WO2020054874A1 - Sensibilisateur de photopolymérisation - Google Patents

Sensibilisateur de photopolymérisation Download PDF

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Publication number
WO2020054874A1
WO2020054874A1 PCT/JP2019/036244 JP2019036244W WO2020054874A1 WO 2020054874 A1 WO2020054874 A1 WO 2020054874A1 JP 2019036244 W JP2019036244 W JP 2019036244W WO 2020054874 A1 WO2020054874 A1 WO 2020054874A1
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bis
group
anthracene
carbon atoms
general formula
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PCT/JP2019/036244
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English (en)
Japanese (ja)
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山田暁彦
田中英彦
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川崎化成工業株式会社
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Priority claimed from PCT/JP2019/015878 external-priority patent/WO2020054116A1/fr
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Publication of WO2020054874A1 publication Critical patent/WO2020054874A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08G59/20—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 epoxy compounds used

Definitions

  • the present invention relates to a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and an oligomer thereof, a method for producing the same, and a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group or an oligomer thereof. It relates to a photopolymerization sensitizer contained.
  • Photocurable resins that are polymerized by active energy rays such as ultraviolet rays and visible light cure quickly and can significantly reduce the amount of organic solvents used compared to thermosetting resins. It is excellent in that it can be reduced.
  • the conventional photocurable resin itself has a poor polymerization initiation function, and usually requires the use of a photopolymerization initiator for curing.
  • the photopolymerization initiator include alkylphenone-based polymerization initiators such as hydroxyacetophenone and benzophenone, acylphosphine oxide-based photopolymerization initiators, and onium salts (Patent Documents 1, 2, and 3).
  • the onium salt absorbs light at about 225 nm to about 350 nm and has no absorption above 350 nm. In this case, there is a problem that the photocuring reaction does not easily proceed, and a photopolymerization sensitizer is generally added. Similarly, many photopolymerization initiators such as alkylphenone-based polymerization initiators have no absorption at 350 nm or more. Anthracene compounds and thioxanthone compounds are known as photopolymerization sensitizers for these photopolymerization initiators, and in particular, anthracene compounds are often used due to the problem of coloration (Patent Document 4).
  • anthracene-based photopolymerization sensitizer a 9,10-dialkoxyanthracene compound is used.
  • a 9,10-dialkoxyanthracene compound such as 9,10-dibutoxyanthracene or 9,10-diethoxyanthracene is used as a photopolymerization sensitizer for an iodonium salt which is a photopolymerization initiator in photopolymerization.
  • the 9,10-dialkoxyanthracene compound blooms during storage of the photopolymerizable composition before photocuring or the cured product after photocuring, so that the photopolymerization sensitizer or the like oozes out on the surface, and the cured product is cured. It is known to cause dusting and coloring problems.
  • the photopolymerization sensitizers migrates to the film covered on the top ( Migration), which may cause a problem of powder blowing or coloring of the photopolymerization sensitizer on the upper film.
  • a 9,10-bis (2-acyloxyalkoxy) anthracene compound in which a polar ester group is introduced into an alkoxy group of a 9,10-dialkoxyanthracene compound is used. It has been reported (Patent Document 10).
  • the 9,10-bis (2-acyloxyalkoxy) anthracene compound has a step of using an alkylene oxide compound at the time of production, which not only increases the number of steps but leads to an increase in cost, but also increases the cost of the alkylene oxide compound, particularly ethylene oxide.
  • the difficulty in availability and handling is a major problem in producing the 9,10-bis (2-acyloxyalkoxy) anthracene compound.
  • the present inventors have disclosed an oligomer of a 9,10-bis (substituted alkoxy) anthracene compound as a compound which exhibits a photopolymerization sensitizing effect and hardly causes migration or the like (Patent Document 12).
  • the oligomer of the 9,10-bis (substituted alkoxy) anthracene compound uses an alkylene oxide in addition to the 9,10-dihydroxyanthracene compound as a raw material for oligomer synthesis, but available alkylene oxide is limited.
  • alkylene oxide which is easily available, has high toxicity, low boiling point, high flammability and is difficult to handle, and requires heat treatment in the synthesis reaction of 9,10-bis (substituted alkoxy) anthracene compound.
  • ethylene oxide which is most easily available, a pressurized hermetically sealed container such as an autoclave is required, and a problem that a special production facility is required remains.
  • the 9,10-bis (substituted alkoxy) anthracene compound as a raw material has low solubility and requires high-temperature conditions.
  • the present inventors have conducted further intensive studies on the structure and physical properties of the anthracene compound.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and the oligomer thereof shown in the present invention can be used in the photopolymerization reaction.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound and its oligomer of the present invention can be produced from easily available compounds as raw materials under mild conditions.
  • a first gist of the present invention resides in a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1).
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, and may be a cycloalkyl group or a cycloalkylalkyl group. However, the alkyl group does not contain an oxygen atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • a second aspect of the present invention resides in the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to the first aspect, wherein A in the general formula (1) is a methylene group.
  • a third aspect of the present invention resides in an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a repeating unit represented by the following general formula (10).
  • n represents the number of repetitions and is 2 to 50
  • A represents an alkylene group having 1 to 20 carbon atoms
  • the alkylene group may be branched by an alkyl group.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.
  • a fourth aspect of the present invention resides in the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to the third aspect, wherein A in the general formula (10) is a methylene group.
  • a fifth gist of the present invention is to provide a method of reacting a 9,10-dihydroxyanthracene compound represented by the following general formula (2) with an ester compound represented by the following general formula (3).
  • the present invention relates to a method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the formula (1).
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • G represents a chlorine atom, a bromine atom or an iodine atom.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • the sixth gist of the present invention is to react a 9,10-dihydroxyanthracene compound represented by the following general formula (2) with a carboxylic acid compound represented by the following general formula (4), 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) is synthesized with a 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). 6), a 9,10-bis (alkoxy) having an ester group represented by the following general formula (1), characterized by reacting an esterifying agent represented by the general formula (7) or (8). Carbonylalkyleneoxy) anthracene compound.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • G represents a chlorine atom, a bromine atom or an iodine atom.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be substituted with a hydroxy group. And some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be substituted with a hydroxy group. And some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • G represents a chlorine atom, a bromine atom, or an iodine atom.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, and the alkyl group may be branched by an alkyl group, and may be a cycloalkyl group or a cycloalkylalkyl group. , May be substituted with a hydroxy group, and a part of carbon atoms may be replaced by an oxygen atom (except when peroxide is formed).
  • R 1 is an alkyl group having a carbon number of 1 to 17 carbon atoms of R 1 is the formula number of carbon atoms of R in (1) except in the case of the 1 3, only 3 for the number of carbon atoms in R It will be a small number.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • a seventh gist of the present invention is to react a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the following general formula (1) with a bifunctional compound represented by the following general formula (11).
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, or may be substituted with a hydroxy group.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group and contains an unsaturated bond.
  • the carbon atom of this alkylene structure may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring.
  • the benzene ring and naphthalene ring may be substituted with an alkyl group.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • Z represents a hydroxy group, a halogen atom, or a glycidyloxy group.
  • n represents the number of repetitions and is 2 to 50
  • A represents an alkylene group having 1 to 20 carbon atoms
  • the alkylene group may be branched by an alkyl group.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.
  • An eighth aspect of the present invention is characterized in that a 9,10-dihydroxyanthracene compound represented by the following general formula (2) is reacted with a bifunctional compound represented by the following general formula (13).
  • the present invention relates to a method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a repeating unit having an ester group represented by the following general formula (10).
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • G represents a chlorine atom, a bromine atom or an iodine atom.
  • n represents the number of repetitions and is 2 to 50
  • A represents an alkylene group having 1 to 20 carbon atoms
  • the alkylene group may be branched by an alkyl group.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.
  • a ninth aspect of the present invention resides in a photopolymerization sensitizer containing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1).
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • a tenth aspect of the present invention resides in a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1), wherein A is a methylene group and R is substituted with a hydroxy group.
  • the photopolymerization sensitizer according to the ninth aspect wherein the photopolymerization sensitizer is a C1 to C20 alkyl group which is not substituted and a part of carbon atoms is not replaced by an oxygen atom.
  • An eleventh aspect of the present invention is directed to a photopolymerization sensitizer containing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a repeating unit having an ester group represented by the following general formula (10).
  • a photopolymerization sensitizer containing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a repeating unit having an ester group represented by the following general formula (10).
  • n represents the number of repetitions and is 2 to 50
  • A represents an alkylene group having 1 to 20 carbon atoms
  • the alkylene group may be branched by an alkyl group.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.
  • a twelfth aspect of the present invention is a photopolymerization-enhancing method comprising an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to the eleventh aspect, wherein A in the general formula (10) is a methylene group. It exists in the sensitizer.
  • a thirteenth aspect of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer according to any one of the ninth to twelfth aspects and a photopolymerization initiator.
  • a fourteenth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition according to the thirteenth aspect and a cationic photopolymerizable compound.
  • a fifteenth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition according to the thirteenth aspect and a photoradical polymerizable compound.
  • a sixteenth aspect of the present invention is directed to a polymerization method of polymerizing the photopolymerizable composition according to the fourteenth aspect or the fifteenth aspect by irradiating an energy ray containing light in a wavelength range of 300 nm to 500 nm. Exist.
  • a seventeenth aspect of the present invention is characterized in that the irradiation source of energy rays containing light in a wavelength range of 300 nm to 500 nm is an ultraviolet LED or a 405 nm semiconductor laser having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm.
