WO2007123017A1 - Polymerizable unsaturated compound and method for producing the same - Google Patents

Polymerizable unsaturated compound and method for producing the same Download PDF

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Publication number
WO2007123017A1
WO2007123017A1 PCT/JP2007/057867 JP2007057867W WO2007123017A1 WO 2007123017 A1 WO2007123017 A1 WO 2007123017A1 JP 2007057867 W JP2007057867 W JP 2007057867W WO 2007123017 A1 WO2007123017 A1 WO 2007123017A1
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group
general formula
represented
formula
acid
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PCT/JP2007/057867
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French (fr)
Japanese (ja)
Inventor
Yoshihiro Hosaka
Nobutaka Shimamura
Kenichi Inoue
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Wako Pure Chemical Industries, Ltd.
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Priority to JP2008512066A priority Critical patent/JPWO2007123017A1/en
Priority to KR1020087027522A priority patent/KR101050728B1/en
Priority to CN2007800045509A priority patent/CN101379111B/en
Publication of WO2007123017A1 publication Critical patent/WO2007123017A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/547—Hydroxy compounds containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00

Definitions

  • the present invention relates to a novel polymerizable unsaturated compound and a novel method for producing the compound. More specifically, a polymerizable unsaturated compound having a fluorene skeleton or the like in the structural unit, excellent in heat resistance and capable of forming a favorable pattern, and easily adjusting the molecular weight, acid value, etc., and at low temperature.
  • the present invention relates to a simple method for producing the compound, which can be synthesized.
  • Polymerizable resin compositions containing various polymerizable unsaturated compounds (resins) are used, for example, as resists for liquid crystal devices and the like, or as solder resists in the production of printed wiring boards.
  • Specific examples of this conventional method include ⁇ 1> an epoxy acrylate having a bisphenol skeleton by reacting an epoxy compound having a bisphenol skeleton with an acrylic acid derivative at 90 to 120 ° C.
  • An epoxy compound having a fluorene skeleton and (meth) acrylic acid are reacted at 90 to 120 ° C to obtain a (meth) acryl having a fluorene skeleton.
  • An acid ester derivative which is then A method of synthesizing the polymerizable unsaturated resin by reacting with lacarboxylic acid dianhydride at 100 to 130 ° C and further reacting with dicarboxylic acid anhydride at 80 to 110 ° C (for example, Patent Document 4) And ⁇ 3> a method of synthesizing an epoxy atalate toy compound and an acid anhydride by reacting at 100 to 130 ° C. (for example, Patent Document 5) and the like are known.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 5-339356
  • Patent Document 2 JP-A-7-92674
  • Patent Document 3 JP-A-8-278630
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2003-165830
  • Patent Document 5 Japanese Patent Laid-Open No. 11 231523
  • the present invention provides a polymerizable unsaturated compound (resin) having a bisphenyl skeleton, particularly a fluorene skeleton in a structural unit, excellent in heat resistance and capable of forming a good pattern, and having a molecular weight, an acid value, etc.
  • An object of the present invention is to provide a method for producing a polyunsaturated unsaturated compound (resin) having a fluorene skeleton and the like that can be easily adjusted and synthesized at a low temperature.
  • the present invention relates to a general formula (1)
  • R 2 R 1 ′ and R 2 ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group
  • R 3 and R 4 each independently represent a hydrogen atom or a compound represented by the general formula (2) COOR 6 (2)
  • R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a general formula (3)
  • R ′ represents a butyl carbo group or an isopropyl carb group
  • T represents carbon
  • ⁇ And ⁇ and ⁇ are each independently a straight chain of 1 to 6 carbon atoms.
  • R 5 and R 5 ' are each independently, represent.
  • a hydrogen atom or a halogen atom represents a divalent group represented by any one of, V and V are each independently a oxygen atom or a NH group
  • Y represents an oxygen atom, NH group or general formula (5)
  • R 8 represents a hydrogen atom or R 7
  • Y represents an oxygen atom
  • R 9 represents a hydrogen atom or R 7
  • Z represents a tetravalent hydrocarbon group
  • a and b each independently represent 0 or 1
  • k Represents a natural number.
  • at least one of R 6 , R 8 and R 9 is a group having a double bond.
  • the present invention also provides a general formula (7)
  • R 3 'and R 4 ' each independently represents a hydrogen atom, a carboxyl group or an alkoxy group, and Y 'represents an oxygen atom, an NH group or a compound represented by formula (8)
  • ⁇ ' represents an oxygen atom, ⁇ group or formula (9)
  • R 3 ′ and R 4 are a carboxyl group or an alkoxycarbonyl group.
  • the present invention relates to a compound comprising the structural unit represented by the general formula (7) and a general formula (10)
  • R 1C> is a hydrogen atom, an alkali metal atom, or a general formula (14)
  • ⁇ ⁇ represents a hydrogen atom or an alkali metal atom
  • V represents an oxygen atom or a — ⁇ — group.
  • R 11 is a hydrogen atom, an alkali metal atom or a general formula (16)
  • M represents a hydrogen atom or an alkali metal atom
  • V represents an oxygen atom or —NH— group
  • T represents
  • a polybasic acid having 3 or more carboxyl groups including those in which a part of the carboxyl group is a carboxylic acid ester) or an anhydride thereof (a part of the carboxyl group is dehydrated and condensed).
  • the acid anhydride group is formed, and a part of which is a carboxylic acid ester).
  • the polymerizable unsaturated compound of the present invention is a compound having a bisphenol skeleton, particularly a fluorene skeleton in a structural unit, which is alkali-soluble and excellent in heat resistance, and comprises the compound. If the composition is used to form a pattern with light or heat, A pattern with good properties can be easily formed. Further, according to the production method of the present invention, the molecular weight that the conventional method has, for example, the reaction is difficult to control because of the reaction at high temperature, and the yield is low due to side reactions, It is possible to produce a compound comprising the target structural unit represented by the general formula (1), which can easily adjust the acid value and the like and has a good yield.
  • FIG. 1 is a diagram showing 1 H-NMR data of a compound obtained in Example 3.
  • FIG. 2 is a diagram showing 1 H-NMR data of the compound obtained in Example 24.
  • FIG. 3 is a diagram showing IR data of the compound obtained in Example 3.
  • FIG. 4 is a diagram showing IR data of the compound obtained in Example 24.
  • FIG. 5 is a graph showing thermal stability (heat resistance) data of the compound obtained in Example 3.
  • FIG. 6 is a graph showing thermal stability (heat resistance) data of the compound obtained in Example 24.
  • the alkyl group represented by R 2 , R 1 'and R 2 ' is linear, branched or cyclic, usually having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, more preferably Specific examples include alkyl groups having 1 carbon atom, such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n -butyl group, isobutyl group, sec-butyl group, tert- A butyl group, a cyclobutyl group, etc. are mentioned, Of these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
  • the alkoxy group represented by R 2 , R 1 ′ and R 2 ′ is linear, branched or cyclic, usually having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, more preferably Specific examples of the alkoxy group include a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, ter t —Butoxy group, cyclobutoxy group and the like can be mentioned, among which methoxy group and ethoxy group are preferable, and methoxy group is more preferable. As these R 2 , R 1 ′ and R 2 ′, a hydrogen atom is more preferable.
  • the bonding position of U with the benzene ring is not particularly limited, but it is bonded at the positions of m and p with respect to V and V bonded to the benzene ring. What is good
  • the bonding position of U to the benzene ring is either 1, 2, 3, 5, 6 or 1, 2, 2, 3, 5 ,, 6 and any combination of powers are listed. Among them, any combination of 1st, 2nd and 6th positions and 1 ', 2' and 6 'positions are preferred, and 1st place among them. The combination with 1 and rank is more preferred! /.
  • a divalent group represented by the formulas (11) and (17) is more preferable. Among them, a divalent group represented by the formula (11) is preferred. The group is even more preferred.
  • halogen atom represented by R 5 and R 5 ′ in the formula (1-1) for example, a fluorine atom
  • R 5 and R 5 ' a hydrogen atom is more preferable.
  • Y in the general formula (1) is more preferably an oxygen atom or a group represented by the general formula (5), more preferably a group represented by the general formula (5).
  • a group represented by general formula (6) is more preferred.
  • R 3 or is an alkyl group having 1 to 6 carbon atoms represented by in R 6 in the general formula (2) as R 4, linear, either good tool specifically branched or cyclic
  • R 4 linear, either good tool specifically branched or cyclic
  • an alkyl group having 1 to 4 carbon atoms is preferred, such as methyl group, ethyl group, n propyl group, isopropyl group, cyclopropyl group, n —butyl group, isobutyl group, sec —butyl group, t ert butyl Group, and cyclobutyl group.
  • alkyl group having 1 to 2 carbon atoms are methyl group and ethyl group.
  • the tetravalent hydrocarbon group represented by Z usually includes an aromatic or aliphatic tetravalent hydrocarbon group.
  • W, W, W and W are a bond, an oxygen atom, a carbo group, a sulfo group or
  • W represents ethanetetrayl group, propanetetrayl group, butanetetrayl group or
  • h in the general formula (31) usually represents an integer of 1 to 3, and an integer of 2 to 3 is preferable among them.
  • the one shown in is more preferred.
  • Examples of the aromatic tetravalent hydrocarbon group represented by the formula (26) include the formulas (26 ′) and (26 ′ ′)
  • aromatic tetravalent hydrocarbon groups represented by the general formula (27) are more preferred.
  • aromatic tetravalent hydrocarbon group in which W is a bond is represented by the formula (27-1)
  • aromatic tetravalent hydrocarbon group in which W is an oxygen atom is represented by the formula (27-2)
  • the aromatic tetravalent hydrocarbon group in which W is a carbonyl group includes those represented by the formula (27-3) ( 27-3)
  • aromatic tetravalent hydrocarbon group in which W is a sulfonyl group includes those represented by the formula (27-4):
  • aromatic tetravalent hydrocarbon groups represented by the general formula (27) include those represented by the formula (27-5):
  • W represents a bond.
  • the aromatic tetravalent hydrocarbon group is represented by the formula (28— 1)
  • W is an oxygen atom.
  • the aromatic tetravalent hydrocarbon group is represented by the formula (28-2)
  • W represents carbo
  • W is a sulfonyl group
  • W is a vinylene group.
  • the aromatic tetravalent hydrocarbon group is represented by the formula (28-5)
  • W is a bond having a bond.
  • the aromatic tetravalent hydrocarbon group is represented by the formula (29— 1)
  • W is an oxygen atom
  • the aromatic tetravalent hydrocarbon group is represented by the formula (29-2)
  • W is a carbonyl group
  • W is a sulfonyl group
  • W is a vinylene group.
  • the aromatic tetravalent hydrocarbon group is represented by the formula (29-5)
  • those having a diol group that is, those represented by the formula (25), (29-1) or (29-3) are more preferred, among them the formula (29-1) or (29-3) More preferred, what is shown.
  • W represents ethanetetrayl.
  • aliphatic tetravalent hydrocarbon group examples include the formula (30-1)
  • W represents propane tetrale
  • Examples of the aliphatic tetravalent hydrocarbon group that is a thio group include, for example, formula (30-2)
  • W represents butanetetrayl.
  • aliphatic tetravalent hydrocarbon group examples include, for example, formula (30-3)
  • the aliphatic tetravalent hydrocarbon group represented by the general formula (31) is usually an aliphatic group in which h is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
  • tetravalent hydrocarbon groups specifically, for example, the formulas (31-1), (31-2), (31-3) Among them, those represented by the formulas (31-2) and (31-3) are preferred, and those represented by the formula (31-3) are more preferred.
  • aliphatic tetravalent hydrocarbon groups those represented by the formula (32) or (33) are preferable, and those represented by the formula (32) are more preferable.
  • aromatic or aliphatic tetravalent hydrocarbon groups are represented by the general formula (34) in the method for producing a compound comprising a structural unit represented by the general formula (7) described later.
  • R 14 represents an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms represented by R 14 in the general formula (37) may be linear, branched or cyclic. Specific examples include a methyl group, Ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, sec-pentyl Group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1-ethyl propyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, t Examples include ert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 1-ethylbutyl group, cyclohex
  • alkyl groups having 1 to 4 carbon atoms are preferred. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and cyclobutyl group are mentioned. Specific examples of the alkyl group having 1 to 2 carbon atoms are methyl group and ethyl group.
  • k in the general formulas (1) and (7) is a natural number, usually an integer of 1 to: L00, and an integer of 2 to 50 is preferred, and an integer of 2 to 20 is preferred. Is more preferred!
  • a group having a double bond in “in the formula, at least one of R 6 , R 8 and R 9 is a group having a double bond”.
  • the (meth) acrylic acid derivative as used herein means an acrylic acid derivative and Z or a metatalic acid derivative.
  • the alkoxycarbonyl group represented by R 3 'and R 4 is linear, branched or cyclic, usually having 2 to 7 carbon atoms, preferably carbon.
  • examples thereof include an alkoxycarbo group having 2 to 5, more preferably 2 to 3, carbon atoms.
  • Carbon group, n-butoxycarbol group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbol group, and cyclobutoxycarbol group are preferred, among which methoxycarbon group, More preferred is ethoxy carbonate base.
  • the group represented by formula (9) is more preferred.
  • Examples of the halogen atom represented by X in the general formula (10) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom and a bromine atom are preferred. Atoms are more preferred.
  • Examples of the linear alkylene group having 1 to 6 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Among these, a linear alkylene group having 1 to 4 carbon atoms is included. Specific examples of the preferred group include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group. Among them, a linear alkylene group having 1 to 2 carbon atoms is more preferred. , Methylene group, and ethylene group. Among them, a linear alkylene group having 1 carbon atom is more preferable, and a methylene group is specifically mentioned.
  • the bonding positions of the two bonding hands of the arylene group represented by T and T are not particularly limited.
  • the positional relationship force between the two bonds is preferred to be the positional relationship between the m-position and the p-position with respect to the benzene ring, and among them, the positional relationship between the p-position is more preferable.
  • T and T are more preferably a linear alkylene group having 1 to 6 carbon atoms.
  • Examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc.
  • a linear alkylene group having 1 to 3 carbon atoms is particularly preferable.
  • Preferable examples include a methylene group, an ethylene group, and a trimethylene group.
  • a methylene group is more specifically preferable as a linear alkylene group having 1 carbon atom.
  • Examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
  • a linear alkylene group having 2 to 4 carbon atoms is preferable.
  • Specific examples include an ethylene group, a trimethylene group, and a tetramethylene group.
  • a straight-chain alkylene group having 2 carbon atoms is more preferable, and an ethylene group is specifically mentioned.
  • a lithium atom, a sodium atom, a potassium atom, and a cesium atom, and a sodium atom and a potassium atom are more preferable.
  • R 1C> is preferably an alkali metal atom or a group represented by the general formula (14) or (15), among which the general formula (14) or (15 Of these, the group represented by formula (14) is particularly preferred.
  • R 11 in the general formula (13) is preferably an alkali metal atom or a group represented by the general formula (16) or (17), among which the general formula (16) or (17) Of these, the group represented by formula (16) is particularly preferred.
  • examples of the compound comprising a more specific structural unit include Y in the general formula (1).
  • Examples include compounds comprising units.
  • an oxygen atom is more preferable.
  • U is a divalent group represented by the formula (1 1). More specifically, those represented by the above general formula (38) can be mentioned.
  • V and V are oxygen atoms.
  • Preferable specific examples of the structural unit represented by the general formula (40) include T and T having 1 carbon atom.
  • T and T each independently represent a linear alkylene group having 1 to 3 carbon atoms; R 1
  • R 2 , R 1 ′, R 2 ′, R 3 , R 4 , R 5 , R 5 , R 8 , R 9 , Z and k are the same as above. ).
  • Examples thereof include a methylene group, an ethylene group, a trimethylene group, and the like.
  • a methylene group is specifically preferred as a linear alkylene group having 1 carbon atom.
  • RR 2 , R 1 ′, R 2 ′, R 5 , and R 5 ′ are preferably all hydrogen atoms.
  • the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group.
  • the aromatic or aliphatic tetravalent hydrocarbon groups represented by (25) to (33), the above formula (25) or (26), the above general formula (29) or the above formula ( Those shown in (32) or (33) are preferred.
  • the structural unit represented by the general formula (41) is particularly preferred.
  • Z represents an aromatic or aliphatic tetravalent hydrocarbon group represented by the above formula (29-1 ′), (29-3 ′) or (32), and R 3 , R 4 , R 8 , R 9 and k are the same as above. ⁇ Are listed.
  • Preferred examples of the structural unit represented by the general formula (19) include specific examples in which U is a divalent group represented by the formula (1-1) or (17), and more specifically, General formula (43)
  • Examples of 'are oxygen atoms and a and b are 1, more specifically, the general formula (45) Same as above. )
  • Preferable specific examples of the structural unit represented by the general formula (45) include T and T having 2 carbon atoms.
  • each of T, and T independently represents a linear alkylene group having 2 to 4 carbon atoms
  • R 2 , R 1 ′, R 2 ′, R 3 , R 4 , R 5 , R 5 ′, Z and k are the same as above. ).
  • Examples thereof include an ethylene group, a trimethylene group, a tetramethylene group, and the like. Specifically, a linear alkylene group having 2 carbon atoms is preferred, and an ethylene group is specifically exemplified.
  • R 2 , R 1 ′, R 2 ′, R 5 and R 5 ′ are preferably all hydrogen atoms.
  • the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group.
  • aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) or (26), the above general formula (29), or the above formula Those shown by (32) or (33) are preferred.
  • Z represents an aliphatic tetravalent hydrocarbon group represented by the above formula (32), and R 3 , R 4 and
  • the acid value of the compound comprising the structural unit represented by the general formula (1) is such that an appropriate performance can be obtained when the compound is used in various applications. Although it is not particularly limited as long as it is set, it is usually 70 to 150 mgKOHZg, preferably 80 to 13 OmgKOHZg.
  • the acid value of the compound comprising the structural unit represented by the general formula (1) is less than 70 mg KOHZg, for example, in the case of producing a color filter using the resin composition obtained from the compound cartridge, For example, the time for alkali development after light or heat curing is prolonged, and if the acid value exceeds 150 mgKOHZg, the fine pattern is liable to be peeled off during alkali development.
  • the acid value is expressed as the number of milligrams of potassium hydroxide required to neutralize the compound lg, and titration is usually performed using a potassium hydroxide aqueous solution or a mixed solution of alcohol such as ethanol and water. It can be obtained by doing so.
  • k representing the degree of polymerization is the structural unit represented by the general formula (1) among all the structural units in the compound. It is not particularly limited as long as it is set so that appropriate performance can be obtained when the compound is used in various applications, but usually 1 to: L00, preferably Is an integer from 2 to 50, more preferably from 2 to 20.
  • the weight average molecular weight in terms of polystyrene of the compound comprising the structural unit represented by the general formula (1) is such that appropriate performance can be obtained when the compound is used in various applications. Although it is not particularly limited as long as it is set as described above, it is usually 10 to 5 million, preferably ⁇ is 2000 to 100,000, and more preferably ⁇ 2000 to 50,000.
  • the compound comprising the structural unit represented by the general formula (1) of the present invention, contains a structural unit other than the structural unit represented by the general formula (1) as a component.
  • the other structural unit is such that Z in the general formula (38) is a divalent hydrocarbon, and includes the structural unit represented by the general formula (38) and the structural unit.
  • Z in the general formula (38) is a divalent hydrocarbon, and includes the structural unit represented by the general formula (38) and the structural unit.
  • Z ′ represents a divalent hydrocarbon group
  • k ′ and k ′ represent natural numbers
  • R 2 , R 1 ′, R ′, R 3 , R 4 , R 5 , R 5 , , R 8 , R 9 , T, T, V, V, and Z are the same as above.
  • Examples include compounds comprising units.
  • the divalent hydrocarbon group represented by Z ′ usually includes an aromatic or aliphatic divalent hydrocarbon group.
  • W and W are a bond, an oxygen atom, a carbonyl group, a sulfol group, or a beryl.
  • W is a bond, a linear alkylene group having 1 to 18 carbon atoms, a vinylene group, 2, 3- It represents an oral belylene group (1-propene-1,3-diyl group), acetylene group or 2-oxotrimethylene group, and i represents an integer of 1 to 3.
  • the two bonds may be bonded to any carbon among the carbons of the cycloalkyl ring.
  • W and W are a bond or a carbonyl group.
  • W in the general formula (54) a bond, a linear alkylene group having 1 to 18 carbon atoms or a vinylene group is more preferable, and a vinylene group is more preferable.
  • i in the general formula (55) usually represents an integer of 1 to 3, and an integer of 2 to 3 is preferable. Among them, 3 is more preferable.
  • Examples of the aromatic divalent hydrocarbon group represented by the formula (49) include the formula (49 ') or (49'')
  • the one shown in is more preferred.
  • the one shown in is more preferred.
  • W represents a bond.
  • the aromatic divalent hydrocarbon group is represented by the formula (52-1)
  • W is an oxygen atom
  • the aromatic divalent hydrocarbon group is represented by the formula (52— 2) (52-2)
  • W is a carbonyl group
  • W is a sulfonyl group
  • W represents a bond.
  • the aromatic divalent hydrocarbon group is represented by the formula (53-1)
  • W is an oxygen atom
  • the aromatic divalent hydrocarbon group is represented by the formula (53-2)
  • W represents carbo
  • W represents sulfo
  • W is a vinylene group
  • the aromatic divalent hydrocarbon group is represented by the formula (53-5)
  • a group represented by formula (49), (53-1) or (53-3) is more preferred, and among them, a formula (49) is more preferred.
  • the aliphatic divalent hydrocarbon groups in which W is a linear alkylene group having 1 to 18 carbon atoms include Formula (54— 1) — (CH 2 ) j— (54-1)
  • j in the general formula (54-1) is usually an integer of 1 to 18, preferably an integer of 1 to 10, more preferably an integer of 1 to 6.
  • the aliphatic divalent hydrocarbon group in which W is a vinylene group includes the formula (54-2 ') or (54- 2 '')
  • the aliphatic divalent hydrocarbon groups in which W is an acetylene group include those represented by the formula (54-4):
  • the aliphatic divalent hydrocarbon group which is a W-carboxytrimethylene group is represented by the formula (54-5).
  • the aliphatic divalent hydrocarbon group represented by the general formula (55) is usually an aliphatic group in which i is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
  • Specific examples of the divalent hydrocarbon group include, for example, the formulas (55-1), (55-2), (55-3)
  • Examples of the aromatic divalent hydrocarbon group represented by the formula (56) include the formula (56 ′) or (56 ′ ′)
  • W is a bond, carbon.
  • Those having a linear alkylene group or beylene group of 1 to 18 or those represented by the formula (56) are more preferred.
  • W in the general formula (54) is a beylene group.
  • those represented by the formula (56), that is, those represented by the formula (54-2 ′), (54-2,), (56 ′) or (56 ′ ′) are more preferable.
  • an aromatic or aliphatic carboxylic acid (aromatic or aliphatic dicarboxylic acid) having two carboxyl groups, or a general formula (58) (Wherein Z ′ is the same as above), and is derived from an aromatic or aliphatic carboxylic acid anhydride (aromatic or aliphatic dicarboxylic acid anhydride) having two carboxyl groups.
  • Preferred examples of the structural unit represented by the general formula (48) include, as a specific example, V and V are oxygen atoms.
  • Preferable specific examples of the structural unit represented by the general formula (59) include T and T each having 1 carbon atom.
  • RR 2 , R 1 ′, R 2 ′, R 5 , and R 5 ′ are all hydrogen atoms.
  • the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group.
  • aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) or (26), the above general formula (29), or the above formula Those shown by (32) or (33) are preferred.
  • the divalent hydrocarbon group represented by Z ' is not particularly limited as long as it is usually an aromatic or aliphatic divalent hydrocarbon group.
  • aromatic or aliphatic divalent hydrocarbon groups represented by the formulas (49) to (56) those represented by the above formula (49), the above general formula (53) or (54), or the formula (56) What is preferred.
  • R 3 , R 4 , R 8 , R 9 , Z, k ′ and k ′ are the same as above. ⁇ Are listed.
  • the other structural unit is a compound in which Z in the general formula (43) is a divalent hydrocarbon, and a compound comprising the structural unit represented by the general formula (43) and the structural unit Is the general formula (62) (Where,,, z, z,,,
  • Preferred examples of the structural unit represented by the general formula (62) include V, V, Y ′ ′ and Y as specific examples.
  • Preferable specific examples of the structural unit represented by the general formula (63) include T and T having 2 carbon atoms.
  • R 2 , R 2 , R 2 , R 5 and R 5 are all preferably hydrogen atoms.
  • the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group.
  • aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) or (26), the above general formula (29), or the above formula Those shown by (32) or (33) are preferred.
  • the divalent hydrocarbon group represented by Z ' is not particularly limited as long as it is usually an aromatic or aliphatic divalent hydrocarbon group.
  • aromatic or aliphatic divalent hydrocarbon groups represented by the formulas (49) to (56) those represented by the above formula (49), the above general formula (53) or (54), or the formula (56) What is preferred.
  • K ′ representing the degree of polymerization represents the number of structural units including Z among all the structural units in the compound
  • k ′ ′ represents the structural unit including Z ′ among all the structural units in the compound.
  • the compound may be composed of a random structure as shown in AABAAABABB (67).
  • a compound may be constituted.
  • Preferred examples of the structural unit represented by the general formula (20) include specific examples in which U is a divalent group represented by the formula (1-1) or (17), and more specifically, General formula (68)
  • Preferred examples of the structural unit represented by the general formula (68) include specific examples in which V and V are oxygen atoms, and more specifically, the general formula (70)
  • the structural unit represented by the general formula (70) include those in which T and T are linear alkylene groups having 3 carbon atoms, and more specifically, the general formula (71)
  • R 2 , R 2 , R 2 , R 5 and R 5 are all preferably hydrogen atoms.
  • the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group.
  • the aromatic or aliphatic tetravalent hydrocarbon groups represented by (25) to (33), the above formula (25) or (26), the above general formula (29) or the above formula ( 32) or (33) is preferred.
  • Preferred examples of the structural unit represented by the general formula (21) include specific examples in which U is a divalent group represented by the formula (1-1) or (17).
  • the structural unit represented by the general formula (73) is preferred. Specific examples thereof include V, V, Y ′ ′ and Y
  • T and T each have 2 carbon atoms.
  • R 2 , R 1 ′, R 2 ′, R 5 and R 5 ′ are preferably all hydrogen atoms.
  • the tetravalent hydrocarbon group represented by Z is usually aromatic or aliphatic. Although it is not particularly limited as long as it is a tetravalent hydrocarbon group, for example, among the aromatic or aliphatic tetravalent hydrocarbon groups represented by the general formulas (25) to (33), the above formula ( 25) or (26), those represented by the above general formula (29) or the above formula (32) or (33) are preferred.
  • k representing the degree of polymerization is the structural unit represented by the general formula (7) among all the structural units in the compound. It is not particularly limited as long as it is set so that appropriate performance can be obtained when the compound is used in various applications, but usually 1 to: L00, preferably Is an integer from 2 to 50, more preferably from 2 to 20.
  • the polystyrene-converted weight average molecular weight of the compound comprising the structural unit represented by the general formula (7) is such that appropriate performance can be obtained when the compound is used in various applications. Although it is not particularly limited as long as it is set as described above, it is usually 10 to 5 million, preferably ⁇ is 2000 to 100,000, and more preferably ⁇ 2000 to 50,000.
  • the compound comprising the structural unit represented by the general formula (7) of the present invention, contains a structural unit other than the structural unit represented by the general formula (7) as a component.
  • Z in the general formula (68) is a divalent hydrocarbon, and the structural unit represented by the general formula (68)
  • the compound containing the unit is represented by the general formula (78).
  • V and V are oxygen atoms.
  • T and T each have 1 carbon atom.
  • R 2 , R 1 ′, R 2 ′ and R 5 ′ are preferably all hydrogen atoms.
  • the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group.
  • aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) or (26), the above general formula (29), or the above formula Those shown by (32) or (33) are preferred.
  • the divalent hydrocarbon group represented by Z ' is not particularly limited as long as it is usually an aromatic or aliphatic divalent hydrocarbon group.
  • aromatic or aliphatic divalent hydrocarbon groups represented by the formulas (49) to (56) those represented by the above formula (49), the above general formula (53) or (54), or the formula (56) What is preferred.
  • the other structural unit is a compound in which Z in the general formula (73) is a divalent hydrocarbon, and a compound comprising the structural unit represented by the general formula (73) and the structural unit Is the general formula (82)
  • Preferred examples of the structural unit represented by the general formula (82) include V, V, Y ′ ′ and Y as specific examples.
  • T and T each have 2 carbon atoms.
  • RR 2 , R 1, R 2 , R 5 and R 5 are all preferably hydrogen atoms.
  • the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group.
  • aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) Or (26), those represented by the above general formula (29), or the above formula (32) or (33) are preferred.
  • the divalent hydrocarbon group represented by Z ' is not particularly limited as long as it is usually an aromatic or aliphatic divalent hydrocarbon group.
  • aromatic or aliphatic divalent hydrocarbon groups represented by the formulas (49) to (56) those represented by the above formula (49), the above general formula (53) or (54), or the formula (56) What is preferred.
  • the compound comprising the structural unit represented by the general formula (7) other than the structural unit is not limited to the structural unit as described above.
  • other structural units may be included in any ratio.
  • K ′ representing the degree of polymerization in the compound represents the number of structural units containing Z among all the structural units in the compound
  • k ′ ′ represents the composition containing Z ′ among all the structural units in the compound.
  • the compound may be composed of a random structure as shown in (87). In addition to A' and B ', C', D ', etc. Using other structural units as components, the compound may be composed of three or more components.
  • the production method of the compound comprising the structural units represented by the general formulas (1) and (7) that is, the production method of the present invention will be described in detail.
  • a method for producing a compound comprising a structural unit a compound comprising a structural unit represented by the general formula (7) and at least one selected from the general formulas (10), (11) and (12) are selected. If the above (meth) acrylic acid derivative is required, the reaction can be carried out in the presence of a solvent.
  • Y '' Y '' Z a b and k are the same as above. ).
  • the compounds represented by the general formulas (10), (11) and (12) are also applied to a compound comprising a structural unit having a hydroxyl group and a carboxyl group represented by R 3 and R 4 .
  • a structure in which a group derived from the (meth) acrylic acid derivative is introduced into the hydroxyl group and Z or carboxyl group by reacting at least one selected (meth) acrylic acid derivative is a method for producing a compound comprising a unit having a carboxyl group represented by R 3 ′ and R 4 ′.
  • the group derived from a (meth) acrylic acid derivative as used herein means a group derived from a (meth) acrylic acid derivative represented by the general formulas (10), (11) and (12).
  • the group derived from the (meth) acrylic acid derivative represented by the general formula (10) is a group represented by R 7 , that is, a beryl carbo ol group or an iso-propyl carbo ol group.
  • the group derived from the (meth) acrylic acid derivative represented by the general formula (11) means the group represented by the general formula (3), and is represented by the (meth) acrylic acid represented by the general formula (12).
  • the group derived from the derivative means a group represented by the general formula (4).
  • one or more (meth) acrylic acid derivatives represented by the general formulas (10), (11) and (12) may be used.
  • the (meth) acrylic acid derivative 1 to 4k of the structural unit represented by the general formula (20) can be introduced, which is represented by the general formula (21). 1 to 2k structural members can be introduced.
  • the (meth) acrylic acid derivative represented by the general formula (10) is first reacted with the compound comprising the structural unit represented by the general formula (20). Other (meth) acrylic acid derivatives are reacted. First, after reacting with other (meth) acrylic acid derivatives, (meth) acrylic acid derivatives represented by the following general formula (10) It goes without saying that it is okay to react.
  • the above [m] method is a compound represented by the general formula (10) for a compound comprising a structural unit having a hydroxyl group and a carboxyl group represented by R 3 'and R 4 '.
  • This is a method for producing a compound comprising a structural unit in which a group derived from a (meth) acrylic acid derivative is introduced into a hydroxyl group by reacting an acrylic acid derivative.
  • a compound comprising the structural unit represented by the general formula (20) is diluted with a solvent if necessary, and a base, a polymerization inhibitor and, if necessary, a catalyst are added thereto, and then the mixture is mixed.
  • a predetermined amount of the (meth) acrylic acid derivative represented by the general formula (10) is added dropwise to the solution at a predetermined temperature at a predetermined time. Let it react for a while.
  • the solution obtained here can be used for the intended application without isolation and purification.
  • a compound comprising the structural unit represented by the general formula (88) may be used in a conventional manner.
  • the compound may be isolated and purified by As a specific isolation and purification method, since the compound is crystallized by dropping the reaction solution into water, it is filtered and the resulting crystallized product is further purified, for example, with water or the like.
  • the compound can be isolated and purified by washing under reduced pressure and drying under reduced pressure.
  • Examples include (meth) acrylic acid halides such as (meth) acrylic acid chloride and (meth) acrylic acid bromide. Among them, (meth) acrylic acid chloride is preferred.
  • the equivalent of the (meth) acrylic acid derivative represented by the general formula (10) is usually 0.1 to the hydroxyl group in the compound comprising the structural unit represented by the general formula (20).
  • ⁇ 3 equivalents can be mentioned, among which 0.5 to 2 equivalents are preferred, and 0.8 to 1.5 equivalents are more preferred.
  • the reaction temperature in the [III] method is the hydroxyl group in the compound comprising the structural unit represented by the general formula (20) and the (meth) acrylic acid represented by the general formula (10).
  • it will not specifically limit if it is a temperature which reacts with a derivative quantitatively, For example, it is 0-50 degreeC normally, Preferably it is 10-30 degreeC.
  • the reaction temperature exceeds 50 ° C, the polymerization of the (meth) acrylic acid derivative partially occurs, causing a rapid increase in molecular weight, and when the reaction temperature is less than 0 ° C, the reaction proceeds slowly. It takes time for the group derived from the acid derivative to reach the desired introduction amount, and this causes problems such as undesirable.
  • the reaction time in the method [III] may be determined so that the introduction amount of the group derived from the (meth) acrylic acid derivative represented by the general formula (10) falls within an appropriate range. . Since the reaction time depends on the equivalent amount of the (meth) acrylic acid derivative used for the reaction and the reaction temperature, it cannot be generally stated, but is usually 0.5 to 50 hours, preferably 0.5 to 20 hours. More preferably, it is set in the range of 0.5 to 10 hours. [0181] The method [III] is usually carried out in the absence of a solvent or in a solvent, preferably in a solvent.
  • the solvent is not particularly limited as long as it can dissolve each component and reaction product used in the reaction, does not adversely affect the reaction, and is water-soluble.
  • aprotic polar solvents such as N, N-dimethylformamide, 1-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, dioxane, methyl isobuty ketone, ⁇ -butyrolataton, lactate ethyl, and cyclohexanone. These solvents are used singly or in combination of two or more, and the amount of the solvent used is not particularly limited as long as it can dissolve the raw materials.
  • the compound comprising the structural unit represented by the general formula (20) and the (meth) acrylic acid derivative represented by the general formula (10) react quantitatively and smoothly.
  • a base includes bases such as generally used tertiary amines such as triethylamine, pyridine, dimethylaminopyridine and the like. These bases are used alone or in combination of two or more, and the number of equivalents of the above base is not particularly limited, but is usually 1 with respect to the (meth) acrylic acid derivative represented by the general formula (10). ⁇ 2 equivalents.
  • a catalyst can be used.
  • These catalysts include, for example, quaternary ammonium salts such as tetrabutylammonium chloride, tetraptylammonium bromide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, and triphenylphosphine.
  • Examples include catalysts such as organic phosphine compounds. These catalysts are used singly or in combination of two or more, and the amount of the catalyst used is not particularly limited, but relative to the mol amount of the compound comprising the structural unit represented by the general formula (20). In order to improve the reaction rate, about 200 mol% may be used.
  • a polymerization inhibitor can be used in order to prevent polymerization due to double bonds during the reaction.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethylol ether, pyrogallol, 4 tert-butynolecatechol, 2,6-ditert butylphenol, phenothiazine, benzoquinone and the like. These polymerization inhibitors are used singly or in combination of two or more, and the above polymerization inhibitors are used.
  • the amount of the stopper used is not particularly limited, but is usually from 0.001 mol% to 2 mol% with respect to the mol amount of the compound comprising the structural unit represented by the general formula (20).
  • a (meth) acrylic acid represented by the general formula (10) is represented on a compound comprising the structural unit represented by the general formula (20) under appropriate reaction conditions.
  • a group derived from a derivative that is, by controlling the reaction conditions such as the equivalent, reaction temperature and reaction time of the (meth) acrylic acid derivative
  • the group derived from the (meth) acrylic acid derivative It is possible to arbitrarily adjust the introduction amount of.
  • the introduction amount of the group derived from the (meth) acrylic acid derivative should be set so that an appropriate performance can be obtained when the compound obtained by this method is used in various applications.
  • the proportion of the group derived from the (meth) acrylic acid derivative is less than 10 mol%, for example, when producing a color filter using a resin composition obtained from a compound comprising the structural unit, for example, If the alkali development time after light or heat curing is long and the proportion of the group derived from the (meth) acrylic acid derivative is more than 80 mol%, it can be crosslinked and cured with a small amount of light irradiation. This is not preferable because the crosslink density becomes too high and a fine pattern is easily peeled off.
  • R 7 in the general formula (10) is a bullcarbo group. Yes, corresponding to the case where X is a chlorine atom.
  • Y in the general formula (1) is a group represented by the general formula (5), R 8 is a butylcarbonyl group, and Y is a general formula (6).
  • R 9 is a hydrogen atom and a and b are 1
  • the method [V] is a method similar to the method [II]. Production of a compound comprising a structural unit in which a and b in formulas (19) and (21) are 1 Is the method.
  • a compound containing the structural unit represented by the general formula (91) is diluted with a solvent, and a polymerization inhibitor and, if necessary, a condensing agent and Z or a catalyst are added to the mixture.
  • a predetermined equivalent amount of the general formula (11) and (12) force selected from the following formula is dropped into the solution, and the mixture is reacted at a predetermined temperature for a predetermined time.
  • the solution obtained here can be used for the intended purpose without isolation and purification.
  • the compound comprising the structural unit represented by the general formula (92) can be obtained by a conventional method. Separation and purification.
  • examples of the (meth) acrylic acid derivative represented by the general formula (11) include glycidyl (meth) acrylate, 1, 2 epoxy-4 butyl (meth) acrylate, 1 , 2-Epoxy 5 Pentyl (meth) acrylate, 1, 2 Epoxy 6 Hexyl (meth) acrylate, 1, 2 Epoxy— 7 Heptyl (meth) acrylate, 1, 2 Epoxy — 8-Octyl (Meta ) 1,2-epoxy- ⁇ -alkyl (meth) acrylate, such as acrylate, among others, glycidyl (meth) acrylate, 1, 2 epoxy 1-butyl (meth) acrylate, 1, 2 epoxy-5 Of these, pentyl (meth) acrylate is preferred, but darisidyl (meth) acrylate is more preferred.
  • the (meth) acrylic acid derivative represented by the general formula (12) includes, for example, 1-hydroxymethyl (meth) acrylate, 2-hydroxy 1-ethyl (meth) acrylate. 3-hydroxy-1-propyl (meth) acrylate, 4-hydroxy-1-butyl (meth) acrylate, 5-hydroxy-1-pentyl (meth) acrylate, 6-hydroxy-1-hexyl (meth) acrylate, etc.
  • the equivalent weight of the (meth) acrylic acid derivative represented by the general formulas (11) and (12) is relative to the carboxyl group in the compound comprising the structural unit represented by the general formula (91). Usually 0.1 to 3 equivalents are mentioned, and 0.5 to 2 equivalents are preferred, and 0.8 to 1.5 equivalents are more preferred.
  • (meth) acrylic acid derivative represented by the general formula (11) a commercially available product may be used as appropriate, which is usually synthesized by a production method used in this field.
  • (meth) acrylic acid derivative represented by the general formula (12) a commercially available product may be used as appropriate, which is usually synthesized by a production method used in this field.
  • the reaction temperature in the method [V] is selected from the carboxyl group in the compound comprising the structural unit represented by the general formula (91), and at least the forces selected from the general formulas (11) and (12). Although it is not particularly limited as long as it is a temperature at which one or more (meth) acrylic acid derivatives react quantitatively, for example, usually ⁇ 10 to 150 ° C., preferably 0 to 120 ° C. . Reaction temperature is 150 When the temperature exceeds ° C, the polymerization of the (meth) acrylic acid derivative partially occurs, causing a rapid increase in molecular weight, and when the temperature is lower than 10 ° C, the reaction proceeds slowly. It takes time for the group to reach the desired amount of introduction, which causes problems such as undesirable.
  • the reaction time in the method [V] is such that the introduction amount of groups derived from at least one (meth) acrylic acid derivative selected from the general formulas (11) and (12) is within an appropriate range.
  • the reaction time may be determined. Since the reaction time depends on the equivalent amount of the (meth) acrylic acid derivative used in the reaction and the reaction temperature, it cannot be generally stated, but is usually 0.5 to 50 hours, preferably 0.5 to 20 hours. More preferably, it is set in the range of 0.5 to 10 hours.
  • the solvent used in the method [V] may be the same as that used in the above [III], as long as the same solvent as used in the above [III] is used.
  • the compound comprising the structural unit represented by the general formula (91) and the (meth) acrylic acid derivative represented by the general formula (12) react quantitatively and smoothly.
  • a condensing agent include, for example, carpositimides such as dicyclohexyl carbodiimide, 1-ethyl 3- [3- (N, N dimethylamino) propyl] carbodiimide hydrochloride, di-2-pyridyl carbonate, di-2-pyridylthio carbonate.
  • a condensing agent such as carbonates.
  • condensing agents are used singly or in combination of two or more, and the number of equivalents of the condensing agent is not particularly limited, but for the (meth) acrylic acid derivative represented by the general formula (12) Usually, 1 to 2 equivalents can be mentioned.
  • a catalyst can be used.
  • These catalysts include, for example, quaternary ammonium salts such as tetrabutylammonium chloride, tetraptylammonium bromide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, and triphenylphosphine.
  • Examples include catalysts such as organic phosphine compounds. These catalysts are used singly or in combination of two or more, and the amount of the catalyst used is not particularly limited, but relative to the mol amount of the compound comprising the structural unit represented by the general formula (91). In order to improve the reaction rate, about 200 mol% is sometimes used.
  • a polymerization inhibitor can be used in order to prevent polymerization due to double bonds in the reaction.
  • the polymerization inhibitor used in the method [V] may be the same as that used in the above [III], as long as the same polymerization inhibitor as in the above [III] is used.
  • a compound comprising the structural unit represented by the general formula (91) under appropriate reaction conditions is selected from at least one selected from the general formulas (11) and (12).
  • a group derived from more than one kind of (meth) acrylic acid derivative that is, by controlling the reaction conditions as described above such as equivalent weight of the (meth) acrylic acid derivative, reaction temperature, reaction time, etc. It is possible to arbitrarily adjust the amount of introduction of a group derived from a (meth) atallylic acid derivative.
  • the introduction amount of the group derived from the (meth) attalic acid derivative should be set so that appropriate performance can be obtained when the compound obtained by this method is used in various applications.
  • the ratio is usually 1 to 100 mol%, preferably 10 to 80 mol% with respect to the mol amount of the carboxyl group of the compound comprising the structural unit represented by the general formula (91). is there.
  • the proportion of the group derived from the (meth) acrylic acid derivative is less than 10 mol%, for example, when producing a color filter using a resin composition obtained from a compound containing the structural unit, For example, the alkali development time after light or heat curing becomes longer, and when the proportion of the group derived from the (meth) acrylic acid derivative is more than 80 mol%, it can be crosslinked and cured with less light irradiation. This is not preferable because the crosslink density becomes too high and the fine pattern easily peels off.
  • R 3 ′ and R 4 ′ in the general formula (7) are carboxy groups, and Y ′ and Y ′ are oxygen atoms or NH groups. Yes, if a and b are 1
  • R 3 in the general formula (1) is a group represented by the general formula (2)
  • R 6 is a group represented by the general formula (3)
  • R 7 and T are R 4 is represented by the general formula (2).
  • R 6 is a hydrogen atom, Y and Y are an oxygen atom or an NH group
  • a and b are equal to 1.
  • the compound represented by the formula (96) corresponds to the case where R 7 in the general formula (12) is a butyl carbo group and T is an ethyl group.
  • R 3 in the general formula (1) is a group represented by the general formula (2)
  • R 6 is a group represented by the general formula (4)
  • R 7 And T is the same group as above
  • R 4 is
  • R 6 is a hydrogen atom
  • Y and Y are an oxygen atom or N
  • a compound represented by the general formula (13) and a polybasic acid (calcium having three or more carboxyl groups) are used. Including those in which a part of the boxyl group is a carboxylic acid ester) or anhydrides thereof (including those in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group) Including a part of which is a carboxylic acid ester.
  • the following [VIII] method can be used.
  • R 12 represents a hydrogen atom, an alkali metal atom or a group represented by the above general formula (15);
  • R 13 represents a hydrogen atom, an alkali metal atom or a group represented by the above general formula (17);
  • R 2 , R 1 ', R 2 , R 3 , R 4 , T, T, U, V, V, Y,,, Y,, Z, a, b and k are as above
  • one or more compounds represented by the general formulas (22) and (23) can be used, and the general formula (34)
  • Polybasic acid anhydrides including those in which a part of the carboxyl group is dehydrated and condensed to form an acid anhydride group, and part of which is a carboxylic acid ester
  • Species or multiple species can be used.
  • a compound represented by the general formula (22) is diluted with a solvent, and if necessary, a catalyst is added thereto.
  • a polybasic acid having 3 or more carboxyl groups represented by (including those in which a part of the carboxyl group is a carboxylic acid ester) is added and reacted at a predetermined temperature for a predetermined time.
  • the solution obtained here can be used for the intended application without isolation and purification. Depending on the application, the solution may be further diluted with a solvent, or the structure represented by the general formula (20).
  • a compound containing the unit may be isolated and purified by a conventional method.
  • the compound represented by the general formula (22) is, for example, the general formula (98).
  • the compound having a bisphenyl skeleton referred to here is, for example, as shown in the above general formula (98), two phenol groups having bonds or formulas (11) to (18). ) Means a compound having a structure crosslinked with a divalent group.
  • Specific examples of the compound having the bisphenyl skeleton when U is represented by the formula (11) include, for example, 9, 9-bis (4-hydroxyphenyl) fluorene, 9, 9-bis (4— Hydroxy-3,5-dimethylphenol) fluorene, 9,9-bis (4-hydroxy-1,3,5-dichlorophenol) fluorene, 9,9-bis (4-hydroxy-1,3,5-dibromophenol) ) Fluorene, 9, 9-bis (4-hydroxy-3-methylphenol) fluorene, 9, 9-bis (4-hydroxysilane 3-chlorophenol) phenololene, 9, 9-bis ( 4-hydroxy-1-3-bromophenol) fluorene, 9, 9-bis (4-hydroxy-1-fluorophenol) fluorene, 9, 9-bis (4-hydroxy-1-methoxyphenol) fluorene, 9, 9-bis (4-aminophenol) fluorene, 9, 9-bis (4-amino-3, 5 Jimechirufue - Le) fluor
  • Specific examples of the compound having a bisphenyl skeleton when U is represented by the formula (12) include, for example, bis (4-hydroxyphenol) ketone, bis (4-hydroxy-1,3,5-dimethyl). Phenol) ketone, bis (4-hydroxy-1,3,5-dichlorophenol) ketone, bis (4-hydro) Xy-1,5-dibromophenol) ketone, bis (4-aminophenol) ketone, bis (4-aminoamino-3,5-dimethylphenol) ketone, bis (4-amino-1,3,5-dichlorophenol) -L) ketone, bis (4 amino-3,5-dibromophenol) ketone and the like.
  • Specific examples of the compound having the bisphenyl skeleton when U is the formula (13) include, for example, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-1,3,5-dimethyl).
  • Specific examples of the compound having the bisphenyl skeleton when U is the formula (14) include, for example, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy- 3,5-Dimethylphenol) hexafluoropropane, bis (4-hydroxy-3,5-dicyclomethyl) hexoxanoleopropane, bis (4-hydroxy-1,3,5-dibromophenol) Hexafluoropropane, bis (4-aminophenol) Hexafluoropropane, bis (4-amino-3,5-dimethylphenol) hexafluoropropane, bis (4-amino-3, 5 — Dichroic mouth) hexafluoropropane, bis (4-amino-3,5-dibromophenol) hexafluoropropane, and the like.
  • Specific examples of the compound having the bisphenyl skeleton in the case where U is the formula (15) include, for example, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-1,3,5- Dimethylphenol) dimethylsilane, bis (4-hydroxy-1,3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxy-1,3,5-dibromophenol) dimethylsilane, bis (4-aminophenol) dimethyl Silane, bis (4-amino-3,5-dimethylphenol) dimethylsilane, bis (4-amino-1,3,5-dichlorophenol) dimethylsilane, bis (4-amino-1,3,5-dibromophenol) dimethyl Silane etc. are mentioned.
  • Specific examples of the compound having the bisphenyl skeleton when U is the formula (16) include bis (4-hydroxyphenol) methane, bis (4-hydroxy-1,3,5-dimethyl), and the like.
  • Specific examples of the compound having the bisphenyl skeleton when U is represented by the formula (17) include, for example, 2, 2 bis (4 hydroxyphenol) propane, 2, 2 bis (4 hydroxy-3) , 5 dimethylphenol) propane, 2,2 bis (4 hydroxy-1,3,5 dichlorophenol) propane, 2,2 bis (4 hydroxy-1,3,5 dibromophenol) propane, 2,2 bis (4 hydroxy) 1-Methylphenol) propane, 2,2bis (4hydroxy-3 cyclochrome) propane, 2,2bis (4hydroxy-3-bromophenol) propan, 2,2bis (4aminophenol) Propane, 2,2 bis (4 amino-3,5 dimethylphenol) propane, 2,2 bis (4 amino-3,5 dichlorophenol) propane, 2,2 bis (4 amino-3,5 dibromophenol) ) Propane, 2, 2 bis (4 amino-3-methylphenol) Bread, 2, 2-bis (4-amino-3 Black port Hue - Le) propane, 2, 2-bis (4 Amino 3 Buromofue - Le) propane.
  • Specific examples of the compound having the bisphenyl skeleton when U is represented by the formula (18) include, for example, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-1,3,5-dimethyl). Ruthenium ether), bis (4-hydroxy-3,5-dicyclophole) ether, bis (4-hydroxy-1,3,5-dibromophenol) ether, bis (4-aminophenol) ether, bis Examples include (4-amino-3,5-dimethylphenol) ether, bis (4-amino-3,5-dichlorophenol) ether, bis (4 amino-3,5-dibromophenol) ether, and the like.
  • the compound represented by the general formula (22) is represented by the general formula (98).
  • the polybasic acid having 3 or more carboxyl groups represented by the general formula (34) (including those in which a part of the carboxyl group is a carboxylic acid ester) is usually an aromatic compound having 3 or more carboxyl groups.
  • An aliphatic or aliphatic carboxylic acid (including those in which a part of the carboxyl group is a carboxylic acid ester).
  • W, W, W and W are a bond, an oxygen atom, a carbo ol group, a sulpho group or
  • W represents an ethanetriyl group, a propanetriyl group or a butanetriyl group.
  • W represents an ethylenetetrayl group or a butanetetrayl group
  • p is an integer of 1 to 3.
  • W to W may be a bond or a carbo group.
  • p usually represents an integer of 1 to 3, and preferably an integer of 2 to 3
  • aromatic tricarboxylic acid represented by the formula (99) include 1, 2, 3 benzene tricarboxylic acid, 1, 2, 4 benzene tricarboxylic acid (trimellitic acid), 1, 3 , 5 Benzenetricarboxylic acid and the like. Among them, 1, 2, 4 benzenetricarboxylic acid (trimellitic acid) is preferable.
  • aromatic tetracarboxylic acid represented by the formula (100) include 1, 2, 3, 4 benzenetetracarboxylic acid, 1, 2, 3, 5 benzenetetracarboxylic acid, 1, 2, 4, 5 Benzenetetracarboxylic acid (pyromellitic acid) and the like, among which 1, 2, 4, 5 benzenetetracarboxylic acid (pyromellitic acid) is preferred!
  • aromatic tetracarboxylic acid represented by the formula (101) include 1, 2, 3, 4 naphthalene tetracarboxylic acid, 1, 2, 3, 5 naphthalene tetracarboxylic acid, 1, twenty three 6-Naphthalenetetra-force norevonic acid, 1, 2, 3, 7--Naphthalenetetra-force norevonic acid, 1, 2, 3
  • W is an aromatic bond
  • tetracarboxylic acids examples include 2, 3, 4, 5 biphenyl tetracarboxylic acid, 2, 3, 4, 6 biphenyl tetracarboxylic acid, 2, 3, 5, 6 biphenyl tetracarboxylic acid, and the like. Can be mentioned.
  • aromatic tetracarboxylic acids in which W is an oxygen atom examples include 2, 3, 4
  • examples of the aromatic tetracarboxylic acid in which W is a carbo group include 2, 3, 4, 5
  • Nzophenone tetracarboxylic acid 2, 3, 4, 6 benzophenone tetracarboxylic acid, 2, 3, 5, 6-benzophenone tetracarboxylic acid and the like.
  • W is sulfol.
  • aromatic tetracarboxylic acid examples include 2, 3, 4, 5 biphenyl sulfone tetracarboxylic acid, 2, 3, 4, 6 biphenyl sulfone tetracarboxylic acid, 2, 3, 5, 6 biphenyl.
  • aromatic tetracarboxylic acid examples include 2, 3, 4, 5 biphenyl sulfone tetracarboxylic acid, 2, 3, 4, 6 biphenyl sulfone tetracarboxylic acid, 2, 3, 5, 6 biphenyl.
  • examples include sulfonetetracarboxylic acid.
  • Examples of the group tetracarboxylic acid include cis—2, 3, 4, 5 stilbene tetracarboxylic acid, trans-2, 3, 4, 5 stilbene tetracarboxylic acid, cis—2, 3, 4, 6 stilpentetracarboxylic acid, trans— 2, 3, 4, 6 stilbene tetracarboxylic acid, cis— 2, 3, 5, 6 stilbene tetracarboxylic acid, trans— 2, 3, 5, 6 stilbene tetracarboxylic acid, etc. Is mentioned.
  • W is an aromatic bond
  • tetracarboxylic acid examples include 2,2 ', 3,4-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, 2,3,4,4, and 1 biphenyl.
  • Tetracarboxylic acid 2, 2 ', 3, 5-biphenyltetracarboxylic acid, 2, 3, 3', 5-biphenyltetracarboxylic acid, 2, 3, 4 ', 5-biphenyltetracarboxylic acid Acid, 2, 2 ', 3, 6-biphenyltetracarboxylic acid, 2, 3, 3', 6-biphenyltetracarboxylic acid, 2, 3, 4, 6, 6-biphenyltetracarboxylic acid, 2, 2 ', 4, 5—Bi-Fereral Carboxylic Acid, 2, 3, 4, 4, 5-Bi-Ferter Carboxylic Acid, 2, 4, 4 ,, 5-Bi-Ferter Tetracarboxylic Acid, 2 , 2 ', 4, 6-biphenyl carbonate, 2, 3, 4, 4, 6-biphenyl carbonate, 2, 4, 4, 6, 6-biphenyl carbonate, etc. It is done.
  • Aromatic tetracarboxylic acids that are carbo groups include, for example, 2, 2 ', 3, 4 benzofuenone tetraforce norebonic acid, 2, 3, 3', 4-ben: / phenone tetraforce norebonic acid, 2 , 3, 4, 4, —benzophenone tetracarboxylic acid, 2, 2 ′, 3, 5—benzophenone tetracarboxylic acid, 2, 3, 3 ′, 5-benzophenone tetracarboxylic acid, 2, 3 , 4 ', 5-benzophenone tetracarboxylic acid, 2, 2', 3, 6-benzophenone tetracarboxylic acid, 2, 3, 3 ', 6-benzophenone tetracarboxylic acid, 2, 3, 4' , 6-Benzophenone tetracarboxylic acid, 2, 2 ', 4, 5-Benzophenone tetracarboxylic acid, 2, 3', 4, 5-Benzophenone te
  • boric acid examples include 2, 2 ', 3, 4 biphenyl sulfone tetracarboxylic acid, 2, 3, 3, 4, biphenyl sulfone tetracarboxylic acid, 2, 3, 4, 4'-biphenyl sulfone.
  • Tetraforce Rubonic acid 2, 2 ', 3, 5 Biphenylsulfone tetracarboxylic acid, 2, 3, 3', 5 Biphenylsulfone tetracarboxylic acid, 2, 3, 4 ', 5 Biphenylsulfone tetracarboxylic acid acid,
  • aromatic tetracarboxylic acids are cis-2,2 ', 3,4 stilbenetetracarboxylic acid, trans-2,2'3,4-stilbenetetracarboxylic acid, cis-2,3,3 3, 4, Stilbene tetracarboxylic acid, trans- 2, 3, 3 ', 4 Stilbene tetracarboxylic acid, cis- 2, 3, 4, 4' Stilbene tetracarboxylic acid, trans- 2, 3, 4, 4 'Stilbene Tetracarboxylic acid, cis— 2, 2 ′, 3, 5-stilbene tetracarboxylic acid, trans— 2, 2 ′,
  • Examples of the group tetracarboxylic acids include 2, 2 ', 3, 3'-biphenyl tetracarboxylic acid, 2, 2', 3, 4, biphenyl tetracarboxylic acid, 2, 2 ', 3, 5, -Biphenyltetracarboxylic acid, 2, 2 ,, 3, 6, biphenyl tetracarboxylic acid, 2, 3, 3, 4, biphenyl tetracarboxylic acid, 2, 3, 3, 5, bibiphenol -Luteracarboxylic acid, 2, 2 ', 4, 4, -biphenyl tetracarboxylic acid, 2, 2', 4, 5, -biphenyltetracarboxylic acid, 2, 2 ', 4, 6,- Biphenyl tetracarboxylic acid, 2, 3 ,, 4, 4, biphenyl tetracarboxylic acid, 2, 3, 4, 4, 5, biphenyl tetracarboxylic acid, 2, 2 ', 5, 5
  • Aromatic tetracarboxylic acids that are carbol groups include, for example, 2, 2 ', 3, 3'-benzophenone tetracarboxylic acid, 2, 2', 3, 4, monobenzophenone tetracarboxylic acid.
  • cis-3, 3, 3, 4, 4, monostilpene tetracarboxylic acid, trans-3, 3, 3, 4, 4, stilbene tetracarboxylic acid, cis-3 , 3 ,, 5, 5, stilbenetetracarboxylic acid, trans-3, 3 ', 5, 5, monostilbenetetracarboxylic acid are preferred, cis-3, 3', 4, 4, 1 More preferred is stilbene tetracarboxylic acid, trans-3, 3, 4, 4, 4 'stilbene tetracarboxylic acid.
  • aromatic tetracarboxylic acids those represented by the formula (100) or the general formula (104) are preferred, and W in the formula (100) or the general formula (104) is a bond or a carbocycle.
  • W is an ethanetril group
  • Examples of the aliphatic tricarboxylic acid include ethanetricarboxylic acid.
  • Examples of the aliphatic tricarboxylic acid in which w is a propanetril group include propanetrialkyl.
  • Examples include boronic acid. Furthermore, an aliphatic tricarboxylic acid in which w is a butanetriyl group and
  • Examples thereof include butanetricarboxylic acid.
  • W represents ethylenetetrayl
  • Examples of the aliphatic tetracarboxylic acid as a group include ethylene tetracarboxylic acid.
  • An example of an aliphatic tetracarboxylic acid in which w is a butanetetrayl group is
  • Examples thereof include butanetetracarboxylic acid.
  • Examples of the aliphatic tetracarboxylic acid represented by the general formula (107) include aliphatic tetracarboxylic acids in which p is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
  • p is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
  • cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid and the like can be mentioned, among which cyclopentanetetracarboxylic acid
  • cyclohexanetetracarboxylic acid is preferred, and cyclohexanetetracarboxylic acid is more preferred.
  • Examples of the aliphatic tetracarboxylic acid represented by the formula (108) include 4- (1,2 dicarboxyethyl) -1, 2, 3, 4-tetrahydronaphthalene 1,2 dicarboxylic acid.
  • Examples of the aliphatic tetracarboxylic acid represented by the formula (109) include 5- (1,2 dicarboxyethyl) 3-methylcyclohexane 1,2 dicarboxylic acid.
  • the carboxyl group of the aromatic or aliphatic carboxylic acid may be a carboxylic acid ester represented by the general formula (37)! /, And has the carboxylic acid ester.
  • the compound was synthesized by a general method in which a commercially available compound was used, for example, an aromatic or aliphatic carboxylic acid represented by the above general formulas (99) to (109) was allowed to act on an alcohol such as methanol or ethanol. If you use something as appropriate,
  • the equivalent amount of the polybasic acid having three or more carboxyl groups represented by the general formula (34) (including those in which a part of the carboxyl groups is a carboxylic acid ester) is represented by the general formula (22).
  • 0.5 to 2 equivalents may be mentioned relative to the compound to be obtained.
  • the reaction temperature in the method [VIII] is a polybasic acid (carboxy group) having 3 or more epoxy groups in the compound represented by the general formula (22) and three or more carboxyl groups represented by the general formula (34). Is not particularly limited as long as it is a temperature at which the carboxyl group in the silyl group reacts quantitatively, for example, usually 60 to 120 ° C, preferably Is 70 ⁇ 90 ° C. When the reaction temperature exceeds 120 ° C, some intramolecular and intermolecular anhydrides of the polybasic acid occur, causing a rapid increase in molecular weight, and below 60 ° C, the reaction proceeds slowly.
  • the reaction time in the method [VIII] is such that the degree of polymerization k in the general formula (20) falls within an appropriate range, that is, comprises the structural unit represented by the general formula (20).
  • the reaction time may be determined so that the weight average molecular weight of the compound falls within an appropriate range.
  • the reaction time depends on the equivalent of the polybasic acid used in the reaction (including those in which a part of the carboxyl group is a carboxylic acid ester) and the reaction temperature. It is set in the range of 5 to 50 hours, preferably 1 to 24 hours, more preferably 2 to 15 hours.
  • the solvent used in the method [VIII] is not particularly limited as long as the same solvent as used in the method [III] is used, as long as the amount of the solvent can be dissolved.
  • a compound represented by the general formula (22) and a polybasic acid having 3 or more carboxy groups represented by the general formula (34) It is preferable to use a catalyst so that it reacts quantitatively and smoothly.
  • these catalysts include quaternary ammonium salts such as tetraptyl ammonium chloride, tetrabutyl ammonium chloride, triethylbenzyl ammonium chloride, and triethyl benzyl ammonium chloride, and organic phosphines such as triphenylphosphine.
  • quaternary ammonium salts such as tetraptyl ammonium chloride, tetrabutyl ammonium chloride, triethylbenzyl ammonium chloride, and triethyl benzyl ammonium chloride
  • organic phosphines such as triphenylphosphine.
  • a catalyst such as a compound.
  • catalysts are used alone or in combination of two or more, and the amount of the catalyst used is not particularly limited, but is 0.001 mol% with respect to the mol amount of the compound represented by the general formula (22). As mentioned above, in order to improve the reaction rate, about 200 mol% may be used.
  • the compound represented by the general formula (22) corresponds to the case where R 1 "in the general formula (13) is the general formula (14) and R 11 is the general formula (16).
  • the compound represented by the general formula (110) includes a polybasic acid having 3 or more carboxyl groups (including those in which a part of the carboxyl group is a carboxylate ester), 3, 3 ′, 4, 4, -Biphenyltetracarboxylic acid, 3, 3 ', 4, 4' monobenzophenone tetracarboxylic acid or 4- (1,2 dicarboxyethyl) 1, 2, 3, 4-tetrahydronaphthalene 1,2 dicarboxylic This corresponds to the case where the acid is limited to the aliphatic tetracarboxylic acid represented by the above formula (108)
  • the compound comprising the structural unit represented by the general formula (111) is represented by R in the general formula (7). 3 and R 4 ′ are carboxyl groups, Y ′ is a group represented by the formula (
  • the hydrocarbon group is limited to an aromatic or aliphatic tetravalent hydrocarbon group represented by the above formula (29-1 ′), (29-3 ′) or (32), and a and b are 1, This is the case.
  • aromatic or aliphatic carboxylic acid aromatic or aliphatic dicarboxylic acid having two carboxyl groups represented by the general formula (57)
  • aromatic or aliphatic carboxylic acid aromatic or aliphatic dicarboxylic acid having two carboxyl groups represented by the general formula (57)
  • formulas (113) to (11) aromatic or aliphatic dicarboxylic acid having two carboxyl groups represented by the general formula (57) include, for example, formulas (113) to (11
  • W and W are a bond, an oxygen atom, a carbo group, a sulfo group or a bead
  • W is a bond, a linear alkylene group having 1 to 18 carbon atoms, vinylene group, 2, 3—
  • W and W in the general formulas (116) and (117) are a bond or a carbon.
  • W represents a bond, a linear alkylene group having 1 to 18 carbon atoms.
  • a beylene group is more preferable, among which a beylene group is more preferable.
  • q usually represents an integer of 1 to 3, and preferably an integer of 2 to 3
  • aromatic dicarboxylic acid represented by the formula (113) include phthalic acid, isophthalic acid, terephthalic acid, and the like. Among these, phthalic acid and terephthalic acid are preferable.
  • aromatic dicarboxylic acid represented by the formula (114) include 1,2 naphthalene dicarboxylic acid, 1,3 naphthalene dicarboxylic acid, 1,4 naphthalene dicarboxylic acid, and 1,5 naphthalene dicarboxylic acid.
  • Acid 1, 6 naphthalene dicarboxylic acid, 1, 7 naphthalene dicarboxylic acid, 1, 8 naphthalene dicarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 2, 6 naphthalene dicarboxylic acid, 2, 7 naphthalene dicarboxylic acid, etc.
  • 8 Naphthalene dicarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 2, 6 naphthalene dicarboxylic acid Rubonic acid is preferred.
  • aromatic dicarboxylic acid represented by the formula (115) include 2,3 pyridine dicarboxylic acid, 2,4 pyridinedicarboxylic acid, 2,5 pyridinedicarboxylic acid, and 2,6 pyridinedicarboxylic acid. Acid, 3, 4 pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid Etc.
  • W is an aromatic dicarboxylic acid.
  • carboxylic acid examples include 2,3-biphenyl dicarboxylic acid, 2,4-biphenol di-norebonic acid, 2,5-bipheninoresi power norlevonic acid, 2,6-biphenylinose power norebon acid, 3,4-biphenol- And rudicarboxylic acid and 3,5-biphenyl dicarboxylic acid.
  • aromatic dicarboxylic acids in which 13 is an oxygen atom examples include 2,3-biphenyl ether dicarboxylic acid, 2,4-biphenyl ether dicarboxylic acid, 2,5-biphenyl ether dicarboxylic acid, 2,6-biphenol- Examples include ruether dicarboxylic acid, 3,4-biphenyl ether dicarboxylic acid, 3,5-biphenyl ether dicarboxylic acid, and the like.
  • aromatic dicarboxylic acids in which 13 is a carbocyclic group examples include 2,3-benzophenone dinorebonic acid, 2,4-benzophenone dicanolebon acid, and 2,5-benzophenone dicanolebon.
  • Examples include acids, 2,6-benzophenone dicanolevon acid, 3,4 benzophenone dicanolevon acid, 3,5-benzophenone dicarboxylic acid, and the like.
  • W is a sulfo group.
  • aromatic dicarboxylic acid examples include 2,3-biphenylsulfone dicarboxylic acid, 2,4-biphenylenosnorejon dicanolevonic acid, 2,5-bibienoresnorejon dicanolevonic acid, 2,6- Examples thereof include biphenylenosnorejon dicanolevonic acid, 3,4-biphenylenolesnorejon dicanolevonic acid, 3,5-biphenylsulfone dicarboxylic acid, and the like.
  • aromatic diene wherein w is a beylene group.
  • carboxylic acid examples include cis-2,3-stilbene dicarboxylic acid, trans-2,3-stilbene dicarboxylic acid, cis-2,4-stilbene dicarboxylic acid, trans-2,4-stilbene dicarboxylic acid, cis — 2, 5—stilbene dicarboxylic acid, trans— 2, 5—stilbene dicarboxylic acid, cis— 2, 6-stilbene dicarboxylic acid, trans— 2, 6-stilbene dicarboxylic acid, cis— 3, 4-stilbene dicarboxylic acid Trans-3,4-stilbene dicarboxylic acid, cis-3,5-stilbene dicarboxylic acid, trans-3,5-stilbene dicarboxylic acid, and the like.
  • aromatic dicarboxylic acids represented by the general formula (117) an aromatic dicarboxylic acid in which W is a bond.
  • Examples of the carboxylic acid include 2,2,1-biphenyldicarboxylic acid, 2,3,1-biphenyldicarboxylic acid, 2,4,1-biphenyldicarboxylic acid, 3,3,1-biphenyldicarboxylic acid, 3 4, 4-biphenyl dicarboxylic acid, 4, 4-biphenyl dicarboxylic acid, etc. 3,3,1-bipheninoresigenic power Norevonic acid, 3,4,1-biphenolo-renocinolevonic acid, 4,4,1-bibi-didicarboxylic acid are preferred, and 4,4'-biphenyl-dicarboxylic acid is more preferred .
  • Examples of the aromatic dicarboxylic acid in which W is an oxygen atom include 2, 2′-bif
  • Ether ether dicarboxylic acid 2, 3, biphenyl ether dicarboxylic acid, 2, 4, biphenyl ether dicarboxylic acid, 3, 3, biphenyl ether dicarboxylic acid, 3, 4, monobiether ether dicarboxylic acid, 4 , 4'-biphenyl ether dicarboxylic acid and the like.
  • aromatic dicarboxylic acid in which W is a carbo group examples include 2
  • Lufone dicarboxylic acid 2, 3, 1-biphenyl sulfone dicarboxylic acid, 2, 4'-biphenyl sulolefon dicanolevonic acid, 3, 3'-biphenylenosnorefon dicanolevonic acid, 3, 4'-bihue
  • Examples thereof include disulfone dicarboxylic acid and 4,4′-biphenyl sulfone dicarboxylic acid.
