WO2023008579A1 - 両性イオン化合物並びにブロックイソシアネート用ブロック剤解離触媒、該ブロック剤解離触媒を含有するブロックイソシアネート組成物、熱硬化性樹脂組成物、硬化物及びその製造法、並びにカーボネート化合物 - Google Patents

両性イオン化合物並びにブロックイソシアネート用ブロック剤解離触媒、該ブロック剤解離触媒を含有するブロックイソシアネート組成物、熱硬化性樹脂組成物、硬化物及びその製造法、並びにカーボネート化合物 Download PDF

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WO2023008579A1
WO2023008579A1 PCT/JP2022/029390 JP2022029390W WO2023008579A1 WO 2023008579 A1 WO2023008579 A1 WO 2023008579A1 JP 2022029390 W JP2022029390 W JP 2022029390W WO 2023008579 A1 WO2023008579 A1 WO 2023008579A1
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substituted
hydrocarbon group
bond
formula
group
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English (en)
French (fr)
Japanese (ja)
Inventor
滉哉 菅原
元嘉 宮城
光貴 小野田
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Koei Chemical Co Ltd
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Koei Chemical Co Ltd
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Priority to US18/291,355 priority Critical patent/US20250122322A1/en
Priority to KR1020247005790A priority patent/KR20240039148A/ko
Priority to JP2023538650A priority patent/JPWO2023008579A1/ja
Priority to CN202280053413.9A priority patent/CN117769574A/zh
Publication of WO2023008579A1 publication Critical patent/WO2023008579A1/ja
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
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    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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    • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
    • C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
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    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1841—Catalysts containing secondary or tertiary amines or salts thereof having carbonyl groups which may be linked to one or more nitrogen or oxygen atoms
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms

Definitions

  • the present invention relates to a zwitterionic compound, a blocking agent dissociation catalyst for blocked isocyanate, a blocked isocyanate composition containing the blocking agent dissociation catalyst, a thermosetting resin composition, a cured product and a method for producing the same, and a carbonate compound.
  • a blocked isocyanate is a compound obtained by reacting an isocyanate with a blocking agent having an active hydrogen group capable of reacting with the isocyanate group.
  • the blocked isocyanate is inactivated at room temperature by blocking the highly reactive isocyanate group with a blocking agent, and has the property that the blocking agent is dissociated by heating to regenerate the isocyanate group. Due to such properties, blocked isocyanates are superior in storage stability and easy to handle as compared with isocyanates. Taking advantage of this feature, it is widely used in applications such as coatings and adhesives as a raw material for one-part polyurethane resins obtained by curing a polyol component and an isocyanate component, for example.
  • blocked isocyanate requires that the blocking agent be dissociated by heating, but in recent years, lowering the dissociation temperature of the blocking agent is required in order to save energy and reduce costs. Attempts have therefore been made to use a catalyst to lower the dissociation temperature of the blocking agent of the blocked isocyanate.
  • a metal organic acid salt is known as such a blocking agent dissociation catalyst.
  • Organic tin catalysts such as dibutyltin dilaurate are often used as metal organic acid salts (Non-Patent Document 1).
  • the present inventors have made intensive studies to solve the above problems, and when the zwitterionic compound represented by formula (1) was used as a blocked dissociation catalyst for blocked isocyanates, it exhibited excellent low-temperature dissociation properties. The inventors have found that and completed the present invention.
  • the present invention provides the following zwitterionic compound, blocking agent dissociation catalyst for blocked isocyanate, blocked isocyanate composition containing the blocking agent dissociation catalyst, thermosetting resin composition, cured product, and production method thereof.
  • R 1 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • X represents a nitrogen atom or an oxygen atom.
  • a represents 0 or 1.
  • R 2 is a substituted or unsubstituted divalent hydrocarbon group
  • B 1 is represented by formula (2) or formula (3).
  • n is an integer of 1 or more.
  • A is an n-valent substituted or unsubstituted hydrocarbon group.
  • R 8 represents a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2 ;
  • R 7 and R 9 are the same or different and represent a bond to R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 , R 7 , R 8 , and R 9 are a bond to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 , R 7 , R 8 and R 9 may be partially or entirely bonded together to form a ring structure, and partially or entirely of R 6 , R 7 , R 8 and R 9 may be mutually bonded to form a ring structure where the group of R 6 , R 7 , R 8 and R 9 that does not form the ring structure has a bond with R 2 or a substituted or unsubstituted carbonized carbon with a bond with R 2 If it is not a hydrogen group, one of the ring structures has a bond that binds to R 2.
  • Z + represents a nitrogen cation or a phosphorus cation.
  • Y + is a nitrogen cation, or a cationic group represented by formula (3) is represented by formula (3-1), formula (3-2), formula (3-1a) or formula (3-2a)
  • R 7 represents a bond with R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2.
  • R 8 , R 10 , R 11 and R 12 are the same or different and represent a bond to R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 7 and R 8 , R 10 , R 11 and R 12 is a bond bonding to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 7 , R 8 When R 10 , R 11 and R 12 are substituted or unsubstituted hydrocarbon groups, some or all of them may be bonded together to form a ring structure.
  • R 7 represents a bond to R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 8 , R 13 , R 14 , R 15 and R 16 are the same or different and represent a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2.
  • R 7 , R 8 , R 13 , R 14 , R 15 and R 16 is a bond bonding to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2 .
  • A is an n-valent substituted or unsubstituted aliphatic hydrocarbon group, an n-valent substituted or unsubstituted alicyclic hydrocarbon group, an n-valent substituted or unsubstituted aromatic hydrocarbon group, or an n-valent substituted or an unsubstituted araliphatic hydrocarbon group.
  • the blocked isocyanate compound consists of an alcohol compound, a phenol compound, an amine compound, a lactam compound, an oxime compound, a ketoenol compound, an active methylene compound, a pyrazole compound, a triazole compound, an imide compound, a mercaptan compound, an imine compound, a urea compound, and a diaryl compound.
  • the blocked isocyanate composition according to [6] which is a blocked isocyanate compound blocked with at least one blocking agent selected from the group.
  • thermosetting resin composition comprising the blocked isocyanate composition according to any one of [6] to [8] and a compound having an isocyanate-reactive group.
  • a cured product obtained by curing the thermosetting resin composition according to [9] or [10].
  • a method for producing a cured product comprising the step of heating and curing the thermosetting resin composition according to [9] or [10].
  • a zwitterionic compound represented by the following formula (1).
  • R 1 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • X represents a nitrogen atom or an oxygen atom.
  • a represents 0 or 1.
  • R 2 is a substituted or unsubstituted divalent hydrocarbon group
  • B 1 is represented by formula (2) or formula (3).
  • n is an integer of 1 or more.
  • A is an n-valent substituted or unsubstituted hydrocarbon group.
  • R 8 is a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2
  • R 6 , R 7 and R 9 are the same or different and represent a bond to R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 and R 7 , R 8 , and R 9 are a bond to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 , R 7 , R 8 and R 9 may be partly or wholly bonded to each other to form a ring structure, in the case where part or all of R 6 , R 7 , R 8 and R 9 are mutually bonded to form a cyclic structure wherein the group of R 6 , R 7 , R 8 and R 9 that does not form the ring structure is a bond to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2 If not, one of the ring structures has a bond that binds to R 2.
  • Z + represents a nitrogen cation or a phosphorus cation.
  • Y + is a nitrogen cation, or a cationic group represented by formula (3) is represented by formula (3-1), formula (3-2), formula (3-1a) or formula (3-2a)
  • R 7 represents a bond with R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2.
  • R 8 , R 10 , R 11 and R 12 are the same or different and represent a bond to R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 7 and R 8 , R 10 , R 11 and R 12 is a bond bonding to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 7 , R 8 When R 10 , R 11 and R 12 are substituted or unsubstituted hydrocarbon groups, some or all of them may be bonded together to form a ring structure.
  • R 7 represents a bond to R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 8 , R 13 , R 14 , R 15 and R 16 are the same or different and represent a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2.
  • R 7 , R 8 , R 13 , R 14 , R 15 and R 16 is a bond bonding to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2 .
  • A is an n-valent substituted or unsubstituted aliphatic hydrocarbon group, an n-valent substituted or unsubstituted alicyclic hydrocarbon group, an n-valent substituted or unsubstituted aromatic hydrocarbon group, or an n-valent substituted or an unsubstituted araliphatic hydrocarbon group, the zwitterionic compound according to [13] or [14].
  • R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • R 1 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • X represents a nitrogen atom or an oxygen atom.
  • a represents 0 or 1; When X is a nitrogen atom, a represents 1, and when X is an oxygen atom, a represents 0.
  • R2 represents a substituted or unsubstituted divalent hydrocarbon group.
  • B1 represents a cationic group represented by formula (2) or formula (3).
  • n is an integer of 1 or more.
  • A represents an n-valent substituted or unsubstituted hydrocarbon group.
  • R 8 represents a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2 ;
  • R 7 and R 9 are the same or different and represent a bond to R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 , R 7 , R 8 , and R 9 are a bond to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 , R 7 , R 8 and R 9 may be partially or entirely bonded together to form a ring structure, and partially or entirely of R 6 , R 7 , R 8 and R 9 may be mutually bonded to form a ring structure where the group of R 6 , R 7 , R 8 and R 9 that does not form the ring structure has a bond with R 2 or a substituted or unsubstituted carbonized carbon with a bond with R 2 If it is not a hydrogen group, one of the ring structures has a bond that binds to R 2.