  • the irradiation source of energy rays containing light in a wavelength range of 300 nm to 500 nm is an ultraviolet LED or a 405 nm semiconductor laser having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and the oligomer thereof according to the present invention not only have a high effect as a photopolymerization sensitizer in a photopolymerization reaction, but also have the compound of the present invention. It is a useful compound in which the degree of migration or blooming of the photopolymerizable sensitizer is extremely low with respect to the photopolymerizable composition and the cured product contained as the photopolymerization sensitizer. Also in the production method, there is no need to use an alkylene oxide compound which is difficult to obtain and handle, and the compound can be produced under mild conditions using a compound which is easy to obtain and handle, and the production process is easy and inexpensive.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is a compound represented by the following general formula (1).
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • the alkylene group having 1 to 20 carbon atoms represented by A includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, Decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group, etc., and the alkylene group may be branched by an alkyl group. .
  • alkyl group having 1 to 8 carbon atoms represented by X or Y a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group , N-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl or 2-ethylhexyl, and the like. Atoms.
  • alkyl group having 1 to 20 carbon atoms represented by R a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t- -Butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n -Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group or
  • Cibutyl group 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, 6-hydroxy-2-ethylhexyl group, 9-hydroxynonyl group, 10- Hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-ethoxypropyl, 2-hydroxy-3-propoxypropyl, 2-hydroxy -3-butoxypropyl group, 2-hydroxy-3-pentyloxypropyl group, 2-hydroxy-3-hexyloxypropyl group, 2-hydroxy-3-octyloxypropyl group, 2-hydroxy-3- (2-ethylhexyl Oxy) propyl group, 2,3-dihydroxy Propyl, 2-hydroxy-3-allyloxy propyl, and 2-hydroxy-3-methallyl propyl group.
  • cycloalkyl group examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, 4-n-dodecylcyclohexyl, decahydronaphthyl, hydroxycyclohexyl, etc.
  • cycloalkylalkyl group examples include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, a cyclodecylmethyl group, and -Cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2-cyclodecylethyl , 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl,
  • 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention include, for example, 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert- Butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonyl) Pyreneoxy) anthracene, 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 9,10-bis (isoprop
  • 9,10-bis (methoxycarbonylpentyleneoxy) anthracene 9,10-bis (ethoxycarbonylpentyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpentyleneoxy) anthracene, 9,10- Bis (tert-butoxycarbonylpentyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylpentyleneoxy) anthracene, 9,10-bis (methoxycarbonylhexyleneoxy) anthracene, 9,10-bis (ethoxycarbonyl) Hexyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylhexyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylhexyleneoxy) anthracene, 9,10-bis (n-butene) (Cicarbonylhexyleneoxy) anthracene, 9,10-bis (methoxycarbonyl
  • X and / or Y as an alkyl group include, for example, 2-ethyl-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylmethyleneoxy) Anthracene, 2-ethyl-9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert -Butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 2-ethyl -9,10-bis (methoxycal Nylpropyleneoxy) anthracene, 2-ethyl -9
  • 2-amyl-9,10-bis (methoxycarbonylmethyleneoxy) anthracene 2-amyl-9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n- Propoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 2-amyl-9, 10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-A Ru-9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 2-amyl-9,10-bis (meth
  • X and / or Y as a halogen atom include, for example, 2-chloro-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylmethyleneoxy) Anthracene, 2-chloro-9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (tert -Butoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-chloro-9, 10-bis (ethoxycarbonyl Ropyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbon
  • 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, and 9,10-bis (n-propoxycarbonyl) are preferred for ease of production.
  • R in the general formula (1) is an alkyl group containing no oxygen atom and having 1 to 20 carbon atoms.
  • a in the general formula (1) is preferably a methylene group having 1 carbon atom.
  • an alkyl group having 3 or more carbon atoms of R is preferable, and 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-3), 9,10 -Bis (n-pentyloxycarbonylmethyleneoxy) anthracene (1-11) and 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene (1-12) are particularly preferred.
  • the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group according to the present invention is a compound having a repeating unit represented by the following general formula (10).
  • n represents the number of repetitions and is 2 to 50
  • A represents an alkylene group having 1 to 20 carbon atoms
  • the alkylene group may be branched by an alkyl group.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.
  • examples of the alkylene group having 1 to 20 carbon atoms represented by A include a methylene group, a methylmethylene group, an ethylmethylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a heptylene.
  • alkylene group is an alkyl group. May be branched.
  • examples of the alkyl or alkenyl group having 1 to 8 carbon atoms represented by X or Y include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group.
  • the alkylene group having 1 to 20 carbon atoms represented by D includes a methylene group, an ethylene group, a methylethylene group, an ethylethylene group, a propylene group, a 1-methylpropylene group, 2-methylpropylene group, 2,2-dimethylpropylene group, butylene group, pentylene group, 3-methylpentylene group, 2,4-diethylpentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group An undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadecylene group, an icosylene group, and the like.
  • the alkylene structure may contain a saturated bond.
  • An element atom may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl groups. May be substituted.
  • Examples of the alkylene group in which the carbon atom of the alkylene group is substituted by an oxygen atom and the like include polyoxyalkylene groups such as a polyoxyethylene group and a polyoxypropylene group.
  • examples of the arylene group having 6 to 20 carbon atoms represented by D include a phenylene group and a naphthylene group, and the arylene group may have a substituent, and May be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (10) of the present invention first, in the general formula (10), A is a methylene group.
  • Tables 1, 2 and 3 show specific examples of the compound of the general formula (12). In the following tables, m in the formula represents 1 to 30.
  • n represents the number of repetitions and is 2 to 50
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms
  • the alkylene group is branched by an alkyl group. May contain an unsaturated bond, the carbon atom of this alkylene structure may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under non-adjacent conditions, or an alicyclic compound, benzene It may contain a ring or a naphthalene ring, and the benzene ring and the naphthalene ring may be substituted with an alkyl group.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.
  • A is not a methylene group but an ethylene group, a propylene group, a butylene group, and a pentylene.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is obtained by using a 9,10-dihydroxyanthracene compound represented by the following general formula (2) as a raw material.
  • a 9,10-dihydroxyanthracene compound represented by the following general formula (2) is synthesized in a one-step reaction using a 9,10-dihydroxyanthracene compound as a raw material (one-step production method) and a two-step reaction through an intermediate (two-step production method). There is.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is obtained by converting the 9,10-dihydroxyanthracene compound represented by the general formula (2) into the following. According to Reaction Scheme-1, it can be obtained by reacting with a corresponding ester compound represented by the general formula (3) in the presence or absence of a basic compound.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • G represents a chlorine atom, a bromine atom or an iodine atom.
  • the 9,10-dihydroxyanthracene compound represented by the general formula (2) used as a raw material is obtained by reducing the corresponding 9,10-anthraquinone compound.
  • the 9,10-dihydroxyanthracene compound used as a raw material is obtained by reducing the corresponding 9,10-anthraquinone compound.
  • Specific examples of the 9,10-dihydroxyanthracene compound serving as a raw material in the reaction include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, 2-ethyl-9,10-dihydroxyanthracene , 2-t-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, 2-bromo-9,10-dihydroxyanthracene and the like. No.
  • the hydroxyl group may be used in a form protected by a known protecting group.
  • 9,10-dihydroxyanthracene an industrial method such as 1,4,4a, 9a-tetrahydroanthraquinone which is a Diels-Alder reaction product of 1,4-naphthoquinone and 1,3-butadiene or By reducing 9,10-anthraquinone using an alkali metal salt of 1,4-dihydro9,10-dihydroxyanthracene as its isomer, 9,10-dihydroxyanthracene can be obtained more easily.
  • 1,4,4a, 9a-tetrahydroanthraquinone obtained by the reaction of 1,4-naphthoquinone and 1,3-butadiene is converted into an aqueous medium in the presence of an alkaline compound such as an alkali metal hydroxide.
  • an alkaline compound such as an alkali metal hydroxide.
  • an alkaline compound such as an alkali metal hydroxide.
  • an alkali metal salt of 9,10-dihydroxyanthracene can be obtained.
  • the resulting aqueous solution of the alkali metal salt of 9,10-dihydroxyanthracene is acidified in the absence of oxygen, whereby a precipitate of 9,10-dihydroxyanthracene can be obtained.
  • a precipitate of 9,10-dihydroxyanthracene can be obtained.
  • a 9,10-dihydroxyanthracene compound having a substituent can be obtained in a similar manner.
  • a precipitate of 9,10-dihydroxyanthracene By acidifying the aqueous solution of the alkali metal salt of 9,10-dihydroxyanthracene obtained in the reaction in the absence of oxygen, a precipitate of 9,10-dihydroxyanthracene can be obtained. By purifying the precipitate, 9,10-dihydroxyanthracene can be obtained. A 9,10-dihydroxyanthracene compound having a substituent can be obtained in a similar manner.
  • ester compound represented by the general formula (3) as a raw material examples include methyl chloroacetate, ethyl chloroacetate (3-12), n-propyl chloroacetate, isopropyl chloroacetate and chloroacetate.
  • a chloro compound and a bromo compound are preferable in terms of reactivity, and particularly, a compound having the following structural formula is preferable.
  • the amount of the ester compound represented by the general formula (3) in Reaction Scheme-1 is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 9, mol times or less with respect to the 9,10-dihydroxyanthracene compound. Preferably, it is 2.2 mole times or more and less than 5.0 mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.
