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WO2025215889A1 - Composition polymérisable, matrice noire, produit durci, procédé de production de produit durci et dispositif d'affichage - Google Patents

Composition polymérisable, matrice noire, produit durci, procédé de production de produit durci et dispositif d'affichage

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Publication number
WO2025215889A1
WO2025215889A1 PCT/JP2024/045794 JP2024045794W WO2025215889A1 WO 2025215889 A1 WO2025215889 A1 WO 2025215889A1 JP 2024045794 W JP2024045794 W JP 2024045794W WO 2025215889 A1 WO2025215889 A1 WO 2025215889A1
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carbon atoms
groups
compound
represented
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Japanese (ja)
Inventor
翔 六谷
真澄 品川
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Adeka Corp
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • G03F7/075—Silicon-containing compounds

Definitions

  • the present invention relates to a composition containing a colorant, an alkali-developable resin, an epoxy compound, a compound having an active hydrogen capable of reacting with the epoxy compound, a tertiary amine compound or a salt thereof, and a solvent.
  • patterned light-blocking films such as black matrices and black column spacers are generally formed.
  • various polymerizable compositions containing a colorant and an alkali-developable resin have been proposed for forming light-blocking films.
  • Patent Document 1 describes the use of a colorant dispersion containing a polymerizable compound (A) having a bisphenol skeleton, a colorant (B), an extender pigment (C), a dispersant (D), and a solvent (E), and describes the use of an alkoxysilane coupling agent in the examples. The same document also describes that the dispersion prevents undercutting in a pattern and enables high contrast.
  • Patent Document 2 describes a polymerizable composition containing a tertiary amine compound or a salt thereof, a cyclic ether compound, an alkali-developable resin, and a compound having active hydrogen capable of reacting with the cyclic ether compound.
  • JP 2016-125027 A Japanese Patent Application Laid-Open No. 2022-061912
  • the object of the present invention is to provide a polymerizable composition that provides a black matrix with excellent pattern perpendicularity, sufficient light-blocking properties, and maintains high adhesion.
  • a polymerizable composition comprising a colorant (A), an alkali-developable resin (B), an epoxy compound (C), a compound having an active hydrogen capable of reacting with the epoxy compound (D), a tertiary amine compound or a salt thereof (E), a solvent (F), and a silane coupling agent (G) represented by the following general formula (I):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group in which some of the methylene groups in the hydrocarbon group having 1 to 20 carbon atoms have been substituted with —O— or —S—, a halogen atom, or a group represented by the following general formula (II): R 1 and R 10 may be bonded to each other directly or via —O— or —S— to form
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 12 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • X 1 and X 3 each independently represent a single bond, —O—, —CO—, —COO—, —OCO—, —NR 13 —, —NR 13 CO—, —CONR 13 —, —S— or —SO 2 —
  • X2 and X4 each independently represent a single bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a group in which some or all of the methylene groups in the divalent hydrocarbon group having 1 to 20 carbon atoms have been substituted with a divalent group selected from the following ⁇ Group A>: ⁇ Group A> is —O—, —CO—, —COO—, —OCO—, —NR 13 —, —NR 13 CO—, —CONR 13 —, —S
  • the alkali-developable resin (B) contains an unsaturated compound having a structure obtained by an esterification reaction between an epoxy addition compound and a polybasic acid anhydride,
  • the polymerizable composition according to any one of [1] to [3], wherein the epoxy addition compound has a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following formula (III):
  • M A1 represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO—, —OCO— or a substituent selected from the group represented by the following formulae (a1), (b1), (c1) and (d1):
  • Some or all of the hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms represented by M A1 may be substituted with halogen atoms, R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 and R A8 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom; some or all of the methylene groups in the hydrocarbon groups having 1 to 20 carbon atoms represented by R A1 , R A2 , R A3 , R A4 , R A5 , R A6 ,
  • R represents a hydrocarbon group having 1 to 20 carbon atoms
  • R B1 and R B3 each independently represent a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic ring-containing group having 3 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms have been substituted with a divalent group selected from the following ⁇ Group B>;
  • R B2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms have been substituted with a divalent group selected from the following ⁇ Group B>, ⁇ Group B> is —O—, —S—, —NR B4 —, —CO—, —O—CO—, —CO—O— and —SO 2 —;
  • R B4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R B
  • R 21 represents a hydrocarbon group
  • R22 , R23 , R24, R25 , R26 , R27 , R28 , R29 , R30 , R31 , R32 , R33 , R34 , R35 , R36 , R37 , R38 , R39 , R40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 and R each 50 independently represents a hydrogen atom, a hydrocarbon group, a hydrocarbon group in which some or all of the methylene groups have been substituted with -O- or -S-, a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic group containing 3 or more carbon atoms, a heterocyclic group containing 3 or more carbon atoms in which some or all of the methylene groups have been substituted with -O- or -S-, or a halogen atom; R 22 and R
  • a display device comprising the cured product according to [11].
  • composition of the present invention has sufficiently high light-blocking properties while maintaining high adhesion, and provides a black matrix with excellent pattern perpendicularity, which was previously difficult to achieve.
  • FIG. 1 is a diagram showing the angle ⁇ corresponding to the junction angle (taper angle) between the pattern and the substrate in the embodiment.
  • the polymerizable composition of the present invention will be described in detail below based on preferred embodiments.
  • the composition of the present invention contains a colorant (A), an alkali-developable resin (B), an epoxy compound (C), a compound having an active hydrogen capable of reacting with the epoxy compound (D), a tertiary amine compound or a salt thereof (E), a solvent (F), and a silane coupling agent (G) represented by the general formula (I) above.
  • Examples of the colorant (A) used in the composition of the present invention include pigments and dyes.
  • the pigments and dyes may be inorganic or organic colorants, respectively. These may be used alone or in combination of two or more.
  • the term "pigment” refers to a colorant insoluble in the solvent described below, and includes inorganic or organic colorants that are insoluble in the solvent, as well as lakes of inorganic or organic dyes.
  • the alkali-developable resin (B), epoxy compound (C), compound (D) having an active hydrogen capable of reacting with the epoxy compound, tertiary amine compound or a salt thereof (E), solvent (F), and silane coupling agent (G) are not considered to be colorants (A).
  • the pigment examples include carbon black obtained by a furnace method, a channel method, or a thermal method, or carbon black such as acetylene black, ketjen black, or lamp black; the carbon black prepared or coated with an epoxy resin; the carbon black prepared by dispersing the carbon black in a resin in a solvent in advance and coating the resin at 20 to 200 mg/g; the carbon black subjected to an acidic or alkaline surface treatment; carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less; and carbon black having a surface area of 100 m or less, the total amount of oxygen calculated from CO and CO2 in the volatile matter at 950°C.
  • carbon black obtained by a furnace method, a channel method, or a thermal method, or carbon black such as acetylene black, ketjen black, or lamp black
  • the carbon black prepared or coated with an epoxy resin the carbon black prepared by dispersing the carbon black in a resin in a solvent in advance and
  • organic or inorganic pigments include carbon black, graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, synthetic iron black, pigment black 7, titanium black, lactam black, and black pigments such as perylene black, chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese-based pigments, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, amber, and lake pigments, each of which has a weight of 9 mg or more per 1000 kJ/g.
  • the above black pigments can be divided into organic black pigments and inorganic black pigments.
  • Organic black pigments are organic black pigments, such as lactam black and perylene black, while inorganic black pigments are inorganic black pigments, such as the various carbon blacks mentioned above.
  • pigments can also be used as the pigments, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 1 85, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 1 14, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147
  • the dyes include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid, azo dyes, and metal complex compounds of cyanine dyes.
  • the colorant is preferably a black pigment, more preferably carbon black, and particularly preferably surface-treated carbon black.
  • surface treatments include sulfonic acid treatment.
  • sulfonic acid-treated carbon black is also referred to as sulfonic acid-treated carbon black.
  • colorant (A) contains sulfonic acid-treated carbon black
  • the proportion of sulfonic acid-treated carbon black in colorant (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.
  • Methods for treating the carbon black with sulfonic acid include a method for coordinating sulfonic acid groups on the surface of the carbon black, such as (1) a method for oxidizing the carbon black with peroxodisulfuric acid or a salt thereof, or (2) a method for treating the carbon black with a sulfonating agent.
  • the method (1) of oxidizing carbon black with peroxodisulfuric acid or a salt thereof can be carried out by any known method. For example, it can be carried out by mixing carbon black, peroxodisulfuric acid or a salt thereof, and an aqueous medium (water or a mixture of water and a water-soluble solvent) using a surfactant or a dispersant, as necessary, and heating the mixture at less than 100°C, preferably 40 to 90°C, for less than 24 hours, preferably 2 to 20 hours, and neutralizing it to a pH of 7, as necessary.