  • Examples of the aromatic dicarboxylic acid in which W is a beylene group include cis-2, 2, succinolebendicanolevonic acid, trans-2, 2, sustinolevenedinorebonic acid, CIS-2, 3, —Stinolevendicanolevonic acid, trans-2, 3, ustinolevendinolic levonolic acid, CIS-2, 4 '—Stinolevendicanolevonic acid, trans-2, 4, ustinolevendinolic levonolic acid, CIS-3, 3, —Stinolevendicanolevonic acid, trans-3, 3, Stinolevendic strength norebonic acid, CIS-3, 4, —Stinolevendicanolevonic acid, trans-3, 4, Stinorevendic strength norlevonic acid, CIS- 4,4, -Stynolevenedicanolevonic acid, trans-4,4, stinolevenedicarboxylic acid and the like.
  • Examples of the carboxylic acid include oxalic acid.
  • W is a straight chain having 1 to 18 carbon atoms
  • Examples of the aliphatic dicarboxylic acid that is an alkylene group include malonic acid, succinic acid, dartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decandicaic acid. Rubonic acid, 1,18-octadecane dicarboxylic acid, etc., among which malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid Of these, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid are more preferred.
  • W power beylene group is aliphatic
  • dicarboxylic acid examples include maleic acid and fumaric acid. Among these, maleic acid is preferable. Furthermore, W is a 2,3-propylene group (1 propene 2,3 diyl group).
  • Examples of the aliphatic dicarboxylic acid include itaconic acid and the like.
  • W is acetylene.
  • Examples of the aliphatic dicarboxylic acid as a group include acetylenedicarboxylic acid.
  • the aliphatic dicarboxylic acid that is a W force oxotrimethylene group includes 1,3-acetate.
  • Examples of the aliphatic dicarboxylic acid represented by the general formula (119) include aliphatic dicarboxylic acids in which q is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
  • Specific examples of the aliphatic dicarboxylic acid represented by the formula (120) include cis-1,2,3,6-tetrahydrophthalenoic acid, trans-1,2,3,6-tetrahydrophthalate. Examples include noreic acid and 3, 4, 5, 6-tetrahydrophthalic acid. Among them, cis-1, 2, 3, 6-tetrahydrophthalic acid is preferable.
  • W is a bond, a straight chain having 1 to 18 carbon atoms.
  • a polybasic acid having three or more carboxyl groups represented by the general formula (34) (including those in which a part of the carboxyl groups is a carboxylate ester);
  • carboxyl groups represented by the general formula (34) including those in which a part of the carboxyl groups is a carboxylate ester
  • the above general formula ( The molar ratio when the acid represented by 34) and the acid represented by the general formula (57) are used in combination is usually 10:90 to 99: 1, preferably 40:60 to 99: 1.
  • the ratio of the acid represented by the general formula (34) is less than 10 mol% of the total acid, the acid value and molecular weight of the obtained compound become small.
  • a color filter using the obtained resin composition In the case of manufacturing, it becomes difficult to form a fine pattern, and there is a risk of problems in heat resistance or solvent resistance.
  • the compound represented by the general formula (121) is an aromatic or aliphatic carboxylic acid having two carboxyl groups (aromatic or aliphatic dicarboxylic acid), terephthalic acid, maleic acid or cis-l. , 2, 3, 6- Corresponds to the case of limiting to tetrahydrophthalic acid.
  • the compound comprising the structural unit represented by the general formula (12 2) is a tetravalent hydrocarbon group represented by Z in which R 3 ′ and R 4 ′ in the general formula (112) are carboxyl groups.
  • the above [IX] method will be described in detail.
  • the compound represented by the general formula (23) is diluted with a solvent, and if necessary, a catalyst is added thereto.
  • a polybasic acid anhydride having three or more carboxyl groups represented by (36) (including those in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group, and part of the carboxyl group is a carboxyl group). Including those that are acid esters.) And react at a predetermined temperature for a predetermined time.
  • the solution obtained here can be used for the intended application without isolation and purification. Depending on the application, the solution may be further diluted with a solvent, or the structure represented by the general formula (21).
  • a compound comprising the unit may be isolated and purified by a conventional method.
  • V and V are oxygen atoms.
  • R 12 and R 13 are hydrogen atoms, and R 12 is a group represented by the general formula (15) and R 13 in the general formula (17), and V and V are oxygen atoms, M and M is a hydrogen atom
  • ⁇ -halogenoalcohols such as bromo-1-pentanol-1-nor, 6-chloro-mono-1-hexanol
  • V and V are ⁇ groups.
  • R 12 and R 13 are hydrogen atoms
  • R 12 is a group represented by the general formula (15) and R 13 is a group represented by the general formula (17)
  • V and V are ⁇ groups, ⁇ and ⁇ are hydrogen atoms
  • Examples of the compound represented by 3 4 1 2 include compounds having a bisphenol skeleton represented by the above general formula (98), wherein V and V are ⁇ groups, and the above general formula (98).
  • R 12 and R 13 are alkali metal atoms
  • R 12 is represented by the general formula (15)
  • R 13 is Examples of the group represented by the general formula (17) and ⁇ and ⁇ being an alkali metal atom include the above general formula (98)
  • a compound obtained by reacting a compound having the bisphenol skeleton represented by the general formula (98) with ⁇ -halogenoalcohol or ⁇ -halogenoalkylamine is preferred.
  • An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
  • an alkali metal hydride such as sodium hydride or potassium hydride
  • sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide examples thereof include compounds obtained by reacting with any force such as alkali metal alkoxides such as sodium tert butoxide and potassium tert butoxide, etc., among others, compounds having a bisphenyl skeleton represented by the above general formula (98), and A compound having a bisphenol skeleton represented by the general formula (98);
  • a compound obtained by reacting a compound obtained by reacting ⁇ -halogenoalcohol or ⁇ halogenoalkylamine with sodium methoxide or potassium methoxide by a conventional method
  • a product including those in which a part of the carboxyl group is dehydrated and condensed to form an acid anhydride group, and a part of which is a carboxylic acid ester
  • 3 or more Aromatic or aliphatic carboxylic acid anhydrides having a loxyl group including those in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group, and part of which is a carboxylic acid ester
  • w, W and W are a bond, an oxygen atom, a carbonyl group, a sulfonyl group or
  • Aromatic tetracarboxylic acid anhydrides represented by general formula (129)
  • w represents an ethanetriyl group, a propanetriyl group or a butanetriyl group).
  • W represents an ethylenetetrayl group or a butanetetrayl group
  • r is an integer of 1 to 3.
  • W to W may be a bond or a carbo group.
  • r usually represents an integer of 1 to 3, of which an integer of 2 to 3 is preferable, and of these, 3 is more preferable.
  • aromatic tricarboxylic acid anhydride represented by the formula (123) include 1, 2, 3 benzene tricarboxylic acid anhydride, 1, 2, 4 benzene tricarboxylic acid anhydride (trimellitic acid).
  • Anhydride among others, 1, 2, 4 Benzenetricarboxylic acid anhydride (trimellitic acid anhydride) is preferred.
  • aromatic tetracarboxylic dianhydride represented by the formula (124) include 1, 2, 3, 4 benzenetetracarboxylic dianhydride, 1, 2, 4, 5 Examples include benzenetetra force rubonic acid dianhydride (pyromellitic dianhydride), among which 1, 2, 4, 5 benzenetetracarboxylic dianhydride (pyromellitic dianhydride) is preferred! / ,.
  • aromatic tetracarboxylic dianhydride represented by the formula (125) include 1, 2, 3, 4 naphthalene tetracarboxylic dianhydride, 1, 2, 5, 6 Naphthalenetetra Carboxylic dianhydride, 1, 2, 6, 7 Naphthalene tetracarboxylic dianhydride, 1, 2, 7, 8 Naphthalene tetracarboxylic dianhydride, 1, 4, 5, 8 Naphthalene tetracarboxylic dianhydride 2, 3, 6, 7 naphthalene tetracarboxylic dianhydride, etc., among others 1, 4, 5, 8 naphthalene tetracarboxylic dianhydride, 2, 3, 6, 7 naphthalene tetra force rubonic acid dianhydride Among these, 1, 4, 5, 8 naphthalene tetracarboxylic dianhydride is more preferable.
  • W is a bond.
  • aromatic tetracarboxylic dianhydride examples include 2,3,4,5 biphenyltetracarboxylic dianhydride, 2,3,5,6 biphenyltetracarboxylic dianhydride, and the like.
  • aromatic tetracarboxylic dianhydride in which W is an oxygen atom examples include
  • W is a carbo group.
  • aromatic tetracarboxylic dianhydride that is 2, 3, 4, 5 benzophenone tetracarboxylic dianhydride, 2, 3, 5, 6 benzophenone tetracarboxylic dianhydride, etc. It is done. Furthermore, aromatic tetracarboxylic dianhydride in which W is a sulfonyl group
  • Examples of the product include 2,3,4,5 biphenylsulfonetetracarboxylic dianhydride, 2,3,5,6-biphenylsulfonetetracarboxylic dianhydride, and the like.
  • W is
  • aromatic tetracarboxylic dianhydrides that are 16 beylene groups include cis—2, 3, 4, 5 stilbene tetracarboxylic dianhydride, trans—2, 3, 4, 5 stilbene tetracarboxylic acid And dianhydride, cis-2,3,5,6 stilbenetetracarboxylic dianhydride, trans-2,3,5,6 stilbenetetracarboxylic dianhydride, and the like.
  • aromatic tetracarboxylic acid anhydrides include 2,2 ', 3,4-biphenyltetracarboxylic rubonic acid anhydride, 2,3,3', 4-biphenyltetracarboxylic acid anhydride, 2,3 , 4, 4 'biphenyl tetracarboxylic acid anhydride, 2, 2', 3, 5 biphenyl tetracarboxylic acid anhydride, 2, 3, 3, 5, biphenyl tetracarboxylic acid anhydride, 2, 3, 4 ,, 5 Biphenyltetracarboxylic anhydride, 2, 2 ', 3, 6 Biphenyltetracarboxylic anhydride, 2, 3, 3', 6 Biphenyltetracarboxylic anhydride, 2, 3, 4 ,, 6 Biphenyl tetracarboxylic acid Water, 2, 2 ', 4, 5—biphenyl tetracarboxylic anhydride, 2, 3 ,, 4, 5—
  • Aromatic tetracarboxylic anhydrides that are ball groups include, for example, 2, 2 ', 3, 4 monobenzophenone tetracarboxylic anhydride, 2, 3, 3', 4 monobenzoic Enone tetracarboxylic acid anhydride, 2, 3, 4, 4 'Benzophenone tetracarboxylic acid anhydride, 2, 2', 3, 5-Benzophenone tetracarboxylic acid anhydride, 2, 3, 3 ' , 5—Benzophenone tetracarboxylic acid anhydride, 2, 3, 4, 5, 5-benzophenone tetracarboxylic acid anhydride, 2, 2 ′, 3, 6-benzophenone tetracarboxylic acid anhydride, 2, 3 , 3 ', 6-Benzophenone tetracarboxylic anhydride, 2, 3, 4, 6-benzophenone tetracarboxylic anhydride, 2, 2', 4, 5-benzophenone tetracarboxylic anhydr
  • aromatic tetracarboxylic anhydrides that are phonyl groups include 2,2 ', 3,4-biphenylsulfonetetracarboxylic anhydride, 2,3,3', 4-biphenylsulfonetetracarboxylic anhydride 2, 3, 4, 4'-biphenylsulfone tetracarboxylic anhydride, 2, 2 ', 3, 5-bisulfone tetracarboxylic anhydride, 2, 3, 3', 5-biphenyl Sulfonic acid tetrasulfuric anhydride, 2, 3, 4 ', 5-bisulfone tetracarboxylic anhydride, 2, 2', 3, 6-bisulfone tetracarboxylic anhydride, 2, 3, 3 ', 6-biphenyl sulfone tetracarboxylic anhydride, 2, 3, 4, 6, 6-bisulfone tetracarboxylic acid Anhydride, 2, 2 ',
  • Examples of the acid anhydride include cis-2, 2 ', 3, 4 stilbene tetracarboxylic acid anhydride, trans-2, 2', 3, 4-stilbene tetracarboxylic acid anhydride, cis-2, 3, 3 ,, 4-stilbenetetracarboxylic anhydride, trans- 2, 3, 3 ', 4 stilbenetetracarboxylic anhydride, cis-2, 3, 4, 4, monostilbenetetracarboxylic anhydride, trans- 2, 3, 4, 4, monostilbene tetracarboxylic anhydride, cis— 2, 2 ′, 3, 5 stilpene tetraforce rubonic acid anhydride, trans— 2, 2 ′, 3, 5 stilbene tetracarboxylic anhydride Cis- 2, 3, 3 ', 5 stilbene tetracarboxylic acid anhydride, trans- 2, 3, 3', 5 stilbene tetracarboxylic acid anhydride, cis- 2, 3, 4 ', 5 stil
  • W is a bond.
  • aromatic tetracarboxylic dianhydrides include, for example, 2, 2 ', 3, 3'-biphenyltetracarboxylic dianhydride, 2, 3, 3', 4'-biphenyl tetracarboxylic dianhydride 3,3,4,4'-biphenyltetracarboxylic dianhydride and the like, among which 3,3 ', 4,4'biphenyltetracarboxylic dianhydride is preferable.
  • Examples of the aliphatic tetracarboxylic dianhydrides include 2, 2 ′, 3, 3′-biphenyl ether tetracarboxylic dianhydride, 2, 3, 3 ′, 4′-biphenyl ether tetracarboxylic dianhydride. Water, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride and the like can be mentioned, among which 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride is preferable. Furthermore, examples of the aromatic tetracarboxylic dianhydride which is a W force carbonyl group include 2
  • tetracarboxylic dianhydrides include cis-2,2 ', 3,3' stilpene tetra force rubonic acid dianhydride, trans-2,2 ', 3,3, monostilbenetetracarboxylic dianhydride Cis-2,3,3,4,1 stilbenetetracarboxylic dianhydride, trans-2,3,3'4,1 stilbenetetracarboxylic dianhydride, cis-3,3'4,4 4, monostilpenetetracarboxylic dianhydride, trans-3,3 ', 4,4' stilbenetetracarboxylic dianhydride, etc., among which cis- 3,3,4,4,1 Stilbene tetracarboxylic dianhydride, trans-3,3 ', 4,4' stilbene tetracarboxylic dianhydride is preferred.
  • W represents ethanetril.
  • Examples of the aliphatic tricarboxylic acid anhydride as a group include ethanetricarboxylic acid anhydride.
  • an aliphatic tricarboxylic acid anhydride in which w is a propanetriyl group is used.
  • w is a butterfly
  • Examples of the aliphatic tricarboxylic acid anhydride which is a 19-yl group include butanetricarboxylic acid anhydride.
  • W represents ethylene
  • Examples of the aliphatic tetracarboxylic dianhydride that is a tetrayl group include ethylene tetracarboxylic dianhydride.
  • an aliphatic te which W is a butanetetrayl group is a butanetetrayl group.
  • tracarboxylic dianhydride examples include butanetetracarboxylic dianhydride.
  • the aliphatic tetracarboxylic dianhydride represented by the general formula (131) is usually an aliphatic tetracarboxylic acid in which r is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
  • Specific examples include cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, and the like. Of these, acid dianhydride and cyclohexanetetracarboxylic dianhydride are preferred, and cyclohexanetetracarboxylic dianhydride is more preferred.
  • Examples of the aliphatic tetracarboxylic dianhydride represented by the formula (132) include 4- (1,2 dicarboxetyl) 1, 2, 3, 4-tetrahydronaphthalene 1,2 dicarboxylic dianhydride. It is done.
  • Examples of the aliphatic tetracarboxylic dianhydride represented by the formula (133) include 5- (1,2 dicarboxetyl) -3-methylcyclohexane-1,2 dicarboxylic dianhydride.
  • aliphatic tetracarboxylic dianhydrides those represented by the formula (132) or (133) are preferred, and those represented by the formula (132) are more preferred.
  • the compound having the carboxylic acid ester in which the carboxyl group in the aromatic or aliphatic carboxylic acid anhydride may be a carboxylic acid ester represented by the general formula (37) is The ability to use commercially available products For example, after causing the aromatic or aliphatic carboxylic acid represented by the general formulas (99) to (109) to work with alcohols such as methanol and ethanol, intramolecular dehydration or intramolecular dealcoholization A compound synthesized by a general method such as condensation may be used as appropriate.
  • the reaction temperature in the method [IX] is the hydroxyl group and the Z or amino group (including these alkali metal salts) in the compound represented by the general formula (23), and the general formula (35).
  • a polybasic acid anhydride having three or more carboxyl groups represented by (36) (including those in which a part of the carboxyl groups is condensed by dehydration to form an acid anhydride group;
  • the temperature is such that it can quantitatively react with the acid anhydride group in the acid ester group). However, for example, it is usually 60 to 120 ° C, preferably 70 to 90 °. C. If the reaction temperature is less than 60 ° C., the reaction proceeds slowly and the unreacted compound represented by the general formula (23) and the polybasic acid anhydride may remain.
  • the reaction time in the method [IX] is such that the degree of polymerization k in the general formula (21) falls within an appropriate range, that is, comprises the structural unit represented by the general formula (21).
  • the reaction time may be determined so that the weight average molecular weight of the compound falls within an appropriate range.
  • the reaction time depends on the equivalent of the polybasic acid anhydride used in the reaction (including a part of which is an anhydride and part of which is a force S carboxylic acid ester) and the reaction temperature. Therefore, although it cannot be generally said, it is usually set in the range of 0.25 to 50 hours, preferably 0.25 to 15 hours, more preferably 0.5 to 8 hours.
  • the solvent used in the method [IX] is not particularly limited as long as the solvent used in the method [III] is the same as that used in the method [III] as long as the raw material can be dissolved.
  • catalysts include, for example, tertiary amines such as triethylamine, pyridine, dimethylaminopyridine and the like, and quaternary ammonia such as tetraptylammonum chloride, tetrabutylammonium bromide, triethylbenzylammonum chloride, triethylbenzilammoumum bromide and the like.
  • a catalyst such as a humic salt or an organic phosphine compound such as triphenylphosphine.
  • catalysts can be used alone or Is used in combination of two or more, and the amount of the catalyst used is not particularly limited, but is 0.001 mol% or more based on the mol amount of the compound represented by the general formula (23), and the reaction rate About 200 mol% may be used to improve the quality.
  • R 1C> in the general formula (13) is the general formula (15), V is an oxygen atom, and M is a hydrogen atom.
  • R 11 is the general formula (17), and
  • the compound includes a polybasic acid anhydride having three or more carboxyl groups (including one in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group, and a part of the carboxyl group is a carboxylate ester.
  • R 3 ′ and R 4 ′ in the general formula (7) are carboxyl groups, Y ′ and Y ′ are oxygen atoms,
  • a compound that can be polymerized with the compound represented by the general formula (23) can be used.
  • an aliphatic carboxylic acid anhydride aromatic or aliphatic dicarboxylic acid anhydride
  • aromatic or aliphatic carboxylic acid anhydride aromatic or aliphatic dicarboxylic acid anhydride having two carboxyl groups represented by the general formula (58) include, for example, formulas (138) to (138)-( 140)
  • w represents a bond, an oxygen atom, a carbonyl group, a sulfol group or a beylene group.
  • Aromatic dicarboxylic acid anhydride represented by the general formula (142), (143)
  • W is a bond, a linear alkylene group having 1 to 18 carbon atoms, vinylene group, 2, 3—
  • the two carboxy groups forming the acid anhydride group may be bonded to any carbon of the cycloalkyl ring as long as the acid anhydride group can be formed.
  • W is more preferably a bond or a carbonyl group.
  • W represents a bond, a linear alkylene group having 1 to 18 carbon atoms.
  • a beylene group is more preferable, among which a beylene group is more preferable.
  • s usually represents an integer of 1 to 3, and preferably an integer of 2 to 3
  • aromatic dicarboxylic acid anhydride represented by the formula (138) include phthalic acid anhydride.
  • aromatic dicarboxylic acid anhydride represented by the formula (139) include 1, 2 naphthalene dicarboxylic acid anhydride, 1, 8 naphthalene dicarboxylic acid anhydride, 2, 3 Examples thereof include phthalenedicarboxylic anhydride.
  • aromatic dicarboxylic acid anhydride represented by the formula (140) include 2,3 pyridinedicarboxylic acid anhydride, 3,4-pyridinedicarboxylic acid anhydride, and the like.
  • W is a bond.
  • aromatic dicarboxylic acid anhydride examples include 2,3 biphenyl dicarboxylic acid anhydride, 3,4 biphenyl dicarboxylic acid anhydride, and the like.
  • W is an oxygen atom
  • aromatic dicarboxylic acid anhydride examples include 2,3-biphenyl ether dicarboxylic acid anhydride, 3,4-biphenyl ether dicarboxylic acid anhydride, and the like. Further, examples of the aromatic dicarboxylic acid anhydride in which W is a carbo group include 2,3
  • Examples include zophenone dicarboxylic acid anhydride and 3,4-benzophenone dicarboxylic acid anhydride. Furthermore, as an aromatic dicarboxylic acid anhydride in which W is a sulfol group,
  • Aromatic dicarboxylic acids in which W is a beylene group examples thereof include 2,3 bisulfone dicarboxylic acid anhydride, 3,4 biphenyl sulfone dicarboxylic acid anhydride, and the like.
  • Aromatic dicarboxylic acids in which W is a beylene group examples thereof include 2,3 bisulfone dicarboxylic acid anhydride, 3,4 biphenyl sulfone dicarboxylic acid anhydride, and the like.
  • Examples of the acid anhydride include cis-2,3 stilbene dicarboxylic acid anhydride, trans-2,3-stilbene dicarboxylic acid anhydride, cis-3,4-stilbene dicarboxylic acid anhydride, t rans-3,4 stilbene dicarboxylic acid An acid anhydride etc. are mentioned.
  • Examples of the aliphatic dicarboxylic acid anhydride include oxalic acid anhydride.
  • W is charcoal
  • Examples of the aliphatic dicarboxylic acid anhydride which is a linear alkylene group having 1 to 18 primes include malonic acid anhydride, succinic acid anhydride, glutaric acid anhydride, adipic acid anhydride, pimelic acid anhydride, and suberin.
  • W power aliphatic dicarboxylic acid anhydride which is diene group,
  • W is a 2,3-probelen group.
  • Examples of the aliphatic dicarboxylic acid anhydride (1 propene 2,3 diyl group) include itaconic acid anhydride.
  • W power 3 ⁇ 4-year-old aliphatic that is xisotrimethylene group
  • dicarboxylic acid anhydride examples include 1,3 acetone dicarboxylic acid anhydride.
  • the aliphatic dicarboxylic acid anhydride represented by the general formula (143) is usually an aliphatic dicarboxylic acid anhydride in which s is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
  • Specific examples include 1,2-cyclobutanedicarboxylic acid anhydride, 1,2-cyclopentanedicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, and the like.
  • 1,2-cyclopentanedicarboxylic acid anhydride and 1,2-cyclohexanedicarboxylic acid anhydride are preferred, and 1,2-cyclohexanedicarboxylic acid anhydride is more preferred.
  • the one shown in 4) is more preferable.
  • these molar ratios when an anhydride (aromatic or aliphatic dicarboxylic acid anhydride) is used in combination is as follows: Usually 10:90 to 99: 1, preferably 40:60 to 99: 1.
  • an anhydride aromatic or aliphatic dicarboxylic acid anhydride
  • a mixture of these may be added to a solution containing the compound represented by the general formula (23) and reacted at once. However, these may be reacted separately and step by step!
  • both ends of the structural unit may be the same group depending on the use of the compound.
  • both ends of the structural unit are represented by the general formulas (146), (146)
  • a compound used to make the terminal group for example, a compound having a bisphenyl skeleton, a polybasic acid having three or more carboxyl groups (part of the carboxyl group) as a raw material of the compound of the present invention Or an acid anhydride thereof, an aromatic or aliphatic carboxylic acid having two carboxyl groups (aromatic or aliphatic dicarboxylic acid) or an acid anhydride thereof is preferable. These are sometimes abbreviated as terminal-constituting compounds.
  • the terminal constituent compound as described above may be introduced in accordance with a conventional method.
  • a compound that has a compound (wax), and a method in which the terminal component compound is further reacted, or an excessive amount of the terminal component compound is used during the condensation reaction. Methods and the like.
  • a compound having a group represented by the above general formula (152) can be obtained by allowing water, alcohol, or the like to act on the compound. Can be.
  • the ability to specifically describe the present invention based on Examples and Comparative Examples The present invention is not limited to these examples.
  • the target compound containing the structural unit represented by the general formula (1) is isolated, but the solution obtained by the reaction can be used as it is for an appropriate use.
  • the acid value of the compound comprising the structural unit represented by the general formula (1) (the compound into which a group derived from an acrylic acid derivative is introduced) is represented by the general formula (1) obtained by the production method of this example.
  • the compound comprising the structural unit shown was diluted with a mixed solution of propylene glycol monomethyl ether acetate and 1-methyl-2-pyrrolidone, and then titrated with an aqueous solution of KOH ethanol (50% by weight) using phenolphthalein as an indicator. .
  • the molecular weight was determined by gel permeation chromatography using tetrahydrofuran as an eluent and a RI (refractive index) detector.
  • the molecular weights shown below are all polystyrene-equivalent weight average molecular weights.
  • the introduction rate of groups derived from acrylic acid derivatives (hereinafter sometimes simply referred to as “acrylation rate”) is!
  • the specific power of the total proton area of the structural unit represented by the general formula (1) and the peak area specific to the group derived from the acrylic acid derivative was determined by NMR (400 MHz).
  • Examples 1 to 13 show the following [XV] method which is a production method of the present invention using a compound comprising a structural unit represented by the following general formula (157) of the present invention.
  • R 8 ′ and R 9 ′ each independently represents a hydrogen atom or a bullcarbonyl group, and ⁇ ⁇ and k are the same as above).
  • reaction conditions such as reaction temperature and reaction time differ.

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Abstract

Disclosed are a compound containing a constitutional unit represented by the general formula (1) below, and a method for producing such a compound. (1) [In the formula, R3 and R4 independently represent a hydrogen atom or a group represented by the following general formula (2): (2); T1 and T2 independently represent a linear alkylene group having 1-6 carbon atoms or an arylene group; U represents a bonding hand or a divalent group represented by one of the following formulae (1-1)-(1-8): (1-1) (1-2) (1-3) (1-4) (1-5) (1-6) (1-7) (1-8); V1 and V2 independently represent an oxygen atom or an -NH- group; Y1 represents an oxygen atom, an -NH- group or a group represented by the general formula (5) below, and Y2 represents an oxygen atom, an -NH- group or a group represented by the general formula (6) below: (5) (6); Z represents a tetravalent hydrocarbon group; a and b independently represent 0 or 1; and k represents a natural number. In this connection, at least one of R6, R8 and R9 represents a group having a double bond.]

Description

明 細 書  Specification
重合性不飽和化合物及びその製造方法  Polymerizable unsaturated compound and method for producing the same
技術分野  Technical field
[0001] 本発明は、新規な重合性不飽和化合物及び当該化合物の新規な製造方法に関 する。さら〖こ詳しくは、構成単位中にフルオレン骨格等を有する、耐熱性に優れ、良 好なパターン形成が可能な重合性不飽和化合物及び分子量、酸価等の調整が容易 であり、且つ低温で合成が可能な、当該化合物の簡便な製造方法に関する。  [0001] The present invention relates to a novel polymerizable unsaturated compound and a novel method for producing the compound. More specifically, a polymerizable unsaturated compound having a fluorene skeleton or the like in the structural unit, excellent in heat resistance and capable of forming a favorable pattern, and easily adjusting the molecular weight, acid value, etc., and at low temperature. The present invention relates to a simple method for producing the compound, which can be synthesized.
背景技術  Background art
[0002] 各種の重合性不飽和化合物 (榭脂）を含有する重合性榭脂組成物は、例えば液晶 装置等のレジスト又はプリント配線板製造時のソルダーレジストとして用いられて 、る [0002] Polymerizable resin compositions containing various polymerizable unsaturated compounds (resins) are used, for example, as resists for liquid crystal devices and the like, or as solder resists in the production of printed wiring boards.
。近年、デバイスの高密度化に伴い、例えば透明性、耐熱性、密着性、耐薬品性等 に優れた重合性榭脂組成物が求められている。そこで、上記の性能を有する重合性 不飽和化合物 (榭脂）として、特に最近では、その硬化物が透明性及び耐熱性に優 れた、ビスフエノール骨格やフルオレン骨格を有する重合性ィ匕合物 (榭脂)が提案さ れている。 . In recent years, with the increase in density of devices, there has been a demand for a polymerizable resin composition having excellent transparency, heat resistance, adhesion, chemical resistance, and the like. Therefore, as a polymerizable unsaturated compound (resin) having the above-mentioned performance, recently, a polymerizable compound having a bisphenol skeleton or a fluorene skeleton, the cured product of which is excellent in transparency and heat resistance. (Resin) has been proposed.
[0003] これらの重合性不飽和化合物 (榭脂)を製造する方法としては、従来より、先ずビス フエノール骨格を有するエポキシィ匕合物と、例えばアクリル酸、メタクリル酸等のアタリ ル酸誘導体とを反応させてビスフエノール骨格を有するエポキシアタリレートイ匕合物 を合成し、次いで、これをカルボン酸誘導体又はカルボン酸無水物と反応させる方法 が知られている。  [0003] Conventionally, as a method for producing these polymerizable unsaturated compounds (resins), first, an epoxy compound having a bisphenol skeleton and an allylic acid derivative such as acrylic acid or methacrylic acid are used. There is known a method in which an epoxy atalate toy compound having a bisphenol skeleton is reacted to synthesize and then reacted with a carboxylic acid derivative or a carboxylic acid anhydride.
[0004] この従来法の具体例としては、例えば〈1〉ビスフ ノール骨格を有するエポキシィ匕 合物とアクリル酸誘導体とを 90〜 120°Cで反応させることにより、ビスフエノール骨格 を有するエポキシアタリレートイ匕合物を合成し、次いで、これを 90〜130°Cでカルボ ン酸無水物及び酸二無水物と反応させることにより、当該重合性不飽和化合物を合 成する方法 (例えば、特許文献 1、特許文献 2、特許文献 3等）、〈2〉フルオレン骨格 を有するエポキシィ匕合物と (メタ）アクリル酸とを 90〜 120°Cで反応させることにより、 フルオレン骨格を有する (メタ)アクリル酸エステル誘導体を合成し、次いでこれをテト ラカルボン酸二無水物と 100〜130°Cで反応させ、さらに 80〜110°Cでジカルボン 酸無水物と反応させて、当該重合性不飽和榭脂を合成する方法 (例えば、特許文献 4等）、〈3〉エポキシアタリレートイ匕合物と酸無水物とを 100〜130°Cで反応させること により合成する方法 (例えば、特許文献 5等)等が知られて ヽる。 [0004] Specific examples of this conventional method include <1> an epoxy acrylate having a bisphenol skeleton by reacting an epoxy compound having a bisphenol skeleton with an acrylic acid derivative at 90 to 120 ° C. A method of synthesizing the polymerizable unsaturated compound by synthesizing the compound and then reacting it with carboxylic acid anhydride and acid dianhydride at 90 to 130 ° C. 1, Patent Document 2, Patent Document 3, etc.), <2> An epoxy compound having a fluorene skeleton and (meth) acrylic acid are reacted at 90 to 120 ° C to obtain a (meth) acryl having a fluorene skeleton. An acid ester derivative, which is then A method of synthesizing the polymerizable unsaturated resin by reacting with lacarboxylic acid dianhydride at 100 to 130 ° C and further reacting with dicarboxylic acid anhydride at 80 to 110 ° C (for example, Patent Document 4) And <3> a method of synthesizing an epoxy atalate toy compound and an acid anhydride by reacting at 100 to 130 ° C. (for example, Patent Document 5) and the like are known.
[0005] し力しながら、これらの方法では、 80°C以上の高温下で反応を進行させる必要があ り、また、アクリル酸誘導体の二重結合に起因する熱重合を抑えるために多量の重合 禁止剤を添加する必要があるという問題点を有している。また、比較的高温下、且つ 、長時間で反応を行う必要があるため、反応の制御が容易ではなぐ二重結合の開 裂等の副反応が起こりやすくなり、その結果、反応液がゲルィヒしたり、目的とする重 合性不飽和化合物 (榭脂)の分子量及び酸価等の調整が困難になる等の問題点を 有していた。このような状況下、穏和な温度条件下で実施可能で、分子量の制御が 容易なフルオレン骨格等を有する重合性不飽和化合物 (榭脂)の製造方法の開発が 望まれている。  [0005] However, in these methods, it is necessary to proceed the reaction at a high temperature of 80 ° C or higher, and a large amount is required to suppress thermal polymerization caused by the double bond of the acrylic acid derivative. There is a problem that it is necessary to add a polymerization inhibitor. In addition, since it is necessary to carry out the reaction at a relatively high temperature and for a long time, side reactions such as the cleavage of double bonds that are difficult to control the reaction are likely to occur, and as a result, the reaction solution is gelled. Or the molecular weight and acid value of the target polyunsaturated compound (resin) are difficult to adjust. Under such circumstances, development of a method for producing a polymerizable unsaturated compound (resin) having a fluorene skeleton and the like that can be carried out under mild temperature conditions and whose molecular weight can be easily controlled is desired.
[0006] 特許文献 1 :特開平 5— 339356号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 5-339356
特許文献 2：特開平 7— 92674号公報  Patent Document 2: JP-A-7-92674
特許文献 3：特開平 8 - 278630号公報  Patent Document 3: JP-A-8-278630
特許文献 4:特開 2003— 165830号公報  Patent Document 4: Japanese Unexamined Patent Publication No. 2003-165830
特許文献 5 :特開平 11 231523号公報  Patent Document 5: Japanese Patent Laid-Open No. 11 231523
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 本発明は、構成単位中にビスフエニル骨格、特にフルオレン骨格を有する、耐熱性 に優れ、良好なパターン形成が可能な重合性不飽和化合物 (榭脂)、また、分子量、 酸価等の調整が容易であり、且つ低温で合成が可能なフルオレン骨格等を有する重 合性不飽和化合物 (榭脂)の製造方法を提供することにある。  [0007] The present invention provides a polymerizable unsaturated compound (resin) having a bisphenyl skeleton, particularly a fluorene skeleton in a structural unit, excellent in heat resistance and capable of forming a good pattern, and having a molecular weight, an acid value, etc. An object of the present invention is to provide a method for producing a polyunsaturated unsaturated compound (resin) having a fluorene skeleton and the like that can be easily adjusted and synthesized at a low temperature.
課題を解決するための手段  Means for solving the problem
[0008] 本発明は、一般式（1)
Figure imgf000005_0001
[0008] The present invention relates to a general formula (1)
Figure imgf000005_0001
[式中、
Figure imgf000005_0002
R2 R1'及び R2'は夫々独立して、水素原子、ハロゲン原子、アルキル基 又はアルコキシ基を表し、 R3及び R4は夫々独立して、水素原子又は一般式（2) COOR6 (2) [Where
Figure imgf000005_0002
R 2 R 1 ′ and R 2 ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 3 and R 4 each independently represent a hydrogen atom or a compound represented by the general formula (2) COOR 6 (2)
{式中、 R6は水素原子、炭素数 1〜6のアルキル基、一般式 (3) {Wherein R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a general formula (3)
OH  OH
7ノ O. (3)  7no O. (3)
R  R
(式中、 R'はビュルカルボ-ル基又はイソプロべ-ルカルポ-ル基を表し、 Tは炭素  (In the formula, R ′ represents a butyl carbo group or an isopropyl carb group, and T represents carbon.
3 数 1〜6の直鎖状アルキレン基を表す。）、又は一般式 (4)  3 represents a linear alkylene group having 1 to 6 numbers. ) Or general formula (4)
7 〇、  7 〇,
R τ; (4)  R τ; (4)
(式中、 Τは炭素数 1〜6の直鎖状アルキレン基を表し、 R'は上記に同じ。）で示され (Wherein Τ represents a linear alkylene group having 1 to 6 carbon atoms, and R ′ is the same as above).
4  Four
る基を表す。 }で示される基を表し、 Τ及び Τは夫々独立して、炭素数 1〜6の直鎖 Represents a group. } And Τ and Τ are each independently a straight chain of 1 to 6 carbon atoms.
1 2  1 2
状アルキレン基又はァリーレン基を表し、 Uは結合手又は式（1 1)〜（1—8) CF3 (1 4)
Figure imgf000005_0003
Represents an alkylene group or an arylene group, and U represents a bond or a formula (1 1) to (1-8) CF 3 (1 4)
Figure imgf000005_0003
H3C CH3 H 3 C CH 3
Si (1-5) zCH2、 0-6) H3C、Cノ CH3 (1-7) ,0\ (1-8) Si (1-5) z CH2 , 0-6) H 3 C , C NO CH 3 (1-7), 0 \ (1-8)
(式中、 R5及び R5'は夫々独立して、水素原子又はハロゲン原子を表す。）の何れか で示される 2価の基を表し、 V及び Vは夫々独立して、酸素原子又は NH 基を (Wherein, R 5 and R 5 'are each independently, represent. A hydrogen atom or a halogen atom) represents a divalent group represented by any one of, V and V are each independently a oxygen atom or a NH group
1 2  1 2
表し、 Yは酸素原子、 NH 基又は一般式 (5) Y represents an oxygen atom, NH group or general formula (5)
OR  OR
O (5)  O (5)
(式中、 R8は水素原子又は R7を表す。）で示される基を表し、 Yは酸素原子、 -NH (Wherein R 8 represents a hydrogen atom or R 7 ), Y represents an oxygen atom, -NH
2  2
一基又は一般式 (6) Single or general formula (6)
,9  , 9
OR"  OR "
(6)  (6)
,0 (式中、 R9は水素原子又は R7を表す。）で示される基を表し、 Zは 4価の炭化水素基 を表し、 a及び bは夫々独立して、 0又は 1を表し、 kは自然数を表す。但し、式中、 R6 、 R8、 R9の何れか少なくとも 1つは二重結合を有する基である。 ]で示される構成単位 を含んで成る化合物である。 , 0 (Wherein R 9 represents a hydrogen atom or R 7 ), Z represents a tetravalent hydrocarbon group, a and b each independently represent 0 or 1, k Represents a natural number. However, in the formula, at least one of R 6 , R 8 and R 9 is a group having a double bond. ] Is a compound comprising the structural unit represented by
また、本発明は、一般式 (7)  The present invention also provides a general formula (7)
Figure imgf000006_0001
Figure imgf000006_0001
{式中、 R3'及び R4'は夫々独立して、水素原子、カルボキシル基又はアルコキシ力 ルポ二ル基を表し、 Y 'は酸素原子、 NH 基又は式（8)
Figure imgf000006_0002
{Wherein R 3 'and R 4 ' each independently represents a hydrogen atom, a carboxyl group or an alkoxy group, and Y 'represents an oxygen atom, an NH group or a compound represented by formula (8)
Figure imgf000006_0002
で示される基を表し、 Υ 'は酸素原子、 ΝΗ 基又は式（9) Υ 'represents an oxygen atom, ΝΗ group or formula (9)
、 Z、 a、 b及び kは上記に
Figure imgf000006_0003
, Z, a, b and k
Figure imgf000006_0003
同じ。但し、式中、 R3'及び R4，のうち、少なくとも 1つはカルボキシル基又はアルコキ シカルボニル基である。 }で示される構成単位を含んで成る化合物である。 the same. However, in the formula, at least one of R 3 ′ and R 4 is a carboxyl group or an alkoxycarbonyl group. } Is a compound comprising a structural unit represented by
さらに、本発明は、上記一般式 (7)で示される構成単位を含んで成る化合物と、一 般式 (10)  Furthermore, the present invention relates to a compound comprising the structural unit represented by the general formula (7) and a general formula (10)
R7— X (1 0) R 7 — X (1 0)
(式中、 Xはハロゲン原子を表し、 R7は上記に同じ。）、一般式（11) R7.O^T ^ J (1 1 ) (Wherein X represents a halogen atom and R 7 is the same as above), general formula (11) R7 .O ^ T ^ J (1 1)
(式中、 R7及び Tは上記に同じ。）及び一般式（12) (Wherein R 7 and T are the same as above) and general formula (12)
3  Three
Ρ7,〇、Τ 〇Η ( 1 2) Ρ7 , 〇, Τ 〇Η (1 2 )
(式中、 R7及び Τは上記に同じ。）から選ばれる少なくとも 1種以上の (メタ)アクリル酸 (Wherein R 7 and Τ are the same as above) at least one (meth) acrylic acid selected from
4  Four
誘導体とを反応させることを特徴とする、上記一般式（1)で示される構成単位を含ん で成る化合物の製造方法である。 Including a structural unit represented by the above general formula (1), characterized by reacting with a derivative A method for producing a compound comprising:
[0011] さらにまた、本発明は、一般式（13)  [0011] Furthermore, the present invention provides a general formula (13)
(13)(13)
Figure imgf000007_0001
Figure imgf000007_0001
{式中、 R1C>は水素原子、アルカリ金属原子、一般式（14) {Wherein R 1C> is a hydrogen atom, an alkali metal atom, or a general formula (14)
°[>^ τ (14) ° [> ^ τ (14)
1 1  1 1
(式中、 Τは上記に同じ。）、又は一般式（15)
Figure imgf000007_0002
(Where Τ is the same as above) or general formula (15)
Figure imgf000007_0002
(式中、 Μは水素原子又はアルカリ金属原子を表し、 Vは酸素原子又は—ΝΗ—基  (In the formula, 水 素 represents a hydrogen atom or an alkali metal atom, and V represents an oxygen atom or a —ΝΗ— group.
1 3  13
を表し、 Τは上記に同じ。）で示される基を表し、 R11は水素原子、アルカリ金属原子 、一般式 (16) And Τ is the same as above. R 11 is a hydrogen atom, an alkali metal atom or a general formula (16)
\ (16) \ (16)
I 2  I 2
(式中、 Τは上記に同じ。）、又は一般式（17)  (Where Τ is the same as above) or general formula (17)
2  2
、V4、M2 (1 7) , V4 , M 2 ( 1 7 )
(式中、 Mは水素原子又はアルカリ金属原子を表し、 Vは酸素原子又は—NH—基 を表し、 T は
Figure imgf000007_0003
(In the formula, M represents a hydrogen atom or an alkali metal atom, V represents an oxygen atom or —NH— group, and T represents
Figure imgf000007_0003
上記に同じ。 }で示される化合物と、カルボキシル基を 3個以上有する多塩基酸 (カル ボキシル基の一部がカルボン酸エステルであるものを含む。）又はその無水物（カル ボキシル基の一部が脱水縮合して酸無水物基を形成しているものを含み、また、そ の一部がカルボン酸エステルであるものを含む。）とを反応させることを特徴とする、 上記一般式 (7)で示される構成単位を含んで成る化合物の製造方法である。  Same as above. } And a polybasic acid having 3 or more carboxyl groups (including those in which a part of the carboxyl group is a carboxylic acid ester) or an anhydride thereof (a part of the carboxyl group is dehydrated and condensed). In which the acid anhydride group is formed, and a part of which is a carboxylic acid ester). A method for producing a compound comprising a structural unit.
発明の効果  The invention's effect
[0012] 本発明の重合性不飽和化合物は、構成単位中にビスフエ-ル骨格、特にフルォレ ン骨格を有する、アルカリ可溶性で、且つ耐熱性に優れた化合物であり、当該化合 物を含んで成る組成物を用いて、これを光又は熱によりパターン形成させれば、耐熱 性が良好なパターンを容易に形成できる。また、本発明の製造方法によれば、従来 法が有していた、例えば高温下で反応させるため反応の制御が困難である、副反応 により歩留まりが低い等の問題を生じさせることなぐ分子量、酸価等の調整が容易 であり、歩留まりの良い、 目的の一般式（1)で示される構成単位を含んで成る化合物 を製造することが可能となる。 [0012] The polymerizable unsaturated compound of the present invention is a compound having a bisphenol skeleton, particularly a fluorene skeleton in a structural unit, which is alkali-soluble and excellent in heat resistance, and comprises the compound. If the composition is used to form a pattern with light or heat, A pattern with good properties can be easily formed. Further, according to the production method of the present invention, the molecular weight that the conventional method has, for example, the reaction is difficult to control because of the reaction at high temperature, and the yield is low due to side reactions, It is possible to produce a compound comprising the target structural unit represented by the general formula (1), which can easily adjust the acid value and the like and has a good yield.
図面の簡単な説明  Brief Description of Drawings
[0013] [図 1]実施例 3で得られた化合物の1 H—NMRデータを示す図である。 FIG. 1 is a diagram showing 1 H-NMR data of a compound obtained in Example 3.
[図 2]実施例 24で得られた化合物の1 H— NMRデータを示す図である。 FIG. 2 is a diagram showing 1 H-NMR data of the compound obtained in Example 24.
[図 3]実施例 3で得られた化合物の IRデータを示す図である。  FIG. 3 is a diagram showing IR data of the compound obtained in Example 3.
[図 4]実施例 24で得られた化合物の IRデータを示す図である。  FIG. 4 is a diagram showing IR data of the compound obtained in Example 24.
[図 5]実施例 3で得られた化合物の熱安定性 (耐熱性)データを示す図である。  FIG. 5 is a graph showing thermal stability (heat resistance) data of the compound obtained in Example 3.
[図 6]実施例 24で得られた化合物の熱安定性 (耐熱性)データを示す図である。 発明を実施するための最良の形態  FIG. 6 is a graph showing thermal stability (heat resistance) data of the compound obtained in Example 24. BEST MODE FOR CARRYING OUT THE INVENTION
[0014] 一般式（1)、（7)及び（13)に於ける I^ I^ R1'及び R2'で示されるハロゲン原子と しては、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、中でも 塩素原子、臭素原子が好ましぐその中でも塩素原子がより好ましい。 [0014] Formula (1), (7) and is a halogen atom represented by in the (13) I ^ I ^ R 1 ' and R 2', for example, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom etc. are mentioned, Among these, a chlorine atom and a bromine atom are preferred, and a chlorine atom is more preferred.
[0015] R2、 R1'及び R2'で示されるアルキル基としては、直鎖状、分枝状又は環状の、 通常炭素数 1〜4、好ましくは炭素数 1〜2、より好ましくは炭素数 1のアルキル基が挙 げられ、具体的には、例えばメチル基、ェチル基、 n—プロピル基、イソプロピル基、 シクロプロピル基、 n—ブチル基、イソブチル基、 sec—ブチル基、 tert—ブチル基、 シクロブチル基等が挙げられ、中でもメチル基、ェチル基が好ましぐその中でもメチ ル基がより好ましい。 [0015] The alkyl group represented by R 2 , R 1 'and R 2 ' is linear, branched or cyclic, usually having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, more preferably Specific examples include alkyl groups having 1 carbon atom, such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n -butyl group, isobutyl group, sec-butyl group, tert- A butyl group, a cyclobutyl group, etc. are mentioned, Of these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
[0016] R2、 R1'及び R2'で示されるアルコキシ基としては、直鎖状、分枝状又は環状の 、通常炭素数 1〜4、好ましくは炭素数 1〜2、より好ましくは炭素数 1のアルコキシ基 が挙げられ、具体的には、例えばメトキシ基、エトキシ基、 n—プロポキシ基、イソプロ ポキシ基、シクロプロポキシ基、 n—ブトキシ基、イソブトキシ基、 sec—ブトキシ基、 ter t—ブトキシ基、シクロブトキシ基等が挙げられ、中でもメトキシ基、エトキシ基が好まし ぐその中でもメトキシ基がより好ましい。 [0017] これら 、 R2、 R1'及び R2'としては、水素原子がより好ましい。 The alkoxy group represented by R 2 , R 1 ′ and R 2 ′ is linear, branched or cyclic, usually having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, more preferably Specific examples of the alkoxy group include a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, ter t —Butoxy group, cyclobutoxy group and the like can be mentioned, among which methoxy group and ethoxy group are preferable, and methoxy group is more preferable. As these R 2 , R 1 ′ and R 2 ′, a hydrogen atom is more preferable.
[0018] 一般式（1)に於ける Uのベンゼン環との結合位置は特に限定されないが、ベンゼン 環に結合している V及び Vに対して、 m位及び p位の位置で結合しているものが好 In the general formula (1), the bonding position of U with the benzene ring is not particularly limited, but it is bonded at the positions of m and p with respect to V and V bonded to the benzene ring. What is good
1 2  1 2
ましぐその中でも p位の位置で結合しているものがより好ましい。具体的には、一般 式（24)  Of these, those bonded at the p-position are more preferred. Specifically, the general formula (24)
Uは上記に同じ。）で示されるように、 Uと結合
Figure imgf000009_0001
U is the same as above. ) Combined with U as shown
Figure imgf000009_0001
するベンゼン環の炭素のうち、 Vが結合している炭素を 4位とし、 Vが結合している  Out of the benzene ring carbons, the carbon to which V is bonded is in the 4-position, and V is bonded
1 2  1 2
炭素を 4，位とした場合の、 Uのベンゼン環への結合位置としては、 Uと結合する炭素 力 1、 2、 3、 5、 6位の何れかと 1，、 2，、 3，、 5，、 6，位の何れ力との組み合わせが挙 げられ、中でも 1、 2、 6位の何れかと 1 '、 2'、 6'位の何れかとの組み合わせが好まし く、その中でも 1位と 1，位との組み合わせがより好まし!/、。  When the carbon is in the 4th position, the bonding position of U to the benzene ring is either 1, 2, 3, 5, 6 or 1, 2, 2, 3, 5 ,, 6 and any combination of powers are listed. Among them, any combination of 1st, 2nd and 6th positions and 1 ', 2' and 6 'positions are preferred, and 1st place among them. The combination with 1 and rank is more preferred! /.
[0019] 一般式（1)に於ける Uとしては、式（1 1)及び（1 7)で示される 2価の基がより好 ましぐその中でも式（1 1)で示される 2価の基がさらに好まし 、。 [0019] As U in the general formula (1), a divalent group represented by the formulas (11) and (17) is more preferable. Among them, a divalent group represented by the formula (11) is preferred. The group is even more preferred.
[0020] 式（1— 1)に於ける R5及び R5'で示されるハロゲン原子としては、例えばフッ素原子As the halogen atom represented by R 5 and R 5 ′ in the formula (1-1), for example, a fluorine atom
、塩素原子、臭素原子、ヨウ素原子等が挙げられ、中でも塩素原子、臭素原子が好 ましぐその中でも臭素原子がより好ましい。 A chlorine atom, a bromine atom, an iodine atom, etc., among which a chlorine atom and a bromine atom are preferable, and a bromine atom is more preferable.
[0021] これら R5及び R5'としては、水素原子がより好ましい。 [0021] As R 5 and R 5 ', a hydrogen atom is more preferable.
[0022] 一般式（1)、（7)及び（13)に於ける V及び Vとしては、酸素原子がより好ましい。  [0022] As V and V in the general formulas (1), (7) and (13), an oxygen atom is more preferable.
1 2  1 2
[0023] 一般式（1)に於ける Yとしては、酸素原子又は一般式 (5)で示される基がより好ま しぐ一般式（5)で示される基がさらに好ましい。  [0023] Y in the general formula (1) is more preferably an oxygen atom or a group represented by the general formula (5), more preferably a group represented by the general formula (5).
[0024] 一般式（1)に於ける Yとしては、酸素原子又は一般式 (6)で示される基がより好ま [0024] As Y in the general formula (1), an oxygen atom or a group represented by the general formula (6) is more preferable.
2  2
しぐ一般式 (6)で示される基がさらに好ましい。  A group represented by general formula (6) is more preferred.
[0025] R3又は R4としての一般式（2)に於ける R6で示される炭素数 1〜6のアルキル基とし ては、直鎖状、分枝状又は環状の何れでも良ぐ具体的には、例えばメチル基、ェチ ル基、 n—プロピル基、イソプロピル基、シクロプロピル基、 n ブチル基、イソブチル 基、 sec ブチル基、 tert ブチル基、シクロブチル基、 n ペンチル基、イソペンチ ル基、 sec ペンチル基、 tert ペンチル基、ネオペンチル基、 2—メチルブチル基 、 1 ェチルプロピル基、シクロペンチル基、 n—へキシル基、イソへキシル基、 sec— へキシル基、 tert—へキシル基、ネオへキシル基、 2—メチルペンチル基、 1, 2—ジ メチルブチル基、 1 ェチルブチル基、シクロへキシル基等が挙げられ、中でも炭素 数 1〜4のアルキル基が好ましぐ具体的には、メチル基、ェチル基、 n プロピル基 、イソプロピル基、シクロプロピル基、 n—ブチル基、イソブチル基、 sec—ブチル基、 t ert ブチル基、シクロブチル基が挙げられ、その中でも炭素数 1〜2のアルキル基 がより好ましぐ具体的には、メチル基、ェチル基が挙げられる。 [0025] R 3 or is an alkyl group having 1 to 6 carbon atoms represented by in R 6 in the general formula (2) as R 4, linear, either good tool specifically branched or cyclic For example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n butyl group, isobutyl Group, sec butyl group, tert butyl group, cyclobutyl group, n pentyl group, isopentyl group, sec pentyl group, tert pentyl group, neopentyl group, 2-methylbutyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, Examples include isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylmethyl group, 1-ethylbutyl group, cyclohexyl group, etc. Specifically, an alkyl group having 1 to 4 carbon atoms is preferred, such as methyl group, ethyl group, n propyl group, isopropyl group, cyclopropyl group, n —butyl group, isobutyl group, sec —butyl group, t ert butyl Group, and cyclobutyl group. Among them, specific examples of alkyl group having 1 to 2 carbon atoms are methyl group and ethyl group.
一般式（1)及び (7)に於いて、 Zで示される 4価の炭化水素基としては、通常芳香 族又は脂肪族系の 4価の炭化水素基が挙げられ、具体的には、例えば式 (25)、 (26 )
Figure imgf000010_0001
In the general formulas (1) and (7), the tetravalent hydrocarbon group represented by Z usually includes an aromatic or aliphatic tetravalent hydrocarbon group. Specifically, for example, Formula (25), (26)
Figure imgf000010_0001
{但し、式（26)中、 4つの結合手は、ナフタレン環の 1〜8位の炭素のうち、何れの炭 素に結合していても良い。 }、一般式（27)、 （28)若しくは（29) (28)
Figure imgf000010_0002
{However, in the formula (26), the four bonds may be bonded to any carbon among the 1-8th carbon atoms of the naphthalene ring. }, General formula (27), (28) or (29) (28)
Figure imgf000010_0002
(式中、 W 、 W及び Wは、結合手、酸素原子、カルボ-ル基、スルホ -ル基又はビ  (W, W, W and W are a bond, an oxygen atom, a carbo group, a sulfo group or
1 2 3  one two Three
二レン基を表す。）で示される芳香族系の 4価の炭化水素基、又は一般式 (30)、 (31 ) Represents a dilene group. ) Aromatic tetravalent hydrocarbon groups represented by the general formula (30), (31)
{ V¾i (30) (3D {V¾i (30) (3D
{式中、 Wは、エタンテトライル基、プロパンテトライル基、ブタンテトライル基又はェ {Wherein W represents ethanetetrayl group, propanetetrayl group, butanetetrayl group or
4  Four
チレンテトライル基を表し、 hは 1〜3の整数を表す。但し、式（31)中、 4つの結合手 は、シクロアルキル環の炭素のうち、何れの炭素に結合していても良い。 }、式（32) 若しくは（33)
Figure imgf000011_0001
Represents a tylenetetrayl group, and h represents an integer of 1 to 3. However, in the formula (31), the four bonds may be bonded to any carbon of the cycloalkyl ring. }, Formula (32) Or (33)
Figure imgf000011_0001
で示される脂肪族系の 4価の炭化水素基が挙げられる。  An aliphatic tetravalent hydrocarbon group represented by
[0027] 一般式（27)〜（29)に於ける W〜Wとしては、結合手又はカルボニル基がより好 [0027] As W to W in the general formulas (27) to (29), a bond or a carbonyl group is more preferable.
1 3  13
ましい。  Good.
[0028] 一般式（31)に於ける hは、通常 1〜3の整数を表し、中でも 2〜3の整数が好ましく [0028] h in the general formula (31) usually represents an integer of 1 to 3, and an integer of 2 to 3 is preferable among them.
、その中でも 3がより好ましい。 Of these, 3 is more preferred.
[0029] 式（25)で示される芳香族系の 4価の炭化水素基としては、式（25' )
Figure imgf000011_0002
[0029] The aromatic tetravalent hydrocarbon group represented by the formula (25) is represented by the formula (25 ').
Figure imgf000011_0002
で示されるものがより好まし 、。  The one shown in is more preferred.
式（26)で示される芳香族系の 4価の炭化水素基としては、式（26' )、（26' ' )
Figure imgf000011_0003
Examples of the aromatic tetravalent hydrocarbon group represented by the formula (26) include the formulas (26 ′) and (26 ′ ′)
Figure imgf000011_0003
で示されるものがより好ましぐその中でも式（26' )で示されるものがさらに好ましい。 一般式 (27)で示される芳香族系の 4価の炭化水素基のうち、 Wが結合手である芳 香族系の 4価の炭化水素基としては、式 (27— 1)
Figure imgf000011_0004
Among them, those represented by formula (26 ′) are more preferred. Of the aromatic tetravalent hydrocarbon groups represented by the general formula (27), the aromatic tetravalent hydrocarbon group in which W is a bond is represented by the formula (27-1)
Figure imgf000011_0004
で示されるものが挙げられる。  The thing shown by is mentioned.
[0032] 一般式 (27)で示される芳香族系の 4価の炭化水素基のうち、 Wが酸素原子である 芳香族系の 4価の炭化水素基としては、式 (27— 2)
Figure imgf000011_0005
Of the aromatic tetravalent hydrocarbon groups represented by the general formula (27), the aromatic tetravalent hydrocarbon group in which W is an oxygen atom is represented by the formula (27-2)
Figure imgf000011_0005
で示されるものが挙げられる。 [0033] 一般式（27)で示される芳香族系の 4価の炭化水素基のうち、 Wがカルボニル基で ある芳香族系の 4価の炭化水素基としては、式（27— 3) (27-3)The thing shown by is mentioned. [0033] Among the aromatic tetravalent hydrocarbon groups represented by the general formula (27), the aromatic tetravalent hydrocarbon group in which W is a carbonyl group includes those represented by the formula (27-3) ( 27-3)
Figure imgf000012_0001
Figure imgf000012_0001
で示されるものが挙げられる。  The thing shown by is mentioned.
[0034] 一般式（27)で示される芳香族系の 4価の炭化水素基のうち、 Wがスルホニル基で ある芳香族系の 4価の炭化水素基としては、式（27— 4)
Figure imgf000012_0002
[0034] Among the aromatic tetravalent hydrocarbon groups represented by the general formula (27), the aromatic tetravalent hydrocarbon group in which W is a sulfonyl group includes those represented by the formula (27-4):
Figure imgf000012_0002
で示されるものが挙げられる。  The thing shown by is mentioned.
[0035] 一般式（27)で示される芳香族系の 4価の炭化水素基のうち、 Wがビニレン基であ る芳香族系の 4価の炭化水素基としては、式 (27— 5)
Figure imgf000012_0003
[0035] Among the aromatic tetravalent hydrocarbon groups represented by the general formula (27), the aromatic tetravalent hydrocarbon groups in which W is a vinylene group include those represented by the formula (27-5):
Figure imgf000012_0003
で示されるものが挙げられる。  The thing shown by is mentioned.
一般式 (28)で示される芳香族系の 4価の炭化水素基のうち、 Wが結合手である芳  Of the aromatic tetravalent hydrocarbon groups represented by the general formula (28), W represents a bond.
2  2
香族系の 4価の炭化水素基としては、式 (28— 1)
Figure imgf000012_0004
The aromatic tetravalent hydrocarbon group is represented by the formula (28— 1)
Figure imgf000012_0004
で示されるものが挙げられる。  The thing shown by is mentioned.
一般式 (28)で示される芳香族系の 4価の炭化水素基のうち、 Wが酸素原子である  Of the aromatic tetravalent hydrocarbon groups represented by the general formula (28), W is an oxygen atom.
2  2
芳香族系の 4価の炭化水素基としては、式 (28— 2)
Figure imgf000012_0005
The aromatic tetravalent hydrocarbon group is represented by the formula (28-2)
Figure imgf000012_0005
で示されるものが挙げられる。  The thing shown by is mentioned.
[0038] 一般式（28)で示される芳香族系の 4価の炭化水素基のうち、 Wがカルボ [0038] Of the aromatic tetravalent hydrocarbon groups represented by the general formula (28), W represents carbo
2  2
ある芳香族系の 4価の炭化水素基としては、式（28— 3)
Figure imgf000013_0001
Some aromatic tetravalent hydrocarbon groups have the formula (28-3)
Figure imgf000013_0001
で示されるものが挙げられる。  The thing shown by is mentioned.
[0039] 一般式（28)で示される芳香族系の 4価の炭化水素基のうち、 Wがスルホニル基で  [0039] Of the aromatic tetravalent hydrocarbon groups represented by the general formula (28), W is a sulfonyl group
2  2
ある芳香族系の 4価の炭化水素基としては、式（28— 4)
Figure imgf000013_0002
Some aromatic tetravalent hydrocarbon groups have the formula (28-4)
Figure imgf000013_0002
で示されるものが挙げられる。  The thing shown by is mentioned.
[0040] 一般式 (28)で示される芳香族系の 4価の炭化水素基のうち、 Wがビニレン基であ  [0040] Of the aromatic tetravalent hydrocarbon groups represented by the general formula (28), W is a vinylene group.
2  2
る芳香族系の 4価の炭化水素基としては、式 (28— 5)
Figure imgf000013_0003
The aromatic tetravalent hydrocarbon group is represented by the formula (28-5)
Figure imgf000013_0003
で示されるものが挙げられる。  The thing shown by is mentioned.
[0041] 一般式 (29)で示される芳香族系の 4価の炭化水素基のうち、 Wが結合手である芳  [0041] Of the aromatic tetravalent hydrocarbon groups represented by the general formula (29), W is a bond having a bond.
3  Three
香族系の 4価の炭化水素基としては、式 (29— 1)
Figure imgf000013_0004
The aromatic tetravalent hydrocarbon group is represented by the formula (29— 1)
Figure imgf000013_0004
で示されるものが挙げられ、中でも式（29— 1 ' )、 (29  In particular, the formula (29— 1 '), (29
Figure imgf000013_0005
Figure imgf000013_0005
で示されるものが好ましぐその中でも式（29— 1 ' )で示されるものがより好ま 、。  Among them, the one shown by the formula (29-1 ′) is more preferred.
[0042] 一般式 (29)で示される芳香族系の 4価の炭化水素基のうち、 Wが酸素原子である  [0042] Of the aromatic tetravalent hydrocarbon groups represented by the general formula (29), W is an oxygen atom
3  Three
芳香族系の 4価の炭化水素基としては、式 (29— 2)  The aromatic tetravalent hydrocarbon group is represented by the formula (29-2)
(29-2)(29-2)
Figure imgf000013_0006
Figure imgf000013_0006
で示されるものが挙げられ、中でも式（29— 2' )、 (29- 2" )
Figure imgf000014_0001
In particular, the formula (29-2 '), (29-2 ")
Figure imgf000014_0001
で示されるものが好ましぐその中でも式（29— 2' )で示されるものがより好まし 、。 一般式（29)で示される芳香族系の 4価の炭化水素基のうち、 Wがカルボニル基で Among them, the one represented by the formula (29-2 ') is more preferred. Of the aromatic tetravalent hydrocarbon groups represented by general formula (29), W is a carbonyl group
3  Three
ある芳香族系の 4価の炭化水素基としては、式（29— 3) Some aromatic tetravalent hydrocarbon groups have the formula (29-3)
(29-3)(29-3)
Figure imgf000014_0002
Figure imgf000014_0002
で示されるものが挙げられ、中でも式（29— 3' )、 (29- 3" )
Figure imgf000014_0003
In particular, the formula (29-3 '), (29-3 ")
Figure imgf000014_0003
で示されるものが好ましぐその中でも式（29— 3 ' )で示されるものがより好まし 、。 一般式（29)で示される芳香族系の 4価の炭化水素基のうち、 Wがスルホニル基で Among them, the one shown by the formula (29-3 ') is more preferred. Of the aromatic tetravalent hydrocarbon groups represented by the general formula (29), W is a sulfonyl group
3  Three
ある芳香族系の 4価の炭化水素基としては、式（29— 4) (29-4)Some aromatic tetravalent hydrocarbon groups have the formula (29-4) (29-4)
Figure imgf000014_0004
Figure imgf000014_0004
で示されるものが挙げられ、中でも式（29— 4' )、 (29-4" )
Figure imgf000014_0005
In particular, the formula (29—4 '), (29-4 ")
Figure imgf000014_0005
で示されるものが好ましぐその中でも式（29—4' )で示されるものがより好まし 、。 一般式 (29)で示される芳香族系の 4価の炭化水素基のうち、 Wがビニレン基であ Among them, the one represented by the formula (29-4 ') is more preferred. Of the aromatic tetravalent hydrocarbon groups represented by the general formula (29), W is a vinylene group.
3  Three
る芳香族系の 4価の炭化水素基としては、式 (29— 5)
Figure imgf000014_0006
The aromatic tetravalent hydrocarbon group is represented by the formula (29-5)
Figure imgf000014_0006
で示されるものが挙げられ、中でも式（29— 5' )、 (29- 5" )
Figure imgf000015_0001
And the formulas (29-5 '), (29-5 ")
Figure imgf000015_0001
で示されるものが好ましぐその中でも式（29— 5 ' )で示されるものがより好まし 、。  Among them, the one shown by the formula (29-5 ') is more preferred.
[0046] 上記芳香族系の 4価の炭化水素基のうち、式（25)、 (26)又は一般式（29)で示さ れるものが好ましぐ中でも式（25)又は一般式（29)に於ける Wが結合手若しくは力 [0046] Among the aromatic tetravalent hydrocarbon groups, those represented by the formula (25), (26) or the general formula (29) are preferred, but the formula (25) or the general formula (29) Where W is the bond or force
3  Three
ルポ-ル基であるもの、即ち、式（25)、（29— 1)又は（29— 3)で示されるものがより 好ましぐその中でも式（29— 1)又は（29— 3)で示されるものがさらに好ま 、。  Of these, those having a diol group, that is, those represented by the formula (25), (29-1) or (29-3) are more preferred, among them the formula (29-1) or (29-3) More preferred, what is shown.
[0047] 一般式 (30)で示される脂肪族系の 4価の炭化水素基のうち、 Wがエタンテトライル [0047] Of the aliphatic tetravalent hydrocarbon groups represented by the general formula (30), W represents ethanetetrayl.
4  Four
基である脂肪族系の 4価の炭化水素基としては、例えば式 (30— 1)
Figure imgf000015_0002
Examples of the aliphatic tetravalent hydrocarbon group are, for example, the formula (30-1)
Figure imgf000015_0002
で示されるものが挙げられる。  The thing shown by is mentioned.
一般式 (30)で示される脂肪族系の 4価の炭化水素基のうち、 Wがプロパンテトライ  Of the aliphatic tetravalent hydrocarbon groups represented by the general formula (30), W represents propane tetrale
4  Four
ル基である脂肪族系の 4価の炭化水素基としては、例えば式（30— 2)
Figure imgf000015_0003
Examples of the aliphatic tetravalent hydrocarbon group that is a thio group include, for example, formula (30-2)
Figure imgf000015_0003
で示されるものが挙げられる。  The thing shown by is mentioned.
一般式 (30)で示される脂肪族系の 4価の炭化水素基のうち、 Wがブタンテトライル  Of the aliphatic tetravalent hydrocarbon groups represented by the general formula (30), W represents butanetetrayl.
4  Four
基である脂肪族系の 4価の炭化水素基としては、例えば式 (30— 3)
Figure imgf000015_0004
Examples of the aliphatic tetravalent hydrocarbon group are, for example, formula (30-3)
Figure imgf000015_0004
で示されるものが挙げられる。  The thing shown by is mentioned.
[0050] 一般式 (31)で示される脂肪族系の 4価の炭化水素基としては、通常 hが 1〜3の整 数、好ましくは 2〜3の整数、より好ましくは 3である脂肪族系の 4価の炭化水素基が 挙げられ、具体的には、例えば式（31— 1)、 (31 - 2) , (31 - 3)
Figure imgf000015_0005
等で示されるものが挙げられ、中でも式（31— 2)、（31— 3)で示されるものが好まし く、その中でも式 (31 - 3)で示されるものがより好ま 、。 [0050] The aliphatic tetravalent hydrocarbon group represented by the general formula (31) is usually an aliphatic group in which h is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3. And tetravalent hydrocarbon groups, specifically, for example, the formulas (31-1), (31-2), (31-3)
Figure imgf000015_0005
Among them, those represented by the formulas (31-2) and (31-3) are preferred, and those represented by the formula (31-3) are more preferred.
[0051] 上記脂肪族系の 4価の炭化水素基のうち、式（32)又は（33)で示されるものが好ま しぐ中でも式（32)で示されるものがより好ましい。 [0051] Among the aliphatic tetravalent hydrocarbon groups, those represented by the formula (32) or (33) are preferable, and those represented by the formula (32) are more preferable.
[0052] これら芳香族又は脂肪族系の 4価の炭化水素基は、後述する一般式 (7)で示され る構成単位を含んで成る化合物の製造方法に於ける、一般式 (34)
Figure imgf000016_0001
[0052] These aromatic or aliphatic tetravalent hydrocarbon groups are represented by the general formula (34) in the method for producing a compound comprising a structural unit represented by the general formula (7) described later.
Figure imgf000016_0001
(式中、 R3'、 R4，及び Zは上記に同じ。）で示されるカルボキシル基を 3個以上有する 多塩基酸 (カルボキシル基の一部がカルボン酸エステルであるものを含む。）、又は 一般式（35)若しくは（36)
Figure imgf000016_0002
(Wherein R 3 ′, R 4 , and Z are the same as above) a polybasic acid having 3 or more carboxyl groups (including those in which a part of the carboxyl group is a carboxylic acid ester), Or general formula (35) or (36)
Figure imgf000016_0002
(式中、 R3'、 R4，及び Zは上記に同じ。）で示されるカルボキシル基を 3個以上有する 多塩基酸無水物 (カルボキシル基の一部が脱水縮合して酸無水物基を形成して 、る ものを含み、また、その一部がカルボン酸エステルであるものを含む。）に由来するも のでもある。 (Wherein R 3 ′, R 4 and Z are the same as above) A polybasic acid anhydride having three or more carboxyl groups represented by the formula (a part of the carboxyl groups undergoes dehydration condensation to form acid anhydride groups And a part of which is a carboxylic acid ester.).
