WO2020111046A1 - Composition contenant des grappes de carbone et procédé de production associé - Google Patents

Composition contenant des grappes de carbone et procédé de production associé Download PDF

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WO2020111046A1
WO2020111046A1 PCT/JP2019/046120 JP2019046120W WO2020111046A1 WO 2020111046 A1 WO2020111046 A1 WO 2020111046A1 JP 2019046120 W JP2019046120 W JP 2019046120W WO 2020111046 A1 WO2020111046 A1 WO 2020111046A1
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group
resin
solvent
meth
monomer
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PCT/JP2019/046120
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English (en)
Japanese (ja)
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正義 柳
恭章 川口
健宏 木下
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昭和電工株式会社
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Priority to CN201980076876.5A priority Critical patent/CN113166288A/zh
Priority to KR1020217012831A priority patent/KR20210068098A/ko
Priority to JP2020557730A priority patent/JPWO2020111046A1/ja
Publication of WO2020111046A1 publication Critical patent/WO2020111046A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
    • 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
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a carbon cluster-containing composition and a method for producing the same.
  • the present application claims priority based on Japanese Patent Application No. 2018-222729 filed in Japan on November 28, 2018, and the content thereof is incorporated herein.
  • Non-Patent Document 1 discloses a polypropylene or high-density polyethylene resin composition containing fullerene (C 60 ).
  • C 60 fullerene
  • Patent Document 1 discloses a resin composition containing a long chain alkyl etherified fullerene derivative having improved compatibility with a resin.
  • the present invention is shown in the following [1] to [10].
  • [1] At least one selected from the group consisting of a carbon cluster (A), a first solvent (B1), a second solvent (B2), an ethylenically unsaturated group-containing monomer (C) and a resin (D).
  • the first solvent (B1) is at least one solvent selected from the group consisting of aromatic solvents and halogen-containing solvents
  • the carbon cluster-containing composition, wherein the second solvent (B2) is a solvent excluding an aromatic solvent and a halogen-containing solvent.
  • the carbon cluster-containing composition according to [1] wherein the carbon cluster (A) is fullerene or a derivative thereof.
  • the carbon cluster-containing composition contains the monomer (C) and the resin (D), The monomer (C) has a reactive group, The carbon cluster-containing composition according to any one of [1] to [4], wherein the resin (D) has a group that reacts with the reactive group of the monomer (C).
  • the carbon cluster-containing composition according to any one of [1] to [5], wherein the resin (D) is an unsaturated (meth)acrylic resin or an unsaturated epoxy ester resin.
  • the content of the carbon cluster (A) is 0.01 to 0.10 parts by mass based on 100 parts by mass of the total amount of the monomer (C) and the resin (D) [1] to [6. ]
  • the manufacturing method of the carbon-cluster containing composition in any one of these.
  • the monomer (C) has a reactive group
  • the resin (D) has a group that reacts with the reactive group of the monomer (C)
  • the monomer (C) and the resin (D) The method for producing a carbon cluster-containing composition according to [8], further including a step (V) of performing an addition reaction with
  • the carbon clusters can be easily dispersed in the composition even if the composition contains a substance having poor compatibility with the carbon clusters, such as a solvent, a monomer, or a resin. As a result, functions such as radical scavenging ability and heat resistance of carbon clusters can be exhibited.
  • the carbon cluster-containing composition of the present invention (hereinafter sometimes referred to as the “composition of the present invention”) comprises a carbon cluster (A), a first solvent (B1), a second solvent (B2), and a monomer. At least one selected from the group consisting of (C) and resin (D).
  • the first solvent (B1) is at least one solvent selected from the group consisting of aromatic solvents and halogen-containing solvents
  • the second solvent (B2) is a solvent excluding aromatic solvents and halogen-containing solvents. Is.
  • the carbon cluster (A) of the present invention refers to a group or fine particles formed by binding or aggregating several to several hundred carbon atoms regardless of the type of carbon-carbon bond. However, it is not necessarily limited to one composed only of 100% carbon, and includes one in which other atoms are mixed.
  • the maximum size of the carbon cluster (A) is preferably 300 nm or less, and more preferably 100 nm or less.
  • the primary particles may be aggregated, but the size of the primary particles influences the dispersion of the carbon cluster compound, so the maximum diameter here is the maximum diameter of the primary particles. ..
  • Carbon clusters include spherical shell-shaped carbon clusters such as fullerene, and tubular carbon clusters such as carbon nanotubes, carbon nanohorns and carbon fibers, soot-like substances, and chemically modified derivatives thereof and aggregates thereof. Is included.
  • the carbon cluster (A) is preferably a compound having a polyhedral structure, more preferably a compound having a structure in which a 5-membered ring and a 6-membered ring are bonded. Specific examples thereof include fullerene and its derivatives, and a soot-like substance having a polyhedral structure that is a by-product during the production of fullerene and not having a closed shell.
  • Fullerene is a spherical shell-like carbon molecule containing a 5-membered ring in the network of carbon atoms in addition to the 6-membered ring found in graphite.
  • fullerenes those having about 60 to 120 carbon atoms such as 60, 70, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96 carbon atoms are known.
  • the number of carbon atoms is not particularly limited, but those having 60 (C60) and 70 (C70) carbon atoms are preferable because they are easily available and have excellent solubility in the first solvent (B1).
  • fullerenes containing different kinds of atoms such as scandium (Sc), lanthanum (La), cerium (Ce), titanium (Ti) and nitrogen (N) can also be used.
  • oxides of fullerenes, (C60) 2 O in which oxides of fullerenes are added to each other, adducts of fullerenes (C60-C60, C70-C60, C70-C70, etc.) can also be used.
  • soot-like substance for example, a compound having the same structure as the partial structure of fullerene and having no closed shell can be cited.
  • the soot-like substance used in the present invention is preferably soot produced as a by-product during fullerene production. It is included in the crude fullerenes produced during the fullerene production process. After removing the fullerenes from the crude fullerenes by solvent extraction, the residue obtained is richer in its soot-like substances.
  • This soot-like substance has a structure in which a 5-membered ring and a 6-membered ring are bonded to each other like fullerene, and includes an amorphous carbon molecule having no closed shell.
  • Examples of a method for producing fullerene that produces a soot-like substance include a resistance heating method, an arc discharge method, a microwave method, a high frequency heating method, a CVD method, a thermal plasma method, a combustion method, a laser method, and a thermal decomposition method. Both are manufactured under an environment of a pressure of 800 hPa or less.
  • the soot-like substance can be obtained by firing a hydrocarbon raw material and an oxygen-containing gas under a reduced pressure environment.