  • the salt of peroxodisulfuric acid include metal salts such as lithium, sodium, potassium and aluminum salts, and ammonium salts.
  • the amount of peroxodisulfuric acid or a salt thereof used is preferably in the range of 0.5 to 5 parts by mass per part by mass of carbon black.
  • the method (2) of treating carbon black with a sulfonating agent can be carried out by any known method, for example, by mixing carbon black and a sulfonating agent or dissolving them in a solvent and stirring the mixture at 200° C. or lower, preferably from 0 to 100° C.
  • the sulfonating agent include concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, halogenated sulfuric acid, amidosulfuric acid, hydrogen sulfite, sulfite, SO 3 -dioxane complex, SO 3 -ketone complex, sulfamic acid, and sulfonated pyridine salt.
  • the solvent examples include water; acidic solvents such as sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic acid, and acetic anhydride; basic solvents such as pyridine, triethylamine, and trimethylamine; ethers such as tetrahydrofuran, dioxane, and diethyl ether; polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane, nitromethane, acetone, acetonitrile, and benzonitrile; esters such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene, xylene, and nitrobenzene; alcoholic solvents such as methanol, ethanol, and isopropanol; and chlorinated solvents such as chloroform, trichlorofluoromethane, methylene chloride, and chlorobenzene
  • the amount of sulfonating agent used is preferably in the range of 0.5 to 20 parts by mass per part by mass of carbon black. When multiple sulfonating agents are used, the total amount of the agents preferably falls within the above range.
  • a known sulfone inhibitor such as a fatty acid, an organic peracid, an acid anhydride, acetic acid, or a ketone, may be added in an amount of 0.01 to 5% within a range that does not inhibit the reaction.
  • organic black pigments increase the resistance of the cured film, making them useful as compositions for black matrices and black column spacers.
  • organic black pigments that can be used include lactam black. Lactam black has excellent light-blocking properties in the visible light range of 400 nm to 700 nm, and by combining it with a tertiary amine compound or its salt (E), it is expected to improve pattern perpendicularity, as well as the light-blocking properties and electrical properties (electrical resistance) of the resulting cured product.
  • Lactam black is a black organic pigment having a lactam structure, its isomeric ring structure, or a combination thereof, and has a structure represented by formula (4) or formula (5) in JP 2016-133574 A, for example.
  • Specific examples of lactam black include IRGAPHOR (registered trademark) BLACK S0100CF and Black 582 from BASF.
  • the proportion of lactam black in the colorant is preferably 50% by mass or more, more preferably 75% by mass or more, and particularly preferably 90% by mass or more.
  • the content of colorant (A) is preferably 45 to 90 parts by mass, more preferably 50 to 85 parts by mass, and particularly preferably 55 to 80 parts by mass, per 100 parts by mass of the total amount of colorant (A), alkali-developable resin (B), epoxy compound (C), compound having active hydrogen capable of reacting with the epoxy compound (D), and tertiary amine compound or a salt thereof (E).
  • the amount of colorant (A) per 100 parts by weight of alkali-developable resin (B) is preferably 60 parts by weight or more and 300 parts by weight or less, more preferably 80 parts by weight or more and 300 parts by weight or less, and particularly preferably 100 parts by weight or more and 300 parts by weight or less.
  • the alkali-developable resin (B) is a resin that can be developed with an alkali, and includes, for example, a compound having a carboxy group in the molecule.
  • the alkali-developable resin (B) preferably has an ethylenically unsaturated bond group such as an acrylic group, a methacrylic group, a vinyl group, or a maleimide group, in order to achieve even better patterning properties.
  • the weight-average molecular weight of alkali-developable resin (B) can be determined by gel permeation chromatography (GPC) in terms of standard polystyrene.
  • the weight-average molecular weight can be obtained, for example, using a GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as the elution solvent, calibration curve polystyrene standards of Mw 1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, and 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and a measurement column of KF-804, KF-803, or KF-802 (manufactured by Showa Denko K.K.).
  • the measurement temperature can be 40°C, and the flow rate can be 1.0 mL/min.
  • the alkali-developable resin (B) preferably has a weight-average molecular weight of 1,000 to 500,000, and it is preferable to use an alkali-developable resin (B) with a weight-average molecular weight of 3,000 or more, and even more preferably an alkali-developable resin (B) with a weight-average molecular weight of 4,000 to 15,000.
  • the alkali-developable resin (B) preferably has an acid value of 5 to 200 mg KOH/g, more preferably 10 to 150 mg KOH/g, and particularly preferably 10 to 120 mg KOH/g, because this makes it easier to obtain sufficient alkali developability and facilitates the production of the polymer compound.
  • the acid value here can be calculated in accordance with JIS K0070.
  • alkali-developable resins (B) that can be used include copolymers of acrylic esters having carboxy groups; and epoxy acrylate resins having carboxy groups.
  • alkali-developable resins (B) can also be unsaturated compounds having a structure obtained by the esterification reaction of an epoxy addition compound with a polybasic acid anhydride (hereinafter also referred to as "alkali-developable resins (B1)").
  • alkali-developable resins (B1) resins using an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following formula (III) are preferred, as they provide compositions with even better pattern verticality.
  • M A1 represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO—, —OCO— or a substituent selected from the group represented by the following formulae (a1), (b1), (c1) and (d1):
  • Some or all of the hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms represented by M A1 may be substituted with halogen atoms, R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 and R A8 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom; some or all of the methylene groups in the hydrocarbon groups having 1 to 20 carbon atoms represented by R A1 , R A2 , R A3 , R A4 , R A5 , R A6 ,
  • R represents a hydrocarbon group having 1 to 20 carbon atoms
  • An epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by formula (III) above typically has the following structure [(e1)]. Furthermore, the reaction product obtained by the esterification reaction of the epoxy addition compound with a polybasic acid anhydride typically has the following structure [(f1)].
  • Y1 represents a residue of an unsaturated monobasic acid
  • Y2 represents a residue of a polybasic acid anhydride
  • * represents a bond.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by M A1 in formula (III) above is an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.
  • a chain alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms is more preferred because it results in good sensitivity when used as an alkali-developable resin (B).
  • Examples of the alkylene group having 1 to 20 carbon atoms represented by M A1 in the above formula (III) include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and icosylene groups.
  • Examples of the alkenylene group having 2 to 20 carbon atoms represented by M A1 in the above formula (III) include 1,2-ethenediyl (also called ethenylene or vinylene), 2-butene-1,4-diyl, and 1,2-dimethyl-1,2-ethenediyl.
  • Examples of the cycloalkylene group having 3 to 20 carbon atoms represented by M A1 in the above formula (III) include cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene groups.
  • Examples of the arylene group having 6 to 20 carbon atoms represented by M A1 in the above formula (III) include phenylene, tolylene, xylylene, naphthylene, biphenylene, fluorene, and indane.
  • the hydrocarbon groups having 1 to 20 carbon atoms represented by R to R , R to R (hereinafter referred to as "R etc. ”) and R in the above formula (III) and the above formulae (a1), (b1), ( c1 ) and ( d1) include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms and arylalkyl groups having 7 to 20 carbon atoms.
  • Alkyl groups having 1 to 20 carbon atoms may be linear or branched.
  • alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and icosyl.
  • alkenyl groups having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 3-cyclohexenyl.
  • cycloalkyl groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, bicyclo[1.1.1]pentanyl, and tetradecahydroanthracenyl.
  • cycloalkylalkyl groups having 4 to 20 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentyl
  • aryl groups having 6 to 20 carbon atoms include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-ethylphenyl, 2-fluorophenyl, and 3-fluorophenyl.
  • Arylalkyl groups having 7 to 20 carbon atoms include the above-mentioned alkyl groups in which one or more hydrogen atoms have been substituted with the above-mentioned aryl groups.
  • Specific examples include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl, and naphthylpropyl, as well as groups in which hydrogen atoms in these rings have been substituted with the above-mentioned aliphatic hydrocarbon groups.
  • some or all of the methylene groups in the hydrocarbon groups having 1 to 20 carbon atoms represented by R A1 to R A8 may be substituted with —C ⁇ C—, —C ⁇ C—, —O— or —S—.
  • the oxygen atoms are not adjacent to each other, the oxygen atoms are not adjacent to the sulfur atoms, and the sulfur atoms are not adjacent to each other.
  • the divalent groups selected from each group described in this specification are not adjacent to each other. Note that the specification that the number of carbon atoms in the hydrocarbon group substituted with a methylene group is 1 or more can be interpreted as 2 or more carbon atoms, regardless of the presence or absence of a methylene group.
  • the hydrocarbon groups having 1 to 20 carbon atoms represented by R to R , R, and R to R in formula (III) and formulas (a1), (b1), ( c1 ), and (d1) above have excellent alkali developability when used as the alkali-developable resin (B), and therefore are more preferably chain alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkylalkyl groups having 4 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and arylalkyl groups having 7 to 10 carbon atoms.
