TW201610018A - Black composition - Google Patents

Abstract

The present invention provides a black composition containing carbon black which may be well dispersed, can colore black to a desired concentration, and can impart excellent heat resistance to a black molded article. Also provided is a method of manufacturing a black molded article using the black composition, and a black molded article made by the method. This invention relates to a compound composed of a black composition containing (A) substrate composition and (B) carbon black, to which (C) imidazole compound which produces a predetermined structure by means of heating is added, wherein the (B) carbon black uses polyamide acid as a dispersing agent for the dispersion process.

Description

Black composition

The present invention relates to a black composition containing carbon black, a method for producing a black molded body using the black composition, and a black molded body produced by the method.

Since the past, various resin compositions have been colored black, so carbon black is used as a colorant. The composition colored with carbon black can be used not only for printing or coating applications, but also as a material for forming a black matrix in various display panels or a light shielding material such as a black column spacer.

In general, carbon black is often used after being dispersed in a solvent such as an organic solvent using a dispersant. As a method of dispersing carbon black using a dispersing agent, a low molecular compound such as an organic dye derivative or a triazine derivative can be used as a dispersing agent, and an alcohol, a glycol solvent, a ketone, or an aprotic polar organic compound is known. A method of dispersing carbon black in an organic solvent such as a solvent (Patent Document 1). According to the method described in Patent Document 1, an organic solvent can be used as a dispersion medium to prepare a carbon black dispersion.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-2005-213405

[Summary of the Invention]

However, when carbon black is dispersed by the method described in Patent Document 1, it is difficult to disperse the carbon black well by a combination of a dispersing agent and an organic solvent. Further, in the method described in Patent Document 1, a black molded body comprising a black composition containing dispersed carbon black is used, and carbon black may be aggregated in the molded body. When carbon black is aggregated in the molded body, the molded body cannot be colored to a black color having a desired concentration.

Further, when the carbon black obtained by the method described in Patent Document 1 is used for the coloring of various compositions, the obtained black composition has a problem of poor heat resistance due to the use of a dispersant having poor heat resistance.

The present invention has been made in view of the above-mentioned problems, and it is intended to provide a black composition which contains a well-dispersed carbon black, can be colored in a black color having a desired concentration, and imparts excellent heat resistance to a black molded body. Moreover, the present invention has an object of providing a method for producing a black molded body using the black composition and a black molded article produced by the method.

The present inventors have found that containing (A) a substrate component and (B) A black composition of carbon black is added (C) a compound which produces an imidazole compound of a predetermined structure by heating, and is solved by using a dispersion-treated (B) carbon black by using polyglycine as a dispersing agent. The above problems further complete the present invention.

The first aspect of the present invention comprises (A) a substrate component, (B) carbon black and (C) by heating to produce formula (C1): (In the formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfonate group. A black composition of a compound of an imidazole compound represented by a phosphino group, a phosphinyl group, a phosphonate group or an organic group, and (B) a carbon black is a dispersion treatment using polylysine as a dispersing agent.

In a second aspect of the present invention, after the black composition of the first aspect is shaped into a predetermined shape, the formed black composition is heated to cause an imidazole compound of the formula (C1) to produce an imidazole compound by heating (C). A method of producing a black molded body which is subjected to heat treatment at a higher temperature.

The third aspect of the present invention relates to a black molded body produced by the method of the second aspect.

According to the present invention, it is possible to provide a black composition containing a carbon black which is well dispersed, a black color which is colored to a desired concentration, and which imparts excellent heat resistance. Further, according to the present invention, a method for producing a black molded body using the black composition and a black molded body produced by the method can be provided.

[Formation of the Invention]

≪Black composition ≫

The black composition is a compound containing (A) a substrate component, (B) carbon black, and (C) an imidazole compound having a predetermined structure by heating (hereinafter also referred to as (C) a thermal imidazole generator). The (B) carbon black contained in the black composition is subjected to dispersion treatment using polylysine as a dispersing agent. Hereinafter, the necessary or optional components which may contain a black composition will be described in order.

<(A) Substrate component>

(A) The base material component is a component which can be formed into a film shape or various three-dimensional three-dimensional shape for the black composition. (A) The base material component is not particularly limited as long as it can impart a desired shape to the black composition. As the base component of (A), a resin material made of a polymer compound or a reactive low molecular compound which generates a polymer compound by crosslinking by heating is used as a typical component.

〔Resin material〕

(A) Among the base material components, examples of the resin material include polyacetal resin, polyamide resin, polycarbonate resin, and polyester resin (polybutylene terephthalate, poly Ethylene terephthalate, polyarylate, etc., FR-AS resin, FR-ABS resin, AS resin, ABS resin, polyphenylene oxide resin, polyphenylene sulfide resin, polyfluorene Resin, poly-myrazine resin, polyetheretherketone resin, fluorine-based resin, polyimine resin, polyamidoximine resin, polyamine amine bismaleimide resin, polyether phthalimide resin, poly Benzooxazole resin, polybenzothiazole resin, polybenzimidazole resin, polyoxynoxy resin, BT resin, polymethylpentene, ultrahigh molecular weight polyethylene, FR-polypropylene, (meth)acrylic resin ( Polymethyl methacrylate, etc., and polystyrene.

[Reactive low molecular compound]

Among the base material components, a reactive low molecular compound which generates a polymer compound by crosslinking by heating, and a polyfunctional epoxy compound having two or more functional groups are mentioned. When the black composition containing a polyfunctional epoxy compound as a substrate component is heated to a predetermined temperature or higher, an epoxy compound having a polyfunctional epoxy compound can be obtained by the action of an imidazole compound which produces a thermal imidazole generator (C) described later. A black molded body having excellent heat resistance or mechanical properties crosslinked with each other.

The polyfunctional epoxy compound is not particularly limited as long as it is a bifunctional or higher epoxy compound. Examples of the polyfunctional epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and double 2-functional epoxy resin such as phenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; dimer acid glycidyl ester, and triglycidyl group Glycidyl ester type epoxy resin such as ester; tetraglycidylamino diphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl meta-xylylenediamine, and tetraglycidyl a glycidylamine type epoxy resin such as bisaminomethylcyclohexane; a heterocyclic epoxy resin such as triglycidyl isocyanurate; phloroglucin triglycidyl ether and trihydroxybiphenyl Triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[ 1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3-bis[4-[1-[4-(2,3- Epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]benzene a trifunctional epoxy resin such as oxy]-2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl Benzophenone, bisresorcinol tetraglycidyl ether, and four epoxypropoxy biphenyl tetrafunctional epoxy resin.

Further, the alicyclic epoxy compound is preferably a polyfunctional epoxy compound because it imparts a high hardness cured product. Specific examples of the alicyclic epoxy compound include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane and a double (3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methyl ring Hexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone denatured 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane Alkyl carboxylate, trimethyl caprolactone denatured 3,4-epoxycyclohexylmethyl-3', 4'-epoxy ring Hexane carboxylate, β-methyl-δ-valerol, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methyl bis (3, 4-epoxycyclohexane), bis(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethyl bis(3,4-epoxycyclohexanecarboxylate), epoxy ring Dioctyl hexahydrophthalate, di-2-ethylhexyl epoxide hexahydrophthalate, epoxy resin having a tricyclodecene oxide group or a compound represented by the following formula (a1) . Among the specific examples of the alicyclic epoxy compound, an alicyclic epoxy compound represented by the following formula (a1) is preferred from the viewpoint of imparting a high hardness cured product.

(In the formula (a1), Z is selected from the group consisting of a single bond, -O-, -O-CO-, -S-, -SO-, -SO ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ - a group of divalent groups of -CBr ₂ -, -C(CBr ₃ ) ₂ -, -C(CF ₃ ) ₂ -, and -R ^a19 -O-CO-, and R ^a19 is a carbon number of 1-8 The alkyl group, R ^a1 ~ R ^a18 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.

In the formula (a1), R ^a19 is an alkylene group having 1 to 8 carbon atoms, preferably a methyl group or an ethyl group.

When R ^a1 to R ^a18 are an organic group, the organic group is not particularly limited ^insofar as it does not impair the object of the present invention. The organic group may be a hydrocarbon group, or may be a group formed by a carbon atom and a halogen atom, or may also contain a carbon atom and a hydrogen atom, and also contain a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom. The basis of a hetero atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom and the like.

The organic group is a hydrocarbon group and a group formed by a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group and a carbon atom, an oxygen atom, and a halogen atom, and a carbon atom, a hydrogen atom, an oxygen atom, and The base of the halogen atom is preferred. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably from 1 to 20, preferably from 1 to 10, particularly preferably from 1 to 5.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n- Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-tridecyl, n-tetradecyl, n a chain alkyl group such as pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl; vinyl, 1- a chain-like alkenyl group such as a propylene group, a 2-n-propenyl group (allyl), a 1-n-butenyl group, a 2-n-butenyl group, and a 3-n-butenyl group; a cyclopropyl group; Cycloalkyl such as butyl, cyclopentyl, cyclohexyl, and cycloheptyl; phenyl, o-tolyl, m-tolyl, p-tolyl, α-naphthyl, β-naphthyl, biphenyl An aryl group such as -4-yl, biphenyl-3-yl, biphenyl-2-yl, anthracenyl, and phenanthryl; benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl An aralkyl group such as α-naphthylethyl or β-naphthylethyl.

Specific examples of the halogenated hydrocarbon group are a chloromethyl group, a dichloromethyl group, Trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, five Halogenated chain alkyl groups such as fluoropropyl, perfluorobutyl, and perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorodecyl, and perfluorodecyl; 2-chlorocyclo Halogenated cycloalkyl groups such as hexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl, and 4-bromocyclohexyl; 2-chloro Phenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl , 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4 Halogenated aryl group such as fluorophenyl; 2-chlorophenylmethyl, 3-chlorophenylmethyl, 4-chlorophenylmethyl, 2-bromophenylmethyl, 3-bromophenylmethyl, 4 a halogenated aralkyl group such as bromophenylmethyl, 2-fluorophenylmethyl, 3-fluorophenylmethyl or 4-fluorophenylmethyl.

Specific examples of the group formed by a carbon atom, a hydrogen atom, and an oxygen atom are a hydroxyl chain such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Alkyl; 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl hydroxycycloalkyl; 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3-di Hydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 3,4-dihydroxyphenyl, and 3,5-dihydroxyphenyl Hydroxyaryl; 2-hydroxyphenylmethyl, 3-hydroxyphenylmethyl, and 4-hydroxyphenylmethyl hydroxyarylalkyl; methoxy, ethoxy, n-propyloxy, iso Propyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy Base, n-octyloxy, 2-ethylhexyloxy, n-oxime Alkoxy, n-fluorenyloxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-ten a chain alkoxy group such as a hexaalkyloxy group, an n-heptadecyloxy group, an n-octadecyloxy group, an n-nonadecyloxy group, and an n-eicosyloxy group; Alkoxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy, and 3- Chain-like alkenyloxy group such as n-butenyloxy group; phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group An aryloxy group such as a phenyl group, a biphenyl-4-yloxy group, a biphenyl-3-yloxy group, a biphenyl-2-yloxy group, a decyloxy group, and a phenanthryloxy group; An arylalkyloxy group such as a oxy group, a phenethyloxy group, an α-naphthylmethyloxy group, a β-naphthylmethyloxy group, an α-naphthylethyloxy group, and a β-naphthylethyloxy group; Oxymethyl, ethoxymethyl, n-propyloxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propyloxyethyl, 3-methyl Oxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propyloxy-n-propyl, 4-methoxy-n- Alkoxyalkyl group, 4-ethoxy-n-butyl group, and 4-n-propyloxy-n-butyl group; methoxymethoxy, ethoxymethoxy, n- Propyloxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propyloxyethoxy, 3-methoxy-n-propyloxy 3-ethoxy-n-propyloxy, 3-n-propyloxy-n-propyloxy, 4-methoxy-n-butyloxy, 4-ethoxy-n Alkoxy alkoxy group such as -butyloxy group and 4-n-propyloxy-n-butyloxy group; 2-methoxyphenyl group, 3-methoxyphenyl group, and 4-methyl group Alkoxyaryl group such as oxyphenyl; 2-methoxyphenoxy, 3-methoxyphenoxy, and alkoxyaryloxy such as 4-methoxyphenoxy; , ethyl acetyl, propyl, butyl, pentylene, hexyl, gamma, octyl, sulfhydryl, and An aliphatic fluorenyl group such as a fluorenyl group; an aromatic fluorenyl group such as a benzamidine group, an α-naphthylmethyl group, and a β-naphthylmethyl group; a methoxycarbonyl group, an ethoxycarbonyl group, and an n-propyloxycarbonyl group; , n-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexylcarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-fluorenyloxycarbonyl, and n-fluorenyloxycarbonyl Alkoxycarbonyl; phenoxycarbonyl, α-naphthyloxycarbonyl, and aryloxycarbonyl such as β-naphthyloxycarbonyl; indolyloxy, ethoxylated, propyloxy, butylatedoxy Aliphatic fluorenyloxy group such as benzyl, pentyloxy, hexyloxy, hexyloxy, decyloxy, decyloxy, and decyloxy; benzhydryloxy An α-naphthylmethyloxy group and an aromatic mercaptooxy group such as a β-naphthylmethyloxy group.

R ^a1 to R ^{a18 are} each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. In particular, from the viewpoint of the hardness of the black molded body formed using the black composition, it is preferred that all of R ^a1 to R ^a18 are hydrogen atoms.

Among the alicyclic epoxy compounds represented by the formula (a1), specific examples of preferred compounds include the following compounds 1 and 2.

Further, as the (A) substrate component, a resin which generates an aromatic ring formation reaction in the molecule and/or a crosslinking reaction between molecules is preferably carried out by heating. (C) The hot imidazole generator is (A) a substrate component described later. Among them, an aromatic ring formation reaction in the molecule and/or a crosslinking reaction between molecules can be promoted by heating.

The aromatic ring forming reaction in the molecule causes the structure of the molecular chain constituting the resin to be straightened, and a black molded body having excellent heat resistance and mechanical properties can be easily obtained by using a black composition. The reaction which is preferable in the aromatic ring formation reaction in the molecule is, for example, a reaction represented by the following formulas (I) to (VI). Further, the reaction in the following formula is only an example of the reaction of forming an aromatic ring, and the structure of the resin which is formed by the heating of the aromatic ring in the molecule by heating as the component of the substrate (A) is not limited to the following formula. The structure of the precursor polymer shown.