  • ester compound represented by the general formula (3) a commercially available product may be purchased, or a compound synthesized with a corresponding carboxylic acid and alcohol may be used.
  • reaction formula-1 when an ester compound represented by the general formula (3) synthesized with the corresponding carboxylic acid and alcohol is used, the ester compound is previously synthesized in the system, and the ester compound represented by the general formula (2) is added thereto.
  • the reaction can be carried out efficiently by adding the 9,10-dihydroxyanthracene compound represented by the formula (1).
  • Examples of the basic compound used in Reaction Scheme-1 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, ⁇ -picoline, lutidine and the like.
  • the amount of the basic compound to be added is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 2.2 mol times or more, and 5.0 times or more with respect to the 9,10-dihydroxyanthracene compound. Less than mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.
  • the reaction is performed in a solvent or without a solvent.
  • the solvent used is not particularly limited as long as it does not react with the ester compound to be used.
  • aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene, and alcohol solvents such as methanol, ethanol and 1-propanol are used. .
  • phase transfer catalyst examples include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctylmethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctyl
  • the amount of the phase transfer catalyst to be added is preferably at least 0.01 mole times, less than 1.0 mole times, more preferably at least 0.05 mole times, and Less than molar times. If it is less than 0.01 mol times, the reaction rate is low, and if it is more than 1.0 mol times, the purity of the product is undesirably reduced.
  • the reaction temperature of the reaction is usually from 0 ° C to 200 ° C, preferably from 10 ° C to 100 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 100 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.
  • the reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 10 hours.
  • unreacted raw materials, solvents and catalysts are removed by a method such as washing, distillation under reduced pressure, filtration and the like, if necessary, alone or in combination.
  • a method such as washing, distillation under reduced pressure, filtration and the like, if necessary, alone or in combination.
  • the product is a solid, crystals precipitate during the reaction, so that solid-liquid separation is performed by filtration, and recrystallization from a poor solvent such as alcohol or hexane is performed as necessary.
  • the crystals can be obtained by drying up as they are.
  • the product is a liquid, it is dried as it is and, if necessary, purified by distillation or the like to obtain a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group.
  • the compound is reacted with the corresponding carboxylic acid represented by the general formula (4) in the presence or absence of a basic compound to react with the corresponding carboxylic acid represented by the general formula (5).
  • a 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and a general formula 6
  • a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) is obtained.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • G represents a chlorine atom, a bromine atom or an iodine atom.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, or may be substituted with a hydroxy group.
  • Some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, or may be substituted with a hydroxy group.
  • Some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • G represents a chlorine atom, a bromine atom, or an iodine atom.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
  • R represents an alkyl group having 4 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be substituted with a hydroxy group. And some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed).
  • R in the general formula (1) represents an alkyl group having 4 to 20 carbon atoms.
  • Reaction Scheme-2 as the 9,10-dihydroxyanthracene compound represented by General Formula (2) used as a raw material, the same compounds as those described in Reaction Scheme-1 can be used. Obtainable.
  • specific examples of the carboxylic acid represented by the general formula (4) as the other raw material include chloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, and 2-chloropropionic acid.
  • chloro compounds and bromo compounds are preferable in terms of availability and reactivity, and chloroacetic acid and bromoacetic acid are particularly preferable.
  • the amount of the carboxylic acid represented by the general formula (4) in the reaction formula-2 is preferably 2.0 mole times or more and less than 10.0 mole times with respect to the 9,10-dihydroxyanthracene compound. Preferably, it is 2.2 mole times or more and less than 5.0 mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.
  • Examples of the basic compound used in Reaction formula-2 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, ⁇ -picoline, lutidine and the like.
  • the amount of the basic compound to be added is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 2.2 mol times or more, and 8.0 times or more with respect to the 9,10-dihydroxyanthracene compound. Less than mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.
  • the reaction is performed in a solvent or without a solvent.
  • the solvent used is not particularly limited as long as it does not react with the raw materials used. Examples thereof include aromatic solvents such as toluene, xylene and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetone, methyl ethyl ketone, and methyl. Ketone solvents such as isobutyl ketone; amide solvents such as dimethylacetamide and dimethylformamide; halogenated carbon solvents such as methylene chloride, ethylene dichloride and chlorobenzene; alcohol solvents such as methanol, ethanol and 1-propanol; and water. Used.
  • phase transfer catalyst examples include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctylmethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctyl
  • the amount of the phase transfer catalyst to be added is preferably at least 0.01 mole times and less than 1.0 mole times, more preferably at least 0.03 mole times, and Less than mole times. If it is less than 0.01 mol times, the reaction rate is low, and if it is more than 1.0 mol times, the purity of the product is undesirably reduced.
  • the reaction temperature of the reaction is usually from 0 ° C to 100 ° C, preferably from 10 ° C to 50 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 100 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.
  • the reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 10 hours.
  • a 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and an alcohol compound represented by the general formula (6) represented by the reaction formula-3 are mixed with or without a catalyst.
  • a method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) by reacting in the presence of the compound will be described.
  • specific examples of the alcohol compound represented by the general formula (6) as a raw material include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. , 1-pentanol, 2-pentanol, 3-pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, dodecanol, cyclohexanol, cyclohexylmethanol, ethylene glycol, propylene glycol and the like.
  • methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclohexanol , Ethylene glycol and propylene glycol are preferred because they are easily available, and particularly preferred are methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol and cyclohexanol.
  • the amount of the alcohol compound represented by the general formula (6) in the reaction formula-3 is preferably based on the amount of the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). It is 5 mol times or more and less than 100 mol times, more preferably 10 mol times or more and less than 50 mol times. If it is less than 5 moles, the reaction will not be completed.
  • Catalysts used in Reaction Scheme-3 include mineral acids (sulfuric acid, hydrochloric acid), organic acids (methanesulfonic acid, p-toluenesulfonic acid), Lewis acids (boron fluoride etherate, aluminum trichloride, titanium tetrachloride, Iron trichloride, zinc dichloride), solid acid catalyst (manufactured by Futamura Chemical Co., Ltd.), Amberlyst (manufactured by Organo), Nafion (manufactured by DuPont, Nafion is a registered trademark of DuPont), tetraalkoxy titanium compound (tetraisopropoxy titanium , Tetra-n-butoxytitanium, tetramethoxytitanium), and organic tin compounds (dibutyltin dilaurate, dibutyltin oxide) and the like.
  • mineral acids sulfuric acid, hydrochloric acid
  • organic acids methane
  • the amount of the catalyst to be added is preferably 0.01 mol% or more and less than 50 mol%, more preferably, 9,9-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). , 0.1 mol% or more and less than 20 mol%. If it is less than 0.01 mol%, the reaction will not be completed, and if it is more than 50 mol%, a side reaction will occur and the yield and purity will be reduced, which is not preferable.
  • the reaction is performed in a solvent or without a solvent.
  • the solvent used is not particularly limited as long as it does not react with the alcohol compound to be used.
  • aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, and carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene are used.
  • aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran
  • ether solvents such as 1,4-dioxane
  • acetone such as methyl isobutyl ketone
  • amide solvents such as dimethylacetamide and dimethylform
  • the reaction temperature of the reaction is usually from 20 ° C to 200 ° C, preferably from 50 ° C to 150 ° C. If the temperature is lower than 20 ° C., the reaction time is too long. If the temperature is higher than 200 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.
  • the reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 15 hours.
  • the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and the halogenated alkyl compound represented by the general formula (7) represented by the reaction formula-4 are added in the presence of a base.
  • a method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) by reacting in the absence of the compound will be described.
  • alkyl halide compound represented by the general formula (7) as a raw material examples include methyl chloride, ethyl chloride, n-propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, and sec chloride.
  • chlorides and bromides are preferable in terms of availability and reactivity, and bromides are particularly preferable.
  • the amount of the alkyl halide compound represented by the general formula (7) in the reaction formula-4 is determined based on the amount of the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). It is preferably at least 2 mole times and less than 10 mole times, more preferably at least 3 mole times and less than 5 mole times. If it is less than 2 moles, the reaction will not be completed, and if it is 10 moles or more, a side reaction will occur and the yield and purity will be reduced, which is not preferable.
  • Examples of the basic compound used in Reaction Formula-4 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, lithium hexamethyldisilazide, and lithium diisopropylamide. , Triethylamine, tributylamine, trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, ⁇ -picoline, lutidine and the like.
  • the amount of the basic compound to be added is preferably 0.5 mol times or more and less than 10 mol times with respect to the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). Preferably, it is 1 mole or more and less than 5 moles. If it is less than 0.5 mole times, the reaction is not completed, and if it is more than 10 mole times, a side reaction occurs to lower the yield and purity, which is not preferable.
  • the reaction is performed in a solvent or without a solvent.
  • the solvent used is not particularly limited as long as it does not react with the alcohol compound to be used.
  • aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, and carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene are used.
  • the reaction temperature of the reaction is usually from 0 ° C to 200 ° C, preferably from 20 ° C to 100 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 200 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.
  • the reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 15 hours.
  • glycidyl ether compound represented by the general formula (8) as a raw material examples include methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, and hexyl glycidyl ether.
  • the amount of the glycidyl ether compound represented by the general formula (8) in the reaction formula-5 is preferably based on the amount of the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). Is 2 mole times or more and less than 10 mole times, more preferably 3 mole times or more and less than 5 mole times. If it is less than 2 moles, the reaction will not be completed, and if it is 10 moles or more, a side reaction will occur and the yield and purity will be reduced, which is not preferable.
