shin-Nakamura Chemical Co., Ltd.) 0.50 g, Pentaerythritol triacrylate (A-TMN-3LM-N: Shin-Nakamura Chemical Co., Ltd.) 1.50 g, trimethylolpropane 0.50 g of triacrylate (A-TMPT: manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.23 g of onium salt (1) shown in Table 2 and colloidal silica isopropyl alcohol dispersion (IPA-ST: silica solid content 30 wt%, (Made by Nissan Chemical Industries, Ltd.) 1.80 g is mixed, and 2.16 g of isopropyl alcohol and 0.15 g of 2-hydroxy-2-methylpropiophenone as a photopolymerization initiator are mixed with the resulting mixture to obtain an acrylic resin. A monomer and photopolymerization agent-containing coating solution was prepared.
The resulting coating solution was coated on a 100 μm thick polyester film using a bar coater so that the coating thickness when dried was about 5 μm. Acrylic resin hard coat film was prepared by irradiating ultraviolet rays from a high pressure mercury UV lamp (120 W / cm) from the coating film side under the condition of an integrated light quantity of about 400 mJ / cm ² and curing treatment, and the obtained hard coat film The surface resistance value of was measured. The surface resistance value was 25 ± 2 ° C., and the humidity was 50 ± 5%. The results are shown in Table 2.
Comparative application example 3
Hard coat films were prepared in the same manner as in Application Examples 9 and 10 except that N- (3-trimethoxysilylpropyl) pyridinium bis (trifluoromethanesulfonyl) imide was used as the onium salt. The surface resistance value of the obtained hard coat film was measured. The results are shown in Table 2.

From the results in Table 2, it was found that the acrylic resin hard coat film prepared by using the hard coat liquid containing the onium salt of the present invention showed a low surface resistance value.

Claims

Formula (1):

(In the formula, Q + represents a nitrogen cation or a phosphor cation. R 1 to R 3 represent an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 are bonded to each other at the terminal to form a pyrrolidine ring or a piperidine ring. , A pyridine ring, a phosphorane ring, a phosphorinane ring, or a phospholine ring, provided that a pyridine ring or a phospholine ring is not present, R 3 is not present, and R 4 is an alkyl group having 1 to 4 carbon atoms. D represents CH 2 , CH (CH 3 ) or CH (CH 3 ) CH 2 , E represents NH or a sulfur atom, m represents an integer of 0 to 3, and n represents an integer of 1 to 4. ) Represents a quaternary onium cation, and A − represents an anion.
The onium salt according to claim 1, wherein Q + is a nitrogen cation.
The onium salt according to claim 1, wherein Q + is a phosphorus cation.
A - onium salt according to any one of claims 1 to 3, which is a fluorine-containing anion or a halide ion.
A - is (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, BF 4 -, PF 6 - or Cl - onium salt according to any one of claims 1 to 3, which is.
A - is CH 3 (CH 2) 10 CH 2 C 6 H 4 SO 3 - onium salt according to any one of the is claims 1 to 3 - or CH 3 C 6 H 4 SO 3 .
An antistatic agent for acrylic resin, comprising at least one onium salt according to any one of claims 1 to 6.
An acrylic resin composition comprising at least one antistatic agent according to claim 7.