The cross-linking reaction between molecules causes the molecular chains constituting the resin to crosslink each other to form a three-dimensional crosslinked structure. Therefore, when a resin containing a resin which generates a crosslinking reaction by heating is used as the black component of the (A) substrate component, a black molded article having excellent heat resistance and mechanical properties can be obtained.

The resin which generates a crosslinking reaction between molecules by heating is preferably a resin having a group selected from a hydroxyl group, a carboxylic anhydride group, a carboxyl group, and an epoxy group in the molecule. When a resin having a hydroxyl group is used, cross-linking occurs between the molecules contained in the resin by dehydration condensation between the hydroxyl groups by the action of the imidazole compound produced by the (C) thermal imidazole generator described later. use In the case of a resin having a carboxylic anhydride group, the carboxyl groups generated by the hydrolysis of the acid anhydride group cause the (I) imidazole compound produced by the thermal imidazole generator to undergo dehydration condensation and crosslinking. When a resin having a carboxyl group is used, the action of the imidazole compound produced by the (C) thermal imidazole generator causes cross-linking between the molecules contained in the resin by dehydration condensation between the carboxyl groups. When a resin having an epoxy group is used, the action of the imidazole compound produced by the (C) thermal imidazole generator causes crosslinking between the molecules contained in the resin by a polyaddition reaction between the epoxy groups.

As a resin which has a hydroxyl group in a molecule, a novolak resin is mentioned, for example. The novolac resin is not particularly limited. For the phenolic 1 molar, it is preferred that the condensing agent such as formaldehyde or formaldehyde is obtained by a condensation reaction under an acidic catalyst at a ratio of 0.5 to 1.0 mol. .

Examples of the phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, and 2,5-di Dimethyl phenols such as cresol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, etc. Ethylphenols, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, p-tert-butyl Alkyl phenols such as phenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone, hydroquinone Polyvalent phenols such as monomethyl ether, pyrogallol, and phloroglucin; alkyl polyvalent phenols such as alkyl resorcinol, alkyl catechol, alkyl hydroquinone (all of the foregoing alkyl groups) It is also a carbon number of 1 to 4), α-naphthol, β-naphthol, hydroxydiphenyl, bisphenol A, and the like. These phenols can be used individually or in combination of 2 or more types.

Among the phenols, m-cresol and p-cresol are also preferred. M-cresol and p-cresol are preferred. By adjusting the blending ratio of the two, various characteristics such as sensitivity and heat resistance of the photoresist can be adjusted. The compounding ratio of m-cresol to p-cresol is not particularly limited, and m-cresol/p-cresol = 3/7 to 8/2 (mass ratio) is preferred. When the ratio of m-cresol is less than the above lower limit, the sensitivity may be lowered, and when it exceeds the above upper limit, the heat resistance may be lowered.

Examples of the acidic catalyst used for the production of the novolak resin include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid, and organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and p-toluenesulfonic acid. Metal salts such as zinc acetate. These acidic catalysts can be used alone or in combination of two or more.

The mass average molecular weight of the novolak resin obtained by polystyrene conversion is preferably 1000 to 50,000 by gel permeation chromatography (GPC).

As a resin having a carboxylic anhydride group in a molecule, a copolymer obtained by polymerizing a monomer mixture having an unsaturated double bond by containing one or more monomers selected from the group consisting of maleic anhydride, citraconic anhydride, and itaconic anhydride Things are better. As such a polymer, a styrene-maleic acid copolymer is preferred.

a resin having a carboxyl group in a molecule, a resin obtained by hydrolyzing an acid anhydride group in a resin having a carboxylic acid anhydride group in the molecule, or a compound selected from the group consisting of (meth)acrylic acid, crotonic acid, maleic acid, and fumaric acid Further, one or more monomers of citraconic acid, mesaconic acid, and itaconic acid, and a copolymer obtained by polymerizing a mixture of monomers having an unsaturated double bond is preferred.

For an epoxy-containing tree having an epoxy group in the molecule The fat is described in detail later.

Among the compounds in which the aromatic ring formation reaction in the molecule is heated or the crosslinking reaction occurs between the molecules in this manner, since the black composition is easily formed into a black molded body having excellent heat resistance, polyglycine and polyphenylene are used. The oxazole precursor, the polybenzothiazole precursor, the polybenzimidazole precursor, the styrene-maleic acid copolymer, and the epoxy group-containing resin are preferred. The resin is carried out for these below.

[polyglycine]

Polylysine is a substrate component of a precursor of a polyimide resin. After the black composition is formed into a desired shape, the black composition is heated at a temperature higher than the temperature at which the imidazole compound (C) of the thermal imidazole generator described later is produced, and an imidazole compound is produced in the black composition. Therefore, when a black composition containing the polyamino acid as the (A) substrate component and (C) the thermal imidazole generator is used, the formation of polyfluorene from the poly-proline is promoted by the action of the imidazole compound produced by heating. The ring-closing reaction of the imine resin forms a black molded body having excellent heat resistance containing a polyimide resin having excellent heat resistance as a matrix.

The molecular weight of the polyamic acid is preferably 5,000 to 30,000 as the mass average molecular weight, and preferably 10,000 to 20,000. When a polyamic acid having a mass average molecular weight within the range is used, a black molded body excellent in heat resistance is easily formed.

For example, a polylysine which is a constituent unit represented by the following formula (A1) can be mentioned.

(In the formula (A1), R ^a20 is a tetravalent organic group, R ^a21 is a divalent organic group, and n is a repeating number of constituent units represented by the formula (A1))

In the formula (A1), the carbon number of R ^a20 and R ^a21 is preferably 2 to 50, more preferably 2 to 30. R ^a20 and R ^{a21 are} each an aliphatic group, may be an aromatic group, or may be a group combining these structures. R ^a20 and R ^a21 may contain a carbon atom and a hydrogen atom, and may further contain a halogen atom, an oxygen atom, and a sulfur atom. When R ^a20 and R ^a21 are an oxygen atom, a nitrogen atom or a sulfur atom, the oxygen atom, the nitrogen atom or the sulfur atom is selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS- groups, which may be included in R ^a20 and R ^a21 The groups derived from -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS- are preferably contained in R ^a20 and R ^a21 .

Polylysine is usually prepared by reacting a tetracarboxylic dianhydride component with a diamine component. Hereinafter, a method for producing a tetracarboxylic dianhydride component, a diamine component, and a polyglycine prepared using polyamic acid will be described.

[tetracarboxylic dianhydride component]

The tetracarboxylic dianhydride component which is a synthetic raw material of poly-proline is only required to be formed by reacting with a diamine component to form polyamic acid, and is not particularly limited. The tetracarboxylic dianhydride component can be suitably selected from tetracarboxylic dianhydride which has been used as a synthetic raw material of polyglycine in the past. The tetracarboxylic dianhydride component may be an aromatic tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride, or an aromatic tetracarboxylic dianhydride. The tetracarboxylic dianhydride component can be used in combination of 2 or more types.

Preferable specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4. '-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, and 3,3' , 4,4'-diphenylphosphonium tetracarboxylic dianhydride, and the like. Among them, 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferred from the viewpoints of price, availability, and the like.

[diamine component]

The diamine component which is a synthetic raw material of polylysine is not particularly limited as long as it can form a polyamic acid by reacting with a tetracarboxylic dianhydride component. The diamine component can be suitably selected from the diamines used in the past as synthetic raw materials for polyglycine. The diamine component may be an aromatic diamine or an aliphatic diamine, preferably an aromatic diamine. Two or more types of diamine components can be used in combination.

Preferable specific examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminobiphenyl. , 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl Bismuth, 4,4'-diamino Diphenyl sulfide, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-amino group Phenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3- Aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-9H-indole, 9,9-bis(4-amino-3-methylphenyl)-9H-indole, 4, 4'-[1,4-phenylene bis(1-methylethane-1,1-diyl)]diphenylamine. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl are used from the viewpoints of price and ease of availability. Alkyl ether is preferred.

[Method for producing polylysine]

The tetracarboxylic dianhydride component described above and the diamine component are reacted in a solvent in which both of them can be dissolved to obtain a polyamic acid. The amount of the tetracarboxylic dianhydride component and the diamine component used in the synthesis of the polyamic acid is not particularly limited. For the tetracarboxylic dianhydride component 1 mole, it is preferred to use a diamine component of 0.50 to 1.50 moles, preferably 0.60 to 1.30 moles, and preferably 0.70 to 1.20 moles.

As a solvent which can be used for the synthesis of poly-proline, for example, N,N,N',N'-tetramethylurea, N-methyl-2-pyrrolidone, N,N-dimethyl group can be mentioned. Aprotic polar organic solvents such as methotrexate, N,N-dimethylacetamide, hexamethylformamide, 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone Agent, or diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, and propylene glycol monoalkyl ether Glycol ethers such as propionate. These solvents can be used in combination of 2 or more types. Among them, N, N, N', N'-tetramethylurea is preferably used.

The amount of the solvent used in the synthesis of the polyamic acid is not particularly limited as long as it can synthesize a polyamic acid having a desired molecular weight. The amount of the solvent to be used is preferably 100 to 4000 parts by mass, and preferably 150 to 2000 parts by mass, based on 100 parts by mass of the total amount of the tetracarboxylic dianhydride component and the diamine component.

The temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted is not particularly limited as long as the reaction can be carried out satisfactorily. The reaction temperature of the typical tetracarboxylic dianhydride component and the diamine component is preferably -5 to 150 ° C, preferably 0 to 120 ° C, and particularly preferably 0 to 70 ° C. Further, the reaction time of the tetracarboxylic dianhydride component and the diamine component varies depending on the reaction temperature, and is preferably 1 to 50 hours, preferably 2 to 40 hours, and 5 to 30 hours. good.

A solution or paste of polylysine is obtained by the above method. This solution or paste can be used directly in the preparation of a black composition. Further, the solid polyamic acid obtained by removing the solvent from the solution of the polyproline or the solvent of the paste may be used for the preparation of the black composition.

[polybenzoxazole precursor]

Polybenzoxazole precursors are typically produced by reacting an aromatic diamine diol with a dicarbonyl compound of a particular structure. The following are for aromatic diamine diols, dicarbonyl compounds and those used in polybenzoxazole precursors. The solvent to be synthesized and the method for producing the polybenzoxazole precursor are explained.

[Aromatic Diaminediol]

The aromatic diamine diol is not particularly limited as long as it can be used only by the user of the synthesis of the conventional polybenzoxazole. As the aromatic diamine diol, a compound represented by the following formula (a2) is preferably used. The aromatic diamine diol may be used alone or in combination of two or more.

(In the formula (a2), R ^a22 is a tetravalent organic group containing one or more aromatic rings, and a combination of two groups of an amine group and a hydroxyl group contained in the aromatic diamine diol represented by the formula (a2), in each combination , the amine group and the hydroxyl group are bonded to the adjacent two carbon atoms on the aromatic ring containing R ^a22 )

In the formula (a2), R ^a22 is a tetravalent organic group containing one or more aromatic rings, and the number of carbon atoms is preferably from 6 to 50, more preferably from 6 to 30. R ^a22 may be an aromatic group, and two or more aromatic groups may be an aliphatic hydrocarbon group and a halogenated aliphatic hydrocarbon group, or may be bonded via a bond containing a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. ^Examples of the bond of the hetero atom contained in the oxygen atom, the sulfur atom, and the nitrogen atom contained in R ^a22 include -CONH-, -NH-, -N=N-, -CH=N-, and -COO-. , -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, etc., with -O-, -CO-, -SO-, -SO ₂ -, -S-, And -SS- is better.

The aromatic ring contained in R ^a22 may be an aromatic hetero ring. The aromatic ring bonded to the amine group and the hydroxyl group in R ^a22 is preferably a benzene ring. When the ring in which the amine group and the hydroxyl group in R ^a22 are bonded is a condensed ring containing two or more rings, the ring to which the amine group and the hydroxyl group in the condensed ring are bonded is preferably a benzene ring.

Preferable examples of R ^a22 include the groups represented by the following formulas (a1-1) to (a1-9).

(In the formula (a1-1), X ¹ is selected from an alkylene group having 1 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO ₂ -, -CO-, -COO-, -CONH-, and a single bond group. In the formulas (a1-2) to (a1-5), Y ¹ may be the same or different. Select one of -CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -CO-, and a single bond

The group represented by the above formula (a1-1) to (a1-9) may have one or a plurality of substituents on the aromatic ring. Preferred examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atom. A fluorinated alkoxy group of 6 is preferred. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferred.