  • Examples of the basic compound used in Reaction Formula-5 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, lithium hexamethyldisilazide, and lithium diisopropylamide. , Triethylamine, tributylamine, trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, ⁇ -picoline, lutidine and the like.
  • the amount of the basic compound to be added is preferably 0.5 mol times or more and less than 10 mol times with respect to the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). Preferably, it is 1 mole or more and less than 5 moles. If it is less than 0.5 mole times, the reaction is not completed, and if it is more than 10 mole times, a side reaction occurs to lower the yield and purity, which is not preferable.
  • the reaction is performed in a solvent or without a solvent.
  • the solvent used is not particularly limited as long as it does not react with the glycidyl ether compound used, and examples thereof include aromatic solvents such as toluene, xylene and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetone and methyl ethyl ketone. And ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, and halogenated carbon solvents such as methylene chloride, ethylene dichloride and chlorobenzene.
  • the reaction temperature of the reaction is usually from 0 ° C to 200 ° C, preferably from 20 ° C to 100 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 200 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.
  • the reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 15 hours.
  • the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (10) of the present invention is a 9,10-bis (alkoxycarbonyl) represented by the general formula (1) It can be obtained by reacting an alkyleneoxy) anthracene compound with a corresponding bifunctional compound represented by the general formula (11) according to the following reaction formula-6.
  • R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be a hydroxy group. And a part of carbon atoms may be replaced by an oxygen atom (except when a peroxide is formed).
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.
  • Z represents a hydroxy group, a halogen atom, or a glycidyloxy group, and n represents the number of repetitions and is 2 to 50.
  • 910-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the general formula (1) as a raw material include 9,10-bis (hydroxycarbonylmethyleneoxy) Anthracene, 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert- Butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonyl) Ropyleneoxy) anthracene, 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (is
  • bifunctional compound represented by the general formula (11) as a raw material include, when Z is a hydroxy group, ethylene glycol, propylene glycol, 1,2-butanediol, 3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-
  • Z is a halogen atom, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1 1,8-dichlorooctane, 1,9-dichlorononane, 1,10-dichlorodecane, 1,11-dichloroundecane, 1,12-dichlorododecane, 1,13-dichlorotridecane, 1,14-dichlorotetradecane, 1,15-dichloropentadecane, 1,16-dichlorohexadecane, 1,17-dichloroheptadecane, 1,18-dichlorooctadecane, 1,19-dichlorononadecane, 1,20-dichloroicosane, 1,2-dibromoethane,
  • any of an aliphatic diglycidyl ether compound, an alicyclic glycidyl ether compound and an aromatic diglycidyl ether compound may be used.
  • the aliphatic diglycidyl ether compound include ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.
  • Examples of the alicyclic diglycidyl ether compound include hydrogenated bisphenol-A diglycidyl ether and hydrogenated bisphenol-F diglycidyl ether.
  • Examples of the aromatic diglycidyl ether include bisphenol A diglycidyl ether and bisphenol F diglycidyl ether. Glycidyl ether, hydroquinone diglycidyl ether and the like can be mentioned. Two or more of these bifunctional compounds may be used in the reaction at the same time.
  • diol compounds are preferred in terms of reactivity.
  • the amount of the bifunctional compound represented by the general formula (11) in the oligomerization reaction is preferably 0.5 mole times or more based on the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. It is less than 0.0 mole times, more preferably 1.0 mole times or more and less than 3.0 mole times. If it is less than 0.5 mole times, the average molecular weight becomes small, the effect of suppressing migration is weakened, and unreacted 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound remains in the product and the purity is reduced. Decrease. If it is 5.0 mol times or more, the average molecular weight becomes small, the effect of suppressing migration is weakened, and the unreacted bifunctional compound remains in the product to lower the purity.
  • the average molecular weight increases. It can be too large, reducing the mobility of the molecule and reducing the sensitizing ability. In that case, the molecular weight may be adjusted by adding a small amount of a monofunctional compound.
  • the catalyst used for the reaction includes mineral acids (sulfuric acid, hydrochloric acid), organic acids (methanesulfonic acid, p-toluenesulfonic acid), Lewis acids (boron fluoride etherate, aluminum trichloride, titanium tetrachloride, iron trichloride, Zinc dichloride) solid acid catalyst (manufactured by Futamura Chemical Co., Ltd.), Amberlyst (manufactured by Organo), Nafion (manufactured by DuPont, Nafion is a registered trademark of DuPont), tetraalkoxy titanium compound (tetraisopropoxy titanium, tetra n-butoxy) Titanium, tetramethoxytitanium), and organic tin compounds (dibuty
  • the amount of the catalyst to be added is preferably 0.01 mol% or more and less than 20 mol%, more preferably 0.1 mol% or more, based on the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. Less than mol%. If it is less than 0.01 mol%, the reaction is not completed, and if it is more than 20 mol%, a side reaction occurs and the yield and purity are undesirably reduced.
  • the bifunctional compound represented by the general formula (11) in the oligomerization reaction is a dihalogen compound or a diglycidyl compound
  • a basic compound is required.
  • the basic compound used include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, and tributylamine.
  • Trihexylamine dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, ⁇ -picoline, lutidine and the like.
  • the amount of the basic compound to be added is preferably 2.0 mol times or more and less than 5.0 mol times, more preferably 2.2 mol times, based on the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. Times or more and less than 3.0 times by mole. If it is less than 2.0 mole times, the reaction will not be completed, and if it is more than 5.0 mole times, a side reaction will occur and the yield and purity will be reduced, which is not preferable.
  • the reaction is performed in a solvent or without a solvent.
  • the solvent used is not particularly limited as long as it does not react with the bifunctional compound used, and examples thereof include aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, and acetone.
  • Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; amide solvents such as dimethylacetamide and dimethylformamide; carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene; and alcohol solvents such as methanol, ethanol and 1-propanol. Used.
  • phase transfer catalyst examples include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutyl
  • the amount of the phase transfer catalyst to be added is preferably at least 0.01 mol times, less than 1.0 mol times, more preferably 0.05 mol times, based on the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. Times or more and less than 0.5 mole times. If it is less than 0.01 mol times, the reaction rate is low, and if it is more than 1.0 mol times, the purity of the product is undesirably reduced.
  • the reaction temperature of the reaction is usually from 0 ° C to 200 ° C, preferably from 20 ° C to 150 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 200 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.
  • the reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 30 hours. More preferably, it is 2 hours to 20 hours.
  • unreacted raw materials, solvents and catalysts are removed by a method such as washing, distillation under reduced pressure, filtration and the like, if necessary, alone or in combination.
  • a method such as washing, distillation under reduced pressure, filtration and the like, if necessary, alone or in combination.
  • the product is a solid, crystals precipitate during the reaction, so that solid-liquid separation is performed by filtration, and recrystallization from a poor solvent such as alcohol or hexane is performed as necessary.
  • the crystals can be obtained by drying up as they are.
  • the product is a liquid, it is dried as it is and, if necessary, purified by distillation or the like to obtain an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group.
  • the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (10) of the present invention can be obtained from the 9,10-dihydroxyanthracene compound represented by the general formula (2) It can be obtained by reacting with a corresponding bifunctional compound represented by the general formula (13) according to the following reaction formula-7.
  • A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group.
  • D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group.
  • the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.
  • G represents a chlorine atom, a bromine atom or an iodine atom, and n represents the number of repetitions and is 2 to 50.
  • 910-dihydroxyanthracene compound represented by the general formula (2) as a raw material examples include 9,10-dihydroxyanthracene and 2-methyl-9,10-dihydroxyanthracene , 2-ethyl-9,10-dihydroxyanthracene, 2-t-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, -Bromo-9,10-dihydroxyanthracene.
  • bifunctional compound represented by the general formula (13) as a raw material examples include bis (chloroacetoxy) methane, 1,2-bis (chloroacetoxy) ethane (13-13), 1,3-bis (chloroacetoxy) propane, 1,2-bis (chloroacetoxy) -2-methylethane, 1,4-bis (chloroacetoxy) butane (13-14), 1,2-bis (chloroacetoxy) 2,2-dimethylethane, 1,5-bis (chloroacetoxy) pentane, 1,6-bis (chloroacetoxy) hexane, 1,5-bis (chloroacetoxy) 3-methylpentane, 1,7-bis ( Chloroacetoxy) heptane, 1,8-bis (chloroacetoxy) octane, 1,6-bis (chloroacetoxy) 2-ethylhexane, 1,9-bi (Chloroacet
  • a chloro compound and a bromo compound are preferable in terms of reactivity, and particularly, a compound having the following structural formula is preferable.
  • bifunctional compound represented by the general formula (13) as a raw material, a commercially available product may be purchased, or a compound synthesized with the corresponding carboxylic acid and diol may be used.
  • the bifunctional compound represented by the general formula (13) When a compound synthesized with the corresponding carboxylic acid and diol is used as the bifunctional compound represented by the general formula (13), the bifunctional compound is synthesized in advance in the system, and the compound represented by the general formula (2) is added thereto.
  • the reaction can be carried out efficiently by adding the 9,10-dihydroxyanthracene compound represented.
