CN113166288A - Composition containing carbon cluster and method for producing same - Google Patents

Composition containing carbon cluster and method for producing same Download PDF

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CN113166288A
CN113166288A CN201980076876.5A CN201980076876A CN113166288A CN 113166288 A CN113166288 A CN 113166288A CN 201980076876 A CN201980076876 A CN 201980076876A CN 113166288 A CN113166288 A CN 113166288A
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meth
resin
group
monomer
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柳正义
川口恭章
木下健宏
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Resonac Holdings Corp
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Showa Denko KK
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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

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

Abstract

The present invention provides a composition in which carbon clusters are uniformly dispersed. The carbon cluster-containing composition contains: a carbon cluster (A); a1 st solvent (B1); a2 nd solvent (B2); and at least 1 selected from the group consisting of an ethylenically unsaturated group-containing monomer (C) and a resin (D). The 1 st solvent (B1) is at least 1 solvent selected from an aromatic solvent and a halogen-containing solvent, and the 2 nd solvent (B2) is a solvent other than the aromatic solvent and the halogen-containing solvent.

Description

Composition containing carbon cluster and method for producing same
Technical Field
The present invention relates to a composition containing carbon clusters and a method for producing the same.
This application claims priority based on Japanese application No. 2018-222729 filed 11/28/2018, the contents of which are incorporated herein by reference.
Background
In recent years, many studies have been made on the production of a resin having properties such as heat resistance by adding a fullerene. For example, non-patent document 1 discloses a fullerene (C) contained therein60) The polypropylene or high-density polyethylene resin composition of (1). However, in order to uniformly disperse the fullerene, it is necessary to mix the fullerene in a state where the resin is melted at approximately 200 ℃ for a long time. Further, the dispersion may become insufficient. Therefore, patent document 1 discloses a resin composition containing a long-chain alkyl-etherified fullerene derivative having improved compatibility with a resin.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2018-90612
Non-patent document
Non-patent document 1: wan, et al, "The Rheological thermosettable and Mechanical Properties of Polypropylene/Fullerene C60 Nanocompositites with Improved Interactive Interaction", Polymer.Eng.Sci.2012, 1457-
Disclosure of Invention
Problems to be solved by the invention
However, since a fullerene derivative having a specific structure needs to be used, the material cost is high, and the range of use is still limited from the viewpoint of compatibility with a solvent or a resin. In the resin composition and final molded article in the production process, a method of more easily dispersing fullerene and expressing functions such as heat resistance is required.
Means for solving the problems
That is, the present invention is represented by the following [1] to [10 ].
[1] A composition comprising carbon clusters, comprising: a carbon cluster (A); a1 st solvent (B1); a2 nd solvent (B2); and at least 1 selected from the group consisting of an ethylenically unsaturated group-containing monomer (C) and a resin (D),
the 1 st solvent (B1) is at least 1 solvent selected from the group consisting of aromatic solvents and halogen-containing solvents,
the above-mentioned 2 nd solvent (B2) is a solvent other than the aromatic solvent and the halogen-containing solvent.
[2] The composition containing a carbon cluster according to [1], wherein the carbon cluster (A) is a fullerene or a derivative thereof.
[3] The composition containing carbon clusters according to [1] or [2], wherein the 1 st solvent (B1) is at least 1 selected from the group consisting of toluene, benzene, and trimethylbenzene.
[4] The carbon cluster-containing composition according to any one of [1] to [3], wherein the 2 nd solvent (B2) is a glycol ether solvent.
[5] The carbon cluster-containing composition according to any one of [1] to [4], which contains the monomer (C) and the resin (D),
the monomer (C) has a reactive group,
the resin (D) has a group capable of reacting with the reactive group of the monomer (C).
[6] 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.
[7] The method for producing a carbon cluster-containing composition according to any one of [1] to [6], wherein the content of the carbon cluster (A) is 0.01 to 0.10 parts by mass relative to 100 parts by mass of the total of the monomer (C) and the resin (D).
[8] A method for producing a carbon cluster-containing composition, comprising the steps of:
a first mixing step (I) of mixing a carbon cluster (a) with a1 st solvent (B1) to obtain a carbon cluster dispersion (I);
a second mixing step (II) of mixing at least 1 selected from the group consisting of the monomer (C) and the resin (D) with a2 nd solvent (B2) to obtain a solution (II); and
a third mixing step (III) of mixing the solution (ii) with the carbon cluster dispersion liquid (i).
[9] The method for producing a composition containing carbon clusters according to [8], further comprising the following step (IV): the polymerization reaction of the monomer (C) is carried out.
[10] The process for producing a composition containing carbon clusters according to [8], further comprising the following step (V): and (D) performing an addition reaction of the monomer (C) having a reactive group and the resin (D) having a group capable of reacting with the reactive group of the monomer (C).
ADVANTAGEOUS EFFECTS OF INVENTION
Even a composition containing a substance having poor compatibility with the carbon clusters, for example, a solvent, a monomer, or a resin, can easily disperse the carbon clusters in the composition. As a result, functions such as radical-capturing ability and heat resistance of the carbon cluster can be expressed.
Detailed Description
The present invention is described in detail below.
[ composition containing carbon clusters ]
The composition containing a carbon cluster of the present invention (hereinafter, may be referred to as "the composition of the present invention") contains a carbon cluster (a), a1 st solvent (B1), a2 nd solvent (B2), and at least 1 selected from a monomer (C) and a resin (D). The 1 st solvent (B1) is at least 1 solvent selected from an aromatic solvent and a halogen-containing solvent, and the 2 nd solvent (B2) is a solvent other than the aromatic solvent and the halogen-containing solvent.
[ carbon Cluster (A) ]
The carbon cluster (a) of the present invention is a cluster or fine particle in which several to several hundred carbon atoms are bonded or aggregated regardless of the type of carbon-carbon bond. However, the carbon content is not necessarily 100% and other atoms may be mixed. The maximum diameter of the carbon cluster (A) is preferably 300nm or less, and more preferably 100nm or less.
The carbon cluster (a) may have primary particles aggregated, and the size of the primary particles affects the dispersion of the carbon cluster compound, and therefore the maximum diameter is the maximum diameter of the primary particles.
The carbon cluster includes a fullerene as a fullerene, and a tubular carbon cluster such as a carbon nanotube, a carbon nanohorn and a carbon fiber, a soot-like substance, and derivatives and aggregates thereof obtained by chemically modifying them.
The carbon cluster (a) is preferably a compound having a polyhedral structure, and more preferably a compound having a structure in which a 5-membered ring and a 6-membered ring are bonded. Specifically, fullerene and its derivative, and soot-like substance having a polyhedral structure and not closed shell, which is generated as a by-product in the production of fullerene, can be exemplified.
Fullerenes are fullerene-like carbon molecules that contain 5-membered rings in addition to the 6-membered rings observed in graphite in a network of carbon atoms. As the fullerene, those having about 60 to 120 carbon atoms such as 60, 70, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, and 96 carbon atoms are known. In the present invention, the number of carbon atoms is not particularly limited, but is preferably 60(C60) and 70(C70) in terms of easy availability and excellent solubility in the 1 st solvent (B1). Furthermore, fullerene containing a different atom such as scandium (Sc), lanthanum (La), cerium (Ce), titanium (Ti), or nitrogen (N) may be used. Further, an oxide of fullerene added to each other (C60)2And adducts of O and fullerene (C60-C60, C70-C60, C70-C70, etc.).
Examples of the soot-like substance include compounds having the same structure as that of a fullerene part and not having a shell closed.
The soot-like substance used in the present invention is preferably soot that is by-produced during fullerene production. Including the crude fullerene produced in the fullerene production process. After the fullerene is removed by solvent extraction from the crude fullerene, the resulting residue contains more soot-like substances. The soot-like substance contains amorphous carbon molecules having a structure in which a 5-membered ring and a 6-membered ring are bonded to each other like fullerene and not enclosing a shell.
Examples of the method for producing fullerene as a by-product 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. Are manufactured under an environment of a pressure of 800hPa or less. For example, in the case of a gas combustion method, the soot-like substance can be obtained by burning a hydrocarbon raw material and an oxygen-containing gas in a reduced pressure atmosphere. As the hydrocarbon feedstock, for example, aromatic hydrocarbons such as toluene and benzene can be used. The pressure reduction condition is preferably 3 to 800hPa, and the heating condition is preferably 1600 to 2000 ℃.