Specific examples of the compound represented by the above formula (a2) include 2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, and 2, 5-diamino-3-fluoro-1,4-benzenediol, 2,5-diamino-3,6-difluoro-1,4-benzenediol, 2,6-diamino-1 , 5-dihydroxynaphthalene, 1,5-diamino-2,6-dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5 -dihydroxynaphthalene, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,3'- Diamino-3,2'-dihydroxybiphenyl, 3,4'-diamino-4,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-di Hydroxy-6,6'-bistrifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-6,6'-bistrifluoromethylbiphenyl, 2,3 '-Diamino-3,2'-dihydroxy-6,6'-bistrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-6,6'- Bis-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-bistrifluoromethylbiphenyl, 3,3'-diamino-4 , 4'-dihydroxy-5,5'-bistrifluoromethylbiphenyl, 2,3'-diamino-3,2'-dihydroxy-5,5'-bistrifluoromethylbiphenyl Base, 3,4'-diamine -4,3'-dihydroxy-5,5'-bistrifluoromethylbiphenyl, bis(4-amino-3-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl) Methane, 3,4'-diamino-4,3'-dihydroxydiphenylmethane, bis(4-amino-3-hydroxy-6-trifluoromethyl)methane, bis(3-amine -4-hydroxy-6-trifluoromethyl)methane, 3,4'-diamino-4,3'-dihydroxy-6,6'-bistrifluoromethyldiphenylmethane, bis(4- Amino-3-hydroxyphenyl)difluoromethane, bis(3-amino-4-hydroxyphenyl)difluoromethane, 3,4'-diamino-4,3'-dihydroxydiphenyl Fluoromethane, bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)difluoromethane, bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)difluoromethane ,3,4'-diamino-4,3'-dihydroxy-6,6'-bistrifluoromethyldiphenyldifluoromethane, bis(4-amino-3-hydroxybenzene Ether, bis(3-amino-4-hydroxyphenyl)ether, 3,4'-diamino-4,3'-dihydroxydiphenyl ether, bis(4-amino-3-hydroxyl) -6-trifluoromethylphenyl)ether, bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)ether, 3,4'-diamino-4,3'-dihydroxy -6,6'-bistrifluoromethyldiphenyl ether, bis(4-amino-3-hydroxyphenyl)one, bis(3-amino-4-hydroxyphenyl)one, 3,4' -diamino-4,3'-dihydroxydiphenyl ketone, bis(4-amino-3-hydroxy-6-trifluoromethyl) ketone, bis(3-amino-4-hydroxy-6-) Trifluoromethyl)one, 3,4'-diamino-4,3'-dihydroxy-6,6'-bistrifluoromethyldiphenyl ketone, 2,2-bis(4-amino- 3-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2-(3-amino-4-hydroxyphenyl)-2-(4'-amino group -3'-hydroxyphenyl)propane, 2,2-bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)propane, 2,2-bis(3-amino-4-hydroxyl) -6-trifluoromethylphenyl)propane, 2-(3-amino-4-hydroxy-6-trifluoromethylphenyl)-2-(4'-amino-3'-hydroxy-6' -trifluoromethylphenyl)propane, 2,2-bis(3-amino-4-hydroxy-5-trifluoromethylphenyl)propane, 2,2-bis(4-amino-3-hydroxyl) Phenyl) hexafluoropropyl , 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2-(3-amino-4-hydroxyphenyl)-2-(4'-amino-3'-hydroxyl Phenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxy- 6-trifluoromethylphenyl)hexafluoropropane, 2-(3-amino-4-hydroxy-6-trifluoromethylphenyl)-2-(4'-amino-3'-hydroxy-6 '-Trifluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-5-trifluoromethylphenyl)hexafluoropropane, bis(4-amino-3- Hydroxyphenyl)anthracene, bis(3-amino-4-hydroxyphenyl)anthracene, 3,4'-diamino-4,3'-dihydroxydiphenylanthracene, bis(4-amino-3) -hydroxy-6-trifluoromethyl)indole, bis(3-amino-4-hydroxy-6- Trifluoromethyl)anthracene, 3,4'-diamino-4,3'-dihydroxy-6,6'-bistrifluoromethyldiphenylanthracene, bis(4-amino-3-hydroxybenzene) Sulfide, bis(3-amino-4-hydroxyphenyl) sulfide, 3,4'-diamino-4,3'-dihydroxydiphenyl sulfide, bis(4-amino- 3-hydroxy-6-trifluoromethyl) sulfide, bis(3-amino-4-hydroxy-6-trifluoromethyl) sulfide, 3,4'-diamino-4,3'-di Hydroxy-6,6'-bistrifluoromethyldiphenyl sulfide, (4-amino-3-hydroxyphenyl)4-amino-3-hydroxyphenyl benzoate, (3-amino group) 4-hydroxyphenyl) 3-amino 4-hydroxyphenyl benzoate, (3-amino-4-hydroxyphenyl) 4-amino-3-hydroxyphenyl benzoate, (4 -amino-3-hydroxyphenyl)3-amino-4-hydroxyphenylbenzoate, N-(4-amino-3-hydroxyphenyl)4-amino-3-hydroxybenzhydrazide Amine, N-(3-amino-4-hydroxyphenyl)3-amino 4-hydroxyphenylbenzamide, N-(3-amino-4-hydroxyphenyl)4-amino-3 -hydroxyphenylbenzamide, N-(4-amino-3-hydroxyphenyl)3-amino-4-hydroxyphenylbenzamide, 2,4'-bis(4-amino- 3-hydroxyphenoxy)biphenyl, 2,4'-bis(3-amino-4-hydroxyphenoxy)biphenyl , 4,4'-bis(4-amino-3-hydroxyphenoxy)biphenyl, 4,4'-bis(3-amino-4-hydroxyphenoxy)biphenyl, bis[4 -(4-Amino-3-hydroxyphenoxy)phenyl]ether, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]ether, 2,4'-bis(4- Amino-3-hydroxyphenoxy)benzophenone, 2,4'-bis(3-amino-4-hydroxyphenoxy)benzophenone, 4,4'-bis(4-amino group -3-hydroxyphenoxy)benzophenone, 4,4'-bis(3-amino-4-hydroxyphenoxy)benzophenone, 2,4'-bis(4-amino-3 -hydroxyphenoxy)octafluorobiphenyl, 2,4'-bis(3-amino-4-hydroxyphenoxy)octafluorobiphenyl, 4,4'-bis(4-amino-3 -hydroxyphenoxy)octafluorobiphenyl, 4,4'-bis(3-amino-4-hydroxyphenoxy) Octafluorobiphenyl, 2,4'-bis(4-amino-3-hydroxyphenoxy)octafluorobenzophenone, 2,4'-bis(3-amino-4-hydroxyphenoxy ) octafluorobenzophenone, 4,4'-bis(4-amino-3-hydroxyphenoxy)octafluorobenzophenone, 4,4'-bis(3-amino-4-hydroxybenzene Oxy) octafluorobenzophenone, 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino)- 4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3 -amino-4-hydroxyphenoxy)phenyl]hexafluoropropane, 2,8-diamino-3,7-dihydroxydibenzofuran, 2,8-diamino-3,7-di Hydroxy hydrazine, 2,6-diamino-3,7-dihydroxyxanthene, 9,9-bis-(4-amino-3-hydroxyphenyl)anthracene, and 9,9-bis-(3- Amino-4-hydroxyphenyl)indole.

Among them, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is preferred.

[dicarbonyl compound]

As the synthetic raw material of the polybenzoxazole precursor, the dicarbonyl compound represented by the following formula (a3) can be used together with the aromatic diamine diol described above. The above aromatic diamine diol can be obtained by condensation with a dicarbonyl compound represented by the following formula (a3) to obtain a polybenzoxazole precursor.

(In the formula (a3), R ^a23 is a divalent organic group, and A represents a hydrogen atom or a halogen atom)

R ^a23 in the formula (a3) may be an aromatic group, may be an aliphatic group, or may be a group of a combination of an aromatic group and an aliphatic group. From the viewpoint of heat resistance, mechanical properties, chemical resistance, and the like of the obtained polybenzoxazole resin, R ^{a23 is} preferably a group containing an aromatic group and/or an alicyclic group, and is contained in R ^a23 . The aromatic group is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group.

R ^a23 may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom. When R ^a23 contains an oxygen atom, a nitrogen atom or a sulfur atom, the oxygen atom, the nitrogen atom or the sulfur atom is selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N. -, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, may be contained in R ^a23 as -O-, -CO- The groups of -SO-, -SO ₂ -, -S-, and -SS- are preferably contained in R ^a23 .

In the formula (a3), one of the two A atoms is a hydrogen atom, and the other is a halogen atom. Alternatively, two A atoms may be a hydrogen atom, or both A atoms may be a halogen atom. When A is a halogen atom, chlorine is preferably used as chlorine, bromine, and iodine, and chlorine is preferred.

When a dialdehyde compound in which both A is a hydrogen atom is used as the dicarbonyl compound represented by the formula (a3), a polybenzoxazole precursor represented by the following formula (A2) is produced.

(In the formula (A2), R ^a22 and R ^{a23 are the} same as the formula (a2) and the formula (a3), and n is the number of repetitions of the unit represented by the formula (A2).

When a dicarboxylic acid dihalide in which both A is a halogen atom is used as the dicarbonyl compound represented by the formula (a3), a polybenzoxazole precursor represented by the following formula (A3) is produced.

(In the formula (A3), R ^a22 and R ^a23 are the same as those of the formula (a2) and the formula (a3), and n is the number of repetitions of the unit represented by the formula (A3).

The dialdehyde compound and the dicarboxylic acid dihalide which are preferred compounds of the dicarbonyl compound will be described below.

(dialdehyde compound)

The dialdehyde compound used as a raw material of the polybenzoxazole precursor is a compound represented by the following formula (2-1). The dialdehyde compound may be used alone or in combination of two or more.

(In the formula (a2-1), R ^{a23 is the} same as the formula (a3))

The preferred aromatic group or the aromatic ring-containing group of R ^a23 in the formula (a2-1) includes the following groups.

(In the above formula, X ² is selected from an alkylene group having 1 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO ₂ - , -CO-, -COO-, -CONH-, and a single bond group. When X ² is a complex number, the plural X ² may be the same or different. Y ² may be the same or different from -CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -CO-, and a single bond. One of p and q is an integer of 0 to 3 ※)

The preferred alicyclic group or the alicyclic group containing R ^a23 in the formula (a2-1) includes the following groups.

(In the above formula, X ² is selected from an alkylene group having 1 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO ₂ - , -CO-, -COO-, -CONH-, and one of a group of single bonds. When X ² is a complex number, the plural X ² may be the same or different. Y ² may be the same or different One of a group of free -CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -CO-, and a single bond. Z is selected from -CH ₂ -, -CH ₂ CH ₁ -, and -CH=CH- are grouped into groups. p is an integer from 0 to 3)

The aromatic ring or alicyclic ring containing R a ²³ as a suitable group may have 1 or a plurality of substituents on the ring. Preferred examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atom. A fluorinated alkoxy group of 6 is preferred. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferred.

When the dialdehyde compound represented by the formula (a2-1) is an aromatic dialdehyde, examples of the preferred examples include phthalaldehydes, pyridine dialdehydes, and pyrazines. Aldehydes, pyrimidine dialdehydes, naphthalene dialdehydes, biphenyl dialdehydes, diphenyl ether dialdehydes, diphenyl nonanedialdehydes, diphenyl sulfide dialdehydes, bis(methyl fluorenyl) Phenoxy)benzene, [1,4-phenylphenylbis(1-methylethylidene)]bisbenzaldehyde, 2,2-bis[4-(methylnonylphenoxy)phenyl] Propane, bis[4-(methylindolylphenoxy)phenyl] sulfide, bis[4-(methylindolylphenoxy)phenyl]anthracene, and decylaldehyde.

Specific examples of the phthalaldehydes include furfural, isophthalaldehyde, terephthalaldehyde, 3-fluorofurfural, 4-fluorofurfural, 2-fluoroisophthalaldehyde, and 4-fluoroisophthalic acid. Dialdehyde, 5-fluoroisophthalaldehyde, 2-fluoroterephthalaldehyde, 3-trifluoromethylfurfural, 4-trifluoromethylfurfural, 2-trifluoromethylisophthalaldehyde, 4- Trifluoromethylisophthalaldehyde, 5-trifluoromethylisophthalaldehyde, 2-trifluoromethylterephthalaldehyde, 3,4,5,6-tetrafluorofurfural, 2,4,5, 6-tetrafluoroisophthalaldehyde, and 2,3,5,6-tetrafluoroterephthalaldehyde.

Specific examples of the pyridine dialdehydes include pyridine-2,3-dialdehyde, pyridine-3,4-dialdehyde, and pyridine-3,5-dialdehyde.

Specific examples of the pyrazine dialdehydes include pyrazine-2,3-dialdehyde, pyrazine-2,5-dialdehyde, and pyrazine-2,6-dialdehyde.

Specific examples of the pyrimidine dialdehydes include pyrimidine-2,4-dialdehyde, pyrimidine-4,5-dialdehyde, and pyrimidine-4,6-dialdehyde.

Specific examples of the naphthalene dialdehydes include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene-3,7-dialdehyde, and 2, 3,4,6,7,8-hexafluoronaphthalene-1,5-dialdehyde, 2,3,4,5,6,8-hexafluoronaphthalene-1,6-dialdehyde, 1,3,4, 5,7,8-hexafluoronaphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-2,6-dialdehyde, 1,5-bis(trifluoromethyl)naphthalene-2,6-di Aldehyde, 1-trifluoromethylnaphthalene-3,7-di Aldehyde, 1,5-bis(trifluoromethyl)naphthalene-3,7-dialdehyde, 1-trifluoromethyl-2,4,5,6,8-pentafluoronaphthalene-3,7-dialdehyde, 1-bis(trifluoromethyl)methoxy-2,4,5,6,8-pentafluoronaphthalene-3,7-dialdehyde, 1,5-bis(trifluoromethyl)-2,4, 6,8-tetrafluoronaphthalene-3,7-dialdehyde, and 1,5-bis[bis(trifluoromethyl)methoxy]-2,4,6,8-tetrafluoronaphthalene-3,7- Dialdehyde and the like.

Specific examples of the biphenyldialdehydes include biphenyl-2,2'-dialdehyde, biphenyl-2,4'-dialdehyde, biphenyl-3,3'-dialdehyde, Biphenyl-4,4'-dialdehyde, 6,6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-2,4'-dialdehyde, 6,6'-Difluorobiphenyl-3,3'-dialdehyde, 6,6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-4 , 4'-dialdehyde, 6,6'-bistrifluoromethylbiphenyl-2,2'-dialdehyde, 6,6'-bistrifluoromethylbiphenyl-2,4'-dialdehyde 6,6'-bistrifluoromethylbiphenyl-3,3'-dialdehyde, 6,6'-bistrifluoromethylbiphenyl-3,4'-dialdehyde, and 6,6' - bistrifluoromethylbiphenyl-4,4'-dialdehyde or the like.

Specific examples of the diphenyl ether dialdehydes include diphenyl ether-2,4'-dialdehyde, diphenyl ether-3,3'-dialdehyde, and diphenyl ether-3,4'. - Dialdehyde, and diphenyl ether-4,4'-dialdehyde.

Specific examples of the diphenylphosphonium dialdehydes include diphenylphosphonium-3,3'-dialdehyde, diphenylphosphonium-3,4'-dialdehyde, and diphenylsulfonium-4,4. '-Dialdehyde and so on.

Specific examples of the diphenyl sulfide dialdehydes include diphenyl sulfide-3,3'-dialdehyde, diphenyl sulfide-3,4'-dialdehyde, and diphenyl sulfide. -4,4'-dialdehyde and the like.

Specific examples of the diphenylketone dialdehydes include two Phenyl ketone-3,3'-dialdehyde, diphenyl ketone-3,4'-dialdehyde, and diphenyl ketone-4,4'-dialdehyde.