  • hydrocarbon groups and groups in which methylene groups in hydrocarbon groups have been substituted with groups other than methylene groups are also referred to as "hydrocarbon groups, etc.”
  • the substituent is preferably selected from the following Substituent Group 1.
  • Substituent group 1 halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxy groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, isocyanate groups, heterocyclic groups having 2 to 10 carbon atoms, and heterocyclic groups having 3 to 20 carbon atoms.
  • the heterocyclic group in Substituent Group 1 refers to a group in which one hydrogen atom has been removed from a heterocyclic compound.
  • the heterocyclic group include, but are not limited to, pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidyl, quinolyl, isoquinolyl, quinoxalyl, quinazolyl, cinnolyl, phthalazyl, puryl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, and benzoyl.
  • Examples include thiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, isoxazolyl, indolyl, benzoxazolyl, benzotriazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl, isocyanuric, and 1,3-dioxolanyl.
  • the group having 3 to 20 carbon atoms and containing a heterocycle in Substituent Group 1 means a group in which a heterocyclic group is bonded to a group other than a heterocyclic group.
  • the bonding site to the hydrocarbon group or the like represented by R A1 may be located on the heterocycle or on the group other than the heterocycle.
  • the group other than the heterocyclic group is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 6 carbon atoms, and any number of bonds, one or more, are possible as long as the number of carbon atoms in the group containing a heterocycle is 20 or less.
  • Examples of hydrocarbon groups having 1 to 6 carbon atoms include those having the specified number of carbon atoms among the groups exemplified as hydrocarbon groups having 1 to 20 carbon atoms represented by the above R A1 , etc.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R may be unsubstituted or may have a hydrogen atom substituted therein. When substituted, the substituent is preferably selected from the above-mentioned Substituent Group 1.
  • Examples of the halogen atom in M A1 and R A1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the number of carbon atoms in a group substituted with a substituent is within the scope of the annotation of the general formula.
  • the number of carbon atoms in the substituted hydrocarbon group, including the number of carbon atoms in the substituent is considered to be 1 to 20, which is the number of carbon atoms in the hydrocarbon group represented by R A1 or the like in the annotation of formula (III) and formulas (a1), (b1), (c1), and (d1).
  • R A1 to R A8 and R A10 to R A38 are preferably a hydrogen atom, a hydrocarbon group of 1 to 3 carbon atoms, an aryl group of 6 to 10 carbon atoms, or a halogen atom, more preferably a hydrogen atom, an alkyl group of 1 to 3 carbon atoms, or an aryl group of 6 to 10 carbon atoms, and most preferably a hydrogen atom or an aryl group of 6 to 10 carbon atoms.
  • the above-mentioned unsaturated monobasic acid refers to an acid that has an unsaturated bond in its structure and one hydrogen atom per molecule that can ionize to form a hydrogen ion.
  • Examples of the above-mentioned unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and sorbic acid.
  • examples of the polybasic acid anhydride that can be reacted after the reaction with the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dica
  • the reaction molar ratios of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride be as follows: That is, the epoxy addition compound is preferably added so that the ratio of carboxy groups of the unsaturated monobasic acid per epoxy group of the epoxy compound is 0.1 to 1.0, and more preferably 0.2 to 1.0. Furthermore, the alkali-developable resin (B) is preferably added so that the ratio of acid anhydride structures of the polybasic acid anhydride per hydroxyl group of the epoxy adduct is 0.1 to 1.0, and more preferably 0.2 to 1.0.
  • the reaction of the epoxy compound represented by formula (III), the unsaturated monobasic acid, and the polybasic acid anhydride can be carried out according to conventional methods.
  • alkali-developable resin (B) a compound obtained by esterifying an epoxy addition compound with a polybasic acid anhydride and then further reacting it with a monofunctional or polyfunctional epoxy compound (hereinafter also referred to as "alkali-developable resin (B2)") can be used.
  • alkali-developable resin (B2) makes it possible to adjust the acid value of the composition of the present invention, and adjusting the acid value allows for fine adjustment of the alkali developability (development speed, pattern shape, etc.).
  • the acid value of the solids content of the alkali-developable resin (B) is within the above-mentioned range, as this provides good alkali developability, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably selected so that the alkali-developable resin (B2) satisfies the above-mentioned acid value.
  • the solids content referred to in this invention refers to the content excluding the solvent, which will be described later.
  • the above monofunctional epoxy compounds include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecy
  • the polyfunctional epoxy compound it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers, as this allows for the production of a cured product with excellent pattern verticality.
  • the bisphenol-type epoxy compound an epoxy compound represented by formula (III) above can be used, as well as bisphenol-type epoxy compounds such as hydrogenated bisphenol-type epoxy compounds.
  • glycidyl ethers examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-
  • novolac epoxy compounds include novolac epoxy compounds (phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds, and other novolac epoxy compounds); alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane.
  • glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester
  • glycidyl amines such as tetraglycidyldiaminodiphenylmethane, triglycidyl p-aminophenol, and N,N-diglycidylaniline
  • heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate
  • dioxide compounds such as dicyclopentadiene dioxide
  • naphthalene-type epoxy compounds triphenylmethane-type epoxy compounds
  • dicyclopentadiene-type epoxy compounds such as dicyclopentadiene-type epoxy compounds.
  • the epoxy compound represented by formula (III), the unsaturated monobasic acid used, and/or the polybasic acid used preferably have one or more of the following structures, and particularly preferably have all of the following structures: A compound in which M A1 in formula (III) is a substituent represented by formula (b1) or (d1); a compound in which R A1 to R A8 and R A10 to R A38 in formula (III) are a hydrogen atom or an aryl group having 6 to 10 carbon atoms; a compound in which one or more unsaturated monobasic acids selected from acrylic acid and methacrylic acid are used; and a compound in which one or more polybasic acid anhydrides selected from biphenyltetracarboxylic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, and biphthalic anhydride are used.
  • alkali-developable resins (B) can also be suitably used.
  • examples of commercially available products include SPC1000, SPC-2000, SPC-3000, SPRR-1X, SPRR-2X, SPRR-3X, SPRR-5X, SPRR-6X, SPRR-7X, SPRR-8X, SPRR-9X, SPRR-10X, SPRR-11X, SPRR-12X, SPRR-13X, SPRR-14X, and SPRR-15X.
  • Examples include R-15X, SPRR-16X, SPRR-17X, SPRR-18X, SPRR-19X, SPRR-20X, and SPRR-21X (all manufactured by Showa Denko K.K.), JET2000, AGOR1060, AGOR3060, ORGA1060, and ORGA2060 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), and CCR-1171H (manufactured by Nippon Kayaku Co., Ltd.).
  • the content of the alkali-developable resin (B) is preferably 5 to 40 parts by mass, more preferably 10 to 35 parts by mass, and particularly preferably 15 to 35 parts by mass, per 100 parts by mass of the total of the colorant (A), alkali-developable resin (B), epoxy compound (C), compound having an active hydrogen capable of reacting with the epoxy compound (D), and tertiary amine compound or a salt thereof (E), because this makes it easier to obtain a cured product with a high-resolution pattern and ensures stable solubility in an alkaline developer.
  • the content of the alkali-developable resin (B) is preferably 3 parts by mass or more and 40 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, and particularly preferably 5 parts by mass or more and 35 parts by mass or less, per 100 parts by mass of the solids content of the composition.
  • the epoxy compound (C) according to the present invention refers to a compound that does not fall under the category of the alkali-developable resin (B) and has one or more epoxy groups.
  • the epoxy compound (C) does not have a carboxy group in the molecule.
  • Examples of such epoxy compounds (C) include aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds.
  • Aromatic epoxy compounds (C-1) An aromatic epoxy compound has an aromatic ring and an epoxy group, but does not have a cycloalkene oxide structure. Compounds having at least one aromatic hydrocarbon ring can also be used as such aromatic epoxy compounds.
  • aromatic epoxy compounds include polyglycidyl ethers of polyhydric phenols having at least one aromatic ring, such as bisphenol A and bisphenol F, or alkylene oxide adducts thereof; epoxy novolac resins (phenol novolac-type epoxy compounds); polyglycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol; polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; polyglycidyl esters of polybasic aromatic compounds having two or more carboxylic acids, such as phthalic acid, ter
  • aromatic epoxy compounds can be used, such as Denacol EX-146, Denacol EX-201, and Denacol EX-711 (manufactured by Nagase ChemteX Corporation); Oxol PG-100 and Oxol EG-280 (manufactured by Osaka Gas Chemicals Co., Ltd.); HP4032, HP4032D, and HP4700 (manufactured by DIC Corporation); YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA and Marproof G-0130SP (manufactured by NOF Corporation); Epiclon N-665 and Epiclon HP-7200 (manufactured by DIC Corporation).
