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WO2007123017A1 - Composé insaturé polymérisable et procédé servant à produire celui-ci - Google Patents

Composé insaturé polymérisable et procédé servant à produire celui-ci 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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English (en)
Japanese (ja)
Inventor
Yoshihiro Hosaka
Nobutaka Shimamura
Kenichi Inoue
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Wako Pure Chemical Industries, Ltd.
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Priority to CN2007800045509A priority Critical patent/CN101379111B/zh
Priority to JP2008512066A priority patent/JPWO2007123017A1/ja
Priority to KR1020087027522A priority patent/KR101050728B1/ko
Publication of WO2007123017A1 publication Critical patent/WO2007123017A1/fr

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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

L'invention concerne un composé contenant une unité constitutive représentée par la formule générale (1) ci-dessous et un procédé servant à produire un tel composé. (1) [Dans la formule, R3 et R4 représentent chacun indépendamment un atome d'hydrogène ou un groupe représenté par la formule générale (2) suivante : (2); T1 et T2 représentent chacun indépendamment un groupe alkylène linéaire ayant 1-6 atomes de carbone ou un groupe arylène; U représente une liaison ou un groupe divalent représenté par l'une des formules (1-1)-(1-8) suivantes : (1-1) (1-2) (1-3) (1-4) (1-5) (1-6) (1-7) (1-8); V1 et V2 représentent chacun indépendamment un atome d'oxygène ou un groupe -NH-; Y1 représente un atome d'oxygène, un groupe -NH- ou un groupe représenté par la formule générale (5) ci-dessous et Y2 représente un atome d'oxygène, un groupe -NH- ou un groupe représenté par la formule générale (6) ci-dessous : (5) (6); Z représente un groupe hydrocarboné tétravalent; a et b représentent chacun indépendamment 0 ou 1; et k représente un nombre entier naturel. A cet égard, au moins l'un de R6, R8 et R9 représente un groupe ayant une double liaison.]
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WO2009119623A1 (fr) * 2008-03-25 2009-10-01 綜研化学株式会社 Résine photosensible et composition de résine photosensible comprenant ladite résine photosensible
JP2010507104A (ja) * 2006-10-16 2010-03-04 チェイル インダストリーズ インコーポレイテッド カルド樹脂を含む樹脂組成物、前記樹脂組成物を用いたパターンの形成方法、および前記方法によって形成されたパターンを用いたカラーフィルター
JP2013221980A (ja) * 2012-04-13 2013-10-28 Jsr Corp 着色組成物、カラーフィルタ及び表示素子
WO2018159975A1 (fr) * 2017-03-03 2018-09-07 주식회사 엘지화학 Composé de résine polymère et composition de résine photosensible pour masque noir comprenant celui-ci

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KR102420415B1 (ko) * 2017-10-17 2022-07-15 덕산네오룩스 주식회사 부착력 또는 접착성이 향상된 감광성 수지 조성물 및 그것들을 사용한 광 차단 층
KR102227606B1 (ko) * 2018-04-06 2021-03-12 주식회사 엘지화학 카도계 바인더 수지, 이를 포함하는 감광성 수지 조성물, 블랙 매트릭스, 컬러필터 및 디스플레이 장치

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JP7036346B2 (ja) 2017-03-03 2022-03-15 エルジー・ケム・リミテッド 高分子樹脂化合物およびこれを含むブラックバンク用感光性樹脂組成物

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