CN112601735B - Compound, colored resin composition, color filter and display device - Google Patents

Compound, colored resin composition, color filter and display device Download PDF

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CN112601735B
CN112601735B CN201980055149.0A CN201980055149A CN112601735B CN 112601735 B CN112601735 B CN 112601735B CN 201980055149 A CN201980055149 A CN 201980055149A CN 112601735 B CN112601735 B CN 112601735B
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carbon atoms
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diyl
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CN112601735A (en
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上田俊雄
森胁章太
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Dongwoo Fine Chem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a compound capable of forming a color filter with excellent heat resistance. The object is achieved by a compound represented by the formula (I), a colored resin composition containing the compound, a color filter and a display device.

Description

Compound, colored resin composition, color filter and display device
Technical Field
The invention relates to a compound, a coloring resin composition, a color filter and a display device.
Background
Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, or solid-state imaging devices such as CCDs and CMOS sensors are manufactured from colored resin compositions. As a colorant used in such a colored resin composition, a compound represented by the formula (x) is known (patent document 1: japanese patent laid-open publication No. 2015-86380).
Disclosure of Invention
Technical problem
However, there are cases where the heat resistance of a color filter formed from a conventionally known colored resin composition containing the above compound is not sufficiently satisfied. Accordingly, the present invention provides a compound capable of forming a color filter having excellent heat resistance.
Means for solving the problems
The present invention includes the following inventions.
[1] A compound represented by the formula (I),
In the formula (I) of the formula (I),
R 1 to R 8 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or an alkoxy group of 1 to 20 carbon atoms which may have a substituent.
R 9 and R 10 each independently represent a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a methylene group contained in the aliphatic hydrocarbon group may be substituted with-O-.
R 11 and R 12 each independently represent a hydrocarbon group having 6 to 20 carbon atoms of an aromatic hydrocarbon ring, the hydrocarbon group may have a substituent, and a methylene group contained in the hydrocarbon group may be substituted with-O-.
R 13 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms ].
[2] A colored resin composition comprising a colorant and a resin, the colorant comprising the compound according to [1 ].
[3] The colored resin composition according to [2], further comprising a polymerizable compound and a polymerization initiator.
[4] A color filter formed from the colored resin composition described in [2] or [3 ].
[5] A display device comprising the color filter of [4 ].
Effects of the invention
According to the present invention, a novel compound capable of forming a color filter excellent in heat resistance is provided.
Detailed Description
< Compounds >
The compound of the present invention is a compound represented by the formula (I) (hereinafter, sometimes referred to as compound (I)). The present invention will be described in detail below using the formula (I), but the compound (I) also includes a resonance structure of the formula (I) or a compound obtained by rotating each group of the formula (I) around a bond axis of a carbon-carbon single bond.
In the formula (I) of the formula (I),
R 1 to R 8 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or an alkoxy group of 1 to 20 carbon atoms which may have a substituent.
R 9 and R 10 each independently represent a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a methylene group contained in the aliphatic hydrocarbon group may be substituted with-O-.
R 11 and R 12 each independently represent a hydrocarbon group having 6 to 20 carbon atoms of an aromatic hydrocarbon ring, the hydrocarbon group may have a substituent, and a methylene group contained in the hydrocarbon group may be substituted with-O-.
R 13 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. ]
Examples of the halogen atom represented by R 1 to R 8 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 8 may be any of straight-chain, branched-chain and cyclic. Specific examples of the linear or branched saturated hydrocarbon group include methyl, ethyl, propyl, isobutyl, butyl, t-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecyl, undecyl and the like. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1, 2-dimethylcyclohexyl, cyclooctyl, 2,4, 6-trimethylcyclohexyl, and 4-cyclohexylcyclohexyl.
Examples of the substituent of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 8 include halogen atoms such as fluorine atom, chlorine atom and iodine atom; a hydroxyl group; -NR aRb(Ra and R b are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.
Examples of the alkoxy group having 1 to 20 carbon atoms represented by R 1 to R 8 include a group in which-O-is bonded to a bond of the saturated hydrocarbon group having 1 to 20 carbon atoms. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyl oxy and the like.
Examples of the substituent of the alkoxy group having 1 to 20 carbon atoms represented by R 1 to R 8 include halogen atoms such as fluorine atom, chlorine atom and iodine atom; a hydroxyl group; -NR cRd(Rc and R d are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; an alkoxycarbonyl group having 1 to 10 carbon atoms in the alkoxy moiety such as methoxycarbonyl group and ethoxycarbonyl group.
Among R 1 to R 8, R 1 to R 4 are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. In addition, in the case where R 1 to R 4 are a hydrogen atom or a methyl group, more preferably in the case where R 1 to R 4 are a hydrogen atom, R 5 to R 8 are each independently preferably a hydrogen atom, a hydroxyl group, a saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or an alkoxy group of 1 to 20 carbon atoms which may have a substituent, more preferably a hydrogen atom or a hydroxyl group.
Preferably, two to four of R 1 to R 8 (preferably R 5 to R 8) are each independently hydroxyl.
The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 9 and R 10 may be either saturated or unsaturated, and is preferably saturated. The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be any of linear, branched and cyclic, and is preferably linear or branched.
Examples of the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include divalent linear aliphatic hydrocarbon groups such as methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl, dodecane-1, 12-diyl, tridecane-1, 13-diyl, tetradecane-1, 14-diyl, pentadecane-1, 15-diyl, hexadecane-1, 16-diyl, heptadecane-1, 17-diyl, and propenylene; and divalent branched aliphatic hydrocarbon groups such as ethane-1, 1-diyl, propane-1, 2-diyl, propane-2, 2-diyl, pentane-2, 4-diyl, 2-methylpropane-1, 3-diyl, 2-methylpropane-1, 2-diyl, 2-dimethylpropane-1, 3-diyl, pentane-1, 4-diyl, and 2-methylbutane-1, 4-diyl.
The cyclic divalent aliphatic hydrocarbon group may be a single ring or multiple rings. Examples of the cyclic divalent aliphatic hydrocarbon group include monocyclic divalent aliphatic hydrocarbon groups such as cyclobutane-1, 3-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 4-diyl and cyclooctane-1, 5-diyl; and polycyclic divalent aliphatic hydrocarbon groups such as norbornane-1, 4-diyl, norbornane-2, 5-diyl, adamantane-1, 5-diyl, adamantane-2, 6-diyl, and the like.
The methylene group contained in the foregoing divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be substituted with-O-. Examples of the group in which the methylene group contained in the divalent aliphatic hydrocarbon group is substituted with-O-include groups represented by the following formula. In the following formula, the left side indicates a bond to a nitrogen atom, and the right side indicates a bond to an oxygen atom.
The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R 9 and R 10 may have a substituent, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and iodine atom; a hydroxyl group; -NR eRf(Re and R f are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.
Examples of the hydrocarbon group having 6 to 20 carbon atoms having an aromatic hydrocarbon ring represented by R 11 and R 12 include a group having a bond to an aromatic hydrocarbon ring (hereinafter referred to as an aromatic hydrocarbon group), an aralkyl group having 7 to 20 carbon atoms, and the like. They may also have substituents.
Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and the like, and benzene ring is preferable.
Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthryl, phenanthryl, tolyl, xylyl, trimethylphenyl, and diisopropylphenyl. Among them, preferred is an aromatic hydrocarbon group having an alkyl group in the ortho position, and examples thereof include a2, 6-dimethylphenyl group, a2, 4, 6-trimethylphenyl group, a2, 6-diisopropylphenyl group and the like. Further, if the volume of the alkyl group in the ortho position is large, there is a tendency that the light resistance is excellent.
In the case where the aromatic hydrocarbon group has a substituent, the aromatic hydrocarbon group may have one or more substituents. In the case where the aromatic hydrocarbon group has a plurality of substituents, the substituents may be the same or different. Examples of the substituent include a hydroxyl group; a carboxyl group; halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a sulfamoyl group; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.
The hydrocarbon group having 1 to 14 carbon atoms may have a substituent such as a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, or the like.
In the case where the aromatic hydrocarbon group which may have a substituent has a methylene group, the methylene group may be substituted with-O-.
Examples of the aralkyl group having 7 to 20 carbon atoms include a group in which an alkanediyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group is bonded to the aromatic hydrocarbon ring described in the above-mentioned aromatic hydrocarbon group. Examples of the aralkyl group include benzyl, phenylethyl, naphthylmethyl, naphthylethyl and the like.
The aralkyl group having 7 to 20 carbon atoms may have a substituent, and when there are a plurality of substituents, each substituent may be the same or different. The substituent may be bonded to the aromatic hydrocarbon ring or to the alkanediyl group, and the substituent which may be bonded to the aromatic hydrocarbon ring is the same as the substituent described for the aromatic hydrocarbon group.
In the case where the aforementioned aralkyl group having 7 to 20 carbon atoms which may have a substituent has a methylene group, the methylene group may also be substituted with-O-.
The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R 13 may be any of linear, branched and cyclic. Specific examples of the linear or branched saturated hydrocarbon group include methyl, ethyl, propyl, isobutyl, butyl, t-butyl, hexyl, heptyl, octyl, and the like. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1, 2-dimethylcyclohexyl, and cyclooctyl.
Examples of the compound (I) include compounds represented by the formulas (I-1) to (I-240) shown in tables 1 to 3.
TABLE 1
TABLE 2
TABLE 3
In tables 1 to 3, A1-1 to A1-4 represent groups represented by the following formulas. In the following formula, the left side indicates a bond to a nitrogen atom, and the right side indicates a bond to an oxygen atom.
In tables 1 to 3, A2-1 to A2-5 represent groups represented by the following formulas. In the following formula, the bond is represented.
In addition, the compound (I) may be a compound represented by the following formula (II), in addition to the compounds represented by the above formulas (I-1) to (I-240), and preferably a compound represented by the following formula (II). The compound represented by formula (II) has good light resistance.
In the formula (II),
R 1 to R 10 represent the same meaning as R 1 to R 10 in formula (I);
x 1 and X 2 each independently represent a hydrocarbon group having 1 to 14 carbon atoms and having at least one member selected from the group consisting of a hydroxyl group and a carboxyl group, and a methylene group contained in the hydrocarbon group may be substituted with-O-;
R 14 and R 15 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 13 carbon atoms;
n1 and n2 each independently represent an integer of 1 to 5;
Wherein (total carbon number of X 1)n1 and (R 14)5-n1) and (total carbon number of X 2)n2 and (R 15)5-n2) are each 14 or less.)
Examples of the hydrocarbon group having 1 to 14 carbon atoms represented by X 1 and X 2 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
Examples of the linear aliphatic hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
Examples of the branched aliphatic hydrocarbon group include isopropyl, sec-butyl, tert-butyl, methylpentyl, ethylpentyl, methylhexyl, ethylhexyl, propylhexyl, and tert-octyl, and preferably isopropyl, sec-butyl, tert-butyl, and ethylhexyl.
Examples of the cyclic aliphatic hydrocarbon group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl groups.
Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, 2, 6-diethylphenyl, and 2-methyl-6-ethylphenyl.
Examples of the group formed by combining them include an alkylcycloalkyl group, a cycloalkylalkyl group, an aralkyl group, and the like.
The methylene group contained in the aforementioned hydrocarbon group having 1 to 14 carbon atoms may be substituted with-O-.
Examples of the hydrocarbon group having 1 to 13 carbon atoms represented by R 14 and R 15 include the same groups as those described for the hydrocarbon group having 1 to 14 carbon atoms represented by X 1 and X 2.
N1 and n2 each independently represent an integer of 1 to 5, more preferably 1 to 2.
(X 1)n1 and (the total number of carbon atoms of R 14)5-n1) and (X 2)n2 and (the total number of carbon atoms of R 15)5-n2) are 14 or less, respectively. When there are a plurality of X 1、X2、R14 and R 15, each of X 1、X2、R14 and R 15 may be the same or different.
The compound (II) may be a compound represented by the following formula (II-a), and specifically, compounds represented by the formulas (II-1) to (II-540) shown in tables 4 to 12 may be mentioned.