  • the hydrocarbon raw material for example, an aromatic hydrocarbon such as toluene or benzene can be used.
  • the reduced pressure condition is preferably 3 to 800 hPa, and the heating condition is preferably 1600° C. to 2000° C.
  • the heating condition is preferably 1600° C. to 2000° C.
  • the mixing ratio of the hydrocarbon raw material and the oxygen-containing gas is preferably 2.5 to 3.5 in terms of an equivalent ratio, and the amount of the hydrocarbon raw material is preferably increased.
  • the reaction can be incomplete combustion.
  • carbon in the hydrocarbon raw material is combined with oxygen and is discharged as carbon monoxide or carbon dioxide, which may make it difficult for the carbons to be bonded to each other.
  • the equivalence ratio is 1 where the ratio of the amount of hydrocarbon raw material that completely burns to the amount of oxygen is exactly 1.
  • the hydrocarbon raw material from which hydrogen has been released is unstable and is likely to aggregate with the surrounding carbons. At this time, a part reacts and chemically bonds.
  • the carbon compound obtained by such a process contains a soot-like substance.
  • the soot-like substance contains amorphous carbon molecules, such as fullerenes, in which a plurality of carbon atoms are bonded to each other, but which cannot reach a predetermined spherical molecular structure like fullerenes.
  • amorphous carbon molecule has the same structure as the partial structure of fullerene, and has an intermediate produced in the process of producing fullerene, a part of spherical fullerene, or a structure in which the shell is not closed. Examples include carbon molecules.
  • This amorphous carbon molecule may form a cluster structure in which a plurality of these carbon molecules are gathered.
  • the cluster structure includes a nested structure in which a carbon molecule having a large size unclosed structure is configured to enclose a carbon molecule having a small size unclosed structure.
  • the carbon cluster (A) may have a substituent unless the expected effects such as solubility in the first solvent (B1), radical scavenging ability and heat resistance are impaired.
  • substituent include indene, malonic acid, methyl phenylbutyrate and the like.
  • the carbon cluster (A) used in the carbon cluster-containing composition of the present invention may be a mixture of fullerenes having different carbon numbers, and examples of commercially available products thereof include a mixture of C60/C70 manufactured by Frontier Carbon Co., Ltd. Be done.
  • a soot-like carbon substance obtained by the method described below may be used as the carbon cluster (A) used in the carbon cluster-containing composition of the present invention.
  • the carbon cluster (A) used in the carbon cluster-containing composition of the present invention may have no substituent from the viewpoint of easy availability.
  • substituents include indene, malonic acid, methyl phenylbutyrate, etc.
  • derivatives of fullerene include ICBA (indene bis adduct), ICMA (indene adduct), PCBM (phenyl-C61-butyric acid methyl ester, etc.),
  • Examples include SAM (1-methyl-1H-pyrrolobenzoic acid adduct) and the like.
  • the carbon cluster (A) used in the carbon cluster-containing composition of the present invention is preferably fullerene or a derivative thereof, from the viewpoint of solubility in the first solvent (B1) and dispersibility in the composition, and has no substituent. Fullerenes are more preferred.
  • the carbon cluster-containing composition of the present invention further contains at least one selected from the group consisting of a monomer (C) and a resin (D)
  • the content of the carbon cluster is such that the monomer (C) and the resin (D) are contained. It may be 0.01 to 0.10 parts by mass, or 0.01 to 0.05 parts by mass with respect to 100 parts by mass in total.
  • the first solvent (B1) used in the present invention is at least one solvent selected from the group consisting of aromatic solvents and halogen-containing solvents.
  • the first solvent (B1) is preferably a solvent in which the carbon clusters (A) are dissolved or uniformly dispersed in order to uniformly disperse the carbon clusters (A).
  • Specific examples of the aromatic solvent include aromatics such as toluene, benzene and trimethylbenzene; aromatics having a halogen group such as o-dichlorobenzene and 1,2-dibromobenzene; other aromatics such as nitrobenzene and anisole; quinoline. And polycyclic aromatic compounds such as 1-methylnaphthalene.
  • halogen-containing solvent examples include halogen-containing compounds such as carbon tetrachloride and dichloromethane. These solvents may be used alone or in combination of two or more.
  • aromatic solvent a solvent in which the solubility of the carbon cluster (A) at 25° C. is 0.5 g/L or more is preferable, and an aromatic such as toluene, benzene or trimethylbenzene is more preferable. In addition, trimethylbenzene is more preferable from the viewpoint of toxicity and availability.
  • the second solvent (B2) used in the present invention is any other solvent except the aromatic solvent and the halogen-containing solvent. That is, it is a solvent other than the first solvent (B1).
  • the second solvent (B2) is preferably compatible with the first solvent (B1) or is a solvent in which the first solvent (B1) can be dispersed.
  • the second solvent (B2) is preferably a solvent in which the monomer (C) and the resin (D) can be dissolved or dispersed in order to uniformly disperse the monomer (C) and the resin (D).
  • an ether compound As the second solvent (B2), an ether compound, a ketone compound, an ester compound or a carboxylic acid amide compound can be used.
  • the ether compound include (poly)alkylene glycol monoalkyl ether; (poly)alkylene glycol monoalkyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran.
  • (poly)alkylene glycol monoalkyl ether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene.
  • Glycol monomethyl ether triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- It includes n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like.
  • the (poly)alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like.
  • Specific examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like.
  • Specific examples of the ester compound include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and methyl 3-methoxypropionate.
  • carboxylic acid amide compound examples include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and the like.
  • These solvents may be used alone or in combination of two or more.
  • a glycol ether solvent is preferable among the above solvents.
  • Ethylene unsaturated group-containing monomer (C) and resin (D) are preferably those which can be dissolved or dispersed in the second solvent (B2).
  • ethylenically unsaturated group-containing monomer (C) a polyfunctional (meth)acrylate used as a reactive diluent, a material monomer necessary for the synthesis of the resin (D), an addition reaction or dehydration of the resin (D) Examples thereof include modifying monomers for adding modification by condensation reaction.
  • alkyl (meth)acrylate examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, iso-butyl (meth)acrylate, Includes tert-butyl (meth)acrylate and n-pentyl methacrylate.
  • aromatic group-containing (meth)acrylate examples include benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, biphenyloxyethyl (meth)acrylate, Naphthalene (meth)acrylate, anthracene (meth)acrylate, cumyl (meth)acrylate, phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate (trade name: Light acrylate P-200A, Kyoei Chemical Co., Ltd.), o-phenoxybenzyl acrylate, m -Phenoxybenzyl acrylate, p-phenoxybenzyl acrylate and the like are included.