When the hydrocarbon raw material and the gas containing oxygen are fired under the reduced pressure atmosphere, hydrogen is desorbed from the hydrocarbon raw material. Here, the mixing ratio of the hydrocarbon feedstock and the oxygen-containing gas is preferably 2.5 to 3.5 in terms of an equivalent ratio, and the amount of the hydrocarbon feedstock is increased. This makes it possible to cause incomplete combustion. If the reaction is completely combusted, carbon in the hydrocarbon feedstock is combined with oxygen and discharged as carbon monoxide and carbon dioxide, and there is a possibility that carbon is not easily combined with each other. The equivalence ratio is defined as 1 as the ratio of the amount of hydrocarbon feedstock that has just been completely combusted to the amount of oxygen.
The hydrocarbon raw material from which hydrogen is removed is unstable, and the surrounding carbons are likely to aggregate with each other. At this time, a part of the reaction proceeds to chemically bond. The carbon compounds obtained in such a process contain soot-like substances.
The soot-like substance contains amorphous carbon molecules that have a molecular structure that cannot be a predetermined spherical shape, such as fullerene, although a plurality of carbons are bonded by bonding of molecules to each other. Examples of such amorphous carbon molecules include intermediate products that are produced during the production of fullerenes and carbon molecules that have a structure similar to the partial structure of fullerenes and have a structure in which some of spherical fullerenes are missing or do not have a shell. The amorphous carbon molecules may have a cluster structure in which a plurality of carbon molecules are concentrated. The cluster structure includes a nested structure in which carbon molecules having a large size and a structure having an unclosed shell include carbon molecules having a small size and a structure having an unclosed shell.
The carbon cluster (a) may have a substituent as long as the desired effects such as solubility in the 1 st solvent (B1), radical-capturing ability, and heat resistance are not impaired. Examples of the substituent include indene, malonic acid, methyl phenylbutyrate and the like.
The carbon cluster (a) used in the composition containing carbon clusters of the present invention may be a mixture of fullerenes having different carbon atoms, and commercially available products thereof include, for example, a mixture of C60/C70 manufactured by フロンティアカーボン.
The carbon cluster (a) used in the composition containing carbon clusters of the present invention may be a soot-like carbon substance obtained by the method described later.
The carbon cluster (a) used in the carbon cluster-containing composition of the present invention may have no substituent from the viewpoint of availability. Examples of the substituent include indene, malonic acid, methyl phenylbutyrate and the like, and examples of the fullerene derivative include ICBA (indene double adduct), ICMA (indene adduct), PCBM (phenyl-C61-methyl butyrate and the like), SAM (1-methyl-1H-pyrrolobenzoic acid adduct) and the like.
The carbon cluster (a) used in the composition containing a carbon cluster of the present invention is preferably a fullerene or a derivative thereof, and more preferably a fullerene having no substituent, from the viewpoint of solubility in the 1 st solvent (B1) and dispersibility in the composition.
When the composition containing carbon clusters of the present invention further contains at least 1 selected from the group consisting of the monomer (C) and the resin (D), the content of the carbon clusters may be 0.01 to 0.10 parts by mass, or 0.01 to 0.05 parts by mass, based on 100 parts by mass of the total of the monomer (C) and the resin (D).
[1 st solvent (B1) ]
The 1 st solvent (B1) used in the present invention is at least 1 solvent selected from the group consisting of aromatic solvents and halogen-containing solvents. In order to uniformly disperse the carbon cluster (a), the 1 st solvent (B1) is preferably a solvent in which the carbon cluster (a) can be dissolved or uniformly dispersed.
Specific examples of the aromatic solvent include aromatic solvents such as toluene, benzene and trimethylbenzene; aromatic compounds having a halogen group such as o-dichlorobenzene and 1, 2-dibromobenzene; other aromatic compounds such as nitrobenzene and anisole; polycyclic aromatic hydrocarbons such as quinoline and 1-methylnaphthalene. Specific examples of the halogen-containing solvent include halogen-containing compounds such as carbon tetrachloride and methylene chloride. These solvents may be used alone, or 2 or more kinds may be used in combination.
Among the above specific examples of the aromatic solvent, a solvent having a solubility of the carbon cluster (A) of 0.5g/L or more at 25 ℃ is preferable, and aromatic solvents such as toluene, benzene, and trimethylbenzene are more preferable. Further, trimethylbenzene is more preferable from the viewpoint of toxicity and availability.
[2 nd solvent (B2) ]
The 2 nd solvent (B2) used in the present invention is a solvent other than the aromatic solvent and the halogen-containing solvent. Namely, a solvent other than the 1 st solvent (B1). The 2 nd solvent (B2) is preferably a solvent having compatibility with the 1 st solvent (B1) or the above 1 st solvent (B1) can be dispersed.
In order to uniformly disperse the monomer (C) and the resin (D), the 2 nd solvent (B2) is preferably a solvent in which the monomer (C) and the resin (D) can be dissolved or dispersed.
As the solvent (B2) 2, an ether compound, a ketone compound, an ester compound, or a carboxylic acid amide compound can be used. Examples of the ether compound include (poly) alkylene glycol monoalkyl ethers; (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. Specific examples of the (poly) alkylene glycol monoalkyl ether 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-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and the like. Specific examples of 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, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, methyl acetate, ethyl propionate, and ethyl propionate, and ethyl propionate, and ethyl propionate, N-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, and the like. Specific examples of the carboxylic acid amide compounds include N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and the like. These solvents may be used alone, or 2 or more kinds may be used in combination.
For example, when the composition of the present invention contains an ethylenically unsaturated group-containing monomer, an unsaturated (meth) acrylic resin, an unsaturated epoxy ester resin, or the like, among the above solvents, a glycol ether solvent is preferable. Specifically, (poly) alkylene glycol monoalkyl ether acetate is more preferably used. Further, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferably used.
"monomer (C) containing ethylenically unsaturated group and resin (D)"
The ethylenically unsaturated group-containing monomer (C) and the resin (D) used in the present invention are preferably those which can be dissolved or dispersed in the above-mentioned 2 nd solvent (B2).
Examples of the ethylenically unsaturated group-containing monomer (C) include a polyfunctional (meth) acrylate used as a reactive diluent, a material monomer necessary for synthesis of the resin (D), and a modifying monomer for modifying the resin (D) by an addition reaction or a dehydration condensation reaction.
Examples of the material monomer include alkyl (meth) acrylate, aromatic group-containing (meth) acrylate, cyclic ring-containing (シクロ hooked) acrylate, fluorine-containing (meth) acrylate, cyclic structure-containing (meth) acrylate, amino group-containing (meth) acrylate, alkoxy polyalkylene glycol (meth) acrylate, hydroxyl group-containing (meth) acrylate, blocked isocyanate group-containing (meth) acrylate, epoxy group-containing (meth) acrylate, (meth) acrylamide, (meth) acrylanilide, (meth) acrylonitrile, and acrolein.
Specific examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and n-pentyl methacrylate. Specific examples of the aromatic group-containing (meth) acrylate include benzyl (meth) acrylate, triphenylmethyl (meth) acrylate, phenyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, diphenoxyethyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, cumyl (meth) acrylate, phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate (trade name: ライトアクリレート P-200A, available from Kyoto chemical Co., Ltd.), o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, P-phenoxybenzyl acrylate, and the like. Specific examples of the cyclic ring-containing (meth) acrylate include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, rosin (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. Specific examples of the heterocycle-containing (meth) acrylate include 1,1, 1-trifluoroethyl (meth) acrylate and the like. Specific examples of the fluorine-containing (meth) acrylate include perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, and the like. Specific examples of the (meth) acrylate having a cyclic structure include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and the like. Specific examples of the amino group-containing (meth) acrylate include 3- (N, N-dimethylamino) propyl (meth) acrylate and the like. Specific examples of the alkoxy polyalkylene glycol (meth) acrylate include methoxy triethylene glycol acrylate, ethoxy diethylene glycol acrylate, methoxy polyethylene glycol methacrylate, and methoxy polyethylene glycol acrylate (trade name: AM-90G, manufactured by Ninghamun chemical Co., Ltd.). Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerol mono (meth) acrylate, and the like. Specific examples of the (meth) acrylate having a blocked isocyanate group include a reaction product of (meth) acryloyloxyethyl isocyanate (i.e., 2-isocyanatoethyl (meth) acrylate) and epsilon-caprolactam, a reaction product of (meth) acryloyloxyethyl isocyanate and propylene glycol monomethyl ether, and the like. Specific examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate and lactone adducts thereof (for example, サイクロマー A200, M100 manufactured by ダイセル chemical , Ltd.), mono (meth) acrylate of 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate, epoxide of dicyclopentenyl (meth) acrylate, epoxide of dicyclopentenyloxyethyl (meth) acrylate, and the like. Specific examples of the (meth) acrylamide include (meth) acrylamide, N-dimethylamide (meth) acrylate, N-diethylamide (meth) acrylate, N-dipropylamide (meth) acrylate, N-di-isopropylamide (meth) acrylate, anthracylamide (meth) acrylate, and the like.