TABLE 4
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-1) H OH OH OH OH A1-1 A1-1 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-2) H H H H H A1-1 A1-1 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-3) H OH H H OH A1-1 A1-1 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-4) H OH OH OH OH A1-1 A1-1 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-5) H H H H H A1-1 A1-1 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-6) H OH H H OH A1-1 A1-1 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-7) H OH OH OH OH A1-1 A1-1 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-8) H H H H H A1-1 A1-1 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-9) H OH H H OH A1-1 A1-1 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-10) H OH OH OH OH A1-1 A1-1 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-11) H H H H H A1-1 A1-1 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-12) H OH H H OH A1-1 A1-1 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-13) H OH OH OH OH A1-1 A1-1 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-14) H H H H H A1-1 A1-1 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-15) H OH H H OH A1-1 A1-1 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-16) H OH OH OH OH A1-1 A1-1 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-17) H H H H H A1-1 A1-1 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-18) H OH H H OH A1-1 A1-1 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-19) H OH OH OH OH A1-1 A1-1 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-20) H H H H H A1-1 A1-1 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-21) H OH H H OH A1-1 A1-1 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-22) H OH OH OH OH A1-1 A1-1 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-23) H H H H H A1-1 A1-1 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-24) H OH H H OH A1-1 A1-1 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-25) H OH OH OH OH A1-1 A1-1 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-26) H H H H H A1-1 A1-1 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-27) H OH H H OH A1-1 A1-1 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-28) H OH OH OH OH A1-1 A1-1 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-29) H H H H H A1-1 A1-1 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-30) H OH H H OH A1-1 A1-1 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-31) H OH OH OH OH A1-1 A1-1 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-32) H H H H H A1-1 A1-1 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-33) H OH H H OH A1-1 A1-1 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-34) H OH OH OH OH A1-1 A1-1 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-35) H H H H H A1-1 A1-1 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-36) H OH H H OH A1-1 A1-1 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-37) H OH OH OH OH A1-1 A1-1 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-38) H H H H H A1-1 A1-1 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-39) H OH H H OH A1-1 A1-1 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-40) H OH OH OH OH A1-1 A1-1 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-41) H H H H H A1-1 A1-1 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-42) H OH H H OH A1-1 A1-1 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-43) H OH OH OH OH A1-1 A1-1 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-44) H H H H H A1-1 A1-1 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-45) H OH H H OH A1-1 A1-1 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-46) H OH OH OH OH A1-1 A1-1 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-47) H H H H H A1-1 A1-1 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-48) H OH H H OH A1-1 A1-1 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-49) H OH OH OH OH A1-1 A1-1 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-50) H H H H H A1-1 A1-1 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-51) H OH H H OH A1-1 A1-1 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-52) H OH OH OH OH A1-1 A1-1 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-53) H H H H H A1-1 A1-1 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-54) H OH H H OH A1-1 A1-1 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-55) H OH OH OH OH A1-1 A1-1 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-56) H H H H H A1-1 A1-1 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-57) H OH H H OH A1-1 A1-1 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-58) H OH OH OH OH A1-1 A1-1 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
(II-59) H H H H H A1-1 A1-1 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
(II-60) H OH H H OH A1-1 A1-1 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
TABLE 5
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-61) H OH OH OH OH A1-2 A1-2 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-62) H H H H H A1-2 A1-2 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-63) H OH H H OH A1-2 A1-2 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-64) H OH OH OH OH A1-2 A1-2 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-65) H H H H H A1-2 A1-2 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-66) H OH H H OH A1-2 A1-2 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-67) H OH OH OH OH A1-2 A1-2 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-68) H H H H H A1-2 A1-2 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-69) H OH H H OH A1-2 A1-2 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-70) H OH OH OH OH A1-2 A1-2 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-71) H H H H H A1-2 A1-2 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-72) H OH H H OH A1-2 A1-2 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-73) H OH OH OH OH A1-2 A1-2 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-74) H H H H H A1-2 A1-2 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-75) H OH H H OH A1-2 A1-2 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-76) H OH OH OH OH A1-2 A1-2 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-77) H H H H H A1-2 A1-2 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-78) H OH H H OH A1-2 A1-2 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-79) H OH OH OH OH A1-2 A1-2 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-80) H H H H H A1-2 A1-2 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-81) H OH H H OH A1-2 A1-2 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-82) H OH OH OH OH A1-2 A1-2 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-83) H H H H H A1-2 A1-2 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-84) H OH H H OH A1-2 A1-2 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-85) H OH OH OH OH A1-2 A1-2 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-86) H H H H H A1-2 A1-2 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-87) H OH H H OH A1-2 A1-2 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-88) H OH OH OH OH A1-2 A1-2 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-89) H H H H H A1-2 A1-2 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-90) H OH H H OH A1-2 A1-2 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-91) H OH OH OH OH A1-2 A1-2 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-92) H H H H H A1-2 A1-2 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-93) H OH H H OH A1-2 A1-2 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-94) H OH OH OH OH A1-2 A1-2 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-95) H H H H H A1-2 A1-2 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-96) H OH H H OH A1-2 A1-2 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-97) H OH OH OH OH A1-2 A1-2 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-98) H H H H H A1-2 A1-2 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-99) H OH H H OH A1-2 A1-2 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-100) H OH OH OH OH A1-2 A1-2 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-101) H H H H H A1-2 A1-2 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-102) H OH H H OH A1-2 A1-2 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-103) H OH OH OH OH A1-2 A1-2 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-104) H H H H H A1-2 A1-2 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-105) H OH H H OH A1-2 A1-2 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-106) H OH OH OH OH A1-2 A1-2 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-107) H H H H H A1-2 A1-2 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-108) H OH H H OH A1-2 A1-2 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-109) H OH OH OH OH A1-2 A1-2 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-110) H H H H H A1-2 A1-2 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-111) H OH H H OH A1-2 A1-2 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-112) H OH OH OH OH A1-2 A1-2 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-113) H H H H H A1-2 A1-2 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-114) H OH H H OH A1-2 A1-2 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-115) H OH OH OH OH A1-2 A1-2 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-116) H H H H H A1-2 A1-2 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-117) H OH H H OH A1-2 A1-2 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-118) H OH OH OH OH A1-2 A1-2 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
(II-119) H H H H H A1-2 A1-2 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
(II-120) H OH H H OH A1-2 A1-2 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
TABLE 6
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-121) H OH OH OH OH A1-3 A1-3 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-122) H H H H H A1-3 A1-3 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-123) H OH H H OH A1-3 A1-3 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-124) H OH OH OH OH A1-3 A1-3 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-125) H H H H H A1-3 A1-3 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-126) H OH H H OH A1-3 A1-3 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-127) H OH OH OH OH A1-3 A1-3 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-128) H H H H H A1-3 A1-3 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-129) H OH H H OH A1-3 A1-3 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-130) H OH OH OH OH A1-3 A1-3 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-131) H H H H H A1-3 A1-3 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-132) H OH H H OH A1-3 A1-3 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-133) H OH OH OH OH A1-3 A1-3 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-134) H H H H H A1-3 A1-3 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-135) H OH H H OH A1-3 A1-3 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-136) H OH OH OH OH A1-3 A1-3 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-137) H H H H H A1-3 A1-3 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-138) H OH H H OH A1-3 A1-3 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-139) H OH OH OH OH A1-3 A1-3 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-140) H H H H H A1-3 A1-3 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-141) H OH H H OH A1-3 A1-3 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-142) H OH OH OH OH A1-3 A1-3 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-143) H H H H H A1-3 A1-3 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-144) H OH H H OH A1-3 A1-3 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-145) H OH OH OH OH A1-3 A1-3 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-146) H H H H H A1-3 A1-3 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-147) H OH H H OH A1-3 A1-3 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-148) H OH OH OH OH A1-3 A1-3 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-149) H H H H H A1-3 A1-3 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-150) H OH H H OH A1-3 A1-3 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-151) H OH OH OH OH A1-3 A1-3 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-152) H H H H H A1-3 A1-3 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-153) H OH H H OH A1-3 A1-3 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-154) H OH OH OH OH A1-3 A1-3 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-155) H H H H H A1-3 A1-3 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-156) H OH H H OH A1-3 A1-3 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-157) H OH OH OH OH A1-3 A1-3 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-158) H H H H H A1-3 A1-3 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-159) H OH H H OH A1-3 A1-3 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-160) H OH OH OH OH A1-3 A1-3 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-161) H H H H H A1-3 A1-3 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-162) H OH H H OH A1-3 A1-3 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-163) H OH OH OH OH A1-3 A1-3 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-164) H H H H H A1-3 A1-3 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-165) H OH H H OH A1-3 A1-3 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-166) H OH OH OH OH A1-3 A1-3 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-167) H H H H H A1-3 A1-3 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-168) H OH H H OH A1-3 A1-3 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-169) H OH OH OH OH A1-3 A1-3 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-170) H H H H H A1-3 A1-3 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-171) H OH H H OH A1-3 A1-3 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-172) H OH OH OH OH A1-3 A1-3 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-173) H H H H H A1-3 A1-3 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-174) H OH H H OH A1-3 A1-3 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-175) H OH OH OH OH A1-3 A1-3 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-176) H H H H H A1-3 A1-3 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-177) H OH H H OH A1-3 A1-3 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-178) H OH OH OH OH A1-3 A1-3 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
(II-179) H H H H H A1-3 A1-3 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
(II-180) H OH H H OH A1-3 A1-3 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
TABLE 7
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-181) H OH OH OH OH A1-4 A1-4 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-182) H H H H H A1-4 A1-4 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-183) H OH H H OH A1-4 A1-4 A4-1 H A3-1 H A4-1 A4-1 H A3-1 H A4-1
(II-184) H OH OH OH OH A1-4 A1-4 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-185) H H H H H A1-4 A1-4 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-186) H OH H H OH A1-4 A1-4 A4-1 A3-1 H A3-1 A4-1 A4-1 A3-1 H A3-1 A4-1
(II-187) H OH OH OH OH A1-4 A1-4 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-188) H H H H H A1-4 A1-4 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-189) H OH H H OH A1-4 A1-4 A4-1 H A3-2 H A4-1 A4-1 H A3-2 H A4-1
(II-190) H OH OH OH OH A1-4 A1-4 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-191) H H H H H A1-4 A1-4 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-192) H OH H H OH A1-4 A1-4 A4-1 A3-2 H A3-2 A4-1 A4-1 A3-2 H A3-2 A4-1
(II-193) H OH OH OH OH A1-4 A1-4 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-194) H H H H H A1-4 A1-4 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-195) H OH H H OH A1-4 A1-4 A4-1 H A3-3 H A4-1 A4-1 H A3-3 H A4-1
(II-196) H OH OH OH OH A1-4 A1-4 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-197) H H H H H A1-4 A1-4 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-198) H OH H H OH A1-4 A1-4 A4-1 A3-3 H A3-3 A4-1 A4-1 A3-3 H A3-3 A4-1
(II-199) H OH OH OH OH A1-4 A1-4 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-200) H H H H H A1-4 A1-4 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-201) H OH H H OH A1-4 A1-4 A4-1 H OH H A4-1 A4-1 H OH H A4-1
(II-202) H OH OH OH OH A1-4 A1-4 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-203) H H H H H A1-4 A1-4 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-204) H OH H H OH A1-4 A1-4 A4-1 OH H OH A4-1 A4-1 OH H OH A4-1
(II-205) H OH OH OH OH A1-4 A1-4 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-206) H H H H H A1-4 A1-4 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-207) H OH H H OH A1-4 A1-4 A4-1 H COOH H A4-1 A4-1 H COOH H A4-1