  • the amount of the bifunctional compound represented by the general formula (13) in the oligomerization reaction is preferably 0.5 mole times or more and less than 5.0 mole times with respect to the 9,10-dihydroxyanthracene compound, More preferably, it is 1.0 mole times or more and less than 3.0 mole times. If it is less than 0.5 mole times, the average molecular weight becomes small, the effect of suppressing migration is weakened, and the unreacted 9,10-dihydroxyanthracene compound remains in the product to lower the purity. If it is 5.0 mol times or more, the average molecular weight becomes small, the effect of suppressing migration is weakened, and the unreacted bifunctional compound remains in the product to lower the purity.
  • the average molecular weight becomes too large, and Mobility may be reduced, and the sensitizing ability may be reduced. In that case, the molecular weight may be adjusted by adding a small amount of a monofunctional compound.
  • Examples of the basic compound used in Reaction Formula-7 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, ⁇ -picoline, lutidine and the like.
  • the amount of the basic compound to be added is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 2.2 mol times or more, and 5.0 times or more with respect to the 9,10-dihydroxyanthracene compound. Less than mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.
  • the reaction is performed in a solvent or without a solvent.
  • the solvent used is not particularly limited as long as it does not react with the ester compound to be used.
  • aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene, and alcohol solvents such as methanol, ethanol and 1-propanol are used. .
  • phase transfer catalyst examples include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium
  • the amount of the phase transfer catalyst to be added is preferably at least 0.01 mole times, less than 1.0 mole times, more preferably at least 0.05 mole times, and Less than molar times. If it is less than 0.01 mol times, the reaction rate is low, and if it is more than 1.0 mol times, the purity of the product is undesirably reduced.
  • the reaction temperature of the reaction is usually 0 ° C or higher and 250 ° C or lower, preferably 10 ° C or higher and 200 ° C or lower. If the temperature is lower than 0 ° C., the reaction takes too much time, and if the temperature is higher than 250 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.
  • the reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 40 hours. More preferably, it is 2 hours to 20 hours.
  • unreacted raw materials, solvents and catalysts are removed by a method such as washing, distillation under reduced pressure, filtration and the like, if necessary, alone or in combination.
  • a method such as washing, distillation under reduced pressure, filtration and the like, if necessary, alone or in combination.
  • the product is a solid, crystals precipitate during the reaction, so that solid-liquid separation is performed by filtration, and recrystallization from a poor solvent such as alcohol or hexane is performed as necessary.
  • the crystals can be obtained by drying up as they are.
  • the product is a liquid, it is dried as it is and, if necessary, purified by distillation or the like, whereby an oligomer of 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound can be obtained.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) and the 9,10-bis (alkoxy) having an ester group represented by the general formula (10) of the present invention The oligomer of the carbonylalkyleneoxy) anthracene compound is excited by light having a specific wavelength, and acts as a photopolymerization sensitizer that transfers the excitation energy to the photopolymerization initiator. Due to this effect, photopolymerization can be started efficiently even with long wavelength light where the activity of the photopolymerization initiator is not sufficient.
  • the photopolymerization sensitizer and the photopolymerization initiator can be mixed with a photopolymerizable compound to form a photopolymerizable composition.
  • the photopolymerizable composition can be easily photocured by irradiation with light of a long wavelength such as ultraviolet LED light having a center wavelength of 405 nm.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) and the 9,10-bis compound having an ester group represented by the general formula (10) of the present invention are also provided. Since the oligomer of the (alkoxycarbonylalkyleneoxy) anthracene compound has an ester group in its structure, it has a high affinity for the photopolymerizable composition and its cured product, and has a high affinity for the photopolymerizable composition and its cured product. It has the characteristic that the degree of migration or blooming in an object is extremely low.
  • a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) and a 9,10-bis having an ester group represented by the general formula (10) of the present invention are provided.
  • the compound in which A is a methylene group having 1 carbon atom is compared with a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having 2 or more carbon atoms in radical polymerization. It is characterized by its high sensitizing ability.
  • This effect is generally caused by the inhibition of radical polymerization of anthracene compounds, which is alleviated by the addition of oxygen atoms at positions 9 and 10.
  • the effect of the anthracene compound having an ester group represented by the general formula (1) of the present invention can be reduced.
  • the compound in which A is a methylene group is thought to come from the steric positional relationship between the anthracene ring and the ester group. It is assumed that the activity as a sensitizer is high.
  • the photopolymerizable composition and its It has the feature that the degree of migration or blooming in the cured product is extremely low.
  • Photopolymerization initiator examples include an onium salt-based polymerization initiator, a benzylmethyl ketal-based polymerization initiator, an ⁇ -hydroxyalkylphenone-based polymerization initiator, an oxime ester-based polymerization initiator, and an ⁇ -aminoacetophenone-based polymerization initiator.
  • an iodonium salt or a sulfonium salt is usually used.
  • iodonium salts include 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentamethoxyphenyl borate, -Isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenyl borate, for example, Irgacure 250 manufactured by BSF (Irgacure is a registered trademark of BSF, Inc.); Road sill 2074 (Road sill is a registered trademark of Rhodia), IK-1 manufactured by San Apro, and the like can be used.
  • sulfonium salt S, S, S ', S'-tetraphenyl-S, S'-(4,4'-thiodiphenyl) disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexa Methoxyphosphate, triphenylsulfonium hexamethoxyphosphate, and the like.
  • examples thereof include CIP-100P, CPI101P, and CPI-200K manufactured by Daicel, Irgacure 270 manufactured by BSF, and UVI6992 manufactured by Dow Chemical. Can be used.
  • These photopolymerization initiators may be used alone or in combination of two or more.
  • an onium salt not only an iodonium salt but also a sulfonium salt, an oligomer of a 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group of the present invention and a 9,10-bis (
  • One of the characteristics is that the oligomer of the alkoxycarbonylalkyleneoxy) anthracene compound has a photopolymerization sensitizing effect.
  • the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following formula is a benzylmethyl ketal-based, ⁇ -hydroxyalkylphenone-based polymerization initiator, biimidazole-based polymerization initiator, or the like. It also has an excellent photopolymerization sensitizing effect on a radical polymerization initiator having no absorption.
  • Examples of the benzyl methyl ketal-based polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651”, manufactured by BSF Inc.) and the like.
  • Examples of the hydroxyalkylphenone-based radical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocure 1173” manufactured by BSF Inc.), 1-hydroxycyclohexyl phenyl ketone (Trade name "IRGACURE 184" manufactured by BSF Inc.), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name) Name "Irgacure 2959", manufactured by BSF Inc.), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-me Rupuropioniru) - benzyl] phenyl ⁇ -2-methyl-1-one (trade name "Irgacur
  • 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651” manufactured by BSF Ltd.) which is a benzylmethyl ketal-based polymerization initiator, ⁇ -hydroxyalkylphenone 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocure 1173", manufactured by BSF Ltd.), 1-hydroxycyclohexyl phenyl ketone (trade name) "Irgacure 184", manufactured by BSF Inc.) is preferred.
  • acetophenone-based polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, Isobutoxy-2-phenylacetophenone, benzyl polymerization initiator benzyl, 4,4'-dimethoxybenzyl, anthraquinone polymerization initiator 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-phenoxyanthraquinone, 2- (Phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone and the like can also be used.
  • biimidazole-based polymerization initiator examples include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, -(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5- 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer.
  • Examples of ⁇ -aminoacetophenone-based polymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907”, BSF Inc.) 2-benzyl-2- (dimethylamino) -4'-morpholinobutyrophenone (trade name "Irgacure 369” manufactured by BSF Inc.), 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-morpholino-4-yl-phenyl) butan-1-one (trade name “Irgacure 379”, manufactured by BSF Inc.) and the like.
  • acylphosphine oxide-based polymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name “Irgacure TPO” manufactured by BSF Inc.) and bis (2,4,6-trimethylbenzoyl) And phenylphosphine oxide (trade name "Irgacure 819" manufactured by BSF Inc.).
  • Examples of the oxime ester-based polymerization initiator include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, and 2- ( occasionally-benzoyloxime) (trade name “Irgacure OXE01”, BSF Inc.) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (schreib-acetyloxime) (trade name “Irgacure OXE02” B.A.) S-F), [8-[[(acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11- (2-ethylhexyl) -11H-benzo [A] carbazol-5-yl]-, (2,4,6-trimethylphenyl) (trade name “Irgacure OXE03”, manufactured by BSF Inc.) and the like. It
  • Triazine-based polymerization initiators include 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (4-methoxyphenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine and the like.
  • Examples of the thioxanthone-based polymerization initiator include 2,4-diethylthioxanthone and 2-isopropylthioxanthone.
  • Onium salt-based assembly initiator benzyl methyl ketal-based polymerization initiator, ⁇ -hydroxyalkylphenone-based polymerization initiator, oxime ester-based photopolymerization initiator, ⁇ -aminoacetophenone-based photopolymerization initiator usable in the present invention
  • the acylphosphine oxide-based photopolymerization initiator, biimidazole-based polymerization initiator, triazine-based polymerization initiator, and thioxanthone-based polymerization initiator can be used alone, respectively. It can also be used.
  • the amount of the photopolymerization sensitizer containing the oligomer of the carbonylalkyleneoxy) anthracene compound relative to the photopolymerization initiator is not particularly limited, but is usually in the range of 1% by weight or more and 100% by weight or less based on the photopolymerization initiator. , Preferably in the range of 2% by weight to 50% by weight.
  • the amount of the photopolymerization sensitizer is less than 1% by weight, it takes too much time to photopolymerize the photopolymerizable compound. On the other hand, if the amount exceeds 100% by weight, an effect commensurate with the addition can be obtained. Absent.
