WO2015098788A1 - Composition contenant un polymère de triazine - Google Patents

Composition contenant un polymère de triazine Download PDF

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WO2015098788A1
WO2015098788A1 PCT/JP2014/083819 JP2014083819W WO2015098788A1 WO 2015098788 A1 WO2015098788 A1 WO 2015098788A1 JP 2014083819 W JP2014083819 W JP 2014083819W WO 2015098788 A1 WO2015098788 A1 WO 2015098788A1
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group
polymer
triazine
containing composition
compound
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直也 西村
小澤　雅昭
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日産化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to a triazine polymer-containing composition.
  • a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and the polymer alone has high heat resistance, high transparency, high refractive index, and high solubility. It has already been found that a low volume shrinkage can be achieved and it is suitable as a film-forming composition for producing an electronic device (Patent Document 1).
  • Patent Document 1 can meet the demand in terms of refractive index, but there is room for improvement in terms of fine pattern formability.
  • Patent Document 2 discloses a pattern-forming composition containing a triazine ring-containing polymer, the polymer has a refractive index of less than 1.7, and a higher refractive index is required. Not suitable for use.
  • the present invention has been made in view of the above circumstances, and can form a thin film having a high refractive index and excellent transparency by low-temperature firing, and can also form a fine pattern having a high refractive index.
  • An object is to provide a coalescence-containing composition.
  • the present inventors have obtained a composition comprising a triazine ring-containing polymer substituted with an arylamino group having a predetermined functional group, and two kinds of crosslinking agents.
  • a composition comprising a triazine ring-containing polymer substituted with an arylamino group having a predetermined functional group, and two kinds of crosslinking agents.
  • a triazine-based polymer-containing composition comprising a polymer containing a repeating unit structure represented by the following formula (1) and at least two kinds of crosslinking agents: ⁇ In the formula, R and R 'each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar 1 represents an aryl group having a hydroxyl group, a carboxyl group, and / or a maleimide group.
  • Ar 2 represents at least one selected from the group represented by formulas (2) to (13).
  • R 1 to R 92 are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1
  • R 93 and R 94 represent a hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms
  • W 1 and W 2 is independently a single bond
  • CR 95 R 96 R 95 and R 96 are each independently a hydrogen atom or an alkyl group optionally having a branched structure of 1 to 10 carbon atoms ( However, these may be combined to form a ring.))
  • C ⁇ O, O, S, SO, SO 2 , or NR 97 R 97 is a hydrogen atom or a carbon number of 1).
  • X 1 Contact Fine X 2 are independently of each other a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or the formula, (14) (Wherein R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group which may have a branched structure of ⁇ 10, and Y 1 and Y 2 each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms.
  • the triazine polymer-containing composition according to any one of 1 to 3, wherein the polymer includes a repeating unit structure represented by the following formula (18): (Wherein R, R ′ and Ar 2 represent the same meaning as described above.) 5.
  • An electronic device comprising a substrate and eleven patterns formed on the substrate is provided.
  • the present invention it is possible to form a thin film having a high refractive index and excellent transparency, and it is possible to form a fine pattern by masking, exposing and curing, and then performing alkali development or the like.
  • two kinds of crosslinking agents are used in combination, there is an advantage that a thin film can be formed by low-temperature firing.
  • the cured film and fine pattern produced from the composition of the present invention can exhibit characteristics such as high heat resistance, high refractive index, and low volume shrinkage due to the crosslinked triazine ring-containing polymer.
  • Luminescence (EL) display touch panel, optical semiconductor (LED) element, solid-state imaging device, organic thin film solar cell, dye-sensitized solar cell, organic thin film transistor (TFT), lens, prism, camera, binoculars, microscope, semiconductor exposure device, etc. It can be suitably used in the field of electronic devices and optical materials, such as one member for manufacturing the device.
  • the high refractive index pattern produced from the composition of the present invention requires a high refractive index pattern including the above-mentioned prevention of transparent electrode bone appearance such as touch panel, light extraction use of organic EL display and black matrix use. It can be suitably used for the intended use.
  • FIG. 1 is a 1 H-NMR spectrum diagram of a polymer compound [4] obtained in Example 1.
  • FIG. FIG. 3 is a graph showing a TG-DTA measurement result of the polymer compound [4] obtained in Example 1.
  • the triazine polymer-containing composition according to the present invention includes a polymer containing a repeating unit structure represented by the following formula (1) and at least two kinds of crosslinking agents.