  • cyclo ring-containing (meth)acrylate examples include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, rosin (meth)acrylate, tetrahydrofurfuryl (meth). Including acrylate.
  • heterocycle-containing (meth)acrylate include 1,1,1-trifluoroethyl (meth)acrylate.
  • fluorine-containing (meth)acrylate examples include perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-iso-propyl (meth)acrylate and the like.
  • cyclic structure-containing (meth)acrylate examples include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and the like.
  • amino group-containing (meth)acrylate examples include 3-(N,N-dimethylamino)propyl(meth)acrylate and the like.
  • alkoxy polyalkylene glycol (meth)acrylates include methoxy-triethylene glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate (trade name: AM-90G, manufactured by Shin Nakamura Chemical Co., Ltd.).
  • hydroxy group-containing (meth)acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerin mono(meth)acrylate and the like.
  • block-isocyanato group-containing (meth)acrylate examples include (meth)acroyloxy, which is a reaction product of (meth)acroyloxyethyl isocyanate (ie, 2-isocyanatoethyl (meth)acrylate) and ⁇ -caprolactam. It includes a reaction product of ethyl isocyanate and propylene glycol monomethyl ether.
  • epoxy group-containing (meth)acrylate examples include glycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate and lactone adducts thereof (for example, Daicel Chemical Industries).
  • the (meth)acrylic acid amide examples include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, and (meth)acrylic acid N,N- It includes dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, (meth)acrylic acid anthracenylamide and the like.
  • unsaturated carboxylic acid such as (meth)acrylic acid
  • unsaturated isocyanate monomer such as 2-isocyanatoethyl (meth)acrylate, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether
  • unsaturated carboxylic acid such as (meth)acrylic acid
  • unsaturated isocyanate monomer such as 2-isocyanatoethyl (meth)acrylate
  • glycidyl (meth)acrylate such as 2-isocyanatoethyl (meth)acrylate
  • Unsaturated epoxies such as In addition to these, as modifying monomers, polybasic acid anhydrides such as tetrahydrophthalic anhydride, adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic
  • the resin (D) include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyalkylene, polyvinyl chloride, polystyrene, polyvinyl acetate, and (meth).
  • An acrylic resin, an epoxy ester resin, etc. are mentioned.
  • the carbon cluster-containing composition is used as a resist material, it is preferable to use a resin having an ethylenically unsaturated group from the viewpoint of photocurability.
  • a (meth)acrylic resin having an ethylenically unsaturated group and/or an epoxy ester resin having an ethylenically unsaturated group it is preferable to use a (meth)acrylic resin having an ethylenically unsaturated group and/or an epoxy ester resin having an ethylenically unsaturated group.
  • the carbon cluster-containing composition as the resist material, effects such as improvement in heat-resistant yellowing and improvement in pattern shape (reduction of edge roughness) can be expected.
  • the constituent monomers listed above for the ethylenically unsaturated group-containing monomer (C) can be used.
  • carboxyl group-containing ethylenically unsaturated compounds such as (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, and maleic acid, and their substitution products, within a range that does not impair the effects of the (meth)acrylic resin; Norbornene and dicyclopentadiene, styrene, ⁇ -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-
  • (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid, or the like is used as a constituent monomer of the (meth)acrylic resin having an ethylenically unsaturated group.
  • Carboxy group-containing ethylenically unsaturated compound, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxy group-containing (meth)acrylates, glycidyl (meth)acrylate and other epoxy group-containing (meth)acrylates Is preferably used.
  • a modifying monomer may be reacted with a carboxy group, a hydroxy group, an epoxy group or the like introduced by these material monomers to improve the properties such as photocurability and developability of the composition.
  • the epoxy ester resin which can be used as the resin (D) is generally a polymerizable compound obtained by ring-opening reaction between an epoxy group in an epoxy compound having two or more epoxy groups and a carboxy group of an unsaturated carboxylic acid. It is a compound having a saturated bond.
  • Such epoxy ester resins are described, for example, in "Polyester Resin Handbook” by Eiichiro Takiyama (edited by Nikkan Kogyo Shimbun, 1988) or "Dictionary of Paint Terms” (edited by Coloring Materials Association, 1993).
  • Examples of the epoxy compound which is a constituent monomer of the epoxy ester resin include cresol novolac type epoxy, phenol novolac type epoxy, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and ethylene glycol.
  • Diglycidyl ether diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, resorzinol diglycidyl ether , Diglycidyl terephthalate, diglycidyl orthophthalate, bisphenol full orange glycidyl ether and the like.
  • Examples of the epoxy compound that is a constituent monomer of the epoxy ester resin include compounds obtained by adding epihalohydrin such as epichlorohydrin to the compounds shown below.
  • Compounds forming an epoxy compound by adding epihalohydrin include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5- Dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexa Fluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4- Hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)di
  • the blending amount of the carbon cluster (A) is preferably 0.001 to 1 part by mass, and 0.01 to 1 part by mass. It is more preferably 0.5 part by mass. When it is 0.001 part by mass or more, the functions such as radical scavenging ability and heat resistance can be sufficiently exhibited. When the amount is 1 part by mass or less, the aggregated particles of the carbon cluster (A) do not increase, and a carbon cluster-containing composition in which the carbon cluster (A) is sufficiently dispersed can be obtained.
  • the second solvent (B2) is preferably 30 to 1000 parts by mass, and more preferably 50 to 800 parts by mass with respect to 100 parts by mass of the monomer (C) and/or the resin (D).
  • the amount of the solvent is 30 parts by mass or more, good handling property can be obtained. If the amount of the solvent is 1000 parts by mass or less, a sufficient film thickness can be obtained when the coating film is formed into a shape.
  • composition of the present embodiment In the first embodiment of the carbon cluster-containing composition of the present invention (hereinafter sometimes referred to as “composition of the present embodiment”), the carbon cluster (A), the first solvent (B1), and the second solvent. (B2), an ethylenically unsaturated group-containing monomer (C), and a resin (D).
  • this ethylenically unsaturated group-containing monomer (C) is a carboxy group-containing ethylenically unsaturated compound (m-2).
  • This resin (D) is an epoxy group-containing copolymer (P1) or an epoxy resin (P3).
  • the carbon cluster (A) any one of the above-mentioned specific examples or a mixture thereof can be used.
  • any one of the specific examples of the above-mentioned first solvent (B1) or a mixed solvent thereof can be used.
  • toluene, benzene, xylene, ethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, or a mixed solvent thereof is preferable, and one or more selected from the group consisting of toluene, benzene, and trimethylbenzene is more preferable. ..
  • any one of the specific examples of the second solvent (B2) or a mixed solvent thereof can be used.
  • glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol are preferable.