[0053] 尚、ここで言う、カルボン酸エステルとは、一般式（37)  [0053] The carboxylic acid ester referred to here is represented by the general formula (37).
-COOR14 (37) -COOR 14 (37)
(式中、 R14は炭素数 1〜6のアルキル基を表す。）で示される基を意味する。 (Wherein R 14 represents an alkyl group having 1 to 6 carbon atoms).
[0054] 一般式（37)に於ける R14で示される炭素数 1〜6のアルキル基としては、直鎖状、 分枝状又は環状の何れでも良ぐ具体的には、例えばメチル基、ェチル基、 n—プロ ピル基、イソプロピル基、シクロプロピル基、 n—ブチル基、イソブチル基、 sec—ブチ ル基、 tert—ブチル基、シクロブチル基、 n—ペンチル基、イソペンチル基、 sec—ぺ ンチル基、 tert—ペンチル基、ネオペンチル基、 2—メチルブチル基、 1ーェチルプ 口ピル基、シクロペンチル基、 n—へキシル基、イソへキシル基、 sec—へキシル基、 t ert—へキシル基、ネオへキシル基、 2—メチルペンチル基、 1, 2—ジメチルブチル 基、 1 ェチルブチル基、シクロへキシル基等が挙げられ、中でも炭素数 1〜4のァ ルキル基が好ましぐ具体的には、メチル基、ェチル基、 n プロピル基、イソプロピ ル基、シクロプロピル基、 n ブチル基、イソブチル基、 sec ブチル基、 tert—ブチ ル基、シクロブチル基が挙げられ、その中でも炭素数 1〜2のアルキル基がより好まし ぐ具体的には、メチル基、ェチル基が挙げられる。 [0054] The alkyl group having 1 to 6 carbon atoms represented by R 14 in the general formula (37) may be linear, branched or cyclic. Specific examples include a methyl group, Ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, sec-pentyl Group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1-ethyl propyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, t Examples include ert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, etc. Among them, alkyl groups having 1 to 4 carbon atoms are preferred. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and cyclobutyl group are mentioned. Specific examples of the alkyl group having 1 to 2 carbon atoms are methyl group and ethyl group.
[0055] 一般式（1)及び（7)に於ける a及び bとしては、 1がより好ましい。  In the general formulas (1) and (7), as a and b, 1 is more preferable.
[0056] 一般式（1)及び（7)に於ける kは、自然数のうち、通常 1〜： L00の整数が挙げられ、 中でも 2〜50の整数が好ましぐその中でも 2〜20の整数がより好まし!/、。  [0056] k in the general formulas (1) and (7) is a natural number, usually an integer of 1 to: L00, and an integer of 2 to 50 is preferred, and an integer of 2 to 20 is preferred. Is more preferred!
[0057] 一般式（1)に於いて「式中、 R6、 R8、 R9の何れか少なくとも 1つは二重結合を有す る基である」中の「二重結合を有する基」とは、（メタ）アクリル酸誘導体由来の基を意 味し、具体的には、 R7で示される基、即ち、ビュルカルボ-ル基若しくはイソプロべ- ルカルボニル基、一般式（3)又は一般式 (4)で示される基を意味する。 In the general formula (1), “a group having a double bond” in “in the formula, at least one of R 6 , R 8 and R 9 is a group having a double bond”. "Means a group derived from a (meth) acrylic acid derivative, specifically, a group represented by R 7 , that is, a butyl carbonyl group or an iso-propyl carbonyl group, the general formula (3) or This means a group represented by the general formula (4).
[0058] 尚、ここで言う、（メタ)アクリル酸誘導体とは、アクリル酸誘導体及び Z又はメタタリ ル酸誘導体を意味する。  [0058] The (meth) acrylic acid derivative as used herein means an acrylic acid derivative and Z or a metatalic acid derivative.
[0059] 一般式（7)に於ける R3'及び R4，で示されるアルコキシカルボ-ル基としては、直鎖 状、分枝状又は環状の、通常炭素数 2〜7、好ましくは炭素数 2〜5、より好ましくは炭 素数 2〜3のアルコキシカルボ-ル基が挙げられ、具体的には、例えばメトキシカル ボ-ル基、エトキシカルボ-ル基、 n プロポキシカルボ-ル基、イソプロポキシカル ボ-ル基、シクロプロポキシカルボ-ル基、 n ブトキシカルボ-ル基、イソブトキシカ ルボニル基、 sec ブトキシカルボ-ル基、 tert ブトキシカルボ-ル基、シクロブトキ シカルボニル基、 n ペンチルォキシカルボ-ル基、イソペンチルォキシカルボ-ル 基、 sec ペンチルォキシカルボ-ル基、 tert ペンチルォキシカルボ-ル基、ネオ ペンチルォキシカルボ-ル基、 2—メチルブトキシカルボ-ル基、 1 ェチルプロポキ シカルボニル基、シクロペンチルォキシカルボ-ル基、 n—へキシルォキシカルボ- ル基、イソへキシルォキシカルボ-ル基、 sec へキシルォキシカルボ-ル基、 tert 一へキシルォキシカルボ-ル基、ネオへキシルォキシカルボ-ル基、 2—メチルペン チルォキシカルボ-ル基、 1, 2—ジメチルブトキシカルボ-ル基、 1 ェチルブトキシ カルボ-ル基、シクロへキシルォキシカルボ-ル基等が挙げられ、中でもメトキシカル ボ-ル基、エトキシカルボ-ル基、 n—プロポキシカルボ-ル基、イソプロポキシカル ボ-ル基、シクロプロポキシカルボ-ル基、 n—ブトキシカルボ-ル基、イソブトキシカ ルボニル基、 sec—ブトキシカルボ-ル基、 tert—ブトキシカルボ-ル基、シクロブトキ シカルボ-ル基が好ましぐその中でもメトキシカルボ-ル基、エトキシカルボ-ル基 力 り好ましい。 [0059] In the general formula (7), the alkoxycarbonyl group represented by R 3 'and R 4 , is linear, branched or cyclic, usually having 2 to 7 carbon atoms, preferably carbon. Examples thereof include an alkoxycarbo group having 2 to 5, more preferably 2 to 3, carbon atoms. Specifically, for example, a methoxycarbon group, an ethoxycarbo group, an n-propoxycarbo group, an isopropoxy group, and the like. Carbon group, cyclopropoxycarbon group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbon group, tert-butoxycarbonyl group, cyclobutoxycarbonyl group, n-pentyloxycarbonyl Group, isopentyloxycarbol group, sec pentyloxycarboro group, tert pentyloxycarboro group, neo pentyloxycarboro group, 2-methylbutoxycarboro group, 1-ethylpropoxy group Carbonyl group, cyclopentyloxycarbol group, n-hexyloxycarboxyl group, isohexyloxycarboxyl group, sec hexyloxycarboxyl group, tert monohexyloxycarboxyl- Group, neohexyloxycarbonyl group, 2-methylpentyloxycarboxyl group, 1,2-dimethylbutoxycarbol group, 1-ethylbutoxy Examples thereof include a carbo carbonyl group, a cyclohexyl oxy carboxy group, etc. Among them, a methoxy carbo ol group, an ethoxy carbo ol group, an n-propoxy carbo ol group, an isopropoxy carbo ol group, a cyclopropoxy, and the like. Carbon group, n-butoxycarbol group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbol group, and cyclobutoxycarbol group are preferred, among which methoxycarbon group, More preferred is ethoxy carbonate base.
[0060] 一般式（7)に於ける Y 'としては、酸素原子又は式 (8)で示される基がより好ましぐ 式（8)で示される基がさらに好まし 、。  [0060] As Y 'in the general formula (7), an oxygen atom or a group represented by the formula (8) is more preferable. A group represented by the formula (8) is more preferable.
[0061] 一般式 (7)に於ける Y 'としては、酸素原子又は式 (9)で示される基がより好ましぐ [0061] As Y 'in the general formula (7), an oxygen atom or a group represented by the formula (9) is more preferable.
2  2
式（9)で示される基がさらに好まし 、。  The group represented by formula (9) is more preferred.
[0062] 一般式（10)に於ける Xで示されるハロゲン原子としては、例えばフッ素原子、塩素 原子、臭素原子、ヨウ素原子等が挙げられ、中でも塩素原子、臭素原子が好ましぐ その中でも塩素原子がより好ましい。 [0062] Examples of the halogen atom represented by X in the general formula (10) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom and a bromine atom are preferred. Atoms are more preferred.
[0063] 一般式（1)、（7)、（14)、（15)、（16)及び（17)に於ける T及び Tで示される炭素 [0063] Carbon represented by T and T in the general formulas (1), (7), (14), (15), (16) and (17)
1 2  1 2
数 1〜6の直鎖状アルキレン基としては、例えばメチレン基、エチレン基、トリメチレン 基、テトラメチレン基、ペンタメチレン基、へキサメチレン基等が挙げられ、中でも炭素 数 1〜4の直鎖状アルキレン基が好ましぐ具体的には、メチレン基、エチレン基、トリ メチレン基、テトラメチレン基が挙げられ、その中でも炭素数 1〜2の直鎖状アルキレ ン基がより好ましぐ具体的には、メチレン基、エチレン基が挙げられ、その中でも炭 素数 1の直鎖状アルキレン基がさらに好ましぐ具体的には、メチレン基が挙げられる  Examples of the linear alkylene group having 1 to 6 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Among these, a linear alkylene group having 1 to 4 carbon atoms is included. Specific examples of the preferred group include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group. Among them, a linear alkylene group having 1 to 2 carbon atoms is more preferred. , Methylene group, and ethylene group. Among them, a linear alkylene group having 1 carbon atom is more preferable, and a methylene group is specifically mentioned.
[0064] T及び Tで示されるァリーレン基の 2つの結合手の結合位置は、特に限定されな [0064] The bonding positions of the two bonding hands of the arylene group represented by T and T are not particularly limited.
1 2  1 2
いが、 2つの結合手の位置関係力 ベンゼン環に対して m位及び p位の位置関係で あるものが好ましぐその中でも p位の位置関係であるものがより好ましい。  However, the positional relationship force between the two bonds is preferred to be the positional relationship between the m-position and the p-position with respect to the benzene ring, and among them, the positional relationship between the p-position is more preferable.
[0065] これら T及び Tとしては、炭素数 1〜6の直鎖状アルキレン基がより好ましい。 [0065] These T and T are more preferably a linear alkylene group having 1 to 6 carbon atoms.
1 2  1 2
[0066] 一般式（3)及び（11)に於ける Tで示される炭素数 1〜6の直鎖状アルキレン基とし  [0066] A linear alkylene group having 1 to 6 carbon atoms represented by T in the general formulas (3) and (11).
3  Three
ては、例えばメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレ ン基、へキサメチレン基等が挙げられ、中でも炭素数 1〜3の直鎖状アルキレン基が 好ましぐ具体的には、メチレン基、エチレン基、トリメチレン基が挙げられ、その中で も炭素数 1の直鎖状アルキレン基がより好ましぐ具体的には、メチレン基が挙げられ る。 Examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc. Among them, a linear alkylene group having 1 to 3 carbon atoms is particularly preferable. Preferable examples include a methylene group, an ethylene group, and a trimethylene group. Among them, a methylene group is more specifically preferable as a linear alkylene group having 1 carbon atom.
[0067] 一般式 (4)及び（12)に於ける Tで示される炭素数 1〜6の直鎖状アルキレン基とし  [0067] A linear alkylene group having 1 to 6 carbon atoms represented by T in the general formulas (4) and (12).
4  Four
ては、例えばメチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレ ン基、へキサメチレン基等が挙げられ、中でも炭素数 2〜4の直鎖状アルキレン基が 好ましぐ具体的には、エチレン基、トリメチレン基、テトラメチレン基が挙げられ、その 中でも炭素数 2の直鎖状アルキレン基がより好ましぐ具体的には、エチレン基が挙 げられる。  Examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Among these, a linear alkylene group having 2 to 4 carbon atoms is preferable. Specific examples include an ethylene group, a trimethylene group, and a tetramethylene group. Among them, a straight-chain alkylene group having 2 carbon atoms is more preferable, and an ethylene group is specifically mentioned.
[0068] 一般式 (3)、（4)、（10)、（11)、（12)、一般式 (5)の R8及び一般式 (6)の R9に於 ける R7としては、ビュルカルボ-ル基がより好まし！/、。 [0068] Formula (3), (4), (10), (11), (12), as at Keru R 7 to R 9 R 8 and of the general formula (5) (6) Bull carbo group is more preferred! /.
[0069] 一般式（13)に於ける R1C>及び 1、一般式（15)に於ける M、並びに一般式（17) に於ける Mで示されるアルカリ金属原子としては、例えばリチウム原子、ナトリウム原 [0069] formula in the (13) R 1C> and 1, the alkali metal atom represented by the general formula (15) in M, and the general formula (17) in at M, for example a lithium atom, Sodium
2  2
子、カリウム原子、ルビジウム原子、セシウム原子、フランシウム原子等が挙げられ、 中でもリチウム原子、ナトリウム原子、カリウム原子、セシウム原子が好ましぐその中 でもナトリウム原子、カリウム原子がより好ましい。  A lithium atom, a sodium atom, a potassium atom, and a cesium atom, and a sodium atom and a potassium atom are more preferable.
[0070] 一般式（13)に於ける R1C>としては、アルカリ金属原子、一般式（14)又は（15)で示 される基がより好ましぐその中でも一般式（14)又は（15)で示される基がさらに好ま しぐその中でも一般式（14)で示される基が特に好ましい。 In the general formula (13), R 1C> is preferably an alkali metal atom or a group represented by the general formula (14) or (15), among which the general formula (14) or (15 Of these, the group represented by formula (14) is particularly preferred.
[0071] 一般式（13)に於ける R11としては、アルカリ金属原子、一般式（16)又は（17)で示 される基がより好ましぐその中でも一般式（16)又は（17)で示される基がさらに好ま しぐその中でも一般式（16)で示される基が特に好ましい。 [0071] R 11 in the general formula (13) is preferably an alkali metal atom or a group represented by the general formula (16) or (17), among which the general formula (16) or (17) Of these, the group represented by formula (16) is particularly preferred.
[0072] 一般式（15)及び（17)に於ける M及び Mとしては、水素原子がより好ましい。 [0072] As M and M in the general formulas (15) and (17), a hydrogen atom is more preferable.
1 2  1 2
[0073] 一般式（15)及び（17)に於ける V及び Vとしては、酸素原子がより好ましい。  [0073] As V and V in the general formulas (15) and (17), an oxygen atom is more preferable.
3 4  3 4
[0074] 本発明の上記一般式（1)で示される構成単位を含んで成る化合物のうち、より具体 的な構成単位を含んで成る化合物としては、例えば一般式（1)に於ける Yが一般式 (5)で示される基であり、 Yが一般式 (6)で示される基であり、 a及び bが 1である一般  [0074] Among the compounds comprising the structural unit represented by the above general formula (1) of the present invention, examples of the compound comprising a more specific structural unit include Y in the general formula (1). A group represented by the general formula (5), Y is a group represented by the general formula (6), and a and b are 1
2 (18) 2 (18)
上記に同
Figure imgf000020_0001
Same as above
Figure imgf000020_0001
じ。）で示される構成単位を含んで成る化合物、又は一般式（1)に於ける Y  Ji. ) Or a compound comprising a structural unit represented by formula (1)
1及び Y 2 が酸素原子又は NH 基である一般式（19)  General formula (19), wherein 1 and Y 2 are oxygen atoms or NH groups
RR
Figure imgf000020_0002
Figure imgf000020_0002
l 5 R2 R3 R4 T T U V V Z a b及び kは上記に同じ。）で示される構成 l 5 R 2 R 3 R 4 TTUVVZ ab and k are the same as above. Configuration indicated by
1 2 1 2  1 2 1 2
単位を含んで成る化合物が挙げられる。  Examples include compounds comprising units.
[0075] 一般式（19)に於ける Y ' '及び Y "としては、酸素原子がより好ましい。 As Y ′ ′ and Y ″ in the general formula (19), an oxygen atom is more preferable.
1 2  1 2
[0076] 一般式（18)で示される構成単位の好ましい具体例としては、 Uが式（1 1)又は（ 1 7)で示される 2価の基であるものが挙げられ、より具体的には、一般式（38)  [0076] Preferable specific examples of the structural unit represented by the general formula (18) include those in which U is a divalent group represented by the formula (11) or (17). Is the general formula (38)
Figure imgf000020_0003
Figure imgf000020_0003
(式中、 R1 R2 R1' R2' R R4 R5 R5 R' V z及び kは上 記に同じ。）で示されるもの、又は一般式（39) (Wherein R 1 R 2 R 1 ′ R 2 ′ RR 4 R 5 R 5 R ′ V z and k are the same as above), or a general formula (39)
Figure imgf000020_0004
Figure imgf000020_0004
(式中、
Figure imgf000020_0005
R2 R1' R2' R3 R4 R8 R9 T T V V Z及び kは上記に同じ。(Where
Figure imgf000020_0005
R 2 R 1 ′ R 2 ′ R 3 R 4 R 8 R 9 TTVVZ and k are the same as above.
)で示されるものが挙げられ、中でも Uが式（1 1)で示される 2価の基であるものがよ り好ましぐより具体的には上記一般式（38)で示されるものが挙げられる。 ), And in particular, U is a divalent group represented by the formula (1 1). More specifically, those represented by the above general formula (38) can be mentioned.
一般式（38)で示される構成単位の好ましい具体例としては、 V及び Vが酸素原  As preferred specific examples of the structural unit represented by the general formula (38), V and V are oxygen atoms.
1 2 子であるものが挙げられ、より具体的には、一般式 (40)  1 2 is a child, more specifically, the general formula (40)
Figure imgf000021_0001
Figure imgf000021_0001
。）で示されるものが挙げられる。  . ).
一般式 (40)で示される構成単位の好ましい具体例としては、 T及び Tが炭素数 1  Preferable specific examples of the structural unit represented by the general formula (40) include T and T having 1 carbon atom.
1 2 1 2
〜3の直鎖状アルキレン基であるものが挙げられ、より具体的には、一般式 (41) To 3 linear alkylene groups, and more specifically, a group represented by the general formula (41)
Figure imgf000021_0002
Figure imgf000021_0002
(式中、 T，及び T，は夫々独立して、炭素数 1〜3の直鎖状アルキレン基を表し、 R1 (In the formula, T and T each independently represent a linear alkylene group having 1 to 3 carbon atoms; R 1
1 2  1 2
、 R2、 R1'、 R2'、 R3、 R4、 R5、 R5，、 R8、 R9、 Z及び kは上記に同じ。）で示されるもの が挙げられる。 , R 2 , R 1 ′, R 2 ′, R 3 , R 4 , R 5 , R 5 , R 8 , R 9 , Z and k are the same as above. ).
[0079] 一般式 (41)に於ける T，及び T ，で示される炭素数 1〜3の直鎖状アルキレン基と  [0079] A linear alkylene group having 1 to 3 carbon atoms represented by T and T in general formula (41) and
1 2  1 2
しては、例えばメチレン基、エチレン基、トリメチレン基等が挙げられ、中でも炭素数 1 の直鎖状アルキレン基が好ましぐ具体的には、メチレン基が挙げられる。  Examples thereof include a methylene group, an ethylene group, a trimethylene group, and the like. Specifically, a methylene group is specifically preferred as a linear alkylene group having 1 carbon atom.
[0080] 一般式 (41)に於いて、 R R2、 R1'、 R2'、 R5、 R5'は、全て水素原子であるものが 好ましい。 In general formula (41), RR 2 , R 1 ′, R 2 ′, R 5 , and R 5 ′ are preferably all hydrogen atoms.
[0081] 一般式 (41)に於いて、 Zで示される 4価の炭化水素基は、通常芳香族又は脂肪族 系の 4価の炭化水素基であれば特に限定されないが、例えば上記一般式 (25)〜（3 3)で示される芳香族又は脂肪族系の 4価の炭化水素基の中でも、上記式 (25)若し くは（26)、上記一般式（29)又は上記式（32)若しくは（33)で示されるものが好まし い。 [0082] 一般式 (41)で示される構成単位の特に好ま Uヽ具体例としては、一般式 (42) [0081] In the general formula (41), the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group. Among the aromatic or aliphatic tetravalent hydrocarbon groups represented by (25) to (33), the above formula (25) or (26), the above general formula (29) or the above formula ( Those shown in (32) or (33) are preferred. [0082] The structural unit represented by the general formula (41) is particularly preferred.
Figure imgf000022_0001
Figure imgf000022_0001
{式中、 Zは上記式（29— 1 ' )、（29— 3 ' )又は（32)で示される芳香族又は脂肪族 系の 4価の炭化水素基を表し、 R3、 R4、 R8、 R9及び kは上記に同じ。 }で示されるもの が挙げられる。 {In the formula, Z represents an aromatic or aliphatic tetravalent hydrocarbon group represented by the above formula (29-1 ′), (29-3 ′) or (32), and R 3 , R 4 , R 8 , R 9 and k are the same as above. } Are listed.
一般式（19)で示される構成単位の好ま 、具体例としては、 Uが式（1— 1)又は（ 1 7)で示される 2価の基であるものが挙げられ、より具体的には、一般式 (43)  Preferred examples of the structural unit represented by the general formula (19) include specific examples in which U is a divalent group represented by the formula (1-1) or (17), and more specifically, General formula (43)
Figure imgf000022_0002
Figure imgf000022_0002
及び kは上記に同じ。）で示されるもの、又は一般式 (44)  And k are the same as above. ) Or general formula (44)
a、 b及び kは
Figure imgf000022_0003
a, b and k are
Figure imgf000022_0003
上記に同じ。）で示されるものが挙げられ、中でも Uが式（1 1)で示される 2価の基 であるものがより好ましぐより具体的には上記一般式 (43)で示されるものが挙げら れる。  Same as above. In particular, those in which U is a divalent group represented by the formula (11) are more preferred, and more specifically those represented by the above general formula (43). It is.
[0084] 一般式 (43)で示される構成単位の好ま 、具体例としては、 V、 V、 Y ' '及び Y  [0084] Preference is given to the structural unit represented by the general formula (43). Specific examples include V, V, Y ′ ′ and Y
1 2 1 ： 1 2 1:
' 'が酸素原子であり、且つ、 a及び bが 1であるものが挙げられ、より具体的には、一 般式 (45) 記に同じ。）で示さ
Figure imgf000023_0001
Examples of 'are oxygen atoms and a and b are 1, more specifically, the general formula (45) Same as above. )
Figure imgf000023_0001
れるものが挙げられる。  Can be mentioned.
一般式 (45)で示される構成単位の好ましい具体例としては、 T及び Tが炭素数 2  Preferable specific examples of the structural unit represented by the general formula (45) include T and T having 2 carbon atoms.
1 2 1 2
〜4の直鎖状アルキレン基であるものが挙げられ、より具体的には、一般式 (46) To 4 linear alkylene groups, and more specifically, the general formula (46)
Figure imgf000023_0002
Figure imgf000023_0002
(式中、 T，，及び T，，は夫々独立して、炭素数 2〜4の直鎖状アルキレン基を表し、  (In the formula, each of T, and T, independently represents a linear alkylene group having 2 to 4 carbon atoms,
1 2  1 2
R2、 R1'、 R2'、 R3、 R4、 R5、 R5'、 Z及び kは上記に同じ。）で示されるものが挙げ られる。 R 2 , R 1 ′, R 2 ′, R 3 , R 4 , R 5 , R 5 ′, Z and k are the same as above. ).
[0086] 一般式 (46)に於ける T，，及び T，，で示される炭素数 2〜4の直鎖状アルキレン基  [0086] A linear alkylene group having 2 to 4 carbon atoms represented by T, and T in general formula (46)
1 2  1 2
としては、例えばエチレン基、トリメチレン基、テトラメチレン基等が挙げられ、中でも 炭素数 2の直鎖状アルキレン基が好ましぐ具体的には、エチレン基が挙げられる。  Examples thereof include an ethylene group, a trimethylene group, a tetramethylene group, and the like. Specifically, a linear alkylene group having 2 carbon atoms is preferred, and an ethylene group is specifically exemplified.
[0087] 一般式 (46)に於いて、
Figure imgf000023_0003
R2、 R1'、 R2'、 R5、 R5'は、全て水素原子であるものが 好ましい。 [0087] In the general formula (46),
Figure imgf000023_0003
R 2 , R 1 ′, R 2 ′, R 5 and R 5 ′ are preferably all hydrogen atoms.
[0088] 一般式 (46)に於 、て、 Zで示される 4価の炭化水素基は、通常芳香族又は脂肪族 系の 4価の炭化水素基であれば特に限定されないが、例えば上記一般式 (25)〜（3 3)で示される芳香族又は脂肪族系の 4価の炭化水素基の中でも、上記式 (25)若し くは（26)、上記一般式（29)又は上記式（32)若しくは（33)で示されるものが好まし い。  In the general formula (46), the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group. Among the aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) or (26), the above general formula (29), or the above formula Those shown by (32) or (33) are preferred.
[0089] 一般式 (46)で示される構成単位の特に好ま Uヽ具体例としては、一般式 (47)
Figure imgf000024_0001
[0089] The structural unit represented by the general formula (46) is particularly preferred.
Figure imgf000024_0001
{式中、 Zは上記式 (32)で示される脂肪族系の 4価の炭化水素基を表し、 R3、 R4及 {In the formula, Z represents an aliphatic tetravalent hydrocarbon group represented by the above formula (32), and R 3 , R 4 and
2  2
び kは上記に同じ。 }で示されるものが挙げられる。  And k are the same as above. } Are listed.
[0090] 一般式（1)で示される構成単位を含んで成る化合物の酸価としては、該化合物が 種々の用途に供される場合に於いて、適切な性能が得られるものとなるように設定さ れれば良ぐ特に限定されないが、通常 70〜150mgKOHZg、好ましくは 80〜13 OmgKOHZgである。ここで、一般式（1)で示される構成単位を含んで成る化合物 の酸価が 70mgKOHZg未満であると、例えば該化合物カゝら得られる榭脂組成物を 用いてカラーフィルターを製造する場合には、例えば光又は熱硬化後のアルカリ現 像の時間が長くなり、また、酸価が 150mgKOHZgを超えるとアルカリ現像時に微 細パターンが剥離し易くなる等の問題を生ずるので好ましくない。尚、酸価は当該化 合物 lgを中和するのに必要な水酸ィ匕カリウムのミリグラム数で表現され、通常水酸化 カリウム水溶液又はエタノール等のアルコールと水との混合溶液を用いて滴定するこ とにより求めることができる。 [0090] The acid value of the compound comprising the structural unit represented by the general formula (1) is such that an appropriate performance can be obtained when the compound is used in various applications. Although it is not particularly limited as long as it is set, it is usually 70 to 150 mgKOHZg, preferably 80 to 13 OmgKOHZg. Here, when the acid value of the compound comprising the structural unit represented by the general formula (1) is less than 70 mg KOHZg, for example, in the case of producing a color filter using the resin composition obtained from the compound cartridge, For example, the time for alkali development after light or heat curing is prolonged, and if the acid value exceeds 150 mgKOHZg, the fine pattern is liable to be peeled off during alkali development. The acid value is expressed as the number of milligrams of potassium hydroxide required to neutralize the compound lg, and titration is usually performed using a potassium hydroxide aqueous solution or a mixed solution of alcohol such as ethanol and water. It can be obtained by doing so.
[0091] 一般式（1)で示される構成単位を含んで成る化合物に於いて、重合度を表す kは、 該化合物中の全構成単位のうち、一般式（1)で示される構成単位の数を表し、該化 合物が種々の用途に供される場合に於いて、適切な性能が得られるものとなるように 設定されれば良ぐ特に限定されないが、通常 1〜： L00、好ましくは 2〜50、より好ま しくは 2〜20の整数である。  [0091] In the compound comprising the structural unit represented by the general formula (1), k representing the degree of polymerization is the structural unit represented by the general formula (1) among all the structural units in the compound. It is not particularly limited as long as it is set so that appropriate performance can be obtained when the compound is used in various applications, but usually 1 to: L00, preferably Is an integer from 2 to 50, more preferably from 2 to 20.
[0092] 一般式（1)で示される構成単位を含んで成る化合物のポリスチレン換算重量平均 分子量は、該化合物が種々の用途に供される場合に於いて、適切な性能が得られる ものとなるように設定されれば良ぐ特に限定されないが、通常 1000〜500万、好ま し <は 2000〜10万、より好まし <は 2000〜5万である。  [0092] The weight average molecular weight in terms of polystyrene of the compound comprising the structural unit represented by the general formula (1) is such that appropriate performance can be obtained when the compound is used in various applications. Although it is not particularly limited as long as it is set as described above, it is usually 10 to 5 million, preferably <is 2000 to 100,000, and more preferably <2000 to 50,000.
[0093] 本発明の一般式（1)で示される構成単位を含んで成る化合物に於いて、該化合物 は、一般式（1)で示される構成単位以外に他の構成単位を成分とすることができ、具 体的には、例えば他の構成単位が、一般式（38)に於ける Zが 2価の炭化水素である ものであり、一般式 (38)で示される構成単位と該構成単位を含んで成る化合物とし ては、一般式 (48) [0093] In the compound comprising the structural unit represented by the general formula (1) of the present invention, the compound contains a structural unit other than the structural unit represented by the general formula (1) as a component. Can Specifically, for example, the other structural unit is such that Z in the general formula (38) is a divalent hydrocarbon, and includes the structural unit represented by the general formula (38) and the structural unit. As a compound consisting of general formula (48)
Figure imgf000025_0001
(式中、 Z'は 2価の炭化水素基を表し、 k'及び k'，は自然数を表し、 R2、 R1'、 R' ，、 R3、 R4、 R5、 R5，、 R8、 R9、 T、 T、 V、 V及び Zは上記に同じ。 )で示される構成
Figure imgf000025_0001
(In the formula, Z ′ represents a divalent hydrocarbon group, k ′ and k ′, represent natural numbers, R 2 , R 1 ′, R ′, R 3 , R 4 , R 5 , R 5 , , R 8 , R 9 , T, T, V, V, and Z are the same as above.
1 2 1 2  1 2 1 2
単位を含んで成る化合物が挙げられる。 Examples include compounds comprising units.
一般式 (48)に於いて、 Z'で示される 2価の炭化水素基としては、通常芳香族又は 脂肪族系の 2価の炭化水素基が挙げられ、具体的には、例えば式 (49)〜（51)
Figure imgf000025_0002
In the general formula (48), the divalent hydrocarbon group represented by Z ′ usually includes an aromatic or aliphatic divalent hydrocarbon group. Specifically, for example, the formula (49 )-(51)
Figure imgf000025_0002
{但し、式（50)中、 2つの結合手は、ナフタレン環の 1〜8位の炭素のうち、何れの炭 素に結合していても良い。 }、一般式（52)若しくは（53)
Figure imgf000025_0003
{However, in the formula (50), the two bonds may be bonded to any carbon of the 1-8th carbon atoms of the naphthalene ring. }, General formula (52) or (53)
Figure imgf000025_0003
(式中、 W及び Wは、結合手、酸素原子、カルボ-ル基、スルホ -ル基又はビ-レ  (In the formula, W and W are a bond, an oxygen atom, a carbonyl group, a sulfol group, or a beryl.
5 6  5 6
ン基を表す。）で示される芳香族系の 2価の炭化水素基、又は一般式 (54)、 (55)
Figure imgf000025_0004
Represents a group. ) Aromatic divalent hydrocarbon group represented by the general formula (54), (55)
Figure imgf000025_0004
{式中、 Wは、結合手、炭素数 1〜18の直鎖状アルキレン基、ビニレン基、 2, 3—プ 口べ-レン基（1—プロペン一 2, 3—ジィル基）、アセチレン基又は 2—ォキソトリメチ レン基を表し、 iは 1〜3の整数を表す。但し、式（55)中、 2つの結合手は、シクロアル キル環の炭素のうち、何れの炭素に結合していても良い。 }、若しくは式（56)
Figure imgf000026_0001
{Wherein W is a bond, a linear alkylene group having 1 to 18 carbon atoms, a vinylene group, 2, 3- It represents an oral belylene group (1-propene-1,3-diyl group), acetylene group or 2-oxotrimethylene group, and i represents an integer of 1 to 3. However, in formula (55), the two bonds may be bonded to any carbon among the carbons of the cycloalkyl ring. } Or formula (56)
Figure imgf000026_0001
(式中、 2つの結合手は、シクロへキセン環の炭素のうち、何れの炭素に結合してい ても良い。）で示される脂肪族系の 2価の炭化水素基が挙げられる。  (Wherein the two bonds may be bonded to any of the carbons of the cyclohexene ring), an aliphatic divalent hydrocarbon group represented by the formula:
[0095] 一般式（52)及び（53)に於ける W及び Wとしては、結合手又はカルボニル基がよ In the general formulas (52) and (53), W and W are a bond or a carbonyl group.
5 6  5 6
り好ましい。  More preferable.
[0096] 一般式（54)に於ける Wとしては、結合手、炭素数 1〜18の直鎖状アルキレン基又 はビニレン基がより好ましぐその中でもビニレン基がさらに好ましい。  [0096] As W in the general formula (54), a bond, a linear alkylene group having 1 to 18 carbon atoms or a vinylene group is more preferable, and a vinylene group is more preferable.
[0097] 一般式（55)に於ける iは、通常 1〜3の整数を表し、中でも 2〜3の整数が好ましぐ その中でも 3がより好ましい。  [0097] i in the general formula (55) usually represents an integer of 1 to 3, and an integer of 2 to 3 is preferable. Among them, 3 is more preferable.
[0098] 式 (49)で示される芳香族系の 2価の炭化水素基としては、式 (49' )又は (49' ' )
Figure imgf000026_0002
[0098] Examples of the aromatic divalent hydrocarbon group represented by the formula (49) include the formula (49 ') or (49'')
Figure imgf000026_0002
で示されるものがより好まし 、。  The one shown in is more preferred.
[0099] 式（50)で示される芳香族系の 2価の炭化水素基としては、式（50' )、（50' ' )又は [0099] As the aromatic divalent hydrocarbon group represented by the formula (50), the formula (50 '), (50' ') or
(50，，，)
Figure imgf000026_0003
(50 ,,,)
Figure imgf000026_0003
で示されるものがより好まし 、。  The one shown in is more preferred.
一般式 (52)で示される芳香族系の 2価の炭化水素基のうち、 Wが結合手である芳  Of the aromatic divalent hydrocarbon groups represented by the general formula (52), W represents a bond.
5  Five
香族系の 2価の炭化水素基としては、式（52—1)
Figure imgf000026_0004
The aromatic divalent hydrocarbon group is represented by the formula (52-1)
Figure imgf000026_0004
で示されるものが挙げられる。  The thing shown by is mentioned.
[0101] 一般式 (52)で示される芳香族系の 2価の炭化水素基のうち、 Wが酸素原子である 芳香族系の 2価の炭化水素基としては、式 (52— 2) (52-2)[0101] Of the aromatic divalent hydrocarbon groups represented by the general formula (52), W is an oxygen atom The aromatic divalent hydrocarbon group is represented by the formula (52— 2) (52-2)
Figure imgf000027_0001
Figure imgf000027_0001
で示されるものが挙げられる。  The thing shown by is mentioned.
[0102] 一般式（52)で示される芳香族系の 2価の炭化水素基のうち、 Wがカルボニル基で [0102] Of the aromatic divalent hydrocarbon groups represented by the general formula (52), W is a carbonyl group
5  Five
ある芳香族系の 2価の炭化水素基としては、式（52— 3)
Figure imgf000027_0002
Some aromatic divalent hydrocarbon groups have the formula (52-3)
Figure imgf000027_0002
で示されるものが挙げられる。  The thing shown by is mentioned.
[0103] 一般式（52)で示される芳香族系の 2価の炭化水素基のうち、 Wがスルホニル基で  [0103] Of the aromatic divalent hydrocarbon groups represented by the general formula (52), W is a sulfonyl group
5  Five
ある芳香族系の 2価の炭化水素基としては、式（52— 4)
Figure imgf000027_0003
Some aromatic divalent hydrocarbon groups have the formula (52-4)
Figure imgf000027_0003
で示されるものが挙げられる。  The thing shown by is mentioned.
[0104] 一般式 (52)で示される芳香族系の 2価の炭化水素基のうち、 W力 '  [0104] Of the aromatic divalent hydrocarbon groups represented by the general formula (52), W force '
5  Five
る芳香族系の 2価の炭化水素基としては、式（52— 5)
Figure imgf000027_0004
As an aromatic divalent hydrocarbon group, the formula (52-5)
Figure imgf000027_0004
で示されるものが挙げられる。  The thing shown by is mentioned.
一般式 (53)で示される芳香族系の 2価の炭化水素基のうち、 Wが結合手である芳  Of the aromatic divalent hydrocarbon groups represented by the general formula (53), W represents a bond.
6  6
香族系の 2価の炭化水素基としては、式（53— 1)
Figure imgf000027_0005
The aromatic divalent hydrocarbon group is represented by the formula (53-1)
Figure imgf000027_0005
で示されるものが挙げられ、中でも式（53— 1 ' ) (53-1 ') In particular, the formula (53— 1 ') (53-1')
Figure imgf000027_0006
Figure imgf000027_0006
で示されるものが好ましい。  Is preferred.
[0106] 一般式 (53)で示される芳香族系の 2価の炭化水素基のうち、 Wが酸素原子である [0106] Of the aromatic divalent hydrocarbon groups represented by the general formula (53), W is an oxygen atom
6  6
芳香族系の 2価の炭化水素基としては、式 (53— 2)
Figure imgf000028_0001
The aromatic divalent hydrocarbon group is represented by the formula (53-2)
Figure imgf000028_0001
で示されるものが挙げられ、中でも式（53
Figure imgf000028_0002
In particular, the formula (53
Figure imgf000028_0002
で示されるものが好ましい。  Is preferred.
[0107] 一般式（53)で示される芳香族系の 2価の炭化水素基のうち、 Wがカルボ [0107] Of the aromatic divalent hydrocarbon groups represented by the general formula (53), W represents carbo
6  6
ある芳香族系の 2価の炭化水素基としては、式（53— 3)  Some aromatic divalent hydrocarbon groups have the formula (53-3)
\ / ^ \ 〇 ノ  \ / ^ \ 〇
？ (53"3) ? (53 " 3)
で示されるものが挙げられ、中でも式（53— 3' )
Figure imgf000028_0003
In particular, the formula (53-3 ')
Figure imgf000028_0003
で示されるものが好ましい。  Is preferred.
[0108] 一般式（53)で示される芳香族系の 2価の炭化水素基のうち、 Wがスルホ [0108] Of the aromatic divalent hydrocarbon groups represented by the general formula (53), W represents sulfo
6  6
ある芳香族系の 2価の炭化水素基としては、式（53— 4)
Figure imgf000028_0004
Some aromatic divalent hydrocarbon groups have the formula (53-4)
Figure imgf000028_0004
で示されるものが挙げられ、中でも式（53
Figure imgf000028_0005
In particular, the formula (53
Figure imgf000028_0005
で示されるものが好ましい。  Is preferred.
[0109] 一般式（53)で示される芳香族系の 2価の炭化水素基のうち、 Wがビニレン基であ [0109] Of the aromatic divalent hydrocarbon groups represented by the general formula (53), W is a vinylene group
6  6
る芳香族系の 2価の炭化水素基としては、式（53— 5)
Figure imgf000028_0006
The aromatic divalent hydrocarbon group is represented by the formula (53-5)
Figure imgf000028_0006
で示されるものが挙げられ、中でも式（53
Figure imgf000028_0007
で示されるものが好ましい。 In particular, the formula (53
Figure imgf000028_0007
Is preferred.
[0110] 上記芳香族系の 2価の炭化水素基のうち、式 (49)又は一般式（53)で示されるもの が好ましぐ中でも式 (49)又は一般式（53)に於ける Wが結合手若しくはカルボ- [0110] Among the above aromatic divalent hydrocarbon groups, those represented by the formula (49) or the general formula (53) are preferred, and the W in the formula (49) or the general formula (53) is preferred. Is a joint or carbo
6 6
ル基であるもの、即ち、式 (49)、 （53— 1)又は（53— 3)で示されるものがより好ましく 、その中でも式 (49)で示されるものがさらに好まし 、。  A group represented by formula (49), (53-1) or (53-3) is more preferred, and among them, a formula (49) is more preferred.
[0111] 一般式 (54)で示される 2価の炭化水素基のうち、 Wが炭素数 1〜18の直鎖状ァ ルキレン基である脂肪族系の 2価の炭化水素基としては、一般式 (54— 1) — (CH2) j— (54-1 ) [0111] Of the divalent hydrocarbon groups represented by the general formula (54), the aliphatic divalent hydrocarbon groups in which W is a linear alkylene group having 1 to 18 carbon atoms include Formula (54— 1) — (CH 2 ) j— (54-1)
(式中、 jは 1〜18の整数を表す。）で示されるものが挙げられる。 (Wherein j represents an integer of 1 to 18).
[0112] 一般式（54—1)に於ける jとしては、通常 1〜18の整数、好ましくは 1〜10の整数、 より好ましくは 1〜6の整数が挙げられる。 [0112] j in the general formula (54-1) is usually an integer of 1 to 18, preferably an integer of 1 to 10, more preferably an integer of 1 to 6.
[0113] 一般式 (54)で示される 2価の炭化水素基のうち、 Wがビニレン基である脂肪族系 の 2価の炭化水素基としては、式（54— 2' )又は（54— 2' ' )
Figure imgf000029_0001
[0113] Among the divalent hydrocarbon groups represented by the general formula (54), the aliphatic divalent hydrocarbon group in which W is a vinylene group includes the formula (54-2 ') or (54- 2 '')
Figure imgf000029_0001
で示されるものが挙げられ、中でも式（54— 2' )で示されるものが好まし!/、。  In particular, the one represented by the formula (54-2 ') is preferred! /.
一般式（54)で示される 2価の炭化水素基のうち、 Wが 2, 3 プロべ-レン基（1 プロペン 2, 3 ジィル基)である脂肪族系の 2価の炭化水素基としては、式（54 3)  Among the divalent hydrocarbon groups represented by the general formula (54), as the aliphatic divalent hydrocarbon groups in which W is a 2,3-propylene group (1 propene 2,3 diyl group), , Formula (54 3)
CH2 CH 2
、 儿 (54-3) で示されるものが挙げられる。  , 儿 (54-3).
[0115] 一般式 (54)で示される 2価の炭化水素基のうち、 Wがアセチレン基である脂肪族 系の 2価の炭化水素基としては、式（54— 4) [0115] Of the divalent hydrocarbon groups represented by the general formula (54), the aliphatic divalent hydrocarbon groups in which W is an acetylene group include those represented by the formula (54-4):
で示されるものが挙げられる。 The thing shown by is mentioned.
一般式（54)で示される 2価の炭化水素基のうち、 Wカ^ーォキソトリメチレン基であ る脂肪族系の 2価の炭化水素基としては、式 (54— 5)
Figure imgf000030_0001
Among the divalent hydrocarbon groups represented by the general formula (54), the aliphatic divalent hydrocarbon group which is a W-carboxytrimethylene group is represented by the formula (54-5).
Figure imgf000030_0001
で示されるものが挙げられる。  The thing shown by is mentioned.
[0117] 一般式 (55)で示される脂肪族系の 2価の炭化水素基としては、通常 iが 1〜3の整 数、好ましくは 2〜3の整数、より好ましくは 3である脂肪族系の 2価の炭化水素基が 挙げられ、具体的には、例えば式（55— 1)、 (55— 2)、 (55- 3)
Figure imgf000030_0002
[0117] The aliphatic divalent hydrocarbon group represented by the general formula (55) is usually an aliphatic group in which i is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3. Specific examples of the divalent hydrocarbon group include, for example, the formulas (55-1), (55-2), (55-3)
Figure imgf000030_0002
等で示されるものが挙げられ、中でも式（55— 2)、（55— 3)で示されるものが好まし ぐその中でも式（55— 3)で示されるものがより好ましい。  Among them, those represented by the formulas (55-2) and (55-3) are preferable, and those represented by the formula (55-3) are more preferable.
式（56)で示される芳香族系の 2価の炭化水素基としては、式（56 ' )又は（56 ' ' )
Figure imgf000030_0003
Examples of the aromatic divalent hydrocarbon group represented by the formula (56) include the formula (56 ′) or (56 ′ ′)
Figure imgf000030_0003
で示されるものがより好ましぐその中でも式（56' )で示されるものがさらに好ましい。  Among them, those represented by formula (56 ′) are more preferred.
[0119] 上記脂肪族系の 2価の炭化水素基のうち、一般式（54)又は式（56)で示されるもの が好ましぐ中でも一般式 (54)に於ける Wが結合手、炭素数 1〜18の直鎖状アル キレン基若しくはビ-レン基であるもの、又は式（56)で示されるものがより好ましぐ その中でも一般式（54)に於ける Wがビ-レン基であるもの、又は式（56)で示される もの、即ち、式（54— 2' )、 (54— 2，，）、 (56' )又は（56' ' )で示されるものがさらに 好ましい。 [0119] Among the above aliphatic divalent hydrocarbon groups, those represented by the general formula (54) or the formula (56) are preferred. In the general formula (54), W is a bond, carbon. Those having a linear alkylene group or beylene group of 1 to 18 or those represented by the formula (56) are more preferred. Among them, W in the general formula (54) is a beylene group. Or those represented by the formula (56), that is, those represented by the formula (54-2 ′), (54-2,), (56 ′) or (56 ′ ′) are more preferable.
[0120] これら芳香族又は脂肪族系の 2価の炭化水素基は、一般式 (57)
Figure imgf000030_0004
[0120] These aromatic or aliphatic divalent hydrocarbon groups have the general formula (57)
Figure imgf000030_0004
(式中、 Z'は上記に同じ。）で示される 2個のカルボキシル基を有する芳香族若しくは 脂肪族カルボン酸 (芳香族若しくは脂肪族ジカルボン酸)、又は一般式 (58)
Figure imgf000030_0005
(式中、 Z'は上記に同じ。）で示される 2個のカルボキシル基を有する芳香族若しくは 脂肪族カルボン酸無水物 (芳香族若しくは脂肪族ジカルボン酸無水物）に由来する ものでもある。 (Wherein Z ′ is the same as above), an aromatic or aliphatic carboxylic acid (aromatic or aliphatic dicarboxylic acid) having two carboxyl groups, or a general formula (58)
Figure imgf000030_0005
(Wherein Z ′ is the same as above), and is derived from an aromatic or aliphatic carboxylic acid anhydride (aromatic or aliphatic dicarboxylic acid anhydride) having two carboxyl groups.
[0121] 一般式 (48)に於ける k'及び k' 'の比率 (k'： k" )は、特に限定されないが、例え ば k，： ，= 10 : 90〜99 : 1が挙げられる。  [0121] The ratio of k 'and k' 'in the general formula (48) (k': k ") is not particularly limited, but for example, k,:, = 10:90 to 99: 1 .
[0122] 一般式 (48)で示される構成単位の好ま 、具体例としては、 V及び Vが酸素原 [0122] Preferred examples of the structural unit represented by the general formula (48) include, as a specific example, V and V are oxygen atoms.
1 2 子であるものが挙げられ、より具体的には、一般式 (59)  1 2 is a child, more specifically, the general formula (59)
Figure imgf000031_0001
Figure imgf000031_0001
上記に同じ。）で示されるものが挙げられる。  Same as above. ).
一般式（59)で示される構成単位の好ましい具体例としては、 T及び Tが炭素数 1  Preferable specific examples of the structural unit represented by the general formula (59) include T and T each having 1 carbon atom.
1 2 1 2
〜3の直鎖状アルキレン基であるものが挙げられ、より具体的には、一般式 (60) To a linear alkylene group of ˜3, and more specifically, a group represented by the general formula (60)
(60) (60)
Figure imgf000031_0002
(式中、 R\ R2、 R1'、 R2'、 R3、 R4、 R5、 R5，、 R8、 R9、 T，、 T，、 Z、 Z，、 k，及び k，，
Figure imgf000031_0002
(Wherein, R \ R 2, R 1 ', R 2', R 3, R 4, R 5, R 5 ,, R 8, R 9, T ,, T ,, Z, Z ,, k, and k,
1 2  1 2
は上記に同じ。）で示されるものが挙げられる。  Is the same as above. ).
[0124] 一般式（60)に於いて、 R R2、 R1'、 R2'、 R5、 R5'は、全て水素原子であるものが 好ましい。 In general formula (60), it is preferable that RR 2 , R 1 ′, R 2 ′, R 5 , and R 5 ′ are all hydrogen atoms.
[0125] 一般式 (60)に於 、て、 Zで示される 4価の炭化水素基は、通常芳香族又は脂肪族 系の 4価の炭化水素基であれば特に限定されないが、例えば上記一般式 (25)〜（3 3)で示される芳香族又は脂肪族系の 4価の炭化水素基の中でも、上記式 (25)若し くは（26)、上記一般式（29)又は上記式（32)若しくは（33)で示されるものが好まし い。  [0125] In the general formula (60), the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group. Among the aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) or (26), the above general formula (29), or the above formula Those shown by (32) or (33) are preferred.
[0126] 一般式 (60)に於いて、 Z'で示される 2価の炭化水素基は、通常芳香族又は脂肪 族系の 2価の炭化水素基であれば特に限定されないが、例えば上記一般式 (49)〜 (56)で示される芳香族又は脂肪族系の 2価の炭化水素基の中でも、上記式 (49)、 上記一般式（53)若しくは（54)又は式（56)で示されるものが好まし 、。  [0126] In the general formula (60), the divalent hydrocarbon group represented by Z 'is not particularly limited as long as it is usually an aromatic or aliphatic divalent hydrocarbon group. Among the aromatic or aliphatic divalent hydrocarbon groups represented by the formulas (49) to (56), those represented by the above formula (49), the above general formula (53) or (54), or the formula (56) What is preferred.
[0127] 一般式 (60)で示される構成単位の特に好ましい具体例としては、一般式 (61)  [0127] As a particularly preferred specific example of the structural unit represented by the general formula (60), the general formula (61)
Figure imgf000032_0001
Figure imgf000032_0001
{式中、 Zは上記式 (49' )、（54— 2' )又は（56' )で示される芳香族又は脂肪族系  {Wherein Z is an aromatic or aliphatic group represented by the above formula (49 '), (54-2') or (56 ')
3  Three
の 2価の炭化水素基を表し、 R3、 R4、 R8、 R9、 Z、 k'及び k'，は上記に同じ。 }で示さ れるものが挙げられる。 R 3 , R 4 , R 8 , R 9 , Z, k ′ and k ′ are the same as above. } Are listed.
また、例えば他の構成単位が、一般式 (43)に於ける Zが 2価の炭化水素であるもの であり、一般式 (43)で示される構成単位と該構成単位を含んで成る化合物としては 、一般式 (62) (式中、 ，，、 z、 z，、
Figure imgf000033_0001
Further, for example, the other structural unit is a compound in which Z in the general formula (43) is a divalent hydrocarbon, and a compound comprising the structural unit represented by the general formula (43) and the structural unit Is the general formula (62) (Where,,, z, z,,
Figure imgf000033_0001
a、 b、 k'及び k' 'は上記に同じ。）で示される構成単位を含んで成る化合物が挙げら れる。 a, b, k ′ and k ′ ′ are the same as above. And a compound comprising a structural unit represented by
一般式 (62)で示される構成単位の好ま 、具体例としては、 V、 V、 Y ' '及び Y  Preferred examples of the structural unit represented by the general formula (62) include V, V, Y ′ ′ and Y as specific examples.
1 2 1 2 1 2 1 2
' 'が酸素原子であり、且つ、 a及び bが 1であるものが挙げられ、より具体的には、一 般式 (63) '' Is an oxygen atom, and a and b are 1. More specifically, the general formula (63)
(63) (63)
Figure imgf000033_0003
Figure imgf000033_0003
(式中、 、 Z、 Z，、 k，及び k，，は上記に同
Figure imgf000033_0002
(In the formula,, Z, Z, k, and k, are the same as above.
Figure imgf000033_0002
じ。）で示されるものが挙げられる。 Ji. ).
一般式 (63)で示される構成単位の好ましい具体例としては、 T及び Tが炭素数 2  Preferable specific examples of the structural unit represented by the general formula (63) include T and T having 2 carbon atoms.
1 2 1 2
〜4の直鎖状アルキレン基であるものが挙げられ、より具体的には、一般式 (64) ，及び k，，は上記
Figure imgf000034_0001
To a linear alkylene group of ˜4, and more specifically, a compound represented by the general formula (64) , And k, are the above
Figure imgf000034_0001
に同じ。）で示されるものが挙げられる。  Same as ).
[0131] 一般式（64)に於いて、
Figure imgf000034_0002
R2、 R 、 R2，、 R5、 R5，は、全て水素原子であるものが 好ましい。 [0131] In the general formula (64),
Figure imgf000034_0002
R 2 , R 2 , R 2 , R 5 and R 5 are all preferably hydrogen atoms.
[0132] 一般式 (64)に於 、て、 Zで示される 4価の炭化水素基は、通常芳香族又は脂肪族 系の 4価の炭化水素基であれば特に限定されないが、例えば上記一般式 (25)〜（3 3)で示される芳香族又は脂肪族系の 4価の炭化水素基の中でも、上記式 (25)若し くは（26)、上記一般式（29)又は上記式（32)若しくは（33)で示されるものが好まし い。  [0132] In the general formula (64), the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group. Among the aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) or (26), the above general formula (29), or the above formula Those shown by (32) or (33) are preferred.
[0133] 一般式 (64)に於いて、 Z'で示される 2価の炭化水素基は、通常芳香族又は脂肪 族系の 2価の炭化水素基であれば特に限定されないが、例えば上記一般式 (49)〜 (56)で示される芳香族又は脂肪族系の 2価の炭化水素基の中でも、上記式 (49)、 上記一般式（53)若しくは（54)又は式（56)で示されるものが好まし 、。  [0133] In the general formula (64), the divalent hydrocarbon group represented by Z 'is not particularly limited as long as it is usually an aromatic or aliphatic divalent hydrocarbon group. Among the aromatic or aliphatic divalent hydrocarbon groups represented by the formulas (49) to (56), those represented by the above formula (49), the above general formula (53) or (54), or the formula (56) What is preferred.
[0134] 尚、一般式（1)で示される構成単位を含んで成る化合物に於いて、該構成単位以 外のものとしては、上記した如き構成単位に限定されるものではなぐまた、一般式（ 1)で示される構成単位が含まれて ヽれば、他の構成単位が任意の割合で含まれて いても良ぐ具体的には、例えば一般式 (48)及び (62)に於ける重合度を表す k'は 、該化合物中の全構成単位のうち、 Zを含む構成単位の数を表し、 k' 'は、該化合物 中の全構成単位のうち、 Z'を含む構成単位の数を表し、該化合物が種々の用途に 供される場合に於いて、適切な性能が得られるものとなるように設定されれば良ぐ特 に限定されないが、 k'及び k"の比率 (k，： k，，）は、例えば k， :k" = 10 : 90〜99 : l が挙げられる。 [0134] In the compound comprising the structural unit represented by the general formula (1), other than the structural unit is not limited to the structural unit as described above. As long as the structural unit represented by (1) is included, other structural units may be included at an arbitrary ratio. Specifically, for example, in the general formulas (48) and (62) K ′ representing the degree of polymerization represents the number of structural units including Z among all the structural units in the compound, and k ′ ′ represents the structural unit including Z ′ among all the structural units in the compound. The number of the compound for various applications The ratio of k ′ and k ″ (k,: k,) is, for example, k, although it is not particularly limited as long as it is set so that appropriate performance can be obtained. ,: K "= 10:90 to 99: l.
[0135] また、一般式（1)で示される構成単位を含んで成る化合物に於いて、一般式（1)で 示される構成単位を Aとし、他の構成単位を Bとした場合、 Aと Bは一般式 (65) 斗 ABABABABAB (65) で示されるような AB の繰り返し構造、一般式 (66)  [0135] In the compound comprising the structural unit represented by the general formula (1), when the structural unit represented by the general formula (1) is A and the other structural unit is B, A and B is a repeating structure of AB as shown by general formula (65) and ABABABABAB (65), and general formula (66)
- AAABBBAAA|- (66) で示されるようなブロック構造又は一般式 (67)  -Block structure as shown by AAABBBAAA |-(66) or general formula (67)
斗 AABAAABABB (67) で示されるようなランダム構造で該化合物を構成しても良ぐさら〖こ Aと Bだけでなく、 C、 D等の他の構成単位を成分として、 3成分以上で該化合物を構成しても良い。  Draft AABAAABABB (67) The compound may be composed of a random structure as shown in AABAAABABB (67). A compound may be constituted.
[0136] 本発明の上記一般式 (7)で示される構成単位を含んで成る化合物のうち、より具体 的な構成単位を含んで成る化合物としては、例えば一般式 (7)に於ける Y 'が式 (8) で示される基であり、 Y，が式（9)で示される基であり、 a及び bが 1である一般式（20) [0136] Among the compounds comprising the structural unit represented by the above general formula (7) of the present invention, as a compound comprising a more specific structural unit, for example, Y 'in the general formula (7) Is a group represented by formula (8), Y is a group represented by formula (9), and a and b are 1, general formula (20)
Figure imgf000035_0001
Figure imgf000035_0001
で示される構成単位を含んで成る化合物、又は一般式（7)に於ける Y '及び Υ 'が  Or a compound comprising a structural unit represented by the formula: or Y ′ and Υ ′ in the general formula (7)
1 2 酸素原子又は ΝΗ 基である一般式 (21)  1 2 General formula (21) which is an oxygen atom or ΝΗ group
Figure imgf000035_0002
Figure imgf000035_0002
(式中、 R1 R2、 ，、 R2，、 R3，、 R4，、 Τ、 Τ、 U、 V、 V、 Υ，，、 Υ，，、 Z、 a、 b及 び kは上記に同じ。 )で示される構成単位を含んで成る化合物が挙げられる。 (Where R 1 R 2 ,,, R 2 , R 3 , R 4 , Τ, Τ, U, V, V, Υ,, Υ,, Z, a, b and And k are the same as above. And a compound comprising a structural unit represented by
一般式（20)で示される構成単位の好ま 、具体例としては、 Uが式（1— 1)又は（ 1 7)で示される 2価の基であるものが挙げられ、より具体的には、一般式 (68)  Preferred examples of the structural unit represented by the general formula (20) include specific examples in which U is a divalent group represented by the formula (1-1) or (17), and more specifically, General formula (68)
(式中、 、 Z及び kは上記に同
Figure imgf000036_0001
(In the formula,, Z and k are the same as above.
Figure imgf000036_0001
じ。）で示されるもの、又は一般式 (69) Ji. ) Or a general formula (69)
Figure imgf000036_0002
Figure imgf000036_0002
(式中、 R R2、 R^.R^.R^.R^.T、T、 V、 V、Z及び kは上記に同じ。；)で示 (Where RR 2 , R ^ .R ^ .R ^ .R ^ .T, T, V, V, Z and k are the same as above;)
1 2 1 2  1 2 1 2
されるものが挙げられ、中でも Uが式（1 1)で示される 2価の基であるものがより好ま しぐより具体的には上記一般式 (68)で示されるものが挙げられる。 Among them, those in which U is a divalent group represented by the formula (11) are more preferred, and more specifically those represented by the general formula (68).
一般式 (68)で示される構成単位の好ま 、具体例としては、 V及び Vが酸素原 子であるものが挙げられ、より具体的には、一般式 (70)  Preferred examples of the structural unit represented by the general formula (68) include specific examples in which V and V are oxygen atoms, and more specifically, the general formula (70)
Figure imgf000036_0003
Figure imgf000036_0003
(式中、 I^R2 ，、1^2，、 ，、1^4，、 、 R5，、T、T、Ζ及び kは上記に同じ。）で (Where I ^ R 2 , 1 ^ 2 ,, 1 ^ 4 ,, R 5 , T, T, Ζ and k are the same as above).
1 2  1 2
示されるものが挙げられる。 What is shown.
一般式（70)で示される構成単位の好ましい具体例としては、 T及び Tが炭素数] 3の直鎖状アルキレン基であるものが挙げられ、より具体的には、一般式（71)
Figure imgf000037_0001
Preferable specific examples of the structural unit represented by the general formula (70) include those in which T and T are linear alkylene groups having 3 carbon atoms, and more specifically, the general formula (71)
Figure imgf000037_0001
で示されるものが挙げられる。  The thing shown by is mentioned.
[0140] 一般式（71)に於いて、
Figure imgf000037_0002
R2、 R 、 R2，、 R5、 R5，は、全て水素原子であるものが 好ましい。 [0140] In the general formula (71),
Figure imgf000037_0002
R 2 , R 2 , R 2 , R 5 and R 5 are all preferably hydrogen atoms.
[0141] 一般式 (71)に於いて、 Zで示される 4価の炭化水素基は、通常芳香族又は脂肪族 系の 4価の炭化水素基であれば特に限定されないが、例えば上記一般式 (25)〜（3 3)で示される芳香族又は脂肪族系の 4価の炭化水素基の中でも、上記式 (25)若し くは（26)、上記一般式（29)又は上記式（32)若しくは（33)で示されるものが好まし い  [0141] In the general formula (71), the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group. Among the aromatic or aliphatic tetravalent hydrocarbon groups represented by (25) to (33), the above formula (25) or (26), the above general formula (29) or the above formula ( 32) or (33) is preferred
[0142] -般式（71)で示される構成単位の特に好ま Uヽ具体例としては、一般式（72)  [0142]-Particularly preferred for the structural unit represented by the general formula (71)
Figure imgf000037_0003
Figure imgf000037_0003
(式中、 R3'、 R4'、 Z及び kは上記に同じ。）で示されるものが挙げられる。 (Wherein R 3 ′, R 4 ′, Z and k are the same as above).
[0143] 一般式（21)で示される構成単位の好ま 、具体例としては、 Uが式（1— 1)又は（ 1 7)で示される 2価の基であるものが挙げられ、より具体的には、一般式（73)  [0143] Preferred examples of the structural unit represented by the general formula (21) include specific examples in which U is a divalent group represented by the formula (1-1) or (17). The general formula (73)
Figure imgf000037_0004
Figure imgf000037_0004
(式中、 R R2、 R1'、 R2'、 R"，、 R4'、 R5、 R5，、 T、 T、 V Y 、Z、a (Wherein, RR 2, R 1 ', R 2', R ",, R 4 ', R 5, R 5 ,, T, T, VY, Z, a
1 2  1 2
b及び kは上記に同じ。）で示されるもの、又は一般式（74) Z、 a、 b及び k
Figure imgf000038_0001
b and k are the same as above. ) Or general formula (74) Z, a, b and k
Figure imgf000038_0001
は上記に同じ。）で示されるものが挙げられ、中でも Uが式（1 1)で示される 2価の 基であるものがより好ましぐより具体的には上記一般式（73)で示されるものが挙げ られる。  Is the same as above. In particular, those in which U is a divalent group represented by the formula (11) are more preferred, and more specifically those represented by the above general formula (73). .
[0144] 一般式（73)で示される構成単位の好ま 、具体例としては、 V、 V、 Y ' '及び Y  [0144] The structural unit represented by the general formula (73) is preferred. Specific examples thereof include V, V, Y ′ ′ and Y
1 2 1 ： 1 2 1:
' 'が酸素原子であり、且つ、 a及び bが 1であるものが挙げられ、より具体的には、一 般式 (75) Examples of the case where '' is an oxygen atom, and a and b are 1, and more specifically, are represented by the general formula (75)
Figure imgf000038_0002
Figure imgf000038_0002
(式中、 I^ R2 ，、1^2，、 ，、1^4，、 、 R5，、T、T、Ζ及び kは上記に同じ。）で (Wherein, I ^ R 2 ,, 1 ^ 2 ,, ,, 1 ^ 4 ,,, R 5 ,, T, T, Ζ and k are the same. Above) in
1 2  1 2
示されるものが挙げられる。  What is shown.
一般式（75)で示される構成単位の好ましい具体例としては、 T及び Tが炭素数 2  As a preferable specific example of the structural unit represented by the general formula (75), T and T each have 2 carbon atoms.
1 2 1 2
〜4の直鎖状アルキレン基であるものが挙げられ、より具体的には、一般式（76) To a linear alkylene group of ˜4, more specifically, a compound represented by the general formula (76)
。
Figure imgf000038_0003
.
Figure imgf000038_0003
)で示されるものが挙げられる。  ).
[0146] 一般式（76)に於いて、
Figure imgf000038_0004
R2、 R1'、 R2'、 R5、 R5'は、全て水素原子であるものが 好ましい。 [0146] In the general formula (76),
Figure imgf000038_0004
R 2 , R 1 ′, R 2 ′, R 5 and R 5 ′ are preferably all hydrogen atoms.
[0147] 一般式 (76)に於 、て、 Zで示される 4価の炭化水素基は、通常芳香族又は脂肪族 系の 4価の炭化水素基であれば特に限定されないが、例えば上記一般式 (25)〜（3 3)で示される芳香族又は脂肪族系の 4価の炭化水素基の中でも、上記式 (25)若し くは（26)、上記一般式（29)又は上記式（32)若しくは（33)で示されるものが好まし い。 [0147] In the general formula (76), the tetravalent hydrocarbon group represented by Z is usually aromatic or aliphatic. Although it is not particularly limited as long as it is a tetravalent hydrocarbon group, for example, among the aromatic or aliphatic tetravalent hydrocarbon groups represented by the general formulas (25) to (33), the above formula ( 25) or (26), those represented by the above general formula (29) or the above formula (32) or (33) are preferred.
[0148] 一般式（76)で示される構成単位の特に好ま Uヽ具体例としては、一般式（77)  [0148] The structural unit represented by the general formula (76) is particularly preferred.
Figure imgf000039_0001
Figure imgf000039_0001
(式中、 R3'、 R4'、 Z及び kは上記に同じ。）で示されるものが挙げられる。 (Wherein R 3 ′, R 4 ′, Z and k are the same as above).
2  2
[0149] 一般式（7)で示される構成単位を含んで成る化合物に於いて、重合度を表す kは、 該化合物中の全構成単位のうち、一般式 (7)で示される構成単位の数を表し、該化 合物が種々の用途に供される場合に於いて、適切な性能が得られるものとなるように 設定されれば良ぐ特に限定されないが、通常 1〜： L00、好ましくは 2〜50、より好ま しくは 2〜20の整数である。  [0149] In the compound comprising the structural unit represented by the general formula (7), k representing the degree of polymerization is the structural unit represented by the general formula (7) among all the structural units in the compound. It is not particularly limited as long as it is set so that appropriate performance can be obtained when the compound is used in various applications, but usually 1 to: L00, preferably Is an integer from 2 to 50, more preferably from 2 to 20.
[0150] 一般式 (7)で示される構成単位を含んで成る化合物のポリスチレン換算重量平均 分子量は、該化合物が種々の用途に供される場合に於いて、適切な性能が得られる ものとなるように設定されれば良ぐ特に限定されないが、通常 1000〜500万、好ま し <は 2000〜10万、より好まし <は 2000〜5万である。  [0150] The polystyrene-converted weight average molecular weight of the compound comprising the structural unit represented by the general formula (7) is such that appropriate performance can be obtained when the compound is used in various applications. Although it is not particularly limited as long as it is set as described above, it is usually 10 to 5 million, preferably <is 2000 to 100,000, and more preferably <2000 to 50,000.
[0151] 本発明の一般式 (7)で示される構成単位を含んで成る化合物に於いて、該化合物 は、一般式 (7)で示される構成単位以外に他の構成単位を成分とすることができ、具 体的には、例えば他の構成単位が、一般式 (68)に於ける Zが 2価の炭化水素である ものであり、一般式 (68)で示される構成単位と該構成単位を含んで成る化合物とし ては、一般式（78)
Figure imgf000040_0001
[0151] In the compound comprising the structural unit represented by the general formula (7) of the present invention, the compound contains a structural unit other than the structural unit represented by the general formula (7) as a component. Specifically, for example, in the other structural unit, Z in the general formula (68) is a divalent hydrocarbon, and the structural unit represented by the general formula (68) The compound containing the unit is represented by the general formula (78).
Figure imgf000040_0001
(式中、！^1、！^2、 1^，、1^2，、 ，、1^4，、 、 R5，、T、T、 V、 V、2、2，、 及び ， (In the formula,! ^ 1,! ^ 2 , 1 ^ ,, 1 ^ 2 ,, ,, 1 ^ 4 ,,, R 5 ,, T, T, V, V, 2,2 ,, and,
1 2 1 2  1 2 1 2
は上記に同じ。 )で示される構成単位を含んで成る化合物が挙げられる。 Is the same as above. And a compound comprising a structural unit represented by
一般式（78)で示される構成単位の好ましい具体例としては、 V及び Vが酸素原  As preferred specific examples of the structural unit represented by the general formula (78), V and V are oxygen atoms.
1 2 子であるものが挙げられ、より具体的には、一般式 (79)  1 2 is a child, more specifically, the general formula (79)
Figure imgf000040_0002
Figure imgf000040_0002
(式中、 R R2、 R'\ R2，、 R3，、 R4，、 R5、 R5，、 T、 T、 Z、 Z，、 k，及び k，，は上記に (Where RR 2 , R '\ R 2 , R 3 , R 4 , R 5 , R 5 , T, T, Z, Z, k and k are
1 2  1 2
同じ。）で示されるものが挙げられる。 the same. ).
一般式（79)で示される構成単位の好ましい具体例としては、 T及び Tが炭素数 1  As a preferable specific example of the structural unit represented by the general formula (79), T and T each have 1 carbon atom.
1 2 1 2
〜3の直鎖状アルキレン基であるものが挙げられ、より具体的には、一般式 (80) k，，は上記
Figure imgf000041_0001
To 3 linear alkylene groups, and more specifically, those represented by the general formula (80) k, is the above
Figure imgf000041_0001
に同じ。）で示されるものが挙げられる。  Same as ).