  • Denacol EX-146, Denacol EX-201, and Denacol EX-711 manufactured by Nagase ChemteX Corporation
  • Oxol PG-100 and Oxol EG-280 manufactured by Osaka Gas Chemicals Co., Ltd.
  • Examples include EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, and NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901, EP-3950S, EP-3950L, and EP-3980S (manufactured by ADEKA Corporation); and TECHMOREVG-3101L (manufactured by Printec Co., Ltd.).
  • Aliphatic epoxy compound (C-2) The aliphatic epoxy compound has an epoxy group and does not contain a cycloalkene oxide structure or an aromatic ring. Specific examples of such aliphatic epoxy compounds include glycidyl ethers of aliphatic alcohols and polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts.
  • More specific examples include glycidyl ethers of polyhydric alcohols such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and diglycidyl ether of neopentyl glycol; polyglycidyl ethers of polyether polyols obtained by
  • Other examples include compounds having a tricyclodecane structure and a glycidyl ether group, such as dimethyloltricyclodecane diglycidyl ether and tricyclodecane diglycidyl ether.
  • Other examples include compounds obtained by reacting an aliphatic glycidyl ether epoxy compound having two or more glycidyl ether groups with a main chain skeleton that contains a rubber component and that contains a group capable of reacting with an epoxy group to form a covalent bond.
  • the aliphatic epoxy compound may also be a hydrogenated product of an aromatic epoxy compound, such as hydrogenated bisphenol A diglycidyl ether.
  • the aliphatic epoxy compound may also be a compound having, as a structural unit, a structure in which an oxiranyl group is directly bonded via a single bond to a cycloalkyl ring derived from an epoxycycloalkyl ring, and having, as a main chain structure, a structure in which the epoxy groups of the epoxycycloalkyl ring are polymerized together, such as a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.
  • aliphatic epoxy compounds can be used, such as Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, and Denacol EX-83. 2.
  • Denacol EX-841, Denacol EX-861, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glysilol ED-503, Adeka Glysilol ED-503G, Adeka Glysilol ED-506, Adeka Glysilol ED-523T (manufactured by ADEKA Corporation), etc.
  • aliphatic epoxy compound either an aliphatic ring-containing epoxy compound having an aliphatic ring such as an aliphatic hydrocarbon ring or an aliphatic heterocycle, or a chain aliphatic epoxy compound having no aliphatic ring can be used.
  • Alicyclic epoxy compound (C-3) Specific examples of the alicyclic epoxy compound include compounds having at least one alicyclic ring and containing a cycloalkene oxide structure, such as cyclohexene oxide and cyclopentene oxide, which are obtained by epoxidizing a cyclohexene- or cyclopentene-ring-containing compound with an oxidizing agent.
  • a cycloalkene oxide structure such as cyclohexene oxide and cyclopentene oxide
  • alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(2-epoxycyclohexylmethyl ...
  • UVR-6100 UVR-6105, UVR-6110, and UVR-6128 (all manufactured by Union Carbide Corporation), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2000, Cyclomer M100, and Epolead GT-401 (all manufactured by Daicel Chemical Industries, Ltd.).
  • the epoxy equivalent of the epoxy compound (C) is preferably 80 g/eq. or more and 300 g/eq. or less, more preferably 100 g/eq. or more and 300 g/eq. or less, and particularly preferably 150 g/eq. or more and 300 g/eq. or less.
  • Epoxy compound (C) preferably contains 50 mass% or more, more preferably 70 mass% or more, and particularly preferably 90 mass% or more of an epoxy compound having an epoxy equivalent of 80 g/eq. or more and less than 300 g/eq.
  • the molecular weight of the epoxy compound (C) is not particularly limited as long as the desired curing properties are obtained, and can be, for example, 300 or more and 3000 or less. From the standpoint of the balance between the storage stability and pattern perpendicularity of the composition, as well as the ease of application and adhesion of the composition, the molecular weight is more preferably 500 or more and 2500 or less, and even more preferably 700 or more and 2000 or less. In the case of a polymer, the molecular weight is the weight average molecular weight, and can be measured using the same method as described in the section on alkali-developable resin (B).
  • the number of epoxy groups contained in the epoxy compound (C) can be set appropriately depending on the desired curing properties, etc.
  • the number of epoxy groups contained per molecule of the epoxy compound (C) is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10, in order to obtain a cured product with excellent pattern perpendicularity.
  • the epoxy compound (C) contains an epoxy compound having a glycidyl group. This is because the composition will have better pattern perpendicularity. Epoxy compounds having a glycidyl group are also referred to as "glycidyl-type epoxy compounds" in this specification.
  • the epoxy compound (C) may contain a glycidyl ether group or a diglycidylamino group as the glycidyl group.
  • the epoxy compound (C) contains a glycidyl ether group or a diglycidylamino group, and it is even more preferable that it contains a glycidyl ether group.
  • the epoxy compound (C) contains a glycidyl-type epoxy compound.
  • the proportion of the glycidyl-type epoxy compound per 100 parts by mass of the epoxy compound is preferably 40 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 80 parts by mass or more.
  • the content of the epoxy compound (C) is preferably 0.2 parts by mass or more and 3.0 parts by mass or less, more preferably 0.5 parts by mass or more and 2.5 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 2.0 parts by mass or less, relative to 100 parts by mass of the total amount of the colorant (A), alkali-developable resin (B), epoxy compound (C), compound having active hydrogen capable of reacting with the epoxy compound (D), and tertiary amine compound or a salt thereof (E).
  • the content of the epoxy compound (C) is preferably 0.2 parts by mass or more and 3.0 parts by mass or less, more preferably 0.5 parts by mass or more and 2.5 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 2.0 parts by mass or less, per 100 parts by mass of the solid content of the composition.
  • the solid content referred to in this invention refers to the amount excluding the solvent, which will be described later.
  • the epoxy compound (C) contains an aromatic epoxy compound, and the content of the aromatic epoxy compound in the epoxy compound (C) is preferably 30% by mass or more, more preferably 40% by mass or more, and may be 60% by mass or more.
  • the epoxy compound (C) contains a glycidyl-type epoxy compound, and it is particularly preferable that it contains a glycidyl-type epoxy compound that is an aromatic epoxy compound.
  • the compound (D) having active hydrogen capable of reacting with an epoxy compound is a compound capable of reacting with an epoxy group, and generally includes compounds that act as a curing agent for an epoxy compound.
  • Examples of the compound having active hydrogen capable of reacting with an epoxy compound include compounds having a group having active hydrogen such as an amino group, a phenol group, a carboxy group, a thiol group, or a sulfonic acid group (hereinafter also referred to as an "active hydrogen group").
  • active hydrogen group it is preferable to contain a compound having two or more of these active hydrogen groups in one molecule.
  • Substances that fall under the category of colorants (A), alkali-developable resins (B), epoxy compounds (C), tertiary amine compounds or their salts (E), and silane coupling agents (G) are not considered to be compounds having active hydrogen capable of reacting with epoxy compounds (D).
  • compounds (D) having active hydrogen atoms that can react with epoxy compounds include amines such as p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-diaminodiphenyl sulfone; carboxylic acids such as adipic acid; phenol novolak, phenol aralkyl, phenols such as bisphenol A and bisphenol F; and other alcohols such as 3-aminophenol, resorcinol, catechol, hydroquinone 3-cyanophenol, 2,3-diaminophenol, 4,4'-dihydroxy-3,3'-diaminobiphenyl, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyldi(trifluoromethyl)methane
  • a compound having a thiol group (hereinafter referred to as a "thiol compound") as compound (D) having active hydrogen capable of reacting with an epoxy compound, as this compound is easily available, the composition has excellent storage stability, and provides excellent pattern perpendicularity.
  • thiol compound a compound having a thiol group
  • the proportion of the thiol compound in compound (D) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.
  • preferred thiol compounds include groups represented by any of the following (D1) to (D6).
  • (D1) to (D6) In the formula, L 11 , L 12 , L 21 , L 22 , L 23 , L 31 , L 32 , L 33 , L 34 , L 41 , L 42 , L 43 , L 44 , L 45 , L 46 , L 51 , L 52 , L 53 , L 61 , L 62 , L 63 and L 64 (hereinafter also referred to as "L 11 to L 64 ”) each independently represent a linear or branched alkylene group having 1 to 10 carbon atoms.
  • R D1 , R D2 and R D3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • a21 represents an integer of 1 to 20.
  • Examples of the alkylene group having 1 to 10 carbon atoms represented by L 11 to L 64 include divalent groups having a structure in which one hydrogen atom has been removed from an alkyl group having 1 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms for example, an alkyl group having a predetermined number of carbon atoms can be used among the alkyl groups having 1 to 20 carbon atoms in the above R A1 etc.