Examples of the modifying monomer include unsaturated carboxylic acids such as (meth) acrylic acid, unsaturated isocyanate monomers such as 2-isocyanatoethyl (meth) acrylate, unsaturated epoxy compounds such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Further, as the modifying monomer, polybasic acid anhydrides such as tetrahydrophthalic anhydride, polybasic acids such as 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, and the like may be used in combination.
Specific examples of the resin (D) include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethane resins, polyalkylene resins, polyvinyl chloride, polystyrene, polyvinyl acetate, (meth) acrylic resins, and epoxy ester resins.
For example, in the case of using a composition containing carbon clusters as a resist material, a resin having an ethylenically unsaturated group is preferably used from the viewpoint of photocurability. In addition, from the viewpoint of developability, a (meth) acrylic resin having an ethylenically unsaturated group and/or an epoxy ester resin having an ethylenically unsaturated group is preferably used. By using a composition containing carbon clusters as a resist material, effects such as improvement in thermal yellowing resistance and improvement in pattern shape (reduction in edge roughness) can be expected.
When a (meth) acrylic resin having an ethylenically unsaturated group is used as the resin (D), the constituent monomers used are those listed above for the ethylenically unsaturated group-containing monomer (C). In addition, as long as the effect of the (meth) acrylic resin is not impaired, an ethylenically unsaturated compound having a carboxyl group such as (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, and maleic acid, and a substituent thereof; aromatic vinyl compounds such as norbornene, dicyclopentadiene, styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetamidostyrene; conjugated diene compounds such as butadiene, isoprene and chloroprene; vinyl compounds such as vinyl chloride, 1-dichloroethylene, vinyl fluoride, 1-difluoroethylene, N-vinylpyrrolidone, vinylpyridine, vinyl acetate and vinyl toluene; unsaturated dicarboxylic acid diester compounds such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; and the like. These radically polymerizable monomers may be used alone or in combination of 2 or more.
When the composition containing carbon clusters is used as a resist material, as the constituent monomer of the (meth) acrylic resin having an ethylenically unsaturated group, a carboxyl group-containing ethylenically unsaturated compound such as (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, and maleic acid, a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate are preferably used. If necessary, the modifying monomer may be reacted with a carboxyl group, a hydroxyl 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 that can be used as the resin (D) is generally a compound having a polymerizable unsaturated bond obtained by a ring-opening reaction of an epoxy group in an epoxy compound having 2 or more epoxy groups with a carboxyl group of an unsaturated carboxylic acid. Such an epoxy ester resin is described in, for example, "no in waterfall, ポリエステル colophony ハンドブック (handbook of polyester resin)" (edited by japan news agency in 1988), or "a paint dictionary (edited by china society, 1993). Examples of the epoxy compound as a constituent monomer of the epoxy ester resin include cresol novolak type epoxy compounds, phenol novolak type epoxy compounds, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, 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, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, bisphenol fluorene glycidyl ether, and the like. Examples of the epoxy compound as a constituent monomer of the epoxy ester resin include compounds obtained by adding an epihalohydrin such as epichlorohydrin to a compound shown below.
Examples of the compound which forms an epoxy compound by addition of an 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) hexafluoropropane, 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) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-dibromophenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3, 5-dimethylphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, cresol novolak, or the like.
Examples of the unsaturated carboxylic acid as a constituent monomer of the epoxy ester resin include (meth) acrylic acid, crotonic acid, cinnamic acid, sorbic acid, itaconic acid, and the like.
Mixing proportion of each component "
The amount of the carbon cluster (a) is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the total of the 1 st solvent (B1) and the 2 nd solvent (B2). When the amount is 0.001 part by mass or more, functions such as radical-capturing ability and heat resistance can be sufficiently expressed. When the amount is 1 part by mass or less, the agglomerated particles of the carbon cluster (A) do not grow, and a composition containing carbon clusters in which the carbon cluster (A) is sufficiently dispersed is obtained. Further, when the composition containing carbon clusters is used for a resist and photocured by adding a photopolymerization initiator or the like, the photocurability is not adversely affected.
The 2 nd solvent (B2) is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, per 100 parts by mass of the monomer (C) and/or the resin (D). If the solvent is 30 parts by mass or more, good workability is obtained. When the solvent is 1000 parts by mass or less, a sufficient film thickness is obtained when a shape such as a coating film is formed.
The composition containing carbon clusters according to the present invention will be described in more detail by the following embodiments.
It does not limit the invention.
[ first embodiment ]
In a first embodiment of the carbon cluster-containing composition of the present invention (hereinafter, may be referred to as "the composition of the present embodiment"), the carbon cluster (a), the 1 st solvent (B1), the 2 nd solvent (B2), the ethylenically unsaturated group-containing monomer (C), and the resin (D) are contained. Wherein the ethylenically unsaturated group-containing monomer (C) is an ethylenically unsaturated compound (m-2) having a carboxyl group. The resin (D) is an epoxy group-containing copolymer (P1) or an epoxy resin (P3).
Any 1 of the above-mentioned specific examples or a mixture thereof can be used for the carbon cluster (A). The 1 st solvent (B1) used in the present embodiment may be any one of 1 or a mixed solvent thereof in the specific examples of the 1 st solvent (B1). Among them, toluene, benzene, xylene, ethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, or a mixed solvent thereof is preferable, and 1 or more selected from toluene, benzene, and trimethylbenzene is more preferable.
The 2 nd solvent (B2) used in the present embodiment may be any one of 1 or a mixed solvent thereof in the specific examples of the 2 nd solvent (B2). Among them, preferred are glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol.
The ethylenically unsaturated group-containing monomer (C) of the present embodiment is a carboxyl group-containing ethylenically unsaturated compound (m-2). The resin (D) is an epoxy group-containing copolymer (P1) or an epoxy resin (P3).
[ ethylenically unsaturated Compound (m-2) having carboxyl group ]
The carboxyl group-containing ethylenically unsaturated compound (m-2) (hereinafter, may be simply referred to as "monomer (m-2)") is not particularly limited as long as it has no epoxy group and has a carboxyl group and an ethylenically unsaturated group which are particularly excellent in reactivity with an epoxy group among acid groups. Examples thereof include unsaturated monobasic acids and unsaturated dibasic acid monoesters. Examples of the unsaturated monobasic acid include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, α -bromo (meth) acrylic acid, β -furyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α -cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate. Examples of the unsaturated dibasic acid monoester include monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate. These carboxyl group-containing ethylenically unsaturated compounds (m-2) may be used alone, or 2 or more kinds may be used. Among them, (meth) acrylic acid is preferable from the viewpoint of availability and reactivity.
The reaction ratio of the carboxyl group-containing ethylenically unsaturated compound (M-2) is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, based on 100 mol% of the total monomers (M1) of the epoxy group-containing copolymer (P1). When the compounding ratio of the carboxyl group-containing ethylenically unsaturated compound (m-2) is 10 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is produced. If the amount is 70 mol% or less, the blending ratio of each monomer (M1) other than the monomer (M-2) is sufficiently secured, and the resin (D) having a desired thermal decomposition resistance or the like can be obtained. The proportion of the carboxyl group-containing ethylenically unsaturated compound (m-2) added to the epoxy group-containing copolymer (P1) is preferably 90 to 100%, more preferably 95 to 100%, based on the number of moles of epoxy groups.
When the addition ratio of the carboxyl group-containing ethylenically unsaturated compound (m-2) is 90% or more, sufficient curability can be exhibited when the photosensitive resin composition is produced.
[ polybasic acid anhydride (d) ]
The polybasic acid anhydride (d) is not particularly limited as long as it has an acid anhydride structure that is highly reactive with hydroxyl groups, but a substance having a ring structure that does not generate a by-product after the reaction is suitable. Specific examples thereof include 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 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 to 65 mol%, based on 100 mol% of the total of the monomers (M1) of the epoxy group-containing copolymer (P1). The amount of the carboxyl group-containing ethylenically unsaturated compound (m-2) added is preferably 20 to 100%, more preferably 30 to 90% by mole.