  • Photopolymerization initiator composition The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention or the 9,10-bis (alkoxy) having an ester group represented by the general formula (10)
  • the photopolymerization sensitizer containing the oligomer of the carbonylalkyleneoxy) anthracene compound can be directly added to the photopolymerizable compound, but the photopolymerization initiator composition is prepared by blending the photopolymerization initiator with the photopolymerization initiator in advance. After that, it can be added to the photopolymerizable compound.
  • the photopolymerization initiator composition of the present invention is represented by at least a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) or a general formula (10) And a photopolymerization sensitizer containing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group.
  • the photopolymerizable composition can be prepared by blending the photopolymerization initiator composition with the photopolymerizable compound.
  • the photopolymerizable composition of the present invention is a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention or an ester represented by the general formula (10) Photopolymerization Initiator Composition Containing Oligomers of 9,10-Bis (alkoxycarbonylalkyleneoxy) anthracene Compounds Having Photogroups, Photopolymerization Initiator Composition Containing Photopolymerization Initiator, Photoradical Polymerizable Compound or Photocation It is a composition containing a polymerizable compound.
  • the photopolymerization sensitizer and the photopolymerization initiator containing the oligomer of the carbonylalkyleneoxy) anthracene compound are separately added to the photoradical polymerizable compound or the photocationic polymerizable compound to form the photoradical polymerizable compound or the photocationic polymerizable compound.
  • a photoinitiator composition may result as a result.
  • a hybrid composition containing both a photoradical polymerizable compound and a photocationic polymerizable compound may be used.
  • an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylate, methacrylate can be used.
  • acrylic esters and methacrylic esters are preferred from the viewpoint of film forming ability and the like.
  • (Meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid Cyclohexyl, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tricyclo [5,2,1,02,6] decanedimethanol diacrylate, isobonyl methacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, Polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, imide acrylate, etc. It is below.
  • These photo-radical polymerizable compounds may be one kind or a mixture of two or more kinds.
  • Examples of the photocationically polymerizable compound include an epoxy compound, an oxetane compound, and a vinyl ether.
  • Typical epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers.
  • Examples of the alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celloxide 2021P, celloxide is a registered trademark of Daicel), bis (3, 4-epoxycyclohexyl) adipate and the like.
  • Examples of the epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone.
  • Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane.
  • Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (manufactured by Toagosei Co., Ltd., trade name: OXT-101), 2-ethylhexyloxetane (manufactured by Toagosei Co., Ltd., tradename: OXT-212), Xylylenebisoxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-121), 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane (manufactured by Toagosei Co., Ltd., trade name: OXT) -221).
  • vinyl ether examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like.
  • These cationic photopolymerizable compounds may be one kind or a mixture of two or more kinds.
  • photopolymerizable compound only the photoradical polymerizable compound may be used, or both the photoradical polymerizable compound and the photocationic polymerizable compound may be used as a mixture.
  • the photopolymerization sensitizer of the present invention can act as a sensitizer in both photoradical polymerization and photocation polymerization, by selecting an appropriate photopolymerization initiator, the photoradical polymerizable compound and photocationic A photopolymerizable composition containing both polymerizable compounds can also be polymerized effectively.
  • the mixing ratio of the photocationically polymerizable compound and the photoradical polymerizable compound is not particularly limited, and is appropriately selected according to the physical properties of a coating or molded product obtained by photopolymerizing and curing the composition.
  • the composition ratio is determined in a weight ratio of the photocationically polymerizable compound to the photoradical polymerizable compound of 1:99 to 99: 1, preferably 20:80 to 80:20.
  • the photocationic polymerizable compound and the photoradical polymerizable compound may be used alone or in combination of two or more. Even when two or more of these photopolymerizable compounds are used, the mixing ratio of the above photocationic polymerizable compound and photoradical polymerizable compound is considered as the ratio of the total amount of each photopolymerizable compound.
  • the photopolymerization initiator used in the photopolymerizable composition of the present invention the above-described photoradical initiator or photocationic initiator can be used.
  • a photo-radical polymerizable compound is used as the photo-polymerizable compound
  • a photo-radical polymerization initiator is used.
  • the photo-radical polymerization initiator may be used as the photo-polymerization initiator, or the photo-cationic polymerization initiator may be used alone or both. May be used in combination.
  • some of the cationic photopolymerization initiators generate cation-initiating active species and radical-initiating active species by light irradiation, and when such initiators are used alone, the cationic photopolymerizable compound and the photoradical It is also possible to initiate both photopolymerizations of the polymerizable compound.
  • the photopolymerizable composition of the present invention may contain a binder polymer such as an acrylic resin, a styrene resin, and an epoxy resin. Further, an alkali-soluble resin may be contained.
  • the amount of the photopolymerization initiator composition used is in the range of 0.005 to 10% by weight, preferably 0.025% by weight, based on the photopolymerizable composition. Not less than 5% by weight.
  • the amount is less than 0.005% by weight, it takes time to photopolymerize the photopolymerizable composition.
  • the amount exceeds 10% by weight the hardness of the photocured product obtained by photopolymerization decreases, It is not preferable because the physical properties of the cured product are deteriorated.
  • the photopolymerizable composition of the present invention is a diluent, a coloring agent, an organic or inorganic filler, a leveling agent, a surfactant, a defoaming agent, a thickener, as long as the effects of the present invention are not impaired.
  • Various resin additives such as a flame retardant, an antioxidant, a stabilizer, a lubricant, and a plasticizer may be blended.
  • a photocured product can be obtained by irradiating the photopolymerizable composition of the present invention with light to polymerize it.
  • the photopolymerizable composition can be molded into a film and photocured, or can be molded into a block and photocured.
  • the liquid photopolymerizable composition is applied to a base material such as a polyester film using a bar coater or the like so as to have a thickness of 5 to 300 microns.
  • a thinner or thicker film by spin coating or screen printing.
  • a high-pressure mercury lamp As a light source to be used, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a gallium-doped lamp, a black light, a 405 nm ultraviolet LED, a 395 nm ultraviolet LED, a 385 nm ultraviolet LED, a 375 nm ultraviolet LED, a 365 nm ultraviolet LED, a blue LED, Examples include a white LED, a D bulb and a V bulb manufactured by Fusion. Also, natural light such as sunlight can be used.
  • the sensitizing effect is obtained even with light having a wavelength range of a long wavelength range such as 365 nm to 405 nm, such as 405 nm UV LED, 395 nm UV LED, 385 nm UV LED, 375 nm UV LED, 365 nm UV LED, and 405 nm semiconductor laser. It is characterized by having such a wavelength, and it is preferable to use such a wavelength.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) and the general formula (10) The oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the formula (1) is preferable because it has strong absorption in the wavelength range.
  • the optical DSC measurement was performed as follows. That is, the DSC measurement apparatus used was XDSC-7200 manufactured by Hitachi High-Tech Co., Ltd., which was equipped with an optical DSC measurement unit and was set up so that DSC measurement could be performed while irradiating light. As a light source for light irradiation, LA-410UV manufactured by Hayashi Watch Industry Co., Ltd. was used, and light of 405 nm was extracted with a bandpass filter so that the sample could be irradiated. The illuminance of light was 50 mW / cm 2 .
  • the light of the light source was guided to the upper part of the sample using glass fiber, and the trigger of the shutter of the light source was controlled so that the DSC measurement could be performed simultaneously with the start of the light irradiation.
  • the sample was precisely weighed in an aluminum pan for measurement of about 1 mg, placed in the DSC measuring section, and then fitted with the optical DSC unit. Thereafter, the measurement section was kept in a nitrogen atmosphere and allowed to stand for 10 minutes to start measurement. The measurement was continued for 6 minutes while irradiating with normal light. After the first measurement, the sample was measured again under the same conditions as it was, and the value obtained by subtracting the second measurement result from the first measurement result was defined as the measurement result of the sample.
  • a sample photopolymerizable composition
  • heat of reaction is generated due to the polymerization, and the light DSC can measure the heat of reaction. Therefore, the progress of polymerization by light irradiation can be measured by light DSC.
  • the total calorific value for one minute after light irradiation was measured, but as long as the same polymerizable compound was used, when the values were compared, the larger the value, the more efficiently the polymerization proceeded. Can be considered.
  • the photopolymerizable composition containing the photopolymerizable sensitizer may be formed into a thin film.
  • Make a product coated on a product cover it with a polyethylene film and store it at a certain temperature (26 ° C) for a certain period of time. And the migration resistance was determined. After peeling off the polyethylene film, the surface composition is washed with acetone and then dried.
  • the UV spectrum of the polyethylene film is measured, and the migration resistance is measured by examining the increase in the absorption intensity caused by the photopolymerization sensitizer. did. Note that an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used for the measurement. For quantitative comparison with the compound of Comparative Example 9,10-dibutoxyanthracene, the obtained absorbance was converted to the absorbance value of 9,10-dibutoxyanthracene.
  • the absorbance at 260 nm of the compound of the present invention and 9,10-dibutoxyanthracene was measured by an ultraviolet / visible spectrophotometer, and the respective molar extinction coefficients were calculated from the absorbance value and the molar concentration. was used to convert.