  • Z + represents a nitrogen cation or a phosphorus cation.
  • B 1x is a group represented by the following formula (10) or the following formula (11).
  • B 1x is a group represented by the following formula (10)
  • it is represented by the formula (7a)
  • R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group
  • R3 represents a substituted or unsubstituted hydrocarbon group
  • R7 represents a substituted or unsubstituted hydrocarbon group.
  • R 1 , R 2 , R ′ , B 1 , A, a, X and n are as defined above.
  • R′ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • R 1 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • X represents a nitrogen atom or an oxygen atom.
  • a represents 0 or 1.
  • R 2 represents a substituted or unsubstituted divalent hydrocarbon group
  • B 1 represents a cationic group represented by formula (2) or formula (3)
  • n is an integer of 1 or more
  • A represents an n-valent substituted or unsubstituted hydrocarbon group.
  • R 8 is a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2
  • R 6 , R 7 and R 9 are the same or different and represent a bond to R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 and R 7 , R 8 , and R 9 are a bond to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 , R 7 , R 8 and R 9 may be partly or wholly bonded to each other to form a ring structure, in the case where part or all of R 6 , R 7 , R 8 and R 9 are mutually bonded to form a cyclic structure wherein the group of R 6 , R 7 , R 8 and R 9 that does not form the ring structure is a bond to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2 If not, one of the ring structures has a bond that binds to R 2.
  • Z + represents a nitrogen cation or a phosphorus cation.
  • a catalyst with excellent low-temperature dissociation properties for blocked isocyanate blocking agents can be provided. Further, it is possible to provide a blocked isocyanate composition containing the blocking agent dissociation catalyst, a thermosetting resin composition containing the blocked isocyanate composition and excellent in low-temperature curability, a cured product, and a method for producing the same.
  • amphoteric ion compound (1) As the blocking agent dissociation catalyst for blocked isocyanate of the present invention, an amphoteric ion compound represented by formula (1) (hereinafter referred to as amphoteric ion compound (1)) can be used. .
  • formula (1) an amphoteric ion compound represented by formula (1) (hereinafter referred to as amphoteric ion compound (1)) can be used.
  • R 1 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • X represents a nitrogen atom or an oxygen atom.
  • a represents 0 or 1.
  • R 2 is a substituted or unsubstituted divalent hydrocarbon group
  • B 1 is represented by formula (2) or formula (3).
  • n is an integer of 1 or more.
  • A is an n-valent substituted or unsubstituted hydrocarbon group.
  • R 8 is a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2
  • R 6 , R 7 and R 9 are the same or different and represent a bond to R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 and R 7 , R 8 , and R 9 are a bond to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2.
  • R 6 , R 7 , R 8 and R 9 may be partly or wholly bonded to each other to form a ring structure, in the case where part or all of R 6 , R 7 , R 8 and R 9 are mutually bonded to form a cyclic structure wherein the group of R 6 , R 7 , R 8 and R 9 that does not form the ring structure is a bond to R 2 or a substituted or unsubstituted hydrocarbon group having a bond to R 2 If not, one of the ring structures has a bond that binds to R 2.
  • Z + represents a nitrogen cation or a phosphorus cation.
  • R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are substituted or unsubstituted is preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, particularly preferably It is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
  • R 1 , R 3 , R 4 , R 5 and R 6 , R 7 , R 8 and R 9 are substituted or unsubstituted aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or araliphatic hydrocarbon groups, preferably substituted or unsubstituted C1-100 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group, more preferably substituted or unsubstituted C1-50 aliphatic A hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group It is a hydrogen group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group.
  • Examples of the "unsubstituted hydrocarbon group” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, decyl group and dodecyl. group, octadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, tolyl group, allyl group and the like.
  • the "unsubstituted aliphatic hydrocarbon group” includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and a decyl group. , dodecyl group, octadecyl group, allyl group and the like.
  • Unsubstituted alicyclic hydrocarbon group includes cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.
  • Unsubstituted aromatic hydrocarbon group includes a phenyl group, a naphthyl group, a tolyl group, and the like.
  • Unsubstituted araliphatic hydrocarbon group includes benzyl group, phenethyl group and the like.
  • examples of the "substituent” include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkylamino group such as a methylamino group, a dialkylamino group such as a dimethylamino group, and a methoxy group.
  • alkoxy groups such as ethoxy groups, phenoxy groups, aryloxy groups such as naphthyloxy groups, aralkyloxy groups such as benzyloxy groups and naphthylmethoxy groups, halogenated alkyl groups such as trifluoromethyl groups, nitro groups, cyano groups, sulfonyl group, alkylcarbonylamino group, alkyloxycarbonylamino group, (alkylamino)carbonylamino group, (dialkylamino)carbonylamino group and the like.
  • the monovalent or divalent hydrocarbon groups of R 1 to R 16 may be substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • the hydrocarbon groups of R 1 to R 16 are substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc.
  • the hydrocarbon groups are, for example, -O-, -N ⁇ , -NH It has at least one group such as -, -S-, -SO 2 -, and the hydrocarbon chain is interrupted by these groups.
  • the alkyl moiety of the alkylamino group, dialkylamino group, alkoxy group, halogenated alkyl group, alkylcarbonylamino group, alkyloxycarbonylamino group, (alkylamino)carbonylamino group and (dialkylamino)carbonylamino group includes methyl , ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, heptyl, octyl, 2-ethylhexyl, etc.
  • Linear or branched carbon number 1 to 12 alkyl groups are included.
  • the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms.
  • aryl moiety of the aryloxy group examples include aryl groups having 6 to 10 carbon atoms. Specific examples of the aryl moiety include a phenyl group and a naphthyl group.
  • aralkyl moiety of the aralkyloxy group examples include aralkyl groups having 7 to 12 carbon atoms. Specific examples of aralkyl moieties include a benzyl group and a naphthylmethyl group.
  • R 2 is a substituted or unsubstituted divalent hydrocarbon group, preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted is a divalent hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms.
  • R 2 is a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group, preferably substituted or unsubstituted A divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably substituted or unsubstituted 1 to 100 carbon atoms 50 divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group, particularly preferably substituted or unsubstituted divalent C 1-30 It is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group.
  • R 2 is a hydrogen atom or a substituted or unsubstituted divalent alkylene group, preferably a substituted or unsubstituted divalent alkylene group having 1 to 100 carbon atoms. , more preferably a substituted or unsubstituted divalent alkylene group having 1 to 50 carbon atoms, particularly preferably a substituted or unsubstituted divalent alkylene group having 1 to 30 carbon atoms.
  • B1 represents a cationic group represented by formula (2) or (3).
  • Y + is a nitrogen cation or a phosphorus cation, preferably a nitrogen cation.
  • R 3 , R 4 and R 5 are substituted or unsubstituted hydrocarbon groups.
  • the substituted or unsubstituted hydrocarbon group is preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a substituted Alternatively, it is an unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
  • R 3 , R 4 and R 5 are substituted or unsubstituted hydrocarbon groups such as substituted or unsubstituted aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, An aromatic hydrocarbon group or an araliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 100 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic A hydrocarbon group, more preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group having 1 to 30 carbon atoms.
  • Cationic groups represented by formula (2) include, for example, trimethylammonium group, triethylammonium group, tripropylammonium group, tributylammonium group, tripentylammonium group, trihexylammonium group, triheptylammonium group, trioctyl ammonium group, trinonylammonium group, tri(decyl)ammonium group, N-ethyl-N,N-dimethylammonium group, N,N-dimethyl-N-propylammonium group, N-butyl-N,N-dimethylammonium group , N,N-diethyl-N-decylammonium group, N,N-diethyl-N-eicosylammonium group, N,N-dibutyl-N-pentylammonium group, N,N-dibutyl-N-hexylammonium group, N,N-di
  • Z + is a nitrogen cation or a phosphorus cation, preferably a nitrogen cation.
  • R 8 is a bond to R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond to R 2 .
  • R 6 , R 7 and R 9 are the same or different and are a bond with R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group with a bond with R 2 .
  • the substituted or unsubstituted hydrocarbon group is preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a substituted Alternatively, it is an unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
  • the substituted or unsubstituted hydrocarbon groups include substituted or unsubstituted A substituted aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 100 carbon atoms, an alicyclic A cyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, more preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group or an aromatic A hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an
  • R 6 , R 7 , R 8 and R 9 are substituted or unsubstituted hydrocarbon groups having a bond with R 2 , preferably R 2 and is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms having a bond of , more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms having a bond with R 2 , A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a bond with R 2 is particularly preferred.
  • R 6 , R 7 , R 8 and R 9 are substituted or unsubstituted aliphatic hydrocarbon groups or alicyclic hydrocarbon groups having a bond with R 2 , an aromatic hydrocarbon group or an araliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 100 carbon atoms having a bond with R 2 , an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, more preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms or an alicyclic hydrocarbon group having a bond with R 2 , an aromatic hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms having a bond with R 2 , an alicyclic hydrocarbon group, It is an aromatic hydrocarbon group or an araliphatic hydrocarbon group,
  • R 6 , R 7 , R 8 and R 9 may combine with each other to form a ring structure.
  • R 6 and R 9 are mutually bonded to form a ring structure, for example, the structure of formula (3a), formula (3b), or formula (3c) below can be taken.