[0154] 一般式（80)に於いて、
Figure imgf000041_0002
R2、 R1'、 R2'、 R5'は、全て水素原子であるものが 好ましい。 [0154] In the general formula (80),
Figure imgf000041_0002
R 2 , R 1 ′, R 2 ′ and R 5 ′ are preferably all hydrogen atoms.
[0155] 一般式 (80)に於 、て、 Zで示される 4価の炭化水素基は、通常芳香族又は脂肪族 系の 4価の炭化水素基であれば特に限定されないが、例えば上記一般式 (25)〜（3 3)で示される芳香族又は脂肪族系の 4価の炭化水素基の中でも、上記式 (25)若し くは（26)、上記一般式（29)又は上記式（32)若しくは（33)で示されるものが好まし い。  [0155] In the general formula (80), the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group. Among the aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) or (26), the above general formula (29), or the above formula Those shown by (32) or (33) are preferred.
[0156] 一般式 (80)に於いて、 Z'で示される 2価の炭化水素基は、通常芳香族又は脂肪 族系の 2価の炭化水素基であれば特に限定されないが、例えば上記一般式 (49)〜 (56)で示される芳香族又は脂肪族系の 2価の炭化水素基の中でも、上記式 (49)、 上記一般式（53)若しくは（54)又は式（56)で示されるものが好まし 、。  [0156] In the general formula (80), the divalent hydrocarbon group represented by Z 'is not particularly limited as long as it is usually an aromatic or aliphatic divalent hydrocarbon group. Among the aromatic or aliphatic divalent hydrocarbon groups represented by the formulas (49) to (56), those represented by the above formula (49), the above general formula (53) or (54), or the formula (56) What is preferred.
[0157] 一般式 (80)で示される構成単位の特に好ましい具体例としては、一般式 (81)
Figure imgf000042_0001
[0157] As a particularly preferred specific example of the structural unit represented by the general formula (80), the general formula (81)
Figure imgf000042_0001
(式中、 R3'、 R4'、 Z、 Z、 k'及び k' 'は上記に同じ。）で示されるものが挙げられる。 (Wherein, R 3 ′, R 4 ′, Z, Z, k ′, and k ′ ′ are the same as above).
1 3  13
また、例えば他の構成単位が、一般式（73)に於ける Zが 2価の炭化水素であるもの であり、一般式 (73)で示される構成単位と該構成単位を含んで成る化合物としては 、一般式 (82)  Further, for example, the other structural unit is a compound in which Z in the general formula (73) is a divalent hydrocarbon, and a compound comprising the structural unit represented by the general formula (73) and the structural unit Is the general formula (82)
Z，
Figure imgf000042_0002
Z,
Figure imgf000042_0002
、 a、 b、 k'及び k' 'は上記に同じ。）で示される構成単位を含んで成る化合物が挙げ られる。  , A, b, k ′ and k ′ ′ are the same as above. And a compound comprising a structural unit represented by
一般式 (82)で示される構成単位の好ま 、具体例としては、 V、 V、 Y ' '及び Y  Preferred examples of the structural unit represented by the general formula (82) include V, V, Y ′ ′ and Y as specific examples.
1 2 1 2 1 2 1 2
' 'が酸素原子であり、且つ、 a及び bが 1であるものが挙げられ、より具体的には、一 般式 (83)
Figure imgf000043_0001
Examples of the case where '' is an oxygen atom, and a and b are 1, and more specifically, are represented by the general formula (83)
Figure imgf000043_0001
(式中、 R R2、 R1'、 R2，、 R3，、 R4，、 R5、 R5，、 T、 T、 Z、 Z，ゝ k，及び k，，は上記に (Where RR 2 , R 1 ′, R 2 , R 3 , R 4 , R 5 , R 5 , T, T, Z, Z, ゝ k, and k are
1 2  1 2
同じ。）で示されるものが挙げられる。  the same. ).
[0160] 一般式 (83)で示される構成単位の好ましい具体例としては、 T及び Tが炭素数 2  [0160] As a preferred specific example of the structural unit represented by the general formula (83), T and T each have 2 carbon atoms.
1 2  1 2
〜4の直鎖状アルキレン基であるものが挙げられ、より具体的には、一般式 (84)  To 4 linear alkylene groups, and more specifically, those represented by the general formula (84)
Figure imgf000043_0002
Figure imgf000043_0002
(式中、！^1、！^2、 1^，、1^2，、 ，、1^4，、 、 R5，、T，，ゝ T，，、 ゝ ，ゝ 及び ，は上 (In the formula,! ^ 1,! ^ 2 , 1 ^ ,, 1 ^ 2 ,, ,, 1 ^ 4 ,,, R 5 ,, T ,,ゝT ,,,ゝ,ゝand, above
1 2  1 2
記に同じ。）で示されるものが挙げられる。  Same as above. ).
[0161] 一般式（84)に於いて、 R R2、 R 、 R2，、 R5、 R5，は、全て水素原子であるものが 好ましい。 In the general formula (84), RR 2 , R 1, R 2 , R 5 and R 5 are all preferably hydrogen atoms.
[0162] 一般式 (84)に於 、て、 Zで示される 4価の炭化水素基は、通常芳香族又は脂肪族 系の 4価の炭化水素基であれば特に限定されないが、例えば上記一般式 (25)〜（3 3)で示される芳香族又は脂肪族系の 4価の炭化水素基の中でも、上記式 (25)若し くは（26)、上記一般式（29)又は上記式（32)若しくは（33)で示されるものが好まし い。 [0162] In the general formula (84), the tetravalent hydrocarbon group represented by Z is not particularly limited as long as it is usually an aromatic or aliphatic tetravalent hydrocarbon group. Among the aromatic or aliphatic tetravalent hydrocarbon groups represented by the formulas (25) to (33), the above formula (25) Or (26), those represented by the above general formula (29), or the above formula (32) or (33) are preferred.
[0163] 一般式 (84)に於いて、 Z'で示される 2価の炭化水素基は、通常芳香族又は脂肪 族系の 2価の炭化水素基であれば特に限定されないが、例えば上記一般式 (49)〜 (56)で示される芳香族又は脂肪族系の 2価の炭化水素基の中でも、上記式 (49)、 上記一般式（53)若しくは（54)又は式（56)で示されるものが好まし 、。  [0163] In the general formula (84), the divalent hydrocarbon group represented by Z 'is not particularly limited as long as it is usually an aromatic or aliphatic divalent hydrocarbon group. Among the aromatic or aliphatic divalent hydrocarbon groups represented by the formulas (49) to (56), those represented by the above formula (49), the above general formula (53) or (54), or the formula (56) What is preferred.
[0164] 尚、一般式（7)で示される構成単位を含んで成る化合物に於!ヽて、該構成単位以 外のものとしては、上記した如き構成単位に限定されるものではなぐまた、一般式（ 7)で示される構成単位が含まれて ヽれば、他の構成単位が任意の割合で含まれて いても良ぐ具体的には、例えば一般式（78)及び (82)に於ける重合度を表す k'は 、該化合物中の全構成単位のうち、 Zを含む構成単位の数を表し、 k' 'は、該化合物 中の全構成単位のうち、 Z'を含む構成単位の数を表し、該化合物が種々の用途に 供される場合に於いて、適切な性能が得られるものとなるように設定されれば良ぐ特 に限定されないが、 k'及び k"の比率 (k，： k，，）は、例えば k， :k" = 10 : 90〜99 : l が挙げられる。  [0164] In addition, in the compound comprising the structural unit represented by the general formula (7), other than the structural unit is not limited to the structural unit as described above. As long as the structural unit represented by the general formula (7) is included, other structural units may be included in any ratio. Specifically, for example, in the general formulas (78) and (82) K ′ representing the degree of polymerization in the compound represents the number of structural units containing Z among all the structural units in the compound, and k ′ ′ represents the composition containing Z ′ among all the structural units in the compound. The number of units is not particularly limited as long as it is set so as to obtain appropriate performance when the compound is used in various applications. Examples of the ratio (k,: k,) include k,: k "= 10: 90 to 99: l.
[0165] また、一般式 (7)で示される構成単位を含んで成る化合物に於いて、一般式 (7)で 示される構成単位を A，とし、他の構成単位を B，とした場合、 A'と B'は一般式 (85) [0165] In the compound comprising the structural unit represented by the general formula (7), when the structural unit represented by the general formula (7) is A and the other structural unit is B, A 'and B' are general formulas (85)
-^Α'ΒΆ'ΒΆ'ΒΆ'ΒΆ'Β' + (85) で示されるような Α' Β'—の繰り返し構造、一般式 (86) -^ Α'ΒΆ'ΒΆ'ΒΆ'ΒΆ'Β '+ repeating structure of Α' Β'— as shown by (85), general formula (86)
+Α'Α'Α'Β'Β'Β'Α'Α'Α' + (86) で示されるようなブロック構造又は一般式 (87)  + Α'Α'Α'Β'Β'Β'Α'Α'Α '+ Block structure or general formula as shown in (86) (87)
-^ΑΆ'ΒΆΆΆ'ΒΆ'Β'Β' + (87) で示されるようなランダム構造で該化合物を構成しても良ぐさらに A'と B'だけでなく 、 C'、 D '等の他の構成単位を成分として、 3成分以上で該化合物を構成しても良い  -^ ΑΆ'ΒΆΆΆ'ΒΆ'Β'Β '+ (87) The compound may be composed of a random structure as shown in (87). In addition to A' and B ', C', D ', etc. Using other structural units as components, the compound may be composed of three or more components.
[0166] 次に、一般式（ 1)及び (7)で示される構成単位を含んで成る化合物の製造方法、 即ち、本発明の製造方法について詳細に説明する。本発明の一般式（1)で示される 構成単位を含んで成る化合物の製造方法としては、一般式 (7)で示される構成単位 を含んで成る化合物と、一般式（10)、 （11)及び（12)力 選ばれる少なくとも 1種以 上の (メタ)アクリル酸誘導体とを要すれば溶媒の存在下反応させれば良ぐ具体的 な製造方法としては、例えば下記 [ I ]法 [0166] Next, the production method of the compound comprising the structural units represented by the general formulas (1) and (7), that is, the production method of the present invention will be described in detail. Represented by the general formula (1) of the present invention As a method for producing a compound comprising a structural unit, a compound comprising a structural unit represented by the general formula (7) and at least one selected from the general formulas (10), (11) and (12) are selected. If the above (meth) acrylic acid derivative is required, the reaction can be carried out in the presence of a solvent.
[ I ] [I]
Figure imgf000045_0001
Figure imgf000045_0001
V X Z及び kは上記に同じ。）で示されるもの、又は下記 [ II ]法  V X Z and k are the same as above. ) Or the following [II] method
[ II ] [II]
XX
Figure imgf000045_0002
Figure imgf000045_0002
Y ' ' Y ' ' Z a b及び kは上記に同じ。）で示されるものが挙げられる。  Y '' Y '' Z a b and k are the same as above. ).
1 2  1 2
上記 [ I ]法は、ヒドロキシル基と R3，及び R4，で示されるカルボキシル基とを有する 構成単位を含んで成る化合物に対して、一般式（10)、 （11)及び（12)力も選ばれる 少なくとも 1種以上の (メタ)アクリル酸誘導体を反応させることにより、ヒドロキシル基 及び Z又はカルボキシル基に該 (メタ)アクリル酸誘導体由来の基が導入された構成 単位を含んで成る化合物を製造する方法であり、上記 [ II ]法は、 R3'及び R4'で示 されるカルボキシル基を有する構成単位を含んで成る化合物に対して、一般式（11) 及び（ 12)力 選ばれる少なくとも 1種以上の (メタ)アクリル酸誘導体を反応させること により、カルボキシル基に該 (メタ)アクリル酸誘導体由来の基が導入された構成単位 を含んで成る化合物を製造する方法である。 In the above [I] method, the compounds represented by the general formulas (10), (11) and (12) are also applied to a compound comprising a structural unit having a hydroxyl group and a carboxyl group represented by R 3 and R 4 . A structure in which a group derived from the (meth) acrylic acid derivative is introduced into the hydroxyl group and Z or carboxyl group by reacting at least one selected (meth) acrylic acid derivative The above method [II] is a method for producing a compound comprising a unit having a carboxyl group represented by R 3 ′ and R 4 ′. ) And (12) Force By reacting at least one selected (meth) acrylic acid derivative, a compound comprising a structural unit in which a group derived from the (meth) acrylic acid derivative is introduced into a carboxyl group is obtained. It is a manufacturing method.
[0168] 尚、ここで言う、（メタ)アクリル酸誘導体由来の基とは、一般式（10)、 （11)及び（12 )で示される (メタ)アクリル酸誘導体に由来する基を意味し、具体的には、一般式（1 0)で示される (メタ)アクリル酸誘導体に由来する基は、 R7で示される基、即ち、ビ- ルカルボ-ル基又はイソプロべ-ルカルポ-ル基を意味し、一般式（11)で示される（ メタ)アクリル酸誘導体に由来する基は、一般式 (3)で示される基を意味し、一般式（ 12)で示される (メタ)アクリル酸誘導体に由来する基は、一般式 (4)で示される基を 意味する。 [0168] The group derived from a (meth) acrylic acid derivative as used herein means a group derived from a (meth) acrylic acid derivative represented by the general formulas (10), (11) and (12). Specifically, the group derived from the (meth) acrylic acid derivative represented by the general formula (10) is a group represented by R 7 , that is, a beryl carbo ol group or an iso-propyl carbo ol group. The group derived from the (meth) acrylic acid derivative represented by the general formula (11) means the group represented by the general formula (3), and is represented by the (meth) acrylic acid represented by the general formula (12). The group derived from the derivative means a group represented by the general formula (4).
[0169] また、上記 [ I ]及び [ II ]法に於いて、一般式（10)、 （11)及び（12)で示される (メ タ）アクリル酸誘導体は 1種乃至複数種用いることができ、また、該 (メタ)アクリル酸誘 導体は、上記一般式 (20)で示される構成単位の構造上 1乃至 4k個のものを導入す ることができ、上記一般式 (21)で示される構成単位の構造上 1乃至 2k個のものを導 人することができる。  [0169] In the above [I] and [II] methods, one or more (meth) acrylic acid derivatives represented by the general formulas (10), (11) and (12) may be used. In addition, as the (meth) acrylic acid derivative, 1 to 4k of the structural unit represented by the general formula (20) can be introduced, which is represented by the general formula (21). 1 to 2k structural members can be introduced.
[0170] 一般式（10)で示される (メタ)アクリル酸誘導体を含む 2種以上の (メタ)アクリル酸 誘導体を組み合わせて用いる場合には、先ず一般式（20)で示される構成単位を含 んで成る化合物と、一般式（10)で示される (メタ)アクリル酸誘導体とを反応させた後 に、得られた反応物と他の (メタ）アクリル酸誘導体 {例えば一般式（11)や（12)で示 されるもの }とを反応させることが好ま ヽ。一般式（10)で示される (メタ）アクリル酸誘 導体と、他の (メタ)アクリル酸誘導体とを混合して、両誘導体を一挙に反応させようと すると、一般式（10)で示される (メタ)アクリル酸誘導体の反応性が、他の (メタ)アタリ ル酸誘導体に比べて高いことに起因して、一般式（10)で示される (メタ)アクリル酸誘 導体と他の (メタ)アクリル酸誘導体同士が反応してしま！ヽ、（メタ)アクリル酸誘導体の 副生成物が生成し、結果として一般式（18)で示される構成単位を含んで成る化合 物の歩留まりの低下を起こしてしまう。これを防ぐために、（メタ)アクリル酸誘導体を別 々及び段階的に反応させることが好ま 、。 [0170] When two or more (meth) acrylic acid derivatives including the (meth) acrylic acid derivative represented by the general formula (10) are used in combination, the structural unit represented by the general formula (20) is first included. And the (meth) acrylic acid derivative represented by the general formula (10) is reacted with the obtained reaction product and another (meth) acrylic acid derivative {for example, the general formula (11) or ( It is preferable to react with those shown in 12). When a (meth) acrylic acid derivative represented by the general formula (10) is mixed with another (meth) acrylic acid derivative and both derivatives are reacted at once, the general formula (10) is obtained. Due to the higher reactivity of (meth) acrylic acid derivatives compared to other (meth) acrylic acid derivatives, (meth) acrylic acid derivatives represented by general formula (10) and other (meta) ) Acrylic acid derivatives react with each other! As a result, a by-product of the (meth) acrylic acid derivative is formed, and as a result, the yield of the compound containing the structural unit represented by the general formula (18) is lowered. To prevent this, separate (meth) acrylic acid derivatives It is preferable to react one step at a time.
[0171] 尚、上記では、一般式（20)で示される構成単位を含んで成る化合物に対して、先 ず一般式（10)で示される (メタ)アクリル酸誘導体を反応させ、次 ヽで他の (メタ)ァク リル酸誘導体を反応させているが、先ず他の (メタ)アクリル酸誘導体を反応させた後 に、次 ヽで一般式（10)で示される (メタ）アクリル酸誘導体を反応させても良 ヽことは いうまでもない。  [0171] In the above, the (meth) acrylic acid derivative represented by the general formula (10) is first reacted with the compound comprising the structural unit represented by the general formula (20). Other (meth) acrylic acid derivatives are reacted. First, after reacting with other (meth) acrylic acid derivatives, (meth) acrylic acid derivatives represented by the following general formula (10) It goes without saying that it is okay to react.
[0172] また、一般式（ 11)及び（ 12)で示される (メタ)アクリル酸誘導体を組み合わせて用 Vヽる場合には、一般式（20)又は（21)で示される構成単位を含んで成る化合物と反 応させる際に、これらの (メタ)アクリル酸誘導体を混合して、一挙に反応させても良い し、これらの (メタ)アクリル酸誘導体を別々及び段階的に反応させても良!、。  [0172] Further, when the (meth) acrylic acid derivatives represented by the general formulas (11) and (12) are used in combination, the structural unit represented by the general formula (20) or (21) is included. These (meth) acrylic acid derivatives may be mixed and reacted at once when reacting with the compound consisting of, or these (meth) acrylic acid derivatives may be reacted separately and stepwise. Good!
[0173] [ I ]法で示される製造方法の好ましい具体例としては、例えば下記 [ III ]法  [0173] Preferable specific examples of the production method shown by the method [I] include, for example, the following method [III]
Figure imgf000047_0001
Figure imgf000047_0001
は上記に同じ。）で示されるものが挙げられる。  Is the same as above. ).
[0174] 上記 [ m ]法は、ヒドロキシル基と R3'及び R4'で示されるカルボキシル基とを有する 構成単位を含んで成る化合物に対して、一般式（10)で示される (メタ）アクリル酸誘 導体を反応させることにより、ヒドロキシル基に該 (メタ)アクリル酸誘導体由来の基が 導入された構成単位を含んで成る化合物を製造する方法である。 [0174] The above [m] method is a compound represented by the general formula (10) for a compound comprising a structural unit having a hydroxyl group and a carboxyl group represented by R 3 'and R 4 '. This is a method for producing a compound comprising a structural unit in which a group derived from a (meth) acrylic acid derivative is introduced into a hydroxyl group by reacting an acrylic acid derivative.
[0175] ここで、上記 [ III ]法について詳細に説明する。 [ III ]法は、例えば一般式（20)で 示される構成単位を含んで成る化合物を要すれば溶媒で希釈し、これに塩基、重合 禁止剤及び要すれば触媒を加えた後、この混合溶液に、下記の如き所定の当量の 一般式（10)で示される (メタ)アクリル酸誘導体を滴下し、所定の温度で、所定の時 間反応させる。ここで得られた溶液は、単離、精製を行うことなぐ 目的の用途に使用 することができ、用途によっては、一般式 (88)で示される構成単位を含んで成る化 合物を常法により単離、精製すれば良い。具体的な単離、精製方法としては、反応 液を水中に滴下することにより、当該化合物が晶析してくるため、これを濾取し、得ら れた晶析物をさらに、例えば水等で洗浄した後、減圧乾燥することにより、該化合物 が単離、精製できる。 [0175] Here, the above [III] method will be described in detail. In the method [III], for example, a compound comprising the structural unit represented by the general formula (20) is diluted with a solvent if necessary, and a base, a polymerization inhibitor and, if necessary, a catalyst are added thereto, and then the mixture is mixed. A predetermined amount of the (meth) acrylic acid derivative represented by the general formula (10) is added dropwise to the solution at a predetermined temperature at a predetermined time. Let it react for a while. The solution obtained here can be used for the intended application without isolation and purification. Depending on the application, a compound comprising the structural unit represented by the general formula (88) may be used in a conventional manner. It may be isolated and purified by As a specific isolation and purification method, since the compound is crystallized by dropping the reaction solution into water, it is filtered and the resulting crystallized product is further purified, for example, with water or the like. The compound can be isolated and purified by washing under reduced pressure and drying under reduced pressure.
[0176] [ III ]法に於いて、一般式（10)で示される (メタ）アクリル酸誘導体としては、例えば  [0176] In the [III] method, as the (meth) acrylic acid derivative represented by the general formula (10), for example,
(メタ)アクリル酸クロライド、（メタ)アクリル酸ブロマイド等の (メタ)アクリル酸ハロゲン 化物が挙げられ、中でも (メタ）アクリル酸クロライドが好ま 、。  Examples include (meth) acrylic acid halides such as (meth) acrylic acid chloride and (meth) acrylic acid bromide. Among them, (meth) acrylic acid chloride is preferred.
[0177] 一般式（10)で示される (メタ)アクリル酸誘導体の当量としては、一般式（20)で示さ れる構成単位を含んで成る化合物に於けるヒドロキシル基に対して、通常 0. 1〜3当 量が挙げられ、中でも 0. 5〜2当量が好ましぐその中でも 0. 8〜1. 5当量がより好 ましい。  [0177] The equivalent of the (meth) acrylic acid derivative represented by the general formula (10) is usually 0.1 to the hydroxyl group in the compound comprising the structural unit represented by the general formula (20). ~ 3 equivalents can be mentioned, among which 0.5 to 2 equivalents are preferred, and 0.8 to 1.5 equivalents are more preferred.
[0178] 一般式（10)で示される (メタ)アクリル酸誘導体は、市販のものを用いる力 (メタ)ァ クリル酸にハロゲン化剤を作用させる一般的な方法により合成したものを適宜用いれ ば良い。  [0178] As the (meth) acrylic acid derivative represented by the general formula (10), a force synthesized using a commercially available product (meth) acrylic acid synthesized by a general method in which a halogenating agent is allowed to act can be used as appropriate. good.
[0179] [ III ]法に於ける反応温度は、一般式（20)で示される構成単位を含んで成る化合 物に於けるヒドロキシル基と、一般式（10)で示される (メタ)アクリル酸誘導体とが定 量的に反応するような温度であれば、特に限定されないが、例えば通常 0〜50°C、 好ましくは 10〜30°Cである。反応温度が 50°Cを超えると、該 (メタ)アクリル酸誘導体 の重合が一部起こり、分子量が急激に増大する原因となり、また 0°C未満では反応の 進行が遅ぐ該 (メタ)アクリル酸誘導体由来の基が目的とする導入量に達するために は時間が力かるので好ましくない等の問題を生ずる。  [0179] The reaction temperature in the [III] method is the hydroxyl group in the compound comprising the structural unit represented by the general formula (20) and the (meth) acrylic acid represented by the general formula (10). Although it will not specifically limit if it is a temperature which reacts with a derivative quantitatively, For example, it is 0-50 degreeC normally, Preferably it is 10-30 degreeC. When the reaction temperature exceeds 50 ° C, the polymerization of the (meth) acrylic acid derivative partially occurs, causing a rapid increase in molecular weight, and when the reaction temperature is less than 0 ° C, the reaction proceeds slowly. It takes time for the group derived from the acid derivative to reach the desired introduction amount, and this causes problems such as undesirable.
[0180] [ III ]法に於ける反応時間は、一般式（10)で示される (メタ）アクリル酸誘導体由来 の基の導入量が適切な範囲となるように、反応時間を決定すれば良い。当該反応時 間は、反応に用 、られる (メタ)アクリル酸誘導体の当量や反応温度に依存するため 、一概には言えないが、通常 0. 5〜50時間、好ましくは 0. 5〜20時間、より好ましく は 0. 5〜 10時間の範囲に設定される。 [0181] [ III ]法は、通常無溶媒又は溶媒中で行われる力 好ましくは溶媒中で行われる。 [0180] The reaction time in the method [III] may be determined so that the introduction amount of the group derived from the (meth) acrylic acid derivative represented by the general formula (10) falls within an appropriate range. . Since the reaction time depends on the equivalent amount of the (meth) acrylic acid derivative used for the reaction and the reaction temperature, it cannot be generally stated, but is usually 0.5 to 50 hours, preferably 0.5 to 20 hours. More preferably, it is set in the range of 0.5 to 10 hours. [0181] The method [III] is usually carried out in the absence of a solvent or in a solvent, preferably in a solvent.
[0182] 溶媒としては、反応に用いる各成分及び反応生成物を溶解することができ、且つ、 反応に悪影響を与えず、さらに、水溶性であれば特に限定されないが、具体的には 、例えば N, N—ジメチルホルムアミド、 1ーメチルー 2—ピロリドン、プロピレングリコー ルモノメチルエーテルアセテート、ジメチルスルホキシド、ジォキサン、メチルイソブチ ルケトン、 γ ブチロラタトン、乳酸ェチル、シクロへキサノン等の非プロトン性極性溶 媒が挙げられる。これらの溶媒は、夫々単独で又は 2種以上を組み合わせて用いら れ、上記溶媒の使用量は、原料を溶解し得る量であれば特に限定されない。  [0182] The solvent is not particularly limited as long as it can dissolve each component and reaction product used in the reaction, does not adversely affect the reaction, and is water-soluble. Specifically, for example, Examples include aprotic polar solvents such as N, N-dimethylformamide, 1-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, dioxane, methyl isobuty ketone, γ-butyrolataton, lactate ethyl, and cyclohexanone. These solvents are used singly or in combination of two or more, and the amount of the solvent used is not particularly limited as long as it can dissolve the raw materials.
[0183] [ III ]法に於いて、一般式 (20)で示される構成単位を含んで成る化合物と、一般 式（ 10)で示される (メタ)アクリル酸誘導体とが定量的かつスムーズに反応するように 塩基を使用することが好ましい。これらの塩基としては、例えばトリェチルァミン、ピリ ジン、ジメチルァミノピリジン等の一般的に用いられる三級アミン等の塩基が挙げられ る。これらの塩基は、夫々単独で又は 2種以上を組み合わせて用いられ、上記塩基 の当量数は、特に限定されないが、一般式（10)で示される (メタ)アクリル酸誘導体 に対して、通常 1〜2当量が挙げられる。  [0183] In the method [III], the compound comprising the structural unit represented by the general formula (20) and the (meth) acrylic acid derivative represented by the general formula (10) react quantitatively and smoothly. It is preferable to use a base. Examples of these bases include bases such as generally used tertiary amines such as triethylamine, pyridine, dimethylaminopyridine and the like. These bases are used alone or in combination of two or more, and the number of equivalents of the above base is not particularly limited, but is usually 1 with respect to the (meth) acrylic acid derivative represented by the general formula (10). ˜2 equivalents.
[0184] また、 [ III ]法に於いて、触媒を使用することができる。これらの触媒としては、例え ばテトラブチルアンモ -ゥムクロライド、テトラプチルアンモ -ゥムブロマイド、トリェチ ルベンジルアンモ -ゥムクロライド、トリェチルベンジルアンモ-ゥムブロマイド等の四 級アンモ-ゥム塩や、トリフエ-ルホスフィン等の有機ホスフィンィ匕合物等の触媒が挙 げられる。これらの触媒は、夫々単独で又は 2種以上を組み合わせて用いられ、上記 触媒の使用量は、特に限定されないが、一般式 (20)で示される構成単位を含んで 成る化合物の mol量に対して、 0. 001mol%以上が挙げられ、反応速度を向上させ る為に、 200mol%程度使用することもある。  [0184] In the method [III], a catalyst can be used. These catalysts include, for example, quaternary ammonium salts such as tetrabutylammonium chloride, tetraptylammonium bromide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, and triphenylphosphine. Examples include catalysts such as organic phosphine compounds. These catalysts are used singly or in combination of two or more, and the amount of the catalyst used is not particularly limited, but relative to the mol amount of the compound comprising the structural unit represented by the general formula (20). In order to improve the reaction rate, about 200 mol% may be used.
[0185] さらにまた、 [ III ]法に於いて、反応中での二重結合に起因する重合を防止するた めに重合禁止剤を使用することができる。重合禁止剤としては、例えばハイドロキノン 、ハイドロキノンモノメチノレエーテル、ピロガロール、 4 tert—ブチノレカテコール、 2, 6—ジ tert ブチルフエノール、フエノチアジン、ベンゾキノン等が挙げられる。これ らの重合禁止剤は、夫々単独で又は 2種以上を組み合わせて用いられ、上記重合禁 止剤の使用量は、特に限定されないが、一般式 (20)で示される構成単位を含んで 成る化合物の mol量に対して、通常 0. 001mol%〜2mol%が挙げられる。 [0185] Furthermore, in the method [III], a polymerization inhibitor can be used in order to prevent polymerization due to double bonds during the reaction. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethylol ether, pyrogallol, 4 tert-butynolecatechol, 2,6-ditert butylphenol, phenothiazine, benzoquinone and the like. These polymerization inhibitors are used singly or in combination of two or more, and the above polymerization inhibitors are used. The amount of the stopper used is not particularly limited, but is usually from 0.001 mol% to 2 mol% with respect to the mol amount of the compound comprising the structural unit represented by the general formula (20).
[0186] [ III ]法は、適当な反応条件で、一般式 (20)で示される構成単位を含んで成るィ匕 合物に対して、一般式（10)で示される (メタ)アクリル酸誘導体由来の基を導入する ことにより、即ち、該 (メタ）アクリル酸誘導体の当量、反応温度、反応時間等の上記の 如き反応条件を制御することにより、該 (メタ)アクリル酸誘導体由来の基の導入量を 任意に調節することが可能である。当該 (メタ)アクリル酸誘導体由来の基の導入量 は、本法によって得られる化合物が種々の用途に供される場合に於いて、適切な性 能が得られるものとなるように設定されれば良ぐ特に限定されないが、一般式 (20) で示される構成単位を含んで成る化合物のヒドロキシル基の mol量に対して、通常 1 〜100mol%、好ましくは 10〜80mol%の割合である。当該 (メタ）アクリル酸誘導体 由来の基の割合が 10mol%より少ないと、例えば当該構成単位を含んで成る化合物 カゝら得られる榭脂組成物を用いてカラーフィルターを製造する場合には、例えば光 又は熱硬化後のアルカリ現像の時間が長くなり、また、該 (メタ）アクリル酸誘導体由 来の基の割合が 80mol%より多いと、少ない光照射で架橋させ、硬化させることがで きるが、架橋密度が高くなりすぎて微細パターンが剥離しやすくなる等の問題を生ず るので好ましくない。  [0186] In the method [III], a (meth) acrylic acid represented by the general formula (10) is represented on a compound comprising the structural unit represented by the general formula (20) under appropriate reaction conditions. By introducing a group derived from a derivative, that is, by controlling the reaction conditions such as the equivalent, reaction temperature and reaction time of the (meth) acrylic acid derivative, the group derived from the (meth) acrylic acid derivative It is possible to arbitrarily adjust the introduction amount of. The introduction amount of the group derived from the (meth) acrylic acid derivative should be set so that an appropriate performance can be obtained when the compound obtained by this method is used in various applications. Although not particularly limited, it is usually 1 to 100 mol%, preferably 10 to 80 mol%, based on the mol amount of the hydroxyl group of the compound comprising the structural unit represented by the general formula (20). When the proportion of the group derived from the (meth) acrylic acid derivative is less than 10 mol%, for example, when producing a color filter using a resin composition obtained from a compound comprising the structural unit, for example, If the alkali development time after light or heat curing is long and the proportion of the group derived from the (meth) acrylic acid derivative is more than 80 mol%, it can be crosslinked and cured with a small amount of light irradiation. This is not preferable because the crosslink density becomes too high and a fine pattern is easily peeled off.
[0187] [ III ]法で示される製造方法のより詳細な具体例としては、例えば下記 [ IV ]法  [0187] As a more specific example of the production method shown by the method [III], for example, the following method [IV]
Figure imgf000050_0001
Figure imgf000050_0001
で示されるものが挙げられる。  The thing shown by is mentioned.
尚、式（89)で示される化合物は、一般式（10)に於ける R7がビュルカルボ-ル基で あり、 Xが塩素原子である場合に相当する。一般式 (90)で示される化合物は、一般 式（1)に於ける Yが一般式（5)で示される基、且つ、 R8がビュルカルボニル基であり 、 Yが一般式 (6)で示される基、且つ、 R9が水素原子であり、 a及び bが 1である場合In the compound represented by the formula (89), R 7 in the general formula (10) is a bullcarbo group. Yes, corresponding to the case where X is a chlorine atom. In the compound represented by the general formula (90), Y in the general formula (1) is a group represented by the general formula (5), R 8 is a butylcarbonyl group, and Y is a general formula (6). When R 9 is a hydrogen atom and a and b are 1
2 2
に相当する。  It corresponds to.
[ II ]法で示される製造方法の好ましい具体例としては、例えば下記 [ V ]法  Preferable specific examples of the production method shown by the method [II] include, for example, the following method [V]
Figure imgf000051_0001
Figure imgf000051_0001
'、 Υ ' '、 Ζ及び kは上記に同じ。）で示されるものが挙げられる。  ', Υ' ', Ζ and k are the same as above. ).
2  2
[0190] 上記 [ V ]法は、上記 [ II ]法と同様の方法である力 一般式（19)及び（21)に於 ける a及び bが 1である構成単位を含んで成る化合物の製造方法である。  [0190] The method [V] is a method similar to the method [II]. Production of a compound comprising a structural unit in which a and b in formulas (19) and (21) are 1 Is the method.
[0191] ここで、上記 [ V ]法について詳細に説明する。 [ V ]法は、例えば一般式（91)で 示される構成単位を含んで成る化合物を溶媒で希釈し、これに重合禁止剤並びに要 すれば縮合剤及び Z又は触媒を加えた後、この混合溶液に、下記の如き所定の当 量の一般式（ 11)及び（ 12)力 選ばれる少なくとも 1種以上の (メタ)アクリル酸誘導 体を滴下し、所定の温度で、所定の時間反応させる。ここで得られた溶液は、単離、 精製を行うことなぐ目的の用途に使用することができ、用途によっては、一般式 (92 )で示される構成単位を含んで成る化合物を常法により単離、精製すれば良い。具 体的な単離、精製方法としては、反応液を溶媒で希釈した後に、要すれば縮合剤の 残留物を濾過して取り除いた後、濾液を水中に滴下することにより、当該化合物が晶 祈してくるため、これを濾取し、得られた晶析物をさらに、例えば水、アルコール等で 洗浄した後、減圧乾燥することにより、該化合物が単離、精製できる。 [0192] [ V ]法に於いて、一般式（11)で示される (メタ）アクリル酸誘導体としては、例えば グリシジル (メタ）アタリレート、 1, 2 エポキシ— 4 ブチル (メタ）アタリレート、 1, 2- エポキシ 5 ペンチル (メタ）アタリレート、 1, 2 エポキシ 6 へキシル (メタ）ァク リレート、 1, 2 エポキシ— 7 ヘプチル (メタ）アタリレート、 1, 2 エポキシ— 8—ォ クチル (メタ）アタリレート等の 1, 2—エポキシ— ω—アルキル (メタ）アタリレートが挙 げられ、中でもグリシジル (メタ）アタリレート、 1, 2 エポキシ一 4 ブチル (メタ）アタリ レート、 1, 2 エポキシー5 ペンチル (メタ）アタリレートが好ましぐその中でもダリ シジル (メタ）アタリレートがより好まし 、。 [0191] Here, the above [V] method will be described in detail. In the method [V], for example, a compound containing the structural unit represented by the general formula (91) is diluted with a solvent, and a polymerization inhibitor and, if necessary, a condensing agent and Z or a catalyst are added to the mixture. A predetermined equivalent amount of the general formula (11) and (12) force selected from the following formula is dropped into the solution, and the mixture is reacted at a predetermined temperature for a predetermined time. The solution obtained here can be used for the intended purpose without isolation and purification. Depending on the purpose, the compound comprising the structural unit represented by the general formula (92) can be obtained by a conventional method. Separation and purification. As a specific isolation and purification method, after diluting the reaction solution with a solvent, if necessary, the residue of the condensing agent is removed by filtration, and then the filtrate is dropped into water to crystallize the compound. In order to pray, this is collected by filtration, and the resulting crystallized product is further washed with, for example, water or alcohol, and then dried under reduced pressure, whereby the compound can be isolated and purified. [0192] In the [V] method, examples of the (meth) acrylic acid derivative represented by the general formula (11) include glycidyl (meth) acrylate, 1, 2 epoxy-4 butyl (meth) acrylate, 1 , 2-Epoxy 5 Pentyl (meth) acrylate, 1, 2 Epoxy 6 Hexyl (meth) acrylate, 1, 2 Epoxy— 7 Heptyl (meth) acrylate, 1, 2 Epoxy — 8-Octyl (Meta ) 1,2-epoxy-ω-alkyl (meth) acrylate, such as acrylate, among others, glycidyl (meth) acrylate, 1, 2 epoxy 1-butyl (meth) acrylate, 1, 2 epoxy-5 Of these, pentyl (meth) acrylate is preferred, but darisidyl (meth) acrylate is more preferred.
[0193] [ V ]法に於いて、一般式（12)で示される (メタ）アクリル酸誘導体としては、例えば 1—ヒドロキシメチル (メタ）アタリレート、 2—ヒドロキシ一 1—ェチル (メタ）アタリレート、 3 -ヒドロキシ 1 プロピル (メタ）アタリレート、 4 ヒドロキシ 1 ブチル (メタ）ァク リレート、 5 ヒドロキシ一 1—ペンチル (メタ）アタリレート、 6 ヒドロキシ一 1—へキシ ル (メタ）アタリレート等の ω—ヒドロキシ— 1—アルキル (メタ）アタリレートが挙げられ、 中でも 2 ヒドロキシ 1 ェチル (メタ）アタリレート、 3 ヒドロキシ 1 プロピル (メ タ）アタリレート、 4 ヒドロキシ一 1—ブチル (メタ）アタリレート、が好ましぐその中でも 2—ヒドロキシ— 1—ェチル (メタ）アタリレートがより好ましい。  [0193] In the method [V], the (meth) acrylic acid derivative represented by the general formula (12) includes, for example, 1-hydroxymethyl (meth) acrylate, 2-hydroxy 1-ethyl (meth) acrylate. 3-hydroxy-1-propyl (meth) acrylate, 4-hydroxy-1-butyl (meth) acrylate, 5-hydroxy-1-pentyl (meth) acrylate, 6-hydroxy-1-hexyl (meth) acrylate, etc. Ω—Hydroxy— 1-alkyl (meth) ate acrylates, 2 Hydroxy 1 ethyl (meth) acrylate, 3 Hydroxy 1 propyl (meth) acrylate, 4 Hydroxy 1-butyl (meth) acrylate Among these, 2-hydroxy-1-ethyl (meth) acrylate is more preferable.
[0194] 一般式（11)及び（12)で示される (メタ）アクリル酸誘導体の当量としては、一般式（ 91)で示される構成単位を含んで成る化合物に於けるカルボキシル基に対して、通 常 0. 1〜3当量が挙げられ、中でも 0. 5〜2当量が好ましぐその中でも 0. 8〜1. 5 当量がより好ましい。  [0194] The equivalent weight of the (meth) acrylic acid derivative represented by the general formulas (11) and (12) is relative to the carboxyl group in the compound comprising the structural unit represented by the general formula (91). Usually 0.1 to 3 equivalents are mentioned, and 0.5 to 2 equivalents are preferred, and 0.8 to 1.5 equivalents are more preferred.
[0195] 一般式（11)で示される (メタ)アクリル酸誘導体は、市販のものを用いる力 通常こ の分野で用いられる製造方法により合成したものを適宜用いれば良 、。  [0195] As the (meth) acrylic acid derivative represented by the general formula (11), a commercially available product may be used as appropriate, which is usually synthesized by a production method used in this field.
[0196] 一般式（12)で示される (メタ)アクリル酸誘導体は、市販のものを用いる力 通常こ の分野で用いられる製造方法により合成したものを適宜用いれば良 、。  [0196] As the (meth) acrylic acid derivative represented by the general formula (12), a commercially available product may be used as appropriate, which is usually synthesized by a production method used in this field.
[0197] [ V ]法に於ける反応温度は、一般式（91)で示される構成単位を含んで成る化合 物に於けるカルボキシル基と、一般式（11)及び（12)力 選ばれる少なくとも 1種以 上の (メタ)アクリル酸誘導体とが定量的に反応するような温度であれば、特に限定さ れないが、例えば通常— 10〜150°C、好ましくは 0〜120°Cである。反応温度が 150 °cを超えると、該 (メタ)アクリル酸誘導体の重合が一部起こり、分子量が急激に増大 する原因となり、また 10°C未満では反応の進行が遅ぐ該 (メタ)アクリル酸誘導体 由来の基が目的とする導入量に達するためには時間が力かるので好ましくない等の 問題を生ずる。 [0197] The reaction temperature in the method [V] is selected from the carboxyl group in the compound comprising the structural unit represented by the general formula (91), and at least the forces selected from the general formulas (11) and (12). Although it is not particularly limited as long as it is a temperature at which one or more (meth) acrylic acid derivatives react quantitatively, for example, usually −10 to 150 ° C., preferably 0 to 120 ° C. . Reaction temperature is 150 When the temperature exceeds ° C, the polymerization of the (meth) acrylic acid derivative partially occurs, causing a rapid increase in molecular weight, and when the temperature is lower than 10 ° C, the reaction proceeds slowly. It takes time for the group to reach the desired amount of introduction, which causes problems such as undesirable.
[0198] [ V ]法に於ける反応時間は、一般式（11)及び（12)力 選ばれる少なくとも 1種以 上の (メタ)アクリル酸誘導体由来の基の導入量が適切な範囲となるように、反応時間 を決定すれば良い。当該反応時間は、反応に用いられる (メタ)アクリル酸誘導体の 当量や反応温度に依存するため、一概には言えないが、通常 0. 5〜50時間、好まし くは 0. 5〜20時間、より好ましくは 0. 5〜10時間の範囲に設定される。  [0198] The reaction time in the method [V] is such that the introduction amount of groups derived from at least one (meth) acrylic acid derivative selected from the general formulas (11) and (12) is within an appropriate range. Thus, the reaction time may be determined. Since the reaction time depends on the equivalent amount of the (meth) acrylic acid derivative used in the reaction and the reaction temperature, it cannot be generally stated, but is usually 0.5 to 50 hours, preferably 0.5 to 20 hours. More preferably, it is set in the range of 0.5 to 10 hours.
[0199] [ V ]法に於ける溶媒は、上記 [ III ]法と同様の溶媒を用いれば良ぐ溶媒の使用 量も上記 [ III ]法と同様量で良い。  [0199] The solvent used in the method [V] may be the same as that used in the above [III], as long as the same solvent as used in the above [III] is used.
[0200] [ V ]法に於いて、一般式 (91)で示される構成単位を含んで成る化合物と、一般 式（ 12)で示される (メタ)アクリル酸誘導体とが定量的かつスムーズに反応するように 縮合剤を使用することが好ましい。これらの縮合剤としては、例えばジシクロへキシル カルボジイミド、 1—ェチル 3— [3— (N, N ジメチルァミノ）プロピル]カルボジイミ ド塩酸塩等のカルポジイミド類、ジ 2—ピリジルカルボネート、ジ 2—ピリジルチオ カルボネート等のカルボネート類等の縮合剤が挙げられる。これらの縮合剤は、夫々 単独で又は 2種以上を組み合わせて用いられ、上記縮合剤の当量数は、特に限定さ れないが、一般式（12)で示される (メタ)アクリル酸誘導体に対して、通常 1〜2当量 が挙げられる。  [0200] In the method [V], the compound comprising the structural unit represented by the general formula (91) and the (meth) acrylic acid derivative represented by the general formula (12) react quantitatively and smoothly. It is preferable to use a condensing agent. These condensing agents include, for example, carpositimides such as dicyclohexyl carbodiimide, 1-ethyl 3- [3- (N, N dimethylamino) propyl] carbodiimide hydrochloride, di-2-pyridyl carbonate, di-2-pyridylthio carbonate. And a condensing agent such as carbonates. These condensing agents are used singly or in combination of two or more, and the number of equivalents of the condensing agent is not particularly limited, but for the (meth) acrylic acid derivative represented by the general formula (12) Usually, 1 to 2 equivalents can be mentioned.
[0201] また、 [ V ]法に於いて、触媒を使用することができる。これらの触媒としては、例え ばテトラブチルアンモ -ゥムクロライド、テトラプチルアンモ -ゥムブロマイド、トリェチ ルベンジルアンモ -ゥムクロライド、トリェチルベンジルアンモ-ゥムブロマイド等の四 級アンモ-ゥム塩や、トリフエ-ルホスフィン等の有機ホスフィンィ匕合物等の触媒が挙 げられる。これらの触媒は、夫々単独で又は 2種以上を組み合わせて用いられ、上記 触媒の使用量は、特に限定されないが、一般式 (91)で示される構成単位を含んで 成る化合物の mol量に対して、 0. O01mol%以上が挙げられ、反応速度を向上させ る為に、 200mol%程度使用することもある。 [0202] さらにまた、 [ V ]法に於いて、反応中での二重結合に起因する重合を防止するた めに重合禁止剤を使用することができる。 [ V ]法に於ける重合禁止剤は、上記 [ III ]法と同様の重合禁止剤を用いれば良ぐ重合禁止剤の使用量も上記 [ III ]法と同 ¾量で良い。 [0201] In the method [V], a catalyst can be used. These catalysts include, for example, quaternary ammonium salts such as tetrabutylammonium chloride, tetraptylammonium bromide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, and triphenylphosphine. Examples include catalysts such as organic phosphine compounds. These catalysts are used singly or in combination of two or more, and the amount of the catalyst used is not particularly limited, but relative to the mol amount of the compound comprising the structural unit represented by the general formula (91). In order to improve the reaction rate, about 200 mol% is sometimes used. [0202] Furthermore, in the method [V], a polymerization inhibitor can be used in order to prevent polymerization due to double bonds in the reaction. The polymerization inhibitor used in the method [V] may be the same as that used in the above [III], as long as the same polymerization inhibitor as in the above [III] is used.
[0203] [ V ]法は、適当な反応条件で、一般式 (91)で示される構成単位を含んで成る化 合物に対して、一般式（ 11)及び（ 12)力 選ばれる少なくとも 1種以上の (メタ）アタリ ル酸誘導体由来の基を導入することにより、即ち、該 (メタ）アクリル酸誘導体の当量、 反応温度、反応時間等の上記の如き反応条件を制御することにより、該 (メタ)アタリ ル酸誘導体由来の基の導入量を任意に調節することが可能である。当該 (メタ)アタリ ル酸誘導体由来の基の導入量は、本法によって得られる化合物が種々の用途に供 される場合に於いて、適切な性能が得られるものとなるように設定されれば良ぐ特に 限定されな ヽが、一般式 (91)で示される構成単位を含んで成る化合物のカルボキ シル基の mol量に対して、通常 l〜100mol%、好ましくは 10〜80mol%の割合で ある。当該 (メタ)アクリル酸誘導体由来の基の割合が 10mol%より少ないと、例えば 当該構成単位を含んで成る化合物カゝら得られる榭脂組成物を用いてカラーフィルタ 一を製造する場合には、例えば光又は熱硬化後のアルカリ現像の時間が長くなり、 また、該 (メタ)アクリル酸誘導体由来の基の割合が 80mol%より多いと、少ない光照 射で架橋させ、硬化させることができるが、架橋密度が高くなりすぎて微細パターンが 剥離しやすくなる等の問題を生ずるので好ましくない。  [0203] In the method [V], a compound comprising the structural unit represented by the general formula (91) under appropriate reaction conditions is selected from at least one selected from the general formulas (11) and (12). By introducing a group derived from more than one kind of (meth) acrylic acid derivative, that is, by controlling the reaction conditions as described above such as equivalent weight of the (meth) acrylic acid derivative, reaction temperature, reaction time, etc. It is possible to arbitrarily adjust the amount of introduction of a group derived from a (meth) atallylic acid derivative. The introduction amount of the group derived from the (meth) attalic acid derivative should be set so that appropriate performance can be obtained when the compound obtained by this method is used in various applications. Although not particularly limited, the ratio is usually 1 to 100 mol%, preferably 10 to 80 mol% with respect to the mol amount of the carboxyl group of the compound comprising the structural unit represented by the general formula (91). is there. When the proportion of the group derived from the (meth) acrylic acid derivative is less than 10 mol%, for example, when producing a color filter using a resin composition obtained from a compound containing the structural unit, For example, the alkali development time after light or heat curing becomes longer, and when the proportion of the group derived from the (meth) acrylic acid derivative is more than 80 mol%, it can be crosslinked and cured with less light irradiation. This is not preferable because the crosslink density becomes too high and the fine pattern easily peels off.
[0204] [ V ]法で示される製造方法のより詳細な具体例としては、例えば下記 [ VI ]法 [0204] As a more specific example of the production method shown by the [V] method, for example, the following [VI] method
Figure imgf000054_0001
Figure imgf000054_0001
(95)  (95)
(式中、
Figure imgf000054_0002
R2、 R1'、 R"、 T、 T、 U、 V、 V、 Y，，、 Y，，、 Z及び kは上記に同じ 。）で示されるもの、又は下記 [ VII ]法 (Where
Figure imgf000054_0002
R 2 , R 1 ', R ", T, T, U, V, V, Y, ..., Y, ..., Z and k are the same as above . ) Or the following [VII] method
Figure imgf000055_0001
Figure imgf000055_0001
。）で示されるものが挙げられる。  . ).
[0205] 尚、一般式（93)で示される化合物は、一般式（7)に於ける R3'及び R4'がカルボキ シル基であり、 Y '及び Y 'が酸素原子又は NH 基であり、 a及び bが 1である場 In the compound represented by the general formula (93), R 3 ′ and R 4 ′ in the general formula (7) are carboxy groups, and Y ′ and Y ′ are oxygen atoms or NH groups. Yes, if a and b are 1
1 2  1 2
合に相当する。式（94)で示される化合物は、一般式（11)に於ける R7力イソプロべ- ルカルボ-ル基であり、 Tカ チル基である場合に相当する。一般式（95)で示され Equivalent to The compound represented by the formula (94) is an R 7 force isopropyl carbonate group in the general formula (11), and corresponds to the case where it is a T acetyl group. Indicated by general formula (95)
3  Three
る化合物は、一般式（1)に於ける R3が一般式 (2)で示される基、且つ、 R6が一般式（ 3)で示される基であり、且つ、 R7及び Tが上記と同じ基であり、 R4が一般式（2)で示 In the compound, R 3 in the general formula (1) is a group represented by the general formula (2), R 6 is a group represented by the general formula (3), and R 7 and T are R 4 is represented by the general formula (2).
3  Three
される基、且つ、 R6が水素原子であり、 Y及び Yが酸素原子又は NH 基であり R 6 is a hydrogen atom, Y and Y are an oxygen atom or an NH group
1 2  1 2
、 a及び bが 1である場合に相当する。式（96)で示される化合物は、一般式（12)に於 ける R7がビュルカルボ-ル基であり、 Tがェチル基である場合に相当する。一般式（ , A and b are equal to 1. The compound represented by the formula (96) corresponds to the case where R 7 in the general formula (12) is a butyl carbo group and T is an ethyl group. General formula (
4  Four
97)で示される化合物は、一般式（1)に於ける R3が一般式 (2)で示される基、且つ、 R6が一般式 (4)で示される基であり、且つ、 R7及び Tが上記と同じ基であり、 R4がー In the compound represented by (97), R 3 in the general formula (1) is a group represented by the general formula (2), R 6 is a group represented by the general formula (4), and R 7 And T is the same group as above, and R 4 is
4  Four
般式 (2)で示される基、且つ、 R6が水素原子であり、 Y及び Yが酸素原子又は N A group represented by the general formula (2), R 6 is a hydrogen atom, and Y and Y are an oxygen atom or N
1 2  1 2
H 基であり、 a及び bが 1である場合に相当する。  Corresponds to the H group, where a and b are 1.
[0206] 本発明の一般式 (7)で示される構成単位を含んで成る化合物の製造方法としては 、一般式（13)で示される化合物と、カルボキシル基を 3個以上有する多塩基酸 (カル ボキシル基の一部がカルボン酸エステルであるものを含む。）又はその無水物（カル ボキシル基の一部が脱水縮合して酸無水物基を形成しているものを含み、また、そ の一部がカルボン酸エステルであるものを含む。）とを溶媒の存在下反応させれば良 ぐ具体的な製造方法としては、例えば下記 [ VIII ]法 [0206] As a method for producing a compound comprising the structural unit represented by the general formula (7) of the present invention, a compound represented by the general formula (13) and a polybasic acid (calcium having three or more carboxyl groups) are used. Including those in which a part of the boxyl group is a carboxylic acid ester) or anhydrides thereof (including those in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group) Including a part of which is a carboxylic acid ester. As a specific production method, the following [VIII] method can be used.
[ νπΐ ] [νπΐ]
(式中、
Figure imgf000056_0001
V 、 Z及び kは上記に同じ。 ) で示されるもの、又は下記 [ IX ]法 (Where
Figure imgf000056_0001
V, Z and k are the same as above. ) Or the following [IX] method
Figure imgf000056_0002
Figure imgf000056_0002
(式中、 R12は水素原子、アルカリ金属原子又は上記一般式（15)で示される基を表し 、 R13は水素原子、アルカリ金属原子又は上記一般式（17)で示される基を表し、
Figure imgf000056_0003
R2、 R1'、 R2，、 R3，、 R4，、 T 、 T 、 U、 V 、 V 、 Y ，，、 Y ，，、 Z、 a、 b及び kは上記に (Wherein R 12 represents a hydrogen atom, an alkali metal atom or a group represented by the above general formula (15); R 13 represents a hydrogen atom, an alkali metal atom or a group represented by the above general formula (17);
Figure imgf000056_0003
R 2 , R 1 ', R 2 , R 3 , R 4 , T, T, U, V, V, Y,,, Y,, Z, a, b and k are as above
1 2 1 2 1 2  1 2 1 2 1 2
同じ。）で示されるものが挙げられる。 the same. ).
上記 [ VIII ]法は、一般式（13)で示される化合物のうち、エポキシ基を有するもの に対して、一般式（34)で示されるカルボキシル基を 3個以上有する多塩基酸 (カル ボキシル基の一部がカルボン酸エステルであるものを含む。）を反応させること〖こより 、ヒドロキシル基及びカルボキシル基を有する一般式（20)で示される構成単位を含 んで成る化合物を製造する方法であり、上記 [ IX ]法は、一般式（13)で示される化 合物のうち、ヒドロキシル基及び Z又はアミノ基を有するもの（これらのアルカリ金属塩 を含む。）に対して、一般式（35)又は（36)で示されるカルボキシル基を 3個以上有 する多塩基酸無水物 (カルボキシル基の一部が脱水縮合して酸無水物基を形成して いるものを含み、また、その一部がカルボン酸エステルであるものを含む。）を反応さ せることにより、カルボキシル基を有する一般式（21)で示される構成単位を含んで成 る化合物を製造する方法である。 In the above [VIII] method, the polybasic acid (carboxyl group) having 3 or more carboxyl groups represented by the general formula (34) with respect to those having an epoxy group among the compounds represented by the general formula (13). A part of which is a carboxylic acid ester.) And a compound comprising a structural unit represented by the general formula (20) having a hydroxyl group and a carboxyl group, and the above-mentioned [IX] method is a compound represented by the general formula (13). A polybasic acid anhydride having three or more carboxyl groups represented by the general formula (35) or (36) with respect to those having a hydroxyl group and Z or amino group (including alkali metal salts thereof). By reacting (including those in which a part of the carboxyl group is dehydrated and condensed to form an acid anhydride group, and part of which is a carboxylic acid ester), the carboxyl group is reacted. And a method for producing a compound comprising the structural unit represented by the general formula (21).
[0208] また、上記 [ VIII ]及び [ IX ]法に於いて、一般式（22)及び（23)で示される化合 物は 1種乃至複数種用いることができ、また、一般式（34)で示されるカルボキシル基 を 3個以上有する多塩基酸 (カルボキシル基の一部がカルボン酸エステルであるもの を含む。）及び一般式（35)又は（36)で示されるカルボキシル基を 3個以上有する多 塩基酸無水物 (カルボキシル基の一部が脱水縮合して酸無水物基を形成して 、るも のを含み、また、その一部がカルボン酸エステルであるものを含む。）は、 1種乃至複 数種用いることができる。  [0208] In the above [VIII] and [IX] methods, one or more compounds represented by the general formulas (22) and (23) can be used, and the general formula (34) A polybasic acid having 3 or more carboxyl groups represented by (including those in which a part of the carboxyl group is a carboxylic acid ester) and 3 or more carboxyl groups represented by the general formula (35) or (36) Polybasic acid anhydrides (including those in which a part of the carboxyl group is dehydrated and condensed to form an acid anhydride group, and part of which is a carboxylic acid ester) are 1 Species or multiple species can be used.
[0209] ここで、上記 [ VIII ]法について詳細に説明する。 [ VIII ]法は、例えば一般式（22 )で示される化合物を溶媒で希釈し、要すればこれに触媒を加えた後、この混合溶液 に、下記の如き所定の当量の一般式（34)で示されるカルボキシル基を 3個以上有 する多塩基酸 (カルボキシル基の一部がカルボン酸エステルであるものを含む。）を 加え、所定の温度で、所定の時間反応させる。ここで得られた溶液は、単離、精製を 行うことなぐ 目的の用途に使用することができ、用途によっては、該溶液をさらに溶 媒で希釈したり、一般式 (20)で示される構成単位を含んで成る化合物を常法により 単離、精製すれば良い。  [0209] Here, the above [VIII] method will be described in detail. In the method [VIII], for example, a compound represented by the general formula (22) is diluted with a solvent, and if necessary, a catalyst is added thereto. A polybasic acid having 3 or more carboxyl groups represented by (including those in which a part of the carboxyl group is a carboxylic acid ester) is added and reacted at a predetermined temperature for a predetermined time. The solution obtained here can be used for the intended application without isolation and purification. Depending on the application, the solution may be further diluted with a solvent, or the structure represented by the general formula (20). A compound containing the unit may be isolated and purified by a conventional method.
[0210] [ VIII ]法に於いて、一般式（22)で示される化合物としては、例えば一般式（98)
Figure imgf000057_0001
[0210] In the method [VIII], the compound represented by the general formula (22) is, for example, the general formula (98).
Figure imgf000057_0001
(式中、
Figure imgf000057_0002
R1'、 R2'、 U、 V及び Vは上記に同じ。）で示されるビスフエ-ル骨 格を有する化合物と、ェピクロロヒドリン、ェピブ口モヒドリン、 4 クロロー 1, 2 ェポ キシブタン、 4ーブロモー 1, 2 エポキシブタン、 5 クロロー 1, 2 エポキシペンタ ン、 5 ブロモー 1, 2 エポキシペンタン、 6 クロロー 1, 2 エポキシへキサン、 6 ーブロモー 1, 2 エポキシへキサン、 7 クロロー 1, 2 エポキシヘプタン、 7 ブロ モー 1, 2 エポキシヘプタン、 8 クロロー 1, 2 エポキシオクタン、 8 ブロモー 1, 2—エポキシオクタン等の ω—ハロゲノエポキシィ匕合物とを反応させることによって得 られる化合物が挙げられ、中でも上記一般式（98)で示されるビスフ ニル骨格を有 する化合物と、ェピクロロヒドリン、ェピブ口モヒドリン、 4 クロ口一 1, 2 エポキシブタ ン、 4ーブロモー 1, 2 エポキシブタン、 5 クロロー 1, 2 エポキシペンタン、 5 ブ 口モー 1, 2—エポキシペンタンの ω—ハロゲノエポキシ化合物とを反応させることに よって得られる化合物が好ましぐその中でも上記一般式（98)で示されるビスフエ二 ル骨格を有する化合物と、ェピクロロヒドリン、ェピブ口モヒドリンの ω ハロゲノエポ キシィ匕合物とを反応させることによって得られる化合物がより好ましい。 (Where
Figure imgf000057_0002
R 1 ', R 2 ', U, V and V are the same as above. ) Bisphenol bones And epoxichlorohydrin, epib mouth mohydrin, 4-chloro-1,2 epoxybutane, 4-bromo-1,2 epoxybutane, 5 chloro-1,2 epoxypentane, 5 bromo-1,2 epoxypentane, 6 Chloro-1,2 Epoxyhexane, 6-Bromo-1,2 Epoxyhexane, 7 Chloro-1,2 Epoxyheptane, 7 Bromo 1,2 Epoxyheptane, 8 Chloro-1,2 Epoxyoctane, 8 Bromo1,2—Epoxy Examples include compounds obtained by reacting ω -halogenoepoxy compounds such as octane, among which a compound having a bisphenyl skeleton represented by the above general formula (98), epichlorohydrin, epip Mouth Mohydrin, 4 Black, 1, 2 Epoxy Butane, 4-Bromo 1, 2 Epoxy Butane, 5 Chloro 1, 2 Epoxy Pentane, 5 Molecules obtained by reacting ω-halogenoepoxy compounds of 1,2-epoxypentane are preferred. Among them, compounds having a bisphenol skeleton represented by the above general formula (98) and More preferred is a compound obtained by reacting chlorohydrin or ω-halogenoepoxy compound of Epib mouth mohydrin.
[0211] 尚、ここで言う、ビスフ ニル骨格を有する化合物とは、例えば上記一般式（98)で 示されるように、 2つのフエ-ル基が結合手又は式（1 1)〜（1 8)の何れかで示さ れる 2価の基で架橋された構造の化合物を意味する。  [0211] The compound having a bisphenyl skeleton referred to here is, for example, as shown in the above general formula (98), two phenol groups having bonds or formulas (11) to (18). ) Means a compound having a structure crosslinked with a divalent group.
[0212] 一般式（98)で示されるビスフ ニル骨格を有する化合物のうち、 Uが結合手である 場合のものの具体例としては、例えば 4, 4，ービフエノール、 3, 3，ービフエノール、 4 , 4，—ビア-リン、 3, 3，—ビア-リン等が挙げられる。  [0212] Among the compounds having the bisphenyl skeleton represented by the general formula (98), specific examples of compounds in which U is a bond include, for example, 4, 4, -biphenol, 3, 3, -biphenol, 4, 4 , —Via-Rin, 3, 3, —Via-Rin etc.
[0213] Uが式（1 1)である場合の当該ビスフエニル骨格を有する化合物の具体例として は、例えば 9, 9—ビス（4—ヒドロキシフエ-ル）フルオレン、 9, 9—ビス（4—ヒドロキシ —3, 5—ジメチルフエ-ル）フルオレン、 9, 9—ビス（4—ヒドロキシ一 3, 5—ジクロロ フエ-ル）フルオレン、 9, 9—ビス（4—ヒドロキシ一 3, 5—ジブロモフエ-ル）フルォレ ン、 9, 9—ビス（4—ヒドロキシ一 3—メチルフエ-ル）フルオレン、 9, 9—ビス（4—ヒド 口キシ一 3—クロ口フエ-ル）フノレオレン、 9, 9—ビス（4—ヒドロキシ一 3—ブロモフエ -ル）フルオレン、 9, 9—ビス（4—ヒドロキシ一 3—フルオロフェ -ル）フルオレン、 9, 9—ビス（4—ヒドロキシ一 3—メトキシフエ-ル）フルオレン、 9, 9—ビス（4—ァミノフエ -ル）フルオレン、 9, 9—ビス（4—アミノー 3, 5—ジメチルフエ-ル）フルオレン、 9, 9 —ビス（4—ァミノ一 3, 5—ジクロロフエ-ル）フルオレン、 9, 9—ビス（4—ァミノ一 3, 5—ジブロモフエ-ル）フルオレン、 9, 9—ビス（4—アミノー 3—メチルフエ-ル）フル オレン、 9, 9—ビス（4—ァミノ一 3—クロ口フエ-ル）フルオレン、 9, 9—ビス（4—アミ ノー 3—ブロモフエ-ル）フルオレン、 9, 9—ビス（4—アミノー 3—フルオロフェ -ル） フルオレン、 9, 9 ビス（4 アミノー 3—メトキシフエ-ル）フルオレン等が挙げられる [0213] Specific examples of the compound having the bisphenyl skeleton when U is represented by the formula (11) include, for example, 9, 9-bis (4-hydroxyphenyl) fluorene, 9, 9-bis (4— Hydroxy-3,5-dimethylphenol) fluorene, 9,9-bis (4-hydroxy-1,3,5-dichlorophenol) fluorene, 9,9-bis (4-hydroxy-1,3,5-dibromophenol) ) Fluorene, 9, 9-bis (4-hydroxy-3-methylphenol) fluorene, 9, 9-bis (4-hydroxysilane 3-chlorophenol) phenololene, 9, 9-bis ( 4-hydroxy-1-3-bromophenol) fluorene, 9, 9-bis (4-hydroxy-1-fluorophenol) fluorene, 9, 9-bis (4-hydroxy-1-methoxyphenol) fluorene, 9, 9-bis (4-aminophenol) fluorene, 9, 9-bis (4-amino-3, 5 Jimechirufue - Le) fluorene, 9, 9 —Bis (4-amino-1,3,5-dichlorophenol) fluorene, 9,9-bis (4-amino-1,3,5-dibromophenol) fluorene, 9,9-bis (4-amino-3-methylphenol) ) Fluorene, 9, 9-bis (4-amino-3-fluoroethylene) fluorene, 9, 9-bis (4-amino 3-bromophenol) fluorene, 9, 9-bis (4 -Amino-3-fluorophenol) fluorene, 9, 9 bis (4 amino-3-methoxyphenol) fluorene, etc.
[0214] また、ハロゲン原子等の置換基を有しているフルオレン環 {式（1— 1) }である場合 の当該ビスフエニル骨格を有する化合物の具体例としては、例えば 2, 7 ジブロモ —9, 9 ビス（4 ヒドロキシフエ-ル）フルオレン、 2, 7 ジブ口モー 9, 9 ビス（4 —ヒドロキシ一 3, 5 ジメチルフエニル）フルオレン、 2, 7 ジブ口モー 9, 9 ビス（4 —ヒドロキシ一 3, 5 ジクロロフエ-ル）フルオレン、 2, 7 ジブ口モー 9, 9 ビス（4 —ヒドロキシ一 3, 5 ジブロモフエニル）フルオレン、 2, 7 ジブ口モー 9, 9 ビス（4 —ヒドロキシ一 3—メチルフエ-ル）フルオレン、 2, 7 ジブ口モー 9, 9 ビス（4 ヒド 口キシ一 3 クロ口フエ-ル）フノレオレン、 2, 7 ジブ口モー 9, 9 ビス（4 ヒドロキシ —3 ブロモフエ-ル）フルオレン、 2, 7 ジブ口モー 9, 9 ビス（4 ヒドロキシ一 3 —フルオロフェ -ル）フルオレン、 2, 7 ジブ口モー 9, 9 ビス（4 ヒドロキシ一 3— メトキシフエ-ル）フルオレン、 2, 7 ジブロモ一 9, 9 ビス（4 ァミノフエ-ル）フル オレン、 2, 7 ジブ口モー 9, 9 ビス（4 アミノー 3, 5 ジメチルフエ-ル）フルォレ ン、 2, 7 ジブロモ一 9, 9 ビス（4 ァミノ一 3, 5 ジクロロフエ-ル）フルオレン、 2 , 7 ジブ口モー 9, 9 ビス（4 アミノー 3, 5 ジブロモフエ-ル）フルオレン、 2, 7 —ジブロモ一 9, 9 ビス（4 ァミノ一 3—メチルフエ-ル）フルオレン、 2, 7 ジブ口 モ一 9, 9 ビス（4 ァミノ一 3 クロ口フエ-ル）フルオレン、 2, 7 ジブロモ一 9, 9 —ビス（4 アミノー 3 ブロモフエ-ル）フルオレン、 2, 7 ジブ口モー 9, 9 ビス（4 —ァミノ一 3 フルオロフェ -ル）フルオレン、 2, 7 ジブロモ一 9, 9 ビス（4 ァミノ 3—メトキシフエ-ル）フルオレン等が挙げられる。 [0214] Further, specific examples of the compound having the bisphenyl skeleton in the case of the fluorene ring {formula (1-1)} having a substituent such as a halogen atom include 2, 7 dibromo-9, 9 Bis (4 hydroxyphenol) fluorene, 2, 7 dib mouth-moe 9, 9 Bis (4 — hydroxy 1 3,5 dimethylphenyl) fluorene, 2, 7 Dib mouth moe 9, 9 Bis (4 — hydroxy 1 3,5 dichlorophenol) fluorene, 2,7 dib-mouthed 9,9 bis (4 —hydroxy-l 3,5 dibromophenyl) fluorene, 2,7 dib-mouthed 9,9 bis (4—hydroxy-l 3— Methylphenol) Fluorene, 2, 7 Jib Mouth 9, 9 Bis (4-Hydro-Chemical Xylose 3-Feole) Funoleolene, 2, 7 Jib Mouth 9,9 Bis (4-Hydroxy —3 Bromophenol) Fluorene, 2, 7 Jib mouth Mo 9, 9 Bis (4 hydroxy 1 3 -fluoro Phenolic) Fluorene, 2,7 Jib Mouth 9,9 Bis (4 hydroxy-1-3-methoxyphenol) fluorene, 2,7 Dibromo 9,9 Bis (4 aminophenol) fluorene, 2,7 Jib Mouth 9, 9 Bis (4 amino-3,5 dimethylphenol) fluorene, 2, 7 Dibromo 9,9 Bis (4 amino 1,3 dichlorophenol) fluorene, 2, 7 Jib mouth 9,9 Bis (4 amino-3,5 dibromophenol) fluorene, 2, 7 —dibromo-1,9,9 Bis (4 amino-1-carbon 3-fluorine), 2,7 Jib mouth 9,9 Bis (4 amino-1 3 Black mouth) Fluorene, 2, 7 Dibromo-1,9,9-bis (4 amino-3 bromophenol) fluorene, 2,7 Jib mouth, 9,9 Bis (4 —amino-1-fluorophenol) fluorene 2,7 Dibromo-1,9,9 Bis (4-amino-3-methoxyphenol) fluorene, etc. And the like.