[ epoxy group-containing copolymer (P1) ]
The monomer (M1) for forming the epoxy group-containing copolymer (P1) (hereinafter, also referred to simply as "copolymer (P1)") according to the resin (D) of the present embodiment contains an epoxy group-containing ethylenically unsaturated compound (M-1) and at least 1 selected from a polymerizable monomer (M-3) having a bridged hydrocarbon group having 10 to 20 carbon atoms and a polymerizable monomer (M-4) represented by the following general formula (4). The monomer (M1) may further include an aromatic ring-containing polymerizable monomer (M-5), another polymerizable monomer (M-6), and the like. By further having a polymerizable monomer (m-5) having an aromatic ring, an 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, may be simply referred to as "monomer (m-1)") is not particularly limited as long as it is a monomer having an epoxy group and an ethylenically unsaturated group, but not having a carboxyl group. Specific examples thereof include glycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and lactone adducts thereof (for example, サイクロマー (registered trademark) A200 and M100 manufactured by ダイセル chemical , Inc.), mono (meth) acrylate of 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexane carboxylate, epoxide of dicyclopentenyl (meth) acrylate, epoxide of dicyclopentenyloxyethyl (meth) acrylate, and the like. These epoxy group-containing ethylenically unsaturated compounds (m-1) may be used alone, or 2 or more kinds may be used. In particular, glycidyl (meth) acrylate is suitable from the viewpoint of ease of availability and good reactivity.
In order to impart a photosensitive group exhibiting photocurability, a structural unit derived from an epoxy group-containing ethylenically unsaturated compound (m-1) and a carboxyl group-containing ethylenically unsaturated compound (m-2) described below are essential components in the resin (D) according to one embodiment of the present invention. By introducing a photosensitive group exhibiting photocurability, a cured film having sufficient hardness and high solvent resistance is exhibited.
[ polymerizable monomer (m-3) ]
The polymerizable monomer (m-3) (hereinafter, also referred to simply as "monomer (m-3)") has a bridged hydrocarbon group having 10 to 20 carbon atoms. Here, the bridged hydrocarbon refers to a substance having a structure represented by the following formula (1) or (2), such as adamantane or norbornane, and the bridged hydrocarbon group refers to a group corresponding to a remaining part of the structure after a part of hydrogen has been removed. The polymerizable monomer (m-3) does not include the polymerizable monomer (m-4) described later.
Figure BDA0003077445230000151
(in the formula (1), A, B represents a straight-chain or branched alkylene group (including cyclic groups), R3 represents a hydrogen atom or a methyl group, A, B may be the same or different, and A, B may be cyclic by linking the branches thereof.)
Figure BDA0003077445230000152
(in the formula (2), A ', B' and D each represent a linear or branched alkylene group (including a cyclic group), and R4 represents a hydrogen atom or a methyl group
The monomer (m-3) is preferably a (meth) acrylate having a bridged hydrocarbon group having 10 to 20 carbon atoms, and more preferably an adamantyl (meth) acrylate or a (meth) acrylate having a structure represented by the following formula (3).
Figure BDA0003077445230000153
(in the formula (3), R5 to R7 each represent a hydrogen atom or a methyl group, R8 and R9 each represent a hydrogen atom or a methyl group, or may be bonded to each other to form a saturated or unsaturated ring, preferably a 5-or 6-membered ring, which represents a bond to a (meth) acryloyloxy group.)
Examples of the monomer (m-3) include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate. These may be used alone or in combination of 2 or more.
[ polymerizable monomer (m-4) ]
The polymerizable monomer (m-4) (hereinafter, also referred to simply as "monomer (m-4)", in some cases) is a monomer represented by the following general formula (4).
Figure BDA0003077445230000161
(in the formula (4), X and X' independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, R1 and R2 independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R1 and R2 may be bonded to each other to form a cyclic structure.)
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' in the general formula (4) which represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. Examples of the substituent of the optionally substituted hydrocarbon group having 1 to 20 carbon atoms represented by R1 and R2 include an alkoxy group and an aryl group. Examples of R1 and R2 include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a tert-pentyl group, a stearyl group, a lauryl group, and a 2-ethylhexyl group; alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; an alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; and an alkyl group substituted with an aryl group such as a phenylalkyl group.
Examples of the monomer (m-4) having a chemical structure represented by the general formula (4) include norbornene (bicyclo [2.2.1]]Hept-2-ene), 5-methylbicyclo [2.2.1]Hept-2-ene, 5-ethylbicyclo [2.2.1]]Hept-2-ene, tetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, 8-methyltetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, 8-ethyltetracyclo [4.4.0.12,5.17,10]Dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.02,6]Dec-8-ene, tricyclo [5.2.1.02,6]Dec-3-ene, tricyclo [4.4.0.12,5]Undec-3-ene, tricyclo [6.2.1.01,8]Undec-9-ene, tricyclo [6.2.1.01,8]Undec-4-ene, tetracyclo [4.4.0.12,5.17,10.01,6]Dodec-3-ene, 8-methyltetracyclo [4.4.0.12,5.17,10.01,6]Dodec-3-ene, 8-ethylidene tetracyclo [4.4.0.12,5.17,12]Dodec-3-ene, 8-ethylidene tetracyclo [4.4.0.12,5.17 ,10.01,6]Dodec-3-ene, pentacyclic [6.5.1.1 ]3,6.02,7.09,13]Pentadec-4-ene, pentacyclic [7.4.0.1 ]2,5.19,12.08 ,13]Pentadecen-3-ene, and the like. These may be used alone or in combination of 2 or more.
By using the above monomer (m-3) and/or the above monomer (m-4), smooth coatability, high thermal decomposition resistance and high thermal yellowing resistance of the cured film are facilitated. The decrease in the solubility of the copolymer in the solvent can be suppressed. One or both of the monomer (m-3) and the monomer (m-4) may be used.
[ polymerizable monomer (m-5) containing aromatic Ring ]
The aromatic ring-containing polymerizable monomer (m-5) (hereinafter, also referred to simply as "monomer (m-5)") is a monomer having an aromatic ring without a carboxyl group or an epoxy group. Examples thereof include aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetamidostyrene; benzyl (meth) acrylate, rosin (meth) acrylate, phenyl (meth) acrylate, cumyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate (trade name: ライトアクリレート P-200A, product of Kyoritsu chemical Co., Ltd.), nonylphenoxy polyethylene glycol mono (meth) acrylate, o-phenoxybenzyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, P-phenoxybenzyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, diphenoxyethyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, naphthyl (meth) acrylate, and anthracenyl (meth) acrylate. Among them, from the viewpoint of elastic recovery, it is more preferable to introduce at least 1 structural unit selected from benzyl (meth) acrylate, styrene, a biphenyl skeleton, a naphthalene skeleton, and an anthracene skeleton into the resin (D) used in the present invention.
[ other polymerizable monomer (m-6) ]
The epoxy group-containing copolymer (P1) according to the present embodiment may be obtained by copolymerizing a polymerizable monomer (m-6) (hereinafter, may be simply referred to as "monomer (m-6)") other than the monomers (m-1) to (m-5). The other polymerizable monomer (m-6) is a copolymerizable monomer other than the monomers (m-1), (m-3), (m-4), (m-5) and (m-2). The monomer (m-6) is generally a radical polymerizable compound having an ethylenically unsaturated group. Examples of the monomer (m-6) include (meth) acrylates, (meth) acrylamides, maleimides, unsaturated dicarboxylic diesters, dienes such as butadiene, and the like. Specific examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, rosin (meth) acrylate, allyl (meth) acrylate, and mixtures thereof, Tetrahydrofurfuryl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, and the like. Specific examples of the (meth) acrylamide include (meth) acrylamide, N-dimethylamide (meth) acrylate, N-diethylamide (meth) acrylate, N-dipropylamide (meth) acrylate, N-di-isopropylamide (meth) acrylate, anthracylamide (meth) acrylate, and the like. Specific examples of the maleimide compound include vinyl compounds such as (meth) acrylanilide, (meth) acryloylnitrile, acrolein, vinyl chloride, 1-dichloroethylene, vinyl fluoride, 1-difluoroethylene, N-vinylpyrrolidone and vinyl acetate; n-cyclohexylmaleimide, N-laurylmaleimide, etc. Specific examples of the unsaturated dicarboxylic acid diester include diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate and the like. These may be used alone or in combination of 2 or more, as required.
[ ratio of structures derived from respective monomers of the epoxy group-containing copolymer (P1) ]
In the copolymer (P1) according to the present invention, when the monomer (M1) comprises the monomer (M-1) and, if necessary, comprises the monomer (M-3), the monomer (M-4) or the monomer (M-5), the ratio derived from the structures of the monomers is determined by using the molar ratio of the polymerizable monomers added for the copolymerization reaction. The blending ratio (molar ratio) of the monomers is not particularly limited, but the blending ratio of the monomer (m-1) is preferably 9 to 70 mol%, more preferably 13 to 65 mol%. When the compounding ratio of the monomer (m-1) is 9 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is produced. When the compounding ratio of the monomer (m-1) is 70 mol% or less, the compounding ratio of the monomer (m-3) and/or the monomer (m-4) becomes sufficiently large, and a resin (D) having a desired thermal decomposition resistance and refractive index is obtained.