  • R a is a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituent having a bond with R 2 or an unsubstituted hydrocarbon group
  • E 1 , E 2 and E 3 are substituted or unsubstituted divalent hydrocarbon groups or substituted or unsubstituted divalent hydrocarbon groups having a bond with R 2
  • G represents an oxygen atom or a sulfur atom.
  • a divalent hydrocarbon group in E 1 , E 2 and E 3 a divalent hydrocarbon group having a bond with R 2 , and a divalent hydrocarbon group substituted with a divalent hydrocarbon group; In some cases, it may be substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • the hydrocarbon groups of E 1 , E 2 and E 3 are substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom and a sulfur atom
  • the hydrocarbon groups are, for example, —O—, —N ⁇ , --NH--, --S--, etc., and the divalent hydrocarbon chain is interrupted by these groups.
  • the substituted or unsubstituted hydrocarbon group is preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms is particularly preferred.
  • the substituted or unsubstituted hydrocarbon group when R a is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group includes a substituted or unsubstituted aliphatic hydrocarbon group, an alicyclic hydrocarbon group, An aromatic hydrocarbon group or an araliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 100 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic A hydrocarbon group, more preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group having 1 to 30 carbon atoms.
  • R a is a substituted or unsubstituted hydrocarbon group having a bond with R 2 , preferably a substituted or unsubstituted C 1-100 group with a bond with R 2 more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms having a bond with R 2 , particularly preferably a substituted or unsubstituted hydrocarbon group having a bond with R 2 is a hydrocarbon group having 1 to 30 carbon atoms.
  • R a is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group having a bond with R 2 and preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group having a bond with R 2 and having 1 to 100 carbon atoms.
  • a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group having a bond with R 2 particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group having a bond with R 2 .
  • the substituted or unsubstituted divalent hydrocarbon group for E 1 , E 2 and E 3 is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted is a divalent hydrocarbon group having 1 to 12 carbon atoms, particularly preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms.
  • the substituted or unsubstituted divalent hydrocarbon group is a substituted or unsubstituted divalent hydrocarbon group.
  • a divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group preferably a substituted or unsubstituted divalent aliphatic hydrocarbon having 1 to 20 carbon atoms.
  • an alicyclic hydrocarbon group an aromatic hydrocarbon group or an araliphatic hydrocarbon group, more preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic A hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or araliphatic hydrocarbon group.
  • E 1 , E 2 and E 3 are substituted or unsubstituted hydrocarbon groups having a bond with R 2
  • preferably substituted or unsubstituted hydrocarbon groups having a bond with R 2 is a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms having a bond with R 2 , particularly preferably A substituted or unsubstituted C 1-6 divalent hydrocarbon group having a bond with R 2 .
  • E 1 , E 2 and E 3 are substituted or unsubstituted divalent aliphatic hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups having a bond with R 2 or an araliphatic hydrocarbon group, preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms having a bond with R 2 , an alicyclic hydrocarbon group, an aromatic A hydrocarbon group or an araliphatic hydrocarbon group, more preferably a substituted or unsubstituted C 1-12 divalent aliphatic hydrocarbon group or alicyclic hydrocarbon group having a bond with R 2 , an aromatic hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms having a bond with R 2 , alicyclic It is a hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group,
  • R 6 and R 9 are mutually bonded to form a ring structure.
  • a ring structure can also be formed in the same manner.
  • the cationic group represented by the formula (3) is preferably a cationic group represented by the following formula (3-1) or the following formula (3-2), particularly preferably the following formula (3-1). It is a cationic group that Formula (3-1):
  • R 7 represents a bond with R 2 or a substituted or unsubstituted hydrocarbon group.
  • R 8 , R 10 , R 11 and R 12 are the same or different, a bond with R 2 , a hydrogen atom, A substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted hydrocarbon group having a bond with R 2.
  • Any one of R 7 , R 8 , R 10 , R 11 and R 12 is R 2 or a substituted or unsubstituted hydrocarbon group having a bond with R 2.
  • R 7 , R 8 , R 10 , R 11 and R 12 are substituted or unsubstituted hydrocarbon groups , some or all of them may be bonded to each other to form a ring structure.
  • R 7 represents a bond with R 2 or a substituted or unsubstituted hydrocarbon group.
  • R 8 , R 13 , R 14 , R 15 and R 16 are the same or different, a bond with R 2 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2.
  • Any of R 7 , R 8 , R 13 , R 14 , R 15 and R 16 or one is a substituted or unsubstituted hydrocarbon group having a bond bonding to R 2 or a bond to R 2.
  • R 7 , R 8 , R 13 , R 14 , R 15 and R 16 is a substituted or unsubstituted hydrocarbon group, some or all of which may be bonded together to form a ring structure.
  • R 7 is a bond with R 2 or a substituted or unsubstituted hydrocarbon group.
  • R 8 , R 10 , R 11 and R 12 are the same or different and are a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted carbon group having a bond with R 2 It is a hydrogen group.
  • the substituted or unsubstituted hydrocarbon group is preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a substituted Alternatively, it is an unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
  • the substituted or unsubstituted hydrocarbon group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic having 1 to 100 carbon atoms A hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, more preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms, an alicyclic hydrocarbon group A hydrogen group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group or an aromatic hydrocarbon group or an an aromatic hydrocarbon group or an
  • R 7 , R 8 , R 10 , R 11 and R 12 are substituted or unsubstituted hydrocarbon groups having a bond with R 2
  • a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms having a bond with R 2 more preferably a substituted or unsubstituted carbon atom having 1 to 50 carbon atoms having a bond with R 2
  • R 7 , R 8 , R 10 , R 11 and R 12 are substituted or unsubstituted aliphatic hydrocarbon groups having a bond with R 2 ;
  • cationic group represented by formula (3-1) examples include a 1,3-dimethylimidazolium group, a 1-ethyl-3-methylimidazolium group, and a 1-methyl-3-propylimidazolium group.
  • R 7 is a bond with R 2 , a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2 .
  • R 8 , R 13 , R 14 , R 15 and R 16 are the same or different and are a bond to R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted group having a bond to R 2 . It is a substituted hydrocarbon group.
  • the substituted or unsubstituted hydrocarbon group is preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a substituted Alternatively, it is an unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
  • R 7 , R 8 , R 13 , R 14 , R 15 and R 16 are substituted or unsubstituted hydrocarbon groups, substituted or unsubstituted hydrocarbon groups
  • the hydrogen group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group, preferably substituted or unsubstituted, having 1 to 100 carbon atoms.
  • R 7 , R 8 , R 13 , R 14 , R 15 and R 16 are substituted or unsubstituted hydrocarbon groups having a bond with R 2
  • it is preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms having a bond with R 2 , more preferably a substituted or unsubstituted C 1 to 100 hydrocarbon group having a bond with R 2 50 hydrocarbon group, particularly preferably a substituted or unsubstituted C 1-30 hydrocarbon group having a bond with R 2 .
  • R 7 , R 8 , R 13 , R 14 , R 15 and R 16 are substituted or unsubstituted aliphatic hydrocarbons having bonds with R 2 group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 100 carbon atoms having a bond with R 2 , an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, more preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms having a bond with R 2 , an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group, particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms having a bond with R 2 , an alicyclic hydrocarbon group, an aromatic hydrocarbon group or
  • cationic group represented by formula (3-2) examples include a 1-methylpyridinium group, a 1-ethylpyridinium group, a 1-propylpyridinium group, a 1-butylpyridinium group, and a 1-pentylpyridinium group.
  • R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 may form a ring structure together with a carbon atom, a nitrogen atom or a phosphorus atom.
  • R 11 and R 12 , R 15 and R 16 together with the carbon atoms to which they are attached form a ring structure for example, the following formula (3-1a) or formula (3 -2a) can be a benzimidazolium ring structure or a quinolinium ring structure.
  • R 7 , R 8 , R 10 , R 13 and R 14 are as defined above; R w , R x , R y and R z are each a bond with R 2 ; represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 11 and R 12 , R 15 and R 16 form a ring structure
  • R 1 and R 3 , R 1 and R 7 , R 1 and R 8 , R 3 and R 4 , R 7 and R 8 , R 8 and R 9 , R 8 and R 10 , R 10 and R 11 , R 12 and R 7 , R 13 and R 14 can similarly form a ring structure.
  • A is a substituted or unsubstituted n-valent hydrocarbon group, preferably a substituted or unsubstituted n-valent aliphatic hydrocarbon group having 1 to 30 carbon atoms, and 3 to 30 substituted or unsubstituted n-valent alicyclic hydrocarbon group, substituted or unsubstituted n-valent aromatic hydrocarbon group having 6 to 200 carbon atoms, or substituted or unsubstituted n having 7 to 200 carbon atoms is any valent araliphatic hydrocarbon group.
  • n-valent hydrocarbon group means a group remaining after removing n hydrogens from the hydrocarbon group
  • n-valent aliphatic hydrocarbon group refers to n
  • n-valent alicyclic hydrocarbon group means a group remaining after n hydrogens have been removed from the alicyclic hydrocarbon group
  • N-valent aromatic hydrocarbon group means a group remaining after removing n hydrogens from an aromatic hydrocarbon group
  • n-valent araliphatic hydrocarbon group means an araliphatic hydrocarbon It means the remaining group after removing n hydrogens from the group.