[0215] Uが式（1 2)である場合の当該ビスフ ニル骨格を有する化合物の具体例として は、例えばビス（4—ヒドロキシフエ-ル）ケトン、ビス（4—ヒドロキシ一 3, 5—ジメチル フエ-ル）ケトン、ビス（4—ヒドロキシ一 3, 5—ジクロロフエ-ル）ケトン、ビス（4—ヒドロ キシ一 3, 5—ジブロモフエ-ル）ケトン、ビス（4—ァミノフエ-ル）ケトン、ビス（4—アミ ノ一 3, 5—ジメチルフエ-ル）ケトン、ビス（4—ァミノ一 3, 5—ジクロロフエ-ル）ケトン 、ビス（4 アミノー 3, 5—ジブロモフエ-ル）ケトン等が挙げられる。 [0215] Specific examples of the compound having a bisphenyl skeleton when U is represented by the formula (12) include, for example, bis (4-hydroxyphenol) ketone, bis (4-hydroxy-1,3,5-dimethyl). Phenol) ketone, bis (4-hydroxy-1,3,5-dichlorophenol) ketone, bis (4-hydro) Xy-1,5-dibromophenol) ketone, bis (4-aminophenol) ketone, bis (4-aminoamino-3,5-dimethylphenol) ketone, bis (4-amino-1,3,5-dichlorophenol) -L) ketone, bis (4 amino-3,5-dibromophenol) ketone and the like.
[0216] Uが式（1 3)である場合の当該ビスフ ニル骨格を有する化合物の具体例として は、例えばビス（4—ヒドロキシフエ-ル)スルホン、ビス（4—ヒドロキシ一 3, 5—ジメチ ルフエニル）スルホン、ビス（4—ヒドロキシ一 3, 5—ジクロロフエニル）スルホン、ビス（ 4—ヒドロキシ一 3, 5—ジブロモフエ-ル）スルホン、ビス（4—ァミノフエ-ル）スルホン 、ビス（4—アミノー 3, 5—ジメチルフエ-ル)スルホン、ビス（4—アミノー 3, 5—ジクロ 口フエ-ル)スルホン、ビス（4—アミノー 3, 5—ジブロモフエ-ル)スルホン等が挙げら れる。 [0216] Specific examples of the compound having the bisphenyl skeleton when U is the formula (13) include, for example, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-1,3,5-dimethyl). Sulfenyl) sulfone, bis (4-hydroxy-1,3,5-dichlorophenyl) sulfone, bis (4-hydroxy-1,3,5-dibromophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (4- Examples include amino-3,5-dimethylphenol) sulfone, bis (4-amino-3,5-dichlorophenyl) sulfone, and bis (4-amino-3,5-dibromophenol) sulfone.
[0217] Uが式（1 4)である場合の当該ビスフ ニル骨格を有する化合物の具体例として は、例えばビス（4—ヒドロキシフエ-ル）へキサフルォロプロパン、ビス（4—ヒドロキシ —3, 5—ジメチルフエ-ル）へキサフルォロプロパン、ビス（4ーヒドロキシ—3, 5—ジ クロ口フエ-ル）へキサフノレオ口プロパン、ビス（4—ヒドロキシ一 3, 5—ジブロモフエ- ル）へキサフルォロプロパン、ビス（4ーァミノフエ-ル）へキサフルォロプロパン、ビス（ 4—アミノー 3, 5—ジメチルフエ-ル）へキサフルォロプロパン、ビス（4—アミノー 3, 5 —ジクロ口フエ-ル）へキサフルォロプロパン、ビス（4—アミノー 3, 5—ジブロモフエ- ル）へキサフルォロプロパン等が挙げられる。  [0217] Specific examples of the compound having the bisphenyl skeleton when U is the formula (14) include, for example, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy- 3,5-Dimethylphenol) hexafluoropropane, bis (4-hydroxy-3,5-dicyclomethyl) hexoxanoleopropane, bis (4-hydroxy-1,3,5-dibromophenol) Hexafluoropropane, bis (4-aminophenol) Hexafluoropropane, bis (4-amino-3,5-dimethylphenol) hexafluoropropane, bis (4-amino-3, 5 — Dichroic mouth) hexafluoropropane, bis (4-amino-3,5-dibromophenol) hexafluoropropane, and the like.
[0218] Uが式（1 5)である場合の当該ビスフ ニル骨格を有する化合物の具体例として は、例えばビス（4—ヒドロキシフエ-ル）ジメチルシラン、ビス（4—ヒドロキシ一 3, 5— ジメチルフエ-ル）ジメチルシラン、ビス（4—ヒドロキシ一 3, 5—ジクロロフエ-ル）ジメ チルシラン、ビス（4—ヒドロキシ一 3, 5—ジブロモフエ-ル）ジメチルシラン、ビス（4— ァミノフエ-ル）ジメチルシラン、ビス（4—アミノー 3, 5—ジメチルフエ-ル）ジメチルシ ラン、ビス（4—ァミノ一 3, 5—ジクロロフエ-ル）ジメチルシラン、ビス（4—ァミノ一 3, 5—ジブロモフエ-ル）ジメチルシラン等が挙げられる。  [0218] Specific examples of the compound having the bisphenyl skeleton in the case where U is the formula (15) include, for example, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-1,3,5- Dimethylphenol) dimethylsilane, bis (4-hydroxy-1,3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxy-1,3,5-dibromophenol) dimethylsilane, bis (4-aminophenol) dimethyl Silane, bis (4-amino-3,5-dimethylphenol) dimethylsilane, bis (4-amino-1,3,5-dichlorophenol) dimethylsilane, bis (4-amino-1,3,5-dibromophenol) dimethyl Silane etc. are mentioned.
[0219] Uが式（1 6)である場合の当該ビスフ ニル骨格を有する化合物の具体例として は、例えばビス（4—ヒドロキシフエ-ル)メタン、ビス（4—ヒドロキシ一 3, 5—ジメチル フエ-ル）メタン、ビス（4—ヒドロキシ一 3, 5—ジクロロフエ-ル）メタン、ビス（4—ヒドロ キシ一 3, 5—ジブロモフエ-ル)メタン、ビス（4—ァミノフエ-ル)メタン、ビス（4—アミ ノ一 3, 5—ジメチルフエ-ル)メタン、ビス（4—ァミノ一 3, 5—ジクロロフエ-ル)メタン 、ビス（4 アミノー 3, 5—ジブロモフエ-ル)メタン等が挙げられる。 [0219] Specific examples of the compound having the bisphenyl skeleton when U is the formula (16) include bis (4-hydroxyphenol) methane, bis (4-hydroxy-1,3,5-dimethyl), and the like. Phenol) methane, bis (4-hydroxy-1,3,5-dichlorophenyl) methane, bis (4-hydro) Xy-1,5-dibromophenol) methane, bis (4-aminophenol) methane, bis (4-amino-1,3,5-dimethylphenol) methane, bis (4-amino-1,3,5-dichlorophenol) -L) methane, bis (4 amino-3,5-dibromophenol) methane and the like.
[0220] Uが式（1 7)である場合の当該ビスフ ニル骨格を有する化合物の具体例として は、例えば 2, 2 ビス（4 ヒドロキシフエ-ル）プロパン、 2, 2 ビス（4 ヒドロキシ —3, 5 ジメチルフエ-ル）プロパン、 2, 2 ビス（4 ヒドロキシ一 3, 5 ジクロロフ ェ -ル）プロパン、 2, 2 ビス（4 ヒドロキシ一 3, 5 ジブロモフエ-ル）プロパン、 2 , 2 ビス（4 ヒドロキシ一 3—メチルフエ-ル）プロパン、 2, 2 ビス（4 ヒドロキシ —3 クロ口フエ-ル）プロパン、 2, 2 ビス（4 ヒドロキシ一 3 ブロモフエ-ル）プロ パン、 2, 2 ビス（4 ァミノフエ-ル）プロパン、 2, 2 ビス（4 アミノー 3, 5 ジメ チルフエ-ル）プロパン、 2, 2 ビス（4 アミノー 3, 5 ジクロロフエ-ル）プロパン、 2, 2 ビス（4 アミノー 3, 5 ジブロモフエ-ル）プロパン、 2, 2 ビス（4 アミノー 3—メチルフエ-ル）プロパン、 2, 2 ビス（4 アミノー 3 クロ口フエ-ル）プロパン、 2, 2-ビス（4 ァミノ 3 ブロモフエ-ル）プロパン等が挙げられる。  [0220] Specific examples of the compound having the bisphenyl skeleton when U is represented by the formula (17) include, for example, 2, 2 bis (4 hydroxyphenol) propane, 2, 2 bis (4 hydroxy-3) , 5 dimethylphenol) propane, 2,2 bis (4 hydroxy-1,3,5 dichlorophenol) propane, 2,2 bis (4 hydroxy-1,3,5 dibromophenol) propane, 2,2 bis (4 hydroxy) 1-Methylphenol) propane, 2,2bis (4hydroxy-3 cyclochrome) propane, 2,2bis (4hydroxy-3-bromophenol) propan, 2,2bis (4aminophenol) Propane, 2,2 bis (4 amino-3,5 dimethylphenol) propane, 2,2 bis (4 amino-3,5 dichlorophenol) propane, 2,2 bis (4 amino-3,5 dibromophenol) ) Propane, 2, 2 bis (4 amino-3-methylphenol) Bread, 2, 2-bis (4-amino-3 Black port Hue - Le) propane, 2, 2-bis (4 Amino 3 Buromofue - Le) propane.
[0221] Uが式（1 8)である場合の当該ビスフ ニル骨格を有する化合物の具体例として は、例えばビス（4—ヒドロキシフエ-ル）エーテル、ビス（4—ヒドロキシ一 3, 5—ジメチ ルフエ-ル）エーテル、ビス（4ーヒドロキシー 3, 5—ジクロ口フエ-ル）エーテル、ビス (4—ヒドロキシ一 3, 5—ジブロモフエ-ル）エーテル、ビス（4—ァミノフエ-ル）エーテ ル、ビス（4—アミノー 3, 5—ジメチルフエ-ル）エーテル、ビス（4—アミノー 3, 5—ジ クロ口フエ-ル）エーテル、ビス（4 アミノー 3, 5—ジブロモフエ-ル）エーテル等が 挙げられる。  [0221] Specific examples of the compound having the bisphenyl skeleton when U is represented by the formula (18) include, for example, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-1,3,5-dimethyl). Ruthenium ether), bis (4-hydroxy-3,5-dicyclophole) ether, bis (4-hydroxy-1,3,5-dibromophenol) ether, bis (4-aminophenol) ether, bis Examples include (4-amino-3,5-dimethylphenol) ether, bis (4-amino-3,5-dichlorophenol) ether, bis (4 amino-3,5-dibromophenol) ether, and the like.
[0222] これらのビスフ ニル骨格を有する化合物のうち、 Uが式（1 1)又は式（1 7)で 示される 2価の基であるものが好ましぐ中でも Uが式（1 1)で示される 2価の基であ るものがより好ましぐその中でも一般式（98)に於ける V及び Vが酸素原子であるも  Among these compounds having a bisphenyl skeleton, those in which U is a divalent group represented by formula (11) or formula (17) are preferred, and U is represented by formula (11). Among them, the divalent group shown is more preferred, and V and V in the general formula (98) are oxygen atoms.
1 2  1 2
のがさらに好ましぐその中でも、ベンゼン環及びフルオレン環に置換基を有さないも のが特に好ましぐ具体的には、例えば 9, 9 ビス（4ーヒドロキシフエ-ル）フルォレ ン等が挙げられる。  Among these, more preferred are those having no substituents on the benzene ring and fluorene ring, such as 9,9bis (4-hydroxyphenol) fluorene. .
[0223] 一般式（22)で示される化合物は、市販のものを用いる力、一般式（98)で示される ビスフエ-ル骨格を有する化合物と、ェピクロロヒドリン、ェピブ口モヒドリン、 4 クロ口 —1, 2 エポキシブタン、 4ーブロモー 1, 2 エポキシブタン、 5 クロロー 1, 2 ェ ポキシペンタン、 5 ブロモー 1, 2 エポキシペンタン、 6 クロロー 1, 2 エポキシ へキサン、 6 ブロモー 1, 2 エポキシへキサン、 7 クロロー 1, 2 エポキシヘプタ ン、 7 ブロモー 1, 2 エポキシヘプタン、 8 クロロー 1, 2 エポキシオクタン、 8— ブロモー 1, 2—エポキシオクタン等の ω—ハロゲノエポキシ化合物とを、通常この分 野で用いられる製造方法により合成したものを適宜用いれば良 、。 [0223] The compound represented by the general formula (22) is represented by the general formula (98). Compounds with a bisphenol skeleton and epichlorohydrin, epip mouth mohydrin, 4 black mouth —1, 2 epoxy butane, 4-bromo-1, 2 epoxy butane, 5 chloro 1,2 epoxyoxy pentane, 5 bromo 1, 2 Epoxypentane, 6 Chloro-1,2 Epoxyhexane, 6 Bromo-1, 2 Epoxyhexane, 7 Chloro1,2 Epoxyheptane, 7 Bromo1,2 Epoxyheptane, 8 Chloro1,2 Epoxyoctane, 8— Bromo1 1, ω-halogenoepoxy compounds such as 2-epoxyoctane and the like, which are synthesized by a production method usually used in this field, can be appropriately used.
一般式（34)で示されるカルボキシル基を 3個以上有する多塩基酸 (カルボキシル 基の一部がカルボン酸エステルであるものを含む。）としては、通常 3個以上のカルボ キシル基を有する、芳香族又は脂肪族カルボン酸 (カルボキシル基の一部がカルボ ン酸エステルであるものを含む。）が挙げられ、具体的には、例えば式（99)
Figure imgf000062_0001
The polybasic acid having 3 or more carboxyl groups represented by the general formula (34) (including those in which a part of the carboxyl group is a carboxylic acid ester) is usually an aromatic compound having 3 or more carboxyl groups. An aliphatic or aliphatic carboxylic acid (including those in which a part of the carboxyl group is a carboxylic acid ester).
Figure imgf000062_0001
で示される芳香族トリカルボン酸、式（100)、 (101)
Figure imgf000062_0002
Aromatic tricarboxylic acids of formula (100), (101)
Figure imgf000062_0002
{但し、式（101)中、 4つのカルボキシル基は、ナフタレン環の 1〜8位の炭素のうち、 何れの炭素に結合していても良い。 }、若しくは一般式（102)〜（ 104)  {However, in the formula (101), the four carboxyl groups may be bonded to any carbon among the 1-8th carbon atoms of the naphthalene ring. } Or general formula (102)-(104)
Figure imgf000062_0003
Figure imgf000062_0003
(式中、 W 、 W及び W は、結合手、酸素原子、カルボ-ル基、スルホ -ル基又はビ  (W, W, W and W are a bond, an oxygen atom, a carbo ol group, a sulpho group or
8 9 10  8 9 10
二レン基を表す。）で示される芳香族テトラカルボン酸、一般式（105)
Figure imgf000063_0001
Represents a dilene group. ) Aromatic tetracarboxylic acid represented by the general formula (105)
Figure imgf000063_0001
(式中、 W は、ェタントリイル基、プロパントリィル基又はブタントリィル基を表す。 )  (In the formula, W represents an ethanetriyl group, a propanetriyl group or a butanetriyl group.)
11  11
で示される脂肪族トリカルボン酸、又は一般式（106)、 (107)
Figure imgf000063_0002
Or an aliphatic tricarboxylic acid represented by the general formula (106), (107)
Figure imgf000063_0002
{式中、 W は、エチレンテトライル基又はブタンテトライル基を表し、 pは 1〜3の整数  {In the formula, W represents an ethylenetetrayl group or a butanetetrayl group, and p is an integer of 1 to 3.
12  12
を表す。但し、式（107)中、 4つのカルボキシル基は、シクロアルキル環の炭素のうち 、何れの炭素に結合していても良い。 }、式（108)若しくは（109)
Figure imgf000063_0003
Represents. However, in the formula (107), the four carboxyl groups may be bonded to any carbon among the carbons of the cycloalkyl ring. }, Formula (108) or (109)
Figure imgf000063_0003
で示される脂肪族テトラカルボン酸が挙げられる。  The aliphatic tetracarboxylic acid shown by these is mentioned.
[0225] 一般式（102)〜（104)に於ける W〜W としては、結合手又はカルボ-ル基がよ [0225] In general formulas (102) to (104), W to W may be a bond or a carbo group.
8 10  8 10
り好ましい。  More preferable.
[0226] 一般式（107)に於ける pは、通常 1〜3の整数を表し、中でも 2〜3の整数が好ましく [0226] In general formula (107), p usually represents an integer of 1 to 3, and preferably an integer of 2 to 3
、その中でも 3がより好ましい。 Of these, 3 is more preferred.
[0227] 式（99)で示される芳香族トリカルボン酸としては、具体的には、例えば 1, 2, 3 べ ンゼントリカルボン酸、 1, 2, 4 ベンゼントリカルボン酸（トリメリット酸）、 1, 3, 5 べ ンゼントリカルボン酸等が挙げられ、中でも 1, 2, 4 ベンゼントリカルボン酸（トリメリ ット酸）が好ましい。 [0227] Specific examples of the aromatic tricarboxylic acid represented by the formula (99) include 1, 2, 3 benzene tricarboxylic acid, 1, 2, 4 benzene tricarboxylic acid (trimellitic acid), 1, 3 , 5 Benzenetricarboxylic acid and the like. Among them, 1, 2, 4 benzenetricarboxylic acid (trimellitic acid) is preferable.
[0228] 式（100)で示される芳香族テトラカルボン酸としては、具体的には、例えば 1, 2, 3 , 4 ベンゼンテトラカルボン酸、 1, 2, 3, 5 ベンゼンテトラカルボン酸、 1, 2, 4, 5 ベンゼンテトラカルボン酸 (ピロメリット酸)等が挙げられ、中でも 1, 2, 4, 5 ベン ゼンテトラカルボン酸 (ピロメリット酸）が好まし!/、。  Specific examples of the aromatic tetracarboxylic acid represented by the formula (100) include 1, 2, 3, 4 benzenetetracarboxylic acid, 1, 2, 3, 5 benzenetetracarboxylic acid, 1, 2, 4, 5 Benzenetetracarboxylic acid (pyromellitic acid) and the like, among which 1, 2, 4, 5 benzenetetracarboxylic acid (pyromellitic acid) is preferred!
[0229] 式（101)で示される芳香族テトラカルボン酸としては、具体的には、例えば 1, 2, 3 , 4 ナフタレンテトラカルボン酸、 1, 2, 3, 5 ナフタレンテトラカルボン酸、 1, 2, 3 6 -ナフタレンテトラ力ノレボン酸、 1, 2, 3, 7- -ナフタレンテトラ力ノレボン酸、 1, 2, 3[0229] Specific examples of the aromatic tetracarboxylic acid represented by the formula (101) include 1, 2, 3, 4 naphthalene tetracarboxylic acid, 1, 2, 3, 5 naphthalene tetracarboxylic acid, 1, twenty three 6-Naphthalenetetra-force norevonic acid, 1, 2, 3, 7--Naphthalenetetra-force norevonic acid, 1, 2, 3
8- -ナフタレンテトラ力ノレボン酸、 1, 2, 4, 5 -ナフタレンテトラ力ノレボン酸、 1, 2, 48-Naphtalene tetra-force norevic acid, 1, 2, 4, 5 -Naphthalene tetra-force norevon acid, 1, 2, 4
6 -ナフタレンテトラ力ノレボン酸、 1, 2, 4, 7- -ナフタレンテトラ力ノレボン酸、 1, 2, 46-Naphthalenetetra-force norevonic acid, 1, 2, 4, 7- -Naphthalenetetra-force norevonic acid, 1, 2, 4
8- -ナフタレンテトラ力ノレボン酸、 1, 2, 5, 6 -ナフタレンテトラ力ノレボン酸、 1, 2, 58- -Naphthalene tetra-force nolevonic acid, 1, 2, 5, 6 -Naphthalene tetra-force nolevonic acid, 1, 2, 5
7- -ナフタレンテトラ力ノレボン酸、 1, 2, 5, 8- -ナフタレンテトラ力ノレボン酸、 1, 2, 67- -Naphthalene tetra strength norebonic acid, 1, 2, 5, 8- -Naphthalene tetra strength norevonic acid, 1, 2, 6
7- -ナフタレンテトラ力ノレボン酸、 1, 2, 6, 8- -ナフタレンテトラ力ノレボン酸、 1, 3, 57- -Naphthalene tetra-force nolevonic acid, 1, 2, 6, 8- -Naphthalene tetra-force nolevonic acid, 1, 3, 5
7- -ナフタレンテトラ力ノレボン酸、 1, 3, 5, 8- -ナフタレンテトラ力ノレボン酸、 1, 3, 67- -Naphthalene tetra-force nolevonic acid, 1, 3, 5, 8- -Naphthalene tetra-force nolevonic acid, 1, 3, 6
7- -ナフタレンテトラ力ノレボン酸、 1, 3, 6, 8- -ナフタレンテトラ力ノレボン酸、 1, 4, 57- -Naphthalene tetra-force nolevonic acid, 1, 3, 6, 8- -Naphthalene tetra-force nolevonic acid, 1, 4, 5
8- -ナフタレンテトラ力ノレボン酸、 1, 4, 6, 7- -ナフタレンテトラ力ノレボン酸、 2, 3, 68- -Naphthalene tetra-force nolevonic acid, 1, 4, 6, 7- -Naphthalene tetra-force nolevonic acid, 2, 3, 6
, 7 ナフタレンテトラカルボン酸等が挙げられ、中でも 1, 4, 5, 8 ナフタレンテトラ カルボン酸、 2, 3, 6, 7 ナフタレンテトラカルボン酸が好ましぐその中でも 1, 4, 5 , 8—ナフタレンテトラカルボン酸がより好ましい。 1, 4, 5, 8 Naphthalene tetracarboxylic acid, 2, 3, 6, 7 Naphthalene tetracarboxylic acid is preferred among them 1, 4, 5, 8—Naphthalene Tetracarboxylic acid is more preferred.
一般式（102)で示される芳香族テトラカルボン酸のうち、 Wが結合手である芳香族  Of the aromatic tetracarboxylic acids represented by general formula (102), W is an aromatic bond
8  8
テトラカルボン酸としては、例えば 2, 3, 4, 5 ビフエ-ルテトラカルボン酸、 2, 3, 4 , 6 ビフエ-ルテトラカルボン酸、 2, 3, 5, 6 ビフエ-ルテトラカルボン酸等が挙げ られる。また、 Wが酸素原子である芳香族テトラカルボン酸としては、例えば 2, 3, 4 Examples of tetracarboxylic acids include 2, 3, 4, 5 biphenyl tetracarboxylic acid, 2, 3, 4, 6 biphenyl tetracarboxylic acid, 2, 3, 5, 6 biphenyl tetracarboxylic acid, and the like. Can be mentioned. Examples of aromatic tetracarboxylic acids in which W is an oxygen atom include 2, 3, 4
8  8
, 5 ビフエニルエーテルテトラカルボン酸、 2, 3, 4, 6 ビフエニルエーテルテトラ力 ルボン酸、 2, 3, 5, 6 ビフエ-ルエーテルテトラカルボン酸等が挙げられる。さらに 、 Wがカルボ-ル基である芳香族テトラカルボン酸としては、例えば 2, 3, 4, 5 べ , 5 biphenyl ether tetracarboxylic acid, 2, 3, 4, 6 biphenyl ether tetra force rubonic acid, 2, 3, 5, 6 biphenyl ether tetracarboxylic acid and the like. Further, examples of the aromatic tetracarboxylic acid in which W is a carbo group include 2, 3, 4, 5
8 8
ンゾフエノンテトラカルボン酸、 2, 3, 4, 6 べンゾフエノンテトラカルボン酸、 2, 3, 5 , 6—べンゾフエノンテトラカルボン酸等が挙げられる。さらにまた、 Wがスルホ-ル Nzophenone tetracarboxylic acid, 2, 3, 4, 6 benzophenone tetracarboxylic acid, 2, 3, 5, 6-benzophenone tetracarboxylic acid and the like. Furthermore, W is sulfol.
8  8
基である芳香族テトラカルボン酸としては、例えば 2, 3, 4, 5 ビフエニルスルホンテ 卜ラカルボン酸、 2, 3, 4, 6 ビフエ-ルスルホンテ卜ラカルボン酸、 2, 3, 5, 6 ビフ ェニルスルホンテトラカルボン酸等が挙げられる。また、 wがビ-レン基である芳香 Examples of the aromatic tetracarboxylic acid as a group include 2, 3, 4, 5 biphenyl sulfone tetracarboxylic acid, 2, 3, 4, 6 biphenyl sulfone tetracarboxylic acid, 2, 3, 5, 6 biphenyl. Examples include sulfonetetracarboxylic acid. Also, fragrance where w is a beylene group
8  8
族テトラカルボン酸としては、例えば cis— 2, 3, 4, 5 スチルベンテトラカルボン酸、 trans - 2, 3, 4, 5 スチルベンテトラカルボン酸、 cis— 2, 3, 4, 6 スチルペンテ トラカルボン酸、 trans— 2, 3, 4, 6 スチルベンテトラカルボン酸、 cis— 2, 3, 5, 6 スチルベンテトラカルボン酸、 trans— 2, 3, 5, 6 スチルベンテトラカルボン酸等 が挙げられる。 Examples of the group tetracarboxylic acid include cis—2, 3, 4, 5 stilbene tetracarboxylic acid, trans-2, 3, 4, 5 stilbene tetracarboxylic acid, cis—2, 3, 4, 6 stilpentetracarboxylic acid, trans— 2, 3, 4, 6 stilbene tetracarboxylic acid, cis— 2, 3, 5, 6 stilbene tetracarboxylic acid, trans— 2, 3, 5, 6 stilbene tetracarboxylic acid, etc. Is mentioned.
一般式（103)で示される芳香族テトラカルボン酸のうち、 Wが結合手である芳香族  Of the aromatic tetracarboxylic acids represented by the general formula (103), W is an aromatic bond
9  9
テトラカルボン酸としては、例えば 2, 2' , 3, 4ービフエ-ルテトラカルボン酸、 2, 3, 3 ' , 4—ビフエ-ルテトラカルボン酸、 2, 3, 4, 4，一ビフエ-ルテトラカルボン酸、 2, 2 ' , 3, 5—ビフエ-ルテトラカルボン酸、 2, 3, 3' , 5—ビフエ-ルテトラカルボン酸、 2 , 3, 4' , 5—ビフエ-ルテトラカルボン酸、 2, 2' , 3, 6—ビフエ-ルテトラカルボン酸 、 2, 3, 3' , 6—ビフエ-ルテトラカルボン酸、 2, 3, 4，， 6—ビフエ-ルテトラカルボン 酸、 2, 2' , 4, 5—ビフエ-ルテ卜ラカルボン酸、 2, 3，， 4, 5—ビフエ-ルテ卜ラカル ボン酸、 2, 4, 4，， 5—ビフエ-ルテ卜ラカルボン酸、 2, 2' , 4, 6—ビフエ-ルテ卜ラカ ルボン酸、 2, 3，， 4, 6—ビフエ-ルテ卜ラカルボン酸、 2, 4, 4，， 6—ビフエ-ルテ卜 ラカルボン酸等が挙げられる。また、 Wが酸素原子である芳香族テトラカルボン酸と Examples of the tetracarboxylic acid include 2,2 ', 3,4-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, 2,3,4,4, and 1 biphenyl. Tetracarboxylic acid, 2, 2 ', 3, 5-biphenyltetracarboxylic acid, 2, 3, 3', 5-biphenyltetracarboxylic acid, 2, 3, 4 ', 5-biphenyltetracarboxylic acid Acid, 2, 2 ', 3, 6-biphenyltetracarboxylic acid, 2, 3, 3', 6-biphenyltetracarboxylic acid, 2, 3, 4, 6, 6-biphenyltetracarboxylic acid, 2, 2 ', 4, 5—Bi-Fereral Carboxylic Acid, 2, 3, 4, 4, 5-Bi-Ferter Carboxylic Acid, 2, 4, 4 ,, 5-Bi-Ferter Tetracarboxylic Acid, 2 , 2 ', 4, 6-biphenyl carbonate, 2, 3, 4, 4, 6-biphenyl carbonate, 2, 4, 4, 6, 6-biphenyl carbonate, etc. It is done. An aromatic tetracarboxylic acid in which W is an oxygen atom and
9  9
しては、例えば 2, 2' , 3, 4—ビフエ-ルエーテルテトラカルボン酸、 2, 3, 3' , 4—ビ フエニルエーテルテトラカルボン酸、 2, 3, 4, 4'ービフエニルエーテルテトラカルボ ン酸、 2, 2' , 3, 5—ビフエ-ルエーテルテトラカルボン酸、 2, 3, 3，， 5—ビフエ-ル エーテルテトラカルボン酸、 2, 3, 4，， 5—ビフエ-ルエーテルテトラカルボン酸、 2, 2' , 3, 6—ビフエ-ルエーテルテトラカルボン酸、 2, 3, 3' , 6—ビフエ-ルエーテル テ卜ラカルボン酸、 2, 3, 4，， 6—ビフエ-ルエーテルテ卜ラカルボン酸、 2, 2' , 4, 5 ービフエ-ルエーテルテトラカルボン酸、 2, 3，， 4, 5—ビフエ-ルエーテルテトラ力 ルボン酸、 2, 4, 4，， 5—ビフエ-ルエーテルテ卜ラカルボン酸、 2, 2' , 4, 6—ビフエ -ルエーテルテトラカルボン酸、 2, 3，， 4, 6—ビフエ-ルエーテルテトラカルボン酸 、 2, 4, 4，， 6—ビフエ-ルエーテルテトラカルボン酸等が挙げられる。さらに、 W力 S For example, 2, 2 ', 3, 4-biphenyl ether tetracarboxylic acid, 2, 3, 3', 4-biphenyl ether tetracarboxylic acid, 2, 3, 4, 4'-biphenyl ether Tetracarboxylic acid, 2, 2 ', 3, 5-biphenyl ether tetracarboxylic acid, 2, 3, 3, 5, 5-biphenyl ether tetracarboxylic acid, 2, 3, 4, 5, 5-biphenyl ether Tetracarboxylic acid, 2, 2 ', 3, 6-biphenyl ether tetracarboxylic acid, 2, 3, 3', 6-biphenyl ether tetracarboxylic acid, 2, 3, 4, 6, 6-biphenyl ether ester Lacarboxylic acid, 2, 2 ', 4, 5-biphenyl ether tetracarboxylic acid, 2, 3, 4, 5, 5-biphenyl ether tetra force Rubonic acid, 2, 4, 4, 5, 5-biphenyl ether tetracarboxylic acid 2, 2 ', 4, 6-biphenyl ether tetracarboxylic acid, 2, 3, 4, 4, 6-biether ether tetracarboxylic acid 2, 4, 4 ,, 6-Bifue - ether tetracarboxylic acid and the like. Furthermore, W force S
9 カルボ-ル基である芳香族テトラカルボン酸としては、例えば 2, 2' , 3, 4一べンゾフ エノンテトラ力ノレボン酸、 2, 3, 3' , 4—ベン:/フエノンテトラ力ノレボン酸、 2, 3, 4, 4， —ベンゾフエノンテトラカルボン酸、 2, 2' , 3, 5—ベンゾフエノンテトラカルボン酸、 2 , 3, 3' , 5—ベンゾフエノンテトラカルボン酸、 2, 3, 4' , 5—ベンゾフエノンテトラカル ボン酸、 2, 2' , 3, 6—ベンゾフエノンテトラカルボン酸、 2, 3, 3' , 6—ベンゾフエノン テトラカルボン酸、 2, 3, 4' , 6—ベンゾフエノンテトラカルボン酸、 2, 2' , 4, 5—ベン ゾフエノンテトラカルボン酸、 2, 3' , 4, 5—べンゾフエノンテトラカルボン酸、 2, 4, 4， , 5 ベンゾフエノンテトラカルボン酸、 2, 2' , 4, 6 ベンゾフエノンテトラカルボン酸 、 2, 3，， 4, 6 ベンゾフエノンテトラカルボン酸、 2, 4, 4，， 6 ベンゾフエノンテトラ カルボン酸等が挙げられる。さらにまた、 Wがスルホニル基である芳香族テトラカル 9 Aromatic tetracarboxylic acids that are carbo groups include, for example, 2, 2 ', 3, 4 benzofuenone tetraforce norebonic acid, 2, 3, 3', 4-ben: / phenone tetraforce norebonic acid, 2 , 3, 4, 4, —benzophenone tetracarboxylic acid, 2, 2 ′, 3, 5—benzophenone tetracarboxylic acid, 2, 3, 3 ′, 5-benzophenone tetracarboxylic acid, 2, 3 , 4 ', 5-benzophenone tetracarboxylic acid, 2, 2', 3, 6-benzophenone tetracarboxylic acid, 2, 3, 3 ', 6-benzophenone tetracarboxylic acid, 2, 3, 4' , 6-Benzophenone tetracarboxylic acid, 2, 2 ', 4, 5-Benzophenone tetracarboxylic acid, 2, 3', 4, 5-Benzophenone tetracarboxylic acid, 2, 4, 4, , 5 Benzophenone tetracarboxylic acid, 2, 2 ', 4, 6 Benzophenone tetracarboxylic acid, 2, 3, 4, 4, 6 Benzophenone tetracarboxylic acid, 2, 4, 4, 6, 6 Benzophenone And tetracarboxylic acid. Furthermore, an aromatic tetracarbyl in which W is a sulfonyl group
9  9
ボン酸としては、例えば 2, 2' , 3, 4 ビフエ-ルスルホンテトラカルボン酸、 2, 3, 3， , 4 ビフエ-ルスルホンテトラカルボン酸、 2, 3, 4, 4'—ビフエニルスルホンテトラ力 ルボン酸、 2, 2' , 3, 5 ビフエ-ルスルホンテトラカルボン酸、 2, 3, 3 ' , 5 ビフエ ニルスルホンテトラカルボン酸、 2, 3, 4' , 5 ビフエ-ルスルホンテトラカルボン酸、Examples of the boric acid include 2, 2 ', 3, 4 biphenyl sulfone tetracarboxylic acid, 2, 3, 3, 4, biphenyl sulfone tetracarboxylic acid, 2, 3, 4, 4'-biphenyl sulfone. Tetraforce Rubonic acid, 2, 2 ', 3, 5 Biphenylsulfone tetracarboxylic acid, 2, 3, 3', 5 Biphenylsulfone tetracarboxylic acid, 2, 3, 4 ', 5 Biphenylsulfone tetracarboxylic acid acid,
2, 2' , 3, 6 ビフエ-ルスルホンテトラカルボン酸、 2, 3, 3' , 6 ビフエ-ルスルホ ンテ卜ラカルボン酸、 2, 3, 4，， 6 ビフエ-ルスルホンテ卜ラカルボン酸、 2, 2' , 4, 5 —ビフエ-ルスルホンテトラカルボン酸、 2, 3，， 4, 5 ビフエ-ルスルホンテトラカル ボン酸、 2, 4, 4，， 5 ビフエ-ルスルホンテトラカルボン酸、 2, 2' , 4, 6 ビフエ- ルスルホンテトラカルボン酸、 2, 3，， 4, 6 ビフエ-ルスルホンテトラカルボン酸、 2, 4, 4，， 6—ビフエ-ルスルホンテトラカルボン酸等が挙げられる。また、 Wがビ-レン 2, 2 ', 3, 6 Biphenyl sulfone tetracarboxylic acid, 2, 3, 3', 6 Biphenyl sulfone tetracarboxylic acid, 2, 3, 4, 6, 6 Biphenyl sulfone tetracarboxylic acid, 2, 2 ', 4, 5 — Biphenylsulfonetetracarboxylic acid, 2, 3 ,, 4, 5 Biphenylsulfonetetracarboxylic acid, 2, 4, 4, 5, Biphenylsulfonetetracarboxylic acid, 2, 2 ', 4, 6 Biphenylsulfone tetracarboxylic acid, 2, 3, 4, 4, 6 bisulfone tetracarboxylic acid, 2, 4, 4, 6-bisulfone tetracarboxylic acid and the like. W is beerene
9 基である芳香族テトラカルボン酸としては、例えば cis— 2, 2' , 3, 4 スチルベンテト ラカルボン酸、 trans— 2, 2' , 3, 4—スチルベンテトラカルボン酸、 cis— 2, 3, 3，， 4 スチルベンテトラカルボン酸、 trans— 2, 3, 3' , 4 スチルベンテトラカルボン酸、 cis— 2, 3, 4, 4' スチルベンテトラカルボン酸、 trans— 2, 3, 4, 4' スチルベン テトラカルボン酸、 cis— 2, 2' , 3, 5—スチルベンテトラカルボン酸、 trans— 2, 2' , Examples of 9 aromatic tetracarboxylic acids are cis-2,2 ', 3,4 stilbenetetracarboxylic acid, trans-2,2'3,4-stilbenetetracarboxylic acid, cis-2,3,3 3, 4, Stilbene tetracarboxylic acid, trans- 2, 3, 3 ', 4 Stilbene tetracarboxylic acid, cis- 2, 3, 4, 4' Stilbene tetracarboxylic acid, trans- 2, 3, 4, 4 'Stilbene Tetracarboxylic acid, cis— 2, 2 ′, 3, 5-stilbene tetracarboxylic acid, trans— 2, 2 ′,
3, 5 スチルベンテトラカルボン酸、 cis— 2, 3, 3，， 5 スチルベンテトラカルボン酸 、 trans - 2, 3, 3，， 5—スチルベンテトラカルボン酸、 cis— 2, 3, 4，， 5—スチルベ ンテトラカルボン酸、 trans— 2, 3, 4，， 5—スチルベンテトラカルボン酸、 cis— 2, 2，3, 5 Stilbene tetracarboxylic acid, cis— 2, 3, 3 ,, 5 Stilbene tetracarboxylic acid, trans-2, 3, 3 ,, 5-stilbene tetracarboxylic acid, cis— 2, 3, 4 ,, 5— Stilbenetetracarboxylic acid, trans-2, 3, 4 ,, 5-stilbenetetracarboxylic acid, cis-2, 2,
, 3, 6 スチルベンテトラカルボン酸、 trans— 2, 2' , 3, 6 スチルペンテトラカルボ ン酸、 cis— 2, 3, 3，， 6—スチルベンテトラカルボン酸、 trans— 2, 3, 3，， 6—スチ ルペンテトラカルボン酸、 cis— 2, 3, 4，， 6 スチルベンテトラカルボン酸、 trans— 2 , 3, 4，， 6 スチルベンテトラカルボン酸、 cis— 2, 2' , 4, 5 スチルベンテトラカル ボン酸、 trans— 2, 2' , 4, 5—スチルベンテトラカルボン酸、 cis— 2, 3，， 4, 5—ス チルベンテトラカルボン酸、 trans— 2, 3' , 4, 5 スチルベンテトラカルボン酸、 cis - 2, 4, 4，， 5—スチルベンテトラカルボン酸、 trans— 2, 4, 4，， 5—スチルベンテト ラカルボン酸、 cis— 2, 2', 4, 6—スチルベンテトラカルボン酸、 trans— 2, 2', 4, 6 スチルベンテトラカルボン酸、 cis— 2, 3，， 4, 6 スチルベンテトラカルボン酸、 tr ans-2, 3', 4, 6—スチルベンテトラカルボン酸、 cis— 2, 4, 4，， 6—スチルペンテ トラカルボン酸、 trans— 2, 4, 4，， 6 スチルベンテトラカルボン酸等が挙げられる。 一般式（104)で示される芳香族テトラカルボン酸のうち、 W が結合手である芳香 , 3, 6 Stilbene tetracarboxylic acid, trans— 2, 2 ', 3, 6 Stilbene tetracarboxylic acid, cis— 2, 3, 3, 6-stilbene tetracarboxylic acid, trans— 2, 3, 3, , 6-Styrene tetracarboxylic acid, cis—2, 3, 4 ,, 6 Stilbene tetracarboxylic acid, trans—2, 3, 4 ,, 6 Stilbene tetracarboxylic acid, cis—2, 2 ′, 4, 5 Stilbene Tetracarbonic acid, trans-2,2 ', 4,5-stilbenetetracarboxylic acid, cis-2,3,4,5-stilbenetetracarboxylic acid, trans-2,3', 4,5 stilbene Tetracarboxylic acid, cis-2,4,4,, 5-stilbenetetracarboxylic acid, trans-2,4,4,5, stilbentate Lacarboxylic acid, cis— 2, 2 ′, 4, 6-stilbene tetracarboxylic acid, trans— 2, 2 ′, 4, 6 stilbene tetracarboxylic acid, cis— 2, 3 ,, 4, 6 stilbene tetracarboxylic acid, tr ans-2, 3 ', 4, 6-stilbenetetracarboxylic acid, cis-2, 4, 4, 6, 6-stilpentetracarboxylic acid, trans-2, 4, 4, 4, 6 stilbenetetracarboxylic acid . Of the aromatic tetracarboxylic acids represented by the general formula (104), W is an aromatic bond
10  Ten
族テトラカルボン酸としては、例えば 2, 2', 3, 3'—ビフエ-ルテトラカルボン酸、 2, 2', 3, 4，ービフエ-ルテトラカルボン酸、 2, 2', 3, 5，ービフエ-ルテトラカルボン酸 、 2, 2，， 3, 6，—ビフエ-ルテトラカルボン酸、 2, 3, 3，， 4， ビフエ-ルテトラカル ボン酸、 2, 3, 3，， 5，—ビフエ-ルテ卜ラカルボン酸、 2, 2', 4, 4，—ビフエ-ルテ卜 ラカルボン酸、 2, 2', 4, 5，—ビフエ-ルテトラカルボン酸、 2, 2', 4, 6，—ビフエ- ルテ卜ラカルボン酸、 2, 3，， 4, 4，—ビフエ-ルテ卜ラカルボン酸、 2, 3，， 4, 5，—ビ フエ-ルテトラカルボン酸、 2, 2', 5, 5，—ビフエ-ルテトラカルボン酸、 2, 2', 5, 6 ，—ビフエ-ルテトラカルボン酸、 2, 3，， 4，， 5 ビフエ-ルテトラカルボン酸、 2, 3，， 5, 5，一ビフエ-ルテトラカルボン酸、 2, 2', 6, 6，一ビフエ-ルテトラカルボン酸、 2 , 3', 4', 6 ビフエ-ルテトラカルボン酸、 2, 3', 5', 6 ビフエニルテトラカルボン 酸、 3, 3，， 4, 4，—ビフエ-ルテ卜ラカルボン酸、 3, 3，， 4, 5，—ビフエ-ルテ卜ラカ ルボン酸、 3, 3', 5, 5，ービフエ-ルテトラカルボン酸等が挙げられ、中でも 3, 3', 4 , 4，ービフエ-ルテトラカルボン酸、 3, 3', 5, 5，ービフエ-ルテトラカルボン酸が好 ましぐその中でも 3, 3', 4, 4'ービフエ-ルテトラカルボン酸がより好ましい。また、 W が酸素原子である芳香族テトラカルボン酸としては、例えば 2, 2', 3, 3'—ビフExamples of the group tetracarboxylic acids include 2, 2 ', 3, 3'-biphenyl tetracarboxylic acid, 2, 2', 3, 4, biphenyl tetracarboxylic acid, 2, 2 ', 3, 5, -Biphenyltetracarboxylic acid, 2, 2 ,, 3, 6, biphenyl tetracarboxylic acid, 2, 3, 3, 4, biphenyl tetracarboxylic acid, 2, 3, 3, 5, bibiphenol -Luteracarboxylic acid, 2, 2 ', 4, 4, -biphenyl tetracarboxylic acid, 2, 2', 4, 5, -biphenyltetracarboxylic acid, 2, 2 ', 4, 6,- Biphenyl tetracarboxylic acid, 2, 3 ,, 4, 4, biphenyl tetracarboxylic acid, 2, 3, 4, 4, 5, biphenyl tetracarboxylic acid, 2, 2 ', 5, 5 , —Biphenyltetracarboxylic acid, 2, 2 ′, 5, 6, —biphenyltetracarboxylic acid, 2, 3, 4, 4, 5 biphenyltetracarboxylic acid, 2, 3 ,, 5, 5 , 1 biphenyl tetracarboxylic acid, 2, 2 ', 6, 6, 1 biphenyl tetracarbo Acid, 2, 3 ', 4', 6 biphenyltetracarboxylic acid, 2, 3 ', 5', 6 biphenyltetracarboxylic acid, 3, 3 ,, 4, 4, -biphenyltetracarboxylic acid 3, 3, 4, 5, 5, biphenyl carboxylic acid, 3, 3 ', 5, 5, biphenyl tetracarboxylic acid, among others, 3, 3', 4, 4, bibiue Among these, 3-tetratetracarboxylic acid and 3,3 ′, 5,5, biphenyltetracarboxylic acid are preferred, and 3,3 ′, 4,4′-biphenyltetracarboxylic acid is more preferred. Examples of aromatic tetracarboxylic acids in which W is an oxygen atom include 2, 2 ', 3, 3'-bif
10 Ten
ェニルエーテルテトラカルボン酸、 2, 2', 3, 4'ービフエニルエーテルテトラカルボン 酸、 2, 2', 3, 5，—ビフエ-ルエーテルテトラカルボン酸、 2, 2', 3, 6，—ビフエ-ル エーテルテトラカルボン酸、 2, 3, 3', 4，ービフエ-ルエーテルテトラカルボン酸、 2, 3, 3', 5，ービフエ-ルエーテルテトラカルボン酸、 2, 2', 4, 4，ービフエ-ルエーテ ルテトラカルボン酸、 2, 2', 4, 5，ービフエ-ルエーテルテトラカルボン酸、 2, 2，， 4 , 6，ービフエニルエーテルテトラカルボン酸、 2, 3', 4, 4，ービフエニルエーテルテト ラカルボン酸、 2, 3，， 4, 5，—ビフエ-ルエーテルテトラカルボン酸、 2, 2', 5, 5，— ビフエニルエーテルテトラカルボン酸、 2, 2', 5, 6，ービフエニルエーテルテトラカル ボン酸、 2, 3，， 4，， 5—ビフエ-ルエーテルテトラカルボン酸、 2, 3，， 5, 5，—ビフエ -ルエーテルテトラカルボン酸、 2, 2', 6, 6，ービフエ-ルエーテルテトラカルボン酸 、 2, 3，， 4，， 6—ビフエ-ルエーテルテ卜ラカルボン酸、 2, 3', 5', 6—ビフエ-ルェ 一テルテトラカルボン酸、 3, 3', 4, 4，ービフエ-ルエーテルテトラカルボン酸、 3, 3 ', 4, 5，—ビフエ-ルエーテルテトラカルボン酸、 3, 3', 5, 5，—ビフエ-ルエーテ ルテトラカルボン酸等が挙げられ、中でも 3, 3', 4, 4'ービフエ-ルエーテルテトラ力 ルボン酸、 3, 3', 5, 5，ービフエ-ルエーテルテトラカルボン酸が好ましぐその中で も 3, 3', 4, 4，ービフエ-ルエーテルテトラカルボン酸がより好ましい。さらに、 W が Phenyl ether tetracarboxylic acid, 2, 2 ', 3, 4'-biphenyl ether tetracarboxylic acid, 2, 2', 3, 5, biphenyl ether tetracarboxylic acid, 2, 2 ', 3, 6, Biphenyl ether tetracarboxylic acid, 2, 3, 3 ', 4, Biphenyl ether tetracarboxylic acid, 2, 3, 3', 5, Biphenyl ether tetracarboxylic acid, 2, 2 ', 4, 4, -Ruether tetracarboxylic acid, 2, 2 ', 4, 5, biphenyl ether tetracarboxylic acid, 2, 2, 4, 6, 6, biphenyl ether tetracarboxylic acid, 2, 3', 4, 4, Biphenyl ether tetracarboxylic acid, 2, 3 ,, 4, 5, biphenyl ether tetracarboxylic acid, 2, 2 ', 5, 5, biphenyl ether tetracarboxylic acid, 2, 2', 5, 6, -Biphenyl ether tetracar Bonic acid, 2, 3 ,, 4, 5, 5-biphenyl ether tetracarboxylic acid, 2, 3, 5, 5, 5, biphenyl ether tetracarboxylic acid, 2, 2 ', 6, 6, biphenyl ether tetra Carboxylic acid, 2, 3, 4, 4, 6-biphenyl ether tetracarboxylic acid, 2, 3 ', 5', 6-biphenyl tertetracarboxylic acid, 3, 3 ', 4, 4, -biphenol Examples include ruether tetracarboxylic acid, 3, 3 ', 4, 5, biphenyl ether tetracarboxylic acid, 3, 3', 5, 5, biphenyl ether tetracarboxylic acid, among others, 3, 3 ', 4,4'-biphenyl ether tetracarboxylic acid Rubonic acid, 3, 3 ', 5, 5, biphenyl ether tetracarboxylic acid is preferred among them, 3, 3', 4, 4, biphenyl ether tetracarboxylic acid Is more preferable. In addition, W
10 カルボ-ル基である芳香族テトラカルボン酸としては、例えば 2, 2', 3, 3'—べンゾ フエノンテトラカルボン酸、 2, 2', 3, 4，一ベンゾフエノンテトラカルボン酸、 2, 2，， 3 , 5，一ベンゾフエノンテトラカルボン酸、 2, 2', 3, 6'—ベンゾフエノンテトラカルボン 酸、 2, 3, 3', 4，一ベンゾフエノンテトラカルボン酸、 2, 3, 3', 5，一ベンゾフエノンテ トラカルボン酸、 2, 2，， 4, 4，一ベンゾフエノンテトラカルボン酸、 2, 2，， 4, 5，一べ ンゾフエノンテトラカルボン酸、 2, 2', 4, 6，一ベンゾフエノンテトラカルボン酸、 2, 3， , 4, 4'一べンゾフエノンテトラカルボン酸、 2, 3', 4, 5，一べンゾフエノンテトラカル ボン酸、 2, 2', 5, 5，一ベンゾフエノンテトラカルボン酸、 2, 2', 5, 6，一ベンゾフエノ ンテトラカルボン酸、 2, 3', 4', 5—ベンゾフエノンテトラカルボン酸、 2, 3', 5, 5，一 ベンゾフエノンテトラ力ノレボン酸、 2, 2', 6, 6'—べンゾフエノンテトラ力ノレボン酸、 2, 3', 4', 6—ベンゾフエノンテトラカルボン酸、 2, 3', 5', 6—ベンゾフエノンテトラ力 ルボン酸、 3, 3', 4, 4，一べンゾフエノンテトラカルボン酸、 3, 3', 4, 5，一べンゾフ エノンテトラカルボン酸、 3, 3', 5, 5'—べンゾフエノンテトラカルボン酸等が挙げられ 、中でも 3, 3', 4, 4，一ベンゾフエノンテトラカルボン酸、 3, 3', 5, 5，一ベンゾフエノ ンテトラカルボン酸が好ましぐその中でも 3, 3', 4, 4'一べンゾフエノンテトラカルボ ン酸がより好ましい。さらにまた、 W がスルホニル基である芳香族テトラカルボン酸と  10 Aromatic tetracarboxylic acids that are carbol groups include, for example, 2, 2 ', 3, 3'-benzophenone tetracarboxylic acid, 2, 2', 3, 4, monobenzophenone tetracarboxylic acid. Acid 2, 2, 3, 5, 5, monobenzophenone tetracarboxylic acid, 2, 2 ', 3, 6'-benzophenone tetracarboxylic acid, 2, 3, 3', 4, monobenzophenone tetra Carboxylic acid, 2, 3, 3 ', 5, Monobenzophenone tetracarboxylic acid, 2, 2, 4, 4, 4, Benzophenone tetracarboxylic acid, 2, 2, 4, 4, 5, Benzophenone tetra Carboxylic acid, 2, 2 ', 4, 6, Monobenzophenone tetracarboxylic acid, 2, 3, 4, 4, 4' monobenzophenone tetracarboxylic acid, 2, 3 ', 4, 5, monoben Zophenone tetracarboxylic acid, 2, 2 ', 5, 5, monobenzophenone tetracarboxylic acid, 2, 2', 5, 6, monobenzophenone tetracarboxylic acid, 2, 3 ', 4', 5— Benzophenone Lacarboxylic acid, 2, 3 ', 5, 5, 1 Benzophenone tetra strength norebonic acid, 2, 2', 6, 6'-Benzofenone tetra strength norebonic acid, 2, 3 ', 4', 6- Benzophenone tetracarboxylic acid, 2, 3 ', 5', 6-benzophenone tetra force rubonic acid, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic acid, 3, 3', 4, 5, 1-benzozoenone tetracarboxylic acid, 3, 3 ', 5, 5'-benzophenone tetracarboxylic acid, among others, 3, 3', 4, 4, monobenzophenone tetracarboxylic acid, Among these, 3, 3 ', 5, 5, monobenzophenone tetracarboxylic acid is preferred, and 3, 3', 4, 4 'monobenzophenone tetracarboxylic acid is more preferred. Furthermore, an aromatic tetracarboxylic acid in which W is a sulfonyl group and
10  Ten
しては、例えば 2, 2', 3, 3，一ビフエ-ルスルホンテトラカルボン酸、 2, 2', 3, 4，一 ビフエ-ルスルホンテトラカルボン酸、 2, 2', 3, 5，一ビフエ-ルスルホンテトラカルボ ン酸、 2, 2', 3, 6，一ビフエ-ルスルホンテトラカルボン酸、 2, 3, 3', 4，一ビフエ- ルスルホンテトラカルボン酸、 2, 3, 3', 5，一ビフエ-ルスルホンテトラカルボン酸、 2 , 2', 4, 4，ービフエ-ルスルホンテトラカルボン酸、 2, 2', 4, 5，一ビフエ-ルスルホ ンテトラカルボン酸、 2, 2', 4, 6，一ビフエ-ルスルホンテトラカルボン酸、 2, 3', 4, 4'—ビフエ-ルスルホンテトラカルボン酸、 2, 3', 4, 5'—ビフエニルスルホンテトラ カルボン酸、 2， 2'， 5, 5，一ビフエニルスルホンテトラカルボン酸、 2， 2', 5, 6，一ビ フエニルスルホンテトラカルボン酸、 2, 3，， 4，， 5 ビフエニルスルホンテトラカルボン 酸、 2, 3', 5， 5，一ビフエ-ルスルホンテトラカルボン酸、 2， 2，， 6, 6，一ビフエニル スルホンテトラカルボン酸、 2, 3，， 4，， 6 ビフエ-ルスルホンテトラカルボン酸、 2, 3', 5', 6—ビフエ-ルスルホンテトラカルボン酸、 3, 3，， 4, 4'—ビフエ-ルスルホ ンテトラカルボン酸、 3, 3', 4, 5'—ビフエ-ルスルホンテトラカルボン酸、 3, 3，， 5, 5，ービフエニルスルホンテトラカルボン酸等が挙げられ、中でも 3, 3，， 4, 4，一ビフ ェ-ルスルホンテトラカルボン酸、 3， 3，， 5, 5，一ビフエ-ルスルホンテトラカルボン 酸が好ましぐその中でも 3, 3', 4, 4，ービフエ-ルスルホンテトラカルボン酸がより 好ましい。また、 W がビ-レン基である芳香族テトラカルボン酸としては、例えば cis For example, 2, 2 ', 3, 3, mono-bisulfone tetracarboxylic acid, 2, 2', 3, 4, mono-bisulfone tetracarboxylic acid, 2, 2 ', 3, 5, 1 biphenyl sulfone tetracarboxylic acid, 2, 2 ', 3, 6, 1 biphenyl sulfone tetracarboxylic acid, 2, 3, 3', 4, 1 biphenyl sulfone tetracarboxylic acid, 2, 3, 3 ', 5, 1 biphenyl sulfone tetracarboxylic acid, 2 , 2 ', 4, 4, -biphenylsulfonetetracarboxylic acid, 2, 2', 4, 5, monobisulfonetetracarboxylic acid, 2, 2 ', 4, 6, monobisulfonetetracarboxylic acid Acid, 2, 3 ', 4, 4'-biphenylsulfone tetracarboxylic acid, 2, 3', 4, 5'-biphenyl sulfone tetracarboxylic acid, 2, 2 ', 5, 5, monobiphenyl sulfone Tetracarboxylic acid, 2, 2 ', 5, 6, monobiphenyl sulfone tetracarboxylic acid, 2, 3, 4, 5, biphenyl sulfone tetracarboxylic acid, 2, 3', 5, 5, monobiphenyl Rusulfone tetracarboxylic acid, 2, 2, 6, 6, 6, monobiphenyl sulfone tetracarboxylic acid, 2, 3, 4, 4, 6 biphenyl sulfone tetracarboxylic acid, 2, 3 ', 5', 6-biphenyl -Lulsulfone tetracarboxylic acid, 3, 3, 4, 4, 4'-biphenylsulfone tetracarboxylic acid, 3, 3 ', 4, 5'-biphenylsulfone tetracarboxylic acid Acid, 3, 3, 5, 5, 5, biphenyl sulfone tetracarboxylic acid, etc., among others, 3, 3, 4, 4, monobisulfone tetracarboxylic acid, 3, 3, 5 Among these, 3,3 ′, 4,4, bibisulfonetetracarboxylic acid is more preferred. Examples of aromatic tetracarboxylic acids in which W is a beylene group include cis
10  Ten
—2, 2', 3, 3'—スチルベンテトラカルボン酸、 trans— 2, 2'， 3， 3，一スチルベン テトラカルボン酸、 cis— 2, 2', 3， 4，一スチルベンテトラカルボン酸、 trans— 2， 2， , 3, 4' スチルベンテトラカルボン酸、 cis— 2, 2', 3, 5，一スチルベンテトラカルボ ン酸、 trans— 2, 2', 3, 5，一スチルベンテトラカルボン酸、 cis— 2, 2', 3, 6，一ス チルベンテトラカルボン酸、 trans— 2， 2，， 3, 6，一スチルベンテトラカルボン酸、 cis -2, 3, 3', 4' スチルベンテトラカルボン酸、 trans— 2, 3， 3'， 4' スチルベン テトラカルボン酸、 cis— 2, 3, 3，， 5，一スチルベンテトラカルボン酸、 trans— 2， 3， 3', 5，一スチルベンテトラカルボン酸、 cis— 2, 2', 4, 4' スチルベンテトラカルボ ン酸、 trans— 2, 2，， 4, 4，一スチルベンテトラカルボン酸、 cis— 2, 2，， 4, 5，一ス チルベンテトラカルボン酸、 trans— 2， 2，， 4, 5，一スチルベンテトラカルボン酸、 cis -2, 2', 4, 6' スチルベンテトラカルボン酸、 trans— 2, 2'， 4， 6' スチルベン テトラカルボン酸、 cis— 2, 3', 4， 4，—スチルベンテトラカルボン酸、 trans— 2， 3， , 4, 4' スチルベンテトラカルボン酸、 cis— 2, 3', 4, 5，一スチルベンテトラカルボ ン酸、 trans— 2, 3', 4, 5，一スチルベンテトラカルボン酸、 cis— 2, 2，， 5, 5，一ス チルベンテトラカルボン酸、 trans— 2， 2，， 5, 5，一スチルベンテトラカルボン酸、 cis - 2, 2' , 5, 6' スチルベンテトラカルボン酸、 trans— 2, 2' , 5, 6' スチルベン テトラカルボン酸、 cis— 2, 3' , 4，， 5—スチルベンテトラカルボン酸、 trans— 2, 3， , 4' , 5 スチルベンテトラカルボン酸、 cis— 2, 3' , 5, 5，一スチルベンテトラカルボ ン酸、 trans— 2， 3' , 5， 5' スチルベンテトラカルボン酸、 cis— 2, 2' , 6, 6'—ス チルベンテトラカルボン酸、 trans— 2, 2，， 6, 6' スチルベンテトラカルボン酸、 cis - 2, 3，， 4，， 6—スチルベンテトラカルボン酸、 trans— 2, 3，， 4' , 6—スチルベン テトラカルボン酸、 cis— 2, 3' , 5' , 6—スチルベンテトラカルボン酸、 trans— 2， 3， , 5' , 6—スチルベンテトラカルボン酸、 cis— 3, 3' , 4, 4' スチルベンテトラカルボ ン酸、 trans— 3, 3，， 4, 4，—スチルベンテトラカルボン酸、 cis— 3, 3，， 4, 5，—ス チルベンテトラカルボン酸、 trans— 3, 3' , 4, 5'—スチルベンテトラカルボン酸、 cis - 3, 3，， 5, 5'—スチルベンテトラカルボン酸、 trans— 3， 3'， 5, 5，一スチルベン テトラカルボン酸等が挙げられ、中でも cis— 3， 3，， 4, 4，一スチルペンテトラカルボ ン酸、 trans— 3, 3，， 4, 4，—スチルベンテトラカルボン酸、 cis— 3, 3，， 5, 5，—ス チルベンテトラカルボン酸、 trans— 3, 3' , 5, 5，一スチルベンテトラカルボン酸が好 ましぐその中でも cis— 3, 3' , 4, 4，一スチルベンテトラカルボン酸、 trans— 3, 3，， 4, 4' スチルベンテトラカルボン酸がより好ましい。 —2, 2 ′, 3, 3′—stilbene tetracarboxylic acid, trans—2, 2 ′, 3, 3, monostilbene tetracarboxylic acid, cis—2, 2 ′, 3, 4, monostilbene tetracarboxylic acid, trans— 2, 2,, 3, 4 ′ stilbene tetracarboxylic acid, cis— 2, 2 ′, 3, 5, monostilbene tetracarboxylic acid, trans— 2, 2 ′, 3, 5, monostilbene tetracarboxylic acid Cis—2, 2 ′, 3, 6, monostilbene tetracarboxylic acid, trans—2, 2, 3, 3, 6, monostilbene tetracarboxylic acid, cis −2, 3, 3 ′, 4 ′ stilbene tetra Carboxylic acid, trans-2, 3, 3 ', 4' stilbene tetracarboxylic acid, cis-2, 3, 3, 3, 5, monostilbene tetracarboxylic acid, trans-2, 3, 3 ', 5, monostilbenetetra Carboxylic acid, cis- 2, 2 ', 4, 4' Stilbene tetracarboxylic acid, trans- 2, 2, 4, 4, 4, Monostilbene tetracarboxylic acid, cis- 2, 2, 4, 4, 5, Rubentetracarboxylic acid, trans-2, 2, 2, 4, 5, monostilbenetetracarboxylic acid, cis-2, 2 ', 4, 6' stilbenetetracarboxylic acid, trans-2, 2 ', 4, 6' stilbene Tetracarboxylic acid, cis-2,3 ', 4,4, -stilbenetetracarboxylic acid, trans-2,3,4,4' stilbenetetracarboxylic acid, cis-2,3 ', 4,5, monostilbene Tetracarbonic acid, trans-2, 3 ', 4, 5, monostilbenetetracarboxylic acid, cis-2, 2, 2, 5, 5, monostilbenetetracarboxylic acid, trans-2, 2, 2, 5, 5, monostilbene tetracarboxylic acid, cis -2, 2 ', 5, 6' stilbene tetracarboxylic acid, trans- 2, 2 ', 5, 6' stilbene tetracarboxylic acid, cis- 2, 3 ', 4 ,, 5-stilbene tetracarboxylic acid, trans- 2, 3,, 4 ', 5 Stilbene tetracarboxylic acid, cis— 2, 3 ′, 5, 5, monostilbene tetracarboxylic acid, trans— 2, 3 ′, 5, 5 ′ stilbene tetracarboxylic acid, cis— 2, 2 ', 6, 6'-stilbene tetracarboxylic acid, trans- 2, 2, 6, 6, 6' stilbene tetracarboxylic acid, cis-2, 3, 4, 4, 6-stilbene tetracarboxylic acid, trans— 2, 3 ,, 4 ′, 6-stilbene tetracarboxylic acid, cis— 2, 3 ′, 5 ′, 6-stilbene tetracarboxylic acid, trans— 2, 3,, 5 ′, 6-stilbene tetracarboxylic acid Cis-3,3 ', 4,4' stilbenetetracarboxylic acid, trans-3,3,4,4, -stilbenetetracarboxylic acid, cis-3,3,4,5, -sty Bentetracarboxylic acid, trans-3,3 ', 4,5'-stilbenetetracarboxylic acid, cis-3,3,5,5'-stilbenetetracarboxylic acid, trans-3,3', 5,5, 1 stilbene tetracarboxylic acid, etc. Among them, cis-3, 3, 3, 4, 4, monostilpene tetracarboxylic acid, trans-3, 3, 3, 4, 4, stilbene tetracarboxylic acid, cis-3 , 3 ,, 5, 5, stilbenetetracarboxylic acid, trans-3, 3 ', 5, 5, monostilbenetetracarboxylic acid are preferred, cis-3, 3', 4, 4, 1 More preferred is stilbene tetracarboxylic acid, trans-3, 3, 4, 4, 4 'stilbene tetracarboxylic acid.
[0233] 上記芳香族テトラカルボン酸のうち、式（100)又は一般式（104)で示されるものが 好ましぐ中でも式（100)又は一般式（104)に於ける W が結合手若しくはカルボ二 [0233] Among the aromatic tetracarboxylic acids, those represented by the formula (100) or the general formula (104) are preferred, and W in the formula (100) or the general formula (104) is a bond or a carbocycle. Two
10  Ten
ル基であるものがより好ましい。  More preferably, it is a sulfur group.
[0234] 一般式（105)で示される脂肪族トリカルボン酸のうち、 W がエタントリィル基である  [0234] Of the aliphatic tricarboxylic acids represented by the general formula (105), W is an ethanetril group
11  11
脂肪族トリカルボン酸としては、例えばェタントリカルボン酸等が挙げられる。また、 w がプロパントリィル基である脂肪族トリカルボン酸としては、例えばプロパントリカル Examples of the aliphatic tricarboxylic acid include ethanetricarboxylic acid. Examples of the aliphatic tricarboxylic acid in which w is a propanetril group include propanetrialkyl.
11 11
ボン酸等が挙げられる。さらに、 w がブタントリィル基である脂肪族トリカルボン酸と  Examples include boronic acid. Furthermore, an aliphatic tricarboxylic acid in which w is a butanetriyl group and
11  11
しては、例えばブタントリカルボン酸等が挙げられる。  Examples thereof include butanetricarboxylic acid.
[0235] 一般式（106)で示される脂肪族テトラカルボン酸のうち、 W がエチレンテトライル  [0235] Among the aliphatic tetracarboxylic acids represented by the general formula (106), W represents ethylenetetrayl
12  12
基である脂肪族テトラカルボン酸としては、例えばエチレンテトラカルボン酸等が挙げ られる。また、 w がブタンテトライル基である脂肪族テトラカルボン酸としては、例え  Examples of the aliphatic tetracarboxylic acid as a group include ethylene tetracarboxylic acid. An example of an aliphatic tetracarboxylic acid in which w is a butanetetrayl group is
12  12
ばブタンテトラカルボン酸等が挙げられる。 [0236] 一般式（107)で示される脂肪族テトラカルボン酸としては、通常 pが 1〜3の整数、 好ましくは 2〜3の整数、より好ましくは 3である脂肪族テトラカルボン酸が挙げられ、 具体的には、例えばシクロブタンテトラカルボン酸、シクロペンタンテトラカルボン酸、 シクロへキサンテトラカルボン酸等が挙げられ、中でもシクロペンタンテトラカルボン酸Examples thereof include butanetetracarboxylic acid. [0236] Examples of the aliphatic tetracarboxylic acid represented by the general formula (107) include aliphatic tetracarboxylic acids in which p is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3. Specifically, for example, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid and the like can be mentioned, among which cyclopentanetetracarboxylic acid
、シクロへキサンテトラカルボン酸が好ましぐその中でもシクロへキサンテトラカルボ ン酸がより好ましい。 Of these, cyclohexanetetracarboxylic acid is preferred, and cyclohexanetetracarboxylic acid is more preferred.
[0237] 式（108)で示される脂肪族テトラカルボン酸としては、 4ー（1, 2 ジカルボキシェ チル）ー1, 2, 3, 4ーテトラヒドロナフタレン 1, 2 ジカルボン酸が挙げられる。  [0237] Examples of the aliphatic tetracarboxylic acid represented by the formula (108) include 4- (1,2 dicarboxyethyl) -1, 2, 3, 4-tetrahydronaphthalene 1,2 dicarboxylic acid.
[0238] 式（109)で示される脂肪族テトラカルボン酸としては、 5—（1, 2 ジカルボキシェ チル） 3—メチルシクロへキサン 1, 2 ジカルボン酸が挙げられる。  [0238] Examples of the aliphatic tetracarboxylic acid represented by the formula (109) include 5- (1,2 dicarboxyethyl) 3-methylcyclohexane 1,2 dicarboxylic acid.
[0239] 上記脂肪族テトラカルボン酸のうち、式（108)又は（109)で示されるものが好ましく 、中でも式（108)で示されるものがより好ましい。  [0239] Of the aliphatic tetracarboxylic acids, those represented by the formula (108) or (109) are preferable, and those represented by the formula (108) are more preferable.
[0240] また、上記芳香族又は脂肪族カルボン酸のうちのカルボキシル基は、上記一般式（ 37)で示されるカルボン酸エステルとなって!/、ても良く、該カルボン酸エステルを有す る化合物は、市販のものを用いる力、例えば上記一般式（99)〜（109)で示される芳 香族又は脂肪族カルボン酸にメタノール、エタノール等のアルコールを作用させる一 般的な方法により合成したものを適宜用いれば良 、。  [0240] Further, the carboxyl group of the aromatic or aliphatic carboxylic acid may be a carboxylic acid ester represented by the general formula (37)! /, And has the carboxylic acid ester. The compound was synthesized by a general method in which a commercially available compound was used, for example, an aromatic or aliphatic carboxylic acid represented by the above general formulas (99) to (109) was allowed to act on an alcohol such as methanol or ethanol. If you use something as appropriate,
[0241] 一般式（34)で示されるカルボキシル基を 3個以上有する多塩基酸 (カルボキシル 基の一部がカルボン酸エステルであるものを含む。）の当量としては、一般式（22)で 示される化合物に対して、通常 0. 5〜2当量が挙げられる。  [0241] The equivalent amount of the polybasic acid having three or more carboxyl groups represented by the general formula (34) (including those in which a part of the carboxyl groups is a carboxylic acid ester) is represented by the general formula (22). In general, 0.5 to 2 equivalents may be mentioned relative to the compound to be obtained.