  • the hydrocarbon group having 1 to 20 carbon atoms used for R D1 , R D2 and R D3 the same groups as those exemplified in the description of the hydrocarbon group having 1 to 20 carbon atoms in the above R A1 etc. can be used.
  • alkylene groups having 1 to 10 carbon atoms represented by L 11 to L 64 and the hydrocarbon groups having 1 to 20 carbon atoms represented by R D1 , R D2 and R D3 are unsubstituted or one or two or more hydrogen atoms in these groups are substituted, and when substituted, the substituents may be the same as the substituents substituting one or two or more hydrogen atoms in the hydrocarbon group represented by R A1 above.
  • L 11 to L 64 are preferably alkylene groups having 1 to 5 carbon atoms, and particularly preferably linear alkylene groups having 1 to 3 carbon atoms or branched alkylene groups having 3 to 5 carbon atoms, and particularly preferably branched alkylene groups having 3 to 5 carbon atoms.
  • linear alkylene group having 1 to 3 carbon atoms represented by L 11 to L 64 include methylene, ethylene (ethane-1,2-diyl), and propylene (propane-1,3-diyl).
  • branched alkylene groups having 3 to 5 carbon atoms represented by L 11 to L 64 include propane-1,1-diyl, propane-1,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, pentane-1,1-diyl, pentane-1,2-diyl, pentane-1,3-diyl, and pentane-1,4-diyl.
  • L 11 and L 12 in (D1) are the same group. This also applies to L 21 to L 23 in (D2), L 31 to L 34 in (D3), L 41 to L 46 in (D4), L 51 to L 53 in (D5), and L 61 to L 64 in (D6).
  • R D1 , R D2 and R D3 are preferably alkyl groups having 1 to 20 carbon atoms, more preferably alkyl groups having 1 to 10 carbon atoms, and particularly preferably alkyl groups having 1 to 3 carbon atoms.
  • the compound represented by (D3) is preferred, and among these, those in which L 31 to L 34 are the same and are branched alkylene groups having 3 to 5 carbon atoms are particularly preferred.
  • the compound (D) having an active hydrogen capable of reacting with an epoxy compound preferably has a molecular weight of 100 or more and 1,000 or less, more preferably 300 or more and 900 or less, and particularly preferably 350 or more and 800 or less.
  • the type of thiol group in the thiol compound may be a primary thiol group, a secondary thiol group, a tertiary thiol group, or the like. From the perspective of more effectively demonstrating the effect of excellent pattern verticality of the present invention, it is preferable that the type of thiol group is a secondary thiol group.
  • the amount of secondary thiol in the thiol compound is preferably 30% by mass or more, and more preferably 40% by mass or more.
  • the number of thiol groups contained in one molecule is preferably 2 to 10, more preferably 3 to 8, and particularly preferably 3 to 5, in order to further enhance the effects of the thiol compound being excellent in storage stability and pattern perpendicularity.
  • thiol compounds include dodecanethiol (monofunctional thiol compound), Karenz MT (registered trademark) BD1 (trade name, bifunctional thiol compound, 1,4-bis(3-mercaptobutyryloxy)butane, Showa Denko K.K.), Karenz MT (registered trademark) NR1 (trade name, trifunctional thiol compound, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, Showa Denko K.K.), Karenz MT (registered trademark) PE1 (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis(3-mercaptobutyrate), Showa Denko K.K.), and EGMP
  • the compound (D) having an active hydrogen capable of reacting with an epoxy compound has an ester bond in the molecule.
  • the content of the compound (D) having active hydrogen capable of reacting with an epoxy compound is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, and particularly preferably 1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the total amount of the colorant (A), alkali-developable resin (B), epoxy compound (C), compound (D) having active hydrogen capable of reacting with the epoxy compound, and tertiary amine compound or a salt thereof (E).
  • the content of the compound (D) having an active hydrogen capable of reacting with the epoxy compound is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, and particularly preferably 1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the solid content of the composition.
  • the solid content referred to in this invention refers to the content excluding the solvent, which will be described later.
  • a tertiary amine compound refers to a compound in which one nitrogen atom is bonded to three different carbon atoms.
  • the tertiary amine compound or its salt (E) include aliphatic tertiary amine compounds or their salts, and aromatic tertiary amine compounds or their salts.
  • Aliphatic tertiary amines are amines that do not have an aromatic ring, while aromatic tertiary amines are amines that have at least one aromatic ring.
  • aromatic tertiary amine compounds or their salts are preferred, and among aromatic tertiary amines, heterocyclic aromatic tertiary amine compounds or their salts having a heterocycle are more preferred, heterocyclic aromatic compounds that are azoles or their salts are even more preferred, and imidazole compounds or their salts are particularly preferred.
  • Suitable examples of tertiary amine compounds that are imidazole compounds include compounds in which a hydrocarbon group or the like is bonded to one of the two nitrogen atoms on the imidazole ring and not to the other nitrogen atom.
  • Examples of the hydrocarbon group or the like referred to here include hydrocarbon groups having 1 to 20 carbon atoms and groups in which one or more methylene groups in a hydrocarbon group having 1 to 20 carbon atoms have been substituted with a divalent group selected from the following ⁇ Group B>.
  • Salts of tertiary amine compounds include organic acid salts and inorganic acid salts of tertiary amine compounds. Examples of organic acid salts include carboxylates and sulfonates of stearic acid, behenic acid, etc., and examples of inorganic acid salts include sulfates, hydrochlorides, nitrates, phosphates, etc.
  • the most preferred tertiary amine compound is a compound represented by the following general formula (IV).
  • the compound represented by the following general formula (IV) preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.
  • R B1 and R B3 each independently represent a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic-containing group having 3 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or the hydrocarbon group having 1 to 20 carbon atoms in which one or more methylene groups have been substituted with a divalent group selected from the following ⁇ Group B>;
  • R B2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms have been substituted with a divalent group selected from the following ⁇ Group B>, ⁇ Group B> is —O—, —S—, —NR B4 —, —CO—, —O—CO—, —CO—O— and —SO 2 —;
  • R B4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R B4s , they may
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R B1 , R B2 , R B3 and R B4 include aliphatic hydrocarbon groups such as alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms and cycloalkylalkyl groups having 4 to 20 carbon atoms, and aromatic hydrocarbon groups such as aryl groups having 6 to 20 carbon atoms and arylalkyl groups having 7 to 20 carbon atoms.
  • alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and icosyl.
  • alkenyl groups having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 3-cyclohexenyl.
  • cycloalkyl groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentanyl, and tetradecahydroanthracenyl.
  • cycloalkylalkyl groups having 4 to 20 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentyl
  • aryl groups having 6 to 20 carbon atoms include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, and 3-ethylphenyl.
  • Arylalkyl groups having 7 to 20 carbon atoms include the above-mentioned alkyl groups in which one or more hydrogen atoms have been substituted with the above-mentioned aryl groups.
  • Specific examples include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl, and naphthylpropyl, as well as groups in which hydrogen atoms in these rings have been substituted with the above-mentioned aliphatic hydrocarbon groups.
  • the heterocyclic group represented by R B1 and R B3 means a group in which one hydrogen atom has been removed from a heterocyclic compound.
  • the heterocyclic group mentioned above is not particularly limited, but examples thereof include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidyl, quinolyl, isoquinolyl, quinoxalyl, quinazolyl, cinnolyl, phthalazyl, puryl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzophenone ...
  • Examples include thiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, isoxazolyl, indolyl, benzoxazolyl, benzotriazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl, isocyanuric, and 1,3-dioxolanyl.
  • the group having 3 to 20 carbon atoms and containing a heterocycle means a group in which a heterocycle group and a group other than a heterocycle group are bonded.
  • the bonding site may be located on either the heterocycle or the group other than the heterocycle.
  • the group other than the heterocycle group is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 6 carbon atoms, and any number of bonds, one or more, are possible as long as the group containing a heterocycle has 20 or less carbon atoms.
  • hydrocarbon group having 1 to 6 carbon atoms examples include divalent groups having a predetermined number of carbon atoms, obtained by removing one hydrogen atom from the groups exemplified as hydrocarbon groups having 1 to 20 carbon atoms, represented by R B1 etc.
  • groups containing a heterocycle and having 3 to 20 carbon atoms include groups having the following structure:
  • each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Z represents an alkylene group having 1 to 6 carbon atoms.
  • * in the formula represents a bond. A bond spanning multiple rings indicates that the bond may be on any of these rings.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms among the examples of the alkyl group having 1 to 20 carbon atoms represented by R B1 etc.
  • Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include divalent groups corresponding to the alkyl group having 1 to 6 carbon atoms.
  • the heterocyclic groups represented by R B1 , R B2 and R B3 , the heterocyclic ring-containing groups having 3 to 20 carbon atoms, the hydrocarbon groups having 1 to 20 carbon atoms and the hydrocarbon groups having 1 to 20 carbon atoms in which some or all of the methylene groups have been substituted with groups selected from ⁇ Group B> may have hydrogen atoms substituted or may be unsubstituted. If substituted, the substituents are preferably selected from the following Substituent Group 2.