When the monomer (M-3) and/or the monomer (M-4) is used, the compounding ratio thereof is preferably more than 0 mol% to 40 mol%, more preferably more than 0 mol% to 30 mol%, based on 100 mol% of the total amount of the monomers (M1) of the epoxy group-containing copolymer (P1). When the compounding ratio is 1 mol% or more, the desired thermal decomposition resistance, thermal yellowing resistance, and good solubility in a solvent are obtained.
When the monomer (M-5) is used, the compounding ratio thereof is preferably more than 0 mol% to 50 mol%, more preferably more than 0 mol% to 40 mol%, based on 100 mol% of the total amount of the monomers (M1) of the epoxy group-containing copolymer (P1).
When the monomer (M-6) is used, the compounding ratio thereof is preferably more than 0 mol% to 10 mol%, more preferably more than 0 mol% to 5 mol%, based on 100 mol% of the total amount of the monomers (M1) of the epoxy group-containing copolymer (P1).
[ copolymerization reaction (method for producing epoxy group-containing copolymer (P1) ]
The epoxy group-containing copolymer (P1) according to the present invention can be produced by copolymerization 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, the monomer used for copolymerization may be dissolved in a solvent, and then a polymerization initiator may be added to the solution to react at 50 to 140 ℃, more preferably 60 to 130 ℃ for 1 to 20 hours, still more preferably 1 to 12 hours. Further, the reaction may be carried out while dropping the monomer and the polymerization initiator used for the copolymerization in a solvent adjusted to 50 to 140 ℃.
The solvent that can be used in the copolymerization reaction is not particularly limited as long as it is a substance that is inactive to radical polymerization, and a commonly used organic solvent can be used.
The copolymerization solvent used was the above-mentioned No. 2 solvent (B2).
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, based on 100 parts by mass of the total amount of the monomers used in the copolymerization. In particular, by setting the amount of the solvent to 1000 parts by mass or less, the viscosity of the copolymer (P1) can be controlled within an appropriate range while suppressing the decrease in the molecular weight of the copolymer (P1) by chain transfer. Further, by setting the amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented, polymerization reaction can be stably performed, and coloring and gelation of the copolymer (P1) can be prevented.
The polymerization initiator that can be used in the 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. Specific examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), azobis (2-methylpropionate) dimethyl ester, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, and 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate.
These may be used alone or in combination of 2 or more, and it is desirable to select a radical polymerization initiator having an appropriate half-life depending on the polymerization temperature.
The amount of the polymerization initiator to be used in the copolymerization reaction is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers to be used in the copolymerization reaction.
[ epoxy resin (P3) ]
The epoxy resin (P3) used in the present embodiment is preferably selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a 2-functional epoxy resin having a biphenyl skeleton (P3-3).
Examples of the novolak type epoxy resin (P3-1) include cresol novolak type epoxy resins, phenol novolak type epoxy resins, and the like. These novolak-type epoxy resins may be used alone, or 2 or more kinds may be used.
Examples of the bisphenol epoxy resin (P3-2) include bisphenol a epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin. These bisphenol type epoxy resins may be used alone, or 2 or more kinds may be used. Among them, bisphenol a type epoxy resins are preferable from the viewpoint of availability and reactivity.
The 2-functional epoxy resin having a biphenyl skeleton (P3-3) is not particularly limited as long as it has a biphenyl skeleton in the molecule and 2 epoxy groups. Examples of the biphenyl skeleton include those represented by the following formula (5).
Figure BDA0003077445230000211
In the formula (5), R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and E, E' each independently represents an organic group having an epoxy group.
Specific examples of the 2-functional epoxy resin having a biphenyl skeleton include YX4000 manufactured by Mitsubishi ケミカル (in the following formula (6), R' is CH)3) YX4000K (in the following formula (6), R' is CH3) YX4000H (in the following formula (6), R' is CH3) YL6121HA (in the following formula (6), a compound wherein R 'is H and R' is CH3Mixtures of compounds of (a) and the like.
Figure BDA0003077445230000212
[ second embodiment ]
In a second embodiment of the carbon cluster-containing composition of the present invention (hereinafter, may be referred to as "the composition of the present embodiment"), the carbon cluster (a), the 1 st solvent (B1), the 2 nd solvent (B2), the ethylenically unsaturated group-containing monomer (C), and the resin (D) are contained. Wherein the ethylenically unsaturated group-containing monomer (C) is an epoxy group-containing ethylenically unsaturated compound (m-1). The resin (D) is a carboxyl group-containing copolymer (P2) or a carboxyl group-containing resin (P4).
The carbon cluster (a), the 1 st solvent (B1), and the 2 nd solvent (B2) can be the same as those used in the first embodiment.
The carboxyl group-containing copolymer (P2) or the carboxyl group-containing resin (P4) is subjected to ring-opening addition with the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1) to generate a hydroxyl group. It is preferable that the polybasic acid anhydride (d) is further added to the hydroxyl group to obtain an ethylenically unsaturated resin (a2) or (a4) as a resin having an ethylenically unsaturated group to be described later.
As the epoxy group-containing ethylenically unsaturated compound (m-1) and the polybasic acid anhydride (d), the same ones as those described in the first embodiment can be used. The proportion of the epoxy group-containing ethylenically unsaturated compound (m-1) added to the carboxyl group-containing copolymer (P2) is preferably 90 to 100%, more preferably 95 to 100%, based on the number of moles of carboxyl groups. When the addition ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is 90% or more, sufficient curability can be exhibited when the photosensitive resin composition is produced.
When the total amount of all the monomers (M2) used in the epoxy group-containing copolymer (P2) is 100 mol%, the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (M-1) is preferably 10 to 70 mol%, more preferably 15 to 65 mol%. When the compounding 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 produced.
[ carboxyl group-containing copolymer (P2) ]
All the monomers (M2) of the carboxyl group-containing copolymer (P2) (hereinafter, also referred to simply as "copolymer (P2)") relating to the resin (D) of the present embodiment contain at least an ethylenically unsaturated compound (M-2) containing a carboxyl group, and may further contain, if necessary, a polymerizable monomer (M-3) having a bridged hydrocarbon group having 10 to 20 carbon atoms, a polymerizable monomer (M-4) represented by the above general formula (4), a polymerizable monomer (M-5) containing an aromatic ring, another polymerizable monomer (M-6), and the like.
The carboxyl group-containing ethylenically unsaturated compound (m-2), polymerizable monomer (m-3), polymerizable monomer (m-4), aromatic ring-containing polymerizable monomer (m-5), and other polymerizable monomer (m-6) according to the present embodiment are the same as those described in the first embodiment, and the description thereof will be omitted.
[ ratio of structures derived from monomers of the carboxyl group-containing copolymer (P2) ]
In the copolymer (P2) according to the present invention, when all the monomers (M2) include the carboxyl group-containing ethylenically unsaturated compound (M-2) and, if necessary, further include the polymerizable monomer (M-3) having a bridged hydrocarbon group having 10 to 20 carbon atoms, the polymerizable monomer (M-4) represented by the above general formula (4), the aromatic ring-containing polymerizable monomer (M-5), and the like, the ratio derived from the structure of each monomer is used as the value of the molar ratio of the polymerizable monomers added for copolymerization. The blending ratio (molar ratio) of the monomers is not particularly limited, but when the total of all the monomers (M2) is 100 mol%, the blending ratio of the monomer (M-2) is preferably 9 to 70 mol%, more preferably 13 to 65 mol%. When the compounding ratio of the monomer (m-2) is 9 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is produced. When the compounding ratio of the monomer (m-2) is 70 mol% or less, the compounding ratio of the monomer (m-3), the monomer (a-4) and the monomer (m-5) becomes sufficiently large, and the resin (D) having a desired thermal decomposition resistance is obtained.
When the monomer (M-3) and/or the monomer (M-4) is used, the compounding ratio thereof is preferably more than 0 mol% to 40 mol%, more preferably more than 0 mol% to 30 mol%, based on 100 mol% of the total amount of all the monomers (M2) in the copolymer (P2). When the compounding ratio is 1 mol% or more, the desired thermal decomposition resistance, thermal yellowing resistance, and good solubility in a solvent are obtained.
When the monomer (M-5) is used, the compounding ratio thereof is preferably more than 0 mol% to 50 mol%, more preferably more than 0 mol% to 40 mol%, based on 100 mol% of the total amount of all the monomers (M2) in the copolymer (P2).
When the monomer (M-6) is used, the compounding ratio thereof is preferably more than 0 mol% to 10 mol%, more preferably more than 0 mol% to 5 mol%, based on 100 mol% of the total amount of all the monomers (M2) in the epoxy group-containing copolymer (P2).