(II-208) H OH OH OH OH A1-4 A1-4 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-209) H H H H H A1-4 A1-4 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-210) H OH H H OH A1-4 A1-4 A4-1 COOH H COOH A4-1 A4-1 COOH H COOH A4-1
(II-211) H OH OH OH OH A1-4 A1-4 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-212) H H H H H A1-4 A1-4 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-213) H OH H H OH A1-4 A1-4 A4-2 H A3-1 H A4-2 A4-2 H A3-1 H A4-2
(II-214) H OH OH OH OH A1-4 A1-4 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-215) H H H H H A1-4 A1-4 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-216) H OH H H OH A1-4 A1-4 A4-2 A3-1 H A3-1 A4-2 A4-2 A3-1 H A3-1 A4-2
(II-217) H OH OH OH OH A1-4 A1-4 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-218) H H H H H A1-4 A1-4 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-219) H OH H H OH A1-4 A1-4 A4-2 H A3-2 H A4-2 A4-2 H A3-2 H A4-2
(II-220) H OH OH OH OH A1-4 A1-4 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-221) H H H H H A1-4 A1-4 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-222) H OH H H OH A1-4 A1-4 A4-2 A3-2 H A3-2 A4-2 A4-2 A3-2 H A3-2 A4-2
(II-223) H OH OH OH OH A1-4 A1-4 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-224) H H H H H A1-4 A1-4 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-225) H OH H H OH A1-4 A1-4 A4-2 H A3-3 H A4-2 A4-2 H A3-3 H A4-2
(II-226) H OH OH OH OH A1-4 A1-4 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-227) H H H H H A1-4 A1-4 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-228) H OH H H OH A1-4 A1-4 A4-2 A3-3 H A3-3 A4-2 A4-2 A3-3 H A3-3 A4-2
(II-229) H OH OH OH OH A1-4 A1-4 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-230) H H H H H A1-4 A1-4 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-231) H OH H H OH A1-4 A1-4 A4-2 H OH H A4-2 A4-2 H OH H A4-2
(II-232) H OH OH OH OH A1-4 A1-4 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-233) H H H H H A1-4 A1-4 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-234) H OH H H OH A1-4 A1-4 A4-2 OH H OH A4-2 A4-2 OH H OH A4-2
(II-235) H OH OH OH OH A1-4 A1-4 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-236) H H H H H A1-4 A1-4 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-237) H OH H H OH A1-4 A1-4 A4-2 H COOH H A4-2 A4-2 H COOH H A4-2
(II-238) H OH OH OH OH A1-4 A1-4 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
(II-239) H H H H H A1-4 A1-4 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
(II-240) H OH H H OH A1-4 A1-4 A4-2 COOH H COOH A4-2 A4-2 COOH H COOH A4-2
TABLE 8
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-241) H OH OH OH OH A1-1 A1-1 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-242) H H H H H A1-1 A1-1 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-243) H OH H H OH A1-1 A1-1 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-244) H OH OH OH OH A1-1 A1-1 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-245) H H H H H A1-1 A1-1 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-246) H OH H H OH A1-1 A1-1 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-247) H OH OH OH OH A1-1 A1-1 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-248) H H H H H A1-1 A1-1 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-249) H OH H H OH A1-1 A1-1 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-250) H OH OH OH OH A1-1 A1-1 H A4-1 OH H H H H OH A4-1 H
(II-251) H H H H H A1-1 A1-1 H A4-1 OH H H H H OH A4-1 H
(II-252) H OH H H OH A1-1 A1-1 H A4-1 OH H H H H OH A4-1 H
(II-253) H OH OH OH OH A1-1 A1-1 H A4-1 COOH H H H H COOH A4-1 H
(II-254) H H H H H A1-1 A1-1 H A4-1 COOH H H H H COOH A4-1 H
(II-255) H OH H H OH A1-1 A1-1 H A4-1 COOH H H H H COOH A4-1 H
(II-256) H OH OH OH OH A1-1 A1-1 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-257) H H H H H A1-1 A1-1 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-258) H OH H H OH A1-1 A1-1 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-259) H OH OH OH OH A1-1 A1-1 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-260) H H H H H A1-1 A1-1 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-261) H OH H H OH A1-1 A1-1 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-262) H OH OH OH OH A1-1 A1-1 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-263) H H H H H A1-1 A1-1 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-264) H OH H H OH A1-1 A1-1 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-265) H OH OH OH OH A1-1 A1-1 H A4-2 OH H H H H OH A4-2 H
(II-266) H H H H H A1-1 A1-1 H A4-2 OH H H H H OH A4-2 H
(II-267) H OH H H OH A1-1 A1-1 H A4-2 OH H H H H OH A4-2 H
(II-268) H OH OH OH OH A1-1 A1-1 H A4-2 COOH H H H H COOH A4-2 H
(II-269) H H H H H A1-1 A1-1 H A4-2 COOH H H H H COOH A4-2 H
(II-270) H OH H H OH A1-1 A1-1 H A4-2 COOH H H H H COOH A4-2 H
(II-271) H OH OH OH OH A1-1 A1-1 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-272) H H H H H A1-1 A1-1 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-273) H OH H H OH A1-1 A1-1 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-274) H OH OH OH OH A1-1 A1-1 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-275) H H H H H A1-1 A1-1 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-276) H OH H H OH A1-1 A1-1 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-277) H OH OH OH OH A1-1 A1-1 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-278) H H H H H A1-1 A1-1 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-279) H OH H H OH A1-1 A1-1 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-280) H OH OH OH OH A1-1 A1-1 H A4-3 OH H H H H OH A4-3 H
(II-281) H H H H H A1-1 A1-1 H A4-3 OH H H H H OH A4-3 H
(II-282) H OH H H OH A1-1 A1-1 H A4-3 OH H H H H OH A4-3 H
(II-283) H OH OH OH OH A1-1 A1-1 H A4-3 COOH H H H H COOH A4-3 H
(II-284) H H H H H A1-1 A1-1 H A4-3 COOH H H H H COOH A4-3 H
(II-285) H OH H H OH A1-1 A1-1 H A4-3 COOH H H H H COOH A4-3 H
(II-286) H OH OH OH OH A1-2 A1-2 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-287) H H H H H A1-2 A1-2 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-288) H OH H H OH A1-2 A1-2 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-289) H OH OH OH OH A1-2 A1-2 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-290) H H H H H A1-2 A1-2 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-291) H OH H H OH A1-2 A1-2 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-292) H OH OH OH OH A1-2 A1-2 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-293) H H H H H A1-2 A1-2 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-294) H OH H H OH A1-2 A1-2 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-295) H OH OH OH OH A1-2 A1-2 H A4-1 OH H H H H OH A4-1 H
(II-296) H H H H H A1-2 A1-2 H A4-1 OH H H H H OH A4-1 H
(II-297) H OH H H OH A1-2 A1-2 H A4-1 OH H H H H OH A4-1 H
(II-298) H OH OH OH OH A1-2 A1-2 H A4-1 COOH H H H H COOH A4-1 H
(II-299) H H H H H A1-2 A1-2 H A4-1 COOH H H H H COOH A4-1 H
(II-300) H OH H H OH A1-2 A1-2 H A4-1 COOH H H H H COOH A4-1 H
TABLE 9
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-301) H OH OH OH OH A1-2 A1-2 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-302) H H H H H A1-2 A1-2 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-303) H OH H H OH A1-2 A1-2 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-304) H OH OH OH OH A1-2 A1-2 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-305) H H H H H A1-2 A1-2 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-306) H OH H H OH A1-2 A1-2 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-307) H OH OH OH OH A1-2 A1-2 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-308) H H H H H A1-2 A1-2 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-309) H OH H H OH A1-2 A1-2 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-310) H OH OH OH OH A1-2 A1-2 H A4-2 OH H H H H OH A4-2 H
(II-311) H H H H H A1-2 A1-2 H A4-2 OH H H H H OH A4-2 H
(II-312) H OH H H OH A1-2 A1-2 H A4-2 OH H H H H OH A4-2 H
(II-313) H OH OH OH OH A1-2 A1-2 H A4-2 COOH H H H H COOH A4-2 H
(II-314) H H H H H A1-2 A1-2 H A4-2 COOH H H H H COOH A4-2 H
(II-315) H OH H H OH A1-2 A1-2 H A4-2 COOH H H H H COOH A4-2 H
(II-316) H OH OH OH OH A1-2 A1-2 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-317) H H H H H A1-2 A1-2 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-318) H OH H H OH A1-2 A1-2 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-319) H OH OH OH OH A1-2 A1-2 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-320) H H H H H A1-2 A1-2 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-321) H OH H H OH A1-2 A1-2 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-322) H OH OH OH OH A1-2 A1-2 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-323) H H H H H A1-2 A1-2 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-324) H OH H H OH A1-2 A1-2 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-325) H OH OH OH OH A1-2 A1-2 H A4-3 OH H H H H OH A4-3 H
(II-326) H H H H H A1-2 A1-2 H A4-3 OH H H H H OH A4-3 H
(II-327) H OH H H OH A1-2 A1-2 H A4-3 OH H H H H OH A4-3 H
(II-328) H OH OH OH OH A1-2 A1-2 H A4-3 COOH H H H H COOH A4-3 H
(II-329) H H H H H A1-2 A1-2 H A4-3 COOH H H H H COOH A4-3 H
(II-330) H OH H H OH A1-2 A1-2 H A4-3 COOH H H H H COOH A4-3 H
(II-331) H OH OH OH OH A1-3 A1-3 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-332) H H H H H A1-3 A1-3 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-333) H OH H H OH A1-3 A1-3 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-334) H OH OH OH OH A1-3 A1-3 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-335) H H H H H A1-3 A1-3 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-336) H OH H H OH A1-3 A1-3 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-337) H OH OH OH OH A1-3 A1-3 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-338) H H H H H A1-3 A1-3 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-339) H OH H H OH A1-3 A1-3 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-340) H OH OH OH OH A1-3 A1-3 H A4-1 OH H H H H OH A4-1 H
(II-341) H H H H H A1-3 A1-3 H A4-1 OH H H H H OH A4-1 H
(II-342) H OH H H OH A1-3 A1-3 H A4-1 OH H H H H OH A4-1 H
(II-343) H OH OH OH OH A1-3 A1-3 H A4-1 COOH H H H H COOH A4-1 H
(II-344) H H H H H A1-3 A1-3 H A4-1 COOH H H H H COOH A4-1 H
(II-345) H OH H H OH A1-3 A1-3 H A4-1 COOH H H H H COOH A4-1 H
(II-346) H OH OH OH OH A1-3 A1-3 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-347) H H H H H A1-3 A1-3 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-348) H OH H H OH A1-3 A1-3 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-349) H OH OH OH OH A1-3 A1-3 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-350) H H H H H A1-3 A1-3 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-351) H OH H H OH A1-3 A1-3 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-352) H OH OH OH OH A1-3 A1-3 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-353) H H H H H A1-3 A1-3 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-354) H OH H H OH A1-3 A1-3 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-355) H OH OH OH OH A1-3 A1-3 H A4-2 OH H H H H OH A4-2 H
(II-356) H H H H H A1-3 A1-3 H A4-2 OH H H H H OH A4-2 H
(II-357) H OH H H OH A1-3 A1-3 H A4-2 OH H H H H OH A4-2 H
(II-358) H OH OH OH OH A1-3 A1-3 H A4-2 COOH H H H H COOH A4-2 H
(II-359) H H H H H A1-3 A1-3 H A4-2 COOH H H H H COOH A4-2 H
(II-360) H OH H H OH A1-3 A1-3 H A4-2 COOH H H H H COOH A4-2 H
TABLE 10
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-361) H OH OH OH OH A1-3 A1-3 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-362) H H H H H A1-3 A1-3 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-363) H OH H H OH A1-3 A1-3 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-364) H OH OH OH OH A1-3 A1-3 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-365) H H H H H A1-3 A1-3 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-366) H OH H H OH A1-3 A1-3 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-367) H OH OH OH OH A1-3 A1-3 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-368) H H H H H A1-3 A1-3 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-369) H OH H H OH A1-3 A1-3 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-370) H OH OH OH OH A1-3 A1-3 H A4-3 OH H H H H OH A4-3 H
(II-371) H H H H H A1-3 A1-3 H A4-3 OH H H H H OH A4-3 H
(II-372) H OH H H OH A1-3 A1-3 H A4-3 OH H H H H OH A4-3 H
(II-373) H OH OH OH OH A1-3 A1-3 H A4-3 COOH H H H H COOH A4-3 H
(II-374) H H H H H A1-3 A1-3 H A4-3 COOH H H H H COOH A4-3 H
(II-375) H OH H H OH A1-3 A1-3 H A4-3 COOH H H H H COOH A4-3 H
(II-376) H OH OH OH OH A1-4 A1-4 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-377) H H H H H A1-4 A1-4 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-378) H OH H H OH A1-4 A1-4 H A4-1 A3-1 H H H H A3-1 A4-1 H
(II-379) H OH OH OH OH A1-4 A1-4 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-380) H H H H H A1-4 A1-4 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-381) H OH H H OH A1-4 A1-4 H A4-1 A3-2 H H H H A3-2 A4-1 H
(II-382) H OH OH OH OH A1-4 A1-4 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-383) H H H H H A1-4 A1-4 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-384) H OH H H OH A1-4 A1-4 H A4-1 A3-3 H H H H A3-3 A4-1 H
(II-385) H OH OH OH OH A1-4 A1-4 H A4-1 OH H H H H OH A4-1 H
(II-386) H H H H H A1-4 A1-4 H A4-1 OH H H H H OH A4-1 H
(II-387) H OH H H OH A1-4 A1-4 H A4-1 OH H H H H OH A4-1 H
(II-388) H OH OH OH OH A1-4 A1-4 H A4-1 COOH H H H H COOH A4-1 H
(II-389) H H H H H A1-4 A1-4 H A4-1 COOH H H H H COOH A4-1 H
(II-390) H OH H H OH A1-4 A1-4 H A4-1 COOH H H H H COOH A4-1 H
(II-391) H OH OH OH OH A1-4 A1-4 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-392) H H H H H A1-4 A1-4 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-393) H OH H H OH A1-4 A1-4 H A4-2 A3-1 H H H H A3-1 A4-2 H
(II-394) H OH OH OH OH A1-4 A1-4 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-395) H H H H H A1-4 A1-4 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-396) H OH H H OH A1-4 A1-4 H A4-2 A3-2 H H H H A3-2 A4-2 H
(II-397) H OH OH OH OH A1-4 A1-4 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-398) H H H H H A1-4 A1-4 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-399) H OH H H OH A1-4 A1-4 H A4-2 A3-3 H H H H A3-3 A4-2 H
(II-400) H OH OH OH OH A1-4 A1-4 H A4-2 OH H H H H OH A4-2 H
(II-401) H H H H H A1-4 A1-4 H A4-2 OH H H H H OH A4-2 H
(II-402) H OH H H OH A1-4 A1-4 H A4-2 OH H H H H OH A4-2 H
(II-403) H OH OH OH OH A1-4 A1-4 H A4-2 COOH H H H H COOH A4-2 H
(II-404) H H H H H A1-4 A1-4 H A4-2 COOH H H H H COOH A4-2 H
(II-405) H OH H H OH A1-4 A1-4 H A4-2 COOH H H H H COOH A4-2 H
(II-406) H OH OH OH OH A1-4 A1-4 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-407) H H H H H A1-4 A1-4 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-408) H OH H H OH A1-4 A1-4 H A4-3 A3-1 H H H H A3-1 A4-3 H
(II-409) H OH OH OH OH A1-4 A1-4 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-410) H H H H H A1-4 A1-4 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-411) H OH H H OH A1-4 A1-4 H A4-3 A3-2 H H H H A3-2 A4-3 H
(II-412) H OH OH OH OH A1-4 A1-4 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-413) H H H H H A1-4 A1-4 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-414) H OH H H OH A1-4 A1-4 H A4-3 A3-3 H H H H A3-3 A4-3 H
(II-415) H OH OH OH OH A1-4 A1-4 H A4-3 OH H H H H OH A4-3 H
(II-416) H H H H H A1-4 A1-4 H A4-3 OH H H H H OH A4-3 H
(II-417) H OH H H OH A1-4 A1-4 H A4-3 OH H H H H OH A4-3 H
(II-418) H OH OH OH OH A1-4 A1-4 H A4-3 COOH H H H H COOH A4-3 H
(II-419) H H H H H A1-4 A1-4 H A4-3 COOH H H H H COOH A4-3 H
(II-420) H OH H H OH A1-4 A1-4 H A4-3 COOH H H H H COOH A4-3 H
TABLE 11
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-421) H OH OH OH OH A1-1 A1-1 H H A3-1 H H H H A3-1 H H
(II-422) H H H H H A1-1 A1-1 H H A3-1 H H H H A3-1 H H
(II-423) H OH H H OH A1-1 A1-1 H H A3-1 H H H H A3-1 H H
(II-424) H OH OH OH OH A1-1 A1-1 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-425) H H H H H A1-1 A1-1 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-426) H OH H H OH A1-1 A1-1 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-427) H OH OH OH OH A1-1 A1-1 H H A3-2 H H H H A3-2 H H
(II-428) H H H H H A1-1 A1-1 H H A3-2 H H H H A3-2 H H
(II-429) H OH H H OH A1-1 A1-1 H H A3-2 H H H H A3-2 H H
(II-430) H OH OH OH OH A1-1 A1-1 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-431) H H H H H A1-1 A1-1 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-432) H OH H H OH A1-1 A1-1 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-433) H OH OH OH OH A1-1 A1-1 H H A3-3 H H H H A3-3 H H
(II-434) H H H H H A1-1 A1-1 H H A3-3 H H H H A3-3 H H
(II-435) H OH H H OH A1-1 A1-1 H H A3-3 H H H H A3-3 H H