  • R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
  • both of them may be hydrogen atoms.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms in view of further improving the heat resistance of the polymer. Is even more preferable.
  • the structure may be any of a chain, a branch, and a ring.
  • alkyl group examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl.
  • N-pentyl 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2 , 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pe Til, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3- Dimethyl-n-butyl, 2,2-di
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms in view of further improving the heat resistance of the polymer. preferable.
  • the structure of the alkyl moiety may be any of a chain, a branch, and a ring.
  • alkoxy group examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n -Butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n -Hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy 3,3-dimethyl-n-butoxy, 1-ethoxy,
  • the number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 40. In view of further improving the heat resistance of the polymer, 6 to 16 carbon atoms are more preferable, and 6 to 13 are even more preferable. preferable.
  • aryl group examples include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, ⁇ -naphthyl, ⁇ -naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9-phenanthryl group and the like.
  • the number of carbon atoms of the aralkyl group is not particularly limited, but preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched or cyclic. Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, Examples include 4-isobutylphenylmethyl, ⁇ -naphthylmethyl group and the like.
  • Ar 1 is not particularly limited as long as it is an aryl group having a hydroxyl group, a carboxyl group and / or a maleimide group, but those represented by the following formulas (15) to (17) are preferred.
  • R 102 to R 110 each independently represent the same meaning as R 1 above.
  • those represented by the following formula are preferable from the viewpoint of improving the solubility of the obtained cured product in an alkaline developer.
  • the triazine ring-containing polymer of the present invention preferably includes a repeating unit structure represented by the following formula (18), and more preferably includes a repeating unit structure represented by the following formula (19).
  • Ar 2 represents at least one selected from the group represented by formulas (2) to (13).
  • R 1 to R 92 are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group that may have a branched structure having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms.
  • X 1 and X 2 each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (14).
  • R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms.
  • An alkoxy group which may have a branched structure is represented, and Y 1 and Y 2 each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms.
  • Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
  • Examples of the alkylene group that may have a branched structure having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups.
  • Ar is preferably at least one of the formulas (2), (5) to (13), and the formulas (2), (5), (7), (8), (11) to (13) More preferably, at least one selected from Specific examples of the aryl group represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulae.
  • an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.
  • a repeating unit structure represented by the following formula (20) in view of further improving the solubility in a highly safe solvent such as a resist solvent, and a repeating unit structure represented by the following formula (21). It is more preferable that it contains.
  • the weight average molecular weight of the polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000. From the viewpoint of further improving the heat resistance and reducing the shrinkage rate. It is preferably 2000 or more, preferably 50000 or less, more preferably 30000 or less, and even more preferably 10,000 or less from the viewpoint of further increasing the solubility and decreasing the viscosity of the obtained solution.
  • the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.
  • the triazine ring-containing polymer used in the present invention can be produced by the technique disclosed in Patent Document 1 described above.
  • a triazine ring-containing polymer having a repeating structure (26) is obtained by reacting a triazine compound (24) having a phenylamino group and a diamino compound (25) in a suitable organic solvent.
  • the compound represented by the above formula (24) can be produced from a cyanuric halide and 3-aminophenol by a known method. Further, the reaction may be carried out by adding a diamino compound into the reaction system of cyanuric halide and 3-aminophenol.
  • the amount of each raw material charged is arbitrary as long as the target polymer is obtained, but is preferably 0.01 to 10 equivalents of diamino compound (25) to 1 equivalent of triazine compound (24). 0.1 to 0.8 equivalent or 1 to 5 equivalent is more preferable.
  • the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, but is preferably about ⁇ 30 to 150 ° C., more preferably ⁇ 10 to 100 ° C.
  • organic solvent various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, dimethyl sulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ′, N′-tetramethylmalonic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, N, N'-dimethylpropylene urea Amide solvents such as, and mixed solvents thereof Among these, N, N-dimethylformamide, dimethyl s thereof,
  • the order of blending the components is arbitrary, but a method of adding the diamino compound (25) to a solution containing the triazine compound (24) and the organic solvent is preferable.
  • Components added later may be added neat or in a solution dissolved in an organic solvent as described above, but the latter method is preferred in view of ease of operation and ease of reaction control. It is.
  • the addition may be gradually added by dropping or the like, or may be added all at once.
  • various bases usually used during polymerization or after polymerization may be added.