  • the ethylenically unsaturated group-containing monomer (C) of this embodiment is a carboxy group-containing ethylenically unsaturated compound (m-2).
  • the resin (D) is an epoxy group-containing copolymer (P1) or an epoxy resin (P3).
  • Carboxy-containing ethylenically unsaturated compound (m-2) The carboxy group-containing ethylenically unsaturated compound (m-2) (hereinafter sometimes simply referred to as "monomer (m-2)”) has no epoxy group and reacts with an epoxy group among acid groups. There is no particular limitation as long as it is a monomer having a carboxy group and an ethylenically unsaturated group having good properties. For example, unsaturated monobasic acid or unsaturated dibasic acid monoester may be mentioned.
  • unsaturated monobasic acids examples include (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth ) Acryloyloxyethyl hexahydrophthalic acid, ⁇ -bromo(meth)acrylic acid, ⁇ -furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, ⁇ -cyanocinnamic acid, monomethyl maleate, monoethyl maleate, Examples thereof include unsaturated carboxylic acids such as monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate.
  • unsaturated dibasic acid monoesters examples include monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate.
  • carboxy group-containing ethylenically unsaturated compounds (m-2) may be used alone or in combination of two or more.
  • (meth)acrylic acid is preferable from the viewpoint of easy availability and reactivity.
  • the reaction ratio of the carboxyl group-containing ethylenically unsaturated compound (m-2) is preferably 10 to 70 mol% when the total amount of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol%. , And more preferably 15 to 65 mol %.
  • the blending ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is 10 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared.
  • it is 70 mol% or less the mixing ratio of each monomer (M1) other than the monomer (m-2) is sufficiently secured, and the resin (D) having desired thermal decomposition resistance and the like can be obtained.
  • the proportion of the carboxy group-containing ethylenically unsaturated compound (m-2) to be added to the number of moles of the epoxy group of the epoxy group-containing copolymer (P1) is preferably 90 to 100%. , And more preferably 95 to 100%.
  • the addition ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is 90% or more, sufficient curability can be exhibited in the photosensitive resin composition.
  • the polybasic acid anhydride (d) is not particularly limited as long as it has an acid anhydride structure having a good reactivity with a hydroxy group, but a polybasic acid anhydride (d) having a ring structure in which by-products are not generated after the reaction is preferable. is there.
  • 1,2,3,6-tetrahydrophthalic anhydride hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride , Methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride, succinic anhydride, octenylsuccinic anhydride and the like.
  • the reaction ratio of the polybasic acid anhydride (d) is preferably 10 to 70 mol %, more preferably 15 when the total amount of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol %. ⁇ 65 mol %. It is preferably 20 to 100%, and more preferably 30 to 90% with respect to the number of moles to which the carboxy group-containing ethylenically unsaturated compound (m-2) is added.
  • the monomer (M1) forming the epoxy group-containing copolymer (P1) (hereinafter sometimes simply referred to as “copolymer (P1)”) related to the resin (D) of the present embodiment is an epoxy group-containing monomer.
  • the monomer (M1) may further contain an aromatic ring-containing polymerizable monomer (m-5) and other polymerizable monomers (m-6). By further including the aromatic ring-containing polymerizable monomer (m-5), the epoxy group-containing copolymer (P1) having more excellent colorant dispersibility can be obtained.
  • Epoxy group-containing ethylenically unsaturated compound (m-1) The epoxy group-containing ethylenically unsaturated compound (m-1) (hereinafter sometimes simply referred to as "monomer (m-1)”) does not have a carboxy group and contains an epoxy group and an ethylenically unsaturated group. It is not particularly limited as long as it has a monomer.
  • glycidyl (meth)acrylate 2-glycidyloxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, and lactone adducts thereof (for example, , Cyclomer (registered trademark) A200, M100 manufactured by Daicel Chemical Industries, Ltd., mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, dicyclopentenyl ( Examples thereof include an epoxidized product of (meth)acrylate and an epoxidized product of dicyclopentenyloxyethyl (meth)acrylate.
  • These epoxy group-containing ethylenically unsaturated compounds (m-1) may be used alone or in combination of two or more kinds.
  • glycidyl (meth)acrylate
  • the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) and the carboxy group-containing ethylenically unsaturated compound (m-2) described later impart a photocurable photosensitive group
  • the polymerizable monomer (m-3) (hereinafter sometimes simply referred to as “monomer (m-3)”) has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.
  • the bridged cyclic hydrocarbon means one having a structure represented by the following formula (1) or (2) represented by adamantane and norbornane, and the bridged cyclic hydrocarbon group is , Refers to a group corresponding to the rest of the structure except for some hydrogen.
  • the polymerizable monomer (m-3) does not include the polymerizable monomer (m-4) described later.
  • a and B each represent a linear or branched alkylene group (including cyclic group), R3 represents a hydrogen atom or a methyl group.
  • a and B may be the same or different. , Or the branches of A and B may be connected to form a ring.
  • A', B', and D each represent a linear or branched alkylene group (including cyclic group), and R4 represents a hydrogen atom or a methyl group.
  • A', B', and D. May be the same or different, and the branches of A′, B′, and D may be connected to form a ring.
  • the monomer (m-3) is preferably a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and has an adamantyl (meth)acrylate or a structure represented by the following formula (3) ( More preferred is (meth)acrylate. ..
  • R5 to R7 each represent a hydrogen atom or a methyl group.
  • R8 and R9 may be a hydrogen atom or a methyl group, or may be bonded to each other to form a saturated or unsaturated ring.
  • the ring is preferably a 5-membered ring or a 6-membered ring.* represents a bond linked to the (meth)acryloyloxy group.
  • Examples of the monomer (m-3) include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate and the like. These may be used alone or in combination of two or more.
  • polymerizable monomer (m-4) The polymerizable monomer (m-4) (hereinafter sometimes simply referred to as “monomer (m-4)”) is a monomer represented by the following general formula (4).
  • X and X′ in the formula (4) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 are each independently A hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may have a cyclic structure connecting R1 and R2.
  • the monomer (m-4) is not particularly limited as long as it has the chemical structure represented by the general formula (4).
  • examples of X and X'representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Group, isobutyl group, t-butyl group and the like.
  • examples of the substituent of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, which is represented by R1 and R2 include an alkoxy group and an aryl group.
  • R1 and R2 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group.
  • a linear or branched alkyl group such as; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group, etc.
  • Examples thereof include a cyclic group; an alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group and a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a phenylaralkyl group.
  • Examples of the monomer (m-4) having the chemical structure represented by the general formula (4) include norbornene (bicyclo[2.2.1]hept-2-ene) and 5-methylbicyclo[2.2.1]. ] Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5 . 1 7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 2,5 . 1 7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .
  • Use of the above-mentioned monomer (m-3) and/or the above-mentioned monomer (m-4) contributes to smooth coatability of the cured film, high thermal decomposition resistance, and high heat yellowing. It is possible to suppress a decrease in the solubility of the copolymer in a solvent.
  • One of the monomer (m-3) and the monomer (m-4) may be used, or both of them may be used.
  • the aromatic ring-containing polymerizable monomer (m-5) (hereinafter sometimes simply referred to as “monomer (m-5)”) is a monomer having no carboxy group or epoxy group and having an aromatic ring.
  • styrene ⁇ -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p -Aromatic vinyl compounds such as methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene; benzyl (meth)acrylate, rosin (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, Phenoxyethyl (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate (trade name: Light acrylate P-200A, manufactured by Kyoei Chemical Co.
  • the resin (D) used in the present invention has at least one selected from the group consisting of benzyl (meth)acrylate, styrene, biphenyl skeleton, naphthalene skeleton and anthracene skeleton from the viewpoint of elastic recovery rate. It is more preferable to introduce a structural unit.
  • the epoxy group-containing copolymer (P1) is a polymerizable monomer (m-6) other than the monomers (m-1) to (m-5) (hereinafter, simply referred to as “monomer (m- 6)” in some cases.)) may be copolymerized.
  • Other polymerizable monomers (m-6) are the same as the above-mentioned monomers (m-1), (m-3), (m-4), (m-5) and the above-mentioned monomer (m-2). Is a copolymerizable monomer of.
  • This monomer (m-6) is generally a radically polymerizable compound having an ethylenically unsaturated group.
  • this monomer (m-6) include (meth)acrylic acid esters, (meth)acrylic acid amides, maleimides, unsaturated dicarboxylic acid diesters, and dienes such as butadiene.
  • Specific examples of (meth)acrylic acid esters include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, iso-propyl(meth)acrylate, n-butyl(meth)acrylate, sec.
  • the (meth)acrylic acid amide include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N- It includes dipropylamide, (meth)acrylic acid N,N-di-iso-propylamide, (meth)acrylic acid anthracenylamide and the like.
  • maleimides include vinyl compounds such as (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone and vinyl acetate; N- Cyclohexyl maleimide, N-lauryl maleimide and the like are included.
  • unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate and the like. These may be used alone or in combination of two or more, if necessary.
  • the monomer (M1) contains the monomer (m-1), and if necessary, for example, the monomer (m-3), the monomer (m-4) or When the monomer (m-5) is included, the ratio of the structure derived from each monomer is the value of the molar ratio of each polymerizable monomer added for the copolymerization reaction.
  • the mixing ratio (molar ratio) of each monomer is not particularly limited, but the mixing ratio of the monomer (m-1) is preferably 9 to 70 mol%, more preferably 13 to 65 mol%.
  • the blending ratio of the monomer (m-1) is 9 mol% or more, sufficient curability can be exhibited in the photosensitive resin composition.
  • the blending ratio of the monomer (m-1) is 70 mol% or less, the blending ratio of the monomer (m-3) and/or the monomer (m-4) becomes sufficiently large, and the desired thermal decomposition resistance and refractive index can be obtained.
  • the resin (D) which has is obtained.
  • the mixing ratio is 0 mol based on 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1). % To more than 40 mol %, and more preferably more than 0 to 30 mol %. When the blending ratio is 1 mol% or more, desired thermal decomposition resistance, thermal yellowing resistance, and good solubility in a solvent can be obtained.
  • the mixing ratio should be more than 0 mol% to 50 mol% based on 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1). Is preferred, and more preferably more than 0 mol% to 40 mol %.
  • the monomer (m-6) When the monomer (m-6) is used, its blending ratio is more than 0 mol% to 10 mol% with respect to 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1). Is preferable, and more than 0 mol% to 5 mol% is more preferable.
  • the epoxy group-containing copolymer (P1) according to the present invention can be produced by using the copolymerization reaction of the monomer (M1).
  • the copolymerization reaction carried out in the present invention can be carried out according to a radical polymerization method known in the art. For example, after dissolving a monomer used for copolymerization in a solvent, a polymerization initiator is added to the solution, and the temperature is 50 to 140° C., more preferably 60 to 130° C., 1 to 20 hours, more preferably 1 to 12 hours. All you have to do is react. Further, the monomer used for the copolymerization and the polymerization initiator may be added dropwise to the solvent adjusted to 50 to 140° C. for the reaction.
  • the solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
  • the above-mentioned second solvent (B2) can be used as the copolymerization reaction solvent.
  • the amount of the solvent used in the copolymerization reaction is not particularly limited, but is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, when the total amount of the monomers used in the copolymerization is 100 parts by mass.
  • the amount of the solvent used is 1000 parts by mass or less, a decrease in the molecular weight of the copolymer (P1) is suppressed by a chain transfer action, and the viscosity of the copolymer (P1) is controlled within an appropriate range. be able to.
  • an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably carried out, and coloring and gelation of the copolymer (P1) can be prevented.
  • the polymerization initiator that can be used in this copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound can be used.
  • the amount of the polymerization initiator used in this copolymerization reaction is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass when the total amount of the monomers used in the copolymerization is 100 parts by mass. 10 parts by mass.
  • Epoxy resin (P3) The epoxy resin (P3) used in this embodiment is selected from the group consisting of novolac type epoxy resin (P3-1), bisphenol type epoxy resin (P3-2), and bifunctional epoxy resin having a biphenyl skeleton (P3-3). It is preferably selected.
  • novolac type epoxy resin examples include cresol novolac type epoxy resin and phenol novolac type epoxy resin. These novolac type epoxy resins may be used alone or in combination of two or more kinds.
  • Examples of the bisphenol type epoxy resin (P3-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin. These bisphenol type epoxy resins may be used alone or in combination of two or more. Among these, the bisphenol A type epoxy resin is preferable from the viewpoint of easy availability and reactivity.
  • the bifunctional epoxy resin having a biphenyl skeleton (P3-3) is not particularly limited as long as it has a biphenyl skeleton and has two epoxy groups in the molecule.
  • Examples of the biphenyl skeleton include those represented by the following formula (5).
  • R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • E and E′ each independently represent an organic group having an epoxy group.
  • bifunctional epoxy resin having a biphenyl skeleton examples include YX4000 (R′ is CH 3 in the following formula (6)) and YX4000K (R′ in the following formula (6)) manufactured by Mitsubishi Chemical Corporation. CH 3 ), YX4000H (in the formula (6) below, R′ is CH 3 ), YL6121HA (in the following formula (6), R′ is H, and R′ is CH 3. And the like) and the like.