  • a "substituted or unsubstituted hydrocarbon group” means (i) a hydrocarbon group which may have a substituent, (ii) a hydrocarbon group which may be substituted with a heteroatom, (iii) It has a substituent and includes a hydrocarbon group substituted with a heteroatom.
  • substituted or unsubstituted aliphatic hydrocarbon group includes (iv) an optionally substituted aliphatic hydrocarbon group and (v) an optionally heteroatom-substituted aliphatic hydrocarbon group. groups, (vi) including aliphatic hydrocarbon groups with substituents and substituted with heteroatoms;
  • a "substituted or unsubstituted alicyclic hydrocarbon group” means (vii) an alicyclic hydrocarbon group which may have a substituent, and (viii) an alicyclic ring which may be substituted with a heteroatom.
  • Formula hydrocarbon groups, (ix) include alicyclic hydrocarbon groups with substituents and substituted with heteroatoms.
  • substituted or unsubstituted aromatic hydrocarbon group includes (x) an optionally substituted aromatic hydrocarbon group and (xi) an optionally heteroatom-substituted aromatic hydrocarbon group. (xii) substituents, including heteroatom-substituted aromatic hydrocarbon groups.
  • substituted or unsubstituted araliphatic hydrocarbon group includes (xiii) an optionally substituted aromatic aliphatic hydrocarbon group and (xiv) an optionally substituted araliphatic (xv) substituents, including araliphatic hydrocarbon groups substituted with heteroatoms.
  • substituted or unsubstituted n-valent hydrocarbon group refers to (i) an optionally substituted n-valent hydrocarbon group and (ii) a heteroatom-substituted (iii) n-valent hydrocarbon groups that have a substituent and are substituted with a heteroatom.
  • substituted or unsubstituted n-valent aliphatic hydrocarbon group is (iv) an optionally substituted n-valent aliphatic hydrocarbon group and (v) substituted with a heteroatom.
  • n-valent aliphatic hydrocarbon groups that have a substituent and are substituted with a heteroatom are substituted with a heteroatom.
  • the “substituted or unsubstituted n-valent alicyclic hydrocarbon group” is (vii) an optionally substituted n-valent alicyclic hydrocarbon group and (viii) a heteroatom-substituted n-valent alicyclic hydrocarbon groups that may be substituted, and (ix) substituents and heteroatom-substituted n-valent alicyclic hydrocarbon groups.
  • the "substituted or unsubstituted n-valent aromatic hydrocarbon group” is (x) an optionally substituted n-valent aromatic hydrocarbon group and (xi) a heteroatom-substituted n-valent aromatic hydrocarbon groups, and (xii) substituents and heteroatom-substituted n-valent aromatic hydrocarbon groups.
  • the "substituted or unsubstituted n-valent araliphatic hydrocarbon group" is (xiii) an optionally substituted n-valent araliphatic hydrocarbon group and (xiv) a heteroatom-substituted n-valent araliphatic hydrocarbon groups which may be substituted, and (xv) substituents and heteroatom-substituted n-valent araliphatic hydrocarbon groups.
  • the unsubstituted n-valent hydrocarbon group includes methane, ethane, propane, isopropane, butane, sec-butane, tert-butane, pentane, hexane, heptane, decane, dodecane, octadecane, cyclopropane, Examples include groups obtained by removing n hydrogen atoms from cyclopentane, cyclohexane, benzene, naphthalene, toluene, phenylethane, and propylene.
  • one or both of the hydrogen atoms of the aromatic ring and the hydrogen atoms of the methyl group or ethyl group may be removed.
  • the removed hydrogen atoms are hydrogen atoms bonded to different carbon atoms.
  • A is a hydrocarbon group excluding the isocyanate groups of the following isocyanate compounds (i) to (v): be.
  • isocyanate includes monofunctional isocyanate and polyfunctional isocyanate.
  • an aliphatic isocyanate (ii) cycloaliphatic isocyanates, (iii) aromatic isocyanates, (iv) araliphatic isocyanates,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and A are hydrocarbon groups,
  • the number of substituents possessed by the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and araliphatic hydrocarbon group is 1 to 5, preferably 1 to 3, more preferably 1 or 2. can be individual.
  • X represents a nitrogen atom or an oxygen atom, preferably a nitrogen atom.
  • n is an integer of 1 or more, preferably an integer of 1 to 20, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.
  • Et is an ethyl group
  • Pr is a propyl group
  • i Pr is an isopropyl group
  • Bu is a butyl group
  • Bnz is a benzyl group.
  • the zwitterionic compound (1) preferably (1-2-1a-1) to (1-2-33a-1), (1-2-1b-1) to (1-2-33b-1), (1-2-1c-1) ⁇ (1-2-33c-1), (1-2-1a-2) ⁇ (1-2-33a-2), (1-2-1b-2) ⁇ (1-2-33b-2), (1-2-1c-2) ⁇ (1-2-33c-2), (1-2-1a-6) ⁇ (1-2-33a-6), (1-2-1b-6) ⁇ (1-2-33b-6), (1-2-1c-6) ⁇ (1-2-33c-6), (1-2-1a-14) ⁇ (1-2-33a-14), (1-2-1b-14) ⁇ (1-2-33b-14), (1-2-1c-14) ⁇ (1-2-33c-14) compounds represented by (1-2-12a-1) and (1-2-12a-2) are particularly preferred.
  • a method for producing the zwitterionic compound (1) includes, for example, a method of stirring the compound represented by formula (8) in a solvent (manufacturing method 1).
  • R′ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • R 1 , R 2 , A, a, X and B 1 are as defined above.
  • the reaction can usually be carried out at a temperature from 0°C to the boiling point of the solvent. Generally, it can be carried out at a temperature from 0° C. to the boiling temperature of the solvent.
  • the reaction temperature is preferably 20°C to 150°C, more preferably 40°C to 150°C, even more preferably 40°C to 120°C. In the case of compounds in which X is an oxygen atom in formula (8), the reaction temperature is preferably 20 to 60°C.
  • the reaction time is usually 1 to 20 hours, preferably 1 to 10 hours.
  • solvents examples include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, acetone, and methanol.
  • the amount of the solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (8).
  • a solvent can also be used in mixture of 2 or more types as needed.
  • the reaction may be carried out under an inert gas atmosphere such as nitrogen, argon, or helium that does not affect the reaction.
  • the resulting zwitterionic compound (1) can be purified by conventional methods such as concentration and recrystallization.
  • the compound represented by formula (8) used in production method 1 may be produced, for example, by the following method.
  • Method A A method including (step 1) and (step 2).
  • B 1x is a group represented by the following formula (10) or the following formula (11).
  • B 1x is a group represented by the following formula (10)
  • it is represented by the formula (7a)
  • R′ is a hydrogen atom or a substituted or unsubstituted carbon atom. represents a hydrogen group, R 3 or R 7.
  • R 1 , R 2 , R 3 , R 7 , B 1 , A, a, X and n are as defined above.
  • Step 1 The compound represented by Formula (6) is obtained by reacting the compound represented by Formula (4) with the isocyanate compound represented by Formula (5).
  • Step 2 A compound represented by the formula (8) is obtained by reacting a compound represented by the formula (6) with a carbonate compound represented by the formula (7a) or (7b) to obtain a compound represented by the formula ( A compound in which R' is R 3 or R 7 in 8) (hereinafter referred to as compound (8b')) can be obtained.
  • Compound (8b′) is a compound represented by formula (8), and is included in compounds in which R′ in formula (8) is a substituted or unsubstituted hydrocarbon group (hereinafter referred to as compound (8b)). be.
  • R 6 , R 8 and R 9 are as defined above.
  • Step 1 (Step 1) will be explained.
  • the urethane compound or urea compound represented by Formula (6) can be obtained by reacting the compound represented by Formula (4) with the isocyanate compound represented by Formula (5).
  • Et is an ethyl group
  • Pr is a propyl group
  • i Pr is an isopropyl group
  • Bu is a butyl group
  • Bnz is a benzyl group.
  • X, a, R 1 , R 2 , R 10 are as defined above.
  • X(R 1 ) a is NH or N(CH 3 )
  • R 2 is CH 2 , CH 2 CH 2 , CH 2 (CH 2 ) 4 or CH 2
  • R 10 is CH3 , Et, iPr , Bu, Bnz , or CH2CH2OCH3 .
  • X, a, R 1 , R 2 , R 10 As defined above, but preferably X(R 1 ) a is either NH or N(CH 3 ) and R 2 is CH 2 , CH 2 CH 2 , CH 2 (CH 2 ) 4 CH 2 and R 10 is CH 3 , Et, i Pr, Bu, Bnz, CH 2 CH 2 OCH 3 .
  • x is an integer of 0 to 20, preferably an integer of 1 to 20.
  • the isocyanate compound represented by formula (5) is preferably a compound represented by (5-1), (5-2), (5-6) or (5-14), and particularly preferably (5 -1), (5-2), and (5-14).
  • Et is an ethyl group
  • Pr is a propyl group
  • i Pr is an isopropyl group
  • Bu is a butyl group
  • Bnz is a benzyl group.
  • X, a, R 1 , R 2 , R 10 are as defined above.
  • X(R 1 ) a is NH or N(CH 3 )
  • R 2 is CH 2 , CH 2 CH 2 or CH 2 (CH 2 ) 4 CH 2 and R 10 is CH3 , Et, iPr , Bu, Bnz , or CH2CH2OCH3 .