  • this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxidized Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6 , 6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
  • the amount of the base added is preferably 1 to 100 equivalents and more preferably 1 to 10 equivalents with respect to 1 equivalent of the triazine compound (24). These bases may be used as an aqueous solution. Although it is preferable that the raw material component does not remain in the obtained polymer, a part of the raw material may remain as long as the effect of the present invention is not impaired. In any of the scheme methods, after completion of the reaction, the product can be easily purified by a reprecipitation method or the like.
  • a part of halogen atoms of at least one terminal triazine ring is substituted with alkyl, aralkyl, aryl, alkylamino, alkoxysilyl group-containing alkylamino, aralkylamino, arylamino, alkoxy, aralkyloxy, aryloxy.
  • alkylamino, alkoxysilyl group-containing alkylamino, aralkylamino, and arylamino groups are preferable, alkylamino and arylamino groups are more preferable, and arylamino groups are more preferable. Examples of the alkyl group and alkoxy group are the same as those described above.
  • ester group examples include methoxycarbonyl and ethoxycarbonyl groups.
  • aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, ⁇ -naphthyl, ⁇ -naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9-phenanthryl group and the like.
  • aralkyl group examples include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenyl.
  • examples include methyl, 4-isobutylphenylmethyl, ⁇ -naphthylmethyl group and the like.
  • alkylamino group examples include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, t-butylamino, n-pentylamino, 1-methyl- n-butylamino, 2-methyl-n-butylamino, 3-methyl-n-butylamino, 1,1-dimethyl-n-propylamino, 1,2-dimethyl-n-propylamino, 2,2-dimethyl -N-propylamino, 1-ethyl-n-propylamino, n-hexylamino, 1-methyl-n-pentylamino, 2-methyl-n-pentylamino, 3-methyl-n-pentylamino, 4-methyl -N-pentylamino, 1,1-dimethyl-n-butylamino, 1,2-
  • aralkylamino group examples include benzylamino, methoxycarbonylphenylmethylamino, ethoxycarbonylphenylmethylamino, p-methylphenylmethylamino, m-methylphenylmethylamino, o-ethylphenylmethylamino, m-ethylphenylmethyl.
  • arylamino group examples include phenylamino, methoxycarbonylphenylamino, ethoxycarbonylphenylamino, naphthylamino, methoxycarbonylnaphthylamino, ethoxycarbonylnaphthylamino, anthranylamino, pyrenylamino, biphenylamino, terphenylamino, fluorenyl An amino group etc. are mentioned.
  • the alkoxysilyl group-containing alkylamino group may be any of monoalkoxysilyl group-containing alkylamino, dialkoxysilyl group-containing alkylamino, trialkoxysilyl group-containing alkylamino group, and specific examples thereof include 3-trimethoxysilyl.
  • aryloxy group examples include phenoxy, naphthoxy, anthranyloxy, pyrenyloxy, biphenyloxy, terphenyloxy, and fluorenyloxy groups.
  • aralkyloxy group examples include benzyloxy, p-methylphenylmethyloxy, m-methylphenylmethyloxy, o-ethylphenylmethyloxy, m-ethylphenylmethyloxy, p-ethylphenylmethyloxy, 2-propyl Examples include phenylmethyloxy, 4-isopropylphenylmethyloxy, 4-isobutylphenylmethyloxy, ⁇ -naphthylmethyloxy groups and the like.
  • These groups can be easily introduced by substituting a halogen atom on the triazine ring with a compound that gives a corresponding substituent.
  • a halogen atom on the triazine ring For example, as shown in the following formula scheme 2, an aniline (derivative) or the like can be introduced.
  • an organic monoamine By adding and reacting an organic monoamine, a triazine ring-containing polymer (27) having a phenylamino group at at least one terminal is obtained.
  • Alkyl monoamines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, 1-methyl-n-butylamine, 2-methyl- n-butylamine, 3-methyl-n-butylamine, 1,1-dimethyl-n-propylamine, 1,2-dimethyl-n-propylamine, 2,2-dimethyl-n-propylamine, 1-ethyl-n -Propylamine, n-hexylamine, 1-methyl-n-pentylamine, 2-methyl-n-pentylamine, 3-methyl-n-pentylamine, 4-methyl-n-pentylamine, 1,1-dimethyl -N-but
  • aralkyl monoamines include benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine and the like.
  • aryl monoamine examples include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o- And phenylaniline, 4-amino-p-terphenyl, 2-aminofluorene, and the like.