  • composition of the present embodiment In the second embodiment of the carbon cluster-containing composition of the present invention (hereinafter sometimes referred to as “composition of the present embodiment”), the carbon cluster (A), the first solvent (B1), and the second solvent. (B2), an ethylenically unsaturated group-containing monomer (C), and a resin (D).
  • the ethylenically unsaturated group-containing monomer (C) is the epoxy group-containing ethylenically unsaturated compound (m-1).
  • This resin (D) is a carboxy group-containing copolymer (P2) or a carboxy group-containing resin (P4).
  • the carbon cluster (A), the first solvent (B1) and the second solvent (B2) the same ones as in the first embodiment can be used.
  • the carboxy group-containing copolymer (P2) or the carboxy group-containing resin (P4) undergoes ring opening addition to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1) to generate a hydroxy group.
  • a polybasic acid anhydride (d) is further added to the hydroxy group to obtain an ethylenically unsaturated resin (A2) or (A4) which is a resin having an ethylenically unsaturated group described later.
  • the epoxy group-containing ethylenically unsaturated compound (m-1) and the polybasic acid anhydride (d) the same ones as in the first embodiment can be used.
  • the addition ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) to the number of moles of carboxy contained in the carboxy group-containing copolymer (P2) is preferably 90 to 100%, more preferably 95-100%.
  • the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 when the total amount of all monomers (M2) used in the epoxy group-containing copolymer (P2) is 100 mol %. It is ⁇ 70 mol %, more preferably 15-65 mol %.
  • the blending ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is 10 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared.
  • Carboxy group-containing copolymer (P2) All the monomers (M2) of the carboxy group-containing copolymer (P2) (hereinafter sometimes simply referred to as “copolymer (P2)”) related to the resin (D) of the present embodiment are at least carboxy groups.
  • the polymerizable monomer (m-4) represented by (4), the aromatic ring-containing polymerizable monomer (m-5), and other polymerizable monomer (m-6) may be contained.
  • the polymerizable monomer (m-6) is the same as that described in the first embodiment, and the description is omitted.
  • the mixing ratio (molar ratio) of each monomer is not particularly limited, but the mixing ratio of the monomer (m-2) is preferably 9 to 70 mol% when the total of all monomers (M2) is 100 mol %. , And more preferably 13 to 65 mol %.
  • the blending ratio of the monomer (m-2) is 9 mol% or more, sufficient curability can be exhibited in the photosensitive resin composition. If the blending ratio of the monomer (m-2) is 70 mol% or less, the blending ratio of the monomer (m-3), the monomer (a-4) and the monomer (m-5) will be sufficiently high, and the desired amount will be obtained.
  • a resin (D) having thermal decomposition resistance is obtained.
  • the mixing ratio thereof is more than 0 mol% based on 100 mol% of the total amount of all the monomers (M2) of the copolymer (P2). It is preferably ⁇ 40 mol %, more preferably more than 0 mol% to 30 mol %.
  • the blending ratio is 1 mol% or more, desired thermal decomposition resistance, thermal yellowing resistance, and good solubility in a solvent can be obtained.
  • the blending ratio is preferably more than 0 mol% to 50 mol% based on 100 mol% of the total amount of all the monomers (M2) of the copolymer (P2). More preferably, it is more than 0 mol% to 40 mol %.
  • the monomer (m-6) is used, its blending ratio is from more than 0 mol% to 10 mol% based on 100 mol% of the total amount of all monomers (M2) of the epoxy group-containing copolymer (P2). It is preferable that it is more than 0 mol% to 5 mol%.
  • the carboxy group-containing copolymer (P2) according to the present invention can be produced by using a copolymerization reaction, like the copolymer (P1) according to the first embodiment.
  • the carboxy group-containing resin (P4) used in this embodiment is a resin having a carboxy group obtained by reacting the epoxy resin (P3) with the polyfunctional carboxylic acid (e).
  • the epoxy resin (P3) the epoxy resin (P3) used in the first embodiment can be used.
  • the polyfunctional carboxylic acid (e) is not particularly limited. It may be either a saturated or unsaturated polyfunctional carboxylic acid. Specific examples thereof include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid and sebacic acid.
  • the polyfunctional carboxylic acid (e) may be used alone or in combination of two or more. Among these, adipic acid and itaconic acid are preferable from the viewpoint of reactivity.
  • the carboxy group-containing resin (P4) preferably contains 30 to 80% by mass of the structural unit derived from the epoxy resin (P3) and 20 to 70% by mass of the structural unit derived from the polyfunctional carboxylic acid (e).
  • the molar ratio of the constitutional unit derived from the polyfunctional carboxylic acid (e) to the constitutional unit derived from the epoxy resin (P3) in the carboxy group-containing resin (P4) is 0.1 to 0.8. It is more preferably 0.15 to 0.7.
  • the carboxy group-containing resin (P4) used in this embodiment can be produced, for example, by subjecting the epoxy resin (P3) and the polyfunctional carboxylic acid (e) to an addition reaction in the presence of an addition catalyst.
  • the conditions of the addition reaction for obtaining the carboxy group-containing resin (P4) used in this embodiment may be appropriately set according to a conventional method.
  • each raw material and the addition catalyst are added to a solvent, preferably in an atmosphere of an oxygen gas concentration of 5 to 7% by volume, preferably at 50 to 150° C., more preferably at 60 to 140° C., at 1 to 12%. Just go on time.
  • the solvent that can be used in the above-mentioned addition reaction is not particularly limited, and a known solvent can be appropriately used.
  • the solvent used for the addition reaction of the first embodiment can be used.
  • the addition catalyst that can be used in the above-mentioned addition reaction is not particularly limited, and known ones can be appropriately used.
  • the catalyst used in the addition reaction of the first embodiment can be used.
  • the carbon cluster (A), the first solvent (B1), and the second solvent contains (B2) and a resin (D).
  • this resin (D) is an ethylenically unsaturated resin (A1) or an ethylenically unsaturated resin (A3).
  • the carbon cluster (A), the first solvent (B1) and the second solvent (B2) those used in the first embodiment can be similarly used.
  • the ethylenically unsaturated resin (A1) is composed of a monomer comprising a carboxy group-containing ethylenically unsaturated compound (m-2) and a polybasic acid anhydride (d) which is optionally used, and an epoxy group-containing copolymer (P1).
  • a resin (D) precursor containing
  • the ethylenically unsaturated resin (A3) includes a monomer composed of a carboxy group-containing ethylenically unsaturated compound (m-2) and a polybasic acid anhydride (d) optionally used, and an epoxy resin (P3).