[0242] [ VIII ]法に於ける反応温度は、一般式（22)で示される化合物に於けるエポキシ 基と、一般式（34)で示されるカルボキシル基を 3個以上有する多塩基酸 (カルボキ シル基の一部がカルボン酸エステルであるものを含む。）に於けるカルボキシル基と が定量的に反応するような温度であれば、特に限定されないが、例えば通常 60〜1 20°C、好ましくは 70〜90°Cである。反応温度が 120°Cを超えると、該多塩基酸の分 子内及び分子間無水物化が一部起こり、分子量が急激に増大する原因となり、また 6 0°C未満では反応の進行が遅ぐ未反応の一般式（22)で示される化合物及び該多 塩基酸が残存する恐れがあるので好ましくない等の問題が生ずる。 [0243] [ VIII ]法に於ける反応時間は、一般式（20)に於ける重合度 kが適切な範囲となる ように、即ち、一般式 (20)で示される構成単位を含んで成る化合物の重量平均分子 量が適切な範囲となるように、反応時間を決定すれば良い。当該反応時間は、反応 に用いられる多塩基酸 (カルボキシル基の一部がカルボン酸エステルであるものを含 む。）の当量や反応温度に依存するため、一概には言えないが、通常 0. 5〜50時間 、好ましくは 1〜24時間、より好ましくは 2〜15時間の範囲に設定される。 [0242] The reaction temperature in the method [VIII] is a polybasic acid (carboxy group) having 3 or more epoxy groups in the compound represented by the general formula (22) and three or more carboxyl groups represented by the general formula (34). Is not particularly limited as long as it is a temperature at which the carboxyl group in the silyl group reacts quantitatively, for example, usually 60 to 120 ° C, preferably Is 70 ~ 90 ° C. When the reaction temperature exceeds 120 ° C, some intramolecular and intermolecular anhydrides of the polybasic acid occur, causing a rapid increase in molecular weight, and below 60 ° C, the reaction proceeds slowly. Since there is a possibility that the unreacted compound represented by the general formula (22) and the polybasic acid may remain, problems such as undesirable are caused. [0243] The reaction time in the method [VIII] is such that the degree of polymerization k in the general formula (20) falls within an appropriate range, that is, comprises the structural unit represented by the general formula (20). The reaction time may be determined so that the weight average molecular weight of the compound falls within an appropriate range. The reaction time depends on the equivalent of the polybasic acid used in the reaction (including those in which a part of the carboxyl group is a carboxylic acid ester) and the reaction temperature. It is set in the range of 5 to 50 hours, preferably 1 to 24 hours, more preferably 2 to 15 hours.
[0244] [ VIII ]法に於ける溶媒は、上記 [ III ]法と同様の溶媒を用いれば良ぐ溶媒の使 用量は、原料を溶解し得る量であれば特に限定されな ヽ。  [0244] The solvent used in the method [VIII] is not particularly limited as long as the same solvent as used in the method [III] is used, as long as the amount of the solvent can be dissolved.
[0245] [ VIII ]法に於 、て、一般式（22)で示される化合物と、一般式（34)で示されるカル ボキシル基を 3個以上有する多塩基酸 (カルボキシル基の一部がカルボン酸エステ ルであるものを含む。）とが定量的かつスムーズに反応するように触媒を使用すること が好ましい。これらの触媒としては、例えばテトラプチルアンモ -ゥムクロライド、テトラ ブチルアンモ -ゥムブロマイド、トリェチルベンジルアンモ-ゥムクロライド、トリェチル ベンジルアンモ -ゥムブロマイド等の四級アンモ-ゥム塩や、トリフエ-ルホスフィン等 の有機ホスフィンィ匕合物等の触媒が挙げられる。これらの触媒は、夫々単独で又は 2 種以上を組み合わせて用いられ、上記触媒の使用量は、特に限定されないが、一般 式（22)で示される化合物の mol量に対して、 0. 001mol%以上が挙げられ、反応速 度を向上させる為に、 200mol%程度使用することもある。  [0245] In the method [VIII], a compound represented by the general formula (22) and a polybasic acid having 3 or more carboxy groups represented by the general formula (34) It is preferable to use a catalyst so that it reacts quantitatively and smoothly. Examples of these catalysts include quaternary ammonium salts such as tetraptyl ammonium chloride, tetrabutyl ammonium chloride, triethylbenzyl ammonium chloride, and triethyl benzyl ammonium chloride, and organic phosphines such as triphenylphosphine. Examples thereof include a catalyst such as a compound. These catalysts are used alone or in combination of two or more, and the amount of the catalyst used is not particularly limited, but is 0.001 mol% with respect to the mol amount of the compound represented by the general formula (22). As mentioned above, in order to improve the reaction rate, about 200 mol% may be used.
[0246] [ VIII ]法で示される製造方法のより詳細な具体例としては、例えば下記 [ X ]法  [0246] As a more detailed specific example of the production method shown by the [VIII] method, for example, the following [X] method
Figure imgf000072_0001
Figure imgf000072_0001
(式中、 R1 R2、 R 、 R2，、 T 、 T 、 U、 V 、 V 、 Z及び kは上記に同じ。）で示される (Wherein R 1 R 2 , R 1 , R 2 , T, T, U, V, V, Z and k are the same as above)
1 2 1 2 1  1 2 1 2 1
ものが挙げられる。 [0247] 尚、一般式 (22)で示される化合物は、一般式（13)に於ける R1"が一般式（14)で あり、 R11が一般式（16)である場合に相当する。一般式（110)で示される化合物は、 カルボキシル基を 3個以上有する多塩基酸 (カルボキシル基の一部がカルボン酸ェ ステルであるものを含む。）を 3, 3' , 4, 4，ービフエ-ルテトラカルボン酸、 3, 3 ' , 4, 4'一べンゾフエノンテトラカルボン酸又は 4ー（1, 2 ジカルボキシェチル） 1, 2, 3, 4ーテトラヒドロナフタレン 1, 2 ジカルボン酸 {上記式（108)で示される脂肪族 テトラカルボン酸 }に限定した場合に相当する。一般式（111)で示される構成単位を 含んで成る化合物は、一般式（7)に於ける R3，及び R4'がカルボキシル基であり、 Y 'が式（8)で示される基であり、 Y 'が式（9)で示される基であり、 Zで示される 4価の Things. [0247] The compound represented by the general formula (22) corresponds to the case where R 1 "in the general formula (13) is the general formula (14) and R 11 is the general formula (16). The compound represented by the general formula (110) includes a polybasic acid having 3 or more carboxyl groups (including those in which a part of the carboxyl group is a carboxylate ester), 3, 3 ′, 4, 4, -Biphenyltetracarboxylic acid, 3, 3 ', 4, 4' monobenzophenone tetracarboxylic acid or 4- (1,2 dicarboxyethyl) 1, 2, 3, 4-tetrahydronaphthalene 1,2 dicarboxylic This corresponds to the case where the acid is limited to the aliphatic tetracarboxylic acid represented by the above formula (108) The compound comprising the structural unit represented by the general formula (111) is represented by R in the general formula (7). 3 and R 4 ′ are carboxyl groups, Y ′ is a group represented by the formula (8), Y ′ is a group represented by the formula (9), and a tetravalent group represented by Z
2  2
炭化水素基を、上記式 (29— 1 ' )、（29— 3' )又は（32)で示される芳香族又は脂肪 族系の 4価の炭化水素基に限定し、 a及び bが 1である場合に相当する。  The hydrocarbon group is limited to an aromatic or aliphatic tetravalent hydrocarbon group represented by the above formula (29-1 ′), (29-3 ′) or (32), and a and b are 1, This is the case.
[0248] 上記 [ VIII ]法に於 、て、一般式（34)で示されるカルボキシル基を 3個以上有する 多塩基酸 (カルボキシル基の一部がカルボン酸エステルであるものを含む。）以外に 、一般式（22)で示される化合物と重合することのできる化合物を用いることができ、 具体的には、例えば一般式（57)で示される 2個のカルボキシル基を有する芳香族又 は脂肪族カルボン酸 (芳香族又は脂肪族ジカルボン酸)を用いる方法としては、下記 [ XI ]法 [0248] In the above [VIII] method, in addition to the polybasic acid having 3 or more carboxyl groups represented by the general formula (34) (including those in which a part of the carboxyl groups is a carboxylate ester) A compound that can be polymerized with the compound represented by the general formula (22) can be used. Specifically, for example, an aromatic or aliphatic group having two carboxyl groups represented by the general formula (57) can be used. As a method using carboxylic acid (aromatic or aliphatic dicarboxylic acid), the following [XI] method
Figure imgf000074_0001
Figure imgf000074_0001
2)  2)
(式中、！^1、！^2、！^，、1^2，、 ，、1^4，、丁、T、U、 V、 V、 ゝ ，ゝ 及び ，は上 (In the formula,! ^ 1,! ^ 2,! ^ ,, 1 ^ 2 ,, ,, 1 ^ 4 ,, Ding, T, U, V, V ,ゝ,ゝand, above
1 2 1 2  1 2 1 2
記に同じ。）で示されるものが挙げられる。 Same as above. ).
一般式（57)で示される 2個のカルボキシル基を有する芳香族又は脂肪族カルボン 酸 (芳香族又は脂肪族ジカルボン酸）としては、具体的には、例えば式（113)〜（11  Specific examples of the aromatic or aliphatic carboxylic acid (aromatic or aliphatic dicarboxylic acid) having two carboxyl groups represented by the general formula (57) include, for example, formulas (113) to (11
(1 15)
Figure imgf000074_0002
(1 15)
Figure imgf000074_0002
{但し、式（114)中、 2つのカルボキシル基は、ナフタレン環の 1〜8位の炭素のうち、 何れの炭素に結合していても良い。 }、一般式（116)若しくは（117)  {However, in the formula (114), the two carboxyl groups may be bonded to any carbon of the 1-8th carbon atoms of the naphthalene ring. }, General formula (116) or (117)
(1 17)
Figure imgf000074_0003
(1 17)
Figure imgf000074_0003
(式中、 W 及び W は、結合手、酸素原子、カルボ-ル基、スルホ -ル基又はビ- (Wherein W and W are a bond, an oxygen atom, a carbo group, a sulfo group or a bead)
13 14 13 14
レン基を表す。）で示される芳香族ジカルボン酸、又は一般式（118)、 (119) 〇H (1 19)Represents a ren group. ) Or an aromatic dicarboxylic acid represented by the general formula (118), (119) 〇H (1 19)
Figure imgf000074_0004
{式中、 W は、結合手、炭素数 1〜18の直鎖状アルキレン基、ビニレン基、 2, 3—
Figure imgf000074_0004
{Wherein W is a bond, a linear alkylene group having 1 to 18 carbon atoms, vinylene group, 2, 3—
15 15
プロべ-レン基（1—プロペン一 2, 3 ジィル基）、アセチレン基又は 2—ォキソトリメ チレン基を表し、 qは 1〜3の整数を表す。但し、式（119)中、 2つのカルボキシル基 は、シクロアルキル環のうち、何れの炭素に結合していても良い。 }、若しくは式（120 )
Figure imgf000075_0001
It represents a probelene group (1-propene-1,3-diyl group), acetylene group or 2-oxotrimethylene group, and q represents an integer of 1 to 3. However, in formula (119), the two carboxyl groups may be bonded to any carbon in the cycloalkyl ring. } Or formula (120)
Figure imgf000075_0001
(式中、 2つのカルボキシル基は、シクロへキセン環の炭素のうち、何れの炭素に結 合して 、ても良!、。 )で示される脂肪族ジカルボン酸が挙げられる。  (Wherein the two carboxyl groups may be bonded to any carbon of the carbons of the cyclohexene ring!).
[0250] 一般式（116)及び（117)に於ける W 及び W としては、結合手又はカルボ-ル [0250] W and W in the general formulas (116) and (117) are a bond or a carbon.
13 14  13 14
基がより好ましい。  Groups are more preferred.
[0251] 一般式（118)に於ける W としては、結合手、炭素数 1〜18の直鎖状アルキレン基  [0251] In general formula (118), W represents a bond, a linear alkylene group having 1 to 18 carbon atoms.
15  15
又はビ-レン基がより好ましぐその中でもビ-レン基がさらに好ましい。  Of these, a beylene group is more preferable, among which a beylene group is more preferable.
[0252] 一般式（119)に於ける qは、通常 1〜3の整数を表し、中でも 2〜3の整数が好ましく[0252] In general formula (119), q usually represents an integer of 1 to 3, and preferably an integer of 2 to 3
、その中でも 3がより好ましい。 Of these, 3 is more preferred.
[0253] 式（113)で示される芳香族ジカルボン酸としては、具体的には、例えばフタル酸、 イソフタル酸、テレフタル酸等が挙げられ、中でもフタル酸、テレフタル酸が好ましい [0253] Specific examples of the aromatic dicarboxylic acid represented by the formula (113) include phthalic acid, isophthalic acid, terephthalic acid, and the like. Among these, phthalic acid and terephthalic acid are preferable.
[0254] 式（114)で示される芳香族ジカルボン酸としては、具体的には、例えば 1, 2 ナフ タレンジカルボン酸、 1, 3 ナフタレンジカルボン酸、 1, 4 ナフタレンジカルボン酸 、 1, 5 ナフタレンジカルボン酸、 1, 6 ナフタレンジカルボン酸、 1, 7 ナフタレン ジカルボン酸、 1, 8 ナフタレンジカルボン酸、 2, 3 ナフタレンジカルボン酸、 2, 6 ナフタレンジカルボン酸、 2, 7 ナフタレンジカルボン酸等が挙げられ、中でも 1, 8 ナフタレンジカルボン酸、 2, 3 ナフタレンジカルボン酸、 2, 6 ナフタレンジ力 ルボン酸が好ましい。 Specific examples of the aromatic dicarboxylic acid represented by the formula (114) include 1,2 naphthalene dicarboxylic acid, 1,3 naphthalene dicarboxylic acid, 1,4 naphthalene dicarboxylic acid, and 1,5 naphthalene dicarboxylic acid. Acid, 1, 6 naphthalene dicarboxylic acid, 1, 7 naphthalene dicarboxylic acid, 1, 8 naphthalene dicarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 2, 6 naphthalene dicarboxylic acid, 2, 7 naphthalene dicarboxylic acid, etc. , 8 Naphthalene dicarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 2, 6 naphthalene dicarboxylic acid Rubonic acid is preferred.
[0255] 式（115)で示される芳香族ジカルボン酸としては、具体的には、例えば 2, 3 ピリ ジンジカルボン酸、 2, 4 ピリジンジカルボン酸、 2, 5 ピリジンジカルボン酸、 2, 6 ピリジンジカルボン酸、 3, 4 ピリジンジカルボン酸、 3, 5—ピリジンジカルボン酸 等が挙げられる。 [0255] Specific examples of the aromatic dicarboxylic acid represented by the formula (115) include 2,3 pyridine dicarboxylic acid, 2,4 pyridinedicarboxylic acid, 2,5 pyridinedicarboxylic acid, and 2,6 pyridinedicarboxylic acid. Acid, 3, 4 pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid Etc.
[0256] 一般式（116)で示される芳香族ジカルボン酸のうち、 W が結合手である芳香族ジ  [0256] Among the aromatic dicarboxylic acids represented by the general formula (116), W is an aromatic dicarboxylic acid.
13  13
カルボン酸としては、例えば 2, 3—ビフエ-ルジカルボン酸、 2, 4—ビフエ-ルジカ ノレボン酸、 2, 5—ビフエニノレジ力ノレボン酸、 2, 6—ビフエニノレジ力ノレボン酸、 3, 4— ビフエ-ルジカルボン酸、 3, 5—ビフエ-ルジカルボン酸等が挙げられる。また、 W  Examples of the carboxylic acid include 2,3-biphenyl dicarboxylic acid, 2,4-biphenol di-norebonic acid, 2,5-bipheninoresi power norlevonic acid, 2,6-biphenylinose power norebon acid, 3,4-biphenol- And rudicarboxylic acid and 3,5-biphenyl dicarboxylic acid. W
13 が酸素原子である芳香族ジカルボン酸としては、例えば 2, 3—ビフエ-ルエーテル ジカルボン酸、 2, 4—ビフエ-ルエーテルジカルボン酸、 2, 5—ビフエ-ルエーテル ジカルボン酸、 2, 6—ビフエ-ルエーテルジカルボン酸、 3, 4—ビフエ-ルエーテル ジカルボン酸、 3, 5—ビフエ-ルエーテルジカルボン酸等が挙げられる。さらに、 W  Examples of aromatic dicarboxylic acids in which 13 is an oxygen atom include 2,3-biphenyl ether dicarboxylic acid, 2,4-biphenyl ether dicarboxylic acid, 2,5-biphenyl ether dicarboxylic acid, 2,6-biphenol- Examples include ruether dicarboxylic acid, 3,4-biphenyl ether dicarboxylic acid, 3,5-biphenyl ether dicarboxylic acid, and the like. And W
13 がカルボ-ル基である芳香族ジカルボン酸としては、例えば 2, 3—べンゾフエノンジ 力ノレボン酸、 2, 4一べンゾフエノンジカノレボン酸、 2, 5—べンゾフエノンジカノレボン酸 、 2, 6—べンゾフエノンジカノレボン酸、 3, 4一べンゾフエノンジカノレボン酸、 3, 5—べ ンゾフエノンジカルボン酸等が挙げられる。さらにまた、 W がスルホ-ル基である芳  Examples of aromatic dicarboxylic acids in which 13 is a carbocyclic group include 2,3-benzophenone dinorebonic acid, 2,4-benzophenone dicanolebon acid, and 2,5-benzophenone dicanolebon. Examples include acids, 2,6-benzophenone dicanolevon acid, 3,4 benzophenone dicanolevon acid, 3,5-benzophenone dicarboxylic acid, and the like. Furthermore, W is a sulfo group.
13  13
香族ジカルボン酸としては、例えば 2, 3—ビフエニルスルホンジカルボン酸、 2, 4— ビフエニノレスノレホンジカノレボン酸、 2, 5—ビフエニノレスノレホンジカノレボン酸、 2, 6—ビ フエニノレスノレホンジカノレボン酸、 3, 4ービフエニノレスノレホンジカノレボン酸、 3, 5—ビフ ェニルスルホンジカルボン酸等が挙げられる。また、 w がビ-レン基である芳香族ジ  Examples of the aromatic dicarboxylic acid include 2,3-biphenylsulfone dicarboxylic acid, 2,4-biphenylenosnorejon dicanolevonic acid, 2,5-bibienoresnorejon dicanolevonic acid, 2,6- Examples thereof include biphenylenosnorejon dicanolevonic acid, 3,4-biphenylenolesnorejon dicanolevonic acid, 3,5-biphenylsulfone dicarboxylic acid, and the like. In addition, aromatic diene wherein w is a beylene group.
13  13
カルボン酸としては、例えば cis— 2, 3—スチルベンジカルボン酸、 trans— 2, 3—ス チルベンジカルボン酸、 cis— 2, 4—スチルベンジカルボン酸、 trans— 2, 4—スチ ルベンジカルボン酸、 cis— 2, 5—スチルベンジカルボン酸、 trans— 2, 5—スチル ベンジカルボン酸、 cis— 2, 6—スチルベンジカルボン酸、 trans— 2, 6—スチルベ ンジカルボン酸、 cis— 3, 4—スチルベンジカルボン酸、 trans— 3, 4—スチルベン ジカルボン酸、 cis— 3, 5—スチルベンジカルボン酸、 trans— 3, 5—スチルベンジ カルボン酸等が挙げられる。  Examples of the carboxylic acid include cis-2,3-stilbene dicarboxylic acid, trans-2,3-stilbene dicarboxylic acid, cis-2,4-stilbene dicarboxylic acid, trans-2,4-stilbene dicarboxylic acid, cis — 2, 5—stilbene dicarboxylic acid, trans— 2, 5—stilbene dicarboxylic acid, cis— 2, 6-stilbene dicarboxylic acid, trans— 2, 6-stilbene dicarboxylic acid, cis— 3, 4-stilbene dicarboxylic acid Trans-3,4-stilbene dicarboxylic acid, cis-3,5-stilbene dicarboxylic acid, trans-3,5-stilbene dicarboxylic acid, and the like.
[0257] 一般式（117)で示される芳香族ジカルボン酸のうち、 W が結合手である芳香族ジ [0257] Among the aromatic dicarboxylic acids represented by the general formula (117), an aromatic dicarboxylic acid in which W is a bond.
14  14
カルボン酸としては、例えば 2, 2，一ビフエニルジカルボン酸、 2, 3，一ビフエ-ルジ カルボン酸、 2, 4，一ビフエ-ルジカルボン酸、 3, 3，一ビフエ-ルジカルボン酸、 3, 4，ービフエ-ルジカルボン酸、 4, 4，ービフエ-ルジカルボン酸等が挙げられ、中で も 3, 3，一ビフエニノレジ力ノレボン酸、 3, 4，一ビフエ-ノレジカノレボン酸、 4, 4，一ビフエ -ルジカルボン酸が好ましぐその中でも 4, 4'ービフエ-ルジカルボン酸がより好ま しい。また、 W が酸素原子である芳香族ジカルボン酸としては、例えば 2, 2'ービフ Examples of the carboxylic acid include 2,2,1-biphenyldicarboxylic acid, 2,3,1-biphenyldicarboxylic acid, 2,4,1-biphenyldicarboxylic acid, 3,3,1-biphenyldicarboxylic acid, 3 4, 4-biphenyl dicarboxylic acid, 4, 4-biphenyl dicarboxylic acid, etc. 3,3,1-bipheninoresigenic power Norevonic acid, 3,4,1-biphenolo-renocinolevonic acid, 4,4,1-bibi-didicarboxylic acid are preferred, and 4,4'-biphenyl-dicarboxylic acid is more preferred . Examples of the aromatic dicarboxylic acid in which W is an oxygen atom include 2, 2′-bif
14  14
ェ-ルエーテルジカルボン酸、 2, 3，ービフエ-ルエーテルジカルボン酸、 2, 4，ービ フエ-ルエーテルジカルボン酸、 3, 3，ービフエ-ルエーテルジカルボン酸、 3, 4，一 ビフエ-ルエーテルジカルボン酸、 4, 4'ービフエ-ルエーテルジカルボン酸等が挙 げられる。さらに、 W がカルボ-ル基である芳香族ジカルボン酸としては、例えば 2  Ether ether dicarboxylic acid, 2, 3, biphenyl ether dicarboxylic acid, 2, 4, biphenyl ether dicarboxylic acid, 3, 3, biphenyl ether dicarboxylic acid, 3, 4, monobiether ether dicarboxylic acid, 4 , 4'-biphenyl ether dicarboxylic acid and the like. Furthermore, examples of the aromatic dicarboxylic acid in which W is a carbo group include 2
14  14
, 2'一べンゾフエノンジカノレボン酸、 2, 3'一べンゾフエノンジカノレボン酸、 2, 4'—べ ンゾフエノンジカノレボン酸、 3, 3'一べンゾフエノンジカノレボン酸、 3, 4'一べンゾフエ ノンジカルボン酸、 4, 4'一べンゾフエノンジカルボン酸等が挙げられる。さらにまた、 W がスルホ-ル基である芳香族ジカルボン酸としては、例えば 2, 2'—ビフエ-ルス , 2 'monobenzophenone dicanolevonic acid, 2, 3' monobenzophenone dicanolevonic acid, 2, 4'-benzophenone dicanolevonic acid, 3, 3 'monobenzofenone Examples include dicanolevonic acid, 3,4 ′ monobenzophenone dicarboxylic acid, and 4,4 ′ monobenzophenone dicarboxylic acid. Furthermore, examples of the aromatic dicarboxylic acid in which W is a sulfo group include, for example, 2, 2′-biphenyls.
14 14
ルホンジカルボン酸、 2, 3，一ビフエニルスルホンジカルボン酸、 2, 4'—ビフエ-ル スノレホンジカノレボン酸、 3, 3'ービフエニノレスノレホンジカノレボン酸、 3, 4'ービフエ二 ルスルホンジカルボン酸、 4, 4'ービフエ-ルスルホンジカルボン酸等が挙げられる。 また、 W がビ-レン基である芳香族ジカルボン酸としては、例えば cis— 2, 2，ース チノレべンジカノレボン酸、 trans - 2, 2，ースチノレべンジ力ノレボン酸、 CIS - 2, 3， —ス チノレべンジカノレボン酸、 trans - 2, 3，ースチノレべンジ力ノレボン酸、 CIS - 2, 4' —ス チノレべンジカノレボン酸、 trans - 2, 4，ースチノレべンジ力ノレボン酸、 CIS - 3, 3， —ス チノレべンジカノレボン酸、 trans - 3, 3，ースチノレべンジ力ノレボン酸、 CIS - 3, 4， —ス チノレべンジカノレボン酸、 trans - 3, 4，ースチノレべンジ力ノレボン酸、 CIS -4, 4， —ス チノレべンジカノレボン酸、 trans - 4, 4，ースチノレべンジカルボン酸等が挙げられる。  Lufone dicarboxylic acid, 2, 3, 1-biphenyl sulfone dicarboxylic acid, 2, 4'-biphenyl sulolefon dicanolevonic acid, 3, 3'-biphenylenosnorefon dicanolevonic acid, 3, 4'-bihue Examples thereof include disulfone dicarboxylic acid and 4,4′-biphenyl sulfone dicarboxylic acid. Examples of the aromatic dicarboxylic acid in which W is a beylene group include cis-2, 2, succinolebendicanolevonic acid, trans-2, 2, sustinolevenedinorebonic acid, CIS-2, 3, —Stinolevendicanolevonic acid, trans-2, 3, ustinolevendinolic levonolic acid, CIS-2, 4 '—Stinolevendicanolevonic acid, trans-2, 4, ustinolevendinolic levonolic acid, CIS-3, 3, —Stinolevendicanolevonic acid, trans-3, 3, Stinolevendic strength norebonic acid, CIS-3, 4, —Stinolevendicanolevonic acid, trans-3, 4, Stinorevendic strength norlevonic acid, CIS- 4,4, -Stynolevenedicanolevonic acid, trans-4,4, stinolevenedicarboxylic acid and the like.
[0258] 上記芳香族ジカルボン酸のうち、式（113)又は一般式（117)で示されるものが好 ましぐ中でも式（113)又は一般式（117)に於ける W が結合手若しくはカルボ-ル  [0258] Among the above aromatic dicarboxylic acids, those represented by the formula (113) or the general formula (117) are preferred, and W in the formula (113) or the general formula (117) is a bond or carbo- Le
14  14
基であるものがより好ましい。  What is a group is more preferable.
[0259] 一般式（118)で示される脂肪族ジカルボン酸のうち、 W が結合手である脂肪族ジ [0259] Among the aliphatic dicarboxylic acids represented by the general formula (118), an aliphatic dicarboxylic acid in which W is a bond.
15  15
カルボン酸としては、シユウ酸等が挙げられる。また、 W が炭素数 1〜18の直鎖状  Examples of the carboxylic acid include oxalic acid. W is a straight chain having 1 to 18 carbon atoms
15  15
アルキレン基である脂肪族ジカルボン酸としては、マロン酸、コハク酸、ダルタル酸、 アジピン酸、ピメリン酸、スベリン酸、ァゼライン酸、セバシン酸、 1, 10—デカンジカ ルボン酸、 1, 18—ォクタデカンジカルボン酸等が挙げられ、中でもマロン酸、コハク 酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、ァゼライン酸、セバシン酸、 1 , 1 0—デカンジカルボン酸が好ましぐその中でもマロン酸、コハク酸、グルタル酸、アジ ピン酸、ピメリン酸、スベリン酸がより好ましい。さらに、 W 力ビ-レン基である脂肪族 Examples of the aliphatic dicarboxylic acid that is an alkylene group include malonic acid, succinic acid, dartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decandicaic acid. Rubonic acid, 1,18-octadecane dicarboxylic acid, etc., among which malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid Of these, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid are more preferred. In addition, W power beylene group is aliphatic
15  15
ジカルボン酸としては、マレイン酸、フマル酸等が挙げられ、中でもマレイン酸が好ま しい。さらにまた、 W が 2, 3—プロべ-レン基（1 プロペン 2, 3 ジィル基）であ  Examples of the dicarboxylic acid include maleic acid and fumaric acid. Among these, maleic acid is preferable. Furthermore, W is a 2,3-propylene group (1 propene 2,3 diyl group).
15  15
る脂肪族ジカルボン酸としては、ィタコン酸等が挙げられる。また、 w がアセチレン  Examples of the aliphatic dicarboxylic acid include itaconic acid and the like. W is acetylene.
15  15
基である脂肪族ジカルボン酸としては、アセチレンジカルボン酸等が挙げられる。ま た、 W 力 ォキソトリメチレン基である脂肪族ジカルボン酸としては、 1, 3 ァセト Examples of the aliphatic dicarboxylic acid as a group include acetylenedicarboxylic acid. In addition, the aliphatic dicarboxylic acid that is a W force oxotrimethylene group includes 1,3-acetate.
15 15
ンジカルボン酸等が挙げられる。  And dicarboxylic acid.
[0260] 一般式（119)で示される脂肪族ジカルボン酸としては、通常 qが 1〜3の整数、好ま しくは 2〜3の整数、より好ましくは 3である脂肪族ジカルボン酸が挙げられ、具体的に は、例えば 1, 2 シクロブタンジカルボン酸、 1, 3 シクロブタンジカルボン酸、 1 , 2 —シクロペンタンジカルボン酸、 1, 3 シクロペンタンジカルボン酸、 1, 2 シクロへ キサンジカルボン酸、 1, 3 シクロへキサンジカルボン酸、 1, 4ーシクロへキサンジ カルボン酸等が挙げられ、中でも 1, 2 シクロペンタンジカルボン酸、 1, 3 シクロ ペンタンジカルボン酸、 1, 2 シクロへキサンジカルボン酸、 1, 3 シクロへキサンジ カルボン酸、 1, 4ーシクロへキサンジカルボン酸が好ましぐその中でも 1, 2 シクロ へキサンジカルボン酸、 1, 3 シクロへキサンジカルボン酸、 1, 4ーシクロへキサン ジカルボン酸がより好まし!/、。  [0260] Examples of the aliphatic dicarboxylic acid represented by the general formula (119) include aliphatic dicarboxylic acids in which q is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3. Specifically, for example, 1,2 cyclobutanedicarboxylic acid, 1,3 cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3 cyclopentanedicarboxylic acid, 1,2 cyclohexanedicarboxylic acid, 1,3 cyclohexane Hexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc., among which 1,2 cyclopentanedicarboxylic acid, 1,3 cyclopentanedicarboxylic acid, 1,2 cyclohexanedicarboxylic acid, 1,3 cyclohexanedi Among these, carboxylic acid and 1,4-cyclohexanedicarboxylic acid are preferred. 1,2-cyclohexanedicarboxylic acid, 1,3 cyclohexanedicarboxylic acid, 1,4-cyclohexane More preferably is hexane dicarboxylic acid! /,.
[0261] 式（120)で示される脂肪族ジカルボン酸としては、具体的には、例えば cis— 1, 2, 3, 6—テトラヒドロフタノレ酸、 trans— 1, 2, 3, 6—テトラヒドロフタノレ酸、 3, 4, 5, 6— テトラヒドロフタル酸等が挙げられ、中でも cis— 1, 2, 3, 6—テトラヒドロフタル酸が好 ましい。  [0261] Specific examples of the aliphatic dicarboxylic acid represented by the formula (120) include cis-1,2,3,6-tetrahydrophthalenoic acid, trans-1,2,3,6-tetrahydrophthalate. Examples include noreic acid and 3, 4, 5, 6-tetrahydrophthalic acid. Among them, cis-1, 2, 3, 6-tetrahydrophthalic acid is preferable.
[0262] 上記脂肪族ジカルボン酸のうち、一般式（118)又は式（120)で示されるものが好 ましぐ中でも一般式（118)に於ける W が結合手、炭素数 1〜18の直鎖状アルキレ  [0262] Among the above aliphatic dicarboxylic acids, those represented by the general formula (118) or the formula (120) are preferable. In the general formula (118), W is a bond, a straight chain having 1 to 18 carbon atoms. Chain alkyle
15  15
ン基又はビ-レン基であるもの、又は式（120)で示されるものがより好ましぐその中 でも一般式（118)に於ける W がビ-レン基であるもの、又は式（120)で示されるも のがさらに好ましい。 Among them, those represented by formula (120) are more preferred, and those in which W in formula (118) is a beylene group, or formula (120 ) Is more preferable.
[0263] [ XI ]法に於 、て、一般式（34)で示されるカルボキシル基を 3個以上有する多塩 基酸 (カルボキシル基の一部がカルボン酸エステルであるものを含む。）と、一般式（ 57)で示される 2個のカルボキシル基を有する芳香族又は脂肪族カルボン酸 (芳香 族又は脂肪族ジカルボン酸)を併用する場合に於ける、これらのモル比のうち、上記 一般式（34)で示される酸と上記一般式（57)で示される酸を併用する場合のモル比 は、通常 10 : 90〜99 : 1、好ましくは 40 : 60〜99 : 1である。一般式（34)で示される 酸の割合が全酸の 10モル％未満である場合、得られる化合物の酸価及び分子量が 小さくなり、例えば当該化合物力 得られる榭脂組成物を用いてカラーフィルターを 製造する場合には、微細パターンを形成するのが困難になり、また、耐熱性または耐 溶剤性に問題が生じる恐れがあるため、好ましくない等の問題を生ずる。  [0263] In the method [XI], a polybasic acid having three or more carboxyl groups represented by the general formula (34) (including those in which a part of the carboxyl groups is a carboxylate ester); Of these molar ratios in the case where an aromatic or aliphatic carboxylic acid having two carboxyl groups represented by the general formula (57) (aromatic or aliphatic dicarboxylic acid) is used in combination, the above general formula ( The molar ratio when the acid represented by 34) and the acid represented by the general formula (57) are used in combination is usually 10:90 to 99: 1, preferably 40:60 to 99: 1. When the ratio of the acid represented by the general formula (34) is less than 10 mol% of the total acid, the acid value and molecular weight of the obtained compound become small. For example, a color filter using the obtained resin composition In the case of manufacturing, it becomes difficult to form a fine pattern, and there is a risk of problems in heat resistance or solvent resistance.
[0264] [ XI ]法に於 、て、一般式（34)で示されるカルボキシル基を 3個以上有する多塩 基酸 (カルボキシル基の一部がカルボン酸エステルであるものを含む。）と、一般式（ 57)で示される 2個のカルボキシル基を有する芳香族又は脂肪族カルボン酸 (芳香 族又は脂肪族ジカルボン酸)の併用方法としては、これらを混合したものを一般式（2 2)で示される化合物を含む溶液に加えて、一挙に反応させても良いし、これらを別 々及び段階的に反応させても良 、。  [0264] In the method [XI], a polybasic acid having three or more carboxyl groups represented by the general formula (34) (including those in which a part of the carboxyl groups is a carboxylate ester); As a combined method of the aromatic or aliphatic carboxylic acid having two carboxyl groups represented by the general formula (57) (aromatic or aliphatic dicarboxylic acid), a mixture of them is represented by the general formula (22). In addition to the solution containing the compound shown, it may be reacted at once, or these may be reacted separately and stepwise.
[0265] [ XI ]法で示される製造方法のより詳細な具体例としては、例えば下記 [ XII ]法 [0265] As a more specific example of the production method shown by the [XI] method, for example, the following [XII] method
o、 o,
[XII] [XII]
Figure imgf000080_0001
Figure imgf000080_0001
(122)  (122)
(式中、 I^R2 Ι^，、Κ2，、Τ、T、U、 V、 V、Z、Z、 k，及び k，，は上記に同じ。） (In the formula, I ^ R 2 Ι ^, Κ 2 , Τ, T, U, V, V, Z, Z, k, and k, are the same as above.)
1 2 1 2 1 3  1 2 1 2 1 3
で示されるものが挙げられる。  The thing shown by is mentioned.
[0266] 尚、一般式（121)で示される化合物は、 2個のカルボキシル基を有する芳香族又 は脂肪族カルボン酸 (芳香族又は脂肪族ジカルボン酸)をテレフタル酸、マレイン酸 又は cis— l, 2, 3, 6—テトラヒドロフタル酸に限定した場合に相当する。一般式（12 2)で示される構成単位を含んで成る化合物は、上記一般式（112)に於ける R3'及び R4'がカルボキシル基であり、 Zで示される 4価の炭化水素基を、上記式（29— 1')、 ( 29— 3 ')又は（32)で示される芳香族又は脂肪族系の 4価の炭化水素基に限定し、 Z'で示される 2価の炭化水素基を、上記式 (49')、 （54— 2')又は（56')で示される 芳香族又は脂肪族系の 2価の炭化水素基に限定した場合に相当する。 [0266] The compound represented by the general formula (121) is an aromatic or aliphatic carboxylic acid having two carboxyl groups (aromatic or aliphatic dicarboxylic acid), terephthalic acid, maleic acid or cis-l. , 2, 3, 6- Corresponds to the case of limiting to tetrahydrophthalic acid. The compound comprising the structural unit represented by the general formula (12 2) is a tetravalent hydrocarbon group represented by Z in which R 3 ′ and R 4 ′ in the general formula (112) are carboxyl groups. Is limited to the aromatic or aliphatic tetravalent hydrocarbon group represented by the above formula (29-1 ′), (29-3 ′) or (32), and the divalent carbon group represented by Z ′ This corresponds to the case where the hydrogen group is limited to the aromatic or aliphatic divalent hydrocarbon group represented by the above formula (49 '), (54-2') or (56 ').
[0267] 次に、上記 [ IX ]法について詳細に説明する。 [ IX ]法は、例えば一般式（23)で 示される化合物を溶媒で希釈し、要すればこれに触媒を加えた後、この混合溶液に 、下記の如き所定の当量の一般式（35)又は（36)で示されるカルボキシル基を 3個 以上有する多塩基酸無水物 (カルボキシル基の一部が脱水縮合して酸無水物基を 形成しているものを含み、また、その一部がカルボン酸エステルであるものを含む。） を加え、所定の温度で、所定の時間反応させる。ここで得られた溶液は、単離、精製 を行うことなく、 目的の用途に使用することができ、用途によっては、該溶液をさらに 溶媒で希釈したり、一般式 (21)で示される構成単位を含んで成る化合物を常法によ り単離、精製すれば良い。 [0267] Next, the above [IX] method will be described in detail. In the method [IX], for example, the compound represented by the general formula (23) is diluted with a solvent, and if necessary, a catalyst is added thereto. Or a polybasic acid anhydride having three or more carboxyl groups represented by (36) (including those in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group, and part of the carboxyl group is a carboxyl group). Including those that are acid esters.) And react at a predetermined temperature for a predetermined time. The solution obtained here can be used for the intended application without isolation and purification. Depending on the application, the solution may be further diluted with a solvent, or the structure represented by the general formula (21). A compound comprising the unit may be isolated and purified by a conventional method.
[0268] [ IX ]法に於いて、一般式（23)で示される化合物のうち、 V及び Vが酸素原子で [0268] In the method [IX], among the compounds represented by the general formula (23), V and V are oxygen atoms.
1 2  1 2
あり、 R12及び R13が水素原子であるもの、並びに R12が一般式（15)及び R13が一般 式（17)で示される基であり、且つ、 V及び Vが酸素原子、 M及び Mが水素原子 R 12 and R 13 are hydrogen atoms, and R 12 is a group represented by the general formula (15) and R 13 in the general formula (17), and V and V are oxygen atoms, M and M is a hydrogen atom
3 4 1 2  3 4 1 2
であるものとしては、例えば上記一般式（98)で示されるビスフエ-ル骨格を有する化 合物のうち、 V及び Vが酸素原子であるもの、上記一般式（98)で示されるビスフ  For example, among the compounds having a bisphenol skeleton represented by the above general formula (98), those in which V and V are oxygen atoms, bisphenol represented by the above general formula (98), and the like.
1 2  1 2
ニル骨格を有する化合物と、ホルムアルデヒド等の炭素数 1の化合物とを反応させる ことによって得られる化合物、並びに上記一般式（98)で示されるビスフエ-ル骨格を 有する化合物と、 2 クロ口一 1—エタノール、 2 ブロモ 1—エタノール、 3 クロ口 —1—プロノ ノーノレ、 3—ブロモ 1—プロノ ノーノレ、 4—クロ口一 1—ブタノーノレ、 4— ブロモー 1ーブタノ一ノレ、 5 クロロー 1 ペンタノ一ノレ、 5 ブロモー 1 ペンタノ一 ノレ、 6 クロ口一 1—へキサノーノレ、 6 ブロモ 1—へキサノーノレ等の ω ハロゲノ アルコールとを反応させることによって得られる化合物が挙げられ、中でも上記一般 式（98)で示されるビスフエ-ル骨格を有する化合物と、 2 クロロー 1 エタノール、 2 ブロモ 1—エタノーノレ、 3 クロ口一 1—プロパノーノレ、 3 ブロモ 1—プロパノ 一ノレ、 4 クロ口一 1—ブタノーノレ、 4 ブロモ 1—ブタノーノレの ω ハロゲノアノレコ 一ルとを反応させることによって得られる化合物が好ましぐその中でも上記一般式（ 98)で示されるビスフエ-ル骨格を有する化合物と、 2 クロロー 1 エタノール、 2— ブロモー 1 エタノールの ω—ハロゲノアルコールとを反応させることによって得られ る化合物がより好ましい。  A compound obtained by reacting a compound having a nyl skeleton with a compound having 1 carbon atom such as formaldehyde, and a compound having a bisphenol skeleton represented by the above general formula (98); Ethanol, 2 Bromo 1-Ethanol, 3 Black mouth —1—Prono Norole, 3—Bromo 1—Prono Norole, 4—Black mouth 1—Butanol, 4—Bromo 1-Butanol, 5 Chloro 1 Pentanol, 5 Examples thereof include compounds obtained by reacting ω-halogenoalcohols such as bromo-1-pentanol-1-nor, 6-chloro-mono-1-hexanol and 6-bromo-1-hexanol, and among others, bisphenols represented by the above general formula (98). -Compounds with a skeleton, 2 chloro-1 ethanol, 2 bromo 1-ethanolanol, 3 black mouth 1-propanol, 3 Compounds obtained by reacting lomo 1-propano monoole, 4 black mouth 1-butanol and 4 bromo 1-butanol are preferred, and bisphenol represented by the above general formula (98) is preferred. A compound obtained by reacting a compound having a skeleton with a ω-halogenoalcohol of 2-chloro-1 ethanol or 2-bromo-1 ethanol is more preferred.
[0269] [ IX ]法に於いて、一般式（23)で示される化合物のうち、 V及び Vがー ΝΗ 基 [0269] In the method [IX], among the compounds represented by the general formula (23), V and V are ー groups.
1 2  1 2
であり、 R12及び R13が水素原子であるもの、並びに R12が一般式（15)及び R13が一般 式（17)で示される基であり、且つ、 V及び Vがー ΝΗ 基、 Μ及び Μが水素原子 R 12 and R 13 are hydrogen atoms, R 12 is a group represented by the general formula (15) and R 13 is a group represented by the general formula (17), and V and V are ー groups, Μ and Μ are hydrogen atoms
3 4 1 2 であるものとしては、例えば上記一般式（98)で示されるビスフエ-ル骨格を有する化 合物のうち、 V及び Vがー ΝΗ 基であるもの、並びに上記一般式（98)で示される ビスフエ-ル骨格を有する化合物と、 1 クロロメチルァミン、 1ーブロモメチルァミン、 2 クロロー 1ーェチノレアミン、 2 ブロモー 1ーェチノレアミン、 3 クロロー 1 プロピ ルァミン、 3—ブロモ—1—プロピルァミン、 4—クロ口— 1—ブチルァミン、 4—ブロモ 1ーブチルァミン、 5 クロロー 1 ペンチルァミン、 5 ブロモー 1 ペンチルアミ ン、 6 クロ口一 1—へキシルァミン、 6 ブロモ 1—へキシルァミン等の ω ハロゲ ノアルキルァミンとを反応させることによって得られる化合物が挙げられ、中でも上記 一般式（98)で示されるビスフエ-ル骨格を有する化合物と、 2 クロロー 1 ェチル ァミン、 2 ブロモ—1—ェチルァミン、 3 クロ口 1—プロピルァミン、 3 ブロモ 1 プロピルアミン、 4 クロロー 1ーブチルァミン、 4ーブロモー 1ーブチルァミンの ω ーハロゲノアルキルァミンとを反応させることによって得られる化合物が好ましぐその 中でも上記一般式（98)で示されるビスフエニル骨格を有する化合物と、 2 クロロー 1ーェチルァミン、 2—ブロモー 1ーェチルァミンの ω —ハロゲノアルキルァミンとを反 応させることによって得られる化合物がより好ましい。 Examples of the compound represented by 3 4 1 2 include compounds having a bisphenol skeleton represented by the above general formula (98), wherein V and V are ΝΗ groups, and the above general formula (98). Indicated by A compound having a bisphenol skeleton and 1 chloromethylamine, 1-bromomethylamine, 2 chloro-1-ethinoreamine, 2 bromo-1-ethenoreamine, 3 chloro-1-propylamine, 3-bromo-1-propylamine, 4-chloro mouth — Obtained by reacting ω-haloalkylamines such as 1-butylamine, 4-bromo-1-butylamine, 5 chloro-1 pentylamine, 5 bromo-1 pentylamine, 6 chloro 1-hexylamine, 6 bromo 1-hexylamine, etc. Compounds having a bisphenol skeleton represented by the above general formula (98), 2 chloro-1 ethylamine, 2 bromo-1-ethylamine, 3 chloro 1-propylamine, 3 bromo1 propylamine, 4 Chloro-1-butylamine, 4-bromo-1-butylamine Of these, compounds obtained by reacting a ω-halogenoalkylamine with a bisphenyl skeleton represented by the above general formula (98), and 2-chloro-1-ethylamine, 2-bromo-1-ethylamine ω -Compounds obtained by reacting with halogenoalkylamines are more preferred.
[0270] [ IX ]法に於いて、一般式（23)で示される化合物のうち、 R12及び R13がアルカリ金 属原子であるもの、並びに R12が一般式（15)、 R13が一般式（17)で示される基であり 、且つ、 Μ及び Μがアルカリ金属原子であるものとしては、例えば上記一般式（98) [0270] In the method [IX], among the compounds represented by the general formula (23), R 12 and R 13 are alkali metal atoms, and R 12 is represented by the general formula (15) and R 13 is Examples of the group represented by the general formula (17) and Μ and Μ being an alkali metal atom include the above general formula (98)
1 2  1 2
で示されるビスフエ-ル骨格を有する化合物、及び上記一般式（98)で示されるビス フエ-ル骨格を有する化合物と ω—ハロゲノアルコール又は ω—ハロゲノアルキルァ ミンとを反応させることによって得られる化合物を、水酸化ナトリウム、水酸化カリウム 等のアルカリ金属水酸ィ匕物、水素化ナトリウム、水素化カリウム等の水素化アルカリ金 属、ナトリウムメトキシド、カリウムメトキシド、ナトリウムエトキシド、カリウムエトキシド、ナ トリウム tert ブトキシド、カリウム tert ブトキシド等のアルカリ金属アルコキシド等の 何れ力と常法により反応させることによって得られる化合物が挙げられ、中でも上記 一般式（98)で示されるビスフ ニル骨格を有する化合物、及び上記一般式（98)で 示されるビスフエ-ル骨格を有する化合物と ω —ハロゲノアルコール又は ω ハロゲ ノアルキルァミンとを反応させることによって得られる化合物を、ナトリウムメトキシド又 はカリウムメトキシドと常法により反応させることによって得られる化合物が好ましい。  And a compound obtained by reacting a compound having the bisphenol skeleton represented by the general formula (98) with ω-halogenoalcohol or ω-halogenoalkylamine. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal hydride such as sodium hydride or potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, Examples thereof include compounds obtained by reacting with any force such as alkali metal alkoxides such as sodium tert butoxide and potassium tert butoxide, etc., among others, compounds having a bisphenyl skeleton represented by the above general formula (98), and A compound having a bisphenol skeleton represented by the general formula (98); A compound obtained by reacting a compound obtained by reacting ω-halogenoalcohol or ωhalogenoalkylamine with sodium methoxide or potassium methoxide by a conventional method is preferred.
[0271] 一般式（35)又は（36)で示されるカルボキシル基を 3個以上有する多塩基酸無水 物 (カルボキシル基の一部が脱水縮合して酸無水物基を形成しているものを含み、ま た、その一部がカルボン酸エステルであるものを含む。）としては、通常 3個以上の力 ルポキシル基を有する芳香族又は脂肪族カルボン酸無水物 (カルボキシル基の一部 が脱水縮合して酸無水物基を形成しているものを含み、また、その一部がカルボン 酸エステルであるものを含む。）が挙げられ、具体的には、例えば式（123) [0271] Polybasic acid anhydride having three or more carboxyl groups represented by the general formula (35) or (36) As a product (including those in which a part of the carboxyl group is dehydrated and condensed to form an acid anhydride group, and a part of which is a carboxylic acid ester), usually 3 or more Aromatic or aliphatic carboxylic acid anhydrides having a loxyl group (including those in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group, and part of which is a carboxylic acid ester) Specifically, for example, for example, the formula (123)
Figure imgf000083_0001
Figure imgf000083_0001
で示される芳香族トリカルボン酸無水物、式（124)、（125) Aromatic tricarboxylic acid anhydrides of formula (124), (125)
Figure imgf000083_0002
Figure imgf000083_0002
{但し、式（125)中、酸無水物基を形成する 4つのカルボキシル基は、酸無水物基を 形成できれば、ナフタレン環の 1〜8位の炭素のうち、何れの炭素に結合していても 良い。 }若しくは一般式（126)〜（128)  {However, in the formula (125), the four carboxyl groups that form an acid anhydride group are bonded to any of the carbons 1 to 8 of the naphthalene ring as long as they can form an acid anhydride group. Also good. } Or general formula (126)-(128)
Figure imgf000083_0003
Figure imgf000083_0003
(式中、 w 、W 及び W は、結合手、酸素原子、カルボニル基、スルホニル基又は  (Wherein w, W and W are a bond, an oxygen atom, a carbonyl group, a sulfonyl group or
16 17 18  16 17 18
ビニレン基を表す。）で示される芳香族テトラカルボン酸無水物、一般式（129) Represents a vinylene group. Aromatic tetracarboxylic acid anhydrides represented by general formula (129)
Figure imgf000083_0004
(式中、 w は、ェタントリイル基、プロパントリィル基又はブタントリィル基を表す。）で
Figure imgf000083_0004
(Wherein w represents an ethanetriyl group, a propanetriyl group or a butanetriyl group).
19 19
示される脂肪族トリカルボン酸無水物、又は一般式（130)、 (131)  Aliphatic tricarboxylic acid anhydride represented by the general formula (130), (131)
Figure imgf000084_0001
Figure imgf000084_0001
{式中、 W は、エチレンテトライル基又はブタンテトライル基を表し、 rは 1〜3の整数  {In the formula, W represents an ethylenetetrayl group or a butanetetrayl group, and r is an integer of 1 to 3.
20  20
を表す。但し、式（131)中、酸無水物基を形成する 4つのカルボキシル基は、酸無水 物基を形成できれば、シクロアルキル環の炭素のうち、何れの炭素に結合していても 良い。 }、式（132)若しくは（133)  Represents. However, in the formula (131), the four carboxyl groups forming the acid anhydride group may be bonded to any carbon of the cycloalkyl ring as long as the acid anhydride group can be formed. }, Formula (132) or (133)
Figure imgf000084_0002
Figure imgf000084_0002
で示される脂肪族テトラカルボン酸二無水物が挙げられる。  The aliphatic tetracarboxylic dianhydride shown by these is mentioned.
[0272] 一般式（126)〜（128)に於ける W 〜W としては、結合手又はカルボ-ル基がよ [0272] In general formulas (126) to (128), W to W may be a bond or a carbo group.
16 18  16 18
り好ましい。  More preferable.
[0273] 一般式（131)に於ける rは、通常 1〜3の整数を表し、中でも 2〜3の整数が好ましく 、その中でも 3がより好ましい。  [0273] In general formula (131), r usually represents an integer of 1 to 3, of which an integer of 2 to 3 is preferable, and of these, 3 is more preferable.
[0274] 式（123)で示される芳香族トリカルボン酸無水物としては、具体的には、例えば 1, 2, 3 ベンゼントリカルボン酸無水物、 1, 2, 4 ベンゼントリカルボン酸無水物（トリ メリット酸無水物）等が挙げられ、中でも 1, 2, 4 ベンゼントリカルボン酸無水物（トリ メリット酸無水物）が好ま U、。  [0274] Specific examples of the aromatic tricarboxylic acid anhydride represented by the formula (123) include 1, 2, 3 benzene tricarboxylic acid anhydride, 1, 2, 4 benzene tricarboxylic acid anhydride (trimellitic acid). Anhydride), among others, 1, 2, 4 Benzenetricarboxylic acid anhydride (trimellitic acid anhydride) is preferred.
[0275] 式（124)で示される芳香族テトラカルボン酸二無水物としては、具体的には、例え ば 1, 2, 3, 4 ベンゼンテトラカルボン酸二無水物、 1, 2, 4, 5 ベンゼンテトラ力 ルボン酸二無水物（ピロメリット酸二無水物）等が挙げられ、中でも 1, 2, 4, 5 ベン ゼンテトラカルボン酸二無水物（ピロメリット酸二無水物）が好まし!/、。  [0275] Specific examples of the aromatic tetracarboxylic dianhydride represented by the formula (124) include 1, 2, 3, 4 benzenetetracarboxylic dianhydride, 1, 2, 4, 5 Examples include benzenetetra force rubonic acid dianhydride (pyromellitic dianhydride), among which 1, 2, 4, 5 benzenetetracarboxylic dianhydride (pyromellitic dianhydride) is preferred! / ,.
[0276] 式（125)で示される芳香族テトラカルボン酸二無水物としては、具体的には、例え ば 1, 2, 3, 4 ナフタレンテトラカルボン酸二無水物、 1, 2, 5, 6 ナフタレンテトラ カルボン酸二無水物、 1, 2, 6, 7 ナフタレンテトラカルボン酸二無水物、 1, 2, 7, 8 ナフタレンテトラカルボン酸二無水物、 1, 4, 5, 8 ナフタレンテトラカルボン酸 二無水物、 2, 3, 6, 7 ナフタレンテトラカルボン酸二無水物等が挙げられ、中でも 1, 4, 5, 8 ナフタレンテトラカルボン酸二無水物、 2, 3, 6, 7 ナフタレンテトラ力 ルボン酸二無水物が好ましぐその中でも 1, 4, 5, 8 ナフタレンテトラカルボン酸二 無水物がより好ましい。 [0276] Specific examples of the aromatic tetracarboxylic dianhydride represented by the formula (125) include 1, 2, 3, 4 naphthalene tetracarboxylic dianhydride, 1, 2, 5, 6 Naphthalenetetra Carboxylic dianhydride, 1, 2, 6, 7 Naphthalene tetracarboxylic dianhydride, 1, 2, 7, 8 Naphthalene tetracarboxylic dianhydride, 1, 4, 5, 8 Naphthalene tetracarboxylic dianhydride 2, 3, 6, 7 naphthalene tetracarboxylic dianhydride, etc., among others 1, 4, 5, 8 naphthalene tetracarboxylic dianhydride, 2, 3, 6, 7 naphthalene tetra force rubonic acid dianhydride Among these, 1, 4, 5, 8 naphthalene tetracarboxylic dianhydride is more preferable.
[0277] 一般式（126)で示される芳香族テトラカルボン酸二無水物のうち、 W が結合手で  [0277] Of the aromatic tetracarboxylic dianhydrides represented by the general formula (126), W is a bond.
16  16
ある芳香族テトラカルボン酸二無水物としては、例えば 2, 3, 4, 5 ビフエニルテトラ カルボン酸二無水物、 2, 3, 5, 6 ビフエ-ルテトラカルボン酸二無水物等が挙げら れる。また、 W が酸素原子である芳香族テトラカルボン酸二無水物としては、例えば  Examples of the aromatic tetracarboxylic dianhydride include 2,3,4,5 biphenyltetracarboxylic dianhydride, 2,3,5,6 biphenyltetracarboxylic dianhydride, and the like. Examples of the aromatic tetracarboxylic dianhydride in which W is an oxygen atom include
16  16
2, 3, 4, 5 ビフエ-ルエーテルテトラカルボン酸二無水物、 2, 3, 5, 6 ビフエ- ルエーテルテトラカルボン酸二無水物等が挙げられる。さらに、 W がカルボ-ル基  2, 3, 4, 5 biphenyl ether tetracarboxylic dianhydride, 2, 3, 5, 6 biphenyl ether tetracarboxylic dianhydride, and the like. In addition, W is a carbo group.
16  16
である芳香族テトラカルボン酸二無水物としては、例えば 2, 3, 4, 5 べンゾフエノン テトラカルボン酸二無水物、 2, 3, 5, 6 べンゾフエノンテトラカルボン酸二無水物等 が挙げられる。さらにまた、 W がスルホニル基である芳香族テトラカルボン酸二無水  Examples of the aromatic tetracarboxylic dianhydride that is 2, 3, 4, 5 benzophenone tetracarboxylic dianhydride, 2, 3, 5, 6 benzophenone tetracarboxylic dianhydride, etc. It is done. Furthermore, aromatic tetracarboxylic dianhydride in which W is a sulfonyl group
16  16
物としては、例えば 2, 3, 4, 5 ビフエ-ルスルホンテトラカルボン酸二無水物、 2, 3 , 5, 6—ビフエニルスルホンテトラカルボン酸二無水物等が挙げられる。また、 W が  Examples of the product include 2,3,4,5 biphenylsulfonetetracarboxylic dianhydride, 2,3,5,6-biphenylsulfonetetracarboxylic dianhydride, and the like. W is
16 ビ-レン基である芳香族テトラカルボン酸二無水物としては、例えば cis— 2, 3, 4, 5 スチルベンテトラカルボン酸二無水物、 trans— 2, 3, 4, 5 スチルベンテトラカル ボン酸二無水物、 cis— 2, 3, 5, 6 スチルベンテトラカルボン酸二無水物、 trans— 2, 3, 5, 6 スチルベンテトラカルボン酸二無水物等が挙げられる。  Examples of aromatic tetracarboxylic dianhydrides that are 16 beylene groups include cis—2, 3, 4, 5 stilbene tetracarboxylic dianhydride, trans—2, 3, 4, 5 stilbene tetracarboxylic acid And dianhydride, cis-2,3,5,6 stilbenetetracarboxylic dianhydride, trans-2,3,5,6 stilbenetetracarboxylic dianhydride, and the like.
[0278] 一般式（127)で示される芳香族テトラカルボン酸無水物のうち、 W が結合手であ [0278] Of the aromatic tetracarboxylic anhydrides represented by the general formula (127), W is a bond.
17  17
る芳香族テトラカルボン酸無水物としては、例えば 2, 2' , 3, 4ービフエニルテトラ力 ルボン酸無水物、 2, 3, 3' , 4ービフエニルテトラカルボン酸無水物、 2, 3, 4, 4' ビフエ-ルテトラカルボン酸無水物、 2, 2' , 3, 5 ビフエ-ルテトラカルボン酸無水 物、 2, 3, 3，， 5 ビフエ-ルテトラカルボン酸無水物、 2, 3, 4，， 5 ビフエ-ルテト ラカルボン酸無水物、 2, 2' , 3, 6 ビフエ-ルテトラカルボン酸無水物、 2, 3, 3' , 6 ビフエ-ルテトラカルボン酸無水物、 2, 3, 4，， 6 ビフエ-ルテトラカルボン酸無 水物、 2, 2' , 4, 5—ビフエ-ルテ卜ラカルボン酸無水物、 2, 3，， 4, 5—ビフエ-ルテ トラカルボン酸無水物、 2, 4, 4' , 5—ビフエ-ルテトラカルボン酸無水物等が挙げら れる。また、 W が酸素原子である芳香族テトラカルボン酸無水物としては、例えば 2 Examples of aromatic tetracarboxylic acid anhydrides include 2,2 ', 3,4-biphenyltetracarboxylic rubonic acid anhydride, 2,3,3', 4-biphenyltetracarboxylic acid anhydride, 2,3 , 4, 4 'biphenyl tetracarboxylic acid anhydride, 2, 2', 3, 5 biphenyl tetracarboxylic acid anhydride, 2, 3, 3, 5, biphenyl tetracarboxylic acid anhydride, 2, 3, 4 ,, 5 Biphenyltetracarboxylic anhydride, 2, 2 ', 3, 6 Biphenyltetracarboxylic anhydride, 2, 3, 3', 6 Biphenyltetracarboxylic anhydride, 2, 3, 4 ,, 6 Biphenyl tetracarboxylic acid Water, 2, 2 ', 4, 5—biphenyl tetracarboxylic anhydride, 2, 3 ,, 4, 5—biphenyl tetracarboxylic anhydride, 2, 4, 4 ′, 5-biphenyl And tetratetracarboxylic acid anhydride. Examples of the aromatic tetracarboxylic acid anhydride in which W is an oxygen atom include 2
17  17
, 2' , 3, 4—ビフエ-ルエーテルテトラカルボン酸無水物、 2, 3, 3' , 4—ビフエ-ル エーテルテトラカルボン酸無水物、 2, 3, 4, 4'ービフエ-ルエーテルテトラカルボン 酸無水物、 2, 2' , 3, 5—ビフエ-ルエーテルテトラカルボン酸無水物、 2, 3, 3' , 5 ービフエ-ルエーテルテトラカルボン酸無水物、 2, 3, 4，， 5—ビフエ-ルエーテルテ トラカルボン酸無水物、 2, 2' , 3, 6—ビフエ-ルエーテルテトラカルボン酸無水物、 2, 3, 3' , 6—ビフエ-ルエーテルテトラカルボン酸無水物、 2, 3, 4' , 6—ビフエ- ルエーテルテトラカルボン酸無水物、 2, 2' , 4, 5—ビフエ-ルエーテルテトラカルボ ン酸無水物、 2, 3' , 4, 5—ビフエニルエーテルテトラカルボン酸無水物、 2, 4, 4' , 5—ビフエ-ルエーテルテトラカルボン酸無水物等が挙げられる。さらに、 W がカル  , 2 ', 3, 4-Biphenyl ether tetracarboxylic acid anhydride, 2, 3, 3', 4-Biphenyl ether tetracarboxylic acid anhydride, 2, 3, 4, 4'-biphenyl ether tetracarboxylic acid anhydride Anhydride, 2, 2 ', 3, 5-Biphenyl ether tetracarboxylic acid anhydride, 2, 3, 3', 5-Biphenyl ether tetracarboxylic acid anhydride, 2, 3, 4, 5, 5-biphenyl ether Tracarboxylic acid anhydride, 2, 2 ', 3, 6-biphenyl ether tetracarboxylic acid anhydride, 2, 3, 3', 6-biphenyl ether tetracarboxylic acid anhydride, 2, 3, 4 ', 6 —Biphenyl ether tetracarboxylic acid anhydride, 2, 2 ′, 4, 5—Biphenyl ether tetracarboxylic acid anhydride, 2, 3 ′, 4, 5—Biphenyl ether tetracarboxylic acid anhydride, 2, 4 4, 4 ', 5-biphenyl ether tetracarboxylic acid anhydride and the like. In addition, W
17 ボ-ル基である芳香族テトラカルボン酸無水物としては、例えば 2, 2' , 3, 4一べンゾ フエノンテトラカルボン酸無水物、 2, 3, 3' , 4一べンゾフエノンテトラカルボン酸無水 物、 2, 3, 4, 4'一べンゾフエノンテトラカルボン酸無水物、 2, 2' , 3, 5—べンゾフエ ノンテトラカルボン酸無水物、 2, 3, 3' , 5—べンゾフエノンテトラカルボン酸無水物、 2, 3, 4，， 5—ベンゾフエノンテトラカルボン酸無水物、 2, 2' , 3, 6—ベンゾフエノン テトラカルボン酸無水物、 2, 3, 3' , 6—べンゾフエノンテトラカルボン酸無水物、 2, 3 , 4，， 6—ベンゾフエノンテトラカルボン酸無水物、 2, 2' , 4, 5—ベンゾフエノンテトラ カルボン酸無水物、 2, 3' , 4, 5—べンゾフエノンテトラカルボン酸無水物、 2, 4, 4， , 5—べンゾフエノンテトラカルボン酸無水物等が挙げられる。さらにまた、 W がスル  17 Aromatic tetracarboxylic anhydrides that are ball groups include, for example, 2, 2 ', 3, 4 monobenzophenone tetracarboxylic anhydride, 2, 3, 3', 4 monobenzoic Enone tetracarboxylic acid anhydride, 2, 3, 4, 4 'Benzophenone tetracarboxylic acid anhydride, 2, 2', 3, 5-Benzophenone tetracarboxylic acid anhydride, 2, 3, 3 ' , 5—Benzophenone tetracarboxylic acid anhydride, 2, 3, 4, 5, 5-benzophenone tetracarboxylic acid anhydride, 2, 2 ′, 3, 6-benzophenone tetracarboxylic acid anhydride, 2, 3 , 3 ', 6-Benzophenone tetracarboxylic anhydride, 2, 3, 4, 6-benzophenone tetracarboxylic anhydride, 2, 2', 4, 5-benzophenone tetracarboxylic anhydride 2, 3, ′, 4,5-benzophenone tetracarboxylic acid anhydride, 2,4,4,5, benzophenone tetracarboxylic acid anhydride, and the like. Furthermore, W
17 ホニル基である芳香族テトラカルボン酸無水物としては、例えば 2, 2' , 3, 4ービフエ ニルスルホンテトラカルボン酸無水物、 2, 3, 3' , 4ービフエ-ルスルホンテトラカルボ ン酸無水物、 2, 3, 4, 4'ービフエ-ルスルホンテトラカルボン酸無水物、 2, 2' , 3, 5—ビフエ-ルスルホンテトラカルボン酸無水物、 2, 3, 3' , 5—ビフエ-ルスルホンテ トラカルボン酸無水物、 2, 3, 4' , 5—ビフエ-ルスルホンテトラカルボン酸無水物、 2 , 2' , 3, 6—ビフエ-ルスルホンテトラカルボン酸無水物、 2, 3, 3' , 6—ビフエ-ル スルホンテトラカルボン酸無水物、 2, 3, 4，， 6—ビフエ-ルスルホンテトラカルボン酸 無水物、 2, 2' , 4, 5 ビフエ-ルスルホンテトラカルボン酸無水物、 2, 3' , 4, 5— ビフエ-ルスルホンテトラカルボン酸無水物、 2, 4, 4，， 5 ビフエ-ルスルホンテトラ カルボン酸無水物等が挙げられる。また、 W がビ-レン基である芳香族テトラカルボ 17 Examples of aromatic tetracarboxylic anhydrides that are phonyl groups include 2,2 ', 3,4-biphenylsulfonetetracarboxylic anhydride, 2,3,3', 4-biphenylsulfonetetracarboxylic anhydride 2, 3, 4, 4'-biphenylsulfone tetracarboxylic anhydride, 2, 2 ', 3, 5-bisulfone tetracarboxylic anhydride, 2, 3, 3', 5-biphenyl Sulfonic acid tetrasulfuric anhydride, 2, 3, 4 ', 5-bisulfone tetracarboxylic anhydride, 2, 2', 3, 6-bisulfone tetracarboxylic anhydride, 2, 3, 3 ', 6-biphenyl sulfone tetracarboxylic anhydride, 2, 3, 4, 6, 6-bisulfone tetracarboxylic acid Anhydride, 2, 2 ', 4, 5 Biphenylsulfone tetracarboxylic acid anhydride, 2, 3', 4, 5-Biphenylsulfone tetracarboxylic acid anhydride, 2, 4, 4, 5, 5-biphenyl And rusulfone tetracarboxylic acid anhydride. In addition, aromatic tetracarbol, where W is a beylene group.
17  17
ン酸無水物としては、例えば cis— 2, 2' , 3, 4 スチルベンテトラカルボン酸無水物 、 trans - 2, 2' , 3, 4—スチルベンテトラカルボン酸無水物、 cis— 2, 3, 3，， 4ース チルベンテトラカルボン酸無水物、 trans— 2, 3, 3' , 4 スチルベンテトラカルボン 酸無水物、 cis - 2, 3, 4, 4，一スチルベンテトラカルボン酸無水物、 trans— 2, 3, 4 , 4，一スチルベンテトラカルボン酸無水物、 cis— 2, 2' , 3, 5 スチルペンテトラ力 ルボン酸無水物、 trans— 2, 2' , 3, 5 スチルベンテトラカルボン酸無水物、 cis— 2 , 3, 3' , 5 スチルベンテトラカルボン酸無水物、 trans— 2, 3, 3' , 5 スチルベン テトラカルボン酸無水物、 cis— 2, 3, 4' , 5 スチルベンテトラカルボン酸無水物、 tr ans- 2, 3, 4' , 5—スチルベンテトラカルボン酸無水物、 cis— 2, 2' , 3, 6—スチル ベンテトラカルボン酸無水物、 trans— 2, 2' , 3, 6 スチルベンテトラカルボン酸無 水物、 cis— 2, 3, 3，， 6 スチルベンテトラカルボン酸無水物、 trans— 2, 3, 3' , 6 スチルベンテトラカルボン酸無水物、 cis— 2, 3, 4，， 6 スチルペンテトラカルボ ン酸無水物、 trans— 2, 3, 4，， 6 スチルベンテトラカルボン酸無水物、 cis— 2, 2， , 4, 5 スチルベンテトラカルボン酸無水物、 trans— 2, 2' , 4, 5 スチルベンテト ラカルボン酸無水物、 cis— 2, 3' , 4, 5 スチルベンテトラカルボン酸無水物、 tran s- 2, 3' , 4, 5 スチルベンテトラカルボン酸無水物、 cis— 2, 4, 4' , 5 スチルベ ンテトラカルボン酸無水物、 trans— 2, 4, 4，， 5 スチルベンテトラカルボン酸無水 物等が挙げられる。 Examples of the acid anhydride include cis-2, 2 ', 3, 4 stilbene tetracarboxylic acid anhydride, trans-2, 2', 3, 4-stilbene tetracarboxylic acid anhydride, cis-2, 3, 3 ,, 4-stilbenetetracarboxylic anhydride, trans- 2, 3, 3 ', 4 stilbenetetracarboxylic anhydride, cis-2, 3, 4, 4, monostilbenetetracarboxylic anhydride, trans- 2, 3, 4, 4, monostilbene tetracarboxylic anhydride, cis— 2, 2 ′, 3, 5 stilpene tetraforce rubonic acid anhydride, trans— 2, 2 ′, 3, 5 stilbene tetracarboxylic anhydride Cis- 2, 3, 3 ', 5 stilbene tetracarboxylic acid anhydride, trans- 2, 3, 3', 5 stilbene tetracarboxylic acid anhydride, cis- 2, 3, 4 ', 5 stilbene tetracarboxylic acid Anhydride, tr ans- 2, 3, 4 ', 5-stilbenetetracarboxylic anhydride, cis- 2, 2', 3, 6-stilbenetetracarboxylic acid Water, trans— 2, 2 ', 3, 6 Stilbene tetracarboxylic acid Anhydrous, cis— 2, 3, 3, 6, 6 Stilbene tetracarboxylic anhydride, trans— 2, 3, 3', 6 Stilbene tetra Carboxylic anhydride, cis—2, 3, 4 ,, 6 Stilpene tetracarboxylic acid anhydride, trans—2, 3, 4 ,, 6 Stilbene tetracarboxylic acid anhydride, cis— 2, 2,, 4, 5 stilbene tetracarboxylic anhydride, trans— 2, 2 ', 4, 5 stilbene tetracarboxylic anhydride, cis— 2, 3', 4, 5 stilbene tetracarboxylic anhydride, tran s- 2, 3 ', 4,5 stilbene tetracarboxylic acid anhydride, cis-2, 4, 4 ', 5 stilbene tetracarboxylic acid anhydride, trans-2, 4, 4, 4, 5 stilbene tetracarboxylic acid anhydride.