  • IR Infrared
  • NMR Nuclear magnetic resonance apparatus
  • GPC Number average molecular weight
  • the mixture was stirred for 1 hour while maintaining the temperature of the reaction system at 20 to 30 ° C. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was dissolved in toluene and washed twice with water. The solution was concentrated with an evaporator. When the solution was left overnight, the entire solution was solidified. Methanol was added, and the mixture was heated to 50 ° C. and dissolved. The undissolved anthraquinone was removed by suction filtration, and the filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further subjected to suction filtration to obtain 5.4 g (crude yield 51 mol%) of yellow crystals.
  • the mixture was stirred for 1 hour while maintaining the temperature of the reaction system at 20 to 30 ° C. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was dissolved in toluene, and washed twice with water by a liquid separation operation. The solution was concentrated with an evaporator. The mixture was left overnight, methanol was added, and undissolved anthraquinone was removed by suction filtration. The filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further subjected to suction filtration to obtain 6.2 g (crude yield: 55 mol%) of orange crystals.
  • the aqueous solution of disodium salt of 2-ethyl-9,10-anthracenediol prepared above was added dropwise over 1 hour or more. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, the aqueous layer was removed, and the organic layer was concentrated by an evaporator to obtain 4.5 g (crude yield 48 mol%) of an orange oil.
  • the optical DSC measurement was performed as follows. That is, the DSC measurement apparatus used was XDSC-7200 manufactured by Hitachi High-Tech Co., Ltd., which was equipped with an optical DSC measurement unit and was set up so that DSC measurement could be performed while irradiating light. As a light source for light irradiation, LA-410UV manufactured by Hayashi Watch Industry Co., Ltd. was used, and light of 405 nm was extracted with a bandpass filter so that the sample could be irradiated. The illuminance of light was 50 mW / cm 2 .
  • the light of the light source was guided to the upper part of the sample using glass fiber, and the trigger of the shutter of the light source was controlled so that the DSC measurement could be performed simultaneously with the start of the light irradiation.
  • the sample was precisely weighed in an aluminum pan for measurement of about 1 mg, placed in the DSC measuring section, and then fitted with the optical DSC unit. Thereafter, the measurement section was kept in a nitrogen atmosphere and allowed to stand for 10 minutes to start measurement. The measurement was continued for 6 minutes while irradiating with normal light. After the first measurement, the sample was measured again under the same conditions as it was, and the value obtained by subtracting the second measurement result from the first measurement result was defined as the measurement result of the sample.
  • a sample photopolymerizable composition
  • heat of reaction is generated due to the polymerization, and the light DSC can measure the heat of reaction. Therefore, the progress of polymerization by light irradiation can be measured by light DSC.
  • the total calorific value for one minute after light irradiation was measured, but as long as the same polymerizable compound was used, when the values were compared, the larger the value, the more efficiently the polymerization proceeded. Can be considered.
  • the light Rheometer measurement was performed as follows. The transition of the complex viscosity of the photocurable composition was measured using a light Rheometer MCR102 manufactured by Anton Paar Co., Ltd., and the curing speed was measured from the viscosity increasing speed. Measurement condition: Measuring jig: Parallel plate ( ⁇ 10mm) Thickness: 100 ⁇ m Swing angle: 5.0% constant frequency: 10 Hz constant temperature: 30 ° C.
  • UV irradiator LLBK-UV manufactured by ITEC System (irradiation wavelength: 405 nm)
  • Irradiation intensity 200 mW / cm 2
  • Irradiation start time 30 seconds post-curing time: The time (second) at which the complex viscosity reached 40,000 Pa ⁇ s from the start of light irradiation was defined as the curing time.
  • Example 1 of light curing rate evaluation 3 ', 4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P, celloxide is a registered trademark of Daicel Corporation) as 100 parts by weight as the cationic photopolymerizable compound 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, a photopolymerization initiator (manufactured by BS F, Inc., trade name Irgacure 250; "Irgacure” is B S F (Registered trademark) and 1 part by weight of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 1 as a cationic photopolymerization sensitizer at room temperature.
  • a polymerizable composition was prepared. When a photo-DSC measurement was
  • Example 4 of light curing rate evaluation Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 4.
  • the total calorific value for 5 minutes from the start of the light irradiation was 284 mJ / mg.
  • Example 6 of light curing rate evaluation Photocuring Rate Evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene obtained in the same manner as in Example 6 for monomer synthesis.
  • the optical DSC measurement was carried out in the same manner as in the photo-curing speed evaluation example 1, the total calorific value for 5 minutes from the start of the light irradiation was 226 mJ / mg.
  • Table 4 summarizes the results of Photocuring Speed Evaluation Examples 1 to 9, 17, 18, 21 to 24 and Photocuring Speed Evaluation Comparative Examples 1 to 3, 7, and 8.
  • Example 15 of light curing rate evaluation Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 was changed to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 6.
  • the total calorific value for 5 minutes from the start of light irradiation was 552 mJ / mg.
  • the photopolymerization initiator of Example 10 was 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907”, B.A.S. Photocuring rate except that the photoradical polymerization sensitizer was changed to 0.2 part by weight of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 2 of monomer synthesis.
  • the total calorific value for 5 minutes from the start of light irradiation was 496 mJ / mg.
  • Photo-radical polymerization started with 50 parts by weight of FA-310M (phenoxyethyl methacrylate, manufactured by Hitachi Chemical) and 50 parts by weight of FA-321M (EO-modified bisphenol A dimethacrylate, manufactured by Hitachi Chemical) as radical polymerizable compounds.
  • FA-310M phenoxyethyl methacrylate, manufactured by Hitachi Chemical
  • FA-321M EO-modified bisphenol A dimethacrylate, manufactured by Hitachi Chemical
  • Photo-radical polymerization started with 50 parts by weight of FA-310M (phenoxyethyl methacrylate, manufactured by Hitachi Chemical) and 50 parts by weight of FA-321M (EO-modified bisphenol A dimethacrylate, manufactured by Hitachi Chemical) as radical polymerizable compounds.
  • 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (2 parts) was added as an agent, and 0.17 part of leuco crystal violet (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a color former.
  • Photocuring Rate Evaluation The photocuring rate was the same as in Example 10 except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was replaced with 9,10-bis (octanoyloxy) anthracene, which is a known photopolymerization sensitizer.
  • the total calorific value for 5 minutes from the start of light irradiation was 298 mJ / mg.
  • Table 5 summarizes the results of Photocuring Speed Evaluation Examples 10 to 16, 19, 20, 25 to 29 and Photocuring Speed Evaluation Comparative Examples 4 to 6, 9 to 11.
  • Table 6 summarizes the results of Photocuring Speed Evaluation Examples 30 to 32 and Photocuring Speed Evaluation Comparative Examples 12 to 14.
  • the ester group of the present invention was used in photocationic polymerization.
  • a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having the following general formula (I) as a photopolymerization sensitizer, the total calorific value was increased, and it was found that the polymerization reaction was remarkably accelerated.
  • the present invention is also applicable to photoradical polymerization.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the above By adding the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the above, the total calorific value similarly increased, and it was found that the polymerization reaction was remarkably accelerated. That is, it can be seen that the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention has a photopolymerization sensitizing effect in both photocation polymerization and photoradical polymerization.
  • the ester group of the present invention in photocationic polymerization was used.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having the formula (I) is equivalent to or more than 9,10-dibutoxyanthracene and 9,10-bis (octanoyloxy) anthracene, which are known photopolymerization sensitizers.
  • the ester of the present invention is also used in photoradical polymerization.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a group is equivalent to 9,10-dibutoxyanthracene and 9,10-bis (octanoyloxy) anthracene which are also known photopolymerization sensitizers. It can be seen that the photopolymerization sensitization effect is higher than that.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is a known photopolymerization sensitizer in both photocationic polymerization and photoradical polymerization, which is 9,10-dibutoxy. It can be seen that the compound has a photopolymerization sensitizing effect equal to or higher than that of anthracene.
  • the 9,10-bis (alkoxycarbonylalkylene) having an ester group of the present invention is evident. It can be seen that by adding the oxy) anthracene compound, the time when the complex viscosity reached 40,000 Pa ⁇ s was remarkably shortened. This indicates that the addition of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention significantly accelerates the polymerization rate.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is extremely effective also for an oxime ester-based polymerization initiator, a biimidazole-based polymerization initiator, and a triazine-based polymerization initiator. It can be seen that the photopolymerization sensitizing effect is excellent.
  • One part by weight of the oligomer was mixed at room temperature to prepare a cationic photopolymerizable composition.
  • the total calorific value for one minute from the start of light irradiation was 132 mJ / mg.
  • Photocuring rate evaluation example 34 An oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in “Evaluation Example 33 of Photocuring Rate” was obtained in the same manner as in Example 3 of oligomer synthesis. Same as “Example 33 of photocuring rate evaluation” except that the obtained oligomer was obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 2,4-diethyl-1,5-pentanediol. When the optical DSC measurement was performed, the total calorific value for one minute from the start of the light irradiation was 114 mJ / mg.
  • Example 35 of light curing rate evaluation An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in “Evaluation Example 33 of Photocuring Rate” was obtained in the same manner as in Example 4 of oligomer synthesis. An optical DSC measurement was performed in the same manner as in “Example 33 of photocuring rate evaluation” except that the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 1,9-nonanediol was used. As a result, the total heat generation for one minute from the start of light irradiation was 128 mJ / mg.
  • Example 39 of light curing rate evaluation An oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in “Photocuring Rate Evaluation Example 33” was obtained in the same manner as in Oligomer Synthesis Example 9. Optical DSC measurement was performed in the same manner as in “Example 33 of photocuring rate evaluation” except that the oligomer obtained by reacting 9,10-dihydroxyanthracene with 1,5-bis (bromoacetoxy) 3-methylpentane was used. As a result, the total heat generation for one minute from the start of light irradiation was 89 mJ / mg.