Specific examples of the bis(methylnonylphenoxy)benzenes include benzene 1,3-bis(3-methylnonylphenoxy)benzene and 1,4-bis(3-methylnonylphenoxy). Benzene, and 1,4-bis(4-methylnonylphenoxy)benzene.

Specific examples of [1,4-phenylphenylbis(1-methylethylidene)]bisbenzaldehyde include 3,3'-[1,4-phenylene bis(1-methyl) Ethylene)]bisbenzaldehyde, 3,4'-[1,4-phenylenebis(1-methylethylidene)]bisbenzaldehyde, and 4,4'-[1,4-phenylene Bis(1-methylethylidene)]bisbenzaldehyde and the like.

Specific examples of the 2,2-bis[4-(methylindolylphenoxy)phenyl]propane include 2,2-bis[4-(2-methylnonylphenoxy)phenyl] Propane, 2,2-bis[4-(3-methylnonylphenoxy)phenyl]propane, 2,2-bis[4-(4-methylnonylphenoxy)phenyl]propane, 2, 2-bis[4-(3-methylnonylphenoxy)phenyl]hexafluoropropane and 2,2-bis[4-(4-methylnonylphenoxy)phenyl]hexafluoropropane.

Specific examples of the bis[4-(methylnonylphenoxy)phenyl] sulfides include bis[4-(3-methylnonylphenoxy)phenyl] sulfide and bis[4- (4-Methylmercaptophenoxy)phenyl] sulfide or the like.

Specific examples of the bis[4-(methylnonylphenoxy)phenyl]anthracene include bis[4-(3-methylnonylphenoxy)phenyl]anthracene and bis[4-(4). -Methylmercaptophenoxy)phenyl]anthracene and the like.

Specific examples of the terpene-containing dialdehyde include 茀-2,6-dialdehyde, 茀-2,7-dialdehyde, dibenzofuran-3,7-dialdehyde, and 9,9-bis (4-A).醯 Phenyl) ruthenium, 9,9-bis(3-methylnonylphenyl) fluorene, and 9-(3-methylnonylphenyl)-9-(4'-methylphenyl) hydrazine

Further, a diphenylalkanedialdehyde or a diphenylfluoroalkanedionaldehyde represented by the following formula may also be used as the aromatic dialdehyde compound.

Further, a compound having an oximine bond represented by the following formula can also be applied to an aromatic dialdehyde compound.

When the dicarbonyl compound represented by the formula (a2-1) is an alicyclic dialdehyde containing an alicyclic group, examples of the preferred examples include cyclohexane-1,4-dialdehyde and cyclohexane-1. , 3-dialdehyde, bicyclo [2.2.1] heptane-2,5-dialdehyde, bicyclo [2.2.2] octane-2,5-dialdehyde, bicyclo [2.2.2] oct-7 -ene-2,5-dialdehyde, bicyclo [2.2.1] heptane-2,3-dialdehyde, bicyclo [2.2.1] hept-5-ene-2,3-dialdehyde, tricyclo [ 5.2.1.0 ^2,6 〕 decane-3,4-dialdehyde, tricyclo [5.2.1.0 ^2,6 ] 癸-4-ene-8,9-dialdehyde, perhydronaphthalene-2,3-dialdehyde , perhydronaphthalene-1,4-dialdehyde, perhydronaphthalene-1,6-dialdehyde, perhydro-1,4-methylnaphthalene-2,3-dialdehyde, perhydro-1,4-methyl bridge Naphthalene-2,7-dialdehyde, perhydro-1,4-methylnaphthalene-7,8-dialdehyde, perhydro-1,4:5,8-dimethylnaphthalene-2,3-dialdehyde, All hydrogen-1,4:5,8-dimethylnaphthalene-2,7-dialdehyde, perhydro-1,4:5,8:9,10-trimethyl bridged-2,3-dialdehyde, Cyclohexyl-4,4'-dialdehyde, dicyclohexyl ether-3,4'-dialdehyde, dicyclohexylmethane-3,3'-dialdehyde, dicyclohexylmethane-3,4'-dialdehyde, Dicyclohexylmethane-4,4'-dialdehyde, dicyclohexyldifluoromethane-3,3'-dialdehyde, dicyclohexyldifluoromethane-3,4'-dialdehyde, dicyclohexyldifluoro Alkane-4,4'-dialdehyde, dicyclohexylfluorene-3,3'-dialdehyde, dicyclohexylfluorene-3,4'-dialdehyde, dicyclohexylfluorene-4,4'-dialdehyde, two Cyclohexyl sulfide-3,3'-dialdehyde, dicyclohexyl sulfide-3,4'-dialdehyde, dicyclohexyl sulfide-4,4'-dialdehyde, dicyclohexyl ketone-3,3' -dialdehyde, dicyclohexyl ketone-3,4'-dialdehyde, dicyclohexyl ketone-4,4'-dialdehyde, 2,2-bis(3-methylnonylcyclohexyl)propane, 2,2- Bis(4-methylnonylcyclohexyl)propane, 2,2-bis(3-methylnonylcyclohexyl)hexafluoropropane, 2,2-bis(4-methylnonylcyclohexyl)hexafluoropropane, 1, 3-bis(3-methylnonylcyclohexyl)benzene, 1,4-bis(3-methylindenylcyclohexyl)benzene, 1,4-bis(4-methylnonylcyclohexyl)benzene, 3,3' -[1,4-cyclopentane bis(1-methylethylidene)bicyclohexanecarbaldehyde, 3,4'-[1,4-cyclopentane bis(1-methylethylidene)]bicyclo Hexane formaldehyde, 4,4'-[1,4-cyclopentane bis(1-methylethylidene)bicyclohexanecarbaldehyde, 2,2-bis[4-(3-methylindenylcyclohexyl) Cyclohexyl]propane, 2,2-bis[4-(4-carboxycyclohexyl)cyclohexyl]propane, 2,2-bis[4-(3-carboxycyclohexyl)cyclohexyl]hexafluoropropane 2,2-bis[4-(4-methylnonylphenoxy)cyclohexyl]hexa Propane, bis[4-(3-carboxycyclohexyloxy)cyclohexyl] sulfide, bis[4-(4-methylnonylcyclohexyloxy)cyclohexyl] sulfide, bis[4-(3) -Mercaptocyclohexyloxy)cyclohexyl]indole, bis[4-(4-carbamimidylcyclohexyloxy)cyclohexyl]indole, 2,2'-bicyclo[2.2.1]heptane-5 6'-dialdehyde, 2,2'-bicyclo[2.2.1]heptane-6,6'-dialdehyde, and 1,3-dimethylhydrazine fundane.

Among the dialdehyde compounds described above, from the viewpoint of ease of synthesis or availability, or from the viewpoint of easily obtaining a polybenzoxazole precursor of a polybenzoxazole resin imparting excellent heat resistance and mechanical properties, Phenylenedialdehyde is preferred.

(dicarboxylic acid dihalide)

a dicarboxylic acid dihalide used as a raw material for a polybenzoxazole precursor It is a compound represented by the following formula (a2-2). The dicarboxylic acid dihalide may be used singly or in combination of two or more.

(In the formula (a2-2), R ^{a23 is the} same as the formula (a3), and Ha1 is a halogen atom)

In the formula (a2-2), chlorine, bromine, and iodine are preferred as Ha1, and chlorine is preferred.

A preferred compound of the compound represented by the formula (a2-2), wherein two aldehyde groups of the above compound as a preferred example of the dialdehyde compound are substituted with a halogenated carbonyl group, and a compound substituted with a chlorocarbonyl group is preferably used. Out.

Among the dicarboxylic acid dihalides described above, from the viewpoint of easiness of synthesis or easy availability, or from the viewpoint of easily obtaining a polybenzoxazole precursor of a polybenzoxazole resin imparting excellent heat resistance and mechanical properties. Look, it is better to use terephthalic acid dichloride.

[solvent]

The solvent to be used in the preparation of the polybenzoxazole precursor is not particularly limited, and may be suitably selected from the solvents used in the preparation of the conventional polybenzoxazole precursor. The solvent used for the preparation of the polybenzoxazole precursor is preferably a solvent containing a compound represented by the following formula (a4).

(In the formula (a4), R ^a24 and R ^{a25 are} each independently an alkyl group having 1 to 3 carbon atoms, and R ^a26 is the following formula (a4-1) or the following formula (a4-2): The base shown. In the formula (a4-1), R ^a27 is a hydrogen atom or a hydroxyl group, R ^a28 and R ^a29 are each independently an alkyl group of 1 to 3. In the formula (a4-2), R ^a30 and R ^a31 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)

When a polybenzoxazole precursor is synthesized using a solvent containing a compound represented by the above formula (a4), the polybenzoxazole precursor can be inhibited from heating even when the polybenzoxazole precursor is heat-treated at a low temperature. The transparency caused by the coloring of the resin at the time of the object is lowered, and a polybenzoxazole resin having excellent mechanical properties such as stretchability or chemical resistance can also be produced.

Further, when the polybenzoxazole precursor which is synthesized by using the solvent of the compound represented by the above formula (a4) is heated to produce a polybenzoxazole resin, swelling and cracking on the surface of the polybenzoxazole resin Defects such as foaming can be suppressed. Therefore, when a film containing a polybenzoxazole precursor synthesized using a solvent containing the compound represented by the above formula (a4) is heated to produce a polybenzoxazole resin film, it is easy to produce no film. A film with excellent appearance such as cracks, blisters, and pinholes.

Among the compounds represented by the formula (a4), specific examples when R ^a26 is a group represented by the formula (a4-1) include N,N,2-trimethylpropionamide, N-ethyl, N, 2-dimethylpropanamide, N,N-diethyl-2-methylpropanamide, N,N,2-trimethyl-2-hydroxypropionamide, N-ethyl-N,2 - dimethyl-2-hydroxypropionamide, and N,N-diethyl-2-hydroxy-2-methylpropanamide.

Among the compounds represented by the formula (a4), specific examples when R ^a26 is a group represented by the formula (a4-2) include N,N,N',N'-tetramethylurea, N,N,N. ', N'-tetraethyl urea and the like.

Among the compounds represented by the formula (a4), N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea are preferred as the most preferred ones. The boiling point of N,N,2-trimethylpropionamide at atmospheric pressure is 175 ° C, and the boiling point of N,N,N',N'-tetramethylurea at atmospheric pressure is 177 °C. Thus N,N,2-trimethylpropanamide, and N,N,N',N'-tetramethylurea are soluble in aromatic diamine diols, dicarbonyl compounds, and polybenzazole The boiling point of the solvent of the azole precursor is relatively low. Therefore, a polybenzoxazole precursor synthesized using a solvent containing at least one selected from the group consisting of N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea When the polybenzoxazole resin is formed, when the polybenzoxazole precursor is heated, the solvent is not easily retained in the polybenzoxazole resin formed, and the resulting polybenzoxazole resin is not pulled. Reduced elongation, etc.

N,N,2-trimethylpropionamide, and N,N,N',N'-tetramethylurea in the EU (European Union) REACH Regulation, SVHC for substances not designated as hazardous concerns (Substance of Very High Concern, a substance of high concern, is also useful in the view that it is a less harmful substance.

When the solvent used in the preparation of the polybenzoxazole precursor is a compound represented by the formula (a4), the content of the compound represented by the formula (a4) in the solvent is preferably 70% by mass or more, and preferably 80% by mass or more. It is preferably 90% by mass or more, and most preferably 100% by mass.

When the solvent is a compound represented by the formula (a4), examples of the organic solvent which can be used together with the compound of the formula (a4) include N,N-dimethylformamide and N,N-dimethyl group. Nitrogen-containing polar solvent such as acetamide, N-methyl-2-pyrrolidone, hexamethylformamide, 1,3-dimethyl-2-imidazolidinone; methyl ethyl ketone, methyl iso Ketones such as butyl ketone, cyclohexanone, and isophorone; γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-甲Esters such as γ-butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and n-butyl acetate; cyclic ethers such as dioxane and tetrahydrofuran; and ethyl carbonate; Cyclic esters such as propyl carbonate; aromatic hydrocarbons such as toluene and xylene; and anthraquinones such as dimethyl hydrazine.

[Method for producing polybenzoxazole precursor]

The polybenzoxazole precursor is produced by reacting the aromatic diamine diol and the dicarbonyl compound in a solvent in accordance with a known method. As a representative example of the production method of the following polybenzoxazole precursor, a production method in the case where the dicarbonyl compound is a dialdehyde compound and a method in which the dicarbonyl compound is a dicarboxylic acid halide will be described.

(Reaction of aromatic diamine diol with dialdehyde compound)

The reaction between the aromatic diamine diol and the dialdehyde compound is a Schiff base formation reaction, which can be carried out according to a known method. The reaction temperature is not particularly limited, and is usually 20 to 200 ° C, preferably 20 to 160 ° C, and particularly preferably 100 to 160 ° C.

The reaction between the aromatic diamine diol and the dialdehyde compound is carried out by adding an azeotropic agent to the solvent while performing dehydration under reflux. The entrainment agent is not particularly limited, and may be suitably selected from an organic solvent which forms an azeotropic mixture with water and forms a two-phase system with water at room temperature. Preferable examples of the entrainer include isobutyl acetate, allyl acetate, n-propyl propionate, isopropyl propionate, n-butyl propionate, and isobutyl propionate. Equivalent esters; ethers such as dichloromethyl ether and ethyl isoamyl ether; ketones such as ethyl propyl ketone; and aromatic hydrocarbons such as toluene.

The reaction time of the aromatic diamine diol and the dialdehyde compound is not particularly limited, but is preferably about 2 to 72 hours.

The amount of the dialdehyde compound used in the production of the polybenzoxazole precursor is preferably from 0.5 to 1.5 mol, more preferably from 0.7 to 1.3 mol, per mol of the aromatic diamine diol.

The amount of the solvent to be used is not particularly limited as long as the reaction between the aromatic diamine diol and the dialdehyde compound can be favorably carried out. The total amount of the aromatic diamine diol and the mass of the dialdehyde compound is usually 1 to 40 times, preferably 1.5 to 20 times the mass of the solvent.

The reaction between the aromatic diamine diol and the dialdehyde compound is carried out until the number average molecular weight of the produced polybenzoxazole precursor is 1000~ 20000, preferably to 1200~5000.