[ copolymerization reaction (Process for producing carboxyl group-containing copolymer (P2) ]
The carboxyl group-containing copolymer (P2) according to the present invention can be produced by a copolymerization reaction in the same manner as the copolymer (P1) according to the first embodiment.
[ carboxyl group-containing resin (P4) ]
The carboxyl group-containing resin (P4) used in the present embodiment is a carboxyl group-containing resin obtained by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e).
The epoxy resin (P3) used in the first embodiment (P3) can be used.
[ polyfunctional Carboxylic acid (e) ]
The polyfunctional carboxylic acid (e) is not particularly limited. Any of saturated and unsaturated polyfunctional carboxylic acids may be used. 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 2 or more species may be used. Among them, adipic acid and itaconic acid are preferable from the viewpoint of reactivity.
[ ratio of structural units of the carboxyl group-containing resin (P4) ]
The carboxyl group-containing resin (P4) preferably contains 30 to 80 mass% of a structural unit derived from the epoxy resin (P3) and 20 to 70 mass% of a structural unit derived from the polyfunctional carboxylic acid (e). The molar ratio of the structural unit derived from the polyfunctional carboxylic acid (e) to the structural unit derived from the epoxy resin (P3) in the carboxyl group-containing resin (P4) is preferably 0.1 to 0.8, more preferably 0.15 to 0.7.
[ method for producing carboxyl group-containing resin (P4) ]
The carboxyl group-containing resin (P4) used in the present embodiment can be produced, for example, by an addition reaction of an epoxy resin (P3) and a polyfunctional carboxylic acid (e) in the presence of an addition catalyst.
The conditions for obtaining the addition reaction of the carboxyl group-containing resin (P4) used in the present embodiment may be appropriately set according to a conventional method. The addition reaction may be carried out, for example, in an atmosphere containing 5 to 7 vol% of oxygen, preferably 50 to 150 ℃, more preferably 60 to 140 ℃ for 1 to 12 hours, by adding each raw material and an addition catalyst to a solvent.
The solvent that can be used in the addition reaction is not particularly limited, and a known solvent can be suitably used. For example, a solvent used in the addition reaction of the first embodiment may be used.
The addition catalyst that can be used in the addition reaction is not particularly limited, and a known catalyst can be suitably used. For example, the catalyst used for the addition reaction of the first embodiment may be used.
[ third embodiment ]
In a third embodiment of the composition containing a carbon cluster of the present invention (hereinafter, may be referred to as "the composition of the present embodiment"), the carbon cluster (a), the 1 st solvent (B1), the 2 nd solvent (B2), and the resin (D) are contained. Wherein the resin (D) is an ethylenically unsaturated resin (A1) or an ethylenically unsaturated resin (A3).
The carbon cluster (a), the 1 st solvent (B1), and the 2 nd solvent (B2) can be the same as those used in the first embodiment.
The ethylenically unsaturated resin (a1) is obtained using a resin (D) precursor comprising a monomer composed of a carboxyl group-containing ethylenically unsaturated compound (m-2) and, if necessary, a polybasic acid anhydride (D), and an epoxy group-containing copolymer (P1). Further, the ethylenically unsaturated resin (a3) is obtained using a resin (D) precursor containing a monomer composed of a carboxyl group-containing ethylenically unsaturated compound (m-2) and, if necessary, a polybasic acid anhydride (D), and an epoxy resin (P3). That is, the ethylenically unsaturated resin (a1) and the ethylenically unsaturated resin (A3) are resins containing an ethylenically unsaturated group and, if necessary, a carboxyl group. As the above-mentioned components of the precursor of the resin (D) used in the present embodiment, those used in the first embodiment can be used.
[ Process for producing ethylenically unsaturated resin (A1) or ethylenically unsaturated resin (A3) ]
The ethylenically unsaturated resin (a1) or the ethylenically unsaturated resin (A3) can be produced, for example, by adding the carbon cluster (a) as a polymerization inhibitor and a catalyst to a solution of the epoxy group-containing copolymer (P1) or the epoxy resin (P3), adding the carboxyl group-containing ethylenically unsaturated compound (m-2), subjecting the epoxy group to a ring-opening addition reaction at 50 to 150 ℃, preferably 80 to 130 ℃, and adding the polybasic acid anhydride (d) as needed to perform an addition reaction.
When the carboxyl group-containing ethylenically unsaturated compound (m-2) is reacted, there is no particular problem even if the solvent used for producing the epoxy group-containing copolymer (P1) or the epoxy resin (P3) is contained, and therefore the reaction can be carried out without removing the solvent after the reaction for obtaining the epoxy group-containing copolymer (P1) or the epoxy resin (P3) is completed. Here, the polymerization inhibitor is added to prevent gelation caused by polymerization of the introduced double bond.
[ solvent used in addition reaction ]
The solvent used in the present embodiment is not particularly limited, and a known solvent can be suitably used. The above-mentioned 2 nd solvent (B2) can be used.
[ catalyst ]
Examples of the catalyst used in the present embodiment include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelates. These catalysts may be used alone, or 2 or more of them may be used in combination.
The amount of the catalyst used in the present embodiment is not particularly limited, but is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass, based on 100 parts by mass of the resin precursor.
[ fourth embodiment ]
In a fourth embodiment of the composition containing carbon clusters according to the present invention (hereinafter, may be referred to as "the composition of the present embodiment"), the carbon clusters (a), the 1 st solvent (B1), the 2 nd solvent (B2), and the resin (D) are contained. Wherein the resin (D) is an ethylenically unsaturated resin (A2) or an ethylenically unsaturated resin (A4).
The carbon cluster (a), the 1 st solvent (B1), and the 2 nd solvent (B2) can be the same as those used in the first embodiment.
The ethylenically unsaturated resin (a2) is an ethylenically unsaturated group-containing resin obtained using a precursor comprising an epoxy group-containing ethylenically unsaturated compound (m-1), and a carboxyl group-containing copolymer (P2) or a carboxyl group-containing resin (P4). As the above-mentioned components of the precursor of the resin (D) used in the present embodiment, those used in the second embodiment can be used.
[ Process for producing ethylenically unsaturated resin (A2) or ethylenically unsaturated resin (A4) ]
The ethylenically unsaturated resin (a2) or the ethylenically unsaturated resin (a4) can be produced by, for example, adding a carbon cluster (a) as a polymerization inhibitor and a catalyst to a solution of the carboxyl group-containing copolymer (P2) or the carboxyl group-containing resin (P4), adding an epoxy group-containing ethylenically unsaturated compound (m-1), and subjecting the epoxy group to a ring-opening addition reaction at 50 to 150 ℃, preferably 80 to 130 ℃.
In the reaction of the epoxy group-containing ethylenically unsaturated compound (m-1), there is no particular problem even if the solvent used for the production of the above carboxyl group-containing copolymer (P2) or carboxyl group-containing resin (P4) is included, and therefore the reaction can be carried out without removing the solvent after the reaction for obtaining the carboxyl group-containing copolymer (P2) or carboxyl group-containing resin (P4) is completed. Here, the polymerization inhibitor is added to prevent gelation caused by polymerization of the introduced double bond.
The carbon cluster (a) and the catalyst of the present embodiment may be those used in the first embodiment.
[ solvent used in addition reaction ]
The solvent used in the present embodiment is not particularly limited, and a known solvent can be suitably used. The above-mentioned 2 nd solvent (B2) can be used.
[ fifth embodiment ]
In a fifth embodiment of the composition containing carbon clusters according to the present invention (hereinafter, may be referred to as "the composition of the present embodiment"), the carbon clusters (a), the 1 st solvent (B1), the 2 nd solvent (B2), and the resin (D) are contained.
The carbon cluster (a), the 1 st solvent (B1), and the 2 nd solvent (B2) can be the same as those used in the first embodiment, and particularly, the 2 nd solvent (B2) is preferably tetrahydrofuran.
Specific examples of the resin (D) include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethane resins, polyalkylene resins, polyvinyl chloride, polystyrene, polyvinyl acetate, (meth) acrylic resins, and epoxy ester resins. As the resin (D) used in the present embodiment, commercially available one can be used.
Process for producing composition containing carbon clusters "
One embodiment of the method for producing the carbon cluster-containing composition of the present invention comprises the steps of: a step (I) for obtaining a carbon cluster dispersion liquid (I) by mixing a carbon cluster (A) and a1 st solvent (B1) selected from an aromatic solvent and a halogen-containing solvent; a step (II) of mixing a monomer (C) and/or a resin (D) in a2 nd solvent (B2) other than the 1 st solvent (B1) to obtain a solution (II); and a step (III) of mixing the solution (ii) with the carbon cluster dispersion liquid (i). In the step (III), it is preferable to add and mix the carbon cluster dispersion liquid (i) to the solution (ii).