  • Substituent group 2 an alkoxysilyl group, a halogen atom, a cyano group, a nitro group, —CO—H, —OH, —SH, —NH 2 , —C(R′) ⁇ N—OH, —COOH or —SO 3 H.
  • R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and when there are multiple R's, they may be the same or different.
  • an alkyl group having 1 to 8 carbon atoms used for R' in the above-mentioned Substituent Group 2 an alkyl group having a predetermined number of carbon atoms can be used among the alkyl groups having 1 to 20 carbon atoms listed above as examples of R B1 , etc.
  • R B1 in general formula (IV) is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
  • R B2 in general formula (IV) is preferably a hydrocarbon group having 1 to 20 carbon atoms or a group in which some of the methylene groups in the hydrocarbon group having 1 to 20 carbon atoms have been substituted with a group selected from ⁇ Group B>, and is preferably a hydrocarbon group having 2 to 20 carbon atoms or a group in which some or all of the methylene groups other than those at the bonding site to the nitrogen atom on the imidazole ring have been substituted with a group selected from ⁇ Group B>.
  • R B2 is even more preferably a group represented by the following formula ( ⁇ ):
  • L B1 is an alkylene group having 1 to 4 carbon atoms
  • X B1 is —CO—O— or —O—CO—
  • L B2 is an alkyl group having 3 to 18 carbon atoms, provided that the total number of carbon atoms of L B1 and L B2 is 19 or less.
  • the alkylene group represented by L B1 preferably has 2 to 3 carbon atoms, and most preferably a 1,2-ethanediyl group.
  • L B2 is preferably an alkyl group having 3 to 17 carbon atoms, more preferably a branched alkyl group having 3 to 12 carbon atoms, particularly preferably a branched alkyl group having 5 to 10 carbon atoms, and most preferably a branched alkyl group having 7 to 9 carbon atoms.
  • R B3 in general formula (IV) is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably an ethyl group.
  • tertiary amine compounds represented by general formula (IV) include compounds represented by the following formulas (E1) to (E14).
  • compounds represented by (E1), to (E3), (E9), (E10), or (E12) are preferred in terms of storage stability and pattern perpendicularity, with (E1) or (E2) being more preferred, and (E1) being particularly preferred.
  • the amount of the tertiary amine compound or its salt (E) is preferably 0.01 to 1.0 part by mass, more preferably 0.03 to 0.7 part by mass, and particularly preferably 0.05 to 0.5 part by mass, relative to 100 parts by mass of the total amount of the colorant (A), alkali-developable resin (B), epoxy compound (C), compound having active hydrogen capable of reacting with the epoxy compound (D), and tertiary amine compound or its salt (E).
  • High pattern resistance is particularly advantageous for black matrices used in display devices, in that it helps prevent image distortion caused by the generation of an electric field in a direction different from the electric field normally used to drive the liquid crystal in IPS-driven or FFS-driven liquid crystal displays.
  • the content of the tertiary amine compound or its salt (E) is preferably 0.01 parts by mass or more and 0.90 parts by mass or less, more preferably 0.03 parts by mass or more and 0.7 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 0.45 parts by mass or less, per 100 parts by mass of the solid content of the composition.
  • the solid content referred to in this invention refers to the content excluding the solvent, which will be described later.
  • the polymerizable composition of the present invention has the advantage that the compatibility between the colorant and the dispersant is improved by further adding a solvent, thereby enhancing the light-blocking properties.
  • the solvent is a compound that is liquid at 25°C under 1 atmosphere and does not fall under the above-mentioned (A) to (E).
  • As the solvent generally, a solvent that can dissolve or disperse each of the above-mentioned components ((A) to (E), (G), etc.) can be used as needed.
  • ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone
  • ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether
  • ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol
  • cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether
  • alcohol solvents such as m
  • Solvents include halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and water, and these solvents can be used alone or in combination.
  • ketones and ether ester-based solvents particularly PGMEA, 3-methoxybutyl acetate, and cyclohexanone, are preferred because of their good compatibility with the resist and polymerization initiator in the composition.
  • the content of the above-mentioned solvent is not particularly limited, but is preferably 30 to 95% by mass, and more preferably 50 to 95% by mass, based on 100% by mass of the total amount of the composition.
  • a solvent content within the above range results in a composition with excellent handleability (viscosity and wettability of the composition), reduced unevenness during drying, and liquid stability (no precipitation or sedimentation of the components contained in the composition), and is preferable because it allows for appropriate control of the thickness of the cured product when it is obtained.
  • silane coupling agent (G) used in the composition of the present invention is a compound represented by the following general formula (I).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group in which some of the methylene groups in the hydrocarbon group having 1 to 20 carbon atoms have been substituted with —O— or —S—, a halogen atom, or a group represented by the following general formula (II): R 1 and R 10 may be bonded to each other directly or via —O— or —S— to form
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 10 , R 12 , and R 13 (hereinafter also referred to as "R 1 , etc.") in the general formulas (I) and (II) include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon ring-containing groups having 6 to 20 carbon atoms.
  • the aliphatic hydrocarbon group having 1 to 20 carbon atoms is a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocyclic ring, and may have a substituent.
  • An aliphatic hydrocarbon group having a substituent is a group in which a hydrogen atom in the aliphatic hydrocarbon group has been substituted with a substituent.
  • unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, and cycloalkylalkyl groups having 4 to 20 carbon atoms.
  • aliphatic hydrocarbon groups having 1 to 20 carbon atoms and having a substituent are groups having 1 to 20 carbon atoms in which the hydrogen atoms in an unsubstituted aliphatic hydrocarbon group are substituted with a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxyl groups, amino groups, carboxy groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, and isocyanate groups.
  • the alkyl group having 1 to 20 carbon atoms may be linear or branched.
  • linear alkyl groups include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.
  • branched alkyl groups include isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, isooctyl, tert-octyl, 2-ethylhexyl, and isononyl.
  • the alkenyl group having 2 to 20 carbon atoms may be linear or branched. It may also be a terminal alkenyl group having an unsaturated bond at the terminal, or an internal alkenyl group having an internal unsaturated bond. Examples of terminal alkenyl groups include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl.
  • Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienyl allyl.
  • the cycloalkyl group having 3 to 20 carbon atoms includes saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and groups having 4 to 20 carbon atoms in which hydrogen atoms in the ring of these groups are substituted with alkyl groups.
  • saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.
  • saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentanyl.
  • alkyl groups substituting hydrogen atoms in the ring of saturated monocyclic or saturated polycyclic alkyl groups include the groups exemplified above as alkyl groups having 1 to 20 carbon atoms.
  • groups in which hydrogen atoms in the ring of saturated polycyclic alkyl groups are substituted with alkyl groups include bornyl.
  • the cycloalkylalkyl group having 4 to 20 carbon atoms is a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group.
  • the cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic.
  • Examples of cycloalkylalkyl groups having a monocyclic cycloalkyl group include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, and 2-cyclodecylethyl.
  • Examples of cycloalkylalkyl groups having a polycyclic cycloalkyl group include 3-adamantylpropyl and 3-decahydronaphthylpropyl.
  • the aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms is a hydrocarbon group that contains an aromatic hydrocarbon ring but does not contain a heterocycle, and may have an aliphatic hydrocarbon group or a substituent.
  • a substituted aromatic hydrocarbon ring-containing group is a group in which a hydrogen atom in the aromatic hydrocarbon ring-containing group is substituted with a substituent.
  • unsubstituted aromatic hydrocarbon ring-containing groups having 6 to 20 carbon atoms include aryl groups having 6 to 20 carbon atoms and arylalkyl groups having 7 to 20 carbon atoms.
  • substituted aromatic hydrocarbon ring-containing groups having 6 to 20 carbon atoms are groups having 6 to 20 carbon atoms in which the hydrogen atoms in the unsubstituted aromatic hydrocarbon ring-containing group are substituted with substituents.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxyl groups, amino groups, carboxy groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, and isocyanate groups.
  • An aryl group having 6 to 20 carbon atoms may have a single ring structure, a fused ring structure, or even two linked aromatic hydrocarbon rings.
  • aryl groups with a single ring structure examples include phenyl, tolyl, xylyl, ethylphenyl, and 2,4,6-trimethylphenyl.
  • aryl groups with a fused ring structure examples include naphthyl, anthracenyl, phenanthryl, pyrenyl, 2-fluorenyl, and 2-indenofluorenyl.
  • the aryl group in which two aromatic hydrocarbon rings are linked may be one in which two aromatic hydrocarbon rings of a monocyclic structure are linked together, one in which an aromatic hydrocarbon ring of a monocyclic structure and an aromatic hydrocarbon ring of a fused ring structure are linked together, or one in which an aromatic hydrocarbon ring of a fused ring structure and an aromatic hydrocarbon ring of a fused ring structure are linked together.