  • the ethylenically unsaturated resin (A1) and the ethylenically unsaturated resin (A3) are resins containing an ethylenically unsaturated group and, if necessary, a carboxy group.
  • the above components of the precursor of the resin (D) used in this embodiment those used in the first embodiment can be used.
  • the ethylenically unsaturated resin (A1) or the ethylenically unsaturated resin (A3) is, for example, a solution of an epoxy group-containing copolymer (P1) or an epoxy resin (P3) in a carbon cluster (A) and a polymerization inhibitor, respectively.
  • the carboxy group-containing ethylenically unsaturated compound (m-2) is added, and the epoxy group is subjected to ring-opening addition reaction under the conditions of 50 to 150°C, preferably 80 to 130°C. It can be manufactured by adding a polybasic acid anhydride (d) in accordance with the above and subjecting it to an addition reaction.
  • the solvent used in this embodiment is not particularly limited, and known solvents can be appropriately used.
  • the above-mentioned second solvent (B2) can be used.
  • catalyst used in this embodiment examples include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelate compounds. .. These catalysts may be used alone or in combination of two or more.
  • the amount of the catalyst used in this embodiment is not particularly limited, but is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass when the resin precursor is 100 parts by mass. Parts by mass, more preferably 0.2 to 1 part by mass.
  • the carbon cluster (A), the first solvent (B1), and the second solvent contains (B2) and a resin (D).
  • this resin (D) is an ethylenically unsaturated resin (A2) or an ethylenically unsaturated resin (A4).
  • the carbon cluster (A), the first solvent (B1) and the second solvent (B2) those used in the first embodiment can be similarly used.
  • the ethylenically unsaturated resin (A2) is prepared by using a precursor containing an epoxy group-containing ethylenically unsaturated compound (m-1) and a carboxy group-containing copolymer (P2) or a carboxy group-containing resin (P4).
  • the obtained resin is a resin containing an ethylenically unsaturated group.
  • those used in the second embodiment can be used.
  • the ethylenically unsaturated resin (A2) or the ethylenically unsaturated resin (A4) is, for example, a carbon cluster (A) as a polymerization inhibitor in a solution of the carboxy group-containing copolymer (P2) or the carboxy group-containing resin (P4), respectively.
  • a catalyst and then an epoxy group-containing ethylenically unsaturated compound (m-1) is added, and the epoxy group is subjected to ring-opening addition reaction at 50 to 150°C, preferably 80 to 130°C. can do.
  • the solvent used in this embodiment is not particularly limited, and known solvents can be appropriately used.
  • the above-mentioned second solvent (B2) can be used.
  • composition of the present embodiment In the fifth embodiment of the carbon cluster-containing composition of the present invention (hereinafter sometimes referred to as “composition of the present embodiment”), the carbon cluster (A), the first solvent (B1), and the second solvent. (B2) and resin (D) are contained.
  • the carbon cluster (A), the first solvent (B1) and the second solvent (B2) those used in the first embodiment can be similarly used, and particularly, the second solvent (B2) is tetrahydrofuran. preferable.
  • the resin (D) examples include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyalkylene, polyvinyl chloride, polystyrene, polyvinyl acetate, and (meth).
  • An acrylic resin, an epoxy ester resin, etc. are mentioned.
  • the resin (D) used in this embodiment may be a commercially available product.
  • One embodiment of the method for producing the carbon cluster-containing composition of the present invention is to disperse carbon clusters by mixing carbon clusters (A) and a first solvent (B1) selected from the group consisting of aromatic solvents and halogen-containing solvents.
  • a step (V) of carrying out a polymerization reaction of the monomer or an addition reaction of the resin and the monomer is further included. ..
  • the carbon cluster-containing composition of the present invention can be used as a photosensitive resin composition by further containing a reactive diluent (E) and a photopolymerization initiator (F). Further, a colorant (G) may be included.
  • E reactive diluent
  • F photopolymerization initiator
  • G colorant
  • the blending amount of the first solvent (B1) and the second solvent (B2) in the carbon cluster-containing composition for the photosensitive resin composition is 100 parts by mass when the sum of the components excluding all the solvents in the composition is 100 parts by mass. Generally, it is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, more preferably 100 to 700 parts by mass. When the compounding amount is within this range, it can be used as a photosensitive resin composition having an appropriate viscosity.
  • the blending amount of the reactive diluent (E) in the carbon cluster-containing composition for the photosensitive resin composition is generally 10 to 90% by mass, when the total amount of components excluding all solvents in the composition is 100% by mass. , Preferably 20 to 80% by mass, more preferably 25 to 70% by mass. If it is the compounding quantity of this range, it will become a photosensitive resin composition which has suitable viscosity, and a photosensitive resin composition has suitable photocurability.
  • the reactive diluent (E) is not particularly limited, but one containing an ethylenically unsaturated double bond, preferably a vinyl group or a (meth)acryloyloxy group is preferable. Specific examples thereof include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate and diallylbenzenephosphonate; polycarboxylic acids such as vinyl acetate and vinyl adipate.
  • Monomers methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ⁇ -hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate , Diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, (Meth)acrylic monomers such as dipentaerythritol hexa(meth)acrylate (for example, dipentaerythritol hexaacrylate (DPHA) manufactured by Shin-Nakamura Chemical Co., Ltd.) and tri(meth)acrylate of tris(hydroxyethyl
  • the photopolymerization initiator (F) is not particularly limited, but specific examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1 ,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone and other acetophenones; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal
  • the content of the photopolymerization initiator (F) in the photosensitive resin composition of the present embodiment is generally 0.1 to 30 when the total amount of components excluding all solvents in the photosensitive resin composition is 100 parts by mass.
  • the amount is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass.
  • a blending amount within this range results in a photosensitive resin composition having appropriate photocurability.
  • Colorant (G) There is no particular limitation as long as it can be dissolved or dispersed in the second solvent (B2), and known dyes or pigments can be used. When a dye is used as the colorant (G), it is possible to obtain a colored pattern having a higher brightness than when a pigment is used, and a good alkali developability is exhibited. On the other hand, when a pigment is used as the colorant (G), the heat resistance of the coloring pattern is higher than when a dye is used. Dyes and pigments may be used in combination depending on the required performance and the intended pixel color.
  • dye an acidic dye having an acidic group such as a carboxy group or an acidic dye, from the viewpoint of solubility in a solvent (B) or an alkali developing solution, interaction with other components in the photosensitive resin composition, heat resistance, and the like. It is preferable to use a salt of a dye with a nitrogen compound, a sulfonamide body of an acid dye, or the like. Specific examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90.
  • azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These dyes can be used alone or in combination of two or more, depending on the intended color of the pixel.