  • the amount of the organic monoamine used is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, and even more preferably 0.05 to 50 equivalents based on the halogenated cyanuric compound. .
  • the reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 150 ° C, and still more preferably 80 to 120 ° C.
  • the mixing of the three components of the organic monoamine, the halogenated cyanuric compound and the diaminoaryl compound may be carried out at a low temperature. In this case, the temperature is preferably about ⁇ 50 to 50 ° C., and about ⁇ 20 to 50 ° C. Is more preferable, and ⁇ 20 to 10 ° C. is more preferable.
  • the reaction After the low temperature charging, it is preferable to carry out the reaction by raising the temperature to the polymerization temperature at once (in one step).
  • the two components of the cyanuric halide compound and the diaminoaryl compound may be mixed at a low temperature.
  • the temperature is preferably about ⁇ 50 to 50 ° C., more preferably about ⁇ 20 to 50 ° C., More preferably, it is ⁇ 20 to 10 ° C.
  • crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the above-described triazine ring-containing polymer.
  • examples of such compounds include melamine compounds having a crosslinkable substituent such as a methylol group and methoxymethyl group, substituted urea compounds, compounds containing a crosslinkable substituent such as an epoxy group or an oxetane group, and blocked isocyanates.
  • a compound containing a group is preferable, and in particular, two types selected from a compound having a blocked isocyanate group and a polyfunctional epoxy compound and a polyfunctional (meth) acryl compound that give a photocurable composition without using an initiator.
  • a polyfunctional epoxy compound and a polyfunctional (meth) acrylic compound Seen together is more preferable.
  • These compounds may have at least one crosslink forming substituent when used for polymer terminal treatment, and at least two crosslink forming substituents when used for cross-linking treatment between polymers. It is necessary to have.
  • the polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl.
  • epoxy resins having at least two epoxy groups YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.), epoxy resins having a cyclohexene oxide structure, Epolide GT-401 and GT -403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), bisphenol A type epoxy resin, Epicoat (currently jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (Japan Epoxy Resin Co., Ltd.), Bisphenol F type epoxy resin, Epicoat (currently jER) 807 (Japan Epoxy Resin Co., Ltd.) , Epicoat (a phenol novolac type epoxy resin) , JER) 152, 154 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPPN 201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.
  • the polyfunctional (meth) acrylic compound is not particularly limited as long as it has two or more (meth) acrylic groups in one molecule.
  • Specific examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, and ethoxylated.
  • Polyfunctional (meth) acrylic compounds can be obtained as commercial products. Specific examples thereof include NK ester A-200, same A-400, same A-600, same A-1000, same A- 9300 (Tris (2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE- 100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, Same A- MPT-9EO, AT-20E, ATM-4E, ATM-35E (Shin Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPEA-12, PEG400
  • the acid anhydride compound is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydration condensation of two molecules of carboxylic acid. Specific examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride.
  • the isocyanate group (—NCO) when the isocyanate group (—NCO) has two or more blocked isocyanate groups blocked by an appropriate protective group in one molecule, it is exposed to a high temperature during thermosetting.
  • the protective group (block part) is not particularly limited as long as it is dissociated by thermal dissociation and the resulting isocyanate group causes a crosslinking reaction with the resin.
  • a group represented by the following formula Examples thereof include compounds having two or more in the molecule (note that these groups may be the same or different from each other).
  • R b represents an organic group in the block part.
  • Such a compound can be obtained, for example, by reacting an appropriate blocking agent with a compound having two or more isocyanate groups in one molecule.
  • the compound having two or more isocyanate groups in one molecule include, for example, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), polyisocyanate of trimethylhexamethylene diisocyanate, and dimers thereof. , Trimers, and reaction products of these with diols, triols, diamines, or triamines.
  • the blocking agent examples include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol; phenol, o-nitrophenol , P-chlorophenol, phenols such as o-, m- or p-cresol; lactams such as ⁇ -caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime
  • pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole
  • thiols such as dodecanethiol and benzenethiol.
  • a compound containing a blocked isocyanate is also available as a commercial product.
  • Specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B -7005, B-7030, B-7075, B-5010 (Mitsui Chemicals Polyurethane Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, manufactured by Asahi Kasei Chemicals Corporation), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko Co., Ltd.), and the like.
  • the aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule.