  • Examples of the linking group that links two aromatic hydrocarbon rings include a single bond, a sulfide group (—S—), and a carbonyl group.
  • Examples of the aryl group in which two monocyclic aromatic hydrocarbon rings are linked together include biphenyl and benzoylphenyl.
  • An arylalkyl group having 7 to 20 carbon atoms is a group in which a hydrogen atom in an alkyl group is replaced with an aryl group. Also included in the arylalkyl group are groups with a fused ring structure in which an aryl group is fused to a cycloalkyl group.
  • arylalkyl groups having 7 to 20 carbon atoms include arylalkyl groups that do not have a fused ring structure, such as benzyl, 9-fluorenylmethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl, and naphthylpropyl, as well as arylalkyl groups with a fused ring structure, such as 9-fluorenyl, 1-indenyl, 1-indanyl, and 2-indanyl.
  • the divalent hydrocarbon groups having 1 to 20 carbon atoms represented by M, X2 , and X4 in the general formulas (I) and (II) are groups obtained by removing one hydrogen atom from the above hydrocarbon groups having 1 to 20 carbon atoms.
  • Examples of the divalent hydrocarbon groups having 1 to 20 carbon atoms include alkylene groups having 1 to 20 carbon atoms, alkenylene groups having 2 to 20 carbon atoms, cycloalkylene groups having 3 to 20 carbon atoms, and cycloalkylalkylene groups having 4 to 20 carbon atoms.
  • Examples of the divalent aromatic hydrocarbon ring-containing groups having 6 to 20 carbon atoms include arylene groups having 6 to 20 carbon atoms and arylalkylene groups having 7 to 20 carbon atoms.
  • Examples of the halogen atom represented by R 1 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the ring formed by R 1 and R 10 in the general formula (I) bonding to each other directly or via —O— or —S— include a cyclopentadiene ring, a furan ring, a thiophene ring, a cyclohexadiene ring, a pyran ring, and a thiopyran ring.
  • Examples of the alkyl group having 1 to 8 carbon atoms represented by R 11 in the general formula (II) include those having 1 to 8 carbon atoms among the alkyl groups having 1 to 20 carbon atoms.
  • heterocyclic group having 2 to 10 carbon atoms represented by R 13 in general formula (II) examples include pyridyl, quinolyl, thiazolyl, tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, methylthiophenyl, hexylthiophenyl, benzothiophenyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl, piperazinyl, pyrimidinyl, furyl, thienyl, benzoxazol-2-yl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, and morpholinyl.
  • the heterocyclic group having 2 to 10 carbon atoms represented by R 13 in the general formula (II) may have a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a carboxy group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, and an isocyanate group.
  • the heterocyclic group in the group containing a heterocycle and having 3 to 20 carbon atoms, represented by R 13 in the general formula (II), is the same as the group containing a heterocycle and having 3 to 20 carbon atoms, represented by R B1 and R B3 above.
  • M in the general formula (I) is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent group having 1 to 20 carbon atoms in which some of the methylene groups in the hydrocarbon group have been substituted with -O- or -S-, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms.
  • the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by M in general formula (I) is preferably an alkylene group having 1 to 20 carbon atoms, more preferably a branched alkylene group having 1 to 20 carbon atoms, and particularly preferably a branched alkylene group having 1 to 8 carbon atoms.
  • the aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms represented by M in general formula (I) is preferably an arylcycloalkylene group having 7 to 20 carbon atoms, more preferably an arylcycloalkylene group having a fused ring structure having 7 to 20 carbon atoms, and particularly preferably an arylcycloalkylene group having a fused ring structure having 9 to 20 carbon atoms, is preferably an arylcycloalkylene group having a fused ring structure having 9 to 20 carbon atoms, and the like.
  • Arylcycloalkylene groups include those in which the hydrogen atoms on the ring are replaced with aryl groups, arylalkyl groups, alkyl groups, etc., to give a specified number of carbon atoms.
  • groups that do not have a fused ring structure are preferably groups represented by the following general formula (a). Furthermore, groups with a fused ring structure are preferably groups with 2 to 5 ring structures, more preferably groups with 2 or 3 ring structures, even more preferably groups represented by the following general formula (b), (c), or (d), and particularly preferably groups represented by the following general formula (b) or (c).
  • R 21 represents a hydrocarbon group
  • R22 , R23 , R24, R25 , R26 , R27 , R28 , R29 , R30 , R31 , R32 , R33 , R34 , R35 , R36 , R37 , R38 , R39 , R40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 and R each 50 independently represents a hydrogen atom, a hydrocarbon group, a group in which some or all of the methylene groups in a hydrocarbon group have been substituted with -O- or -S-, a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic-containing group having 3 or more carbon atoms, a heterocyclic-containing group in which some or all of the methylene groups in the group have been substituted with -O- or -S-, or a halogen atom; R 22 and
  • the hydrocarbon groups represented by R 21 to R 26 in formula (a), R 27 to R 34 in formula (b), R 35 to R 42 in formula (c), and R 43 to R 50 in formula (d) respectively include those having 1 to 12, 1 to 11, 1 to 11, and 1 to 7 carbon atoms among the groups exemplified as the hydrocarbon groups having 1 to 20 carbon atoms represented by R 1 etc. in general formula (I).
  • Examples of the halogen atoms represented by R 21 to R 50 in the general formulae (a), (b), (c) and (d) include the atoms exemplified as the halogen atoms represented by R 1 in the general formula (I).
  • heterocyclic groups having 2 to 10 carbon atoms represented by R to R in the general formulae (a), (b), (c), and (d) include the groups exemplified as the heterocyclic groups having 2 to 10 carbon atoms represented by R and R in the general formula (II).
  • the heterocyclic ring-containing groups having 3 to 20 carbon atoms represented by R 21 to R 26 in formula (a), R 27 to R 34 in formula (b), R 35 to R 42 in formula (c), and R 43 to R 50 in formula (d) respectively include those having 1 to 12, 1 to 11, 1 to 11, and 1 to 7 carbon atoms among the groups exemplified as the heterocyclic ring-containing groups having 3 to 20 carbon atoms represented by R 12 and R 13 in formula (II).
  • Examples of the ring formed by combining R 22 and R 23 in the general formula (a) include a cyclobutene ring, a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a cyclohexadiene ring, and a benzene ring.
  • M in the general formula (I) is preferably an unsubstituted alkylene group having 1 to 8 carbon atoms or a group represented by the general formula (b) or (c), as this will ensure that the resulting composition has excellent adhesion to the substrate as well as excellent adhesion after a moist heat resistance test or a heat resistance test.
  • R 27 , R 28 , R 29 , R 30 , R 32 , R 33 and R 34 are each preferably independently a hydrogen atom, a hydrocarbon group having 1 to 11 carbon atoms or a group in which some or all of the methylene groups in the hydrocarbon group having 1 to 11 carbon atoms have been substituted with —O— or —S—, more preferably a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, even more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, because this simplifies synthesis and the resulting composition has even better adhesion to substrates.
  • R 31 is preferably a hydrocarbon group having 1 to 11 carbon atoms, more preferably an aryl group having 6 to 11 carbon atoms, and particularly preferably a phenyl group, because this allows the resulting composition to have even better adhesion to the substrate and is easy to synthesize.
  • R 35 , R 36 , R 37 , R 38 , R 40 , R 41 and R 42 are each preferably independently a hydrogen atom, a hydrocarbon group having 1 to 11 carbon atoms or a group in which some or all of the methylene groups in the hydrocarbon group having 1 to 11 carbon atoms have been substituted with —O— or —S—, more preferably a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, even more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, for ease of synthesis.
  • R 39 is preferably a hydrocarbon group having 1 to 11 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group, because this will result in the resulting composition having even better adhesion to a substrate and is easy to synthesize.
  • X3 is preferably a group having a —CO— structure, such as —CO—, —COO—, —OCO— or —CONR 13 —, more preferably —CONR 13 —, and particularly preferably —CONR 13 —, where R 13 is a hydrogen atom, since this will result in the resulting composition having better adhesion to the substrate.
  • X 1 in the general formula (II) is preferably a group having an oxygen atom, such as —O—, —CO—, —COO—, —OCO—, —NR 13 CO— or —CONR 13 —, and particularly preferably —O—, because the resulting composition has better adhesion to the substrate.
  • X2 is preferably a group having 2 to 8 carbon atoms in which some or all of the methylene groups in the alkylene group have been substituted with —O— groups, or a single bond, since this will result in the resulting composition having better adhesion to the substrate, and is more preferably a group having 2 to 8 carbon atoms in which, among the methylene groups in the alkylene group, the methylene group bonded to X3 has been substituted with an oxygen atom, and is particularly preferably —( CH2CH2O ) 1-4— .