(Reaction of aromatic diamine diol with dicarboxylic acid dihalide)

The reaction temperature at which the aromatic diamine diol is reacted with the dicarboxylic acid dihalide is not particularly limited, and is usually -20 to 150 ° C, preferably -10 to 150 ° C, and preferably -5 to 70 ° C. It is especially good. Hydrogen halide is produced in the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide. To neutralize the hydrogen halide, an organic base such as triethylamine, pyridine or N,N-dimethyl-4-aminopyridine or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in small amounts. Add to the reaction solution.

The reaction time of the aromatic diamine diol and the dicarboxylic acid dihalide is not particularly limited, and is preferably about 2 to 72 hours.

The amount of the dicarboxylic acid dihalide used in the production of the polybenzoxazole precursor is preferably 0.5 to 1.5 moles, and 0.7 to 1.3 moles for the aromatic diamine diol 1 mole. good.

The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide can be favorably carried out. A solvent having a mass of a typical aromatic diamine diol and a dicarboxylic acid dihalide in a total amount of 1 to 40 times, preferably 1.5 to 20 times by mass, may be used.

The reaction of the aromatic diamine diol with the dicarboxylic acid dihalide is carried out until the number of the polybenzoxazole precursors produced has a number average molecular weight of from 1,000 to 20,000, preferably from 1200 to 5,000.

A solution of the polybenzoxazole precursor can be obtained according to the method described above. For the preparation of black components, polybenzoxazole can be used directly. A solution of the precursor. Further, under a reduced pressure, at a low temperature to the extent that the polybenzoxazole precursor is not converted into a polybenzoxazole resin, at least a part of the solvent is removed from the solution of the polybenzoxazole precursor. The paste or solid of the polybenzoxazole precursor can also be used in the preparation of the black composition.

[polybenzothiazole precursor]

Polybenzothiazole precursors are typically produced by reacting an aromatic diamine dithiol with a dicarbonyl compound of a specific structure. As the aromatic diamine dithiol, a compound in which a hydroxyl group of an aromatic diamine diol used in the synthesis of a polybenzoxazole precursor is substituted with a mercapto group can be used. As the dicarbonyl compound, the same ones used in the synthesis of the polybenzoxazole precursor can be used.

A method for reacting an aromatic diamine dithiol with a dicarbonyl compound to synthesize a polybenzothiazole precursor, a reaction condition, and the like, and reacting an aromatic diamine diol with a dicarbonyl compound to synthesize polybenzoic acid The oxazole precursor is the same.

[Polybenzimidazole precursor]

The polybenzimidazole precursor is typically produced by reacting an aromatic tetraamine with a dicarboxylic acid dihalide. As the aromatic tetraamine, a compound in which the hydroxyl group of the aromatic diamine diol used for the synthesis of the polybenzoxazole precursor is substituted with an amine group can be used. As the dicarboxylic acid dihalide, the same one used in the synthesis of the polybenzoxazole precursor can be used.

Reacting an aromatic tetraamine with a dicarboxylic acid dihalide The reaction method, reaction conditions, and the like in the case of synthesizing a polybenzimidazole precursor are the same as those in the case of synthesizing a polybenzoxazole precursor by reacting an aromatic diamine diol with a dicarboxylic acid dihalide.

[styrene-maleic acid copolymer]

The type of the styrene-maleic acid copolymer is not particularly limited as long as it does not inhibit the scope of the object of the present invention. The copolymerization ratio (mass ratio) of styrene/maleic acid in the styrene-maleic acid copolymer is preferably 1/9 to 9/1, more preferably 2/8 to 8/1, and 1/1. 1~8/1 is especially good. The molecular weight of the styrene-maleic acid copolymer is not particularly limited, and the mass average molecular weight in terms of polystyrene is preferably from 1,000 to 100,000, more preferably from 5,000 to 12,000.

[Epoxy group-containing resin]

When the black composition containing the epoxy group-containing resin as the component (A) is heated at a predetermined temperature or higher, the polyfunctional ring is produced by the action of the imidazole compound of (C) a thermal imidazole generator described later. The epoxy groups possessed by the oxygen compound are cross-linked to each other. As a result, a black cured product excellent in heat resistance or mechanical properties is obtained. The epoxy group-containing resin is not particularly limited as long as it is a resin composed of a molecule having an epoxy group.

The epoxy group-containing resin may be a polymer obtained by polymerizing a monomer mixture containing a monomer having an epoxy group or a monomer having an epoxy group. The epoxy group-containing resin has a hydroxyl group, a carboxyl group, an amine group, etc. The reactive functional group polymer may, for example, be an epoxy group introducer using a compound having an epoxy group such as epichlorohydrin. It is easy to adjust, adjust, or adjust the amount of epoxy groups in the polymer. Therefore, as a polymer having an epoxy group, a monomer having a monomer having an epoxy group or a monomer having an epoxy group is used. The polymer obtained by polymerization of the mixture is preferred.

Preferable examples of the epoxy group-containing resin include a phenol novolac type epoxy resin, a brominated phenol novolak type epoxy resin, an o-cresol novolak type epoxy resin, and a bisphenol A novolac type. Epoxy resin, phenolic varnish epoxy resin such as bisphenol AD novolac type epoxy resin; cyclic aliphatic epoxy resin such as epoxide of dicyclopentadiene type phenol resin; epoxide of naphthalene type phenol resin Aromatic epoxy resin.

Further, among the epoxy group-containing resins, it is easy to prepare, or the physical properties of the black molded body formed using the black composition are easily adjusted, so that a homopolymer of an epoxy group (meth) acrylate or Copolymers of (meth) acrylate having an epoxy group with other monomers are preferred.

The (meth) acrylate having an epoxy group may be a (meth) acrylate having a chain aliphatic epoxy group, or may be a (meth) acrylate having an alicyclic epoxy group as described later. Further, the (meth) acrylate having an epoxy group may further contain an aromatic group. Among the (meth) acrylates having an epoxy group, an aliphatic (meth) acrylate having a chain aliphatic epoxy group, or an aliphatic (meth) acrylate having an alicyclic epoxy group Preferably, an aliphatic (meth) acrylate having an alicyclic epoxy group is preferred.

As an aromatic group, it has an epoxy group (methyl) Examples of the acrylate include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxy phenyl ( Methyl) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxy phenylmethyl (meth) acrylate, and 2-glycidyloxy Phenylmethyl (meth) acrylate and the like.

Examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include, for example, an epoxyalkyl (meth) acrylate, and an epoxy alkoxyalkyl (meth) acrylate. The oxy group (-O-) in the ester group (-O-CO-) is bonded to the (meth) acrylate of a chain aliphatic epoxy group. The chain aliphatic epoxy having such a (meth) acrylate may contain 1 or a plurality of oxy groups (-O-) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, and is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

Specific examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, and 3, 4 Epoxyalkyl (meth) acrylate such as epoxybutyl (meth) acrylate or 6,7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (methyl) Acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyloxy- An epoxy alkoxyalkyl (meth) acrylate such as n-hexyl (meth) acrylate or 6-glycidyloxy-n-hexyl (meth) acrylate.

Specific examples of the aliphatic (meth) acrylate having an alicyclic epoxy group include compounds represented by the following formulas (a5-1) to (a5-15). Among them, the compounds represented by the following formulas (a5-1) to (a5-5) are preferred, and the compounds represented by the following formulas (a5-1) to (a5-3) are preferred.

In the above formula, R ^a32 represents a hydrogen atom or a methyl group, R ^a33 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a34 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents 0 to 10; Integer. As R ^a33 , a linear or branched chain alkyl group, such as methyl, ethyl, propyl, tetramethyl, ethyl, ethyl, pentamethyl, and hexamethylene It is better. As R ^a34 , for example, a methyl group, an ethyl group, a propyl group, a tetramethyl group, an ethyl group ethyl group, a pentamethyl group, a hexamethyl group, a phenyl group or a cyclopentyl group are preferred.

As the polymer having an epoxy group, any of a homopolymer of a (meth) acrylate having an epoxy group and a copolymer of a (meth) acrylate having an epoxy group and another monomer may be used. In the epoxy group-containing polymer, the content of the unit derived from the (meth) acrylate having an epoxy group is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. Particularly good, 100% by mass is the best.

When the polymer having an epoxy group is a copolymer of a (meth) acrylate having an epoxy group and another monomer, examples of the other monomer include an unsaturated carboxylic acid and a methyl group having no epoxy group. An acrylate, a (meth) acrylonitrile group, an allyl compound, a vinyl ether, a vinyl ester, a styrene, or the like. These compounds may be used alone or in combination of two or more. The storage stability of the black composition or the copolymerization of the (meth) acrylate having an epoxy group with other monomers from the viewpoint of chemical resistance of a base or the like of a black molded body formed using a black product It is preferred that it does not contain a unit derived from an unsaturated carboxylic acid.

As an example of the unsaturated carboxylic acid, (meth) propyl Acrylic acid; decylamine (meth)acrylate; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrate (anhydride) of these dicarboxylic acids.

Examples of the (meth) acrylate having no epoxy group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and pentyl (A). Linear or branched alkyl (meth) acrylate such as acrylate or t-octyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethyl Hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, thiol (methyl) An acrylate; a (meth) acrylate having a alicyclic skeleton. Among the (meth) acrylates having no epoxy group, a (meth) acrylate having a group having an alicyclic skeleton is preferred.

For the (meth) acrylate having a group of the alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be a single ring or may be a polycyclic ring. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclodecyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Examples of the (meth) acrylate having a cyclone-based skeleton include compounds represented by the following formulas (a6-1) to (a6-8). Among these, a compound represented by the following formula (a6-3) to (a6-8) is preferred, and a compound represented by the following formula (a6-3) or (a6-4) is preferred.

In the above formula, R ^a35 represents a hydrogen atom or a methyl group, R ^a36 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a37 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. And R ^a36 is a single bond, a linear chain or a branched chain alkyl group, for example, a methyl group, an ethyl group, a propyl group, a tetramethyl group, an ethyl group, a pentamethyl group, and a hexamethyl group. Methyl is preferred. As R ^{a37 ,} a methyl group or an ethyl group is preferred.

Examples of the (meth) acrylonitrile group include (meth) acryl fluorenyl group, N-alkyl (meth) acryl fluorenyl group, N-aryl (meth) acryl fluorenyl group, and N, N. -dialkyl(meth)acrylonitrile, N,N-aryl(meth)acrylonitrile, N-methyl-N-phenyl(methyl)propene oxime A group, an N-hydroxyethyl-N-methyl(meth)acrylinyl group or the like.

Examples of the allyl compound include allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, benzoic acid allylic. Allyl esters such as ester, allyl acetate, allyl lactate, allyloxyethanol, and the like.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl ethylene. Ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol ethylene Ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. Aliphatic vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl decyl ether, etc. Alkyl aryl ether and the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, and vinyl. Hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetonitrile An acid ester, a vinyl lactate, a vinyl-β-phenyl butyrate, a vinyl benzoate, a vinyl salicylate, a vinyl chlorobenzoate, a vinyl tetrachlorobenzoate, a vinyl naphthate or the like.

Examples of the styrenes include styrene; methyl group. Styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene , alkyl styrene such as benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl styrene; methoxy styrene, 4- Alkoxystyrenes such as methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromobenzene Ethylene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc. .

The molecular weight of the epoxy group-containing resin is not particularly limited as long as it does not inhibit the object of the present invention, and the mass average molecular weight in terms of polystyrene is preferably 3,000 to 30,000, more preferably 5,000 to 15,000.

As described above, the content of the black component of the base component (A) is preferably 5 to 90% by mass, and preferably 30 to 70% by mass, based on the solid content of the black composition.

<(B) carbon black>

As the (B) carbon black, a dispersion-treated person using polylysine as a dispersing agent was used. The type of carbon black to be subjected to dispersion treatment using polyamic acid is not particularly limited, and various kinds of carbon blacks which have been sold from the past can be used without particular limitation.

As (B) carbon black, the resulting black composition, or In view of the high insulating property of the black molded body formed by the black composition, it is preferred to apply the carbon black to which the acidic group is introduced.

At this time, the acidic group introduced into the carbon black is a functional group showing an acidity as defined by Bronsted. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic group introduced into the carbon black can form a salt. The cation forming a salt with an acidic group is not particularly limited as long as it does not inhibit the object of the present invention. Examples of the cation include various metal ions, cations of a nitrogen-containing compound, ammonium ions, and the like, and alkali metal ions such as sodium ions, potassium ions, and lithium ions or ammonium ions are preferred.

In the carbon black to which the acidic group is introduced as described above, the obtained black composition or the black molded body formed using the black composition has a high selectivity from the viewpoint of high insulating properties. A carbon black having one or more functional groups in which a carboxylic acid base, a sulfonic acid group, and a sulfonic acid base are grouped is preferred.

The method of introducing an acidic group into carbon black is not particularly limited. As a method of introducing an acidic group, the following methods are mentioned, for example.

1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or the like, or an indirect substitution method using a sulfite or a hydrogensulfite.

2) A method of diazo coupling of an organic compound having an amine group and an acidic group, and carbon black.

3) by the etherification method of Williamson by the organic compound having a halogen atom and an acidic group, and the carbon black having a hydroxyl group The method should be.

4) A method of reacting a halogenated carbonyl group with an organic compound having an acidic group protected by a protecting group, and a carbon black having a hydroxyl group.

5) A method of deprotecting a carbon black after a Friedel-Crafts reaction using an organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group.

Among these methods, the introduction treatment of the acidic group is preferably from the viewpoint of ease and safety, and the method 2) is preferred. As the organic compound having an amine group and an acidic group used in the method 2), a compound in which an amine group and an acidic group are bonded to an aromatic group is preferred. As an example of such a compound, an aminobenzenesulfonic acid such as an amine benzenesulfonyl acid or an amino benzoic acid such as 4-aminobenzoic acid can be mentioned.

The number of moles introduced into the acidic group of carbon black is not particularly limited insofar as it does not inhibit the object of the present invention. The number of moles of the acidic group introduced into the carbon black is preferably from 1 to 200 mmol, preferably from 5 to 100 mmol, per 100 g of carbon black.

Further, in the case of (B) carbon black, when a black composition is applied to a substrate to form a black molded body, the decane coupling agent can be used for the purpose of improving the adhesion to the substrate of the black molded body. Process it. The treatment with the decane coupling agent can be carried out at any stage before and after the treatment in which the carbon black is introduced into the acidic group, and can be carried out at any stage after the dispersion treatment using polylysine as a dispersing agent.