  • X, a, R 1 , R 2 , R 10 are as defined above.
  • X(R 1 ) a is NH, N(CH 3 ) or O
  • R 2 is CH 2 , CH 2 CH 2 or CH 2 (CH 2 ) 4 CH 2
  • R 10 is CH3 , Et, iPr , Bu, Bnz , or CH2CH2OCH3 .
  • A, X , a, R1 , R2 , R10 are as defined above.
  • A is a group represented by formula (A-2) or a group represented by formula (A-6), and X(R 1 ) a is NH, N(CH 3 ) or O and R 2 is CH 2 , CH 2 CH 2 , or CH 2 (CH 2 ) 4 CH 2 and R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 is.
  • A, X, a, R 1 , R 2 , R 10 are as defined above.
  • A is a group represented by formula (A-2) or a group represented by formula (A-6), and X(R 1 ) a is NH, N(CH 3 ) or O and R 2 is CH 2 , CH 2 CH 2 , or CH 2 (CH 2 ) 4 CH 2 and R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 is.
  • the isocyanate compound represented by formula (5) is usually used in an amount of 0.5 to 10 mol, preferably 0.8 to 3 mol, per n mol of the compound represented by formula (4).
  • the reaction temperature is usually 10-200°C or the boiling temperature of the solvent.
  • the reaction temperature is preferably 20 to 150°C.
  • the reaction time is usually 1-20 hours, preferably 1-10 hours.
  • a solvent may or may not be used.
  • Solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, acetone, and the like.
  • the amount of the solvent to be used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (4).
  • the reaction may be carried out under an inert gas atmosphere such as nitrogen, argon, or helium that does not affect the reaction.
  • an inert gas atmosphere such as nitrogen, argon, or helium that does not affect the reaction.
  • the obtained compound represented by formula (6) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as the raw material for step 2 without purification.
  • Step 2 (Step 2) will be explained.
  • R' is a hydrogen atom or a substituted or unsubstituted hydrocarbon group , R3 or R7 .
  • R' is preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted It is a substituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
  • an alkyl group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • R' is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or araliphatic hydrocarbon group, preferably a substituted or unsubstituted carbon
  • an alkyl group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • Examples of the "unsubstituted hydrocarbon group” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, decyl group and dodecyl. group, octadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, tolyl group, allyl group and the like.
  • the "unsubstituted aliphatic hydrocarbon group” includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and a decyl group. , dodecyl group, octadecyl group, allyl group and the like.
  • Unsubstituted alicyclic hydrocarbon group includes cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.
  • Unsubstituted aromatic hydrocarbon group includes a phenyl group, a naphthyl group, a tolyl group, and the like.
  • Unsubstituted araliphatic hydrocarbon group includes benzyl group, phenethyl group and the like.
  • carbonate ester (7a) or (7b) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate. , dipentyl carbonate, dihexyl carbonate, etc., alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, etc., preferably dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and particularly preferably dimethyl carbonate. .
  • Et is an ethyl group
  • Pr is a propyl group
  • i Pr is an isopropyl group
  • Bu is a butyl group
  • Bnz is a benzyl group.
  • X , a, R1 , R2 , R7 , R10, R' are as defined above.
  • X(R 1 ) a is NH, N(CH 3 ) or O
  • R 2 is CH 2 , CH 2 CH 2 or CH 2 (CH 2 ) 4 CH 2 and R 7 is CH 3 or Et
  • R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 and R′ is H, CH 3 or Et.
  • X , a, R1 , R2 , R7 , R10, R' are as defined above.
  • X(R 1 ) a is NH, N(CH 3 ) or O
  • R 2 is CH 2 , CH 2 CH 2 or CH 2 (CH 2 ) 4 CH 2 and R 7 is CH 3 or Et
  • R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 and R′ is H, CH 3 or Et.
  • X , a, R1 , R2 , R7 , R10, R' are as defined above.
  • X(R 1 ) a is NH, N(CH 3 ) or 0,
  • R 2 is CH 2 , CH 2 CH 2 or CH 2 (CH 2 ) 4 CH 2 and R 7 is CH 3 or Et
  • R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 and R′ is H, CH 3 or Et.
  • A, X, a, R 1 , R 2 , R 7 , R 10 , R' are as defined above.
  • A is a group represented by formula (A-2) or a group represented by formula (A-6)
  • X(R 1 ) a is NH, N(CH 3 ) or O
  • R 2 is CH 2 , CH 2 CH 2 , or CH 2 (CH 2 ) 4 CH 2
  • R 7 is CH 3 or Et
  • R 10 is CH 3 , Et, i Pr, Bu , Bnz, or CH 2 CH 2 OCH 3
  • R′ is H, CH 3 or Et.
  • A, X , a, R1 , R2 , R7 , R10, R' are as defined above.
  • A is a group represented by formula (A-2) or a group represented by formula (A-6)
  • X(R 1 ) a is NH, N(CH 3 ) or O
  • R 2 is CH 2 , CH 2 CH 2 , or CH 2 (CH 2 ) 4 CH 2
  • R 7 is CH 3 or Et
  • R 10 is CH 3 , Et, i Pr, Bu , Bnz , or CH2CH2OCH3 and R' is H , CH3 or Et.
  • A, X , a, R1 , R2 , R10, R' are as defined above.
  • A is a group represented by formula (A-2) or a group represented by formula (A-6), and X(R 1 ) a is either NH or N(CH 3 ) or O and R 2 is CH 2 , CH 2 CH 2 , or CH 2 (CH 2 ) 4 CH 2 and R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 and R' is H, CH 3 or Et.
  • the reaction temperature is usually 10°C to 120°C or the boiling temperature of the solvent.
  • the reaction time is usually 1-20 hours, preferably 1-10 hours.
  • An excess amount of carbonate compound (7a) or (7b) may be used as a solvent, but other solvents may also be used.
  • Solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, acetone, and the like. When other solvents are used, the amount of the solvent to be used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (6).
  • the reaction may be carried out under an inert gas atmosphere such as nitrogen, argon, helium, etc., which does not affect the reaction.
  • an inert gas atmosphere such as nitrogen, argon, helium, etc., which does not affect the reaction.
  • the obtained compound (8b) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as a raw material for production method 1 or step 3 described later without purification.
  • step 2 the obtained compound (8b) can be used as a starting material in production method 1, but the compound (8b) is reacted with water to obtain a compound of formula (8) in which R' is a hydrogen atom. (hereinafter referred to as compound (8a)) may be produced (hereinafter referred to as step 3) and used as a starting material in production method 1.
  • the amount of water to be used is generally 1-500 mol, preferably 3-250 mol, per 1 mol of compound (8b).
  • step 3 when the reaction solution obtained in step 2 is used as compound (8b) as it is, carbonate compound (7) may remain in the reaction solution. In this case, in step 3, it is preferable to use an excess amount of water.
  • Water can also be used as a solvent. When water is used as a solvent, in addition to the above amount, it can be used in an amount of generally 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of compound (8b).
  • the reaction temperature for reacting compound (8b) with water is usually 10°C or higher, preferably 10°C to 100°C, more preferably 10°C to 80°C.
  • the reaction time is usually 0.1 to 10 hours, preferably 0.1 to 5 hours.
  • a solvent may or may not be used.
  • Water can also be used as a solvent, but when a solvent other than water is used, examples of the solvent include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, acetone, and methanol.
  • the amount of the solvent to be used is generally 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of compound (8b).
  • a solvent can also be used in mixture of 2 or more types as needed.
  • the reaction may be carried out under an inert gas atmosphere such as nitrogen, argon, helium, etc. that does not affect the reaction.
  • an inert gas atmosphere such as nitrogen, argon, helium, etc. that does not affect the reaction.
  • the obtained compound (8a) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as a raw material for production method 1 without purification.
  • the compound represented by the formula (8) can also be produced by the following method in addition to (step 2).
  • a compound represented by the formula (8) can be obtained by reacting a compound represented by the following formula (9) with an isocyanate compound represented by the formula (5) (method B).
  • X , a, R1 , R2 , R7 , R10, R' are as defined above.
  • X(R 1 ) a is NH, N(CH 3 ) or O
  • R 2 is CH 2 , CH 2 CH 2 or CH 2 (CH 2 ) 4 CH 2 and R 7 is CH 3 or Et
  • R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 and R′ is H, CH 3 or Et.
  • X , a, R1 , R2 , R7 , R10, R' are as defined above.
  • X(R 1 ) a is NH, N(CH 3 ) or O
  • R 2 is CH 2 , CH 2 CH 2 or CH 2 (CH 2 ) 4 CH 2 and R 7 is CH 3 or Et
  • R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 and R′ is H, CH 3 or Et.
  • X, a, R 1 , R 2 , R 10 , R' are as defined above.
  • X(R 1 ) a is NH or N(CH 3 ), O
  • R 2 is CH 2 , CH 2 CH 2 , or CH 2 (CH 2 ) 4 CH 2 and R 7 is CH 3 or Et
  • R 10 is CH 3 , Et, i Pr, Bu, Bnz, or CH 2 CH 2 OCH 3 and R′ is H, CH 3 or Et.
  • the reaction usually uses 0.5 to 10 mol, preferably 0.8 to 3 mol, of the isocyanate compound represented by the formula (5) per 1/n mol of the compound represented by the formula (9). do.