(II-436) H OH OH OH OH A1-1 A1-1 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-437) H H H H H A1-1 A1-1 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-438) H OH H H OH A1-1 A1-1 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-439) H OH OH OH OH A1-1 A1-1 H H OH H H H H OH H H
(II-440) H H H H H A1-1 A1-1 H H OH H H H H OH H H
(II-441) H OH H H OH A1-1 A1-1 H H OH H H H H OH H H
(II-442) H OH OH OH OH A1-1 A1-1 H OH H OH H H OH H OH H
(II-443) H H H H H A1-1 A1-1 H OH H OH H H OH H OH H
(II-444) H OH H H OH A1-1 A1-1 H OH H OH H H OH H OH H
(II-445) H OH OH OH OH A1-1 A1-1 H H COOH H H H H COOH H H
(II-446) H H H H H A1-1 A1-1 H H COOH H H H H COOH H H
(II-447) H OH H H OH A1-1 A1-1 H H COOH H H H H COOH H H
(II-448) H OH OH OH OH A1-1 A1-1 H COOH H COOH H H COOH H COOH H
(II-449) H H H H H A1-1 A1-1 H COOH H COOH H H COOH H COOH H
(II-450) H OH H H OH A1-1 A1-1 H COOH H COOH H H COOH H COOH H
(II-451) H OH OH OH OH A1-2 A1-2 H H A3-1 H H H H A3-1 H H
(II-452) H H H H H A1-2 A1-2 H H A3-1 H H H H A3-1 H H
(II-453) H OH H H OH A1-2 A1-2 H H A3-1 H H H H A3-1 H H
(II-454) H OH OH OH OH A1-2 A1-2 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-455) H H H H H A1-2 A1-2 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-456) H OH H H OH A1-2 A1-2 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-457) H OH OH OH OH A1-2 A1-2 H H A3-2 H H H H A3-2 H H
(II-458) H H H H H A1-2 A1-2 H H A3-2 H H H H A3-2 H H
(II-459) H OH H H OH A1-2 A1-2 H H A3-2 H H H H A3-2 H H
(II-460) H OH OH OH OH A1-2 A1-2 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-461) H H H H H A1-2 A1-2 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-462) H OH H H OH A1-2 A1-2 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-463) H OH OH OH OH A1-2 A1-2 H H A3-3 H H H H A3-3 H H
(II-464) H H H H H A1-2 A1-2 H H A3-3 H H H H A3-3 H H
(II-465) H OH H H OH A1-2 A1-2 H H A3-3 H H H H A3-3 H H
(II-466) H OH OH OH OH A1-2 A1-2 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-467) H H H H H A1-2 A1-2 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-468) H OH H H OH A1-2 A1-2 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-469) H OH OH OH OH A1-2 A1-2 H H OH H H H H OH H H
(II-470) H H H H H A1-2 A1-2 H H OH H H H H OH H H
(II-471) H OH H H OH A1-2 A1-2 H H OH H H H H OH H H
(II-472) H OH OH OH OH A1-2 A1-2 H OH H OH H H OH H OH H
(II-473) H H H H H A1-2 A1-2 H OH H OH H H OH H OH H
(II-474) H OH H H OH A1-2 A1-2 H OH H OH H H OH H OH H
(II-475) H OH OH OH OH A1-2 A1-2 H H COOH H H H H COOH H H
(II-476) H H H H H A1-2 A1-2 H H COOH H H H H COOH H H
(II-477) H OH H H OH A1-2 A1-2 H H COOH H H H H COOH H H
(II-478) H OH OH OH OH A1-2 A1-2 H COOH H COOH H H COOH H COOH H
(II-479) H H H H H A1-2 A1-2 H COOH H COOH H H COOH H COOH H
(II-480) H OH H H OH A1-2 A1-2 H COOH H COOH H H COOH H COOH H
TABLE 12
R1～R4 R5 R6 R7 R8 R9 R10 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25
(II-481) H OH OH OH OH A1-3 A1-3 H H A3-1 H H H H A3-1 H H
(II-482) H H H H H A1-3 A1-3 H H A3-1 H H H H A3-1 H H
(II-483) H OH H H OH A1-3 A1-3 H H A3-1 H H H H A3-1 H H
(II-484) H OH OH OH OH A1-3 A1-3 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-485) H H H H H A1-3 A1-3 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-486) H OH H H OH A1-3 A1-3 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-487) H OH OH OH OH A1-3 A1-3 H H A3-2 H H H H A3-2 H H
(II-488) H H H H H A1-3 A1-3 H H A3-2 H H H H A3-2 H H
(II-489) H OH H H OH A1-3 A1-3 H H A3-2 H H H H A3-2 H H
(II-490) H OH OH OH OH A1-3 A1-3 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-491) H H H H H A1-3 A1-3 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-492) H OH H H OH A1-3 A1-3 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-493) H OH OH OH OH A1-3 A1-3 H H A3-3 H H H H A3-3 H H
(II-494) H H H H H A1-3 A1-3 H H A3-3 H H H H A3-3 H H
(II-495) H OH H H OH A1-3 A1-3 H H A3-3 H H H H A3-3 H H
(II-496) H OH OH OH OH A1-3 A1-3 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-497) H H H H H A1-3 A1-3 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-498) H OH H H OH A1-3 A1-3 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-499) H OH OH OH OH A1-3 A1-3 H H OH H H H H OH H H
(II-500) H H H H H A1-3 A1-3 H H OH H H H H OH H H
(II-501) H OH H H OH A1-3 A1-3 H H OH H H H H OH H H
(II-502) H OH OH OH OH A1-3 A1-3 H OH H OH H H OH H OH H
(II-503) H H H H H A1-3 A1-3 H OH H OH H H OH H OH H
(II-504) H OH H H OH A1-3 A1-3 H OH H OH H H OH H OH H
(II-505) H OH OH OH OH A1-3 A1-3 H H COOH H H H H COOH H H
(II-506) H H H H H A1-3 A1-3 H H COOH H H H H COOH H H
(II-507) H OH H H OH A1-3 A1-3 H H COOH H H H H COOH H H
(II-508) H OH OH OH OH A1-3 A1-3 H COOH H COOH H H COOH H COOH H
(II-509) H H H H H A1-3 A1-3 H COOH H COOH H H COOH H COOH H
(II-510) H OH H H OH A1-3 A1-3 H COOH H COOH H H COOH H COOH H
(II-511) H OH OH OH OH A1-4 A1-4 H H A3-1 H H H H A3-1 H H
(II-512) H H H H H A1-4 A1-4 H H A3-1 H H H H A3-1 H H
(II-513) H OH H H OH A1-4 A1-4 H H A3-1 H H H H A3-1 H H
(II-514) H OH OH OH OH A1-4 A1-4 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-515) H H H H H A1-4 A1-4 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-516) H OH H H OH A1-4 A1-4 H A3-1 H A3-1 H H A3-1 H A3-1 H
(II-517) H OH OH OH OH A1-4 A1-4 H H A3-2 H H H H A3-2 H H
(II-518) H H H H H A1-4 A1-4 H H A3-2 H H H H A3-2 H H
(II-519) H OH H H OH A1-4 A1-4 H H A3-2 H H H H A3-2 H H
(II-520) H OH OH OH OH A1-4 A1-4 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-521) H H H H H A1-4 A1-4 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-522) H OH H H OH A1-4 A1-4 H A3-2 H A3-2 H H A3-2 H A3-2 H
(II-523) H OH OH OH OH A1-4 A1-4 H H A3-3 H H H H A3-3 H H
(II-524) H H H H H A1-4 A1-4 H H A3-3 H H H H A3-3 H H
(II-525) H OH H H OH A1-4 A1-4 H H A3-3 H H H H A3-3 H H
(II-526) H OH OH OH OH A1-4 A1-4 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-527) H H H H H A1-4 A1-4 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-528) H OH H H OH A1-4 A1-4 H A3-3 H A3-3 H H A3-3 H A3-3 H
(II-529) H OH OH OH OH A1-4 A1-4 H H OH H H H H OH H H
(II-530) H H H H H A1-4 A1-4 H H OH H H H H OH H H
(II-531) H OH H H OH A1-4 A1-4 H H OH H H H H OH H H
(II-532) H OH OH OH OH A1-4 A1-4 H OH H OH H H OH H OH H
(II-533) H H H H H A1-4 A1-4 H OH H OH H H OH H OH H
(II-534) H OH H H OH A1-4 A1-4 H OH H OH H H OH H OH H
(II-535) H OH OH OH OH A1-4 A1-4 H H COOH H H H H COOH H H
(II-536) H H H H H A1-4 A1-4 H H COOH H H H H COOH H H
(II-537) H OH H H OH A1-4 A1-4 H H COOH H H H H COOH H H
(II-538) H OH OH OH OH A1-4 A1-4 H COOH H COOH H H COOH H COOH H
(II-539) H H H H H A1-4 A1-4 H COOH H COOH H H COOH H COOH H
(II-540) H OH H H OH A1-4 A1-4 H COOH H COOH H H COOH H COOH H
In tables 4 to 12, A1-1 to A1-4 represent the same groups as described above.
In tables 4 to 12, A3-1 to A3-3 represent groups represented by the following formulas. In the following formula, the bond is represented.
In tables 4 to 12, A4-1 to A4-3 represent groups represented by the following formulas. In the following formula, the bond is represented.
The compound represented by the formula (I) can be produced by: reacting a compound represented by formula (pt 1), a compound represented by formula (pt 2), and a compound represented by formula (pt 3). In the present reaction, the total amount of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 2) to be used is preferably 1.5mol to 2.5mol, relative to 1mol of the compound represented by the formula (pt 3).
< Coloring resin composition >
The colored resin composition of the present invention comprises a colorant (A) and a resin (B), wherein the colorant (A) comprises a compound represented by the formula (I).
The colored resin composition of the present invention preferably further comprises a polymerizable compound (C) and a polymerization initiator (D).
The colored resin composition of the present invention may further comprise a polymerization initiator (D1), a solvent (E), and a leveling agent (F).
In this specification, unless otherwise specified, the compounds exemplified as the respective components may be used alone or in combination of plural kinds.
< Colorant (A) >)
The colored resin composition of the present invention contains the compound (I) as the colorant (a). The content of the compound (I) is preferably 0.1 to 150 parts by mass, more preferably 0.3 to 100 parts by mass, still more preferably 0.5 to 80 parts by mass, relative to 100 parts by mass of the resin (B).
The content of the compound (I) in the total amount of the colorant (a) is preferably 20 mass% or more, more preferably 50 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more.
The colored resin composition of the present invention may contain, in addition to the compound (I) as the colorant (a), the dye (A1) and the pigment (A2) as the colorant (a).
The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Examples of dyes include compounds classified into colors other than pigments in color index (published by the institute of dyeing (The Society of Dyers and Colourists)), and known dyes described in a dyeing manual (society of dyeing). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, squaraine dyes (excluding the compound (I)), acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitrodyes, and the like can be cited. Among them, organic solvent-soluble dyes are preferable.
The pigment (A2) is not particularly limited, and a known pigment can be used, and examples thereof include pigments classified as pigments in the color index (published by the institute of dyeing (The Society of Dyers and Colourists)).
Examples of the pigment include yellow pigments such as c.i. pigment yellow 1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214;
orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.;
C.i. pigment blue 15, 15:3, 15:4, 15:6, 60, etc. blue pigments;
violet pigments such as c.i. pigment violet 1, 19, 23, 29, 32, 36, 38;
green pigments such as c.i. pigment green 7, 36, 58;
brown pigments such as pigment brown 23, 25;
Black pigments such as c.i. pigment black 1 and 7.
The content of the colorant (a) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and even more preferably 1 to 50% by mass, relative to the total amount of solid components of the colored resin composition.
Here, the "total amount of solid components" in the present specification means an amount after removing the content of the solvent from the total amount of the colored resin composition. The total amount of the solid components and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.
< Resin (B) >)
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably a resin having a structural unit derived from at least one (a) (hereinafter, referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. The resin (B) also preferably has at least one structural unit selected from the group consisting of: a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond (hereinafter, there is a case of "(b)"), a structural unit derived from a monomer (c) copolymerizable with (a) (but different from (a) and (b) (hereinafter, there is a case of "(c)"), and a structural unit having an ethylenic unsaturated bond in a side chain.
Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, and succinic mono [2- (meth) acryloyloxyethyl ] ester, and acrylic acid, methacrylic acid, and maleic anhydride are preferable.
(B) Preferred are monomers having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth) acryloyloxy group.
In the present specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expression "(meth) acryl" and "(meth) acrylate" have the same meaning.
Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3, 4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate, 3-ethyl-3- (meth) acryloyloxy-methyl oxetane, tetrahydrofurfuryl (meth) acrylate, and the like, and preferably glycidyl (meth) acrylate, 3, 4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate, and 3-ethyl-3- (meth) acryloyloxy-methyl-oxetane.
Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyl toluene, and the like, and styrene, vinyl toluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and the like are preferable.
The resin having a structural unit having an ethylenic unsaturated bond in a side chain can be produced by adding (b) to a copolymer of (a) and (c) or adding (a) to a copolymer of (b) and (c). The resin may be a resin obtained by adding (a) to a copolymer of (b) and (c) and further reacting a carboxylic anhydride.
The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000.
The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.
The acid value of the resin (B) is preferably 20mg-KOH/g to 170mg-KOH/g, more preferably 30mg-KOH/g to 150mg-KOH/g, still more preferably 40mg-KOH/g to 135mg-KOH/g in terms of solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1g of the resin (B), and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.
The content of the resin (B) is preferably 30 to 99.9 mass%, more preferably 50 to 99.5 mass%, and even more preferably 70 to 99 mass%, with respect to the total amount of solid components of the colored resin composition.
When the colored resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), the content of the resin (B) is preferably 7 to 70% by mass, more preferably 13 to 65% by mass, and even more preferably 17 to 60% by mass, relative to the total amount of the solid components of the colored resin composition.
< Polymerizable Compound (C) >)
The polymerizable compound (C) is a compound polymerizable by a living radical and/or an acid generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and the like, and is preferably a (meth) acrylate compound.
Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 5 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass, based on the total amount of solid components.
Polymerization initiator (D) >)
The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate a living radical, an acid, or the like by the action of light or heat and initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator capable of generating active radicals include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropan-1-one-2-imine, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2,4, 6-trimethylbenzoyldiphenyl phosphine oxide, 2' -bis (2-4, 4', 5' -tetrachlorobenzene) biphenyl-5.
When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be shortened, so that the productivity of the color filter is improved.
Polymerization initiation aid (D1) >, polymerization initiation aid
The polymerization initiator aid (D1) is a compound or sensitizer used for promoting the polymerization of a polymerizable compound that initiates polymerization by a polymerization initiator. In the case of containing the polymerization initiator auxiliary (D1), it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator (D1) include 4,4' -bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4' -bis (diethylamino) benzophenone, 9, 10-dimethoxyanthracene, 2, 4-diethylthioxanthone, and N-phenylglycine.
When these polymerization initiator aids (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the amount of the polymerization initiator (D1) falls within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.
Solvent (E) >, solvent (E)
The solvent (E) is not particularly limited, and solvents generally used in the art can be used. Examples thereof include ester solvents (solvents containing-COO-but not-O-in the molecule) an ether solvent (a solvent containing-O-but not-COO-in the molecule) ether ester solvents (solvents containing-COO-and-O-in the molecule) ketone solvent (solvent containing-CO-but not-COO-in the molecule) alcohol solvents (OH contained in the molecule but not-O-) -CO-and-COO-, an aromatic hydrocarbon solvent, an amide solvent, a halogen-based solvent, dimethyl sulfoxide, and the like.
As the solvent, there may be mentioned:
ester solvents (solvents containing-COO-but no-O-in the molecule) such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone;
Ether solvents (solvents containing-O-but not-COO-in the molecule) such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methylethyl ether;
Ether ester solvents (solvents containing-COO-and-O-in the molecule) such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate;
ketone solvents (solvents containing-CO-but not-COO-in the molecule) such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, and cyclohexanone;
Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (including OH but not-O-in the molecule-CO-and-COO-solvents);
Amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
halogen solvents such as chloroform, chlorobenzene, dichloroethylene, and trichloroethylene; etc.