  • hexamethoxymethylmelamine CYMEL (registered trademark) 303 tetrabutoxymethylglycoluril 1170 Cymel series such as Tetramethoxymethylbenzoguanamine 1123 (Nippon Cytec Industries, Ltd.), Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, which are methylated melamine resins
  • melamine compounds such as MX-750LM, Nicarac series such as MX-270 and MX-280, which are methylated urea resins, and MX-280 and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
  • the oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule.
  • OXT-221, OX-SQ-H, OX-SC containing oxetanyl group above And Toagosei Co., Ltd..
  • the phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, a crosslinking reaction proceeds with the polymer of the present invention by a dehydration condensation reaction.
  • a crosslinking reaction proceeds with the polymer of the present invention by a dehydration condensation reaction.
  • the phenoplast compound include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane, bis (3-formyl-4-hydroxyphenyl) methane Bis (4-hydroxy-2,5-dimethylphenyl) formylmethane, ⁇ , ⁇ -bis (4-hydroxy-2,5-dimethylphenyl) -4-formyltoluene and the like.
  • the phenoplast compound is also available as a commercial product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF. BI25X-TPA (above, manufactured by Asahi Organic Materials Co., Ltd.).
  • a polyfunctional (meth) acrylic compound is suitable from the viewpoint that the refractive index lowering due to the crosslinking agent blending can be suppressed and the curing reaction proceeds rapidly, and among these, the triazine ring-containing polymer is preferred. Since it is excellent in compatibility, the polyfunctional (meth) acrylic compound having the following isocyanuric acid skeleton is more preferable. Examples of the polyfunctional (meth) acrylic compound having such a skeleton include NK ester A-9300 and A-9300-1CL (both manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • R 111 to R 113 are each independently a monovalent organic group having at least one (meth) acryl group at the end).
  • the resulting cured film it is liquid at 25 ° C. and its viscosity is 5000 mPa ⁇ s or less, preferably 1 To 3000 mPa ⁇ s, more preferably 1 to 1000 mPa ⁇ s, and even more preferably 1 to 500 mPa ⁇ s, a polyfunctional (meth) acrylic compound (hereinafter referred to as a low-viscosity crosslinking agent) alone or in combination of two or more.
  • a polyfunctional (meth) acrylic compound hereinafter referred to as a low-viscosity crosslinking agent
  • Such low-viscosity cross-linking agents are also commercially available.
  • NK ester A-GLY-3E 85 mPa ⁇ s, 25 ° C.
  • A-GLY -9E 95 mPa ⁇ s, 25 ° C
  • A-GLY-20E 200 mPa ⁇ s, 25 ° C
  • A-TMPT-3EO 60 mPa ⁇ s, 25 ° C
  • A-TMPT-9EO ATM
  • the chain length between (meth) acrylic groups such as -4E (150 mPa ⁇ s, 25 ° C.), ATM-35E (350 mPa ⁇ s, 25 ° C.) (manufactured by Shin-Nakamura Chemical Co., Ltd.) is relatively Long crosslinking agents.
  • NK ester A-GLY-20E (made by Shin-Nakamura Chemical Co., Ltd.) and ATM-35E (made by Shin-Nakamura Chemical Co., Ltd.)
  • a polyfunctional (meth) acrylic compound having the above isocyanuric acid skeleton in consideration of improving the alkali resistance of the cured film obtained, NK ester A-GLY-20E (made by Shin-Nakamura Chemical Co., Ltd.) and ATM-35E (made by Shin-Nakamura Chemical Co., Ltd.) ) And a polyfunctional (meth) acrylic compound having the above isocyanuric acid skeleton.
  • the total amount of the crosslinking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer, but considering the solvent resistance, the lower limit is preferably 2 parts by mass, more preferably 5 parts by mass. In view of controlling the refractive index, the upper limit is preferably 20 parts by mass, more preferably 15 parts by mass.
  • the use ratio of two or more kinds of crosslinking agents is not particularly limited, but when a polyfunctional (meth) acrylic compound and a polyfunctional epoxy compound, which are the preferred combinations described above, are used in combination, the polyfunctional (meth) acrylic is used.
  • the content of the compound and the polyfunctional epoxy compound can be about 1:10 to 10: 1 by mass ratio, preferably 1: 1 to 5: 1, more preferably 1: 1 to 3: 1.
  • an initiator corresponding to each crosslinking agent can be blended.
  • a polyfunctional epoxy compound and a polyfunctional (meth) acrylic compound are used as the crosslinking agent, photocuring proceeds without using an initiator to give a cured film.