In another embodiment of the method for producing a composition containing carbon clusters according to the present invention, the method further comprises a step (V) of performing a polymerization reaction of the monomer or an addition reaction of the resin and the monomer in addition to the above embodiments.
[ photosensitive resin composition ]
The composition containing carbon clusters of the present invention can be used as a photosensitive resin composition by further comprising a reactive diluent (E) and a photopolymerization initiator (F). A colorant (G) may be further contained.
When the total of the components excluding all solvents in the composition is 100 parts by mass, the blending amount of the 1 st solvent (B1) and the 2 nd solvent (B2) in the carbon cluster-containing composition for a photosensitive resin composition is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, and more preferably 100 to 700 parts by mass. When the compounding amount is within this range, the photosensitive resin composition can be used as a photosensitive resin composition having an appropriate viscosity.
The amount of the reactive diluent (E) in the carbon cluster-containing composition for a photosensitive resin composition is generally 10 to 90 mass%, preferably 20 to 80 mass%, and more preferably 25 to 70 mass%, assuming that the total of the components excluding all solvents in the composition is 100 mass%.
When the compounding amount is within this range, the photosensitive resin composition has an appropriate viscosity, and the photosensitive resin composition has an appropriate photocurability.
[ reactive diluent (E) ]
The reactive diluent (E) is not particularly limited, but is preferably a substance containing an ethylenically unsaturated double bond, preferably a vinyl group and a (meth) acryloyloxy group. Specific examples thereof include aromatic vinyl monomers such as styrene, α -methylstyrene, α -chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate and diallyl phenylphosphonate; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; (meth) acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β -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 tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate (for example, dipentaerythritol hexaacrylate (DPHA) manufactured by shinkamura chemical industries, ltd.), tri (meth) acrylate of tris (hydroxyethyl) isocyanurate, and the like; triallyl cyanurate, and the like. These may be used alone, or in combination of 2 or more.
[ photopolymerization initiator (F) ]
The photopolymerization initiator (F) is not particularly limited, and specific examples thereof include benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone and 4- (1-tert-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, 4- (1-tert-butyldioxy-1-methylethyl) benzophenone, and 3,3 ', 4, 4' -tetrakis (tert-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; acylphosphine oxides; and xanthones, and the like. These may be used alone, or in combination of 2 or more. For example, イルガキュア (IRGACURE) OXE-01 manufactured by BASF corporation can be used.
The amount of the photopolymerization initiator (F) blended in the photosensitive resin composition of the present embodiment is generally 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass, assuming that the total of the components excluding all solvents in the photosensitive resin composition is 100 parts by mass. When the compounding amount is within this range, a photosensitive resin composition having appropriate photocurability is obtained.
[ colorant (G) ]
The solvent is not particularly limited as long as it is dissolved or dispersed in the solvent 2 (B2), and a known dye or pigment can be used. In the case of using a dye as the colorant (G), a colored pattern of high brightness can be obtained as compared with the case of using a pigment, and further, good alkali developability is exhibited. On the other hand, in the case of using a pigment as the colorant (G), the heat resistance of the colored pattern is higher than that in the case of using a dye. Dyes and pigments may be used in combination according to the required performance, the color of the pixel as the object.
"dyes"
As the dye, an acid dye having an acid group such as a carboxyl group, a salt of an acid dye and a nitrogen compound, a sulfonamide compound of an acid dye, or the like is preferably used from the viewpoints of solubility in the solvent (B) or an alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, and 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, 92, 112, 113, 120, 129, 147; acid chromium violet K; acid fuchsin; acid green 1,3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1,3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and their derivatives, and the like.
Among them, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These dyes may be used alone or in combination of 2 or more depending on the color of the pixel as a target.
"pigments"
Specific examples of the pigment include yellow pigments such as c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, etc. blue pigments; c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment; green pigments such as c.i. pigment green 7, 36, 58; c.i. brown pigments such as pigment brown 23, 25; c.i. pigment black 1, 7, carbon black, titanium black, iron oxide, and other black pigments. These pigments may be used alone or in combination of 2 or more depending on the color of the pixel as a target.
The amount of the colorant (G) blended in the photosensitive resin composition of the present embodiment is generally 5 to 80 parts by mass, preferably 5 to 70 parts by mass, and more preferably 10 to 60 parts by mass, assuming that the total of the components excluding all solvents in the photosensitive resin composition is 100 parts by mass.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In this example, all parts and% are on a mass basis unless otherwise specified.
[ Synthesis example 1]
Soot-like substances "
Toluene and pure oxygen were mixed in a ratio of 3: the coal was supplied to the reaction tube in the embodiment 1, mixed, and heated at 67hPa and 180 ℃ to obtain coal. Subsequently, washing was performed 2 times with toluene to obtain a soot-like substance.
[ example 1]
8.9g of trimethylbenzene and 0.18g of fullerene (manufactured by フロンティアカーボン, nanom (registered trademark) mix ST, C60/C70 ═ 60/25) were mixed to obtain a carbon cluster dispersion (i).
Subsequently, 137.5g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while being purged with nitrogen, and the temperature was raised to 120 ℃. Subsequently, 13.3g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, パーブチル (registered trademark) O, manufactured by Nichikoku corporation) was added to a monomer mixture comprising 141.7g (1.00 mol) of glycidyl methacrylate, 4.7g (0.02 mol) of tricyclodecanyl methacrylate, and 5.0g (0.05 mol) of styrene, and the mixture was dropped from a funnel over 2 hours into the flask.
After completion of the dropwise addition, the mixture was further stirred at 120 ℃ for 2 hours to effect copolymerization reaction, thereby producing an epoxy group-containing copolymer (P1) solution. To this, 72.0g of acrylic acid as the monomer (m-2) and 0.66g (0.3 part by mass) of triphenylphosphine as a catalyst were added to obtain a solution (ii).
The carbon cluster dispersion liquid (i) is added to and mixed with the solution (ii), to obtain a resin solution as the carbon cluster-containing composition of the first embodiment.
The resin solution obtained above is heated at 110 ℃ for 10 hours while blowing low-oxygen air into which nitrogen gas is injected so that the oxygen concentration becomes 4 to 7 vol%. A resin solution was obtained as the composition containing carbon clusters of the third embodiment described above.
Then, it was confirmed that the acid value was 1.0KOHmg/g or less, and 15.6g of tetrahydrophthalic anhydride was added to the mixture to react at 110 ℃ for 2 hours, thereby obtaining a resin solution having a solid content of 50 mass% (solid content acid value 32.4KOHmg/g, weight average molecular weight 9400).
The acid value (monomer remaining rate) in the reaction solution was measured to calculate the addition reaction rate of acrylic acid to the epoxy group, and the result was 99.1%.
Examples 2 to 3 and comparative examples 1 to 3
In example 2, the amount of fullerene (manufactured by フロンティアカーボン, nanom (registered trademark) mix ST, C60/C70 ═ 60/25) was changed, and in example 3, the amount was changed to the soot-like substance obtained in synthesis example 1. A resin solution as a composition containing carbon clusters was obtained in the same manner as in example 1, except that a slurry obtained by mixing fullerene and ethylene glycol was added instead of the fullerene solution, fullerene was directly added in a powder state, or BHT was added to the comparative example. The results are shown in table 1.
[ Table 1]
Figure BDA0003077445230000321
The meanings of the expressions in the table are shown below.
BHT: di-tert-butylhydroxytoluene
PGMEA: propylene glycol monomethyl ether acetate
TCDMA: tricyclodecanyl methacrylate
St: styrene (meth) acrylic acid ester
GMA: glycidyl methacrylate
TBO: peroxy-2-ethylhexanoic acid tert-butyl ester
MAA: methacrylic acid
THPA: tetrahydrophthalic anhydride
[ example 4]
A carbon cluster dispersion (i) was obtained in the same manner as in example 1.
Subsequently, 133.3g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while being purged with nitrogen, and the temperature was raised to 120 ℃.
Subsequently, 2.9g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by Nichikoku Kogyo, パーブチル (registered trademark) O) was added to a monomer mixture comprising 58.5g (0.68 mol) of methacrylic acid, 33.7g (0.15 mol) of tricyclodecyl methacrylate, and 3.0g (0.02 mol) of benzyl methacrylate, and the mixture was added dropwise from a funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120 ℃ for 2 hours to effect copolymerization reaction, thereby producing a carboxyl group-containing copolymer (P2) solution. To this, 35g of glycidyl methacrylate as the monomer (m-1) and 0.39g (0.3 part by mass) of triphenylphosphine as a catalyst were added to obtain a solution (ii).
The carbon cluster dispersion liquid (i) is added to and mixed with the solution (ii), thereby obtaining a resin solution of the carbon clusters according to the second embodiment.