More preferable solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), N-methylpyrrolidone, chloroform, ethyl lactate and ethyl 3-ethoxypropionate.
In the case where the solvent (E) is contained, the content of the solvent (E) is preferably 60 to 95 mass%, more preferably 65 to 92 mass%, with respect to the total amount of the colored resin composition of the present invention. In other words, the total amount of the solid components of the colored resin composition is preferably 5 to 40 mass%, more preferably 8 to 35 mass%. If the content of the solvent (E) is within the above range, flatness at the time of coating becomes good, and color density at the time of forming a color filter is not insufficient, so that display characteristics tend to become good.
< Leveling agent (F) >)
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. Their side chains may also have polymerizable groups.
Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, TORAY SILICONE C3PA、TORAY SILICONE SH7PA、TORAY SILICONE DC11PA、TORAY SILICONE SH21PA、TORAY SILICONE SH28PA、TORAY SILICONE SH29PA、TORAY SILICONE SH30PA、TORAY SILICONE SH8400( trade names: product of doriconnin (Dow Corning Toray co., ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical co., ltd.) products; TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by michaux new materials japan (Momentive Performance Materials Japan) co-company), and the like.
The fluorine-based surfactant includes surfactants having a fluorocarbon chain in the molecule. Specific examples thereof include fluoroad FC430 and fluoroad FC431 (manufactured by Sumitomo 3M Limited (Sumitomo 3M Limited)), and the like; MEGAFAC (registered trademark )F142D、MEGAFAC F171、MEGAFAC F172、MEGAFAC F173、MEGAFAC F177、MEGAFAC F183、MEGAFAC F554、MEGAFAC R30、MEGAFAC RS-718-K(DIC( strain); EFTOP (registered trademark) EF301, EFTOP EF, EFTOP EF351, EFTOP EF (mitsubishi material electronic chemical industry (Mitsubishi Materials Electronic Chemicals co., ltd.) products); SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC (product of the company glauber 'S salt (ASAHI GLASS co., ltd.), and E5844 (product of the company glauber' S gold fine chemistry (DAIKIN FINE CHEMICAL)) and the like.
Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (DIC product) and the like are exemplified.
In the case of containing the leveling agent (F), the content of the leveling agent (F) is preferably 0.001 to 0.2 mass%, more preferably 0.002 to 0.1 mass%, with respect to the total amount of the colored resin composition. The pigment dispersant is not contained in the content. If the content of the leveling agent (F) is within the above-mentioned range, the flatness of the color filter can be made good.
< Other Components >)
The colored resin composition of the present invention may optionally contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like.
Process for producing colored resin composition
The colored resin composition of the present invention can be prepared by mixing the colorant (a) and the resin (B), and if necessary, the polymerizable compound (C), the polymerization initiator (D), the polymerization initiator auxiliary (D1), the solvent (E), the leveling agent (F), and other components.
Method for producing color filter
Examples of the method for producing a colored pattern from the colored resin composition of the present invention include photolithography, inkjet, and printing. Among them, photolithography is preferable.
The colored resin composition contains a compound represented by the formula (I), and can produce a color filter having particularly excellent heat resistance and light resistance. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) and a solid-state imaging element.
Examples (example)
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, the percentages and parts indicating the amounts and the amounts used are mass references.
The structure of the compounds was confirmed by MASS spectrometry (LC: agilent) product 1200 type; MASS: agilent product LC/MSD type).
Synthesis example 1
50 Parts of 3-bromoanisole (manufactured by tokyo Chemical industry, inc. (Tokyo Chemical Industry Co., ltd.) was dissolved in 36.1 parts of 2,4, 6-trimethylaniline (manufactured by tokyo Chemical industry, inc.) and 434 parts of toluene (manufactured by Kanto Chemical Co., inc.) and 30 parts of potassium hydroxide (manufactured by Kanto Chemical, inc.), 25 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by tokyo Chemical industry, inc.), 1.4 parts of bis (tri-t-butylphosphine) palladium (0) (manufactured by tokyo Chemical industry, inc.) were mixed in the solution. After heating to 90℃and stirring for 5 hours, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 52.1 parts of a crude product (crop product). The obtained crude product was purified by column chromatography to obtain 50.2 parts of the compound represented by the formula (1-1).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 242.3
Exact Mass): +241.2
Synthesis example 2
33 Parts of the compound represented by the formula (1-1), 26.8 parts of methyl 4-chloro-4-oxobutyrate (Tokyo chemical Co., ltd.) and 286 parts of toluene (Kanto chemical Co., ltd.) were mixed and heated while stirring at 100℃for 16 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 30.7 parts of the compound represented by the formula (1-2).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 356.2.2
Exact Mass): +355.2
Synthesis example 3
10 Parts of the compound represented by the formula (1-2) was dissolved in 95 parts of methylene chloride (manufactured by Kabushiki Kaisha), and cooled to 0℃while stirring. 28.2 parts of boron tribromide (Fuji film and Wako pure chemical industries, ltd. (FUJIFILM Wako Pure Chemical Corporation)) were added dropwise while stirring. After the end of the dropwise addition, the temperature was slowly raised and stirred at 10℃for 4 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed, whereby 9.1 parts of a crude product was obtained by distillation. The crude product contained 48% of the compound represented by the formula (1-3) and 36% of the compound represented by the formula (1-4).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 342.2.2
Exact Mass): +341.2
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 328.1.1
Exact Mass): +327.2
Synthesis example 4
A solution of 13.2 parts of thionyl chloride (manufactured by Tokyo chemical Co., ltd.) in 72 parts of methanol (manufactured by Kabushiki Kaisha Co., ltd.) was cooled to 0℃and 9.1 parts of a crude product comprising the compound represented by the formula (1-3) and the compound represented by the formula (1-4) obtained in Synthesis example 3 was introduced while stirring. Warm to room temperature and react for 16 hours. The solvent was distilled off under reduced pressure to obtain 8.3 parts of a crude product containing the compound represented by the formula (1-3). The obtained crude product was purified by silica gel column chromatography to obtain 7.4 parts of a compound represented by the formula (1-3).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 342.2.2
Exact Mass): +341.2
Synthesis example 5
2 Parts of the compound represented by the formula (1-3), 26.3 parts of a borane 1M tetrahydrofuran solution (manufactured by Kanto Chemicals Co., ltd.) and 18 parts of tetrahydrofuran (manufactured by Kanto Chemicals Co., ltd.) were mixed at 0℃and heated to 10℃and stirred for 5 hours. After the reaction, water is added for quenching, and the organic solvent is used for extraction. The solvent was distilled off and the obtained crude product was purified by silica gel column chromatography to obtain 1.64 parts of a compound represented by the formula (1-5).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 300.2.2
Exact Mass): +299.2
Example 1
2.5 Parts of the compound represented by the formula (1-5) and 0.55 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-active pharmaceutical ingredients) were dissolved in 50 parts of toluene (manufactured by Kao chemical Co., ltd.) and 50 parts of n-butanol (manufactured by Kao chemical Co., ltd.) and heated while stirring at 110℃for 6 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 2.7 parts of the compound represented by the formula (I-147).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 677.4
Exact Mass): +676.4
Synthesis example 6
10 Parts of the compound represented by the formula (1-1), 7.4 parts of methylmalonyl chloride (manufactured by Tokyo chemical Co., ltd.) and 87 parts of toluene (manufactured by Kanto chemical Co., ltd.) were mixed and heated while stirring at 100℃for 16 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 9.1 parts of the compound represented by the formula (1-6).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 342.2.2
Exact Mass): +341.2
Synthesis example 7
8.1 Parts of the compound represented by the formula (1-6) was dissolved in 107 parts of methylene chloride (manufactured by Kabushiki Kaisha), and cooled to 0℃while stirring. 24 parts of boron tribromide (Fuji film and Wako pure chemical industries, ltd.) were added dropwise while stirring. After the end of the dropwise addition, the temperature was slowly raised and stirred at 23℃for 3 hours. After the completion of the reaction, the organic layer was extracted and concentrated to obtain 7.2 parts of the compound represented by the formula (1-7).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 314.1
Exact Mass): +313.1
Synthesis example 8
A solution of 10.6 parts of thionyl chloride (manufactured by Tokyo chemical Co., ltd.) in 55.5 parts of methanol (manufactured by Kabushiki Kaisha) was cooled to 0℃and 5 parts of the compound represented by the formula (1-7) was added with stirring. The temperature was raised to 23℃and reacted for 16 hours. The solvent was distilled off under reduced pressure to obtain 6.8 parts of a crude product containing the compound represented by the formula (1-8). The obtained crude product was purified by silica gel column chromatography to obtain 5.6 parts of a compound represented by the formula (1-8).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 328.2.2
Exact Mass): +327.15
Synthesis example 9
5.5 Parts of the compound represented by the formula (1-8), 92.3 parts of borane 1M tetrahydrofuran solution (manufactured by Kabushiki Kaisha) and 49 parts of tetrahydrofuran (manufactured by Kaisha) were mixed at 0℃and heated to 23℃and stirred for 3 hours. After the reaction, water is added for quenching, and the organic solvent is used for extraction. The solvent was distilled off and the obtained crude product was purified by silica gel column chromatography to obtain 2.6 parts of a compound represented by the formula (1-9).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 286.2
Exact Mass): +285.2
Example 2
2 Parts of the compound represented by the formula (1-9) and 0.4 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-seal and Wako pure chemical industries, ltd.) were dissolved in 69 parts of toluene (Kanto chemical Co., ltd.) and 16 parts of n-butanol (Kanto chemical Co., ltd.) and heated while stirring at 120℃for 4 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of the compound represented by the formula (I-27).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 649.7
Exact Mass): +648.3
Synthesis example 10
7 Parts of bromomesitylene (Tokyo chemical industry Co., ltd.), 4.8 parts of 5-methoxy-2-methylaniline (Tokyo chemical industry Co., ltd.), 0.39 part of palladium acetate (Tokyo chemical industry Co., ltd.), 0.84 part of 4,5 '-bis (diphenylphosphino) -9,9' -dimethylxanthene (Tokyo chemical industry Co., ltd.), 6.8 parts of sodium t-butoxide (Tokyo chemical industry Co., ltd.) were dissolved in 126 parts of toluene (Kao chemical industry Co., ltd.), and heated and refluxed at 105℃for 1 hour. After the completion of the reaction, the organic layer was extracted with water, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 7 parts of a compound represented by the formula (1-15).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 256.2.2
Exact Mass): +255.2
Synthesis example 11
6 Parts of the compound represented by the formula (1-15) and 33 parts of monoethyl ester acyl chloride succinate (Tokyo chemical Co., ltd.) were dissolved in 20 parts of toluene (Kagaku chemical Co., ltd.) and heated at 90℃for 8 hours. After the completion of the reaction, the organic layer was extracted with water, and repulped (repulping) with 300 parts of hexane (manufactured by Kabushiki Kaisha) for washing to obtain 4 parts of the compound represented by the formula (1-16).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 384.0
Exact Mass): +383.2
Synthesis example 12
4.2 Parts of the compound represented by the formula (1-16) was dissolved in 20 parts of methylene chloride (manufactured by Kabushiki Kaisha), and 46 parts of boron tribromide (Fuji photo-alignment film and manufactured by Wako pure chemical industries, ltd.) was charged and stirred. After the completion of the reaction, the reaction mixture was quenched with water, extracted with an ethyl acetate solvent, and concentrated to obtain 5 parts of the compound represented by the formula (1-17).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 370.3
Exact Mass): +369.2
Synthesis example 13
4 Parts of a compound represented by the formula (1-17) was dissolved in 40 parts of dehydrated tetrahydrofuran (product of Kanto Chemicals), cooled to 0℃and 105 parts of borane 1M tetrahydrofuran solution (product of Kanto Chemicals) were added with stirring. Heating to 23 ℃, stirring for 20 hours, adding water for quenching, and extracting by using an organic solvent. The solvent was distilled off to obtain 2.8 parts of a compound represented by the formula (1-18).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 314.3.3
Exact Mass): +313.2
Example 3
0.7 Part of the compound represented by the formula (1-18) and 0.12 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-active pharmaceutical ingredients) were dissolved in 2 parts of toluene (manufactured by Kao chemical Co., ltd.) and 3 parts of n-butanol (manufactured by Kao chemical Co., ltd.) and heated while stirring at 110℃for 13 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.1 part of the compound represented by the formula (I-150).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 705.8
Exact Mass): +704.4
Synthesis example 14
20 Parts of 2, 6-diisopropylaniline (Tokyo chemical Co., ltd.), 22.4 parts of 3-bromoanisole (Tokyo chemical Co., ltd.), 0.6 part of palladium acetate (Tokyo chemical Co., ltd.), 0.9 part of a 1mol/L solution of tri-t-butylphosphine-hexane (Fuji film and Wako pure chemical industries, ltd.), and 21.7 parts of sodium t-butoxide (Tokyo chemical Co., ltd.) were dissolved in 228 parts of toluene (Kao chemical Co., ltd.) and heated to reflux at 110℃for 5 hours. After the completion of the reaction, the organic layer was extracted with water, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 32 parts of a compound represented by the formula (1-19).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 284.2.2
Exact Mass): +283.2
Synthesis example 15
5 Parts of a compound represented by the formula (1-19) was dissolved in 85 parts of dimethylformamide (Fuji photo-Pacific film and Wako pure chemical industries, ltd.) under an ice bath (ice bath). To this was slowly added 3.5 parts of sodium hydride (Fuji film and Wako pure chemical industries, ltd.). After stirring for 10 minutes, 3.8 parts of 1-bromo-4-methoxybutane (Tokyo chemical industry Co., ltd.) was slowly added thereto, and the mixture was heated to 120℃and heated to reflux. After the completion of the reaction, the organic layer was extracted after being quenched again with water slowly in an ice bath, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 6.5 parts of the compound represented by the formula (1-20).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 370.5
Exact Mass): +369.5
Synthesis example 16
5 Parts of a compound represented by the formula (1-20) was dissolved in 100 parts of methylene chloride (manufactured by Kagaku chemical Co., ltd.), 147 parts of boron tribromide (Fuji photo-active compound and manufactured by Wako pure chemical industries, ltd.) was charged and stirred. After the completion of the reaction, the reaction mixture was quenched with water, extracted with ethyl acetate, and concentrated. The obtained crude product was separated by a silica gel column to obtain 3.8 parts of a mixture (hereinafter, referred to as mixture (1-21)) containing 78% of the compound represented by formula (1-21-1) and 22% of the compound represented by formula (1-21-2).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 342.4
Exact Mass): +341.2
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 356.5
Exact Mass): +355.3
(Examples 4 to 5)
4.5 Parts of the mixture (1-21) and 0.45 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-Kagaku Co., ltd.) were dissolved in 30 parts of toluene (Kao chemical Co., ltd.) and 30 parts of n-butanol (Kao chemical Co., ltd.) and heated while stirring at 120℃for 3.5 hours. After the completion of the reaction, the solvent was distilled off, and the mixture was separated and purified by silica gel column chromatography to obtain 1 part of the compound represented by the formula (I-171) and 1 part of the compound represented by the formula (I-177), respectively.