  • An initiator can be used.
  • a photoacid generator or a photobase generator can be used.
  • the photoacid generator may be appropriately selected from known ones.
  • onium salt derivatives such as diazonium salts, sulfonium salts, and iodonium salts can be used.
  • aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) Diaryliodonium salts such as iodonium hexafluorophosphate and di (4-tert-butylphenyl) iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy Phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxy Enylsulfonium he
  • onium salts commercially available products may be used. Specific examples thereof include Sun-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI- L150, SI-L160, SI-L110, SI-L147 (Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6990 (above, Union Carbide) Co., Ltd.), CPI-100P, CPI-100A, CPI-200K, CPI-200S (above, manufactured by San Apro Co., Ltd.), Adekaoptomer SP-150, SP-151, SP-170, SP-171 (above, Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (BASF), CI-2481, CI-2624, CI-2 39, CI-2064 (above, manufactured by Nippon Soda Co., Ltd.),
  • the photobase generator may be appropriately selected from known ones, such as Co-amine complex, oxime carboxylic acid ester, carbamic acid ester, quaternary ammonium salt photobase generator.
  • a photoacid or base generator When a photoacid or base generator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound. If necessary, an epoxy resin curing agent may be blended in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound.
  • a radical photopolymerization initiator when a polyfunctional (meth) acrylic compound is used, a radical photopolymerization initiator can be used.
  • the radical photopolymerization initiator may be appropriately selected from known ones, such as acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime esters, oxime esters, tetramethylthiuram monosulfide, and thioxanthones. Is mentioned.
  • photocleavable photoradical polymerization initiators are preferred.
  • the photocleavable photoradical polymerization initiator is described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, Inc., published in 1991).
  • radical photopolymerization initiators examples include BASF Corporation trade names: Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850. , CG24-61, OXE01, OXE02, Darocur 1116, 1173, MBF, manufactured by BASF, Inc.
  • Product name Lucirin TPO, manufactured by UCB, Inc.
  • radical photopolymerization initiator When using a radical photopolymerization initiator, it is preferably used in the range of 0.1 to 200 parts by weight, preferably in the range of 1 to 150 parts by weight, with respect to 100 parts by weight of the polyfunctional (meth) acrylate compound. Is more preferable.
  • solvents are added to the composition of the present invention to dissolve the triazine ring-containing polymer.
  • the solvent include water, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene Recall monomethyl ether, diethylene glycol monomethyl ether, propylene
  • the solid content concentration in the composition is not particularly limited as long as it does not affect the storage stability, and may be appropriately set according to the target film thickness.
  • the solid content concentration is preferably 0.1 to 50% by mass, and more preferably 0.1 to 40% by mass.
  • surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol Polyoxyethylene alkyl allyl ethers such as ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethyleneso Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name
  • surfactants may be used alone or in combination of two or more.
  • the amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Even more preferred.
  • the said other component can be added at the arbitrary processes at the time of preparing the composition of this invention.
  • the composition of the present invention can be applied to a substrate, then heated as necessary to evaporate the solvent, and then heated or irradiated with light to form a desired cured film.
  • the coating method of the composition is arbitrary, for example, spin coating method, dip method, flow coating method, ink jet method, jet dispenser method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer Methods such as printing, brush coating, blade coating, and air knife coating can be employed.
  • the base material silicon, glass with indium tin oxide (ITO) formed, glass with indium zinc oxide (IZO) formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics
  • the firing temperature is not particularly limited for the purpose of evaporating the solvent. For example, it can be carried out at 40 to 400 ° C.
  • the composition of the present invention forms a thin film by low-temperature firing at less than 150 ° C., particularly 60 to 130 ° C. can do.
  • the baking method is not particularly limited, and for example, it may be evaporated using a hot plate or an oven in an appropriate atmosphere such as air, an inert gas such as nitrogen, or in a vacuum.
  • the firing temperature and firing time may be selected in accordance with the process steps of the target electronic device, and the firing conditions may be selected so that the physical properties of the obtained film meet the required characteristics of the electronic device.
  • the conditions for the light irradiation are not particularly limited, and an appropriate irradiation energy and time may be adopted depending on the triazine ring-containing polymer and the crosslinking agent to be used.
  • a fine pattern can be formed by light irradiation through a mask and development with a developer. In this case, development after exposure can be performed by immersing the exposure resin in, for example, an organic solvent developer or an aqueous developer.