  • the reaction temperature is usually 10°C to 100°C or the boiling temperature of the solvent. It is preferably 20 to 150°C.
  • the reaction time is usually 1 to 20 hours, preferably 1 to 10 hours.
  • a solvent may or may not be used.
  • Solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, acetone, and the like.
  • the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (9).
  • a solvent can also be used in mixture of 2 or more types as needed.
  • the blocked isocyanate compound will be explained.
  • blocked isocyanate compounds include compounds obtained by reacting an isocyanate with a blocking agent and blocking the isocyanate groups in the isocyanate with the blocking agent.
  • the blocked isocyanate compound may be used alone or in combination of two or more.
  • the isocyanate constituting the blocked isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • the isocyanate include the following. (i) an aliphatic isocyanate, (ii) cycloaliphatic isocyanates, (iii) aromatic isocyanates, (iv) araliphatic isocyanates, (v) A modified isocyanate formed from at least one selected from the group consisting of aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates and araliphatic isocyanates.
  • aliphatic isocyanates examples include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer and acid diisocyanate.
  • Alicyclic isocyanates include, for example, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate (IPDI)), bis-(4-isocyanatocyclohexyl)methane, norbornane diisocyanate, and the like.
  • IPDI isophorone diisocyanate
  • aromatic isocyanates examples include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. , 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and the like.
  • araliphatic isocyanates examples include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate and the like.
  • Modified isocyanates include, for example, isocyanate group-terminated compounds and isocyanate compounds obtained by reaction of the above-mentioned isocyanate compounds with active hydrogen group-containing compounds, and/or reaction products of the isocyanate group-terminated compounds (e.g., adduct-type isocyanates, allophanatization reactions, , carbodiimidation reaction, uretdiionization reaction, isocyanurate reaction, uretonimination reaction, isocyanate modified by biuretization reaction, etc.), adduct type isocyanate, isocyanate modified by isocyanurate reaction, biuretization reaction Modified isocyanates (isocyanates with biuret linkages) are preferred.
  • adduct-type isocyanates allophanatization reactions, , carbodiimidation reaction, uretdiionization reaction, isocyanurate reaction, uretonimination reaction, isocyanate modified by biuretization reaction
  • An isocyanate having a biuret bond is obtained by reacting a so-called biuret agent such as water, tert-butanol, or urea with an isocyanate at a biuret agent/isocyanate group molar ratio of about 1/2 to about 1/100. After that, it is obtained by removing unreacted isocyanate and purifying it.
  • Isocyanate having an isocyanurate bond is obtained by, for example, performing a cyclic trimerization reaction with a catalyst or the like, stopping the reaction when the conversion rate reaches about 5 to about 80% by mass, and removing and purifying unreacted isocyanate. . At this time, a mono- to hexahydric alcohol compound can be used in combination.
  • Examples of the isocyanate having a biuret bond include biuret-modified 1,6-hexamethylene diisocyanate (HDI), biuret-modified isophorone diisocyanate (IPDI), and biuret-modified toluene diisocyanate (TDI) shown below.
  • Commercially available products include Desmodur N75, Desmodur N100 and Desmodur N3200 manufactured by Sumika Covestro Urethane Co., Ltd., and Duranate 24A-100, Duranate 22A-75P and Duranate 21S-75E manufactured by Asahi Kasei Corporation. mentioned.
  • Isocyanate having an isocyanurate bond is obtained by, for example, performing an isocyanurate reaction with a catalyst or the like, stopping the reaction when the conversion rate reaches about 5 to about 80% by mass, and removing and purifying unreacted isocyanate. .
  • a mono- to hexahydric alcohol compound can be used in combination.
  • Examples of the above catalysts include: (1) tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium and trimethylbenzylammonium, and organic weak acid salts such as acetic acid and capric acid; (2) hydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium and triethylhydroxyethylammonium, and organic weak acid salts such as acetic acid and capric acid; (3) Metal salts of alkylcarboxylic acids such as tin, zinc, lead, etc.
  • metal alcoholates such as sodium and potassium; (5) aminosilyl group-containing compounds such as hexamethyldisilazane; (6) Mannich bases, (7) combined use of tertiary amines and epoxy compounds, (8) Phosphorus compounds such as tributylphosphine, etc. may be mentioned, and two or more of them may be used in combination.
  • the catalyst may be neutralized with an acidic compound or the like.
  • the acidic compound include inorganic acids such as hydrochloric acid, phosphorous acid and phosphoric acid; Derivatives, ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di(2-ethylhexyl) phosphate, isodecyl phosphate, diisodecyl phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethyl Glycol acid phosphate, butyl pyrophosphate, butyl phosphite, etc. may be used, and two or more of them may be used in combination.
  • Isocyanates having an isocyanurate bond include, for example, isocyanurate-modified HDI, isocyanurate-modified IPDI, and isocyanurate-modified TDI having the structures shown below.
  • Covestro Urethane Co., Ltd. Sumidule N3300, Desmodur 3900, Desmodur Z4470BA, Desmodur XP2763, Desmodur IL1351BA, Desmodur HLBA and Asahi Kasei Corporation Duranate TPA-100, Duranate MFA-75B, Duranate TUL-100 , Duranate TSA-100 and the like.
  • the isocyanate having a urethane bond is, for example, a di- to hexahydric alcohol compound such as trimethylolpropane (hereinafter referred to as TMP) and a diisocyanate, and the molar ratio of the hydroxyl group of the alcohol compound/the isocyanate group of the isocyanate is about 1/2. It is obtained by removing unreacted isocyanate and purifying after reacting at about 1/100. Purification to remove unreacted isocyanate is not always necessary.
  • TMP trimethylolpropane
  • Examples of the isocyanate having a urethane bond include a reaction product of HDI and TMP, a reaction product of IPDI and TMP, and a reaction product of TDI and TMP having the structures shown below.
  • blocking agents for isocyanates in which a part of the isocyanate groups of the isocyanates and modified isocyanates are blocked with known blocking agents include, for example, phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, Phenols such as chlorophenol, oximes such as acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, alcohols such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; pyrazoles such as 3,5-dimethylpyrazole and 1,2-
  • blocking agents examples include alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, ketoenol compounds, active methylene compounds, pyrazole compounds, triazole compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds. Alcohol compounds, lactam compounds, oxime compounds, and pyrazole compounds are preferred.
  • the blocking agent can be dissociated in a short period of time even at 120°C. Preferred are fluorinated alcohol compounds, particularly preferred.
  • Alcohol compounds include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether. , propylene glycol monomethyl ether, benzyl alcohol, and the like.
  • Alcohol compounds include fluorinated alcohol compounds such as 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol.
  • the alcohol compound is preferably a fluoroalcohol compound, particularly preferably 2,2,2-trifluoroethanol.
  • Phenol compounds include phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, chlorophenol 2-hydroxypyridine, and the like.
  • Amine compounds include diisopropylamine and the like.
  • Lactam compounds include ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and the like, preferably ⁇ -caprolactam.
  • the oxime compound preferably includes a compound represented by the following formula (L).
  • Formula (L): HO-N R'' (L) (Wherein, R'' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)
  • R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. is.
  • alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, 1-methylpropyl group, pentyl group, hexyl group and heptyl group. , octyl group, 1-ethylpentyl group, nonyl group, 2-ethylhexyl group, undecyl group, tridecyl group, pentadecyl group and heptadecyl group.
  • the oxime compound includes formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, etc., preferably methyl ethyl ketoxime.
  • pyrazole compounds include 1,2-pyrazole and 3,5-dimethylpyrazole
  • triazole compounds include 1,2,4-triazole and the like, preferably 3,5-dimethylpyrazole.
  • active methylene compounds include methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate.
  • blocked isocyanate composition of the present invention known polyurethane production catalysts, additives, pigments, solvents, etc. that are commonly used in the art can be used, if necessary.
  • Known catalysts for polyurethane production are not particularly limited, and examples include dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, Tin compounds such as tin acetylacetonate, tin acetate, tin octylate and tin laurate; bismuth compounds such as bismuth octylate, bismuth naphthenate and bismuth acetylacetonate; tetra-n-butyl titanate and tetraisopropyl titanate , titanium compounds such as titanium terephthalate, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N
  • Additives are not particularly limited, and include, for example, hindered amine-based, benzotriazole-based, and benzophenone-based UV absorbers; perchlorate-based, hydroxylamine-based anti-coloring agents; Antioxidants such as system, sulfur-based and hydrazide-based antioxidants, tin-based, zinc-based and amine-based urethanization catalysts, leveling agents, rheology control agents, pigment dispersants and the like.
  • the pigment is not particularly limited, and examples include organic pigments such as quinacridone-based, azo-based, and phthalocyanine-based pigments; inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and silica; Pigments such as pigments and anticorrosive pigments can be used.
  • organic pigments such as quinacridone-based, azo-based, and phthalocyanine-based pigments
  • inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and silica
  • Pigments such as pigments and anticorrosive pigments can be used.
  • solvents include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits and naphtha, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, butyl acetate, and acetic acid.
  • esters such as cellosolve; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; Examples thereof include hydric alcohols and water, and these solvents may be used alone or in combination of two or more.
  • thermosetting resin composition of the present invention will be explained.
  • thermosetting resin composition of the present invention contains the blocked isocyanate composition of the present invention and a compound having an isocyanate-reactive group.