一般式（128)で示される芳香族テトラカルボン酸二無水物のうち、 W が結合手で  Of the aromatic tetracarboxylic dianhydrides represented by the general formula (128), W is a bond.
18  18
ある芳香族テトラカルボン酸二無水物としては、例えば 2, 2' , 3, 3'—ビフエ二ルテト ラカルボン酸二無水物、 2, 3, 3' , 4'ービフエ-ルテトラカルボン酸二無水物、 3, 3， , 4, 4'ービフエ-ルテトラカルボン酸二無水物等が挙げられ、中でも 3, 3' , 4, 4' ビフエ-ルテトラカルボン酸二無水物が好ましい。また、 W が酸素原子である芳香 Some aromatic tetracarboxylic dianhydrides include, for example, 2, 2 ', 3, 3'-biphenyltetracarboxylic dianhydride, 2, 3, 3', 4'-biphenyl tetracarboxylic dianhydride 3,3,4,4'-biphenyltetracarboxylic dianhydride and the like, among which 3,3 ', 4,4'biphenyltetracarboxylic dianhydride is preferable. Also, the fragrance where W is an oxygen atom
18  18
族テトラカルボン酸二無水物としては、例えば 2, 2' , 3, 3'—ビフエ-ルエーテルテ トラカルボン酸二無水物、 2, 3, 3' , 4'ービフエ-ルエーテルテトラカルボン酸二無 水物、 3, 3' , 4, 4'ービフエ-ルエーテルテトラカルボン酸二無水物等が挙げられ、 中でも 3, 3' , 4, 4'ービフエ-ルエーテルテトラカルボン酸二無水物が好ましい。さ らに、 W 力カルボニル基である芳香族テトラカルボン酸二無水物としては、例えば 2Examples of the aliphatic tetracarboxylic dianhydrides include 2, 2 ′, 3, 3′-biphenyl ether tetracarboxylic dianhydride, 2, 3, 3 ′, 4′-biphenyl ether tetracarboxylic dianhydride. Water, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride and the like can be mentioned, among which 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride is preferable. Furthermore, examples of the aromatic tetracarboxylic dianhydride which is a W force carbonyl group include 2
18 18
, 2' , 3, 3，一ベンゾフエノンテトラカルボン酸二無水物、 2, 3, 3' , 4，一ベンゾフエノ ンテトラカルボン酸二無水物、 3, 3' , 4, 4，一べンゾフエノンテトラカルボン酸二無水 物等が挙げられ、中でも 3, 3' , 4, 4'一べンゾフエノンテトラカルボン酸二無水物が 好ましい。さらにまた、 W がスルホ-ル基である芳香族テトラカルボン酸二無水物と  , 2 ', 3, 3, monobenzophenone tetracarboxylic dianhydride, 2, 3, 3', 4, monobenzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4, monoben Examples include zophenone tetracarboxylic dianhydride, among which 3,3 ′, 4,4 ′ monobenzophenone tetracarboxylic dianhydride is preferable. Furthermore, an aromatic tetracarboxylic dianhydride in which W is a sulfole group and
18  18
しては、例えば 2, 2' , 3, 3，一ビフエ-ルスルホンテトラカルボン酸二無水物、 2, 3, 3' , 4，—ビフエ-ルスルホンテトラカルボン酸二無水物、 3, 3' , 4, 4，—ビフエ-ル スルホンテトラカルボン酸二無水物等が挙げられ、中でも 3, 3' , 4, 4'ービフエ-ル スルホンテトラカルボン酸二無水物が好ましい。また、 W がビ-レン基である芳香族  For example, 2, 2 ′, 3, 3, monobisulfone sulfone tetracarboxylic dianhydride, 2, 3, 3 ′, 4, biphenyl sulfone tetracarboxylic dianhydride, 3, 3 ′, 4,4, -biphenyl sulfonetetracarboxylic dianhydride and the like, and 3,3 ′, 4,4′-biphenyl sulfonetetracarboxylic dianhydride is preferable. An aromatic group in which W is a beylene group
18  18
テトラカルボン酸二無水物としては、例えば cis— 2, 2' , 3, 3' スチルペンテトラ力 ルボン酸二無水物、 trans— 2, 2' , 3, 3，一スチルベンテトラカルボン酸二無水物、 cis— 2, 3, 3，， 4，一スチルベンテトラカルボン酸二無水物、 trans— 2, 3, 3' , 4，一 スチルベンテトラカルボン酸二無水物、 cis— 3, 3' , 4, 4，一スチルペンテトラカルボ ン酸ニ無水物、 trans— 3, 3' , 4, 4' スチルベンテトラカルボン酸二無水物等が挙 げられ、中でも cis— 3, 3，， 4, 4，一スチルベンテトラカルボン酸二無水物、 trans— 3, 3' , 4, 4' スチルベンテトラカルボン酸二無水物が好ましい。  Examples of tetracarboxylic dianhydrides include cis-2,2 ', 3,3' stilpene tetra force rubonic acid dianhydride, trans-2,2 ', 3,3, monostilbenetetracarboxylic dianhydride Cis-2,3,3,4,1 stilbenetetracarboxylic dianhydride, trans-2,3,3'4,1 stilbenetetracarboxylic dianhydride, cis-3,3'4,4 4, monostilpenetetracarboxylic dianhydride, trans-3,3 ', 4,4' stilbenetetracarboxylic dianhydride, etc., among which cis- 3,3,4,4,1 Stilbene tetracarboxylic dianhydride, trans-3,3 ', 4,4' stilbene tetracarboxylic dianhydride is preferred.
[0280] 上記芳香族テトラカルボン酸無水物のうち、式（124)又は一般式（128)で示される ものが好ましぐ中でも式（124)又は一般式（128)に於ける W が結合手若しくは力 [0280] Among the aromatic tetracarboxylic acid anhydrides, those represented by the formula (124) or the general formula (128) are preferred, and W in the formula (124) or the general formula (128) is a bond. Or force
18  18
ルボニル基であるものがより好まし 、。  More preferred are those which are rubonyl groups.
[0281] 一般式（129)で示される脂肪族トリカルボン酸無水物のうち、 W がエタントリィル  [0281] Of the aliphatic tricarboxylic acid anhydrides represented by the general formula (129), W represents ethanetril.
19  19
基である脂肪族トリカルボン酸無水物としては、例えばェタントリカルボン酸無水物等 が挙げられる。また、 w がプロパントリィル基である脂肪族トリカルボン酸無水物とし  Examples of the aliphatic tricarboxylic acid anhydride as a group include ethanetricarboxylic acid anhydride. In addition, an aliphatic tricarboxylic acid anhydride in which w is a propanetriyl group is used.
19  19
ては、例えばプロパントリカルボン酸無水物等が挙げられる。さらに、 w がブタントリ  Examples thereof include propanetricarboxylic acid anhydride. Furthermore, w is a butterfly
19 ィル基である脂肪族トリカルボン酸無水物としては、例えばブタントリカルボン酸無水 物等が挙げられる。  Examples of the aliphatic tricarboxylic acid anhydride which is a 19-yl group include butanetricarboxylic acid anhydride.
[0282] 一般式（130)で示される脂肪族テトラカルボン酸二無水物のうち、 W がエチレン テトライル基である脂肪族テトラカルボン酸二無水物としては、例えばエチレンテトラ カルボン酸二無水物等が挙げられる。また、 W がブタンテトライル基である脂肪族テ [0282] Of the aliphatic tetracarboxylic dianhydrides represented by the general formula (130), W represents ethylene Examples of the aliphatic tetracarboxylic dianhydride that is a tetrayl group include ethylene tetracarboxylic dianhydride. In addition, an aliphatic te which W is a butanetetrayl group.
20  20
トラカルボン酸二無水物としては、例えばブタンテトラカルボン酸二無水物等が挙げ られる。  Examples of tracarboxylic dianhydride include butanetetracarboxylic dianhydride.
[0283] 一般式（131)で示される脂肪族テトラカルボン酸二無水物としては、通常 rが 1〜3 の整数、好ましくは 2〜3の整数、より好ましくは 3である脂肪族テトラカルボン酸二無 水物が挙げられ、具体的には、例えばシクロブタンテトラカルボン酸二無水物、シクロ ペンタンテトラカルボン酸二無水物、シクロへキサンテトラカルボン酸二無水物等が 挙げられ、中でもシクロペンタンテトラカルボン酸二無水物、シクロへキサンテトラカル ボン酸二無水物が好ましぐその中でもシクロへキサンテトラカルボン酸二無水物が より好まし 、。  [0283] The aliphatic tetracarboxylic dianhydride represented by the general formula (131) is usually an aliphatic tetracarboxylic acid in which r is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3. Specific examples include cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, and the like. Of these, acid dianhydride and cyclohexanetetracarboxylic dianhydride are preferred, and cyclohexanetetracarboxylic dianhydride is more preferred.
[0284] 式（132)で示される脂肪族テトラカルボン酸二無水物としては、 4一（1, 2 ジカル ボキシェチル） 1, 2, 3, 4ーテトラヒドロナフタレン 1, 2 ジカルボン酸二無水物 が挙げられる。  [0284] Examples of the aliphatic tetracarboxylic dianhydride represented by the formula (132) include 4- (1,2 dicarboxetyl) 1, 2, 3, 4-tetrahydronaphthalene 1,2 dicarboxylic dianhydride. It is done.
[0285] 式（133)で示される脂肪族テトラカルボン酸二無水物としては、 5—（1, 2 ジカル ボキシェチル）ー3—メチルシクロへキサン— 1, 2 ジカルボン酸二無水物が挙げら れる。  [0285] Examples of the aliphatic tetracarboxylic dianhydride represented by the formula (133) include 5- (1,2 dicarboxetyl) -3-methylcyclohexane-1,2 dicarboxylic dianhydride.
[0286] 上記脂肪族テトラカルボン酸二無水物のうち、式（132)又は（133)で示されるもの が好ましぐ中でも式（132)で示されるものがより好ましい。  Among the aliphatic tetracarboxylic dianhydrides, those represented by the formula (132) or (133) are preferred, and those represented by the formula (132) are more preferred.
[0287] また、上記芳香族又は脂肪族カルボン酸無水物のうちのカルボキシル基は、上記 一般式（37)で示されるカルボン酸エステルとなっていても良ぐ該カルボン酸エステ ルを有する化合物は、市販のものを用いる力 例えば上記一般式（99)〜（109)で 示される芳香族又は脂肪族カルボン酸にメタノール、エタノール等のアルコールを作 用させた後、分子内脱水又は分子内脱アルコール縮合等の一般的な方法により合 成したものを適宜用いれば良 、。  [0287] Further, the compound having the carboxylic acid ester in which the carboxyl group in the aromatic or aliphatic carboxylic acid anhydride may be a carboxylic acid ester represented by the general formula (37) is The ability to use commercially available products For example, after causing the aromatic or aliphatic carboxylic acid represented by the general formulas (99) to (109) to work with alcohols such as methanol and ethanol, intramolecular dehydration or intramolecular dealcoholization A compound synthesized by a general method such as condensation may be used as appropriate.
[0288] 一般式（35)又は（36)で示されるカルボキシル基を 3個以上有する多塩基酸無水 物 (カルボキシル基の一部が脱水縮合して酸無水物基を形成しているものを含み、ま た、その一部がカルボン酸エステルであるものを含む。）の当量としては、一般式（23 )で示される化合物に対して、通常 0. 5〜2当量が挙げられる。 [0288] Polybasic acid anhydrides having three or more carboxyl groups represented by the general formula (35) or (36) (including those in which part of the carboxyl groups is condensed by dehydration to form an acid anhydride group) In addition, as an equivalent of a part of which is a carboxylic acid ester, the general formula (23 ) Is usually 0.5 to 2 equivalents.
[0289] [ IX ]法に於ける反応温度は、一般式（23)で示される化合物に於けるヒドロキシル 基及び Z又はアミノ基 (これらのアルカリ金属塩を含む。）と、一般式（35)又は（36) で示されるカルボキシル基を 3個以上有する多塩基酸無水物（カルボキシル基の一 部が脱水縮合して酸無水物基を形成しているものを含み、また、その一部がカルボ ン酸エステルであるものを含む。）に於ける酸無水物基とが定量的に反応するような 温度であれば、特に限定されないが、例えば通常 60〜120°C、好ましくは 70〜90 °Cである。反応温度が 60°C未満では反応の進行が遅ぐ未反応の一般式（23)で示 される化合物及び該多塩基酸無水物が残存する恐れがあるので好ましくない等の問 題を生ずる。 [0289] The reaction temperature in the method [IX] is the hydroxyl group and the Z or amino group (including these alkali metal salts) in the compound represented by the general formula (23), and the general formula (35). Or a polybasic acid anhydride having three or more carboxyl groups represented by (36) (including those in which a part of the carboxyl groups is condensed by dehydration to form an acid anhydride group; In particular, the temperature is such that it can quantitatively react with the acid anhydride group in the acid ester group). However, for example, it is usually 60 to 120 ° C, preferably 70 to 90 °. C. If the reaction temperature is less than 60 ° C., the reaction proceeds slowly and the unreacted compound represented by the general formula (23) and the polybasic acid anhydride may remain.
[0290] [ IX ]法に於ける反応時間は、一般式（21)に於ける重合度 kが適切な範囲となる ように、即ち、一般式 (21)で示される構成単位を含んで成る化合物の重量平均分子 量が適切な範囲となるように、反応時間を決定すれば良い。当該反応時間は、反応 に用いられる多塩基酸無水物（その一部が無水物であるものを含み、また、その一部 力 Sカルボン酸エステルであるものを含む。）の当量や反応温度に依存するため、ー概 には言えないが、通常 0. 25〜50時間、好ましくは 0. 25〜15時間、より好ましくは 0 . 5〜8時間の範囲に設定される。  [0290] The reaction time in the method [IX] is such that the degree of polymerization k in the general formula (21) falls within an appropriate range, that is, comprises the structural unit represented by the general formula (21). The reaction time may be determined so that the weight average molecular weight of the compound falls within an appropriate range. The reaction time depends on the equivalent of the polybasic acid anhydride used in the reaction (including a part of which is an anhydride and part of which is a force S carboxylic acid ester) and the reaction temperature. Therefore, although it cannot be generally said, it is usually set in the range of 0.25 to 50 hours, preferably 0.25 to 15 hours, more preferably 0.5 to 8 hours.
[0291] [ IX ]法に於ける溶媒は、上記 [ III ]法と同様の溶媒を用いれば良ぐ溶媒の使用 量は、原料を溶解し得る量であれば特に限定されな 、。  [0291] The solvent used in the method [IX] is not particularly limited as long as the solvent used in the method [III] is the same as that used in the method [III] as long as the raw material can be dissolved.
[0292] [ IX ]法に於いて、一般式（23)で示される化合物と、一般式（35)又は（36)で示さ れるカルボキシル基を 3個以上有する多塩基酸無水物（カルボキシル基の一部が脱 水縮合して酸無水物基を形成しているものを含み、また、その一部がカルボン酸エス テルであるものを含む。）とが定量的かつスムーズに反応するように触媒を使用するこ とが好ましい。これらの触媒としては、例えばトリェチルァミン、ピリジン、ジメチルァミノ ピリジン等の三級アミン等や、例えばテトラプチルアンモ -ゥムクロライド、テトラプチ ルアンモ -ゥムブロマイド、トリェチルベンジルアンモ-ゥムクロライド、トリェチルベン ジルアンモ -ゥムブロマイド等の四級アンモ-ゥム塩や、例えばトリフエ-ルホスフィン 等の有機ホスフィンィ匕合物等の触媒が挙げられる。これらの触媒は、夫々単独で又 は 2種以上を組み合わせて用いられ、上記触媒の使用量は、特に限定されないが、 一般式（23)で示される化合物の mol量に対して、 0. 001mol%以上が挙げられ、反 応速度を向上させる為に、 200mol%程度使用することもある。 [0292] In the method [IX], a compound represented by the general formula (23) and a polybasic acid anhydride having three or more carboxyl groups represented by the general formula (35) or (36) (carboxyl group Some of them are dehydrated and condensed to form acid anhydride groups, and some of them are carboxylic acid esters. Is preferably used. These catalysts include, for example, tertiary amines such as triethylamine, pyridine, dimethylaminopyridine and the like, and quaternary ammonia such as tetraptylammonum chloride, tetrabutylammonium bromide, triethylbenzylammonum chloride, triethylbenzilammoumum bromide and the like. Examples thereof include a catalyst such as a humic salt or an organic phosphine compound such as triphenylphosphine. These catalysts can be used alone or Is used in combination of two or more, and the amount of the catalyst used is not particularly limited, but is 0.001 mol% or more based on the mol amount of the compound represented by the general formula (23), and the reaction rate About 200 mol% may be used to improve the quality.
[0293] [ IX ]法で示される製造方法のより詳細な具体例としては、例えば下記 [ XIII ]法 [0293] Specific examples of the production method shown by the [IX] method include, for example, the following [XIII] method.
Figure imgf000091_0001
Figure imgf000091_0001
(136)  (136)
(式中、 R1 R2、 R 、 R2，、 T、 T、 U、 V、 V、 Z及び kは上記に同じ。）で示される (Wherein R 1 R 2 , R, R 2 , T, T, U, V, V, Z and k are the same as above)
1 2 1 2 2  1 2 1 2 2
ものが挙げられる。  Things.
[0294] 尚、一般式（134)で示される化合物は、一般式（13)に於ける R1C>が一般式（15)で あり、且つ、 Vが酸素原子、 Mが水素原子であり、 R11が一般式（17)であり、且つ、 [0294] In the compound represented by the general formula (134), R 1C> in the general formula (13) is the general formula (15), V is an oxygen atom, and M is a hydrogen atom. R 11 is the general formula (17), and
3 1  3 1
Vが酸素原子、 Mが水素原子である場合に相当する。一般式（135)で示される化 This corresponds to the case where V is an oxygen atom and M is a hydrogen atom. Formula shown by general formula (135)
4 2 4 2
合物は、カルボキシル基を 3個以上有する多塩基酸無水物（カルボキシル基の一部 が脱水縮合して酸無水物基を形成しているものを含み、また、その一部がカルボン 酸エステルであるものを含む。）を 4ー（1, 2 ジカルボキシェチル） 1, 2, 3, 4 テトラヒドロナフタレン 1 , 2 ジカルボン酸二無水物 {上記式（132)で示される脂 肪族テトラカルボン酸二無水物 }に限定した場合に相当する。一般式（136)で示さ れる構成単位を含んで成る化合物は、一般式（7)に於ける R3'及び R4'がカルボキシ ル基であり、 Y '及び Y 'が酸素原子であり、 Zで示される 4価の炭化水素基を、上記 The compound includes a polybasic acid anhydride having three or more carboxyl groups (including one in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group, and a part of the carboxyl group is a carboxylate ester. 4- (1,2 dicarboxyethyl) 1, 2, 3, 4 tetrahydronaphthalene 1,2 dicarboxylic dianhydride {aliphatic tetracarboxylic acid represented by the above formula (132) This corresponds to the case of limiting to dianhydride}. In the compound comprising the structural unit represented by the general formula (136), R 3 ′ and R 4 ′ in the general formula (7) are carboxyl groups, Y ′ and Y ′ are oxygen atoms, The tetravalent hydrocarbon group represented by Z
1 2  1 2
式 (32)で示される脂肪族系の 4価の炭化水素基に限定し、 a及び bが 1である場合に 相当する。  This is limited to the aliphatic tetravalent hydrocarbon group represented by the formula (32), and corresponds to the case where a and b are 1.
[0295] 上記 [ IX ]法に於いて、一般式（35)又は（36)で示されるカルボキシル基を 3個以 上有する多塩基酸無水物 (カルボキシル基の一部が脱水縮合して酸無水物基を形 成しているものを含み、また、その一部がカルボン酸エステルであるものを含む。）以 外に、一般式（23)で示される化合物と重合することのできる化合物を用いることがで き、具体的には、例えば一般式（58)で示される 2個のカルボキシル基を有する芳香 族又は脂肪族カルボン酸無水物（芳香族又は脂肪族ジカルボン酸無水物）を用いる 方法としては、下記 [ XIV ]法 [0295] In the above-mentioned [IX] method, a polybasic acid anhydride having three or more carboxyl groups represented by the general formula (35) or (36) Including those that form a physical group, and some of which are carboxylic esters.) In addition, a compound that can be polymerized with the compound represented by the general formula (23) can be used. Specifically, for example, an aromatic compound having two carboxyl groups represented by the general formula (58) or As a method using an aliphatic carboxylic acid anhydride (aromatic or aliphatic dicarboxylic acid anhydride), the following [XIV] method
(式中(In the formula
Figure imgf000092_0001
Figure imgf000092_0001
、 Z'、 a、 b、 k'及び k' 'は上記に同じ。）で示されるものが挙げられる。  , Z ′, a, b, k ′ and k ′ ′ are the same as above. ).
一般式（58)で示される 2個のカルボキシル基を有する芳香族又は脂肪族カルボン 酸無水物（芳香族又は脂肪族ジカルボン酸無水物）としては、具体的には、例えば 式（138)〜（140)
Figure imgf000092_0002
Specific examples of the aromatic or aliphatic carboxylic acid anhydride (aromatic or aliphatic dicarboxylic acid anhydride) having two carboxyl groups represented by the general formula (58) include, for example, formulas (138) to (138)-( 140)
Figure imgf000092_0002
{但し、式（139)中、酸無水物基を形成する 2つのカルボキシル基は、酸無水物基を 形成できれば、ナフタレン環の 1〜8位の炭素のうち、何れの炭素に結合していても 良い。 }、若しくは一般式（141)
Figure imgf000093_0001
{However, in the formula (139), the two carboxyl groups that form an acid anhydride group are bonded to any of the carbons 1 to 8 of the naphthalene ring as long as they can form an acid anhydride group. Also good. } Or general formula (141)
Figure imgf000093_0001
(式中、 w は、結合手、酸素原子、カルボ-ル基、スルホ -ル基又はビ-レン基を  (W in the formula, w represents a bond, an oxygen atom, a carbonyl group, a sulfol group or a beylene group.
21  twenty one
表す。）で示される芳香族ジカルボン酸無水物、又は一般式（142)、 (143)
Figure imgf000093_0002
To express. ) Aromatic dicarboxylic acid anhydride represented by the general formula (142), (143)
Figure imgf000093_0002
{式中、 W は、結合手、炭素数 1〜18の直鎖状アルキレン基、ビニレン基、 2, 3—  {Wherein W is a bond, a linear alkylene group having 1 to 18 carbon atoms, vinylene group, 2, 3—
22  twenty two
プロべ-レン基（ 1 プロペン 2, 3 ジィル基）又は 2 ォキソトリメチレン基を表し 、 sは 1〜3の整数を表す。但し、式（143)中、酸無水物基を形成する 2つのカルボキ シル基は、酸無水物基を形成できれば、シクロアルキル環の炭素のうち、何れの炭素 に結合していても良い。 }、若しくは式（144)
Figure imgf000093_0003
A propylene group (1 propene 2,3 diyl group) or a 2-oxotrimethylene group, and s represents an integer of 1 to 3. However, in the formula (143), the two carboxy groups forming the acid anhydride group may be bonded to any carbon of the cycloalkyl ring as long as the acid anhydride group can be formed. } Or formula (144)
Figure imgf000093_0003
(式中、酸無水物基を形成する 2つのカルボキシル基は、酸無水物基を形成できれ ば、シクロへキセン環の炭素のうち、何れの炭素に結合していても良い。）で示される 脂肪族ジカルボン酸無水物が挙げられる。  (Wherein the two carboxyl groups forming the acid anhydride group may be bonded to any carbon of the cyclohexene ring as long as the acid anhydride group can be formed). And aliphatic dicarboxylic acid anhydrides.
[0297] 一般式（141)に於ける W としては、結合手又はカルボニル基がより好ましい。 [0297] In general formula (141), W is more preferably a bond or a carbonyl group.
21  twenty one
[0298] 一般式（142)に於ける W としては、結合手、炭素数 1〜18の直鎖状アルキレン基  [0298] In general formula (142), W represents a bond, a linear alkylene group having 1 to 18 carbon atoms.
22  twenty two
又はビ-レン基がより好ましぐその中でもビ-レン基がさらに好ましい。  Of these, a beylene group is more preferable, among which a beylene group is more preferable.
[0299] 一般式（143)に於ける sは、通常 1〜3の整数を表し、中でも 2〜3の整数が好ましく[0299] In general formula (143), s usually represents an integer of 1 to 3, and preferably an integer of 2 to 3
、その中でも 3がより好ましい。 Of these, 3 is more preferred.
[0300] 式（138)で示される芳香族ジカルボン酸無水物としては、具体的には、例えばフタ ル酸無水物等が挙げられる。 [0300] Specific examples of the aromatic dicarboxylic acid anhydride represented by the formula (138) include phthalic acid anhydride.
[0301] 式（139)で示される芳香族ジカルボン酸無水物としては、具体的には、例えば 1, 2 ナフタレンジカルボン酸無水物、 1, 8 ナフタレンジカルボン酸無水物、 2, 3 ナ フタレンジカルボン酸無水物等が挙げられる。 [0301] Specific examples of the aromatic dicarboxylic acid anhydride represented by the formula (139) include 1, 2 naphthalene dicarboxylic acid anhydride, 1, 8 naphthalene dicarboxylic acid anhydride, 2, 3 Examples thereof include phthalenedicarboxylic anhydride.
[0302] 式（140)で示される芳香族ジカルボン酸無水物としては、具体的には、例えば 2, 3 ピリジンジカルボン酸無水物、 3, 4—ピリジンジカルボン酸無水物等が挙げられる  [0302] Specific examples of the aromatic dicarboxylic acid anhydride represented by the formula (140) include 2,3 pyridinedicarboxylic acid anhydride, 3,4-pyridinedicarboxylic acid anhydride, and the like.
[0303] 一般式（141)で示される芳香族ジカルボン酸無水物のうち、 W が結合手である芳 [0303] Of the aromatic dicarboxylic acid anhydrides represented by the general formula (141), W is a bond.
21  twenty one
香族ジカルボン酸無水物としては、例えば 2, 3 ビフヱ-ルジカルボン酸無水物、 3 , 4 ビフヱニルジカルボン酸無水物等が挙げられる。また、 W が酸素原子である  Examples of the aromatic dicarboxylic acid anhydride include 2,3 biphenyl dicarboxylic acid anhydride, 3,4 biphenyl dicarboxylic acid anhydride, and the like. W is an oxygen atom
21  twenty one
芳香族ジカルボン酸無水物としては、例えば 2, 3 ビフエ-ルエーテルジカルボン 酸無水物、 3, 4ービフ -ルエーテルジカルボン酸無水物等が挙げられる。さらに、 W がカルボ-ル基である芳香族ジカルボン酸無水物としては、例えば 2, 3 ベン Examples of the aromatic dicarboxylic acid anhydride include 2,3-biphenyl ether dicarboxylic acid anhydride, 3,4-biphenyl ether dicarboxylic acid anhydride, and the like. Further, examples of the aromatic dicarboxylic acid anhydride in which W is a carbo group include 2,3
21 twenty one
ゾフエノンジカルボン酸無水物、 3, 4—ベンゾフヱノンジカルボン酸無水物等が挙げ られる。さらにまた、 W がスルホ-ル基である芳香族ジカルボン酸無水物としては、  Examples include zophenone dicarboxylic acid anhydride and 3,4-benzophenone dicarboxylic acid anhydride. Furthermore, as an aromatic dicarboxylic acid anhydride in which W is a sulfol group,
21  twenty one
例えば 2, 3 ビフエ-ルスルホンジカルボン酸無水物、 3, 4 ビフエ-ルスルホンジ カルボン酸無水物等が挙げられる。また、 W がビ-レン基である芳香族ジカルボン  Examples thereof include 2,3 bisulfone dicarboxylic acid anhydride, 3,4 biphenyl sulfone dicarboxylic acid anhydride, and the like. Aromatic dicarboxylic acids in which W is a beylene group
21  twenty one
酸無水物としては、例えば cis— 2, 3 スチルベンジカルボン酸無水物、 trans— 2, 3—スチルベンジカルボン酸無水物、 cis— 3, 4—スチルベンジカルボン酸無水物、 t rans- 3, 4 スチルベンジカルボン酸無水物等が挙げられる。  Examples of the acid anhydride include cis-2,3 stilbene dicarboxylic acid anhydride, trans-2,3-stilbene dicarboxylic acid anhydride, cis-3,4-stilbene dicarboxylic acid anhydride, t rans-3,4 stilbene dicarboxylic acid An acid anhydride etc. are mentioned.
[0304] 上記芳香族ジカルボン酸無水物のうち、式（138)で示されるものが好ましい。 [0304] Of the aromatic dicarboxylic acid anhydrides, those represented by the formula (138) are preferred.
[0305] 一般式（142)で示される脂肪族ジカルボン酸無水物のうち、 W が結合手である脂 [0305] Of the aliphatic dicarboxylic acid anhydrides represented by the general formula (142), a fat wherein W is a bond
22  twenty two
肪族ジカルボン酸無水物としては、シユウ酸無水物等が挙げられる。また、 w が炭  Examples of the aliphatic dicarboxylic acid anhydride include oxalic acid anhydride. W is charcoal
22 素数 1〜18の直鎖状アルキレン基である脂肪族ジカルボン酸無水物としては、例え ばマロン酸無水物、コハク酸無水物、グルタル酸無水物、アジピン酸無水物、ピメリン 酸無水物、スベリン酸無水物、ァゼライン酸無水物、セバシン酸無水物、 1, 10—デ カンジカルボン酸無水物、 1, 18—ォクタデカンジカルボン酸無水物等が挙げられ、 中でも、マロン酸無水物、コハク酸無水物、グルタル酸無水物、アジピン酸無水物、 ピメリン酸無水物、スベリン酸無水物、ァゼライン酸無水物、セバシン酸無水物、 1, 1 0—デカンジカルボン酸無水物が好ましぐその中でもマロン酸無水物、コハク酸無 水物、グルタル酸無水物、アジピン酸無水物、ピメリン酸無水物、スベリン酸無水物 力 り好ましい。さらに、 W 力 、二レン基である脂肪族ジカルボン酸無水物としては 22 Examples of the aliphatic dicarboxylic acid anhydride which is a linear alkylene group having 1 to 18 primes include malonic acid anhydride, succinic acid anhydride, glutaric acid anhydride, adipic acid anhydride, pimelic acid anhydride, and suberin. Acid anhydride, azelaic acid anhydride, sebacic acid anhydride, 1,10-decanedicarboxylic acid anhydride, 1,18-octadecanedicarboxylic acid anhydride, etc., among which malonic acid anhydride, succinic acid Anhydride, glutaric acid anhydride, adipic acid anhydride, pimelic acid anhydride, suberic acid anhydride, azelaic acid anhydride, sebacic acid anhydride, 1, 10-decane dicarboxylic acid anhydride is preferred among them Acid anhydride, succinic acid anhydrous, glutaric acid anhydride, adipic acid anhydride, pimelic acid anhydride, suberic acid anhydride It is preferable. In addition, as W power, aliphatic dicarboxylic acid anhydride which is diene group,
22  twenty two
、例えばマレイン酸無水物等が挙げられる。さらにまた、 W が 2, 3—プロべ-レン基  Examples thereof include maleic anhydride. Furthermore, W is a 2,3-probelen group.
22  twenty two
(1 プロペン 2, 3 ジィル基)である脂肪族ジカルボン酸無水物としては、例えば ィタコン酸無水物等が挙げられる。また、 W 力 ¾一才キソトリメチレン基である脂肪族  Examples of the aliphatic dicarboxylic acid anhydride (1 propene 2,3 diyl group) include itaconic acid anhydride. In addition, W power ¾-year-old aliphatic that is xisotrimethylene group
22  twenty two
ジカルボン酸無水物としては、例えば 1, 3 アセトンジカルボン酸無水物等が挙げら れる。  Examples of the dicarboxylic acid anhydride include 1,3 acetone dicarboxylic acid anhydride.
[0306] 一般式（143)で示される脂肪族ジカルボン酸無水物としては、通常 sが 1〜3の整 数、好ましくは 2〜3の整数、より好ましくは 3である脂肪族ジカルボン酸無水物が挙 げられ、具体的には、例えば 1, 2—シクロブタンジカルボン酸無水物、 1, 2—シクロ ペンタンジカルボン酸無水物、 1, 2—シクロへキサンジカルボン酸無水物等が挙げ られ、中でも 1, 2—シクロペンタンジカルボン酸無水物、 1, 2—シクロへキサンジカ ルボン酸無水物が好ましぐその中でも 1, 2—シクロへキサンジカルボン酸無水物が より好まし 、。  [0306] The aliphatic dicarboxylic acid anhydride represented by the general formula (143) is usually an aliphatic dicarboxylic acid anhydride in which s is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3. Specific examples include 1,2-cyclobutanedicarboxylic acid anhydride, 1,2-cyclopentanedicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, and the like. 1,2-cyclopentanedicarboxylic acid anhydride and 1,2-cyclohexanedicarboxylic acid anhydride are preferred, and 1,2-cyclohexanedicarboxylic acid anhydride is more preferred.
[0307] 式（144)で示される脂肪族ジカルボン酸無水物としては、具体的には、例えば cis  [0307] Specific examples of the aliphatic dicarboxylic acid anhydride represented by the formula (144) include cis
1, 2, 3, 6—テトラヒドロフタル酸無水物、 3, 4, 5, 6—テトラヒドロフタル酸無水物 等が挙げられ、中でも cis— 1, 2, 3, 6—テトラヒドロフタル酸無水物が好ましい。  1, 2, 3, 6-tetrahydrophthalic anhydride, 3, 4, 5, 6-tetrahydrophthalic anhydride, and the like. Among them, cis-1, 2, 3, 6-tetrahydrophthalic anhydride is preferable. .
[0308] 上記脂肪族ジカルボン酸無水物のうち、一般式（142)又は式（144)で示されるも のが好ましぐ中でも一般式（142)に於ける W がビ-レン基であるもの、又は式（14  [0308] Among the above aliphatic dicarboxylic acid anhydrides, those represented by general formula (142) or formula (144) are preferred, and W in general formula (142) is a beylene group. Or formula (14
22  twenty two
4)で示されるものがより好まし 、。  The one shown in 4) is more preferable.
[0309] [ XIV ]法に於いて、一般式（35)又は（36)で示されるカルボキシル基を 3個以上 有する多塩基酸無水物 (カルボキシル基の一部が脱水縮合して酸無水物基を形成 しているものを含み、また、その一部がカルボン酸エステルであるものを含む。）と、一 般式（58)で示される 2個のカルボキシル基を有する芳香族又は脂肪族カルボン酸 無水物（芳香族又は脂肪族ジカルボン酸無水物）を併用する場合に於ける、これらの モル比のうち、上記テトラカルボン酸無水物と上記ジカルボン酸無水物を併用する場 合のモル比は、通常 10 : 90〜99 : 1、好ましくは 40 : 60〜99 : 1である。テトラカルボ ン酸無水物の割合が全酸の 10モル％未満である場合、得られる化合物の酸価及び 分子量が小さくなり、例えば当該化合物力 得られる榭脂組成物を用いてカラーフィ ルターを製造する場合には、微細パターンを形成するのが困難になり、また、耐熱性 または耐溶剤性に問題が生じる恐れがあるため、好ましくない等の問題を生ずる。 [0309] In the method [XIV], a polybasic acid anhydride having three or more carboxyl groups represented by the general formula (35) or (36) (a part of the carboxyl groups is dehydrated and condensed to form an acid anhydride group) And a part of which is a carboxylic acid ester) and an aromatic or aliphatic carboxylic acid having two carboxyl groups represented by the general formula (58) Among these molar ratios when an anhydride (aromatic or aliphatic dicarboxylic acid anhydride) is used in combination, the molar ratio when the tetracarboxylic acid anhydride and the dicarboxylic acid anhydride are used together is as follows: Usually 10:90 to 99: 1, preferably 40:60 to 99: 1. When the proportion of tetracarboxylic acid anhydride is less than 10 mol% of the total acid, the acid value and molecular weight of the resulting compound are reduced. When producing a filter, it is difficult to form a fine pattern, and there is a risk of problems in heat resistance or solvent resistance.
[0310] [ XIV ]法に於いて、一般式（35)又は（36)で示されるカルボキシル基を 3個以上 有する多塩基酸無水物 (カルボキシル基の一部が脱水縮合して酸無水物基を形成 しているものを含み、また、その一部がカルボン酸エステルであるものを含む。）と、一 般式（58)で示される 2個のカルボキシル基を有する芳香族又は脂肪族カルボン酸 無水物（芳香族又は脂肪族ジカルボン酸無水物）の併用方法としては、これらを混合 したものを一般式（23)で示される化合物を含む溶液に加えて、一挙に反応させても 良!、し、これらを別々及び段階的に反応させても良!、。  [0310] In the method [XIV], a polybasic acid anhydride having three or more carboxyl groups represented by the general formula (35) or (36) (an acid anhydride group formed by dehydration condensation of a part of the carboxyl groups) And a part of which is a carboxylic acid ester) and an aromatic or aliphatic carboxylic acid having two carboxyl groups represented by the general formula (58) As a method of using an anhydride (aromatic or aliphatic dicarboxylic acid anhydride) in combination, a mixture of these may be added to a solution containing the compound represented by the general formula (23) and reacted at once. However, these may be reacted separately and step by step!
[0311] これら上記の構成単位を含んで成る化合物の製造方法によれば、当該化合物の用 途に応じて、構成単位の両末端を同一の基にしても良い。具体的には、例えば構成 単位の両末端を、一般式（146)、 (146) [0311] According to the method for producing a compound comprising the above structural unit, both ends of the structural unit may be the same group depending on the use of the compound. Specifically, for example, both ends of the structural unit are represented by the general formulas (146), (146)
Figure imgf000096_0001
Figure imgf000096_0001
(式中、 R R2、 Ι^，、Κ2，、υ、 V及び Vは上記に同じ。）、一般式（147)
Figure imgf000096_0002
(Where RR 2 , Ι ^, Κ 2 , υ, V and V are the same as above), general formula (147)
Figure imgf000096_0002
(式中、
Figure imgf000096_0003
，、Κ2，、υ、 V及び Vは上記に同じ。）、一般式（148) ) は上記に同じ。）又は一般
Figure imgf000096_0004
(Where
Figure imgf000096_0003
, Κ 2 , υ, V and V are the same as above. ) And general formula (148)) are the same as above. ) Or general
Figure imgf000096_0004
式（149)
Figure imgf000096_0005
Formula (149)
Figure imgf000096_0005
(式中、 R R2、 R 、 R2，、 T、 T、 U、 V、 V、 V及び Vは上記に同じ。）で示され るビスフエニル骨格を有する化合物に由来する基や、一般式（ 150)
Figure imgf000097_0001
 (Wherein, RR 2, R, R 2 ,, T, T, U, V, V, V and V are the same. Above) shown in A group derived from a compound having a bisphenyl skeleton or a general formula (150)
Figure imgf000097_0001
(式中、 IT'、R4'及び Zは上記に同じ。）、一般式（151)
Figure imgf000097_0002
(Wherein IT ′, R 4 ′ and Z are the same as above), general formula (151)
Figure imgf000097_0002
(式中、 Zは上記に同じ。）、一般式（152)
Figure imgf000097_0003
(Wherein Z is the same as above), general formula (152)
Figure imgf000097_0003
(式中、 は水素原子又はアルキル基を表し、 Zは上記に同じ。）又は一般式（153)
Figure imgf000097_0004
(Wherein represents a hydrogen atom or an alkyl group, Z is the same as above) or the general formula (153)
Figure imgf000097_0004
(式中、 Z'は上記に同じ。）で示されるカルボキシル基を 3個以上有する多塩基酸若 しくはその無水物或 、は 2個のカルボキシル基を有する芳香族若しくは脂肪族カル ボン酸 (芳香族若しくは脂肪族ジカルボン酸)又はその無水物に由来する基にしても 良い。尚、末端を同一の基にする為に使用される化合物としては、本発明の化合物 の原料となる、例えばビスフエニル骨格を有する化合物、カルボキシル基を 3個以上 有する多塩基酸 (カルボキシル基の一部がカルボン酸エステルであるものを含む。） 又はこれらの酸無水物、 2個のカルボキシル基を有する芳香族若しくは脂肪族カル ボン酸 (芳香族若しくは脂肪族ジカルボン酸)又はこれらの酸無水物が好ましく挙げ られ、これらを以下末端構成化合物と略記する場合がある。  (Wherein Z ′ is the same as above), a polybasic acid having 3 or more carboxyl groups or an anhydride thereof, or an aromatic or aliphatic carboxylic acid having 2 carboxyl groups ( An aromatic or aliphatic dicarboxylic acid) or an anhydride thereof. In addition, as a compound used to make the terminal group the same, for example, a compound having a bisphenyl skeleton, a polybasic acid having three or more carboxyl groups (part of the carboxyl group) as a raw material of the compound of the present invention Or an acid anhydride thereof, an aromatic or aliphatic carboxylic acid having two carboxyl groups (aromatic or aliphatic dicarboxylic acid) or an acid anhydride thereof is preferable. These are sometimes abbreviated as terminal-constituting compounds.
これら構成単位の両末端を同一の基にする方法、即ち、末端構成化合物の導入方 法としては、上記した如き末端構成化合物を常法に従って導入すれば良ぐ例えば 縮合反応によって目的の構成単位を有する化合物 (榭脂)を合成した後に更に末端 構成化合物を反応させる方法や、縮合反応時に、末端構成化合物を過剰量用いる 方法等が挙げられる。また、両末端が上記一般式（151)で示される基である化合物 の場合には、当該化合物に水、アルコール等を作用させることにより、上記一般式（1 52)で示される基を有する化合物にすることができる。 As a method for making both ends of these structural units the same group, that is, a method for introducing a terminal constituent compound, the terminal constituent compound as described above may be introduced in accordance with a conventional method. A compound that has a compound (wax), and a method in which the terminal component compound is further reacted, or an excessive amount of the terminal component compound is used during the condensation reaction. Methods and the like. In the case of a compound in which both ends are a group represented by the above general formula (151), a compound having a group represented by the above general formula (152) can be obtained by allowing water, alcohol, or the like to act on the compound. Can be.
実施例  Example
[0313] 以下に、実施例及び比較例に基づいて本発明を具体的に説明する力 本発明は これらの例によって何ら限定されるものではない。尚、本実施例では、目的とする一 般式（1)で示される構成単位を含んで成る化合物を単離しているが、反応によって 得られた溶液をそのまま適当な用途に供することもできる。一般式（1)で示される構 成単位を含んで成る化合物 (アクリル酸誘導体由来の基が導入された化合物）の酸 価は、本実施例の製造方法によって得られた一般式（1)で示される構成単位を含ん で成る化合物をプロピレングリコールモノメチルエーテルアセテート及び 1ーメチルー 2—ピロリドンの混合溶液で希釈した後、フエノールフタレインを指示薬として KOHェ タノール（50重量％)水溶液で滴定して決定した。また、分子量は、テトラヒドロフラン を溶離液として RI (屈折率)検出器を持ったゲルパーミエーシヨンクロマトグラフィーに より求めた。以下に示す分子量は全てポリスチレン換算の重量平均分子量である。さ らに、アクリル酸誘導体由来の基の導入率 (以後、単にアクリル化率と略記する場合 がある。）は、ェ!！ NMR (400MHz)によって、一般式（1)で示される構成単位の全 プロトン面積と、アクリル酸誘導体由来の基に特有のピーク面積の比力 求めた。  [0313] Hereinafter, the ability to specifically describe the present invention based on Examples and Comparative Examples The present invention is not limited to these examples. In this example, the target compound containing the structural unit represented by the general formula (1) is isolated, but the solution obtained by the reaction can be used as it is for an appropriate use. The acid value of the compound comprising the structural unit represented by the general formula (1) (the compound into which a group derived from an acrylic acid derivative is introduced) is represented by the general formula (1) obtained by the production method of this example. The compound comprising the structural unit shown was diluted with a mixed solution of propylene glycol monomethyl ether acetate and 1-methyl-2-pyrrolidone, and then titrated with an aqueous solution of KOH ethanol (50% by weight) using phenolphthalein as an indicator. . The molecular weight was determined by gel permeation chromatography using tetrahydrofuran as an eluent and a RI (refractive index) detector. The molecular weights shown below are all polystyrene-equivalent weight average molecular weights. Furthermore, the introduction rate of groups derived from acrylic acid derivatives (hereinafter sometimes simply referred to as “acrylation rate”) is! The specific power of the total proton area of the structural unit represented by the general formula (1) and the peak area specific to the group derived from the acrylic acid derivative was determined by NMR (400 MHz).
[0314] 実施例 1〜13は、本発明の下記一般式（157)で示される構成単位を含んで成る 化合物を、本発明の製造方法である下記 [ XV ]法 [0314] Examples 1 to 13 show the following [XV] method which is a production method of the present invention using a compound comprising a structural unit represented by the following general formula (157) of the present invention.
Figure imgf000099_0001
Figure imgf000099_0001
(157)  (157)
(式中、 R8'及び R9'は夫々独立して、水素原子又はビュルカルボ二ル基を表し、 Ζι 及び kは上記に同じ。）で示される方法によって合成した例であり、夫々の実施例によ つて、 Zで示される 4価の炭化水素基の種類や、反応温度、反応時間等の反応条件 が異なる。 (Wherein R 8 ′ and R 9 ′ each independently represents a hydrogen atom or a bullcarbonyl group, and ι ι and k are the same as above). Depending on the examples, the type of tetravalent hydrocarbon group represented by Z, reaction conditions such as reaction temperature and reaction time differ.
[0315] 実施例 1 [0315] Example 1
〈1〉一般式（ 156)に於ける Zが式 (29— 1 ' )で示される 4価の炭化水素基である構 成単位を含んで成る化合物の合成 (縮合反応）  <1> Synthesis of a compound comprising a structural unit in which Z in the general formula (156) is a tetravalent hydrocarbon group represented by the formula (29-1 ′) (condensation reaction)
9, 9—ビス（4—グリシジルォキシフエ-ル）フルオレン 80. 4g (0. 160mol)に 1— メチル—2—ピロリドン 185. 3gをカ卩え、該フルオレン化合物を溶解させた後、この溶 液に、 3, 3，， 4, 4，—ビフエ-ルテトラカルボン酸（BPTC) 42. 3g (0. 128mol)及 びトリェチルベンジルアンモ -ゥムクロライド 3. 6gを添加し、 80°Cで 4時間撹拌して、 反応させた。得られた反応液を 1—メチル—2—ピロリドン 102. 9gで希釈することに より、淡黄色透明な、一般式（156)に於ける Zが式 (29— 1 ' )で示される 4価の炭化 水素基である構成単位を含んで成る化合物 (榭脂)の溶液を得た。  9, 9-bis (4-glycidyloxyphenol) fluorene 88.4 g (0.160 mol) was charged with 1-methyl-2-pyrrolidone 185.3 g, and the fluorene compound was dissolved. Add 3, 3, 4, 4, 4-biphenyltetracarboxylic acid (BPTC) 42.3 g (0.128 mol) and triethylbenzyl ammonium chloride 3.6 g to the solution at 80 ° C. The reaction was stirred for 4 hours. By diluting the obtained reaction solution with 102.9 g of 1-methyl-2-pyrrolidone, Z in the general formula (156) is a pale yellow transparent tetravalent compound represented by the formula (29-1 ′). A solution of a compound (wax) containing a structural unit which is a hydrocarbon group was obtained.
[0316] 〈2〉一般式（157)に於ける Zが式 (29— 1 ' )で示される 4価の炭化水素基である構 成単位を含んで成る化合物の合成 (アクリル化反応） 上記〈1〉で得られた一般式 (156)で示される構成単位を含んで成る化合物 (榭脂） の溶液に、フエノチアジン 30mg及びトリェチルァミン 38. 9gを加えて、 0°Cで 10分間 撹拌し、次いでこの溶液に、アクリル酸クロライド 29. 0g (0. 320mol)を滴下した。滴 下終了後、 25°Cで 2時間撹拌して、反応させた。得られた反応液を水 3. 8kg中に滴 下して晶析させて濾取し、得られた晶析物をさらに、水 3. 8kgで洗浄した後、 25°Cで 20時間減圧乾燥させることにより、白色の、一般式（157)に於ける Zが式（29— 1 ' ) で示される 4価の炭化水素基である構成単位を含んで成る化合物 (榭脂）{尚、 ¾- NMRデータに基づ 、て求めたアクリルィ匕率から、本実施例で得られた化合物に於 いて、一般式（157)の全構成単位中のビスフエ-ルフルオレンの数を 100mol%とし た場合、アクリルィ匕率は 43mol%であった。 } 123g (収率： 98%)を得た。これを榭脂 1とする。 <2> Synthesis of a compound comprising a structural unit in which Z in the general formula (157) is a tetravalent hydrocarbon group represented by the formula (29-1 ′) (acrylation reaction) 30 mg of phenothiazine and 38.9 g of triethylamine are added to a solution of the compound (wax) containing the structural unit represented by the general formula (156) obtained in the above <1>, and stirred at 0 ° C for 10 minutes. Then, 29.0 g (0.320 mol) of acrylic acid chloride was added dropwise to this solution. After completion of the dropwise addition, the mixture was stirred at 25 ° C for 2 hours to be reacted. The obtained reaction solution was dropped into 3.8 kg of water, crystallized and filtered, and the resulting crystallized product was further washed with 3.8 kg of water and then dried under reduced pressure at 25 ° C for 20 hours. Thus, a white compound containing a structural unit in which Z in the general formula (157) is a tetravalent hydrocarbon group represented by the formula (29-1 ′) (resin) { -From the acrylic ratio determined based on NMR data, in the compound obtained in this example, when the number of bisphenol fluorenes in all structural units of the general formula (157) is 100 mol%, The acrylic ratio was 43 mol%. } 123 g (yield: 98%) was obtained. This is designated as rosin 1.
[0317] 実施例 2〜13では、上記一般式（110)で示されるテトラカルボン酸として、実施例 1で用いた BPTCの代わりに表 1に示す所定のテトラカルボン酸を用いることにより、 一般式（156)及び（157)に於ける Zで示される 4価の炭化水素基が異なる構成単 位を含んで成る化合物を合成した。また、反応条件 {式（154)で示される化合物に対 する該テトラカルボン酸の使用量比、縮合の際の反応時間及びアクリルィ匕の際の反 応時間。 }を表 1に記載の通りに変えることにより、物性（当該化合物の酸価、重量平 均分子量及びアクリル化率。 )が異なる種々の一般式（157)で示される構成単位を 含んで成る化合物を合成した。尚、上記した如き条件以外は、実施例 1の方法に準じ て行った。  [0317] In Examples 2 to 13, by using the predetermined tetracarboxylic acid shown in Table 1 instead of the BPTC used in Example 1 as the tetracarboxylic acid represented by the general formula (110), the general formula In the compounds (156) and (157), compounds comprising different structural units of the tetravalent hydrocarbon group represented by Z were synthesized. Also, reaction conditions {the amount ratio of the tetracarboxylic acid to the compound represented by the formula (154), the reaction time during condensation, and the reaction time during acrylic reaction. } Is changed as shown in Table 1, and the compounds comprising various structural units represented by the general formula (157) having different physical properties (acid value, weight average molecular weight and acrylation rate of the compound) Was synthesized. In addition, it carried out according to the method of Example 1 except the conditions as mentioned above.
[0318] 夫々の実施例に於ける反応条件を表 1に、また、実施例 1〜 13に於ける化合物の 物性を表 2に併せて示す。  [0318] The reaction conditions in each example are shown in Table 1, and the physical properties of the compounds in Examples 1 to 13 are also shown in Table 2.
[0319] また、実施例 1〜13により得られたィ匕合物の1 H— NMR及び IR測定を行った。 [0319] In addition, 1 H-NMR and IR measurements of the compounds obtained in Examples 1 to 13 were performed.
NMRに於いては、アクリル酸誘導体由来の基特有のビ-レン基に結合しているプ 口トンのピークと、カルボキシル基特有のプロトンのピークが確認できた。また、 nre は、 1700cm_1付近にカルボ-ル基特有のピークが確認できた。尚、実施例 3で得ら れた化合物の1 H— NMRデータを図 1に、 IRデータを図 3に示す。 In NMR, a peptone peak bonded to a berylene group specific to an acrylic acid derivative-derived group and a proton peak specific to a carboxyl group were confirmed. Further, nre is carbo near 1700 cm _1 - specific peak Le group was confirmed. The 1 H-NMR data of the compound obtained in Example 3 is shown in FIG. 1, and the IR data is shown in FIG.
[0320] [表 1] 化合物の構造 使用量比 縮合 アクリル化 [0320] [Table 1] Compound structure Usage ratio Condensation Acrylation
テ卜ラカルボン {式（154)で の際の の際の 実施例 No.  Terracaron {Example No. in case of in formula (154)
酸の種類 示される化合物 反応時間 反応時間 樹脂 No. Z,の種類 テトラカルボン酸 1 (h) (h) 実施例 2 樹脂 2 式（29— 3' ) BzPTC 1 / 0.8 6 2  Type of acid Compound shown Reaction time Reaction time Type of resin No. Z, tetracarboxylic acid 1 (h) (h) Example 2 Resin 2 Formula (29-3 ') BzPTC 1 / 0.8 6 2
実施例 3 樹脂 3 式（32) TTC 1 / 0.8 5 2  Example 3 Resin 3 Formula (32) TTC 1 / 0.8 5 2
実施例 4 樹脂 4 式（32) TTC 1 / 0.8 6 2  Example 4 Resin 4 Formula (32) TTC 1 / 0.8 6 2
実施例 5 樹脂 5 式（32) TTC 1 / 0.8 6.5 2  Example 5 Resin 5 Formula (32) TTC 1 / 0.8 6.5 2
実施例 6 樹脂 6 式（32) TTC 1 / 0.8 7 2  Example 6 Resin 6 Formula (32) TTC 1 / 0.8 7 2
実施例 7 樹脂 7 式（32) TTC 1 / 0.8 7.5 2  Example 7 Resin 7 Formula (32) TTC 1 / 0.8 7.5 2
実施例 8 樹脂 8 式（32) TTC 1 1 1 5 2  Example 8 Resin 8 Formula (32) TTC 1 1 1 5 2
実施例 9 樹脂 9 式（32) TTC 1 / 0.8 5 6  Example 9 Resin 9 Formula (32) TTC 1 / 0.8 5 6
実施例 10 樹脂 10 式（32) TTC 1 / 0.8 6 6  Example 10 Resin 10 Formula (32) TTC 1 / 0.8 6 6
実施例 11 樹脂 11 式（32) TTC 1 / 0.8 7 6  Example 11 Resin 11 Formula (32) TTC 1 / 0.8 7 6
実施例 12 樹脂 12 式（32) TTC 1 / 0.7 5 2  Example 12 Resin 12 Formula (32) TTC 1 / 0.7 5 2
実施例 13 樹脂 13 式（32) TTC 1 / 0.6 4.5 2  Example 13 Resin 13 Formula (32) TTC 1 / 0.6 4.5 2
これら実施例 2~ 13に於ける収率は、 95~ 100<½であった。  The yields in Examples 2 to 13 were 95 to 100 <½.
(これ以降に示す実施例 14~37についても、上記と同様に  (For Examples 14 to 37 shown below, the same as above.
95~100<½の収率であり、以下収率については略記する。 )  The yield is 95 to 100 <½, and the yield is abbreviated below. )
BzPTC = 3, 3' , 4, 4'—ベンゾフエノンテトラカルボン酸  BzPTC = 3, 3 ', 4, 4'-benzophenone tetracarboxylic acid
TTC = 4— (1, 2—ジカルボキシェチル）一1, 2, 3, 4  TTC = 4— (1, 2-dicarboxyethyl) 1, 2, 3, 4
—テトラヒドロナフタレン一 1, 2—ジカルボン酸  —Tetrahydronaphthalene mono 1,2-dicarboxylic acid
Figure imgf000101_0001
Figure imgf000101_0001
上記表 1及び 2から明らかなように、実施例 3〜7の結果の比較から、縮合の際の反 応時間を変えることにより、分子量の異なる一般式（157)で示される構成単位を含ん で成る化合物 (榭脂）を容易に合成でき、また、実施例 3、 8、 12及び 13の結果の比 較から明らかなように、式（154)で示される化合物に対する一般式（110)で示される テトラカルボン酸の使用量比を変えることにより、酸価の異なる一般式（157)で示さ れる構成単位を含んで成る化合物 (榭脂)を容易に合成できることも判った。さらに、 実施例 3、 4、 6及び 9〜11の結果の比較 (特に実施例 3と 9、実施例 4と 10及び実施 例 6と 11の結果の比較)から、一般式（156)で示される構成単位を含んで成る化合 物と式 (89)で示されるアクリル酸誘導体との反応時間を変えることにより、アクリルィ匕 率の異なる一般式 (157)で示される構成単位を含んで成る化合物 (榭脂)を容易に 合成でき、さらにまた、実施例 1〜3の結果の比較から、テトラカルボン酸の種類を代 えても、同様に一般式（157)で示される構成単位を含んで成る化合物 (榭脂)を収率 良く得ることが可能となる。 As is clear from Tables 1 and 2 above, the comparison of the results of Examples 3 to 7 shows that By changing the reaction time, it is possible to easily synthesize a compound (resin) containing a structural unit represented by the general formula (157) having a different molecular weight, and the ratio of the results of Examples 3, 8, 12 and 13 As is clear from the comparison, the structural unit represented by the general formula (157) having a different acid value can be obtained by changing the ratio of the tetracarboxylic acid represented by the general formula (110) to the compound represented by the formula (154). It has also been found that a compound comprising sucrose (wax) can be easily synthesized. Furthermore, from the comparison of the results of Examples 3, 4, 6 and 9 to 11 (particularly, the comparison of the results of Examples 3 and 9, Examples 4 and 10 and Examples 6 and 11), it is shown by the general formula (156). By changing the reaction time of the compound comprising the structural unit and the acrylic acid derivative represented by the formula (89), the compound comprising the structural unit represented by the general formula (157) having a different acrylic ratio ( In addition, from the comparison of the results of Examples 1 to 3, a compound comprising the structural unit represented by the general formula (157) is obtained even if the type of tetracarboxylic acid is changed. (Resin) can be obtained with good yield.
[0323] 尚、上記実施例 3〜7では、反応時間を変えることで、分子量が異なる化合物を合 成して 、るが、反応温度並びに式（ 154)で示される化合物及び一般式（110)で示さ れるテトラカルボン酸の濃度を変えることによつても、分子量を制御することが可能で ある。 In Examples 3 to 7, compounds having different molecular weights were synthesized by changing the reaction time. However, the reaction temperature, the compound represented by the formula (154), and the general formula (110) It is also possible to control the molecular weight by changing the concentration of the tetracarboxylic acid shown in.
[0324] 実施例 14〜23は、本発明の下記一般式（159)で示される構成単位を含んで成る 化合物を、本発明の製造方法である下記 [ XVI ]法 [0324] In Examples 14 to 23, the compound containing the structural unit represented by the following general formula (159) of the present invention is converted into the following [XVI] method which is the production method of the present invention.
Figure imgf000103_0001
Figure imgf000103_0001
(159)  (159)
(式中、 R8'、 R9'、 Z、 Z、 k'及び k' 'は上記に同じ。）で示される方法によって合成 (Where R 8 ', R 9 ', Z, Z, k 'and k''are the same as above)
1 3  13
した例であり、夫々の実施例によって、 Z及び Zで示される 4価及び 2価の炭化水素 In each example, tetravalent and divalent hydrocarbons represented by Z and Z
1 3  13
基の種類や、反応温度、反応時間等の反応条件が異なる。 The type of group, reaction temperature, reaction time, and other reaction conditions are different.
実施例 14 Example 14
〈1〉一般式（158)に於ける Zが式 (32)で示される 4価の炭化水素基であり、 Zが  <1> In general formula (158), Z is a tetravalent hydrocarbon group represented by formula (32), and Z is
1 3 式 (56 ' )で示される 2価の炭化水素基である構成単位を含んで成る化合物の合成 ( 縮合反応） 9, 9 ビス（4 グリシジルォキシフエ-ル）フルオレン 80. 4g (0. 160mol)に 1— メチル—2 ピロリドン 185. 3gをカ卩え、該フルオレン化合物を溶解させた後、この溶 液【こ、 cis— 1, 2, 3, 6—テトラヒドロフタノレ酸（CHEC) 13. 6g (0. 080mol)及びトリ ェチルベンジルアンモ -ゥムクロライド 3. 6gを添加し、 80°Cで 1時間撹拌して、反応 させた。次いでこの溶液に、 4ー（1, 2 ジカルボキシェチル） 1, 2, 3, 4ーテトラヒ ドロナフタレン一 1, 2 ジカルボン酸 (TTC) 26. 9g (0. 080mol)を添加し、 80°Cで 8時間撹拌して、反応させた。得られた反応液を 1—メチル—2 ピロリドン 102. 9g で希釈することにより、淡黄色透明な、一般式（158)に於ける Zが式 (32)で示され る 4価の炭化水素基であり、 Zが式 (56' )で示される 2価の炭化水素基である構成単 1 3 Synthesis of a compound containing a structural unit that is a divalent hydrocarbon group represented by the formula (56 ') (condensation reaction) 9, 9 Bis (4 glycidyloxyphenol) fluorene 88.4 g (0.160 mol) 1-methyl-2 pyrrolidone 185.3 g was added and the fluorene compound was dissolved. Add cis-1, 2, 3, 6-tetrahydrophthalenoic acid (CHEC) (13.6 g, 0.080 mol) and triethylbenzylammonium chloride (3.6 g) and stir at 80 ° C for 1 hour. And reacted. Next, 26.9 g (0. 080 mol) of 4- (1,2 dicarboxyethyl) 1,2,3,4-tetrahydranaphthalene-1,2 dicarboxylic acid (TTC) was added to this solution at 80 ° C. And stirred for 8 hours to react. By diluting the obtained reaction solution with 102.9 g of 1-methyl-2 pyrrolidone, Z in the general formula (158) is a pale yellow transparent tetravalent hydrocarbon group represented by the formula (32). And Z is a divalent hydrocarbon group represented by the formula (56 ′)
3  Three
位を含んで成る化合物 (榭脂)の溶液を得た。  A solution of the compound comprising the position (wax) was obtained.
[0326] 〈2〉一般式（159)に於ける Zが式（32)で示される 4価の炭化水素基であり、 Z力 S <2> Z in the general formula (159) is a tetravalent hydrocarbon group represented by the formula (32), and Z force S
1 3 式 (56 ' )で示される 2価の炭化水素基である構成単位を含んで成る化合物の合成 ( アクリル化反応）  1 3 Synthesis of compounds containing structural units that are divalent hydrocarbon groups represented by the formula (56 ') (acrylation reaction)
上記〈1〉で得られた一般式 (158)で示される構成単位を含んで成る化合物 (榭脂） の溶液に、フエノチアジン 30mg及びトリェチルァミン 38. 9gを加えて、 0°Cで 15分間 撹拌し、次いでこの溶液に、アクリル酸クロライド 29. 0g (0. 320mol)を滴下した。滴 下終了後、 25°Cで 6時間撹拌して、反応させた。得られた反応液を水 3. 8kg中に滴 下して晶析させて濾取し、得られた晶析物をさらに、水 3. 8kgで洗浄した後、 25°Cで 20時間減圧乾燥させることにより、白色の、一般式（159)に於ける Zが式（32)で示 される 4価の炭化水素基であり、 Zが式 (56' )で示される 2価の炭化水素基である構  30 mg of phenothiazine and 38.9 g of triethylamine are added to a solution of the compound (wax) containing the structural unit represented by the general formula (158) obtained in the above <1>, and stirred at 0 ° C for 15 minutes. Then, 29.0 g (0.320 mol) of acrylic acid chloride was added dropwise to this solution. After completion of dropping, the mixture was stirred at 25 ° C for 6 hours to be reacted. The obtained reaction solution was dropped into 3.8 kg of water, crystallized and filtered, and the resulting crystallized product was further washed with 3.8 kg of water and then dried under reduced pressure at 25 ° C for 20 hours. Thus, the white Z in the general formula (159) is a tetravalent hydrocarbon group represented by the formula (32), and Z is a divalent hydrocarbon group represented by the formula (56 '). The structure
3  Three
成単位を含んで成る化合物 (榭脂）{尚、 ^ NMRデータに基づいて求めたアタリ ルイ匕率から、本実施例で得られたィ匕合物に於いて、一般式（159)の全構成単位中 のビスフエ-ルフルオレンの数を 100mol%とした場合、アクリル化率は 64mol%で あった。 }を得た。これを榭脂 14とする。  A compound comprising a constituent unit (fat) {in addition, from the atelier ratio determined based on NMR data, in the compound obtained in this example, all of the general formula (159) When the number of bisphenol fluorenes in the structural unit was 100 mol%, the acrylation rate was 64 mol%. }. This is designated as rosin 14.
[0327] 実施例 15〜23では、上記一般式（110)で示されるテトラカルボン酸として、実施 例 14で用いた TTCの代わりに表 3に示す所定のテトラカルボン酸を用い、上記一般 式（121)で示されるジカルボン酸として、実施例 14で用いた CHECの代わりに表 3 に示す所定のジカルボン酸を用いることにより、一般式（158)及び（159)に於ける Z 及び Zで示される 4価及び 2価の炭化水素基が異なる構成単位を含んで成る化合物In Examples 15 to 23, as the tetracarboxylic acid represented by the above general formula (110), the predetermined tetracarboxylic acid shown in Table 3 was used instead of TTC used in Example 14, and the above general formula ( 121) By using the predetermined dicarboxylic acid shown in Table 3 instead of CHEC used in Example 14 as the dicarboxylic acid shown in 121), Z in the general formulas (158) and (159) And a compound in which the tetravalent and divalent hydrocarbon groups represented by Z contain different structural units
3 Three
を合成した。また、反応条件 {式（ 154)で示される化合物に対する該テトラカルボン 酸及び該ジカルボン酸の使用量比、縮合の際の反応時間及びアクリル化の際の反 応時間。 }を表 3に記載の通りに変えることにより、物性（当該化合物の酸価、重量平 均分子量及びアクリルィ匕率。）が異なる種々の一般式（159)で示される構成単位を 含んで成る化合物を合成した。尚、上記した如き条件以外は、実施例 14の方法に準 じて行った。  Was synthesized. Further, reaction conditions {amount ratio of the tetracarboxylic acid and the dicarboxylic acid to the compound represented by the formula (154), a reaction time during the condensation, and a reaction time during the acrylation. } Is changed as shown in Table 3, and the compounds comprising the structural units represented by the various general formulas (159) having different physical properties (acid value, weight average molecular weight and acrylic ratio). Was synthesized. In addition, it carried out according to the method of Example 14 except the conditions as mentioned above.
[0328] 夫々の実施例に於ける反応条件を表 3に、また、実施例 14〜23に於ける、一般式  [0328] The reaction conditions in each example are shown in Table 3, and the general formulas in Examples 14 to 23
(159)で示される構成単位を含んで成る化合物の物性を表 4に併せて示す。  The physical properties of the compound comprising the structural unit represented by (159) are also shown in Table 4.
[0329] また、実施例 14〜23により得られたィ匕合物に於いても1 H— NMR及び IR測定を行 つたところ、上記実施例 1〜13の場合と同様に特徴的なピークが確認できた。 [0329] Further, when the 1 H-NMR and IR measurements were performed on the compounds obtained in Examples 14 to 23, a characteristic peak was observed as in Examples 1 to 13 above. It could be confirmed.