The obtained resin solution was heated at 110 ℃ for 10 hours while blowing low-oxygen air into which nitrogen gas was injected so that the oxygen concentration became 4 to 7 vol%. A resin solution was obtained as the composition containing carbon clusters of the fourth embodiment.
Then, it was confirmed that the acid value was 72.0KOHmg/g or less, and a resin solution having a solid content concentration of 28.6 mass% was obtained (solid acid value 196.8KOHmg/g, weight average molecular weight 18500).
The reaction rate of the acid and the epoxy group was calculated by measuring the acid value in the reaction solution, and the result was 97.8%.
Examples 5 to 6 and comparative examples 4 to 6
In example 5, the amount of fullerene (nanom (registered trademark) mix ST, manufactured by フロンティアカーボン, C60/C70 ═ 60/25) was changed, and in example 6, fullerene was changed to a soot-like substance generated during fullerene synthesis. A resin solution as a composition containing carbon clusters was obtained in the same manner as in example 4, except that a slurry obtained by mixing fullerene and ethylene glycol was added instead of the fullerene solution, fullerene was directly added in a powder state, or BHT was added to the comparative example. The results are shown in table 2.
[ Table 2]
Figure BDA0003077445230000351
The meanings of the expressions in the table are shown below.
BZMA: methacrylic acid benzyl ester
Other expressions are the same as in table 1.
[ example 7]
64.6g of trimethylbenzene and 2g of fullerene (manufactured by フロンティアカーボン, nanom (registered trademark) mix ST, C60/C70 ═ 60/25) were mixed to obtain a carbon cluster dispersion liquid (i).
Then, 100g of the resin was dissolved in 500g of Tetrahydrofuran (THF) to obtain a solution (ii). The carbon cluster dispersion liquid (i) was added to and mixed with the solution (ii), and stirred at room temperature for 30 minutes to prepare a resin liquid as the composition containing carbon clusters according to the fifth embodiment.
Examples 8 to 10 and comparative examples 7 to 10
Examples 8 to 10 and comparative examples 7 to 10 were obtained by changing the method of adding the resin and the fullerene. The results are shown in table 3.
[ Table 3]
Figure BDA0003077445230000371
The acid value and the molecular weight of the ethylenically unsaturated resin contained in the synthesized ethylenically unsaturated resin composition were measured by the following methods.
[ measurement of acid value ]
The measurement was carried out according to JIS K69015.3.2 using a mixed indicator of bromothymol blue and phenol red. The number of mg of potassium hydroxide required for neutralizing the acidic component contained in 1g of the resin (D) as a solid component is referred to.
The solid content was measured as the residual heating content when the sample was heated at 130 ℃ for 2 hours.
[ measurement of weight average molecular weight (Mw) ]
The measurement was performed under the following conditions using Gel Permeation Chromatography (GPC) and converted to standard polystyrene.
Column: ショウデックス (registered trademark) LF-804+ LF-804 (manufactured by Showa Denko K.K.)
Column temperature: 40 deg.C
Sample preparation: 0.2% tetrahydrofuran solution of copolymer
Developing solvent: tetrahydrofuran (THF)
A detector: differential refractometer (ショウデックス (registered trademark) RI-71S) (manufactured by SHOWA DENKO K.K.)
Flow rate: 1mL/min
As shown in tables 1 to 2, although synthesis was possible even when the amount of carbon clusters as polymerization inhibitors was reduced in the examples, gelation occurred without inhibiting crosslinking of double bonds if the method of adding carbon clusters was changed or the amount of BHT was reduced in the comparative examples.
Examples 18 to 23 and comparative examples 11 to 12
On a glass substrate, the resins of examples 1 to 6 and comparative examples 3 and 6 were used, respectively, to prepare blended photosensitive resin compositions shown in table 4. The amounts of the resins in the tables are expressed as solid content values, and the total amount of the solvents included in the resin synthesis is expressed as "solvent" in the tables.
[ evaluation of resistance to thermal yellowing ]
On a glass substrate, using the photosensitive resin compositions of examples 18 to 23 and comparative examples 11 to 12, a coating film was formed by a spin coater so that the film thickness became 2.5 μm. The coating film thus produced was heated at 90 ℃ for 3 minutes to volatilize the solvent in the coating film. Next, the entire surface of the coating film is exposed to light (exposure amount 50 mJ/cm) using an ウシオ (manufactured by Ltd., マルチライト ML-251D/B) and an irradiation optical unit PM25C-1002) And photocuring the mixture. After irradiation, post-curing was carried out at 230 ℃ for 30 minutes. Resin cured film before and after post-curingThe absorbance at the maximum absorption wavelength was measured by using UV-1650PC, a UV spectrometer manufactured by SIMAZU, and Δ Eab was calculated. The results are shown in table 4.
The smaller Δ Eab, the less yellowing, and the better.
[ Table 4]
Figure BDA0003077445230000401
The meanings of the expressions in the table are shown below.
OXE-01: IRGACURE OXE-01, manufactured by BASF corporation
DPHA: dipentaerythritol hexaacrylate, manufactured by NONSHOUN CHEMICAL INDUSTRIAL CO., LTD
Examples 24 to 27 and comparative examples 11 to 14
[ evaluation of thermal yellowing resistance 2]
The resin liquids of examples 7 to 10 and comparative examples 7 to 10 were applied to a glass substrate, and a coating film was formed to have a film thickness of 2.5 μm by a spin coater. The coating film thus produced was heated at 90 ℃ for 3 minutes to volatilize the solvent in the coating film. Followed by 30 minutes post-curing at 230 ℃. The resin cured film before and after post-curing was measured for absorbance at the maximum absorption wavelength by using a UV spectrometer UV-1650PC manufactured by SIMAZU, and Δ Eab was calculated. For easy comparison, relative values based on the value of Δ Eab of example 24 were obtained for examples 24 to 25 and comparative examples 11 to 12, and relative values based on the value of Δ Eab of example 26 were obtained for examples 26 to 27 and comparative examples 13 to 14. The results are shown in table 5.
The smaller Δ Eab, the less yellowing, and the better.
[ Table 5]
Figure BDA0003077445230000421
As shown in tables 4 to 5, it is understood that in the examples, a cured product having excellent thermal yellowing resistance is obtained as compared with the comparative examples.

Claims (10)

1. A composition comprising carbon clusters, comprising:
a carbon cluster (A);
a1 st solvent (B1);
a2 nd solvent (B2); and
at least 1 selected from the group consisting of an ethylenically unsaturated group-containing monomer (C) and a resin (D),
the 1 st solvent (B1) is at least 1 solvent selected from the group consisting of aromatic solvents and halogen-containing solvents,
the 2 nd solvent (B2) is a solvent other than the aromatic solvent and the halogen-containing solvent.
2. The composition containing carbon clusters according to claim 1, wherein the carbon clusters (a) are fullerenes or derivatives thereof.
3. The composition containing carbon clusters according to claim 1 or 2, wherein the 1 st solvent (B1) is 1 or more selected from the group consisting of toluene, benzene, and trimethylbenzene.
4. The carbon cluster-containing composition according to any one of claims 1 to 3, wherein the 2 nd solvent (B2) is a glycol ether-based solvent.
5. The carbon cluster-containing composition according to any one of claims 1 to 4, which contains the monomer (C) and the resin (D),
the monomer (C) has a reactive group,
the resin (D) has a group capable of reacting with the reactive group of the monomer (C).
6. The carbon cluster-containing composition according to any one of claims 1 to 5, wherein the resin (D) is an unsaturated (meth) acrylic resin or an unsaturated epoxy ester resin.
7. The method for producing a carbon cluster-containing composition according to any one of claims 1 to 6, wherein the content of the carbon cluster (A) is 0.01 to 0.10 parts by mass relative to 100 parts by mass of the total of the monomer (C) and the resin (D).
8. A method for producing a carbon cluster-containing composition, comprising the steps of:
a first mixing step (I) of mixing a carbon cluster (a) with a1 st solvent (B1) to obtain a carbon cluster dispersion (I);
a second mixing step (II) of mixing at least 1 selected from the group consisting of the monomer (C) and the resin (D) with a2 nd solvent (B2) to obtain a solution (II); and
a third mixing step (III) of mixing the solution (ii) with the carbon cluster dispersion liquid (i).
9. The method for producing a composition containing carbon clusters according to claim 8, further comprising the following step (IV): carrying out a polymerization reaction of the monomer (C).
10. The method for producing a composition containing carbon clusters according to claim 8, further comprising the following step (V): performing an addition reaction of the monomer (C) having a reactive group and the resin (D) having a group capable of reacting with the reactive group of the monomer (C).
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