  • Photocuring speed evaluation comparative example 16 A known photopolymerization sensitizer is used instead of the oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in "Evaluation Example of Photocuring Rate Example 33” Optical DSC measurement was conducted in the same manner as in “Evaluation Example 33 of photocuring rate” except that 9,10-dibutoxyanthracene was used. The total heat generation for one minute from the start of light irradiation was 99 mJ / mg. there were.
  • Example 38 of evaluation of light curing speed An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in “Photocuring Rate Evaluation Example 36” was obtained in the same manner as in the oligomer synthesis Example 4. An optical DSC measurement was carried out in the same manner as in “Evaluation Example 36 of photocuring rate” except that the oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 1,9-nonanediol was used. As a result, the total heat generation for one minute from the start of light irradiation was 196 mJ / mg.
  • Photocuring speed evaluation comparative example 17 2 parts by weight of 1-hydroxycyclohexylphenyl ketone as a photoinitiator were mixed at room temperature with 100 parts by weight of trimethylolpropane triacrylate as a photoradical polymerizable compound to prepare a photoradical polymerizable composition.
  • the total calorific value for one minute from the start of light irradiation was 76 mJ / mg.
  • Photocuring speed evaluation comparative example 18 The oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in "Evaluation Example of Photocuring Rate 36" is a known photopolymerization sensitizer. Optical DSC measurement was carried out in the same manner as in “Evaluation example 36 of photocuring rate” except for using 9,10-dibutoxyanthracene. The total calorific value for one minute from the start of light irradiation was 125 mJ / mg. .
  • Table 7 summarizes the results of Photocuring Speed Evaluation Examples 33 to 42 and Photocuring Speed Evaluation Comparative Examples 15 to 18.
  • the 9,10-bis (alkoxycarbonyl) of the present invention was used in photocationic polymerization.
  • the total calorific value was increased, indicating that the polymerization reaction was remarkably accelerated.
  • the 9,10-bis (alkoxy) of the present invention is also applicable to photoradical polymerization.
  • the oligomer of the carbonylalkyleneoxy) anthracene compound of the present invention has a photopolymerization sensitizing effect in both photocationic polymerization and photoradical polymerization.
  • the 9,10-bis ( It can be seen that the oligomer of the alkoxycarbonylalkyleneoxy) anthracene compound has a photopolymerization sensitizing effect equal to or higher than that of 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer.
  • the 9,10-bis (alkoxy) of the present invention is also applicable to the photo-radical polymerization.
  • the oligomer of the carbonylalkyleneoxy) anthracene compound has a photopolymerization sensitizing effect equal to or higher than that of 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer.
  • the value obtained by converting the absorbance attributable to 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.007 after storage for one day. 0.007 after storage for 7 days.
  • Example 4 of migration resistance evaluation instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene synthesized by the same method as in Example 4 was used. The test was conducted in the same manner as in Example 1 except for performing the migration resistance evaluation.
  • the value of the absorbance attributable to 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene converted to 9,10-dibutoxyanthracene was 0 after storage for one day. It was 0.0011 and 0.007 after storage for 7 days.
  • Example 6 of migration resistance evaluation instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 6 is used as the photopolymerization sensitizer. Except for this, the test was conducted in the same manner as in Example 1 for evaluating the migration resistance. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the value obtained by converting the absorbance due to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.1% after storage for one day. 007, 0.003 after storage for 7 days.
  • the value of the absorbance attributable to 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene converted to 9,10-dibutoxyanthracene was 0.015 after storage for one day. After storage for 7 days was 0.013.
  • Example 8 of migration resistance evaluation instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 8 is used. The test was conducted in the same manner as in Example 1 except for the migration resistance evaluation.
  • the value obtained by converting the absorbance attributable to 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.012 after storage for one day. 0.010 after storage for 7 days.
  • the value obtained by converting the absorbance due to 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was one day. It was 0.015 after storage and 0.015 after seven days storage.
  • the value obtained by converting the absorbance attributable to 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene is one day after storage. It was 0.014 after storage for 7 days and 0.011.
  • the value obtained by converting the absorbance attributable to 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.1% after storage for one day. 013 and 0.010 after storage for 7 days.
  • Table 8 summarizes the results of the migration resistance evaluation examples 1 to 9, 19, and 20 and the migration resistance evaluation comparative example 1.
  • a low-density polyethylene film (thickness: 30 ⁇ m) was put on the obtained coated product, and one that was stored in a dark place for one day and one that was stored for seven days were prepared. After peeling off and washing the polyethylene film with acetone and drying, the UV spectrum of the polyethylene film was measured and the absorbance at 260 nm was measured. The absorption due to 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was one It was 0.015 after 7 days storage and 0.016 after 7 days storage.
  • Table 9 summarizes the results of the migration resistance evaluation examples 10 to 18, 21, and 22 and the migration resistance evaluation comparative example 2.
  • the photocationic polymerizable composition is a known photocationic polymerization sensitizer.
  • 9,10-Dibutoxyanthracene has migrated to a considerable extent to the film overlying the photocationically polymerizable composition, whereas the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound of the present application In each case, the degree of migration is extremely low, and it can be said that the migration resistance is excellent.
  • the known photoradical polymerization sensitization was also found in the photoradical polymerizable composition.
  • the agent 9,10-dibutoxyanthracene migrates to a considerable extent in the film overlying the photoradical polymerizable composition, whereas the 9,10-bis (alkoxycarbonylalkyleneoxy)
  • the anthracene compound has a very low migration degree and can be said to be excellent in migration resistance.
  • Oligomer Synthesis As a photopolymerization sensitizer, oligomer is synthesized by the same method as in Example 3 instead of oligomer obtained by reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol.
  • the migration resistance was evaluated in the same manner as in Example 23 except that the oligomer of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 2,4-diethyl-1,5-pentanediol was used.
  • a photopolymerization sensitizer As a photopolymerization sensitizer, a known photopolymerization sensitizer is used instead of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol. Except for using 10-dibutoxyanthracene, it was prepared in the same manner as in Example 23 for evaluating migration resistance. As a result of measuring the absorbance at 230 nm of the polyethylene film washed with acetone, the absorbance of 9,10-dibutoxyanthracene was 0.860 after storage for 4 days, and 0.932 after storage for 7 days.
  • a low-density polyethylene film (thickness: 30 ⁇ m) was put on the obtained coated product, and those stored for 4 days and those stored for 7 days in a dark place were prepared. After peeling off, washing the polyethylene film with acetone and drying, the UV spectrum of the polyethylene film was measured, and the absorbance at 230 nm was measured. As a result, it was confirmed that 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1, The absorption due to the oligomer obtained by the reaction with 5-pentanediol was 0.004 after storage for 4 days, and 0.005 after storage for 7 days.
  • Table 10 summarizes the results of the migration resistance evaluation examples 23 to 32 and the migration resistance evaluation comparative examples 3 and 4.
  • the photocationic polymerizable composition is a known photocationic polymerization sensitizer.
  • 9,10-Dibutoxyanthracene has migrated to a considerable extent to the film overlying the cationic photopolymerizable composition, whereas the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound of the present invention has In any case, the degree of migration is extremely low, and it can be said that the oligomer is excellent in migration resistance.
  • the known photoradical polymerization was also included in the photoradical polymerizable composition.
  • the sensitizer 9,10-dibutoxyanthracene migrates to a considerable extent in the film coated on the photoradical polymerizable composition, whereas the 9,10-bis (alkoxycarbonyl) of the invention.
  • the degree of migration of the oligomer of the alkyleneoxy) anthracene compound is extremely low, and it can be said that the oligomer has excellent migration resistance.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and the oligomer thereof according to the present invention are known photopolymerization sensitizers in photocation polymerization and photoradical polymerization.
  • the compound Compared with the 10-dibutoxyanthracene compound, the compound has not only the same photopolymerization sensitizing ability but also a high migration resistance due to its structure having a polar ester group. It is understood that this is a very useful compound.
  • the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and the oligomer thereof according to the present invention exhibit an excellent effect as a photopolymerization sensitizer in a photopolymerization reaction and, at the same time, have a polar ester group.

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Abstract

Le problème à résoudre par la présente invention concerne la fourniture d'un sensibilisateur de photopolymérisation qui présente une vitesse de photopolymérisation suffisante pendant une utilisation pratique, sans provoquer de problèmes tels que la coloration ou la poudre sur l'article durci ou l'aspect d'un additif tel que le sensibilisateur de photopolymérisation sur sa surface due à l'efflorescence ou similaire au moment de la photopolymérisation ou pendant le stockage de l'article durci. La solution selon l'invention porte sur un oligomère : d'un composé 9,10-bis (alcoxycarbonyle alkylèneoxy) anthracène qui a un groupe ester et qui est représenté par la formule générale (1), ou d'un composé 9,10-bis (alcoxycarbonyle alkylèneoxy) anthracène qui a un groupe ester et qui est représenté par la formule générale (10). (Dans les formules générales, A représente un groupe alkylène en C1-20, et le groupe alkylène peut être bifurqué par un groupe alkyle.)
PCT/JP2019/036244 2018-09-15 2019-09-13 Sensibilisateur de photopolymérisation WO2020054874A1 (fr)

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