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 761.4
Exact Mass): +760.5
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 775.7
Exact Mass): +774.5
Synthesis example 17
10 Parts of 2,4, 6-trimethylaniline (Tokyo chemical industry Co., ltd.), 16 parts of 1-bromo-3, 5-dimethoxybenzene (Tokyo chemical industry Co., ltd.), 0.83 part of palladium acetate (Tokyo chemical industry Co., ltd.), 2.1 parts of 4,5 '-bis (diphenylphosphino) -9,9' -dimethylxanthene (Tokyo chemical industry Co., ltd.), and 14.2 parts of sodium t-butoxide (Tokyo chemical industry Co., ltd.) were dissolved in 180 parts of toluene (Kakyo chemical industry Co., ltd.) and heated to reflux was carried out at 105℃for 3 hours. After the completion of the reaction, the organic layer was extracted with water, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 19 parts of a compound represented by the formula (1-22).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 272.5
Exact Mass): +271.2
Synthesis example 18
7.5 Parts of the compound represented by the formula (1-22) and 13.6 parts of monoethyl ester acyl chloride succinate (Tokyo chemical Co., ltd.) were dissolved in 150 parts of toluene (Kagaku chemical Co., ltd.) and heated at 100℃for 5 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 10 parts of a compound represented by the formula (1-23).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 400.5
Exact Mass): +399.2
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Synthesis example 19
2.7 Parts of the compound represented by the formula (1-23) was dissolved in 30 parts of methylene chloride (manufactured by Kabushiki Kaisha), and 7.7 parts of boron tribromide (Fuji film and manufactured by Wako pure chemical industries, ltd.) was charged and stirred. After completion of the reaction, the reaction mixture was quenched with water, extracted with ethyl acetate solvent and concentrated to obtain 2.2 parts of the compound represented by the formula (1-24).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 372.3
Exact Mass): +371.2
Synthesis example 20
0.25 Part of the compound represented by the formula (1-24) was dissolved in 7 parts of dehydrated tetrahydrofuran (product of Kanto Chemicals), cooled to 0℃and charged with 0.4 part of borane 1M tetrahydrofuran solution (product of Kanto Chemicals) while stirring. After heating to 23℃and further stirring for 20 hours, the organic solvent was concentrated after quenching with water to obtain 0.12 part of the compound represented by the formula (1-25).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 316.3
Exact Mass): +315.2
Example 6
0.4 Part of the compound represented by the formula (1-25) and 0.07 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-seal and Wako pure chemical industries, ltd.) were dissolved in 3 parts of toluene (Kao chemical Co., ltd.) and 4.5 parts of n-butanol (Kao chemical Co., ltd.) and heated while stirring at 110℃for 3 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was washed with water and acetone to obtain 0.22 part of the compound represented by the formula (I-145).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 709.7
Exact Mass): +708.3
Synthesis example 21
62 Parts of 2, 2-dimethyl-malonic acid monomethyl ester (ALFA CHEMISTRY (manufactured by alpha chemical Co., ltd.) was dissolved in 413 parts of methylene chloride (manufactured by Kabushiki Kaisha), cooled to 0℃and stirred, and 5 parts of dimethylformamide (manufactured by Kaisha chemical Co., ltd.) and 81 parts of oxalyl chloride (manufactured by Tokyo chemical Co., ltd.) were added dropwise. Thereafter, the temperature was raised to 23℃and stirred for 1 hour. After completion of the reaction, the reaction mixture was concentrated to obtain 54 parts of the compound represented by the formula (1-26).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 165.1
Exact Mass): +164.0
Synthesis example 22
46 Parts of 2,4, 6-trimethylaniline (manufactured by Tokyo chemical Co., ltd.) was dissolved in 219 parts of dimethylformamide (manufactured by Kabushiki Kaisha). While stirring the solution at 23 ℃, 50.4 parts of the compound represented by the above formula (1-26) was added dropwise. After the completion of the dropping, the mixture was stirred for 1 hour. After the completion of the reaction, the solvent was distilled off under reduced pressure to obtain 46 parts of a crude product containing the compound represented by the following formula (1-27). The crude product was purified by silica gel column chromatography to obtain 40 parts of a compound represented by the formula (1-27).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 264.1
Exact Mass): +263.2
Synthesis example 23
14.4 Parts of lithium aluminum hydride (powder) (Tokyo chemical Co., ltd.) was charged into 40 parts of dimethyl ether (Kagaku chemical Co., ltd.) and stirred. The mixed solution was cooled to 0 ℃. On the other hand, 10 parts of the compound represented by the above formula (1-27) was put into 40 parts of dimethyl ether (manufactured by Kabushiki Kaisha), stirred and dissolved. The solution containing the compound represented by the formula (1-27) was added dropwise to the solution containing lithium aluminum hydride (powder) described above over 15 minutes while cooling to 0 ℃ and stirring. Thereafter, the temperature was slowly raised to 80℃and reacted at 80℃for 3 days. After the completion of the reaction, the reaction mixture was poured into 200 parts of water, extracted with water and toluene, and concentrated to obtain 7.0 parts of a crude product. The crude product was purified by silica gel column chromatography to obtain 2.9 parts of a compound represented by the formula (1-28).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 222.1
Exact Mass): +221.2
Synthesis example 24
7.8 Parts of a compound represented by the formula (1-28) was dissolved in 108 parts of methylene chloride (manufactured by Kagaku chemical Co., ltd.), cooled to 0℃and 3.6 parts of imidazole (manufactured by Tokyo chemical Co., ltd.) and 6.4 parts of t-butyldimethylchlorosilane (manufactured by Tokyo chemical Co., ltd.) were added while stirring. The temperature was raised to 23℃and stirred for a further 16 hours. After the completion of the reaction, an extraction operation was performed using water and an organic solvent, whereby 7.8 parts of a crude product was obtained. The obtained crude product was separated and purified by column chromatography to obtain 7.2 parts of a compound represented by the formula (1-29).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 336.4
Exact Mass): +335.3
Synthesis example 25
50 Parts of m-bromophenol (Tokyo chemical industry Co., ltd.) and 30 parts of imidazole (Tokyo chemical industry Co., ltd.) were dissolved in 500 parts of methylene chloride (Kanto chemical industry Co., ltd.) and cooled to 0℃and 48 parts of t-butyldimethyl chlorosilane (Tokyo chemical industry Co., ltd.) were added dropwise. After the completion of the dropwise addition, the temperature was raised to 23℃and the mixture was stirred for 16 hours. After the completion of the reaction, the organic layer was extracted with water, and the solvent was concentrated, and then separated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by the formula (1-10).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 287.0
Exact Mass): +286.0
Synthesis example 26
20 Parts of the compound represented by the formula (1-10) was charged into 31 parts of 1, 4-bisAlkane (manufactured by kano chemical Co., ltd.) and dissolved. Further, 3.2 parts of N, N-dimethylethylenediamine (Tokyo chemical industry Co., ltd.), 20.9 parts of sodium iodide (Tokyo chemical industry Co., ltd.), 2.7 parts of copper (I) iodide (Fuji film and Wako pure chemical industries, ltd.) were mixed in the solution. This was placed in a pressurized vessel and reacted at 120℃for 6 hours. After the completion of the reaction, extraction with water and toluene solvent was performed and concentrated to obtain 20 parts of a crude product. The crude product was purified by silica gel column chromatography to obtain 10.5 parts of a compound represented by the formula (1-30).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] +.1
Exact Mass): +334.0
Synthesis example 27
9.6 Parts of the compound represented by the formula (1-29) and 9.6 parts of the compound represented by the formula (1-30) were put into 84 parts of toluene (manufactured by Kao chemical Co., ltd.) and dissolved. Into this solution, 6.8 parts of sodium t-butoxide (manufactured by Tokyo chemical industry Co., ltd.) and 0.4 part of tri-t-butylphosphorus were addedTetrafluoroborate (Tokyo chemical industry Co., ltd.) and 0.52 parts of tris (dibenzylideneacetone) dipalladium (0) (Tokyo chemical industry Co., ltd.) were dissolved. The mixed solution was subjected to microwave irradiation and reacted at 140℃for 1 hour. Thereafter, the solvent was distilled off under reduced pressure, water was added and extraction operation was performed using an organic solvent, and the solvent was distilled off to obtain 9.6 parts of a crude product. This crude product was separated and purified by silica gel column chromatography to obtain 1.8 parts of a crude product containing the compound represented by the formula (1-31) (hereinafter, may be referred to as crude product (1-31)).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 542.4
Exact Mass): +541.4
Synthesis example 28
1.8 Parts of the crude product (1-31) was dissolved in 17.8 parts of tetrahydrofuran (product of Kanto chemical Co., ltd.) and cooled to 0℃and then 9.2 parts of a tetrabutylammonium fluoride 1M tetrahydrofuran solution (product of Tokyo chemical Co., ltd.) was added dropwise thereto, followed by stirring at 23℃for 16 hours. After the completion of the reaction, water was added, tetrahydrofuran was distilled off and the obtained crude product was subjected to extraction with an organic solvent, and after concentration, 1.4 parts of a crude product of the compound represented by the formula (1-32) was obtained. The crude product thus obtained was separated and purified by column chromatography to obtain 0.76 parts of a compound represented by the formula (1-32).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 314.2
Exact Mass): +313.2
Example 7
0.4 Part of the compound represented by the formula (1-32) and 0.072 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-active pharmaceutical ingredients) were dissolved in 14 parts of toluene (manufactured by Kao chemical Co., ltd.) and 3.24 parts of n-butanol (manufactured by Kao chemical Co., ltd.) and heated while stirring at 140℃for 3 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.25 part of the compound represented by the formula (I-87).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 705.8
Exact Mass): +704.4
Synthesis example 29
45 Parts of 4-amino-3, 5-xylenol (Tokyo chemical Co., ltd.) was dissolved in 400 parts of tetrahydrofuran (Kabushiki Kaisha chemical Co., ltd.). 127 parts of di-t-butyl dicarbonate (manufactured by Tokyo chemical industry Co., ltd.) were added to the solution and dissolved. The reaction was stirred at 23℃for 16 hours. After the completion of the reaction, the solvent was distilled off to obtain 51 parts of a crude product. The obtained crude product was purified by stirring in a mixed solvent of 90 parts of ethyl acetate (manufactured by Kabushiki Kaisha) and 272 parts of n-hexane (manufactured by Kabushiki Kaisha) at 23℃for 2 hours to obtain 47 parts of the compound represented by the formula (1-33).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 238.3.3
Exact Mass): +237.1
Synthesis example 30
20 Parts of 2-bromoethanol (Tokyo chemical Co., ltd.) was dissolved in 333 parts of methylene chloride (Kagaku chemical Co., ltd.). To this solution, 32.4 parts of triethylamine (product of Kanto chemical Co., ltd.) and 0.156 part of 4-dimethylaminopyridine (product of Kanto chemical Co., ltd.) were added, and 28.95 parts of t-butyldimethylchlorosilane (product of Tokyo chemical Co., ltd.) was added while stirring and dissolved. The reaction was stirred at 23℃for 16 hours. The solvent was distilled off to obtain 20 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by the formula (1-34).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 239.1
Exact Mass): +238.0
Synthesis example 31
47 Parts of the compound represented by the formula (1-33) was dissolved in 141.5 parts of the bromine compound represented by the formula (1-34) and 447 parts of dimethylformamide (manufactured by Kabushiki Kaisha). 138.2 parts of potassium carbonate (manufactured by Kanto Kagaku Co., ltd.) was added to the solution, and the mixture was stirred and reacted at 70℃for 16 hours. After the completion of the reaction, the solvent was distilled off, and an extraction operation was performed using an organic solvent, whereby 49 parts of a crude product was obtained. The obtained crude product was purified by column chromatography to obtain 41 parts of a compound represented by the formula (1-35).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h-t-Bu +]+ 339.2
Exact Mass): +395.3
Synthesis example 32
41 Parts of the compound represented by the formula (1-35) was dissolved in 424 parts of 1, 4-bis263 Parts of hydrogen chloride (about 4 mol/L1, 4-di/>) was introduced into an alkane (product of Kanto Chemie Co., ltd.)Alkane solution) (Tokyo chemical industry Co., ltd.) was stirred at 23℃for 1 hour and deprotected. After the completion of the reaction, the solvent was distilled off to obtain 36 parts of a crude product. The obtained crude product was purified by column chromatography to obtain 22 parts of a compound represented by the formula (1-36).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 182.2
Exact Mass): +181.1
Synthesis example 33
22 Parts of a compound represented by the formula (1-36) was dissolved in 293 parts of methylene chloride (manufactured by Kabushiki Kaisha). To this solution, 10.8 parts of imidazole (product of Kanto chemical Co., ltd.) and 22 parts of t-butyldimethylchlorosilane (product of Tokyo chemical Co., ltd.) were added and dissolved. The reaction was stirred at 23℃for 16 hours. The solvent was distilled off to obtain 23 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by the formula (1-37).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 296.3
Exact Mass): +295.2
Synthesis example 34
15 Parts of a compound represented by the formula (1-10) was dissolved in 14.5 parts of a compound represented by the formula (1-37) and 130 parts of toluene (manufactured by Kato chemical Co., ltd.), and 5.7 parts of potassium hydroxide (manufactured by Kato chemical Co., ltd.), 15 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by Tokyo chemical Co., ltd.), and 0.26 parts of bis (tri-t-butylphosphine) palladium (0) (manufactured by Tokyo chemical Co., ltd.) were mixed in the solution. After heating to 90 ℃ and stirring for 20 minutes, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 15 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 12 parts of a compound represented by the formula (1-38).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 502.4.4
Exact Mass): +501.3
Synthesis example 35
12 Parts of a compound represented by the formula (1-38), 11.9 parts of methyl 4-chloro-4-oxobutyrate (Tokyo chemical Co., ltd.) and 41.6 parts of toluene (Kanto chemical Co., ltd.) were mixed and heated while stirring at 90℃for 1 hour. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 5.9 parts of a compound represented by the formula (1-39).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 616.3
Exact Mass): +615.3
Synthesis example 36
5.9 Parts of a compound represented by the formula (1-39) was dissolved in 52.4 parts of tetrahydrofuran (product of Kanto Chemie Co., ltd.) and cooled to 0℃and then 11 parts of a tetrabutylammonium fluoride 1M tetrahydrofuran solution (product of Tokyo chemical Co., ltd.) was added dropwise thereto, followed by stirring at 23℃for 2 hours after the completion of the addition. After the completion of the reaction, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was subjected to extraction operation with an organic solvent, and after concentration, 4.3 parts of the compound represented by the formula (1-40) was obtained.