  • Compounds having an isocyanate-reactive group include compounds having two or more active hydrogen groups such as polyols, polyamines and alkanolamines, preferably polyols. These isocyanate-reactive group-containing compounds may be a mixture of two or more.
  • a polyol in the present invention is a compound having two or more hydroxyl groups.
  • examples thereof include polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and fluorine polyols.
  • acrylic polyol is preferable as the polyol from the viewpoint of weather resistance, chemical resistance and hardness.
  • the polyol is preferably polyester polyol from the viewpoint of mechanical strength and oil resistance. These polyols may be a mixture of two or more.
  • a polyester polyol can be obtained, for example, by condensation reaction of a dibasic acid alone or a mixture of two or more kinds and a polyhydric alcohol alone or a mixture of two or more kinds.
  • dibasic acid examples include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
  • carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, and pentaerythritol. , 2-methylolpropanediol, ethoxylated trimethylolpropane, and the like.
  • polyester polyol As a specific method for producing the polyester polyol, for example, the above components are mixed and heated at about 160 to 220°C to carry out a condensation reaction.
  • polycaprolactones obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone using a polyhydric alcohol can also be used as polyester polyols.
  • polyester polyols can be modified using aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and isocyanates obtained from these. Above all, from the viewpoint of weather resistance and yellowing resistance, the polyester polyol is preferably modified using an aliphatic diisocyanate, an alicyclic diisocyanate, and an isocyanate obtained therefrom.
  • thermosetting resin composition of the present embodiment When used as a water-based base paint, part of the carboxylic acid derived from the dibasic acid or the like in the polyester polyol is allowed to remain, and is neutralized with a base such as amine or ammonia.
  • a base such as amine or ammonia.
  • Polyether polyols include aliphatic amine polyols, aromatic amine polyols, Mannich polyols, polyhydric alcohols, polyhydric phenols, active hydrogen compounds such as bisphenols, and compounds obtained by adding alkylene oxide thereto. These polyether polyols may be a mixture of two or more.
  • aliphatic amine polyols examples include alkylenediamine-based polyols and alkanolamine-based polyols. These polyol compounds are polyfunctional polyol compounds with terminal hydroxyl groups obtained by ring-opening addition of at least one cyclic ether such as ethylene oxide or propylene oxide using alkylenediamine or alkanolamine as an initiator.
  • alkylenediamine known compounds can be used without limitation. Specifically, alkylenediamines having 2 to 8 carbon atoms such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine and neopentyldiamine are preferably used.
  • These aliphatic amine polyols may be a mixture of two or more.
  • Aromatic amine polyol is a polyfunctional polyether polyol compound with terminal hydroxyl groups obtained by ring-opening addition of at least one cyclic ether such as ethylene oxide or propylene oxide using an aromatic diamine as an initiator.
  • aromatic diamines can be used without limitation. Specific examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine and naphthalenediamine.
  • the use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine or a mixture thereof) is particularly preferred.
  • These aromatic amine polyols may be a mixture of two or more.
  • Mannich polyol is an active hydrogen compound obtained by the Mannich reaction of phenol and/or its alkyl-substituted derivatives, formaldehyde and alkanolamine, or obtained by ring-opening addition polymerization of this compound with at least one of ethylene oxide and propylene oxide. It is a polyol compound.
  • These Mannich polyols may be a mixture of two or more.
  • Polyhydric alcohols include dihydric alcohols (eg, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, etc.) and trihydric alcohols.
  • dihydric alcohols eg, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, etc.
  • trihydric alcohols eg, glycerin, trimethylolpropane, pentaerythritol, methylglucoside, sorbitol, sucrose, etc.
  • These polyhydric alcohols may be a mixture of two or more.
  • Polyhydric phenols include pyrogallol and hydroquinone. These polyhydric phenols may be a mixture of two or more.
  • Bisphenols include bisphenol A, bisphenol S, bisphenol F, low condensates of phenol and formaldehyde, and the like. These bisphenols may be a mixture of two or more.
  • the polyether polyol can be obtained, for example, using any one of the following methods (1) to (3).
  • the catalyst examples include hydroxides (lithium, sodium, potassium, etc.), strongly basic catalysts (alcoholates, alkylamines, etc.), composite metal cyanide complexes (metal porphyrin, zinc hexacyanocobaltate complex, etc.), and the like. be done.
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.
  • polyamine examples include those described later, such as ethylenediamines.
  • alkylene oxide examples include those exemplified in (1).
  • polyvalent hydroxy compound examples include the following (i) to (vi).
  • Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose and melibiose.
  • Acrylic polyol for example, polymerizes a polymerizable monomer having one or more active hydrogens in one molecule, or a polymerizable monomer having one or more active hydrogens in one molecule, and, if necessary, the It can be obtained by copolymerizing a polymerizable monomer and another copolymerizable monomer.
  • Examples of the polymerizable monomer having one or more active hydrogens in one molecule include the following (i) to (vi). These may be used alone or in combination of two or more.
  • acrylic acid esters having active hydrogen such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate
  • Methacrylic acids having active hydrogen such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate esters.
  • (iii) (meth)acrylic acid esters having polyvalent active hydrogen such as (meth)acrylic acid monoesters of triols such as glycerin and trimethylolpropane.
  • unsaturated amides such as acrylic acid, methacrylic acid, maleic acid, itaconic acid (unsaturated carboxylic acids such as acrylamide, N-methylol acrylamide, diacetone acrylamide;
  • vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -(meth)acrylopropyltrimethoxysilane;
  • the above monomer (monomer) component is solution polymerized in the presence of a known radical polymerization initiator such as a peroxide or an azo compound, and if necessary Examples include a method of obtaining an acrylic polyol by diluting with an organic solvent or the like.
  • thermosetting resin composition of the present embodiment When the thermosetting resin composition of the present embodiment is used as a water-based base paint, a known method such as solution polymerization of the above-mentioned monomer (monomer) component and conversion to a water layer or emulsion polymerization is used. Thus, water-based acrylic polyols can be produced. In that case, water-solubility or water-dispersibility can be imparted to acrylic polyol by neutralizing acidic moieties such as carboxylic acid-containing monomers such as acrylic acid and methacrylic acid and sulfonic acid-containing monomers with amines or ammonia. can.
  • polyolefin polyols examples include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene having two or more hydroxyl groups, and hydrogenated polyisoprene having two or more hydroxyl groups.
  • the number of hydroxyl groups is preferably 3 because higher coating strength can be obtained.
  • fluoropolyol means a polyol containing fluorine in its molecule.
  • fluoropolyols include fluoroolefins, cyclovinyl ethers, hydroxyalkyl vinyl ethers, monocarboxylic acid vinyl esters, etc. disclosed in JP-A-57-34107 and JP-A-61-275311. A copolymer etc. are mentioned.
  • Japanese Patent Application Laid-Open Nos. 57-34107 and 61-275311 are hereby incorporated by reference in their entireties.
  • the lower limit of the hydroxyl value of the polyol is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and even more preferably 30 mgKOH/g or more.
  • the upper limit of the hydroxyl value of the polyol is not particularly limited, and may be, for example, 200 mgKOH/g or less.
  • the hydroxyl value of the polyol is preferably 10 mgKOH/g or more and 200 mgKOH/g or less, more preferably 20 mgKOH/g or more and 200 mgKOH/g or less, and further preferably 30 mgKOH/g or more and 200 mgKOH/g or less. preferable.
  • the acid value of the polyol is preferably 0 mgKOH/g or more and 30 mgKOH/g or less.
  • the hydroxyl value and acid value can be measured according to JIS K1557.
  • the molar equivalent ratio (NCO/OH) of the isocyanate groups of the above-described blocked isocyanate composition to the hydroxyl groups of the polyol is preferably 0.2 or more and 5.0 or less, more preferably 0.4 or more and 3.0 or less, and 0 0.5 or more and 2.0 or less is more preferable.
  • polyamine those having two or more primary amino groups or secondary amino groups in one molecule are used, and among them, those having three or more in one molecule are preferable.
  • polyamines include diamines such as ethylenediamine, propylenediamine, butylenediamine, triethylenediamine, hexamethylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, and isophoronediamine, bishexamethylenetriamine, Chain polyamines having 3 or more amino groups such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, tetrapropylenepentamine, etc., 1,4,7,10,13,16-hexaazacyclooctadecane , 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane and 1,4,8,11-tetraazacyclotetradecane.
  • diamines such as ethylenediamine, propylenediamine, butylenediamine, triethylenediamine,
  • the alkanolamine means a compound having an amino group and a hydroxyl group in one molecule.
  • Alkanolamines include, for example, monoethanolamine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono-, di-(n- or iso-)propanolamine, ethylene glycol-bis-propylamine. , neopentanolamine, methylethanolamine, and the like.
  • thermosetting resin composition of the present embodiment may contain a melamine-based curing agent such as a complete alkyl type, methylol type, alkylamino group type alkyl, etc., if necessary.
  • a melamine-based curing agent such as a complete alkyl type, methylol type, alkylamino group type alkyl, etc., if necessary.
  • thermosetting resin composition of this embodiment may contain an organic solvent.
  • the compound having an isocyanate-reactive group and the above-described blocked isocyanate composition may contain an organic solvent.
  • the organic solvent is preferably compatible with the above-mentioned blocked isocyanate composition.