The decane coupling agent used for the treatment of (B) carbon black may be suitably selected from decane coupling agents known in the past. Used as (B) carbon black The decane coupling agent to be treated is preferably a decane coupling agent represented by the following formula (B1). When the black composition contains (B) carbon black treated with a decane coupling agent represented by the following formula (B1), when the black molded body formed using the black composition is heated, the insulation of the black molded body can be suppressed from being lowered. .

R ^b1 _a R ^b2 _(3-a) Si-R ^b3 -NH-C(O)-Y ^b -R ^b4 -X ^b . . . (B1) (In the formula (B1), R ^b1 is an alkoxy group, R ^b2 is an alkyl group, a is an integer of 1 to 3, R ^b3 is an alkylene group, and Y ^b is -NH-, -O-, or -S-, R ^b4 is a single bond or an alkyl group, X ^b is a monocyclic ring which may have a substituent or may be a polycyclic nitrogen-containing heteroaryl group, and the ring bonded to -YR ^b4 - in X ^b is a nitrogen-containing 6-membered aromatic ring, -YR ^b4 - bonded to a carbon atom in the aforementioned nitrogen-containing 6-membered aromatic ring)

In the formula (B1), R ^b1 is an alkoxy group. With respect to R ^b1 , the alkoxy group preferably has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 from the viewpoint of reactivity of the decane coupling agent. Preferred examples of R ^b1 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-. Butoxy, n-pentyloxy, and n-hexyloxy. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred.

The stanol gene produced by hydrolysis of the alkoxy group R ^b1 is reacted with a functional group having an active hydrogen atom such as a hydroxyl group or a carboxyl group present on the surface of the carbon black, and the decane coupling agent is bonded to the surface of the carbon black. Therefore, from the viewpoint of the ease of bonding the decane coupling agent to the surface of the carbon black, a is preferably 3.

In the formula (B1), R ^b2 is an alkyl group. With respect to R ^b2 , the alkyl group preferably has 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and particularly preferably 1 or 2 from the viewpoint of reactivity of the decane coupling agent. Preferable specific examples of R ^b2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. , n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, and n-dodecyl.

In the formula (B1), R ^b3 is an alkylene group. For R ^b3 , the alkyl group has preferably 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms. Preferred examples of R ^b3 include a methyl group, a 1,2-extended ethyl group, a 1,1-extended ethyl group, a propane-1,3-diyl group, and a propane-1,2-diyl group. Propane-1,1-diyl, propane-2,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, butane -1,1-diyl, butane-2,2-diyl, butane-2,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, and Alkan-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,9-diyl, decane-1,10-diyl, ten Monoalkane-1,11-diyl, and dodecane-1,12-diyl. Among these alkylene groups, a 1,2-extended ethyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group are preferred.

Y ^b is -NH-, -O-, or -S-, preferably -NH-. This is a bond as shown by -CO-O- or -CO-S-, and the bond shown by -CO-NH- is more susceptible to hydrolysis. When a black molded body is formed by using a black composition of (B) carbon black which is treated by using a compound having Y ^b as -NH- as a decane coupling agent, the structure of a decane coupling agent which acts by an acid or a base or the like The change is difficult, so that the desired effect can be easily obtained by the use of a decane coupling agent.

R ^b4 is a single bond or an alkyl group, and a single bond is preferred. A preferred example when R ^b4 is an alkylene group is the same as R ^b3 .

X ^b is a monocyclic ring which may have a substituent or a polycyclic nitrogen-containing heteroaryl group, and the ring bonded to -Y ^b -R ^b4 - in X ^b is a nitrogen-containing 6-membered aromatic ring, -Y ^b -R ^B4 - is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring. When the reason is not clear, when a black composition containing a compound having such X as a decane coupling agent is used, a black molded article excellent in adhesion to a substrate, water resistance, and solvent resistance can be formed.

When X ^b is a polycyclic heteroaryl group, the heteroaryl group may be a complex of a single monocyclic condensed group, or may be a group in which a plurality of monocyclic rings are bonded via a single bond. When X ^b is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably from 1 to 3. When X ^b is a polycyclic heteroaryl group, the ring in which the nitrogen-containing 6-membered aromatic ring in X ^b is condensed or bonded may or may not contain a hetero atom, and may be an aromatic ring or a non-aromatic ring.

Examples of the substituent which the X ^{b of the} nitrogen-containing heteroaryl group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and carbon. Alkenyloxy group having 2 to 6 atomic number, aliphatic fluorenyl group having 2 to 6 carbon atoms, benzamyl group, nitro group, nitroso group, amine group, hydroxyl group, sulfhydryl group, cyano group, sulfonic acid group, carboxyl group And halogen atoms, etc. The number of substituents which X ^b has is not particularly limited insofar as it does not inhibit the object of the present invention. The number of substituents which X ^b has is preferably 5 or less, and more preferably 3 or less. When X ^b has a complex substituent, the plural substituents may be the same or different.

A preferred example of X ^{b is} a group of the following formula.

Among the above groups, it is preferred that the group of the following formula is X ^b .

Preferred examples of the compound represented by the formula (B1) described above include the following compounds 1 to 8.

The treatment method of the (B) carbon black decane coupling agent is not particularly limited, and it can be carried out according to a known method of treatment with a decane coupling agent. A typical method is a method of reacting (B) a carbon black and a decane coupling agent in the presence of water in an organic solvent in which a decane coupling agent is soluble.

Examples of the organic solvent to be used for the treatment of the (B) carbon black by the decane coupling agent include monovalent alkanols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; Glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, isopropyl glycol, polypropylene glycol, pentamethylglycol, Tri-methylglycol, butanediol, isobutylene glycol, thiodiglycol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,3-propanediol, 1,4-butanediol, 1 , 7-heptanediol, 1,8-octanediol, and 2-butene-1,4-diol, and polyols such as glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monophenyl ether, ethylene glycol Monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol single -t-butyl ether Triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether Propylene glycol monoisopropyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monoisopropyl ether Ethylene glycol ethers; ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate Ester, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethyl Glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxy Butyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl- 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4 -ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl Acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetic acid Glycol ether esters such as esters and 4-methyl-4-methoxypentyl acetate; ketone solvents such as acetone, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The amount of the organic solvent used is not particularly limited as long as it can easily stir the treatment liquid containing the carbon black and the decane coupling agent. The amount of the organic solvent used is preferably from 5 to 60% by mass based on the solid content of the treatment liquid containing (B) carbon black and a decane coupling agent.

The amount of the decane coupling agent used is not particularly limited as long as the desired effect can be obtained. The amount of the decane coupling agent to be used is preferably 0.5 to 15 parts by mass, and preferably 3 to 7 parts by mass, based on 100 parts by mass of the (B) carbon black.

The treatment of the (B) carbon black by the decane coupling agent is carried out in the presence of water. Although water may be added to the treatment liquid containing (B) carbon black and a decane coupling agent, it is not necessary to add water to the treatment liquid. By decane When the treatment of the mixture is carried out in an air atmosphere containing sufficient moisture, the alkoxy group of the decane coupling agent can be hydrolyzed by the moisture in the air to form a stanol group.

The temperature at the time of the treatment of the (B) carbon black by the decane coupling agent is not particularly limited as long as the reaction between the decane coupling agent and the (B) carbon black can be satisfactorily performed. The treatment of (B) carbon black by a decane coupling agent is typically carried out at 25 to 100 °C.

The carbon black (B) described above is contained in a black composition in a state in which polylysine is used as a dispersing agent and dispersed. The molecular chain of polylysine is believed to bind in a point manner on the surface of the carbon black primary particles by hydrogen bonding or interaction with intermolecular forces on the surface of the carbon black. Therefore, on the surface of the primary particles of carbon black, the molecular chain of poly-proline plays a role as a spacer, promotes dispersion of carbon black, and stabilizes dispersion.

Therefore, aggregation of carbon black is less likely to occur in a black composition containing the (B) carbon black prepared by using polylysine as a dispersant. Therefore, the black molded body formed using the black composition has a high optical density (OD) and can exhibit a rich black hue even with a small amount of carbon black.

Further, polylysine was adsorbed on the surface of (B) carbon black as described above. The black composition contains the (C) thermal imidazole generator described later. The imidization of the polyaminic acid by heating can be promoted by heating the (C) imidazole compound produced by the thermal imidazole generator. Therefore, after the black composition is formed into a desired shape, the black molded body is heated at a temperature higher than the temperature at which the (C) thermal imidazole generator generates an imidazole compound, and the (B) carbon black table is used. The polylysine adsorbed on the surface is converted into a polyimine to form a black composition excellent in heat resistance.

Usually, (B) carbon black can be added to the black composition in a carbon black dispersion prepared by using polylysine as a dispersing agent.

Further, when (A) the base component is polyamic acid, the components contained in the black composition may be uniformly mixed under the condition that the (B) carbon black is dispersed, and the polyamine is adsorbed to the carbon black once. On the surface of the particles, a black composition containing (B) carbon black dispersed by polyamic acid was prepared. At this time, the polyamine acid which is a residual amount of the polyaminic acid adsorbed to the (B) carbon black as a dispersing agent can function as the (A) substrate component. In this method, as the mixing device when the black composition is to be prepared, the same dispersion device as that used for the preparation of the carbon black dispersion can be used as will be described later.

[Modulation method of carbon black dispersion]

In the dispersion medium, the (B) carbon black is vigorously stirred in the presence of a polylysine of a dispersing agent, or a shearing force is applied to the (B) carbon black, thereby obtaining a polyglycine via Dispersed (B) carbon black carbon black dispersion.

[polyglycine]

As the polyamic acid to be used as a dispersing agent, the same ones as described for the substrate component can be used. The molecular weight of the polyglycolic acid used as the dispersing agent is preferably 5,000 to 30,000 as the mass average molecular weight, and preferably 10,000 to 20,000. When the molecular weight of polylysine is within this range, use Polylysine which does not cause a large degree of influence on the characteristics of the black composition can well disperse the carbon black.

The amount of polyamic acid used can be well dispersed (B) carbon black, and is not particularly limited. From the viewpoint of the ease of dispersion of the (B) carbon black, the polyamine acid is preferably used in an amount of 20 to 80 parts by mass, and 30 to 70 parts by mass, based on 100 parts by mass of the (B) carbon black. good.

Further, the carbon black dispersion liquid is preferably one which does not contain a resin component other than polyamic acid. When the carbon black dispersion liquid contains a resin component other than polyglycolic acid, the aggregate of the primary particles of the carbon black is covered with the resin, the aggregate becomes difficult to disintegrate, or the aggregate on the surface of the primary particles of carbon black The molecular adsorption of the amine acid is hindered, and the dispersion of the (B) carbon black becomes difficult.

Disperse medium

The type of the dispersion medium is not particularly limited as long as the (B) carbon black can be favorably dispersed. Preferred examples of the dispersion medium include water; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and 1,3- Propylene glycol, isopropyl glycol, polypropylene glycol, pentamethyl glycol, trimethyl glycol, butanediol, isobutylene glycol, thiodiglycol, 1,2-hexanediol, 1,6- Glycol, 2-ethyl-1,3-hexanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1, Polyols such as 3-propanediol, 1,4-butanediol, 1,7-heptanediol, 1,8-octanediol, 2-butene-1,4-diol, and glycerin ; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol single-t- Butyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monoethyl ether, triethyl Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol single Polyol ethers such as phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monoisopropyl ether; acetone acetone, etc. Ketones; esters such as γ-butyrolactone, diacetate, and triethyl phosphate; lower alkoxy alcohols such as 2-methoxyethanol and 2-ethoxyethanol; ethanolamine, diethanolamine, and tris Amines such as ethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, tri-ethylidenetetraamine, tetra-extension ethylpentamine, and pentamethyldiethylethamine; formamide, N, N-dimethyl Indoleamines such as decylamine, N-methylformamide, and N,N-dimethylacetamide; N,N,N',N'-tetramethylurea, and N,N,N', Urea such as N'-tetraethyl urea; 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, morpholine, N- Ethylmorpholine, 2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, imidazole, methylimidazole, hydroxyimidazole, dimethylaminopyridine, 1,3-propane sultone a heterocyclic compound such as hydroxyethylpiperazine or piperazine; an anthracene such as dimethyl hydrazine; an anthracene such as cyclobutyl hydrazine. The dispersion medium may contain a combination of two or more kinds.

Among the above-mentioned dispersion media, an organic solvent containing N, N, N', N'-tetramethylurea is preferred. Containing N, N, N', N'- In the organic solvent of tetramethylurea, carbon black can be quickly and favorably dispersed by dispersing (B) carbon black by using polylysine as a dispersing agent.

When the dispersing medium is N,N,N',N'-tetramethylurea, the content of N,N,N',N'-tetramethylurea in the dispersing medium can only be (B) carbon black. The dispersion state is not particularly limited as long as it is kept in a good range. The content of N, N, N', N'-tetramethylurea in the dispersion medium is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. Excellent, 100% by mass is the best.

The content of the dispersion medium in the carbon black dispersion liquid is not particularly limited as long as the dispersion state of the carbon black can be favorably maintained. The solid black pigment dispersion of the carbon black dispersion has a solid content concentration of 5 to 60% by mass, preferably from 20 to 40% by mass of the dispersion medium.

[Other ingredients]

The carbon black dispersion may contain various additives that have been added to the carbon black dispersion in the past. Examples of such an additive include a viscosity modifier, a surfactant, an antioxidant, an ultraviolet absorber, a pH adjuster, and an antifoaming agent. These additives are used in the same amount as that which has been added to the carbon black dispersion in the range which does not adversely affect the properties of the carbon black dispersion.

[(B) Dispersion method of carbon black]

As the dispersing device used for the dispersion treatment of (B) carbon black, various kinds of dispersing devices which have been used in the past for dispersion of pigments can be used. As a specific example of a preferred dispersing device, a kneader, a salt grinding kneader, and a roll kneading can be used. Machines, planetary mixers, paint shakers, ball mills, sand mills, mills, bead mills, microball mills, homomixers, homogenizers, wet jet mills, high pressure homogenizers, ultrasonic homogenizers, etc. When the dispersing device is a medium to be used, glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like can be used as the medium.

When dispersing by an ultrasonic homogenizer, the above kneader, salt grinding kneader, roll kneader, planetary mixer, homomixer, homogenizer, wet jet mill, high pressure homogenizer, and bead mill are used in advance. It is preferable to use a carbon black which is prepared to be dispersed.