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 388.2
Exact Mass): +387.2
Synthesis example 37
4.3 Parts of the compound represented by the formula (1-40), 56.4 parts of borane 1M tetrahydrofuran solution (manufactured by Kabushiki Kaisha) and 38.2 parts of tetrahydrofuran (manufactured by Kaisha) were mixed at 0℃and heated to 23℃and stirred for 16 hours. After the reaction, water is added for quenching, and the organic solvent is used for extraction. The solvent was distilled off and the obtained crude product was purified by silica gel column chromatography to obtain 2.3 parts of a compound represented by the formula (1-41).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 346.3
Exact Mass): +345.2
Example 8
2.3 Parts of the compound represented by the formula (1-41) and 0.38 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-active pharmaceutical ingredients) were dissolved in 80 parts of toluene (manufactured by Kao chemical Co., ltd.) and 19 parts of n-butanol (manufactured by Kao chemical Co., ltd.) and heated while stirring at 120℃for 4 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of the compound represented by the formula (II-135).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 769.8
Exact Mass): +768.4
Synthesis example 38
100 Parts of 3-iodoanisole (Tokyo chemical Co., ltd.) and 85.5 parts of 4-bromo-2, 6-dimethylaniline (Tokyo chemical Co., ltd.) were dissolved in a mixed solvent of 72 parts of water and 867 parts of toluene (Kao chemical Co., ltd.). 48 parts of potassium hydroxide (manufactured by Kato chemical Co., ltd.), 5 parts of tetrabutylammonium bromide (manufactured by Tokyo chemical Co., ltd.), and 2.2 parts of bis (tri-t-butylphosphine) palladium (0) (manufactured by Tokyo chemical Co., ltd.) were charged while stirring the solution at 23 ℃. The mixed solution was warmed to 90 ℃ and reacted for 16 hours. After the completion of the reaction, extraction with water and toluene solvent and concentration were carried out to obtain 96.8 parts of a crude product. The crude product was purified by silica gel column chromatography to obtain 60.2 parts of a compound represented by the formula (1-42).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 306.0
Exact Mass): +305.0
Synthesis example 39
60 Parts of a compound represented by the formula (1-42) and 29.5 parts of methyl 4-chloro-4-oxobutyrate (Tokyo chemical Co., ltd.) were dissolved in 520 parts of toluene (Kao chemical Co., ltd.) at 23℃and heated to 100℃to react for 16 hours. After the completion of the reaction, an extraction operation was performed using a water-toluene solvent, and after concentration, 64.2 parts of a crude product was obtained. The crude product was purified by silica gel column chromatography to obtain 55.1 parts of a compound represented by the formula (1-43).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 419.9.9
Exact Mass): +419.1
Synthesis example 40
55 Parts of the compound represented by the formula (1-43) was dissolved in 732 parts of methylene chloride (manufactured by Kagaku chemical Co., ltd.) and cooled to 0℃while stirring. While stirring, 197 parts of boron tribromide (Fuji film and Wako pure chemical industries, ltd.) was added dropwise. Stirred at 23℃for 3 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and an aqueous-organic solvent extraction operation was performed to obtain 47.3 parts of a mixture containing 66% of the compound represented by the following formula (1-44) and 23% of the compound represented by the following formula (1-45).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 392.1
Exact Mass): +391.0
Synthesis example 41
A solution of 37.9 parts of thionyl chloride (manufactured by Tokyo chemical Co., ltd.) in 377 parts of methanol (manufactured by Kabushiki Kaisha Co., ltd.) was cooled to 0℃and stirred, while adding 47.3 parts of a mixture comprising 66% of the compound represented by the above formula (1-44) and 23% of the compound represented by the following formula (1-45). The temperature was raised to 23℃and reacted for 16 hours. The solvent was distilled off under reduced pressure to obtain 45.4 parts of a crude product containing the compound represented by the formula (1-45). The obtained crude product was purified by silica gel column chromatography to obtain 40.2 parts of a compound represented by the formula (1-45).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 406.1
Exact Mass): +405.1
Synthesis example 42
40 Parts of the compound represented by the formula (1-45) was dissolved in 355 parts of tetrahydrofuran (manufactured by Kabushiki Kaisha) and stirred. Cooled to 0℃and 442 parts of borane 1M tetrahydrofuran solution (manufactured by Kabushiki Kaisha) were added dropwise. After completion of the dropwise addition, the temperature was raised to 10℃and stirred for 3 hours, and then water was added and an organic layer was obtained by extraction, and the solvent was distilled off to obtain 37.3 parts of a compound represented by the formula (1-46).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 364.1
Exact Mass): +363.08
Synthesis example 43
32 Parts of a compound represented by the formula (1-46) was dissolved in 638 parts of methylene chloride (manufactured by Kagaku chemical Co., ltd.), cooled to 0℃and stirred, and 17.9 parts of imidazole (manufactured by Tokyo chemical Co., ltd.) and 29.1 parts of t-butyldimethylsilyl chloride (manufactured by Tokyo chemical Co., ltd.) were added. The temperature was raised to 23℃and further stirred for 16 hours to effect silylation. After the completion of the reaction, an extraction operation was performed using water and an organic solvent, to obtain 45.8 parts of a crude product. The crude product thus obtained was separated and purified by column chromatography to obtain 40.9 parts of a compound represented by the formula (1-47).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 592.3
Exact Mass): +591.3
Synthesis example 44
20 Parts of the compound represented by the formula (1-47) and 29 parts of methyl acrylate (Tokyo chemical Co., ltd.) were dissolved in 475 parts of dimethylformamide (Kao chemical Co., ltd.). To this solution, 26.2 parts of diisopropylethylamine (Tokyo chemical industry Co., ltd.), 2.05 parts of tris (o-tolyl) phosphine (Tokyo chemical industry Co., ltd.), and 0.758 parts of palladium (II) acetate (Tokyo chemical industry Co., ltd.) were added, and the mixture was stirred at 23℃for 30 minutes. The temperature was raised to 140℃and the reaction was stirred for 32 hours. Here, 14.5 parts of methyl acrylate (product of tokyo chemical industry (ltd)) and 26.2 parts of diisopropylethylamine (product of tokyo chemical industry (ltd)) were additionally charged. Further, the reaction was carried out at 140℃for 2 days. Thereafter, the solvent was distilled off under reduced pressure, water was added and extraction operation was performed using an organic solvent, and 17.2 parts of a crude product (hereinafter, referred to as crude product (1-48) in some cases) was obtained by distilling off the solvent. The crude product contains 40% of the compound represented by the formula (1-48-1) and 40% of the compound represented by the formula (1-48-2).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 484.5
Exact Mass): +483.3
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 598.3
Exact Mass): +597.4
Synthesis example 45
17.2 Parts of the crude product (1-48) was dissolved in 155.4 parts of tetrahydrofuran (product of Kanto chemical Co., ltd.) and cooled to 0℃and then 62.6 parts of a tetrabutylammonium fluoride 1M tetrahydrofuran solution (product of Tokyo chemical Co., ltd.) was added dropwise thereto, followed by stirring at 23℃for 16 hours. After the completion of the reaction, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was subjected to extraction operation with an organic solvent, and after concentration, 13.72 parts of a crude product of the compound represented by the formula (1-49) was obtained. The crude product thus obtained was separated and purified by column chromatography to obtain 8.1 parts of a compound represented by the formula (1-49).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 370.2
Exact Mass): +369.2
Synthesis example 46
6.87 Parts of the compound represented by the formula (1-49) was dissolved in 59.5 parts of methanol (manufactured by Kanto chemical Co., ltd.) and 0.69 parts of palladium on carbon (Pd 10%) (Fuji photo-alignment film and manufactured by Wako pure chemical industries, ltd.) was charged under a normal pressure hydrogen stream and stirred at 23℃for 16 hours. After the completion of the reaction, the reaction mixture was filtered, and the solvent was distilled off to obtain 5.49 parts of a crude product. The crude product thus obtained was purified by column chromatography to obtain 4.26 parts of a compound represented by the formula (1-50).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 372.1
Exact Mass): +371.2
Synthesis example 47
4.2 Parts of the compound represented by the formula (1-50), 2.85 parts of lithium hydroxide monohydrate (Fuji photo-active pharmaceutical ingredients, manufactured by Fuji photo-pure chemical Co., ltd.), 33.3 parts of methanol (manufactured by Kanto chemical Co., ltd.), 37.3 parts of tetrahydrofuran (manufactured by Kanto chemical Co., ltd.), and 21 parts of water were mixed and stirred at 23℃for 16 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 3.11 parts of a compound represented by the formula (1-51).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 358.0
Exact Mass): +357.2
Example 9
3 Parts of a compound represented by the formula (1-51) and 0.48 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-seal and Wako pure chemical industries, ltd.) were dissolved in 104 parts of toluene (Kanto Chemie Co., ltd.) and 24.3 parts of n-butanol (Kanto Chemie Co., ltd.) and heated while stirring at 120℃for 4 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.70 parts of the compound represented by the formula (II-129).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 793.7
Exact Mass): +792.4
Synthesis example 48
100 Parts of 1, 3-dimethoxybenzene (manufactured by Tokyo chemical Co., ltd.) was dissolved in 1330 parts of methylene chloride (manufactured by Kabushiki Kaisha Co., ltd.) and cooled to 0 ℃. 463 parts of bromine (Tokyo chemical industry Co., ltd.) were added dropwise while stirring the solution. After the completion of the dropwise addition, the temperature was raised to 23℃and stirred for 3 hours. After the completion of the reaction, the mixture was extracted with water and a methylene chloride solvent and concentrated to obtain 110 parts of a compound represented by the formula (1-52).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 295.0
Exact Mass): +293.9
Synthesis example 49
25 Parts of a compound represented by the formula (1-52) was dissolved in 111 parts of tetrahydrofuran (product of Kanto chemical Co., ltd.) and cooled to-78℃and 234.2 parts of n-butyllithium 2.5M hexane solution (product of Aldrich Co., ltd.) was added dropwise while stirring. After the addition, the mixture was stirred at-78℃for 45 minutes, and 156 parts of methyl iodide (Tokyo chemical industry Co., ltd.) was added dropwise while cooling to-78 ℃. After the addition, the temperature was raised to 23℃and stirred for 5 hours. After the completion of the reaction, the reaction mixture was gradually poured into 500 parts of ice water. Thereafter, an extraction operation was performed using a water-toluene solvent, and after concentration, 21 parts of a crude product was obtained. The crude product was purified by silica gel column chromatography to obtain 17 parts of a compound represented by the formula (1-53).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 167.1.1
Exact Mass): +166.1
Synthesis example 50
13.5 Parts of the compound represented by the formula (1-53) was dissolved in 200 parts of methylene chloride (manufactured by Kabushiki Kaisha), and cooled to 0℃while stirring. While stirring, 65 parts of bromine (manufactured by Tokyo chemical industries, ltd.) was added dropwise. Thereafter, the temperature was raised to 23℃and stirred for 16 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and a water-dichloromethane solvent extraction operation was performed to obtain 21 parts of a crude product containing the compound represented by the formula (1-54). The obtained crude product was purified by silica gel column chromatography to obtain 15 parts of a compound represented by the formula (1-54).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 323.0.0
Exact Mass): +321.9
Synthesis example 51
14 Parts of a compound represented by the formula (1-54) was dissolved in 124 parts of tetrahydrofuran (product of Kanto chemical Co., ltd.) and cooled to-78℃and 22 parts of a 1.6M hexane solution of butyllithium (product of Aldrich Co., ltd.) was added dropwise with stirring. After the addition, the mixture was stirred for 1 hour while maintaining the temperature at-78 ℃. Thereafter, 50 parts of water was added dropwise while stirring the mixture at-78 ℃. Thereafter, an extraction operation was performed using a water-toluene solvent, and after concentration, 12.5 parts of a crude product containing the compound represented by the formula (1-55) was obtained. The crude product was purified by silica gel column chromatography to obtain 10.4 parts of a compound represented by the formula (1-55).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 245.1
Exact Mass): +244.0
Synthesis example 52
10.4 Parts of the compound represented by the formula (1-55) was dissolved in 200 parts of methylene chloride (manufactured by Kabushiki Kaisha), and cooled to 0℃while stirring. While stirring, 64 parts of boron tribromide (Fuji film and Wako pure chemical industries, ltd.) was added dropwise. Stirred at 23℃for 3 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and an aqueous-organic solvent extraction operation was performed to obtain 11 parts of a crude product containing the compound represented by the formula (1-56). The obtained crude product was purified by silica gel column chromatography to obtain 8.9 parts of a compound represented by the formula (1-56).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 217.0
Exact Mass): +216.0
Synthesis example 53
8.9 Parts of a compound represented by the formula (1-56) was dissolved in 50 parts of dimethylformamide (product of Kanto chemical Co., ltd.), and 28.3 parts of potassium carbonate (product of Kanto chemical Co., ltd.) was added while stirring the solution. Further, 29.4 parts of (2-bromoethoxy) -t-butyldimethylsilane (product of Aldrich Co., ltd.) was charged. The solution was warmed to 70 ℃ and stirred for 16 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and an aqueous-organic solvent extraction operation was performed to obtain 20.6 parts of a crude product containing the compound represented by the formula (1-57). The obtained crude product was purified by silica gel column chromatography to obtain 15.7 parts of a compound represented by the formula (1-57).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 533.2
Exact Mass): +532.2
Synthesis example 54
25 Parts of 3-aminophenol (manufactured by Tokyo chemical Co., ltd.) was dissolved in 333 parts of methylene chloride (manufactured by Kabushiki Kaisha Co., ltd.) and cooled to 0℃with stirring. While stirring the solution at 0 ℃, 20.3 parts of imidazole (product of tokyo chemical industry Co., ltd.) was added, and 41.4 parts of t-butyldimethylchlorosilane (product of tokyo chemical industry Co., ltd.) was further added. Thereafter, the temperature was raised to 23℃and stirred for 16 hours. After the completion of the reaction, an aqueous-organic solvent extraction operation was performed to obtain 48 parts of a crude product containing the compound represented by the formula (1-58). The obtained crude product was purified by silica gel column chromatography to obtain 42 parts of a compound represented by the formula (1-58).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 224.1
Exact Mass): +223.1
Synthesis example 55
12.9 Parts of the compound represented by the formula (1-57) and 4.5 parts of the compound represented by the formula (1-58) were dissolved in 312 parts of toluene (manufactured by Kabushiki Kaisha). To this solution, 18 parts of water was added, and 3.4 parts of potassium hydroxide (manufactured by Kabushiki Kaisha Co., ltd.), 0.5 part of tetrabutylammonium bromide (manufactured by Tokyo chemical Co., ltd.), and 0.51 part of bis (tri-t-butylphosphine) palladium (0) (manufactured by Tokyo chemical Co., ltd.) were added with stirring, and stirred at 23℃for 30 minutes. Thereafter, the temperature was raised to 105℃and reacted for 3 hours. Thereafter, water was added and extraction operation was performed using an organic solvent, and the solvent was distilled off to obtain 12.8 parts of a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 10.2 parts of a compound represented by the formula (1-59).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 676.4
Exact Mass): +675.4
Synthesis example 56
10 Parts of a compound represented by the formula (1-59) and 2.7 parts of methyl 4-chloro-4-oxobutyrate (Tokyo chemical Co., ltd.) were dissolved in 87 parts of toluene (Kao chemical Co., ltd.) at 23℃and heated to 105℃to react for 16 hours. After completion of the reaction, extraction with a water-toluene solvent was performed, and after concentration, 10.3 parts of a crude product containing the compound represented by the formula (1-60) was obtained.