  • organic solvents include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits and naphtha; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and ethyl acetate, butyl acetate, cellosolve acetate and the like.
  • Esters alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol, polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol and glycerin , water, etc., and these solvents may be used alone or in combination of two or more.
  • thermosetting resin composition of the present embodiment can be used as an aqueous thermosetting resin composition dissolved or dispersed in water.
  • an interface Activators and solvents that tend to be miscible with water may also be used.
  • surfactants include anionic surfactants such as aliphatic soaps, rosin acid soaps, alkylsulfonates, dialkylarylsulfonates, alkylsulfosuccinates, polyoxyethylene alkylsulfates, and polyoxyethylene alkylarylsulfates.
  • Nonionic surfactants such as surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, and polyoxyethyleneoxypropylene block copolymers.
  • Solvents that tend to be miscible with water include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutanol, butyl glycol, N-methyl pyrrolidone, butyldiglycol, butyldiglycol acetate and the like.
  • diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutanol, butyl glycol, N-methylpyrrolidone, butyl diglycol are preferable, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Propylene glycol dimethyl ether and dipropylene glycol dimethyl ether are more preferred.
  • These solvents may be used alone or in combination of two or more. Ester solvents such as ethyl acetate, n-butyl acetate, and cellosolve acetate are not preferred because the solvents themselves may hydrolyze during storage.
  • the blending ratio of the blocked isocyanate composition and the compound having an isocyanate-reactive group is determined by the required physical properties and is not particularly limited.
  • Effective isocyanate group amount (mol) of blocked isocyanate compound in /[active hydrogen group amount (mol) of compound having isocyanate-reactive group] range of 0.2 to 5, preferably 0.5 ⁇ 3.
  • the effective isocyanate group of the blocked isocyanate compound means an isocyanate group regenerated when the blocking agent dissociates from the blocked isocyanate compound.
  • thermosetting resin composition of the present invention if necessary, known polyurethane production catalysts, additives, pigments, etc. commonly used in the art can be used, and mixed with known blocked isocyanates. You can use
  • Known catalysts for polyurethane production are not particularly limited, and examples include dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, Tin compounds such as tin acetylacetonate, tin acetate, tin octylate and tin laurate; bismuth compounds such as bismuth octylate, bismuth naphthenate and bismuth acetylacetonate; tetra-n-butyl titanate and tetraisopropyl titanate , titanium compounds such as titanium terephthalate, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N
  • Additives are not particularly limited, and include, for example, hindered amine-based, benzotriazole-based, and benzophenone-based UV absorbers; perchlorate-based, hydroxylamine-based anti-coloring agents; system, sulfur-based, hydrazide-based antioxidants; tin-based, zinc-based, amine-based urethanization catalysts; Stabilizers, plasticizers, surfactants, coupling agents, flame retardants, rust preventives, fluorescent brighteners, pigment dispersants, and other additives used in the art are mentioned.
  • the pigment is not particularly limited, and examples include organic pigments such as quinacridone-based, azo-based, and phthalocyanine-based pigments; inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and silica; Pigments such as pigments and anticorrosive pigments can be used.
  • organic pigments such as quinacridone-based, azo-based, and phthalocyanine-based pigments
  • inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and silica
  • Pigments such as pigments and anticorrosive pigments can be used.
  • Examples of known blocked isocyanates include blocked isocyanates obtained by reacting isocyanates with known blocking agents.
  • known blocking agents include phenol compounds such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol and chlorophenol; oxime compounds such as acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime; - propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, etc.
  • Alcohol compounds such as 3,5-dimethylpyrazole and 1,2-pyrazole, triazole compounds such as 1,2,4-triazole, halogen substitution such as ethylene chlorohydrin and 1,3-dichloro-2-propanol Alcohol compounds, lactam compounds such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and ⁇ -propyllactam, and active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate and ethyl malonate.
  • amine compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, diaryl compounds and the like can also be used.
  • thermosetting resin composition of the present invention can be used for automobiles, buildings, metal products such as steel furniture, wood products such as musical instruments, mechanical vehicles such as construction machinery, building materials such as sashes, and office equipment. paints for electric home appliances, etc., coating materials for artificial leather and rubber rolls, inks, adhesives, adhesives, sealing materials for electronic parts, sealing materials for automobiles and buildings, 3D printers, etc. It can be used as a molding material for
  • thermosetting resin composition of the present invention Next, the method for curing the thermosetting resin composition of the present invention will be explained.
  • thermosetting resin composition which is a mixture of the blocked isocyanate composition and the compound having an isocyanate-reactive group, is heated.
  • reaction temperature varies depending on the blocked isocyanate compound and zwitterionic compound (1) in the blocked isocyanate composition used, it can be about 60 to 250°C, preferably about 80 to 200°C.
  • the reaction time can be about 30 seconds to 5 hours, preferably about 1 minute to 60 minutes.
  • the cured product of the present invention can be produced through the method of curing the thermosetting resin composition of the present invention.
  • R i and R ii are substituted with a group represented by (Q1′), and the rest are substituted with a group represented by (Q2).R i .
  • the reaction mixture contains a compound in which all R ii are substituted with groups represented by (Q1′), or a compound in which all of R i and R ii are substituted with groups represented by (Q2). may be present.
  • reaction was stirred for 1 hour at 25-75°C.
  • the obtained reaction liquid was added to a 500 ml autoclave.
  • Dimethyl carbonate (40.0 g, 445 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. This mixture was reacted at 120° C. for 6 hours.
  • the resulting reaction solution was concentrated under reduced pressure at 60° C. for 1 hour to obtain [TMPADBHDIU][MeCO 3 ] presumed to be a mixture of compounds represented by the above formula as a concentration residue.
  • R i and R ii are substituted with a group represented by (Q1), and the rest are substituted with a group represented by (Q2).
  • the reaction mixture contains a compound in which all ii are substituted with groups represented by (Q1), or a compound in which all of R i and R ii are substituted with groups represented by (Q2). is also good.
  • FIG. 1 shows the 1 H-NMR (DMSO-d 6 ) analysis results of [TMPADBHDIU], which is presumed to be a mixture of compounds represented by the above formula, and FIG. 2 shows the IR analysis results.
  • R iii , R iv and R v are substituted with a group represented by (Q3), and the rest are substituted with groups represented by (Q4′).
  • a compound in which R iii , R iv and R v are all substituted with a group represented by (Q3), or a compound in which R iii , R iv and R v are all substituted with a group represented by (Q4′) may be included in the reaction mixture, m being an integer from 0 to 4.
  • Toluene (50 g) was added to crMDI (25.0 g, NCO group content: 31.0 (%)) (Sumidule 44V20L, manufactured by Sumika Covestro Urethane Co., Ltd.) in a nitrogen-purged 200 ml cylinder flask and dissolved.
  • Dibutylamine (14.2 g, 109 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resulting mixture at 25 to 45 ° C. over 1 hour, and then (3-aminopropyl) dimethylamine (7.68 g, 75 .1 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at 25° C. to 45° C.
  • R iii , R iv and R v are substituted with a group represented by (Q3), and the rest are substituted with groups represented by (Q4).
  • R A compound in which iii , R iv and R v are all substituted with a group represented by (Q3), or a compound in which R iii , R iv and R v are all substituted with a group represented by (Q4) may be included in the reaction mixture, where m is an integer from 0 to 4.
  • TFE 2,2,2-trifluoroethanol
  • MIBK 2,2,2-trifluoroethanol
  • TFE block body of biuret-type HDI, polyester polyol (P-510, manufactured by Kuraray Co., Ltd.), and blocking agent dissociation catalyst [TMPACyHU] obtained in Production Example A-1 were added and stirred for 30 minutes to form a thermosetting resin.
  • a composition was prepared.
  • thermosetting resin composition About 0.6 mL of the prepared thermosetting resin composition was poured onto a hot plate of an automatic curing time measuring device heated to 120°C and stirred. At that time, the curing time is measured from the state where the stirring torque is less than 1% (0.04 mN ⁇ m) immediately after the start of stirring until the stirring torque exceeds 50% (0.86 mN ⁇ m) as the curing time. made an evaluation. Table 1 shows the results.
  • thermosetting composition was prepared in the same manner as in Example 1 except that the blocking agent dissociation catalyst was changed to one shown in Table 1, and the curing time was measured and evaluated. Table 1 shows the results.

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PCT/JP2022/029390 2021-07-30 2022-07-29 両性イオン化合物並びにブロックイソシアネート用ブロック剤解離触媒、該ブロック剤解離触媒を含有するブロックイソシアネート組成物、熱硬化性樹脂組成物、硬化物及びその製造法、並びにカーボネート化合物 Ceased WO2023008579A1 (ja)

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US18/291,355 US20250122322A1 (en) 2021-07-30 2022-07-29 Zwitterionic compound, and blocking agent dissociation catalyst for blocked isocyanate, blocked isocyanate composition containing blocking agent dissociation catalyst, thermosetting resin composition, cured product and method for manufacturing same, and carbonate compound
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WO2020067431A1 (ja) * 2018-09-28 2020-04-02 広栄化学工業株式会社 アミデート化合物の製造方法及びアミデート化合物

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WO2025033431A1 (ja) * 2023-08-10 2025-02-13 株式会社Adeka ブロックイソシアネート組成物、樹脂組成物、樹脂層及び樹脂層の製造方法

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