[0330] [表 3]  [0330] [Table 3]
Figure imgf000105_0001
Figure imgf000105_0001
MA = マレイン酸  MA = maleic acid
TPA = テレフタル酸  TPA = terephthalic acid
* = 反応時間に於ける、「0 +厶」とは、先ず式（1 54)で示される化合物とジカルボン酸とを O時間反応 させた後、この溶液に亍トラカルボン酸を添加して， Δ時間反応させることを意味する。（以下、同じ）  * = “0 + 厶” in the reaction time means that the compound represented by the formula (154) and dicarboxylic acid are first reacted for O hour, and then added to this solution It means to react for Δ hours. (same as below)
[0331] [表 4] 酸価 重量平均 アクリル化率 [0331] [Table 4] Acid value Weight average Acrylation rate
実施例 No. 樹脂 Ν。·  Example No. Resin Ν. ·
(mgKOH/g) 分子量 (mol%)  (mgKOH / g) Molecular weight (mol%)
実施例 1 4 樹脂 1 4 1 1 1 5, 1 00 64  Example 1 4 Resin 1 4 1 1 1 5, 1 00 64
実施例 1 5 樹脂 1 5 109 4,800 72  Example 1 5 Resin 1 5 109 4,800 72
実施例 1 6 樹脂 1 6 97 4,500 63  Example 1 6 Resin 1 6 97 4,500 63
実施例 1 7 樹脂 1 7 91 5,500 34  Example 1 7 Resin 1 7 91 5,500 34
実施例 1 8 樹脂 1 8 98 6,900 34  Example 1 8 Resin 1 8 98 6,900 34
実施例 1 9 樹脂 1 9 94 5,300 33  Example 1 9 Resin 1 9 94 5,300 33
実施例 20 樹脂 20 89 4,900 35  Example 20 Resin 20 89 4,900 35
実施例 21 樹脂 21 92 6,500 34  Example 21 Resin 21 92 6,500 34
実施例 22 樹脂 22 82 7,700 28  Example 22 Resin 22 82 7,700 28
実施例 23 樹脂 23 76 7,300 29  Example 23 Resin 23 76 7,300 29
[0332] 上記表 3及び 4から明らかなように、実施例 14〜23の結果の比較から、テトラカル ボン酸とジカルボン酸を組み合わせて用いることにより、当該化合物の分子量をほぼ 一定に保ったまま酸価を変動させることが可能となる。 [0332] As is apparent from Tables 3 and 4 above, from the comparison of the results of Examples 14 to 23, by using a combination of tetracarboxylic acid and dicarboxylic acid, the molecular weight of the compound was kept substantially constant. The price can be changed.
[0333] 実施例 24〜38は、本発明である下記一般式（160)で示される構成単位を含んで 成る化合物に対して、種々の末端構成化合物を用いることにより、 A'及び A' 'で示さ れる基が構成単位の分子末端に導入された下記一般式（161)及び（162)で示され る化合物を、本発明の製造方法である下記 [ XVII ]法 [0333] In Examples 24 to 38, A ′ and A ′ ′ were obtained by using various terminal constituent compounds with respect to the compound comprising the structural unit represented by the following general formula (160) of the present invention. The compound represented by the following general formulas (161) and (162) in which the group represented by formula (1) is introduced at the molecular terminal of the structural unit is converted into the following [XVII]
Figure imgf000107_0001
Figure imgf000107_0001
( 55) ( 35)  (55) (35)
Figure imgf000107_0002
Figure imgf000107_0002
(162)  (162)
[式中、 R16及び R17は夫々独立して、水素原子、式（163)[Wherein R 16 and R 17 are each independently a hydrogen atom, the formula (163)
Figure imgf000107_0003
Figure imgf000107_0004
Figure imgf000107_0003
Figure imgf000107_0004
で示される基を表し、 A'及び A' 'で示される基は、 A'が水素原子で A' 'が式（165)
Figure imgf000107_0005
In the groups represented by A ′ and A ′ ′, A ′ is a hydrogen atom and A ′ ′ is a group represented by the formula (165)
Figure imgf000107_0005
で示される基、 A'が一般式（166)
Figure imgf000108_0001
A ′ is a group represented by the general formula (166)
Figure imgf000108_0001
(式中、 Zは上記に同じ。）で示される基で A' 'がヒドロキシル基、 A'が一般式（167)
Figure imgf000108_0002
(Wherein Z is the same as above), A ′ ′ is a hydroxyl group, and A ′ is a general formula (167)
Figure imgf000108_0002
(式中、 Zは上記に同じ。）で示される基で A' 'が一般式（168)
Figure imgf000108_0003
(Wherein Z is the same as above), A ′ ′ is a group represented by the general formula (168)
Figure imgf000108_0003
(式中、 Zは上記に同じ。）で示される基、又は A'が一般式（169) (Wherein Z is the same as above), or A ′ is a group represented by the general formula (169)
Figure imgf000108_0004
Figure imgf000108_0004
{式中、 Zは式 (49' ' )、（56' )又は（56' ' )で示される基を表す。 }で示される基で A  {In the formula, Z represents a group represented by the formula (49 ′ ′), (56 ′) or (56 ′ ′)]. } In the group A
4  Four
"が一般式（170)
Figure imgf000108_0005
"Is the general formula (170)
Figure imgf000108_0005
(式中、 Zは上記に同じ。）で示される基を表し、 Z及び kは上記に同じ。 ]で示される  (Wherein Z is the same as above), Z and k are the same as above. Indicated by
4 2  4 2
方法によって合成した例であり、夫々の実施例によって、末端構成化合物の種類や 、反応温度、反応時間等の反応条件が異なる。 This is an example synthesized by a method, and the reaction conditions such as the type of terminal constituent compound, reaction temperature, and reaction time differ depending on each example.
実施例 24 Example 24
〈1〉一般式（161)に於ける Zが式 (32)で示される 4価の炭化水素基である構成単  <1> A structural unit in which Z in the general formula (161) is a tetravalent hydrocarbon group represented by the formula (32)
2  2
位であり、 A'で示される基が水素原子で、 A' 'で示される基が式（165)で示される 基である化合物の合成 (縮合反応） 9, 9 ビス（4— (2 ヒドロキシエトキシ）フエ-ル）フルオレン（BPEF) 43. 9g (0. lOmol)に 1—メチル 2 ピロリドン 110. 9gを加え、該フルオレン化合物を溶解さ せた後、この溶液に、 4一（1, 2 ジカルボキシェチル） 1, 2, 3, 4ーテトラヒドロナ フタレン— 1, 2 ジカルボン酸二無水物（TDA) 30. Og (0. lOmol)及びジメチルァ ミノピリジン 0. 6gを添カ卩し、 80°Cで 2時間撹拌して、反応させた。次いでこの溶液に 、 BPEF8. 8g (0. 02mol)及び 1—メチノレ一 2 ピロリドン 13. 2gを更に添カロし、 80 °Cで 2時間撹拌して、反応させることにより、淡黄色透明な、一般式（161)に於ける Z が式（32)で示される 4価の炭化水素基である構成単位であり、 A'で示される基がSynthesis of a compound in which the group represented by A ′ is a hydrogen atom and the group represented by A ′ ′ is a group represented by formula (165) (condensation reaction) 9, 9 Bis (4- (2 hydroxyethoxy) phenol) fluorene (BPEF) 43.9 g (0. lOmol) 1-methyl 2-pyrrolidone 110.9 g was added and the fluorene compound was dissolved. To this solution was added 4- (1,2 dicarboxyethyl) 1,2,3,4-tetrahydronaphthalene-1,2 dicarboxylic dianhydride (TDA) 30. Og (0. lOmol) and 0.6 g of dimethylaminopyridine. Was added and stirred at 80 ° C for 2 hours to react. Next, BPEF 8.8 g (0.02 mol) and 1-methylol-2-pyrrolidone 13.2 g were further added to this solution, and the mixture was stirred at 80 ° C. for 2 hours and reacted to give a pale yellow transparent, general Z in the formula (161) is a structural unit that is a tetravalent hydrocarbon group represented by the formula (32), and the group represented by A ′ is
2 2
水素原子で、 A' 'で示される基が式（165)で示される基である化合物 (榭脂）の溶液 を得た。  A solution of a compound (wax) having a hydrogen atom and a group represented by A ′ ′ represented by the formula (165) was obtained.
[0335] 〈2〉一般式（162)に於ける Zが式（32)で示される 4価の炭化水素基である構成単  <2> A structural unit in which Z in the general formula (162) is a tetravalent hydrocarbon group represented by the formula (32).
2  2
位であり、 A'で示される基が水素原子で、 A' 'で示される基が式（165)で示される 基である化合物の合成 (アクリル化反応）  Of a compound in which the group represented by A ′ is a hydrogen atom and the group represented by A ′ ′ is a group represented by formula (165) (acrylation reaction)
上記〈1〉で得られた一般式 (161)で示される構成単位を含んで成る化合物 (榭脂） の溶液に、フエノチアジン lOOmg、メタクリル酸グリシジル（GMA) 14. 2g (0. 10mo 1)及び 1—メチル—2 ピロリドン 21. 3gをカ卩え、 80°Cで 6時間撹拌して、反応させた 。得られた反応液を 1—メチル 2 ピロリドン 150. Ogで希釈した後、水 1. 6kg中に 滴下して晶析させて濾取し、得られた晶析物をさらに、水 1. 6kg及び 50%メタノール 水溶液 1. 6kgで洗浄した後、 25°Cで 20時間減圧乾燥させることにより、白色の、一 般式（162)に於ける Zが式 (32)で示される 4価の炭化水素基である構成単位であり  In a solution of the compound (wax) containing the structural unit represented by the general formula (161) obtained in the above <1>, phenothiazine lOOmg, glycidyl methacrylate (GMA) 14.2g (0. 10mo 1) and 1-Methyl-2 pyrrolidone (21.3 g) was added and stirred at 80 ° C. for 6 hours for reaction. The obtained reaction solution was diluted with 1-methyl 2 pyrrolidone 150. Og, dropped into 1.6 kg of water, crystallized and filtered, and the resulting crystallized product was further added with 1.6 kg of water and 50% methanol aqueous solution 1. After washing with 6 kg and drying under reduced pressure at 25 ° C. for 20 hours, white in formula (162) Z is a tetravalent hydrocarbon represented by formula (32) The structural unit that is the group
2  2
、 A'で示される基が水素原子で、 A' 'で示される基が式（165)で示される基である 化合物 (榭脂）{尚、 ^—NMRデータに基づいて求めたアクリルィ匕率から、本実施 例で得られたィ匕合物に於 、て、一般式（162)の全構成単位中のビスフエニルフルォ レンの数を 100mol%とした場合、アクリル化率は 21mol%であった。 }を得た。これ を榭脂 24とする。  A group represented by A ′ is a hydrogen atom, and a group represented by A ′ ′ is a group represented by the formula (165) Compound (Oxidized) {In addition, the acrylic acid ratio obtained from ^ -NMR data Thus, in the compound obtained in this example, when the number of bisphenylfluorenes in all the structural units of the general formula (162) is 100 mol%, the acrylate ratio is 21 mol%. Met. }. This is designated as rosin 24.
[0336] 実施例 25〜30では、上記一般式（135)で示されるテトラカルボン酸二無水物とし て、 TDAを用い、末端構成化合物として、 BPEFを用いることにより、実施例 24と同 じ構造を有する化合物を合成しているが、反応条件 {式（155)で示される化合物に 対する該テトラカルボン酸二無水物、末端構成化合物及びアクリル酸誘導体の使用 量比、縮合の際の反応時間並びにアクリルィ匕の際の反応時間。 }を表 5に記載の通り に変えることにより、物性（当該化合物の酸価、重量平均分子量及びアクリル化率。 ) が異なる当該化合物を合成した。 [0336] In Examples 25 to 30, the same structure as Example 24 was obtained by using TDA as the tetracarboxylic dianhydride represented by the above general formula (135) and BPEF as the terminal component compound. In the reaction conditions {the compound represented by the formula (155) The amount ratio of the tetracarboxylic dianhydride, the terminal constituent compound and the acrylic acid derivative, the reaction time during the condensation, and the reaction time during the acrylic reaction. } Was changed as shown in Table 5 to synthesize the compounds having different physical properties (acid value, weight average molecular weight and acrylate ratio).
[0337] また、夫々の実施例に於ける反応条件を表 5に示す。尚、実施例 28〜30に於いて 、〈1〉の縮合反応では反応時に 1—メチル—2—ピロリドンを 119. 9g使用し、〈2〉の アクリルィ匕反応では反応時のフエノチアジン及び 1ーメチルー 2—ピロリドンの使用量 を、 GMAの使用モル数に比例して増減させた。それ以外は、実施例 24の方法に準 じて行った。  [0337] Table 5 shows the reaction conditions in each example. In Examples 28-30, 119.9 g of 1-methyl-2-pyrrolidone was used during the reaction in the condensation reaction <1>, and phenothiazine and 1-methyl-2 at the reaction were used in the acrylic reaction of <2>. —The amount of pyrrolidone used was increased or decreased in proportion to the number of moles of GMA used. Other than that was carried out according to the method of Example 24.
[0338] [表 5]  [0338] [Table 5]
Figure imgf000110_0001
Figure imgf000110_0001
* = 反応時間に於ける「0 +厶」とは、先ず式（1 55)で示される化合物と亍トラカルボン酸二無水物  * = "0 + 厶" in the reaction time means that the compound represented by the formula (155) and 亍 tracarboxylic dianhydride
とを O時間反応させた後、この溶液に末端構成化合物を添加して、 Δ時間反応させることを意味する。  Is reacted for O hours, and then the terminal component compound is added to this solution and reacted for Δ hours.
[0339] 実施例 31 [0339] Example 31
〈1〉一般式（161)に於ける Zが式 (32)で示される 4価の炭化水素基である構成単  <1> A structural unit in which Z in the general formula (161) is a tetravalent hydrocarbon group represented by the formula (32)
2  2
位であり、 A'で示される基が一般式（166)で示される基で、 A'，がヒドロキシル基で ある化合物の合成 (縮合反応）  Synthesis of a compound in which the group represented by A ′ is a group represented by the general formula (166) and A ′ is a hydroxyl group (condensation reaction)
BPEF43. 9g (0. lOmol)に 1—メチノレ一 2—ピロリドン 119. 9gをカロえ、該フノレオ レン化合物を溶解させた後、この溶液に、 TDA30. 0g (0. lOmol)及びジメチルアミ ノビリジン 0. 6gを添カ卩し、 80°Cで 2時間撹拌して、反応させた。次いでこの溶液に、 TDA6. 0g (0. 02mol)及び 1—メチル— 2—ピロリドン 9. Ogを更に添加し、 80。Cで 2時間撹拌して反応させ、さらに、水 2. 16g (0. 12mol)をカ卩え、 80°Cで 0. 5時間撹 拌して反応させることにより、淡黄色透明な、一般式（161)に於ける Zが式 (32)で示 される 4価の炭化水素基である構成単位であり、 A'で示される基が一般式（166)で 示される基で、 A'，がヒドロキシル基である化合物 (榭脂）の溶液を得た。 BPEF43.9 g (0.lOmol) 1-methylolone 2-pyrrolidone 119.9 g was calored, and the phenolic compound was dissolved in this solution, and then TDA 30.0 g (0.lOmol) and dimethylaminoviridine 0. 6 g was added and stirred at 80 ° C. for 2 hours for reaction. To this solution was then further added TDA 6.0 g (0.02 mol) and 1-methyl-2-pyrrolidone 9. Og 80. The reaction was stirred for 2 hours at C, and 2.16 g (0.12 mol) of water was added and stirred at 80 ° C for 0.5 hours to react. Z in (161) is given by equation (32) A solution of a compound (wax) in which the group represented by A ′ is a group represented by the general formula (166) and A ′ is a hydroxyl group. It was.
[0340] 〈2〉一般式（162)に於ける Zが式 (32)で示される 4価の炭化水素基である構成単 <2> A structural unit in which Z in the general formula (162) is a tetravalent hydrocarbon group represented by the formula (32)
2  2
位であり、 A'で示される基が一般式（166)で示される基で、 A'，がヒドロキシル基で ある化合物の合成 (アクリル化反応）  Synthesis of a compound in which the group represented by A ′ is a group represented by the general formula (166) and A ′ is a hydroxyl group (acrylation reaction)
上記〈1〉で得られた一般式 (161)で示される構成単位を含んで成る化合物 (榭脂） の溶液に、フエノチアジン 100mg、 GMA14. 2g (0. lOmol)及び 1—メチル 2— ピロリドン 21. 3gを加え、 80°Cで 6時間撹拌して、反応させた。得られた反応液を 1— メチル—2 ピロリドン 140. Ogで希釈した後、水 1. 5kg中に滴下して晶析させて濾 取し、得られた晶析物をさらに、水 1. 5kg及び 50%メタノール水溶液 1. 5kgで洗浄 した後、 25°Cで 20時間減圧乾燥させることにより、白色の、一般式（162)に於ける Z  In a solution of the compound (wax) containing the structural unit represented by the general formula (161) obtained in <1> above, 100 mg of phenothiazine, 14.2 g (0. lOmol) of GMA and 1-methyl 2-pyrrolidone 21 3 g was added and stirred at 80 ° C for 6 hours to react. The obtained reaction solution was diluted with 1-methyl-2 pyrrolidone 140. Og, dropped into 1.5 kg of water, crystallized and filtered, and the resulting crystallized product was further added with 1.5 kg of water. After washing with 1.5 kg of 50% methanol aqueous solution and drying under reduced pressure at 25 ° C for 20 hours, the white Z in the general formula (162)
2 が式（32)で示される 4価の炭化水素基である構成単位であり、 A'で示される基が一 般式（166)で示される基で、 A"がヒドロキシル基である化合物 (榭脂）{尚、 XH-N MRデータに基づ 、て求めたアクリルィ匕率から、本実施例で得られた化合物に於!ヽ て、一般式（162)の全構成単位中ビスフエ-ルフルオレンの数を 100mol%とした場 合、アクリルィ匕率は 18mol%であった。 }を得た。これを榭脂 31とする。 2 is a structural unit that is a tetravalent hydrocarbon group represented by the formula (32), a group represented by A ′ is a group represented by the general formula (166), and A ″ is a hydroxyl group榭脂) {Note that based on the X HN MR data from Akurirui匕率obtained Te, Te atヽthe compound obtained in this example, in all the structural units of the general formula (162) Bisufue - Rufuruoren of When the number was 100 mol%, the acrylic resin ratio was 18 mol%.
[0341] 実施例 32では、末端構成化合物として、実施例 31で用いた TDA+H Oと同様に [0341] In Example 32, the terminal component compound was the same as TDA + H 2 O used in Example 31.
2  2
TDAと H Oとを用いることにより、当該化合物の A'で示される基が一般式（166)で  By using TDA and H 2 O, the group represented by A ′ of the compound is represented by the general formula (166)
2  2
示される基で、 A' 'がヒドロキシル基であるものを合成した。また、反応条件 {式（155 )で示される化合物に対する該テトラカルボン酸二無水物、末端構成化合物及びァク リル酸誘導体の使用量比、縮合の際の反応時間並びにアクリルィ匕の際の反応時間。 The group shown was synthesized with A ′ ′ being a hydroxyl group. Also, reaction conditions {amount ratios of the tetracarboxylic dianhydride, terminal component compound and acrylic acid derivative to the compound represented by the formula (155), reaction time during condensation, and reaction time during acrylic reaction .
}を表 6に記載の通りに変えることにより、物性（当該化合物の酸価、重量平均分子量 及びアクリル化率。 )が異なる当該化合物を合成した。 } Was changed as shown in Table 6 to synthesize the compounds having different physical properties (acid value, weight average molecular weight and acrylate ratio).
[0342] また、実施例 32に於ける反応条件を表 6に示す。尚、実施例 32に於いて、〈2〉のァ クリル化反応では反応時のフエノチアジン及び 1 メチル 2—ピロリドンの使用量を[0342] The reaction conditions in Example 32 are shown in Table 6. In Example 32, the amount of phenothiazine and 1-methyl 2-pyrrolidone used in the reaction was determined in the acrylation reaction <2>.
、 GMAの使用モル数に比例して増減させた。それ以外は、実施例 31の方法に準じ て行った。 The ratio was increased or decreased in proportion to the number of moles of GMA used. Other than that, it carried out according to the method of Example 31.
[0343] [表 6] テトラ 伊甲 比 クリル化 末端構 縮合 * ア [0343] [Table 6] Tetra Iko ratio Crylation Terminal structure Condensation * A
成 アクリル酸 I式（1 55)で示される化合物/  Acrylic acid Compound represented by Formula I (155) /
実施例 No. 樹脂 No . カルボン酸 の際の の際の 化合物 誘導体  Example No. Resin No. Compound derivative in the case of carboxylic acid
二無水物 亍トラカルボン酸二無水物 末端 反応時 ¾ 反応時間 の種類 の種類  Dianhydride 亍 tracarboxylic dianhydride terminal reaction time ¾ reaction time type
の種類 構成化合物/"アクリル酸誘導体 } (h) (h) Type Constituents / "Acrylic acid derivatives} (h) (h)
TDA TDA
実施例 32 樹脂 32 TDA + GMA 1 / 1 / 0.2(TDA) +1.2 (H2O) / 2 2+2+0.5 6 Example 32 Resin 32 TDA + GMA 1 / 1/2 / (TDA) + 1.2 (H 2 O) / 2 2 + 2 + 0.5 6
H20 H 2 0
* = 反応時間に於ける「2 + 2+0. 5」とは、先ず式（1 55)で示される化合物と亍トラカルボン酸二無水物とを  * = “2 + 2 + 0.5” in the reaction time means that the compound represented by the formula (155) and 亍 tracarboxylic dianhydride
2時間反応させた後、この溶液に末端構成化合物 (TDA)を添加して、 2時間反応させ、最後に水（H20)を 添加して、 0. 5時間反応させて、 A'及び A' 'で示される基の酸無水物基を加水分解することを意味する。 After reacting for 2 hours, the terminal component compound (TDA) is added to this solution and reacted for 2 hours. Finally, water (H 2 0) is added and reacted for 0.5 hour. This means that the acid anhydride group of the group represented by A ′ ′ is hydrolyzed.
[0344] 実施例 33 [0344] Example 33
〈1〉一般式（161)に於ける Zが式 (32)で示される 4価の炭化水素基である構成単  <1> A structural unit in which Z in the general formula (161) is a tetravalent hydrocarbon group represented by the formula (32)
2  2
位であり、 A'で示される基が一般式（167)で示される基で、 A' 'が一般式（168)で 示される基である化合物の合成 (縮合反応）  Synthesis of a compound in which the group represented by A ′ is a group represented by the general formula (167) and A ′ ′ is a group represented by the general formula (168) (condensation reaction)
BPEF43. 9g (0. lOmol)に 1—メチノレ一 2 ピロリドン 110. 9gをカロえ、該フノレオ レン化合物を溶解させた後、この溶液に、 TDA30. 0g (0. lOmol)及びジメチルアミ ノビリジン 0. 6gを添カ卩し、 80°Cで 2時間撹拌して、反応させた。次いでこの溶液に、 TDA9. 0g (0. 03mol)及び 1—メチル 2 ピロリドン 13. 5gを更に添加し、 80°C で 2時間撹拌して反応させることにより、淡黄色透明な、一般式（161)に於ける Zが  1-Methylolone 2 Pyrrolidone 10.9 g was added to BPEF 43.9 g (0. lOmol), and the phenolic compound was dissolved in this solution. Was added and stirred at 80 ° C for 2 hours to react. Subsequently, 9.0 g (0.03 mol) of TDA and 13.5 g of 1-methyl-2-pyrrolidone were further added to this solution, and the mixture was reacted by stirring at 80 ° C. for 2 hours. Z in
2 式 (32)で示される 4価の炭化水素基である構成単位であり、 A'で示される基が一般 式（167)で示される基で、 A' 'が一般式（168)で示される基である化合物 (榭脂）の 溶液を得た。  2 A structural unit that is a tetravalent hydrocarbon group represented by the formula (32), wherein a group represented by A ′ is a group represented by the general formula (167), and A ′ ′ is represented by the general formula (168). As a result, a solution of the compound (wax) which is a group to be obtained was obtained.
[0345] 〈2〉一般式（162)に於ける Zが式 (32)で示される 4価の炭化水素基である構成単  <2> A structural unit in which Z in the general formula (162) is a tetravalent hydrocarbon group represented by the formula (32)
2  2
位であり、 A'で示される基が一般式（167)で示される基で、 A' 'が一般式（168)で 示される基である化合物の合成 (アクリル化反応）  Synthesis of a compound in which the group represented by A ′ is the group represented by the general formula (167) and A ′ ′ is the group represented by the general formula (168) (acrylation reaction)
上記〈1〉で得られた一般式 (161)で示される構成単位を含んで成る化合物 (榭脂） の溶液に、フエノチアジン 60mg、アクリル酸ヒドロキシェチル（HEA) 7. 0g (0. 06m ol)及び 1—メチル 2 ピロリドン 10. 5gを加えた後、この溶液を 0°Cで攪拌しながら 、ジシクロへキシルカルボジイミド 12. 4g (0. 06mol)を添カ卩した。次いでこの溶液を 30分かけて 25°Cとし、さらに同温度で 2時間攪拌して、反応させた。得られた反応液 を 1—メチル—2 ピロリドン 130. 0gで希釈し、この反応液を濾過してジシクロへキ シル尿素を取り除いた後、この濾液を水 1. 5kg中に滴下して晶析させて濾取し、得 られた晶析物をさらに、水 1. 4kg及び 50%メタノール水溶液 1. 4kgで洗浄した後、 25°Cで 20時間減圧乾燥させることにより、白色の、一般式（162)に於ける Zが式（3 In a solution of the compound (wax) containing the structural unit represented by the general formula (161) obtained in the above <1>, phenothiazine 60 mg, hydroxyethyl acrylate (HEA) 7.0 g (0.06 mol) ) And 10.5 g of 1-methyl-2-pyrrolidone were added, and 12.4 g (0.06 mol) of dicyclohexylcarbodiimide was added while stirring the solution at 0 ° C. Next, this solution was brought to 25 ° C. over 30 minutes and further stirred at the same temperature for 2 hours to be reacted. The obtained reaction solution was diluted with 13.0 g of 1-methyl-2 pyrrolidone, this reaction solution was filtered to remove dicyclohexylurea, and then the filtrate was dropped into 1.5 kg of water for crystallization. Let it filter and get The obtained crystallized product was further washed with 1.4 kg of water and 1.4 kg of a 50% aqueous methanol solution, and then dried under reduced pressure at 25 ° C. for 20 hours to obtain white Z in the general formula (162). Formula (3
2 2
2)で示される 4価の炭化水素基である構成単位であり、 A'で示される基が一般式（1 67)で示される基で、 A"が一般式（168)で示される基である化合物 (榭脂）{尚、 ¾ —NMRデータに基づいて求めたアクリルィ匕率から、本実施例で得られた化合物に 於いて、一般式（162)の全構成単位中のビスフエ-ルフルオレンの数を 100mol% とした場合、アクリルィ匕率は 17mol%であった。 }を得た。これを榭脂 33とする。 A structural unit that is a tetravalent hydrocarbon group represented by 2), wherein a group represented by A ′ is a group represented by the general formula (167), and A ″ is a group represented by the general formula (168). Certain compound (resin) {In addition, ¾ — From the acrylic ratio determined based on NMR data, in the compound obtained in this example, bisphenol fluorene in all the structural units of the general formula (162) When the number was 100 mol%, the acrylic resin ratio was 17 mol%.
[0346] 実施例 34〜37では、末端構成化合物として、実施例 33で用いた TDAの代わりに 表 7に示す所定のカルボン酸無水物を用いることにより、当該化合物の A'で示され る基が式（167)で示される基で、 A' 'が一般式（168)で示される基である化合物又 は A'で示される基が式（169)で示される基で、 A' 'が一般式（170)で示される基で ある化合物を合成した。また、反応条件 {式（155)で示される化合物に対する該テト ラカルボン酸二無水物、末端構成化合物及びアクリル酸誘導体の使用量比、縮合の 際の反応時間並びにアクリルィ匕の際の反応時間。 }を表 7に記載の通りに変えること により、物性（当該化合物の酸価、重量平均分子量及びアクリル化率。）が異なる当 該化合物を合成した。尚、実施例 34〜37に於いて、〈1〉の縮合反応では反応時の 1 —メチルー 2—ピロリドンの使用量を、末端構成化合物の使用モル数に比例して増 減させ、〈2〉のアクリル化反応では反応時のフエノチアジン、ジシクロへキシルカルボ ジイミド及び 1—メチル—2—ピロリドンの使用量を、 HEAの使用モル数に比例して 増減させた。それ以外は、実施例 33の方法に準じて行った。  [0346] In Examples 34 to 37, by using the predetermined carboxylic acid anhydride shown in Table 7 instead of TDA used in Example 33 as a terminal component compound, a group represented by A 'of the compound Is a group represented by the formula (167) and A ′ ′ is a group represented by the general formula (168) or a group represented by A ′ is a group represented by the formula (169), and A ′ ′ is A compound having the group represented by the general formula (170) was synthesized. Further, reaction conditions {amount ratio of the tetracarboxylic dianhydride, terminal component compound and acrylic acid derivative to the compound represented by the formula (155), reaction time during condensation, and reaction time during acrylic reaction. } Was changed as shown in Table 7 to synthesize the compounds having different physical properties (acid value, weight average molecular weight and acrylate ratio). In Examples 34 to 37, in the condensation reaction <1>, the amount of 1-methyl-2-pyrrolidone used in the reaction was increased and decreased in proportion to the number of moles of the terminal component compound, and <2> The amount of phenothiazine, dicyclohexylcarbodiimide and 1-methyl-2-pyrrolidone used during the reaction was increased or decreased in proportion to the number of moles of HEA used. Other than that, it carried out according to the method of Example 33.
[0347] 夫々の実施例に於ける反応条件を表 7に、また、実施例 24〜37に於ける、一般式  [0347] The reaction conditions in each example are shown in Table 7, and the general formulas in Examples 24-37 are shown in Table 7.
(162)で示される構成単位を含んで成る化合物の物性を表 8に併せて示す。  The physical properties of the compound comprising the structural unit represented by (162) are also shown in Table 8.
[0348] また、実施例 24〜37により得られたィ匕合物に於いても1 H— NMR及び IR測定を行 つたところ、上記実施例 1〜13の場合と同様に特徴的なピークが確認できた。尚、実 施例 24で得られた化合物の1 H— NMRデータを図 2に、 IRデータを図 4に示す。 [0348] Further, the 1 H-NMR and IR measurements were performed on the compounds obtained in Examples 24 to 37, and as a result, characteristic peaks were observed as in Examples 1 to 13 above. It could be confirmed. The 1 H-NMR data of the compound obtained in Example 24 is shown in FIG. 2, and the IR data is shown in FIG.
[0349] [表 7] テ卜ラ 使用量比 縮台 * アクリル化 末 ¾冓成 アクリル酸 [0349] [Table 7] Ratio of used amount of taper Shrink base * Acrylic powder ¾ 冓 成 Acrylic acid
カルポン酸 {式〔 で示される化合物/ の際の の際の 実施例 樹脂 の種類 化合物 誘導体  Carponic acid {Examples of the compound represented by the formula [/ Resin type Compound Derivative
二無水物 テ卜ラカルポン酸二無水物 Z末端 反応時間 反応時間 の種類 の種類  Dianhydride teracarponic dianhydride Z-terminal reaction time reaction time type
の種類 構成化合物/アクリル酸誘導体 } (h) 実施例 樹脂 1 / 1 /0.3 / 1 2+2 2 実施例 樹脂 式（ 1 / 1 /0.8 / 1 2+2 2 実施例 樹脂 式 っ 1 / 1 /0.8 / 1 2+2 2 実施例 樹脂 式 ，） 1 / 1 /0.8 / 1 2+2 2 —テ卜ラヒドロフタル酸無水物  Type of constituent compound / acrylic acid derivative} (h) Example Resin 1/1 /0.3 / 1 2 + 2 2 Example Resin Formula (1/1 / 0.8 / 1 2 + 2 2 Example Resin Formula 1/1 /0.8 / 1 2 + 2 2 Example Resin Formula)) 1/1 /0.8 / 1 2 + 2 2 — Terahydrophthalic anhydride
—テ卜ラヒドロフタル酸無水物  —Terahydrophthalic anhydride
= フタル酸無水物  = Phthalic anhydride
* = 反応時間に於ける「〇 +△」とは. 先ず式（ で示される化合物とテ卜ラカルポン酸二無水物 とを O時間反応させた後、この溶液に末端構成化台拘を添加して、△時間反応させることを意味する。  * = “○ + △” in the reaction time. First, the compound represented by the formula () and teracarponic dianhydride were reacted for O hours, and then the terminal composition was added to this solution. Means to react for Δ hours.
[0350] [表 8] [0350] [Table 8]
Figure imgf000114_0001
Figure imgf000114_0002
Figure imgf000114_0001
Figure imgf000114_0002
[0351] 上記表 5〜8力ら明ら力なように、実施 f列 24〜27、 28〜30、 31と 32及び 33と 34の 結果の比較から、式（ 155)で示される化合物に対するアクリル酸誘導体の使用量比 を変えることにより、酸価の異なる一般式（162)で示される構成単位を含んで成るィ匕 合物 (榭脂）を容易に合成でき、実施例 25と 28の結果の比較力も明らかなように、式 (155)で示される化合物に対するテトラカルボン酸無水物の使用量比を変えることに より、分子量の異なる一般式 (162)で示される構成単位を含んで成る化合物 (榭脂） を容易に合成できることも判った。また、実施例 24と 31の結果の比較から、末端構成 化合物を BPEFから TDA + H Oに代えることによって、アクリル化率を変えずに酸価  [0351] As shown in Table 5-8, the comparison of the results of Examples f columns 24 to 27, 28 to 30, 31 and 32, and 33 and 34 showed that the compound represented by formula (155) By changing the ratio of the acrylic acid derivative used, it is possible to easily synthesize a compound (resin) containing a structural unit represented by the general formula (162) having a different acid value. As the comparative power of the results is clear, it comprises a structural unit represented by the general formula (162) having a different molecular weight by changing the amount ratio of tetracarboxylic anhydride to the compound represented by the formula (155). It was also found that the compound (wax) can be easily synthesized. In addition, by comparing the results of Examples 24 and 31, it was found that the acid value was not changed without changing the acrylate ratio by changing the terminal constituent compound from BPEF to TDA + H 2 O.
2  2
の異なる一般式（162)で示される構成単位を含んで成る化合物 (榭脂）が得られ、さ らに、実施例 35〜37の結果の比較から、末端構成化合物をテトラカルボン酸無水物 力 ジカルボン酸無水物に代えることによって酸価、分子量及びアクリル化率の異な る、一般式（162)で示される構成単位を含んで成る化合物 (榭脂)を得ることが可能 となる。  Thus, a compound comprising a structural unit represented by the general formula (162) (resin) having different formulas (162) was obtained. Further, from the comparison of the results of Examples 35 to 37, the terminal structural compound was converted to tetracarboxylic anhydride By substituting dicarboxylic acid anhydride, it becomes possible to obtain a compound (resin) comprising a structural unit represented by the general formula (162) having different acid value, molecular weight and acrylate ratio.
[0352] 実施例 38 実施例 3及び 24で得られた化合物の耐熱性試験 実施例 3及び 24で得られた化合物の熱安定性 (耐熱性）について、密閉セル 示 差走査熱量測定 (SC— DSC)及び示差走査熱量天秤 (TG— DSC)により測定を行 つたところ、 300°Cに於いても、発熱ピーク、吸熱ピーク及び重量変化が見られなか つたことから、 300°Cの高熱に於いても安定であることが判った。特に、実施例 3で得 られたィ匕合物に於いては、 350°C程度でも安定であることが判った。このことから、当 該化合物を含んで成る組成物を硬化させて形成されたパターンは、 300°Cの高熱条 件、特に実施例 3で得られたィ匕合物については、 350°Cの高熱条件に於いても、耐 熱性に優れるものであり、本発明の重合性不飽和化合物は、そのような耐熱性の高 いパターン形成に有用な化合物である。尚、実施例 3で得られたィ匕合物の熱安定性 (耐熱性)データを図 5に、実施例 24で得られた化合物の熱安定性 (耐熱性)データ を図 6に示す。 Example 38 Heat resistance test of compounds obtained in Examples 3 and 24 The thermal stability (heat resistance) of the compounds obtained in Examples 3 and 24 was measured by a closed cell differential scanning calorimetry (SC—DSC) and a differential scanning calorimeter (TG—DSC). Even at ° C, no exothermic peak, endothermic peak, or weight change was observed, indicating that it was stable even at high temperatures of 300 ° C. In particular, it was found that the composite obtained in Example 3 is stable even at about 350 ° C. From this, the pattern formed by curing the composition comprising the compound has a high heat condition of 300 ° C., particularly about 350 ° C. for the compound obtained in Example 3. Even under high heat conditions, it is excellent in heat resistance, and the polymerizable unsaturated compound of the present invention is a compound useful for pattern formation with such high heat resistance. The thermal stability (heat resistance) data of the compound obtained in Example 3 is shown in FIG. 5, and the thermal stability (heat resistance) data of the compound obtained in Example 24 is shown in FIG.
実施例 39 実施例 3及び 24で得られた化合物を用いた硬化膜の形成、硬度並びに 現像性試験 Example 39 Formation of cured film using the compounds obtained in Examples 3 and 24, hardness and developability test
〈1〉実施例 3で得られた化合物 2. 5gにポリエチレングリコールモノメチルエーテル アセテート 15gをカ卩え、該化合物を溶解させた後、さらにシクロへキサノン 1. 5gをカロ えて希釈した。さらに、この溶液に、ジペンタエリスリトールへキサアタリレート 1. lg及 び 2 ベンジル一 2 ジメチルァミノ一 1— (4 モルホリノフエ-ル）一ブタノン一 1 ( チノく'スペシャルティ'ケミカルズ製 IRGCURE369) 0. 05gをカ卩えて混合し、均一な 溶液とした。次いで、この溶液をガラス基板上に塗布した後、 90°Cで 1分間ホットプレ ート上でプレベータして、塗膜を形成した。次に、この塗膜が形成されたガラス基板 にマスクを介して、波長 365nmの UVランプで 3分間露光した。これを、 0. 05重量％ の水酸ィ匕カリウム水溶液で 1分間現像し、 180°Cで 3分間ホットプレート上でポストべ ークすること〖こより、硬化膜を得た。  <1> 15 g of polyethylene glycol monomethyl ether acetate was added to 2.5 g of the compound obtained in Example 3, and after dissolving the compound, 1.5 g of cyclohexanone was further added and diluted. In addition, dipentaerythritol hexatalylate 1. lg and 2 benzyl 1 dimethylamino 1 1- (4 morpholinophenol) 1-butanone 1 (Chinoku 'Specialty' Chemicals IRGCURE369) 0.5 g Were mixed to obtain a uniform solution. Next, this solution was applied onto a glass substrate, and then pre-betated at 90 ° C. for 1 minute on a hot plate to form a coating film. Next, the glass substrate on which the coating film was formed was exposed for 3 minutes with a UV lamp having a wavelength of 365 nm through a mask. This was developed with 0.05% by weight of aqueous potassium hydroxide solution for 1 minute, and post-baked on a hot plate at 180 ° C. for 3 minutes to obtain a cured film.
〈2〉上記〈1〉に準じて、実施例 24で得られた化合物 2. 5gを用いて、同様の硬化膜 を得た。  <2> According to the above <1>, the same cured film was obtained using 2.5 g of the compound obtained in Example 24.
〈3〉上記〈1〉及び〈2〉で得られた硬化膜夫々に対して鉛筆硬度を測定し、また、現 像性を目視により観察した。その結果、何れの硬化膜も鉛筆硬度 4Hであり、現像部 位に残渣は見られな力つた。 [0354] このこと力ら、当該化合物を含んで成る組成物は、現像性に優れるため良好なバタ ーンを形成することができるば力りでなぐ得られたパターンは良好な硬度を有するも のであり、本発明の重合性不飽和化合物は、良好な硬度を有し、現像性に優れるパ ターン形成に有用な化合物である。 <3> Pencil hardness was measured for each of the cured films obtained in the above <1> and <2>, and the image clarity was visually observed. As a result, all of the cured films had a pencil hardness of 4H, and no residue was seen in the development area. [0354] Because of this, since the composition comprising the compound has excellent developability, it can form a good pattern, and the pattern obtained with force can have good hardness. The polymerizable unsaturated compound of the present invention is a compound useful for forming a pattern having good hardness and excellent developability.
産業上の利用可能性  Industrial applicability
[0355] 本発明の重合性不飽和化合物は、構成単位中にビスフエ-ル骨格、特にフルォレ ン骨格を有する、アルカリ可溶性で、且つ耐熱性に優れた化合物であり、当該化合 物を含んで成る組成物を用いて、これを光又は熱によりパターン形成させれば、耐熱 性が良好なパターンを容易に形成できる。また、本発明の製造方法によれば、従来 法が有していた、例えば高温下で反応させるため反応の制御が困難である、副反応 により歩留まりが低い等の問題を生じさせることなぐ分子量、酸価等の調整が容易 であり、歩留まりの良い、目的の一般式（1)で示される構成単位を含んで成る化合物 を製造することが可能となる。 [0355] The polymerizable unsaturated compound of the present invention is a compound having a bisphenol skeleton, particularly a fluorene skeleton in a structural unit, which is alkali-soluble and excellent in heat resistance, and comprises the compound. A pattern having good heat resistance can be easily formed by patterning the composition with light or heat. Further, according to the production method of the present invention, the molecular weight that the conventional method has, for example, the reaction is difficult to control because of the reaction at high temperature, and the yield is low due to side reactions, It is possible to produce a compound comprising the target structural unit represented by the general formula (1), which can easily adjust the acid value and the like and has a good yield.

Claims

請求の範囲 The scope of the claims
一般式 (1) General formula (1)
Figure imgf000117_0001
Figure imgf000117_0001
[式中、
Figure imgf000117_0002
R2、 R1'及び R2'は夫々独立して、水素原子、ハロゲン原子、アルキル基 又はアルコキシ基を表し、 R3及び R4は夫々独立して、水素原子又は一般式（2) — COOR6 (2) [Where
Figure imgf000117_0002
R 2 , R 1 ′ and R 2 ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 3 and R 4 each independently represent a hydrogen atom or the general formula (2) — COOR 6 (2)
{式中、 R6は水素原子、炭素数 1〜6のアルキル基、一般式 (3)
Figure imgf000117_0003
{Wherein R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a general formula (3)
Figure imgf000117_0003
(式中、 R'はビュルカルボ-ル基又はイソプロべ-ルカルポ-ル基を表し、 Tは炭素  (In the formula, R ′ represents a butyl carbo group or an isopropyl carb group, and T represents carbon.
3 数 1〜6の直鎖状アルキレン基を表す。）、又は一般式 (4)  3 represents a linear alkylene group having 1 to 6 numbers. ) Or general formula (4)
Rレ〇、丁4 (4) R 〇, Ding 4 (4)
(式中、 R7はビュルカルボ-ル基又はイソプロべ-ルカルポ-ル基を表し、 Tは炭素 (In the formula, R 7 represents a butyl carbo group or an isopropyl carb group, and T represents carbon.
4 数 1〜6の直鎖状アルキレン基を表す。）で示される基を表す。 }で示される基を表し、 T及び Tは夫々独立して、炭素数 1〜6の直鎖状アルキレン基又はァリーレン基を 4 represents a linear alkylene group of 1 to 6 ) Represents a group represented by } And T and T each independently represent a linear alkylene group or arylene group having 1 to 6 carbon atoms.
1 2 1 2
表し、 Uは結合手又は式（1 1)〜（1 8)
Figure imgf000117_0004
(1 -5) ,CH2 (1 -6) H3C_CH3 入 ( -8) U represents a bond or a formula (1 1) to (1 8)
Figure imgf000117_0004
(1 -5), CH 2 (1 -6) H 3 C_CH 3 input (-8 )
(式中、 R5及び R5'は夫々独立して、水素原子又はハロゲン原子を表す。）の何れか で示される 2価の基を表し、 V及び Vは夫々独立して、酸素原子又は NH 基を (Wherein, R 5 and R 5 'are each independently, represent. A hydrogen atom or a halogen atom) represents a divalent group represented by any one of, V and V are each independently a oxygen atom or a NH group
1 2  1 2
表し、 Yは酸素原子、 NH 基又は一般式 (5) (式中、 R8は水素原子又は R7を表す。）で示される基を表し、 Yは酸素原子、 -NH Y represents an oxygen atom, NH group or general formula (5) (Wherein R 8 represents a hydrogen atom or R 7 ), Y represents an oxygen atom, -NH
2  2
一基又は一般式 (6)
Figure imgf000118_0001
Single or general formula (6)
Figure imgf000118_0001
(式中、 R9は水素原子又は R7を表す。）で示される基を表し、 Zは 4価の炭化水素基 を表し、 a及び bは夫々独立して、 0又は 1を表し、 kは自然数を表す。但し、式中、 R6 、 R8、 R9の何れか少なくとも 1つは二重結合を有する基である。 ]で示される構成単位 を含んで成る化合物。 (Wherein R 9 represents a hydrogen atom or R 7 ), Z represents a tetravalent hydrocarbon group, a and b each independently represent 0 or 1, k Represents a natural number. However, in the formula, at least one of R 6 , R 8 and R 9 is a group having a double bond. ] The compound which comprises the structural unit shown by this.
一般式 (7) General formula (7)
Figure imgf000118_0002
Figure imgf000118_0002
{式中、 R R R1'及び R2'は夫々独立して、水素原子、ハロゲン原子、アルキル基 又はアルコキシ基を表し、 R3'及び R4'は夫々独立して、水素原子、カルボキシル基 又はアルコキシカルボ-ル基を表し、 T及び Tは夫々独立して、炭素数 1〜6の直 {Wherein RRR 1 'and R 2 ' each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 3 'and R 4 ' each independently represent a hydrogen atom, a carboxyl group or Represents an alkoxycarbonyl group, and T and T are each independently a straight chain having 1 to 6 carbon atoms.
1 2  1 2
鎖状アルキレン基又はァリーレン基を表し、 Uは結合手又は式（1 1)〜（1 8) Represents a chain alkylene group or an arylene group, U represents a bond or a formula (11) to (18)
. (^ΟΤΛ r (1 -2) ° ° 0 -3) F3C CF3 . (^ ΟΤΛ r (1 - 2) ° ° 0 -3) F 3 C CF 3
H3C,srCH3 (1 5) 。 、 （1 6) H3C CH3 (1.7) 入 (1 -8) H 3 C, sr CH 3 (1 5) . , (1 6) H 3 C CH 3 (1. 7) Input (1 -8)
(式中、 R5及び R5'は夫々独立して、水素原子又はハロゲン原子を表す。）の何れか で示される 2価の基を表し、 V及び Vは夫々独立して、酸素原子又は NH 基を (Wherein, R 5 and R 5 'are each independently, represent. A hydrogen atom or a halogen atom) represents a divalent group represented by any one of, V and V are each independently a oxygen atom or a NH group
1 2  1 2
表し、 Y 'は酸素原子、 NH 基又は式 (8) Y ′ represents an oxygen atom, NH group or formula (8)
OH  OH
〇 (8) 〇 (8)
で示される基を表し、 Y 'は酸素原子、 NH 基又は式（9) Y ′ represents an oxygen atom, NH group or formula (9)
2  2
0H  0H
。、 (9) で示される基を表し、 Zは 4価の炭化水素基を表し、 a及び bは夫々独立して、 0又は 1 を表し、 kは自然数を表す。但し、式中、 R3'及び R4'のうち、少なくとも 1つはカルボ キシル基又はアルコキシカルボ-ル基である。 }で示される構成単位を含んで成る化 合物。 . , (9) Z represents a tetravalent hydrocarbon group, a and b each independently represent 0 or 1, and k represents a natural number. However, in the formula, at least one of R 3 ′ and R 4 ′ is a carboxyl group or an alkoxycarbonyl group. } A compound comprising a structural unit represented by
[3] 一般式 (1)で示される構成単位が一般式 (18)  [3] The structural unit represented by the general formula (1) is represented by the general formula (18)
(18) (18)
(式中、 前記に同
Figure imgf000119_0001
(Wherein the same as above
Figure imgf000119_0001
じ。 )で示されるものである請求項 1に記載の化合物。  Ji. 2. The compound according to claim 1, which is represented by:
[4] 一般式 ( 1 )で示される構成単位が一般式 (19)  [4] The structural unit represented by the general formula (1) is represented by the general formula (19)
Figure imgf000119_0002
Figure imgf000119_0002
(式中、 Y，，及び Y，，は夫々独立して、酸素原子又は— NH—基を表し、 R\ R2、 R (Where Y, and Y, independently represent an oxygen atom or —NH— group, R \ R 2 , R
1 2  1 2
l 5、 R2，、 R3、 R4、 T、 T、 U、 V、 V、 Z、 a、 b及び kは前記に同じ。）で示されるもの l 5 , R 2 , R 3 , R 4 , T, T, U, V, V, Z, a, b and k are the same as above. )
1 2 1 2  1 2 1 2
である請求項 1に記載の化合物。  The compound of claim 1, wherein
[5] 一般式 (7)で示される構成単位が一般式 (20)  [5] The structural unit represented by the general formula (7) is represented by the general formula (20)
(20) (20)
に同じ。 )
Figure imgf000119_0003
Same as )
Figure imgf000119_0003
で示されるものである請求項 2に記載の化合物。  The compound of Claim 2 which is shown by these.
[6] 一般式 (7)で示される構成単位が一般式 (21) 2、 R
Figure imgf000120_0001
[6] The structural unit represented by the general formula (7) is represented by the general formula (21) 2 , R
Figure imgf000120_0001
、R2，、R3，、R4，、T、T、U、 V、 V、Z、 a、 b及び kは前記に同じ。）で示されるも , R 2 , R 3 , R 4 , T, T, U, V, V, Z, a, b and k are the same as above. )
1 2 1 2  1 2 1 2
のである請求項 2に記載の化合物。 The compound according to claim 2, wherein
一般式 (7) General formula (7)
{
Figure imgf000120_0002
式中、 R2、 R1'及び R2'は夫々独立して、水素原子、ハロゲン原子、アルキル基 又はアルコキシ基を表し、 R3'及び R4'は夫々独立して、水素原子、カルボキシル基 又はアルコキシカルボ-ル基を表し、 T及び Tは夫々独立して、炭素数 1〜6の直 {
Figure imgf000120_0002
In the formula, R 2 , R 1 ′ and R 2 ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 3 ′ and R 4 ′ each independently represent a hydrogen atom, a carboxyl group Represents an alkoxy carbo group, and T and T are each independently a straight chain having 1 to 6 carbon atoms.
1 2  1 2
鎖状アルキレン基又はァリーレン基を表し、 Uは結合手又は式（1 1)〜（1 8) Represents a chain alkylene group or an arylene group, U represents a bond or a formula (11) to (18)
F3C F 3 C
(1 -3) 、 CF3 (1 4)
Figure imgf000120_0003
(1 -3), CF 3 (1 4)
Figure imgf000120_0003
H3C、 .CHa (1 -5) CH2 ( -6) H3- , h3 (—ァ） H 3 C, .CHa (1 -5) CH 2 (-6 ) H 3-, h 3 (—a)
Si 入 ( -8) Si input (-8)
(式中、 R5及び R5'は夫々独立して、水素原子又はハロゲン原子を表す。）の何れか で示される 2価の基を表し、 V及び Vは夫々独立して、酸素原子又は NH 基を (Wherein, R 5 and R 5 'are each independently, represent. A hydrogen atom or a halogen atom) represents a divalent group represented by any one of, V and V are each independently a oxygen atom or a NH group
1 2  1 2
表し、 Y 'は酸素原子、 NH 基又は式 (8) Y ′ represents an oxygen atom, NH group or formula (8)
OH  OH
o、 (8) で示される基を表し、 Y 'は酸素原子、 NH 基又は式（9)  o, represents a group represented by (8), Y ′ represents an oxygen atom, NH group or formula (9)
0H  0H
〇. (9) で示される基を表し、 Zは 4価の炭化水素基を表し、 a及び bは夫々独立して、 0又は 1 を表し、 kは自然数を表す。但し、式中、 R3'及び R4'のうち、少なくとも 1つはカルボ キシル基又はアルコキシカルボ-ル基である。 }で示される構成単位を含んで成る化 合物と、一般式 (10) 〇. Represents a group represented by (9), Z represents a tetravalent hydrocarbon group, a and b are each independently 0 or 1 And k represents a natural number. However, in the formula, at least one of R 3 ′ and R 4 ′ is a carboxyl group or an alkoxycarbonyl group. } And a compound comprising the structural unit represented by the general formula (10)
R7— X (10) R 7 — X (10)
(式中、 R7はビュルカルボ-ル基又はイソプロべ-ルカルポ-ル基を表し、 Xはハロ ゲン原子を表す。）、一般式 (11) 〇、丁^ J— (1 1 ) (In the formula, R 7 represents a butyl carbonyl group or an isopropyl carbonate group, and X represents a halogen atom.), General Formula (11) 〇 、 丁 ^ J— (1 1)
(式中、 R7はビュルカルボ-ル基又はイソプロべ-ルカルポ-ル基を表し、 Tは炭素 (In the formula, R 7 represents a butyl carbo group or an isopropyl carb group, and T represents carbon.
3 数 1〜6の直鎖状アルキレン基を表す。）及び一般式（12) Rレ0、 ΤΓ〇Η (12) 3 represents a linear alkylene group of 1 to 6 ) And general formula (12) R R 0 , ΤΓ〇 Η (12)
(式中、 R7はビュルカルボ-ル基又はイソプロべ-ルカルポ-ル基を表し、 Τは炭素 (In the formula, R 7 represents a bull carbol group or an isopropyl carba group, and Τ represents carbon.
4 数 1〜6の直鎖状アルキレン基を表す。）から選ばれる少なくとも 1種以上の (メタ)ァク リル酸誘導体とを反応させることを特徴とする、一般式（1)  4 represents a linear alkylene group of 1 to 6 ), Which is reacted with at least one (meth) acrylic acid derivative selected from general formula (1)
Figure imgf000121_0001
Figure imgf000121_0001
[式中、
Figure imgf000121_0002
R1'及び R2'は夫々独立して、水素原子、ハロゲン原子、アルキル基 又はアルコキシ基を表し、 R3及び R4は夫々独立して、水素原子又は一般式（2) — COOR6 (2) [Where
Figure imgf000121_0002
R 1 ′ and R 2 ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 3 and R 4 each independently represent a hydrogen atom or the general formula (2) — COOR 6 ( 2)
{式中、 R6は水素原子、炭素数 1〜6のアルキル基、一般式 (3)
Figure imgf000121_0003
{Wherein R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a general formula (3)
Figure imgf000121_0003
(式中、 R'はビュルカルボ-ル基又はイソプロべ-ルカルポ-ル基を表し、 Tは炭素  (In the formula, R ′ represents a butyl carbo group or an isopropyl carb group, and T represents carbon.
3 数 1〜6の直鎖状アルキレン基を表す。）、又は一般式 (4)  3 represents a linear alkylene group having 1 to 6 numbers. ) Or general formula (4)
Rレ 0、丁/ (4) R Re 0, Ding / (4)
(式中、 R7はビュルカルボ-ル基又はイソプロべ-ルカルポ-ル基を表し、 Τは炭素 数 1〜6の直鎖状アルキレン基を表す。）で示される基を表す。 }で示される基を表し、 T及び Tは夫々独立して、炭素数 1〜6の直鎖状アルキレン基又はァリーレン基を(In the formula, R 7 represents a butyl carbo group or an isopropyl carboxy group, and Τ represents carbon. The linear alkylene group of number 1-6 is represented. ) Represents a group represented by } And T and T each independently represent a linear alkylene group or arylene group having 1 to 6 carbon atoms.
1 2 1 2
表し、 Uは結合手又は式（1 1)〜（1 8) (1 -2) ° ° (1 -3) F3C CF3 (1.4) z \
Figure imgf000122_0001
U represents a bond or a formula (1 1) to (1 8) (1 -2) ° ° (1 -3) F 3 C CF 3 ( 1.4 ) z \
Figure imgf000122_0001
H3C、 CH3 ( ，CH2、 (1 6) H3C、 CH3 入 (1 -8) H 3 C, CH 3 (, C H 2 , (1 6) H 3 C, CH 3 input (1 -8)
(式中、 R5及び R5'は夫々独立して、水素原子又はハロゲン原子を表す。）の何れか で示される 2価の基を表し、 V及び Vは夫々独立して、酸素原子又は NH 基を (Wherein, R 5 and R 5 'are each independently, represent. A hydrogen atom or a halogen atom) represents a divalent group represented by any one of, V and V are each independently a oxygen atom or a NH group
1 2  1 2
表し、 Yは酸素原子、 NH 基又は一般式 (5) Y represents an oxygen atom, NH group or general formula (5)
(式中、 R8は水素原子又は R7を表す。）で示される基を表し、 Yは酸素原子、 -NH (Wherein R 8 represents a hydrogen atom or R 7 ), Y represents an oxygen atom, -NH
2  2
一基又は一般式 (6) Single or general formula (6)
9 (6)  9 (6)
(式中、 R9は水素原子又は R7を表す。）で示される基を表し、 Ζは 4価の炭化水素基 を表し、 a及び bは夫々独立して、 0又は 1を表し、 kは自然数を表す。但し、式中、 R6 、 R8、 R9の何れか少なくとも 1つは二重結合を有する基である。 ]で示される構成単位 を含んで成る化合物の製造方法。 (Wherein R 9 represents a hydrogen atom or R 7 ), Ζ represents a tetravalent hydrocarbon group, a and b each independently represent 0 or 1, k Represents a natural number. However, in the formula, at least one of R 6 , R 8 and R 9 is a group having a double bond. ] The manufacturing method of the compound which comprises the structural unit shown by these.
一般式 (13) (13)General formula (13) (13)
Figure imgf000122_0002
Figure imgf000122_0002
{式中、
Figure imgf000122_0003
R2、 R1'及び R2'は夫々独立して、水素原子、ハロゲン原子、アルキル基 又はアルコキシ基を表し、 R1C>は水素原子、アルカリ金属原子、一般式（14) {Where
Figure imgf000122_0003
R 2 , R 1 ′ and R 2 ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, R 1C> represents a hydrogen atom, an alkali metal atom, or a general formula (14)
?>^ τ (14) ?> ^ τ (14)
1 1  1 1
(式中、 Τは炭素数 1〜6の直鎖状アルキレン基又はァリーレン基を表す。）、又は一 般式 (15)
Figure imgf000123_0001
(Wherein Τ represents a straight-chain alkylene group or arylene group having 1 to 6 carbon atoms), or General formula (15)
Figure imgf000123_0001
(式中、 Miは水素原子又はアルカリ金属原子を表し、 は炭素数 1〜6の直鎖状ァ ルキレン基又はァリーレン基を表し、 Vは酸素原子又は—NH 基を表す。）で示さ  (In the formula, Mi represents a hydrogen atom or an alkali metal atom, represents a linear alkylene group or arylene group having 1 to 6 carbon atoms, and V represents an oxygen atom or —NH 2 group).
3  Three
れる基を表し、 R11は水素原子、アルカリ金属原子、一般式（16) \ Τ ^? (16) R 11 is a hydrogen atom, an alkali metal atom, general formula (16) \ Τ ^? (16)
(式中、 Τは炭素数 1〜6の直鎖状アルキレン基又はァリーレン基を表す。）、又は一 (Wherein Τ represents a straight-chain alkylene group or arylene group having 1 to 6 carbon atoms), or
2  2
般式 (17) General formula (17)
、 4、Μ2 (1 7) , 4 , Μ 2 ( 1 7 )
(式中、 Μは水素原子又はアルカリ金属原子を表し、 Τは炭素数 1〜6の直鎖状ァ  (In the formula, Μ represents a hydrogen atom or an alkali metal atom, and Τ represents a linear alkyl group having 1 to 6 carbon atoms.
2 2  twenty two
ルキレン基又はァリーレン基を表し、 Vは酸素原子又は—ΝΗ 基を表す。）で示さ Represents a rualkylene group or an arylene group, and V represents an oxygen atom or a — group. )
4  Four
れる基を表し、 Uは結合手又は式（1 1)〜（1 8) U represents a bond or a formula (1 1) to (1 8)
JTS (1 -1) (1 -2) ° ° (1 -3) F3C、 CF3 (1 4)
Figure imgf000123_0002
JTS (1 -1) (1 -2) ° ° (1 -3) F 3 C, CF 3 (1 4)
Figure imgf000123_0002
H3 S^H3 (1 5) H2、 （1 6) H3C /CH3 ( ） 0\ (1 -8) H 3 S ^ H 3 (1 5 ) H 2 , ( 1 6 ) H 3 C / CH 3 () 0 \ (1 -8)
(式中、 R5及び R5'は夫々独立して、水素原子又はハロゲン原子を表す。）の何れか で示される 2価の基を表し、 V及び Vは夫々独立して、酸素原子又は NH 基を (Wherein, R 5 and R 5 'are each independently, represent. A hydrogen atom or a halogen atom) represents a divalent group represented by any one of, V and V are each independently a oxygen atom or a NH group
1 2  1 2
表す。 }で示される化合物と、カルボキシル基を 3個以上有する多塩基酸 (カルボキシ ル基の一部がカルボン酸エステルであるものを含む。）又はその無水物（カルボキシ ル基の一部が脱水縮合して酸無水物基を形成しているものを含み、また、その一部 がカルボン酸エステルであるものを含む。）とを反応させることを特徴とする、一般式（ To express. } And a polybasic acid having 3 or more carboxyl groups (including those in which part of the carboxyl group is a carboxylic acid ester) or an anhydride thereof (part of the carboxyl group undergoes dehydration condensation). In which an acid anhydride group is formed, and a part of which is a carboxylic acid ester).
Figure imgf000123_0003
{式中、 R R2、 R1'及び R2'は夫々独立して、水素原子、ハロゲン原子、アルキル基 又はアルコキシ基を表し、 R3'及び R4'は夫々独立して、水素原子、カルボキシル基 又はアルコキシカルボ-ル基を表し、 T及び Tは夫々独立して、炭素数 1〜6の直
Figure imgf000123_0003
{Wherein, RR 2 , R 1 ′ and R 2 ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 3 ′ and R 4 ′ each independently represent a hydrogen atom, Represents a carboxyl group or an alkoxycarbonyl group, and T and T are each independently a straight chain having 1 to 6 carbon atoms.
1 2  1 2
鎖状アルキレン基又はァリーレン基を表し、 Uは結合手又は式（1 1)〜（1 8) CF3 (
Figure imgf000124_0001
Represents a chain alkylene group or an arylene group, U represents a bond or a formula (11) to (18) CF 3 (
Figure imgf000124_0001
H3C .CHa (1 -5) CH2 ( -6) H3- , h3 H 3 C .CHa (1 -5) CH 2 ( -6 ) H 3-, h 3
Si (—ァ） 入 ( -8) Si (—A) input (-8)
(式中、 R5及び R5'は夫々独立して、水素原子又はハロゲン原子を表す。）の何れか で示される 2価の基を表し、 V及び Vは夫々独立して、酸素原子又は NH 基を (Wherein, R 5 and R 5 'are each independently, represent. A hydrogen atom or a halogen atom) represents a divalent group represented by any one of, V and V are each independently a oxygen atom or a NH group
1 2  1 2
表し、 Y 'は酸素原子、 NH 基又は式 (8)  Y ′ represents an oxygen atom, NH group or formula (8)
OH  OH
,0、 (8) で示される基を表し、 Y 'は酸素原子、 NH 基又は式（9)  , 0, represents a group represented by (8), Y ′ represents an oxygen atom, NH group or formula (9)
0H  0H
(9) で示される基を表し、 Zは 4価の炭化水素基を表し、 a及び bは夫々独立して、 0又は 1 を表し、 kは自然数を表す。但し、式中、 R3'及び R4'のうち、少なくとも 1つはカルボ キシル基又はアルコキシカルボ-ル基である。 }で示される構成単位を含んで成る化 合物の製造方法。 (9) represents a group, Z represents a tetravalent hydrocarbon group, a and b each independently represent 0 or 1, and k represents a natural number. However, in the formula, at least one of R 3 ′ and R 4 ′ is a carboxyl group or an alkoxycarbonyl group. } The manufacturing method of the compound which comprises the structural unit shown.
[9] 一般式 (7)で示される構成単位を含んで成る化合物が請求項 8に記載の製造方法 によって得られるものである請求項 7に記載の製造方法。  [9] The production method according to claim 7, wherein the compound comprising the structural unit represented by the general formula (7) is obtained by the production method according to claim 8.
[10] 一般式 (7)で示される構成単位が一般式 (20)  [10] The structural unit represented by the general formula (7) is represented by the general formula (20)
(20)
Figure imgf000124_0002
(20)
Figure imgf000124_0002
(式中、
Figure imgf000124_0003
R2、 R1 '、 R2，、 R3，、 R4，、 τ 、 τ 、 u、 V 、 V 、 Z及び kは前記に同じ。 ) で示されるものであり、一般式（1)で示される構成単位が一般式（18) (18) (Where
Figure imgf000124_0003
R 2 , R 1 ′, R 2 , R 3 , R 4 , τ, τ, u, V, V, Z and k are the same as above. ) And the structural unit represented by general formula (1) is represented by general formula (18) (18)
前記に同
Figure imgf000125_0001
Same as above
Figure imgf000125_0001
じ。 )で示されるものである請求項 7に記載の製造方法。  Ji. 8. The production method according to claim 7, wherein
[11] 一般式 (7)で示される構成単位が一般式 (21)  [11] The structural unit represented by the general formula (7) is represented by the general formula (21)
2、 R
Figure imgf000125_0002
2, R
Figure imgf000125_0002
、R2，、R3，、R4，、T、T、U、 V、 V、Z、 a、 b及び kは前記に同じ。）で示されるも , R 2 , R 3 , R 4 , T, T, U, V, V, Z, a, b and k are the same as above. )
1 2 1 2  1 2 1 2
のであり、（メタ)アクリル酸誘導体が一般式（11)  The (meth) acrylic acid derivative has the general formula (11)
〇  Yes
〇、  Yes,
R 7z (11)  R 7z (11)
(式中、 R'及び Tは前記に同じ。）及び一般式（12) (Wherein R ′ and T are the same as above) and general formula (12)
Rレ0、 T,0H (12) R 0 , T, 0H (12)
(式中、 R7及び Τは前記に同じ。）から選ばれる少なくとも 1種以上のものであり、 (Wherein R 7 and Τ are the same as defined above),
4 一 般式 ( 1 )で示される構成単位が一般式 (19)  4 The structural unit represented by the general formula (1) is the general formula (19).
Figure imgf000125_0003
Figure imgf000125_0003
(式中、 Y，，及び Y，，は夫々独立して、酸素原子又は— NH—基を表し、 R\ R2、 R (Where Y, and Y, independently represent an oxygen atom or —NH— group, R \ R 2 , R
1 2  1 2
l5、 R2，、 R3、 R4、 T、 T、 U、 V、 V、 Z、 a、 b及び kは前記に同じ。）で示されるもの l 5 , R 2 , R 3 , R 4 , T, T, U, V, V, Z, a, b and k are the same as above. )
1 2 1 2  1 2 1 2
である請求項 7に記載の製造方法。  The manufacturing method according to claim 7.
[12] 一般式（13)で示される化合物が一般式 (22) は前記に同じ。）で示されるもので
Figure imgf000126_0001
[12] The compound represented by the general formula (13) is represented by the general formula (22) Is the same as above. )
Figure imgf000126_0001
あり、当該化合物と反応させる酸は、カルボキシル基を 3個以上有する多塩基酸 (力 ルボキシル基の一部がカルボン酸エステルであるものを含む。）であり、一般式（7)で 示される構成単位が一般式 (20) The acid to be reacted with the compound is a polybasic acid having 3 or more carboxyl groups (including those in which a part of the carboxy group is a carboxylic acid ester), and has the structure represented by the general formula (7) Unit is general formula (20)
Figure imgf000126_0002
Figure imgf000126_0002
で示されるものである請求項 8に記載の製造方法。 The production method according to claim 8, which is represented by:
一般式（13)で示される化合物が一般式 (23)
Figure imgf000126_0003
The compound represented by the general formula (13) is represented by the general formula (23)
Figure imgf000126_0003
{式中、 R ま水素原子、アルカリ金属原子又は一般式（15)
Figure imgf000126_0004
{Wherein R or hydrogen atom, alkali metal atom or general formula (15)
Figure imgf000126_0004
(式中、 Μ、 Τ及び Vは前記に同じ。）で示される基を表し、 R13は水素原子、アル力 (Wherein, Μ, Τ and V are as defined above), R 13 represents a hydrogen atom, an al force
1 1 3  1 1 3
リ金属原子又は一般式（17) \ TfV4、M2 (17) Li metal atom or general formula (17) \ T f V4 , M 2 ( 17 )
(式中、 M、 T及び Vは前記に同じ。）で示される基を表し、 R\ R2、 R 、 R2，、 U、 (Wherein, M, T and V are the same as above), and R \ R 2 , R 1, R 2 , U,
2 2 4  2 2 4
V及び Vは前記に同じ。 }で示されるものであり、当該化合物と反応させる酸は、力 V and V are the same as above. } The acid that reacts with the compound is
1 2 1 2
ルポキシル基を 3個以上有する多塩基酸無水物 (カルボキシル基の一部が脱水縮合 して酸無水物基を形成しているものを含み、また、その一部がカルボン酸エステルで あるものを含む。）であり、一般式 (7)で示される構成単位が一般式 (21) R2
Figure imgf000127_0001
、 R 、R2，、R3，、R4，、T、T、U、 V、 V、Z、 a、 b及び kは前記に同じ。）で示されるも Polybasic acid anhydrides having 3 or more lpoxyl groups (including those in which a part of the carboxyl group is condensed by dehydration to form an acid anhydride group, and also a part of which is a carboxylic acid ester) The structural unit represented by the general formula (7) is represented by the general formula (21) R 2
Figure imgf000127_0001
, R, R 2 , R 3 , R 4 , T, T, U, V, V, Z, a, b and k are the same as above. )
1 2 1 2  1 2 1 2
のである請求項 8に記載の製造方法。 The manufacturing method according to claim 8, wherein
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KR20180101045A (en) * 2017-03-03 2018-09-12 주식회사 엘지화학 Polymer resion compound and photosensitive resin composition for black bank
JP2019524915A (en) * 2017-03-03 2019-09-05 エルジー・ケム・リミテッド Polymer resin compound and photosensitive resin composition for black bank containing the same
KR102054045B1 (en) 2017-03-03 2019-12-09 주식회사 엘지화학 Polymer resion compound and photosensitive resin composition for black bank
US10633486B2 (en) 2017-03-03 2020-04-28 Lg Chem, Ltd. Polymer resin compound and photosensitive resin composition for black bank comprising same
JP7036346B2 (en) 2017-03-03 2022-03-15 エルジー・ケム・リミテッド Polymer resin compound and photosensitive resin composition for black bank containing the same

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KR20090009236A (en) 2009-01-22
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KR101050728B1 (en) 2011-07-21
TW200801068A (en) 2008-01-01

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