When the (B) carbon black is dispersed, each of carbon black, polylysine, and a dispersion medium in the above range can be used.

By dispersing (B) carbon black by the method described above, carbon black can be favorably dispersed in a short time to obtain a carbon black dispersion.

The content of the black component of the (B) carbon black dispersed as described above is preferably 5 to 70% by mass, and preferably 10 to 60% by mass, based on the solid content of the black composition.

<(C) A compound which produces an imidazole compound by heating>

The black composition contains (C) by heating to produce the following formula (C1): (In the formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfonate group. A compound of the imidazole compound represented by a phosphino group, a phosphinyl group, a phosphonate group or an organic group (the CZ thermal imidazole generator is also described in the present specification).

When the black composition contains the (C) thermal imidazole generator, the black composition is formed into a desired shape, and the formed black composition is heated at a temperature higher than the temperature at which the (C) thermal imidazole generator generates an imidazole compound. Heating is carried out to obtain a black molded body excellent in heat resistance.

The black composition contains dispersed (B) carbon black using polylysine as a dispersing agent. On the other hand, the imidazole compound represented by the formula (C1) produced by heating the black composition can promote the conversion of the polylysine adsorbed on the surface of the primary particles of the carbon black to the polyimine having high heat resistance. Therefore, by using the black composition of the present invention, a black molded body can be produced according to a method including heating, and a black molded body excellent in heat resistance can be obtained.

Further, the imidazole compound represented by the formula (C1) produced by heating the black composition, as described for the component (A), has a material which can be used as the material component of the (A) substrate component. When a reaction or a structure resulting from a cross-linking reaction between molecules is formed, the aromatic ring formation reaction or the crosslinking reaction can be promoted, and the heat resistance of the matrix formed of the component (A) can be improved.

Examples of the organic group in R ^c1 , R ^c2 and R ^c3 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic group. Although the organic group is generally monovalent, it may be a divalent or higher organic group when the cyclic structure is formed.

R ^c1 and R ^c2 may combine to form a cyclic structure, and may further contain a bond of a hetero atom. The cyclic structure may, for example, be a heterocycloalkyl group or a heteroaryl group, or may be a condensed ring.

The combination of the organic groups of R ^c1 , R ^c2 and R ^c3 is not particularly limited as long as the effects of the present invention are not impaired, and the organic group may contain a bond having a hetero atom such as an oxygen atom, a nitrogen atom or a halogen atom. Knot. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a guanamine bond, a urethane bond, and an imide bond (-N= C(-R)-, -C(=NR)-; R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinium bond, an azo bond or the like.

The bond of a hetero atom which may be possessed by an organic group containing R ^c1 , R ^c2 , and R ^c3 is an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond from the viewpoint of heat resistance of the imidazole compound. , ester bond, guanamine bond, urethane bond, imine bond (-N=C(-R)-, -C(=NR)-: R represents a hydrogen atom or a monovalent organic group), carbonate The bond, the sulfonyl bond, and the sulfinium bond are preferred.

When the organic groups of R ^c1 , R ^c2 and R ^{c3 are} a substituent other than a hydrocarbon group, R ^c1 , R ^c2 and R ^c3 are not particularly limited as long as the effects of the present invention are not impaired. Specific examples of R ^c1 , R ^c2 and R ^c3 include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyano group, a cyano group, an isocyanate group, a thiocyano group, and an isothiocyano group. , mercapto, stanol, alkoxy, alkoxycarbonyl, aminomethyl sulfonyl, thioaminomethyl hydrazino, nitro, nitroso, carboxylate, fluorenyl, decyloxy, Sulfosin, sulfonate, phosphino, phosphinyl, phosphonate, alkyl ether, alkenyl ether, alkylthioether, alkenylthio, aryl ether, aryl A thioether group or the like. The hydrogen atom contained in the above substituent may also be substituted by a hydrocarbon group. Further, the hydrocarbon group contained in the above substituent may be any of a linear chain, a branched chain, and a cyclic group.

R ^c1 , R ^c2 and R ^{c3 are} preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom. A hydrogen atom is preferred.

(C) The thermal imidazole generator is not particularly limited as long as it can produce the imidazole compound represented by the above formula (C1) by heating. A compound (thermobase generator) which can be added to a composition which has been added from the past by heat to produce an amine, and a skeleton derived from an amine produced by heating is substituted with an imidazole compound represented by the above formula (C1) In the case of the skeleton, a compound which can be used as the (C) thermal imidazole generator can be obtained.

The preferred (C) thermal imidazole generator is exemplified by the following formula (C2): (In the formula (C2), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfonate group. , phosphino, phosphinyl, phosphonate or organic, R ^c4 and R ^c5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitrous acid A compound represented by a group, a sulfinyl group, a sulfonic acid group, a nitroso group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate or an organic group, and Ar is an aromatic group which may have a substituent.

For the formula (C2), R ^c1 , R ^c2 , and R ^c3 are the same as those described for the formula (C1).

With respect to formula (C2), R ^c4 and R ^c5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfinyl group, a sulfonic acid group, Nitroso, phosphino, phosphinyl, phosphonium, phosphonate, or organic.

Examples of the organic group in R ^c4 and R ^c5 include those exemplified by R ^c1 , R ^c2 and R ^c3 . Similarly to the case of R ^c1 , R ^c2 , and R ^c3 , the organic group may contain a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a ring.

In the above, R ^c4 and R ^c5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, and a carbon number of 7 to 16. Aryloxyalkyl group, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having a cyano group, alkyl group having 1 to 10 carbon atoms having a hydroxyl group, and alkyl group having 1 to 10 carbon atoms An oxy group, a decylamino group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a fluorenyl group having 1 to 10 carbon atoms, and an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents Benzene substituted by a hydrocarbon group, an aryl group having 6 to 20 carbon atoms, an electron-donating group, and/or an electron-attracting group substituted with an aryl group having 6 to 20 carbon atoms, an electron-donating group, and/or an electron-attracting group Methyl, cyano and methylthio groups are preferred. Preferably, both of R ^c4 and R ^c5 are a hydrogen atom, or R ^c4 is a methyl group, and R ^c5 is a hydrogen atom.

For the formula (C2), Ar is an aromatic group which may have a substituent. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic group include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, and a different form. Oxazolyl, isothiazolyl, benzoxazolyl, benzothiazolyl, and benzimidazolyl. Among these aromatic groups, a phenyl group and a thienyl group are also preferred.

Preferred examples of the compound represented by the formula (C2) include the following formula (C3): (In the formula (C3), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfonate group. , phosphino, phosphinyl, phosphonate, or organic. R ^c4 and R ^c5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitros group. a sulfinyl group, a sulfonate group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, or an organic group. R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^{c10 are} each independently Represents a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfinyl group, a sulfonate group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphine group a group, a phosphonate group, an amine group, an ammonium group, or an organic group. Two or more of R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 may form a cyclic structure or may contain a hetero atom. Bonded to the compound shown.

For the formula (C3), R ^c1 , R ^c2 , and R ^c3 are the same as those described for the formula (C1), and R ^c4 and R ^c5 are the same as those described for the formula (C2).

With respect to formula (C3), R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, and a nitrous acid. A sulfoximine, sulfonate, sulfonate, phosphino, phosphinyl, phosphonium, phosphonate, amine, ammonium, or organic group.

Examples of the organic groups in R ^c6 , R ^c7 , R ^c8 , R ^c9 and R ^c10 include those exemplified for R ^c1 , R ^c2 and R ^c3 . The organic group is the same as in the case of R ^c1 and R ^c2 , and a bond or a substituent other than a hydrocarbon group such as a hetero atom may be contained in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic group.

Two or more of R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 may be bonded to each other to form a cyclic structure, and may also contain a bond of a hetero atom. The cyclic structure may, for example, be a heterocycloalkyl group or a heteroaryl group, or may be a condensed ring. For example, R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 may be bonded to each other, and may have atoms of a benzene ring to which R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 are bonded. A condensation ring of naphthalene, anthracene, phenanthrene or anthracene is formed.

In the above, R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, and a carbon number of 4; a cycloalkenyl group of ~13, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, and a carbon number having a hydroxyl group of 1~ 10 alkyl group, carbon number 1 to 10 alkoxy group, carbon number 2 to 11 decylamino group, carbon number 1 to 10 alkylthio group, carbon number 1 to 10 fluorenyl group, carbon number 2 to 11 Substituted by an ester group, an aryl group having 6 to 20 carbon atoms, an electron-donating group, and/or an electron-attracting group substituted with an aryl group having 6 to 20 carbon atoms, an electron-donating group, and/or an electron-attracting group A benzyl group, a cyano group, a methylthio group or a nitro group is preferred.

Further, as R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 , two or more of the atoms of the benzene ring to which R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 are bonded are bonded. It is also preferable to form a condensed ring of naphthalene, anthracene, phenanthrene or anthracene.

Among the compounds represented by the above formula (C3), the following formula (C4): (In the formula (C4), R ^c1 , R ^c2 and R ^{c3 are} synonymous with the formula (C1). R ^c4 to R ^{c9 are} synonymous with the formula (C3). R ^c11 represents a hydrogen atom or an organic group. R ^c6 and R ^{c7 are} not It is preferably a hydroxyl group. The compound represented by two or more of R ^c6 , R ^c7 , R ^c8 and R ^c9 may be bonded to each other to form a cyclic structure or may contain a bond of a hetero atom.

Since the compound represented by the formula (C4) has a substituent -OR ^c11 , it has excellent solubility in an organic solvent.

For the formula (C4), R ^c11 is a hydrogen atom or an organic group. When R ^c11 is an organic group, examples of the organic group include those exemplified for R ^c1 , R ^c2 , and R ^c3 . The organic group may contain a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a cyclic group. R ^{c11 is} preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and preferably a methyl group.

Specific examples of the particularly preferable compound of the (C) thermal imidazole generator include the following.

The content of the (C) thermal imidazole generator in the black composition is preferably 0.01 to 30% by mass, and preferably 0.1 to 5% by mass, based on the solid content of the black composition.

<(D) oxime ester compound>

The black composition may contain (D) an oxime ester compound. The black composition contains an alkali-soluble polyaminic acid as a dispersing agent for dispersing (B) carbon black. Therefore, it is soluble in the alkali imaging solution. On the other hand, since the black composition contains the above (C) thermal imidazole generator, the solubility in the alkali developing solution is lowered by exposure. This is (C) a thermal imidazole generator which can also produce an imidazole compound by the action of light. When the imidazole compound is produced by the (C) thermal imidazole generator by exposure, the polyimide resin is formed by the ring closure of the polyamine contained in the exposed photosensitive composition.

Although such a black composition originally had a photolithographic property, when the black composition contained the (D) oxime ester compound, the lithographic characteristics of the black composition were particularly good. Therefore, when a black composition containing a (D) oxime ester compound is used, a fine pattern of a black molded body can be formed by photolithography. The (D) oxime ester compound acts on at least one of light and heat, and at least one of a base and an acid is produced by decomposition, and the base or acid produced is used as a dispersing agent or (A) in the black composition. The closed loop of the material containing poly-proline is promoted.

The oxime ester compound is not particularly limited as long as it is a compound in which two organic groups are bonded via a oxime ester bond represented by =N-O-CO-. As a preferable oxime ester compound, the following compounds are mentioned.

Content of (D) oxime ester compound in black composition The solid content of the black composition is preferably 0.01 to 30% by mass, more preferably 0.1 to 5% by mass.

<(S) organic solvent>

The black composition is preferably one containing the (S) organic solvent used for dilution. Examples of the (S) organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethyl ether. Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, three Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl (poly)alkylene glycol monoalkyl ethers such as ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (poly)alkylene glycol monoalkyl ether acetates such as acid esters, propylene glycol monoethyl ether acetate, etc.; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol II Other ethers such as ethyl ether and tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2- Ketones such as ketone and 3-heptanone; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxyl Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy Butyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, Ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate Other esters such as ethyl acetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; formamide, N,N-dimethylformamide, N-methylformamidine Amines, amides such as N,N-dimethylacetamide; N,N,N',N'-tetramethylurea, and ureas such as N,N,N',N'-tetraethylurea Class; 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, morpholine, N-ethylmorpholine, 2-oxazole Heterocyclic compounds such as alkanone, 1,3-dimethyl-2-imidazolidinone, dimethylaminopyridine, 1,3-propane sultone, hydroxyethylpiperazine, and piperazine; Axil such as Chia ;; 碸 such as 碸 碸 and so on.

Among them, guanamines such as methotrexate, N,N-dimethylformamide, N-methylformamide, and N,N-dimethylacetamide; N, N, N' , N'-tetramethylurea, and ureas such as N, N, N', N'-tetraethyl urea; 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl- A heterocyclic compound such as 2-pyrrolidone or cyclohexyl pyrrolidone is preferred. These (S) organic solvents may be used alone or in combination of two or more.

The content of the (S) organic solvent is preferably such that the solid content concentration of the black composition is from 1 to 50% by mass, and preferably from 5 to 30% by mass.

<(E) Other ingredients>

The black composition relating to the present invention may contain various additives as necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, a coagulation preventing agent, a thermal polymerization inhibiting agent, an antifoaming agent, and a surfactant.

As the adhesion promoter, a decane coupling agent is preferred. By adding a decane coupling agent to the black composition, it is possible to form a black molded body excellent in adhesion to the substrate.

The decane coupling agent to be used as the adhesion promoter is not particularly limited, and the decane coupling agent used for the treatment of (B) carbon black is preferably a decane coupling agent represented by the above formula (B1).

Among the compounds of the formula (B1), specific examples of the particularly preferred compound of the decane coupling agent used as the adhesion promoter include the above-mentioned compounds 1 to 8 which are preferred examples of the compound represented by the formula (B1).

Preferable examples of the decane coupling agent other than the decane coupling agent represented by the formula (B1) include N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, and N- 2-(Aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, and 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine.

≪Black molded body manufacturing method≫

The method of producing the black molded body using the black composition described above is not particularly limited. A typical method is to form a black composition into a predetermined shape, and the formed black composition is produced in the above (C) thermal imidazole. After the heat treatment at a higher temperature at which the imidazole compound is produced, a black molded body is produced.

The method of forming the black composition into a predetermined shape is not particularly limited. As a method of molding the black composition into a predetermined shape, a method of applying a black composition on various substrates, a method of filling a black composition in a mold having a desired shape, or the like can be given.