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 790.4
Exact Mass): +789.5
Synthesis example 57
10 Parts of a crude product containing the compound represented by the formula (1-60) was dissolved in 26.6 parts of tetrahydrofuran (product of Kanto chemical Co., ltd.) and cooled to 0℃and then 47.4 parts of a tetrabutylammonium fluoride 1M tetrahydrofuran solution (product of Tokyo chemical Co., ltd.) was added dropwise thereto, followed by stirring at 23℃for 16 hours. After the completion of the reaction, water was added, the tetrahydrofuran solvent was distilled off and the obtained crude product was subjected to extraction operation with an organic solvent, and after concentration, 7.87 parts of a crude product of the compound represented by the formula (1-61) was obtained. The crude product thus obtained was separated and purified by column chromatography to obtain 4.1 parts of a compound represented by the formula (1-61).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 448.3
Exact Mass): +447.2
Synthesis example 58
4 Parts of the compound represented by the formula (1-61) was dissolved in 36 parts of tetrahydrofuran (manufactured by Kabushiki Kaisha) and stirred. Cooled to 0℃and 39.2 parts of borane 1M tetrahydrofuran solution (manufactured by Kabushiki Kaisha) were added dropwise. After the completion of the dropwise addition, the temperature was raised to 23℃and stirred for 5 hours, then water was added and an organic layer was obtained by extraction, and the solvent was distilled off to obtain 3.54 parts of a crude product containing the compound represented by the formula (1-62). The crude product thus obtained was separated and purified by column chromatography to obtain 2.5 parts of a compound represented by the formula (1-62).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 406.2
Exact Mass): +405.2
Example 10
2.5 Parts of the compound represented by the formula (1-62) and 0.70 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-active pharmaceutical ingredients, manufactured by Kao chemical Co., ltd.) were dissolved in 108.4 parts of toluene (manufactured by Kao chemical Co., ltd.) and 40.5 parts of n-butanol (manufactured by Kao chemical Co., ltd.) and heated while stirring at 120℃for 16 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.81 parts of the compound represented by the formula (II-138).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 889.8
Exact Mass): +888.4
Synthesis example 59
10 Parts of 2- (1-adamantyl) -4-bromoanisole (Tokyo chemical Co., ltd.), 4 parts of 3-aminoanisole (Tokyo chemical Co., ltd.), 0.35 parts of palladium acetate (Tokyo chemical Co., ltd.), 0.90 parts of 4,5 '-bis (diphenylphosphino) -9,9' -dimethylxanthene (Tokyo chemical Co., ltd.), 6 parts of sodium t-butoxide (Tokyo chemical Co., ltd.) were dissolved in 180 parts of toluene (Kakyo chemical Co., ltd.) and heated to reflux was carried out at 105℃for 2 hours. After the completion of the reaction, water was added and the organic layer was extracted and concentrated to obtain 25 parts of a compound represented by the formula (1-63).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 364.5
Exact Mass): +363.2
Synthesis example 60
8 Parts of the compound represented by the formula (1-63) and 11 parts of monoethyl ester acyl chloride succinate (Tokyo chemical Co., ltd.) were dissolved in 160 parts of toluene (Kagaku chemical Co., ltd.) and heated to 90 ℃. After the completion of the reaction, the solvent was concentrated and purified by column chromatography to obtain 8 parts of the compound represented by the formula (1-64).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 492.3
Exact Mass): +491.3
Synthesis example 61
8 Parts of a compound represented by the formula (1-64) was dissolved in 150 parts of methylene chloride (manufactured by Kagaku chemical Co., ltd.) and added to 195 parts of boron tribromide (Fuji photo-active material and manufactured by Wako pure chemical industries, ltd.) and stirred. After the completion of the reaction, the reaction mixture was poured into 200 parts of water, extracted with an ethyl acetate solvent, and concentrated to obtain 12 parts of a compound represented by the formula (1-65).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 464.0
Exact Mass): +463.2
Synthesis example 62
12 Parts of a compound represented by the formula (1-65) was dissolved in 70 parts of dehydrated tetrahydrofuran (product of Kanto Chemicals), cooled to 0℃and stirred, and 117 parts of a borane 1M tetrahydrofuran solution (product of Kanto Chemicals) was added. After heating to 23℃and further stirring for 16 hours, water was added to quench the mixture, and then the organic solvent was concentrated, and the obtained crude product was separated and purified by column chromatography to obtain 2.5 parts of a compound represented by the formula (1-66).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 408.0
Exact Mass): +407.3
Example 11
2.5 Parts of the compound represented by the formula (1-66) and 0.32 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-active pharmaceutical ingredients) were dissolved in 8 parts of toluene (manufactured by Kao chemical Co., ltd.) and 10 parts of n-butanol (manufactured by Kao chemical Co., ltd.) and heated while stirring at 110℃for 2 hours. After the completion of the reaction, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 0.5 part of the compound represented by the formula (II-372).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] + 893.0
Exact Mass): +892.5
Synthesis example 1 of resin
A flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with an appropriate amount of nitrogen gas to replace the nitrogen gas atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added thereto and heated to 80℃while stirring. Then, a mixed solution of 38 parts of acrylic acid, 289 parts of 3, 4-epoxytricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate, a mixture of 3, 4-epoxytricyclo [5.2.1.0 2,6 ] decan-9-yl acrylate (mixing ratio: 1:1), and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution of 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the flask was kept at 80℃for 4 hours, and then cooled at room temperature to obtain a copolymer (resin (B-1)) solution having a type B viscosity (23 ℃) of 125 mPas and a solid content of 35.1%. The weight average molecular weight Mw of the resulting copolymer was 9200, the dispersity was 2.08 and the acid value of the solid content was 77mg-KOH/g. The resin (B-1) has the following structural units.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.
The device comprises: HLC-8120GPC (manufactured by Tosoh Co., ltd.) (TOSOH CORPORATION)
Column: TSK-GELG HXL 2000HXL
Column temperature: 40 DEG C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0mL/min
Concentration of solid component of liquid to be measured: 0.001 to 0.01 mass%
Injection amount: 50 mu L
A detector: RI (RI)
Calibration standard substance: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (product of Tosoh Co., ltd.)
The polystyrene-equivalent weight average molecular weight/number average molecular weight ratio (Mw/Mn) obtained above was set to be a dispersity.
Examples 12 to 22 and comparative example 1
[ Preparation of colored resin composition ]
The respective components were mixed so as to have the compositions shown in table 13, to obtain colored resin compositions.
TABLE 13
In table 13, each component represents the following compound.
Colorant (A-1): compounds of formula (I-147)
Colorant (A-2): a compound represented by the formula (I-27)
Colorant (A-3): a compound represented by the formula (I-150)
Colorant (A-4): a compound represented by the formula (I-171)
Colorant (A-5): compounds of formula (I-177)
Colorant (A-6): compounds of formula (I-145)
Colorant (A-7): compounds of the formula (I-87)
Colorant (A-8): compounds of the formula (II-135)
Colorant (A-9): compounds of the formula (II-129)
Colorant (A-10): compounds of formula (II-138)
Colorant (A-11): a compound represented by the formula (II-372)
Colorant (A-x): a compound represented by the formula (x)
Resin (B-1): resin (B-1) (solid content conversion)
Solvent (E-1): propylene glycol monomethyl ether acetate
Solvent (E-2): diacetone alcohol
Solvent (E-3): n-methylpyrrolidone
Solvent (E-4): chloroform (chloroform)
Leveling agent (F-1): polyether modified silicone oil (product of Dongli Corning Co., ltd. "TORAY SILICONE SH 8400")
< Preparation of color Filter (colored coating film) 1>
A colored resin composition was applied onto a 5cm square glass substrate (Eagle 2000; product of Corning Co.) by a spin coating method, and then baked at 100℃for 3 minutes to obtain a colored coating film.
< Measurement of chromaticity >
The chromaticity of the colored coating film was obtained as xy chromaticity coordinates (x, Y) and stimulus value Y in the XYZ color system of CIE from a characteristic function of a light spectrum and a C light source measured using a colorimeter (OSP-SP-200; olympus (olympus) product).
< Evaluation of Heat resistance >
The resulting colored coating film was heated in an oven at 230℃for 2 hours.
Chromaticity was measured before and after heating, and according to the measured value, JIS Z8730 was used: 2009 The color difference Δeab was calculated by the method described in (7) calculation method of color difference, and the results are shown in table 14. The smaller Δeab means the smaller the color change. In addition, if the heat resistance of the colored coating film is good, the colored pattern produced from the same colored resin composition may also be called good heat resistance.
< Evaluation of light resistance >
An ultraviolet cut filter (colored optical glass (COLORED OPTICAL GLASS) L38; HOYA CORPORATION) product, which cuts light of 380nm or less, was disposed on the resulting colored coating film, and the upper surface thereof was irradiated with xenon lamp light for 48 hours using a light resistance tester (SUNTEST CPS+: toyo Seisaku (Toyo Seiki Seisaku-sho, ltd.) product).
Chromaticity was measured before and after irradiation, and according to the measured value, JIS Z8730 was used: 2009 The color difference Δeab was calculated by the method described in (7) calculation method of color difference, and the results are shown in table 14. The smaller Δeab means the smaller the color change. As shown in table 14, examples 12 to 22 were excellent in heat resistance and light resistance.
TABLE 14
Example 23 to example 33
[ Preparation of colored resin composition ]
The respective components were mixed so as to have the compositions shown in table 15, to obtain colored resin compositions.
TABLE 15
In table 15, each component represents the following compound.
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; japan chemical company, strain) (Nippon Kayaku co., ltd.) product
Polymerization initiator (D-1): n-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime Compound; new Strong electronics materials, inc. (Changzhou Tronly New Electronic Materials Co., ltd.) preparation
The other symbols represent the same meanings as described above.
Production 2 of color Filter (colored coating film) and evaluation of Heat resistance
A coloring resin composition was applied onto a 5cm square glass substrate (Eagle 2000; product of Corning Co.) by a spin coating method, and then prebaked at 100℃for 3 minutes to form a coloring composition layer. After cooling by standing, the colored composition layer formed on the substrate was irradiated with light at an exposure of 100mJ/cm 2 (365 nm basis) under an atmospheric environment using an exposure machine (TME-150 RSK; manufactured by Tokiwiki Co., ltd.) (TOPCON CORPORATION). After the light irradiation, post baking (post baking) was performed in an oven at 230℃for 30 minutes to obtain a colored coating film.
Chromaticity was measured before and after post-baking, and based on the measured value, JIS Z8730 was used: 2009 The color difference Δeab was calculated by the method described in (7) calculation method of color difference, and the results are shown in table 16.
TABLE 16
Industrial applicability
According to the compound of the present invention, a color filter excellent in heat resistance can be formed.

Claims (5)

1. A compound represented by the formula (I),
In the formula (I) of the present invention,
R 1 to R 8 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or an alkoxy group of 1 to 20 carbon atoms which may have a substituent,
R 9 and R 10 each independently represent a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,
The divalent aliphatic hydrocarbon group is propane-1, 3-diyl, butane-1, 4-diyl or 2, 2-dimethylpropane-1, 3-diyl,
R 11 and R 12 each independently represent a hydrocarbon group having 6 to 20 carbon atoms of an aromatic hydrocarbon ring, the hydrocarbon group having 6 to 20 carbon atoms may have one or more substituents selected from the group consisting of the following formulas A3-2, A3-3, A4-1, A4-2, A4-3 and hydroxy group, a methylene group contained in the hydrocarbon group having 6 to 20 carbon atoms may be substituted with-O-,
R 13 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms,
In the following formula, the left side represents a bond to an aromatic hydrocarbon ring,
2. A colored resin composition comprising a colorant comprising the compound of claim 1 and a resin.
3. The colored resin composition according to claim 2, further comprising a polymerizable compound and a polymerization initiator.
4. A color filter formed from the colored resin composition according to claim 2 or 3.
5. A display device comprising the color filter of claim 4.
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CN106104371A (en) * 2014-03-26 2016-11-09 住友化学株式会社 Liquid crystal indicator
TW201807079A (en) * 2016-08-17 2018-03-01 三星Ｓｄｉ股份有限公司 Core-shell dye, photosensitive resin composition including the same, and color filter
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