  • Pigment Specific examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like; orange pigments such as C.I. I.
  • the blending amount of the colorant (G) in the photosensitive resin composition of the present embodiment is generally 5 to 80 parts by mass, preferably 100 parts by mass, when the total of components excluding all solvents in the photosensitive resin composition is 100 parts by mass. Is 5 to 70 parts by mass, more preferably 10 to 60 parts by mass.
  • Acrylic acid 72.0 g as a monomer (m-2) and triphenylphosphine as a catalyst 0.66 g (0.3 parts by mass) were charged therein to obtain a solution (ii).
  • the carbon cluster dispersion liquid (i) was added to and mixed with the solution (ii) to obtain a resin solution which was the carbon cluster-containing composition of the first embodiment.
  • the resin solution obtained above was heated at 110° C. for 10 hours while blowing low oxygen air into which nitrogen gas was injected so that the oxygen concentration became 4 to 7% by volume.
  • Comparative Example a resin solution, which is a carbon cluster-containing composition, was obtained in the same manner as in Example 1 except that a slurry in which fullerene and ethylene glycol were mixed in place of the fullerene solution, fullerene as a powder was added, or BHT was added. It was The results are shown in Table 1.
  • BHT di-t-butylhydroxytoluene
  • PGMEA propylene glycol monomethyl ether acetate
  • TCDMA tricyclodecanyl methacrylate
  • St styrene
  • GMA glycidyl methacrylate
  • TBO t-butylperoxy-2-ethylhexanoate
  • MAA methacrylic acid
  • THPA Tetrahydrophthalic anhydride
  • Example 4 A carbon cluster dispersion liquid (i) was obtained in the same manner as in Example 1. Next, 133.3 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while substituting with nitrogen and heated to 120°C.
  • a resin solution which is the carbon cluster-containing composition of the fourth embodiment, was obtained. Then, it was confirmed that the acid value was 72.0 KOHmg/g or less, and a resin solution having a solid content concentration of 28.6% by mass (solid content acid value 196.8 KOHmg/g, weight average molecular weight 18500) was obtained. The reaction rate of the acid and the epoxy was calculated by measuring the acid value in the reaction solution, and it was 97.8%.
  • Comparative Example a resin solution which is a carbon cluster-containing composition was obtained in the same manner as in Example 4 except that a slurry in which fullerene and ethylene glycol were mixed instead of the fullerene solution, fullerene as a powder, or BHT was added. It was The results are shown in Table 2.
  • THF tetrahydrofuran
  • Examples 8 to 10 and Comparative examples 7 to 10 were obtained by changing the addition method of the resin and fullerene. The results are shown in Table 3.
  • the acid value and molecular weight of the ethylenically unsaturated resin contained in the synthesized ethylenically unsaturated resin composition were measured by the following methods.
  • the synthesis is possible even if the amount of the carbon clusters as the polymerization inhibitor is reduced, but in the comparative example, it is doubled if the method of adding the carbon clusters is changed or the amount of BHT is reduced. Gelation occurs without being able to suppress the crosslinking of the bonds.
  • Examples 18 to 23 and Comparative Examples 11 to 12 On the glass substrate, the resins of Examples 1 to 6 and Comparative Examples 3 and 6 were used, and a photosensitive resin composition having a composition shown in Table 4 was prepared. In addition, the compounding amount of the resin in the table is described by the value of the solid content, and the solvent contained in the synthesis of the resin is described by being added to the item of “solvent” in the table.
  • OXE-01 manufactured by BASF
  • IRGACURE OXE-01 DPHA dipentaerythritol hexaacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une composition dans laquelle des grappes de carbone sont uniformément dispersées. Une composition contenant des grappes de carbone selon la présente invention contient des grappes de carbone (A), un premier solvant (B1), un second solvant (B2), et au moins une substance qui est sélectionnée dans le groupe consistant en des monomères contenant des groupes éthyléniquement insaturés (C) et des résines (D). Le premier solvant (B1) est composé d'au moins un solvant qui est sélectionné dans le groupe consistant en des solvants aromatiques et des solvants contenant un halogène; et le second solvant (B2) est composé d'un solvant autre que des solvants aromatiques et des solvants contenant un halogène.
PCT/JP2019/046120 2018-11-28 2019-11-26 Composition contenant des grappes de carbone et procédé de production associé WO2020111046A1 (fr)

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KR1020217012831A KR20210068098A (ko) 2018-11-28 2019-11-26 탄소 클러스터 함유 조성물 및 그의 제조 방법
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JP2004537512A (ja) * 2002-04-16 2004-12-16 デンツプライ インターナショナル インコーポレーテッド 防止剤を含む光重合性歯科用組成物
JP2006160799A (ja) * 2004-12-02 2006-06-22 Toyota Industries Corp 塗料組成物、塗料組成物を用いた摺動層の製造方法および摺動層を有する摺動部材
JP2009013377A (ja) * 2007-07-09 2009-01-22 Kureha Corp プロトン伝導性樹脂組成物
JP2013095820A (ja) * 2011-10-31 2013-05-20 Fujifilm Corp 導電性組成物、並びにこれを用いた導電性膜及び導電性積層体
JP2018126496A (ja) * 2017-02-06 2018-08-16 信越化学工業株式会社 生体電極組成物、生体電極、生体電極の製造方法、及び高分子化合物

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EP2062853A1 (fr) * 2007-11-23 2009-05-27 Nanoledge Composites de nanotube en carbone de polymère
JP6576494B2 (ja) 2018-02-20 2019-09-18 国立大学法人大阪大学 長鎖アルキルエーテル化フラーレン誘導体およびその製造方法、並びにそれを用いた樹脂組成物

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JP2004537512A (ja) * 2002-04-16 2004-12-16 デンツプライ インターナショナル インコーポレーテッド 防止剤を含む光重合性歯科用組成物
JP2004177772A (ja) * 2002-11-28 2004-06-24 Jsr Corp 光硬化性組成物およびその用途
JP2006160799A (ja) * 2004-12-02 2006-06-22 Toyota Industries Corp 塗料組成物、塗料組成物を用いた摺動層の製造方法および摺動層を有する摺動部材
JP2009013377A (ja) * 2007-07-09 2009-01-22 Kureha Corp プロトン伝導性樹脂組成物
JP2013095820A (ja) * 2011-10-31 2013-05-20 Fujifilm Corp 導電性組成物、並びにこれを用いた導電性膜及び導電性積層体
JP2018126496A (ja) * 2017-02-06 2018-08-16 信越化学工業株式会社 生体電極組成物、生体電極、生体電極の製造方法、及び高分子化合物

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