  • organic solvent developer examples include NMP, ⁇ -butyrolactone, DMSO and the like
  • aqueous developer examples include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium.
  • An aqueous alkali solution such as hydroxide can be used.
  • the oxirane ring-containing compound include those having one or more, preferably two or more oxirane rings in the molecule. Specific examples thereof include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, and alicyclic epoxies. Resins, epoxy-modified polybutadiene resins, oxetane compounds and the like. These may be used alone or in combination of two or more.
  • the amount of the oxirane-containing compound is not particularly limited, but can be about 10 to 400 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer.
  • the photocurable catalyst examples include a photocation generator.
  • the photocation generator include triarylsulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate; triaryl selenium salts; diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and the like. And diaryliodonium salts. These may be used alone or in combination of two or more.
  • the blending amount of the photocurable catalyst is not particularly limited, but can be about 0.1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer.
  • the preparation method of the said negative pattern formation composition is not specifically limited, What is necessary is just to mix
  • the above-described solvent may be used.
  • the composition can be cured by, for example, irradiating ultraviolet light or the like at 1 to 4000 mJ / cm 2 after being applied by the method described above. Light irradiation may be performed using various known methods such as a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an LED, and laser light. If necessary, when using a base material having a low heat resistance of about 80 to 180 ° C. before and after exposure, it may be heated preferably at 80 ° C. or more and less than 150 ° C., more preferably at 80 to 130 ° C. Development after exposure can be performed by immersing the exposure resin in the organic solvent developer or aqueous developer described above.
  • an azide compound may be further added to the above composition.
  • the azide compound a compound having one or more, preferably two or more 1,2-naphthoquinonediazide groups is preferable, and specific examples thereof include 2,3,4-trihydroxy-benzophenone and 1,2-naphthoquinone- (2) 1,2-naphthoquinone diazide sulfonic acid derivatives such as esters with -diazide-5-sulfonic acid.
  • the amount of the oxirane-containing compound is not particularly limited, but can be about 4 to 60 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer.
  • the method for preparing the positive pattern forming composition is not particularly limited, and may be prepared by blending the components in any order.
  • the above-described solvent may be used.
  • the composition After the composition is applied by the above-described method, it can be cured by, for example, irradiation with ultraviolet light at 1 to 2000 mJ / cm 2 by the above-described light irradiation method.
  • the substrate may be heated at a temperature of about 80 to 180 ° C. before and after exposure and preferably at a temperature of 80 to 150 ° C., more preferably 80 to 130 ° C. .
  • Development after exposure can be performed by immersing the exposure resin in the organic solvent developer or aqueous developer described above.
  • Additives include thermal cation generators such as benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 1-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenyldimethylsulfonium methyl sulfate; 2 , 5-diethylthioxanthone, anthracene, 9,10-ethoxyanthracene and the like, and the additives exemplified in the film-forming composition.
  • thermal cation generators such as benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 1-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenyldimethylsulfonium methyl sulfate
  • 2 5-diethylthioxanthone, anthracene,
  • the cured film and fine pattern of the present invention obtained as described above can achieve high heat resistance, high refractive index, and low volume shrinkage, liquid crystal display, organic electroluminescence (EL) display, touch panel, optical semiconductor Electronic devices such as (LED) elements, solid-state imaging devices, organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, and parts for manufacturing semiconductor exposure devices And can be suitably used in the field of optical materials.
  • LED organic electroluminescence
  • TFTs organic thin film transistors
  • 3-aminophenol [2] (11.00 g, 0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a 500 mL four-necked flask, and 104.14 g of N-methyl-2-pyrrolidone (NMP) was added. Dissolved and cooled to below 0 ° C. Thereafter, 2,4,6-trichloro-1,3,5-triazine [1] (18.34 g, 0.1 mol, manufactured by Evonik Degussa) was added and stirred for 1 hour, and then dissolved in 154.96 g of NMP.
  • NMP N-methyl-2-pyrrolidone
  • L-TmDA-100 the target polymer [4] (hereinafter referred to as L-TmDA-100).
  • the measurement result of 1 H-NMR spectrum of L-TmDA-100 is shown in FIG.
  • the weight average molecular weight Mw measured by GPC of L-TmDA-100 in terms of polystyrene was 8,200
  • the polydispersity Mw / Mn was 2.15.