Examples of the method of applying the black composition to the substrate include a contact transfer type coating device such as a roll coater, a reverse coater, and a bar coating, or a rotator (rotary coating device) or curtain coating. A method of a non-contact type coating device such as a cloth machine.

After the black composition is formed into a predetermined shape, it is preferred to dry the black composition and remove the (S) organic solvent.

The black composition formed into a predetermined shape is heat-treated at a temperature higher than a temperature at which the (C) thermal imidazole generator produces an imidazole compound. (C) Temperature at which the imidazole generator produces an imidazole compound can be determined by TG-DTA (thermogravimetry-differential thermal analysis). Specifically, the TG curve obtained by TG-DTA analysis of the (C) thermal imidazole generator shows the temperature of the lowest temperature side on the bottom line starting from the weight loss by thermal decomposition as (C) thermal imidazole The temperature at which the generating agent generates the imidazole compound by thermal decomposition can be used. The upper limit of the temperature at which the black composition is subjected to heat treatment is not particularly limited as long as it does not inhibit the object of the present invention. The heat treatment can be carried out at a temperature of 400 ° C or less, preferably at a temperature in the range of 130 to 300 ° C.

The heat treatment time is not particularly limited, and it is preferably 20 to 300 minutes. 30 to 180 minutes is preferred.

The black molded body formed by the above method contains well-dispersed carbon black, is colored to a desired concentration of black, and can be used for various purposes due to its excellent heat resistance.

[Examples]

The invention is described in more detail below by way of examples, but the invention is not limited thereto.

In the examples and comparative examples, the following BR-1 to BR-8 were used as the substrate component.

BR-1: Polylysine prepared by the following Preparation Example 1

BR-2: Polylysine prepared by the following Preparation Example 2

BR-3: Polybenzoxazole precursor prepared by the following Modification Example 3

BR-4: Polyimine resin prepared by the following Preparation Example 4

BR-5: styrene-anhydrous maleic acid copolymer (SMA1000, manufactured by Sichuan Crude Oil Co., Ltd.)

BR-6: N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

BR-7: Polybenzimidazole resin prepared by the following Preparation Example 5

BR-8: cresol novolac resin (m-cresol/p-cresol ratio = 6/4, mass average molecular weight: 80000)

[Modulation Example 1]

(modulation of BR-1)

654.4 g of pyromellitic dianhydride, 672.8 g of 4,4'-diaminodiphenyl ether, and 2518 g of NMP were placed in a separable flask having a capacity of 5 L in a nitrogen gas introduction tube, a stirrer, and a cooler. Nitrogen gas was introduced into the flask through a nitrogen introduction tube, and the inside of the flask was placed in a nitrogen atmosphere. Next, while stirring the contents of the flask, the reaction of tetracarboxylic dianhydride and diamine was carried out at 50 ° C for 20 hours, and the solvent was distilled off to obtain BR-1 of polylysine.

[Modulation Example 2]

(modulation of BR-2)

For the change of pyromellitic acid, 228.2 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride and 441.3 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride were changed, and 4,4 were changed. Poly-proline acid BR-2 was obtained in the same manner as BR-1 except that 1170.8 g of 9,9-bis(4-aminophenyl)fluorene was used for the '-diaminodiphenyl ether.

[Modulation Example 3]

(modulation of BR-3)

After adding 4 mmol of 4,4'-diamino-3,3'-dihydroxybiphenyl to 1 mL of NMP in a conical flask containing a rotor, the contents of the flask were stirred for 5 minutes using a magnetic stirrer. Thereafter, 2 mmol of isophthalaldehyde was placed in a flask, and the contents of the flask were refluxed for 3 hours under a nitrogen atmosphere to carry out a reaction. Next, the reaction liquid was dehydrated at the end of vacuum distillation, and the solvent was distilled off to obtain BR-3 of a polybenzoxazole precursor having the following structure. The polybenzoxazole precursor has a number average molecular weight of about 1500.

(In the above formula, n is the unit repetition number in parentheses)

[Modulation Example 4]

(modulation of BR-4)

14.71 g (50 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 10.01 g (50 mmol) of 4,4'-diaminodiphenyl ether and N-methyl-2- 181.3 g of pyrrolidone was placed in a glass reaction vessel equipped with a nitrogen gas introduction tube, a stirrer, and a cooler. The content of the reaction vessel was raised from room temperature to 160 ° C over 1 hour to carry out polymerization and hydrazine imidization to obtain a prepolymerization solution. The polyamidene contained in the prepolymerization solution had a ruthenium iodide ratio of 90% or more and a logarithmic viscosity of 1.02. Moreover, the rotational viscosity of the former polymerization solution at 140 ° C is 1.1 Pa. s.

11 g (about 8 ml) of the obtained polymerization solution was placed in a glass-coated high-pressure autoclave inside the vessel, and the gas phase in the high-pressure autoclave was replaced with nitrogen. Next, after sealing the high-pressure autoclave, the pre-polymerization liquid was heated to 180 ° C, and post-polymerization was carried out, and the solvent was distilled off to obtain BR-4 of a polyimide resin.

[Modulation Example 5]

(modulation of BR-7)

3,3',4,4'-tetraaminobiphenyl 56.35 g (263 mmol) and isophthalic acid 43.69 g (0.263) were placed in a glass reaction vessel equipped with a nitrogen gas introduction tube, a stirrer, and a cooler. Methyl) with triphenyl phosphite. The internal temperature of the flask was raised to 415 ° C over 1 hour while stirring the contents of the flask under a nitrogen atmosphere. After the internal temperature of the flask reached 415 ° C, the reaction was continued for another hour at the same temperature. After the completion of the reaction, the contents of the flask were cooled to room temperature to obtain BR-7 of a polybenzimidazole resin. The obtained polybenzimidazole resin had a mass average molecular weight of 140,000.

For the examples and comparative examples, a black composition was prepared using a carbon black dispersion. The following carbon blacks CB and CB-A were used in the preparation of the carbon black dispersion.

CB: carbon black (Regal 250R, manufactured by Cabot Corporation)

CB-A: A carbon black to be subjected to a treatment for introducing an acidic group, which was prepared according to the following method.

Carbon black treated by a decane coupling agent according to the following method was used in Example 3 and Example 6. The following SC-A was used as a decane coupling agent. Further, SC-A was also used as a adhesion promoter in Example 7.

[Modulation example of CB-A]

550 g of carbon black CB (Regal 250R, manufactured by Cabot Co., Ltd.), 31.5 g of acesulfame sulfonic acid, and 1000 g of ion-exchanged water were placed in a reaction vessel having a sheath and a stirring device set at a sheath temperature of 60 °C. After a solution in which 12.6 g of sodium nitrite was dissolved in 100 g of deionized water was placed in a Brown mixer, the mixture in the stirrer was stirred at 60 ° C for 50 times/min for 2 hours to carry out a diazo coupling reaction. After stirring, the contents of the blender were cooled to room temperature. Next, the carbon black contained in the contents of the mixer was purified by a total filtration method using deionized water. It was found from the washing water that the benzenesulfonic acid derived from the amine benzenesulfonyl acid was not detected, and the benzenesulfonic acid group was introduced into the carbon black by the diazo coupling reaction. The purified carbon black was dried overnight at 75 ° C and then pulverized to obtain a carbon black (CB-A) into which a benzenesulfonic acid group was introduced.

[矽 偶 coupling agent treatment]

50 g of carbon black of the type described in Table 1 and 200 g of an isopropanol solution of a decane coupling agent having a concentration of 1.25 mass% were mixed at 60 ° C for 3 hours. The suspension containing carbon black after stirring was heated at 100 ° C to volatilize isopropanol and by-product methanol, and then a powder of carbon black treated with a decane coupling agent was obtained.

Using the carbon black described above, a carbon black dispersion was prepared in accordance with the following method.

When preparing a carbon black dispersion, the following DP- is used as a dispersant. 1~DP-3.

DP-1: Polylysine (BR-1) obtained by the above Preparation Example 1

DP-2: Polylysine (BR-2) obtained by the above Preparation Example 2

DP-3: urethane-based polymer dispersant (BYK-167, BYK. Japan Co., Ltd.)

When the carbon black dispersion is prepared, N, N, N', N'-tetramethylurea (TMU) or N-methyl-2-pyrrolidone (NMP) is used as a solvent.

[Carbon black dispersion preparation method]

10 g of untreated carbon black or 10.5 g of carbon black treated with a decane coupling agent and 3 g of the dispersant of the type described in Table 1 to the solvent of the type described in Table 1 reached a total amount of 100 g of the carbon black dispersion. . The resulting mixture was stirred, and carbon black was dispersed to obtain a carbon black dispersion.

For the examples and comparative examples, the following compounds were used as the hot imidazole generator. The temperature of the imidazole produced by the following compounds was less than 180 °C.

For the examples and comparative examples, as the organic solvent for diluting the black composition, N,N,N',N'-tetramethylurea (TMU), N-methyl-2-pyrrolidone (NMP), or N,N-dimethylacetamide (DMAc).

[Examples 1 to 17 and Comparative Examples 1 to 8]

In Examples 1 to 17 and Comparative Example 2, the substrate component of the type and amount described in Table 1 and 27.5 g of the carbon black dispersion of the composition described in Table 1 and the thermal imidazole generator 0.3 g and Table 1 were uniformly mixed. 66.3 g of the organic solvent of the type described was obtained, and a black composition was obtained.

In Comparative Example 1 and Comparative Examples 3 to 8, the substrate component of the type and amount described in Table 1 and 27.5 g of the carbon black dispersion of the composition described in Table 1 were uniformly mixed with the organic solvent of the type described in Table 1. 66.3 g, a black composition was obtained.

Further, in Example 7, 0.1 g of the above SC-A in which a decane coupling agent was added as a adhesion promoter was added to the black composition, and 0.3 g of the following compound was added as an oxime ester compound in Example 16.

The heat resistance and optical density of the black molded body (film) formed using the obtained black composition were evaluated in accordance with the following methods.

<heat resistance evaluation>

The black composition was applied onto a wafer substrate using a spin coater. The coating film on the wafer substrate was heated at 180 ° C for 1 hour to form a cured film (black molded body) having a film thickness of about 1.0 μm.

From the formed cured film, 5 μg of the sample for heat resistance evaluation was taken out. The sample for heat resistance evaluation was measured by a differential heat/thermogravimetric measuring apparatus (TG/DTA-6200, manufactured by Seiko Instruments Inc.) under the conditions of a temperature increase rate of 10 ° C/min in an air stream to obtain TG. curve. The 5% weight reduction temperature of the sample was determined from the obtained TG curve. The measurement results of the 5% weight loss temperature are shown in Table 2.

<Optical Density Evaluation>

A cured film (black molded body) having a film thickness of about 1.0 μm was formed in the same manner as the heat resistance evaluation.

The OD value of the formed cured film was measured using a transmittance measuring instrument (D-200II, manufactured by Gretag Macbeth Co., Ltd.). The OD value obtained by the measurement is shown in Table 2.

<Model Formation Evaluation>

The black composition of Example 16 was confirmed for the pattern formation by photolithography according to the following method.

The black composition of Example 16 was applied onto a glass substrate (100 mm × 100 mm) using a spin coater, and then the film was heated at 100 ° C for 120 seconds to form a coating film having a film thickness of 1.0 μm.

Using a mirror projection lithography machine (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), a negative-type mask having a line pattern of 5 μm in line width was formed with an exposure gap of 50 μm, and the formed coating film was irradiated. Ultraviolet light. The exposure amount was 20 mJ/cm ² . The exposed coating film was developed using a 0.4% by mass aqueous KOH solution at 25 ° C for 30 seconds.

After development, a line pattern was formed after 30 minutes of roasting at 230 °C. When the formed line pattern was observed by an optical microscope, it was found that a line having a line width of 5 μm was not formed by peeling off from the glass substrate.

In other words, the black composition of Example 16 has a good pattern forming ability by photolithography.

According to Tables 1 and 2, it is known that the black component of the embodiment containing the substrate component, carbon black dispersed by poly-proline, and the thermal imidazole generator of a predetermined structure produces an imidazole compound in the specific heat imidazole generator. The black molded body formed by heating at a higher temperature has a high optical density and excellent heat resistance because it contains carbon black which is well dispersed.

According to Comparative Example 1 and Comparative Examples 3 to 8, it was found that the black component contained the substrate component and the carbon black dispersed by the polyamic acid, and the heat resistance was not contained in the thermal imidazole generating agent having a predetermined structure. The formation of an excellent black molded body becomes difficult.

According to the second comparative example, even if the black composition contains the substrate component, the carbon black, and the thermal imidazole generator having a predetermined structure, if the carbon black is not dispersed by the polyamic acid, it is difficult to form a film having high optical density and excellent heat resistance. Black molded body. As a result of observing the cured film formed using the black composition of Comparative Example 2, carbon black aggregation in the cured film was confirmed.

Claims (6)

A black composition characterized by comprising (A) a substrate component, (B) carbon black and (C) heated to produce formula (C1): (In the formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfonate group. A compound of the imidazole compound represented by a phosphonyl group, a phosphinyl group, a phosphonate group or an organic group; and the above (B) carbon black is a dispersion treated by using polyglycine as a dispersing agent. The black composition of claim 1, which comprises the following carbon black dispersion which is obtained by dispersing carbon black in the above-mentioned (B) carbon black using polylysine as a dispersing agent in a dispersion medium. . The black composition of claim 1 or 2, wherein the compound (C) obtained by heating to produce the imidazole compound represented by the above formula (C1) is the formula (C2): (In the formula (C2), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfonate group. , phosphino, phosphinyl, phosphonate or organic, R ^c4 and R ^c5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitrous acid A compound represented by a group, a sulfinyl group, a sulfonate group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group or an organic group, and Ar is an aromatic group which may have a substituent. The black composition according to any one of claims 1 to 3, wherein the (A) substrate component is a resin which is produced by heating an aromatic ring in a molecule and/or a cross-linking reaction between molecules. A method for producing a black molded body, characterized in that after the black composition according to any one of claims 1 to 4 is formed into a predetermined shape, the formed black composition is heated to be higher than the above (C). The imidazole compound shown in (C1) is subjected to heat treatment at a temperature at which the temperature of the imidazole compound is higher. A black formed body characterized by being produced by the method of claim 5.