  • Example 2 Preparation of composition [Example 2] Under nitrogen, 12.00 g of L-TmDA-100 obtained in Example 1 was added to a 200 mL eggplant flask, and 18.00 g of propylene glycol monomethyl ether (PGME) was added as a solvent. L-TmDA-100-M) was prepared. The obtained L-TmDA-100-M was diluted to 10% by mass with PGME, and the refractive index was measured to be 1.7494 (@ 550 nm).
  • PGME propylene glycol monomethyl ether
  • Example 3 Fabrication of fine pattern [Example 3] L-TmDA-100-M 18.95 g prepared in Example 2, polyfunctional acrylate (AT-20E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.74 g, polyfunctional epoxy (Epolide GT-401, Daicel Chemical Industries ( Co., Ltd.) 0.37 g, photo radical initiator (Irgacure OXE02, manufactured by BASF) 0.52 g, photoacid generator (CPI-210S, manufactured by San Apro Co., Ltd.) 0.45 g, and PGME 24.0 g were added to form a solid. 45 g of a composition (LP-W) having a content of 20% by mass was prepared.
  • polyfunctional acrylate AT-20E, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • polyfunctional epoxy Epolide GT-401, Daicel Chemical Industries ( Co., Ltd.) 0.37 g
  • photo radical initiator Irgacure OXE02, manufactured by BASF
  • the composition was filtered using a 0.45 ⁇ m filter and then applied onto a glass substrate using a spin coater.
  • a coating film was formed by baking (soft baking) on a hot plate at 100 ° C. for 30 seconds.
  • This coating film was irradiated with ultraviolet rays having an irradiation amount of 365 m at 200 mJ / cm 2 by an ultraviolet irradiation device MA6 (manufactured by SUSS).
  • post-bake on a hot plate at 100 ° C. for 25 minutes, develop by immersing in a NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time, and rinse with running pure water. went.
  • Example 4 Production of cured film [Example 4] L-TmDA-100-M 18.95 g prepared in Example 2, polyfunctional acrylate (AT-20E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.74 g, polyfunctional epoxy (Epolide GT-401, Daicel Chemical Industries ( Co., Ltd.) 0.37 g, photo radical initiator (Irgacure OXE02, manufactured by BASF) 0.52 g, photoacid generator (CPI-210S, manufactured by San Apro Co., Ltd.) 0.45 g, and PGME 24.0 g were added to form a solid. 45 g of a composition (LP-W) having a content of 20% by mass was prepared.
  • polyfunctional acrylate AT-20E, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • polyfunctional epoxy Epolide GT-401, Daicel Chemical Industries ( Co., Ltd.) 0.37 g
  • photo radical initiator Irgacure OXE02, manufactured by BASF
  • This composition was filtered using a 0.45 ⁇ m filter and then applied onto a silicon wafer substrate using a spin coater.
  • a coating film was formed by baking (soft baking) on a hot plate at 100 ° C. for 30 seconds.
  • This coating film was irradiated with ultraviolet rays having an irradiation amount of 365 m at 200 mJ / cm 2 by an ultraviolet irradiation device MA6 (manufactured by SUSS). Thereafter, post-baking was performed on a hot plate at 100 ° C. for 25 minutes to produce a cured film.
  • the refractive index in 550 nm was measured with the ellipsometer, it was refractive index 1.711 (@ 550 nm).
  • permeability of 400 nm was measured about the obtained cured film, the transmittance

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Abstract

L'invention porte sur une composition contenant un polymère de triazine qui peut être utilisée pour former, par cuisson à basse température, un film mince qui a un indice de réfraction élevé et une excellente transparence et qui peut également être utilisée pour former un motif fin qui a un indice de réfraction élevé. La composition contenant un polymère de triazine comprend : un polymère qui comprend un motif de structure répété tel que représenté, par exemple, par la formule (23), le motif de structure répété ayant un noyau triazine et un groupe hydroxyle phénolique ; et au moins deux types d'agents de photoréticulation.
PCT/JP2014/083819 2013-12-24 2014-12-22 Composition contenant un polymère de triazine WO2015098788A1 (fr)

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Cited By (8)

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CN109071807A (zh) * 2016-02-09 2018-12-21 日产化学株式会社 含有三嗪环的聚合物和包含该聚合物的组合物
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WO2022225002A1 (fr) * 2021-04-23 2022-10-27 日産化学株式会社 Polymère à teneur en cycle triazine, et composition pour formation de film contenant celui-ci

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