  • X4 is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and more preferably a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, because this will result in the resulting composition having better adhesion to substrates.
  • aliphatic hydrocarbon groups having 1 to 20 carbon atoms an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 2 to 8 carbon atoms is more preferred, and a linear alkylene group having 2 to 8 carbon atoms is particularly preferred.
  • a in the general formula (II) is preferably 1 to 3, more preferably 2 to 3, and particularly preferably 3.
  • b in the general formula (II) is preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0.
  • R 11 is preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.
  • the silane coupling agent (G) used in the present invention preferably has multiple groups represented by general formula (II), more preferably has 2 to 5 groups represented by general formula (II), and particularly preferably has two groups represented by general formula (II), because the resulting composition has even better adhesion to the substrate and is easy to synthesize.
  • R3 and R8 of the silane coupling agent (G) is a group represented by general formula (II), and it is particularly preferable that R3 and R8 in general formula (I) are groups represented by general formula (II).
  • R1 , R2 , R3, R4 , R5 , R6 , R7 , R8 , R9 , and R10 are groups other than those represented by general formula (II), they are preferably hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, or groups in which some or all of the methylene groups in the hydrocarbon groups having 1 to 20 carbon atoms have been substituted with -O- or -S-, and more preferably hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms.
  • R3 and R8 are groups represented by the general formula (II)
  • R1 , R2 , R4 , R5 , R6 , R7 , R9 and R10 are hydrogen atoms.
  • the silane coupling agent (G) can be synthesized by an addition reaction between a compound having a reactive group represented by the skeleton of the following general formula (Ia) and a silane compound.
  • M2 represents a direct bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, a group in which some of the methylene groups in the hydrocarbon group having 1 to 20 carbon atoms have been substituted with —O— or —S—, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO— or —OCO—;
  • R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 and R 70 each independently represent a hydrogen atom, a reactive group as shown below, a hydrocarbon group having 1 to 20 carbon atoms, a group in which a portion of the
  • Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by M2 include the groups having 1 to 20 carbon atoms represented by M above.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 61 and the like include the groups having 1 to 20 carbon atoms shown above for R 1 and the like.
  • Examples of the ring that can be formed by R 61 and R 70 bonding to each other directly or via —O— or —S— include the same rings that can be formed by R 1 and R 10 described above.
  • Reactive groups possessed by the skeleton of the above general formula (Ia) include a cyano group, a nitro group, a hydroxyl group, an amino group, a carboxy group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, and an isocyanate group.
  • the above silane compounds include alkyl-functional alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane; alkenyl-functional alkoxysilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane; (meth)acrylate-functional alkoxysilanes such as 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 2-methacryl
  • silane coupling agent (G) examples include the following compounds G-1 to G-8.
  • the silane coupling agent (G) is preferably (G-1), (G-2), or (G-3), more preferably (G-1) or (G-3), and especially preferably (G-3), because it results in a cured product with excellent adhesion.
  • the content of the silane coupling agent (G) in the composition is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 3.0 parts by mass or less, per 100 parts by mass of the solid content of the composition.
  • the solid content referred to in this invention excludes the solvent, which will be described later.
  • the composition of the present invention preferably further contains an ethylenically unsaturated compound (H), which results in a composition with excellent pattern perpendicularity.
  • the ethylenically unsaturated compound refers to a compound that has one or more ethylenically unsaturated bond groups, does not have a carboxy group, and does not fall under any of the above-mentioned components (A) to (G).
  • the use of a compound (H) having a molecular weight of 1,000 or less is preferable, as this further increases sensitivity.
  • Examples of the ethylenically unsaturated compound (H) include t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate,
  • ethylenically unsaturated compound H
  • examples of such commercially available products include KAYARAD DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.); ARONIX M-215 and M-350 (all manufactured by Toagosei Co., Ltd.); and NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the molecular weight of the ethylenically unsaturated compound (H) is preferably 1,000 or less, more preferably 100 or more and 900 or less, and particularly preferably 200 or more and 800 or less, in order to achieve excellent sensitivity and excellent chemical resistance in the resulting cured product.
  • the number of ethylenically unsaturated bond groups contained in the molecule of the ethylenically unsaturated compound (H) is preferably 3 to 10, more preferably 4 to 8, and particularly preferably 4 to 6, in order to obtain a composition with excellent pattern perpendicularity.
  • the content of the ethylenically unsaturated compound (H) is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, and particularly preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total amount of the colorant (A), alkali-developable resin (B), epoxy compound (C), compound having active hydrogen capable of reacting with the epoxy compound (D), and tertiary amine compound or a salt thereof (E).
  • the content of the ethylenically unsaturated compound (H) is preferably from 1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, and particularly preferably from 1 to 10 parts by mass, per 100 parts by mass of the solid content of the composition.
  • the solid content referred to in this invention refers to the content excluding the aforementioned solvent.
  • the composition of the present invention preferably further contains a polymerization initiator (I), since this results in a composition with excellent pattern perpendicularity.
  • a polymerization initiator (I) used in the composition of the present invention any conventionally known radical polymerization initiator can be used. Furthermore, the polymerization initiator (I) does not fall under any of the above-mentioned components (A) to (G).
  • radical polymerization initiators include photoradical polymerization initiators and thermal radical polymerization initiators. Photoradical polymerization initiators are more preferred due to their high reactivity.
  • the photoradical polymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light, and any conventionally known compound can be used.
  • Preferred examples of photoradical polymerization initiators include acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, and oxime ester compounds.
  • acetophenone compounds include diethoxyacetophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, Examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin is
  • benzyl compounds examples include benzyl.
  • benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.
  • Thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
  • compositions in which the polymerization initiator (I) is an oxime ester compound are preferred because they exhibit excellent vertical patterning properties.
  • oxime ester compounds include compounds having a group represented by the following formula (VI):
  • R I1 and R I2 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic-containing group having 3 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic-containing group having 3 to 20 carbon atoms are substituted with the following ⁇ Group C>, ⁇ Group C> includes —O—, —CO—, —COO—, —OCO—, —NR I3 —, —NR I3 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— and CSO—; R I3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, m I1 represents 0
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R I1 , R I2 and R I3 in formula (VI) above include those mentioned above as examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R A1 etc. in formula (III).
  • heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocycle and having 3 to 20 carbon atoms represented by R I1 and R I2 in the above formula (VI), are the same as the heterocyclic groups having 2 to 10 carbon atoms and the group containing a heterocycle and having 3 to 20 carbon atoms given as examples of the heterocyclic group in the above-mentioned Substituent group 1.
  • the hydrocarbon groups having 1 to 20 carbon atoms may have hydrogen atoms substituted or may be unsubstituted. If substituted, the substituent is preferably selected from Substituent Group 3 below, and is particularly preferably a halogen atom.
  • Substituent group 3 halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxy groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, isocyanate groups, heterocyclic groups having 2 to 10 carbon atoms, and heterocyclic-containing groups having 3 to 20 carbon atoms.
  • heterocyclic groups having 2 to 10 carbon atoms and heterocyclic-containing groups having 3 to 20 carbon atoms are the same as the heterocyclic groups having 2 to 10 carbon atoms and heterocyclic-containing groups having 3 to 20 carbon atoms given as examples of heterocyclic groups in Substituent group 1 above.
  • the compound represented by formula (VII) below has particularly high sensitivity and provides good pattern perpendicularity, and is therefore preferably used in the composition of the present invention.
  • R I1 , R I2 and m I1 are the same as R I1 , R I2 and m I1 in formula (VI), respectively;
  • R I4 and R I5 each independently represent a hydrogen atom, a cyano group, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle and having 3 to 20 carbon atoms, or a group in which some or all of the methylene groups in the hydrocarbon group having 1 to 20 carbon atoms or the group containing a heterocycle and having 3 to 20 carbon atoms have been substituted with -O- or -CO-;
  • X I1 represents an oxygen atom, a sulfur atom, a selenium atom, CR I6 R I7 , CO, NR I8 or PR I9 ;
  • R I6 , R I7 , R I8 and R I9 each independently represent a hydrogen atom, a
  • the multiple R I4s may be the same or different from each other.
  • the multiple R I5s may be the same or different from each other.
  • the hydrocarbon groups having 1 to 20 carbon atoms represented by R I4 , R I5 , R I6 , R I7 , R I8 and R I9 (hereinafter also referred to as "R I4 to R I9 ") in formula (VII) can be any of the hydrocarbon groups having 1 to 20 carbon atoms represented by R A1 etc. in formula (III).
  • the heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocycle having 3 to 20 carbon atoms, represented by R I4 to R I9 in the above formula (VII), are the same as the heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocycle having 3 to 20 carbon atoms described for R 13 in formula (II).
  • examples of the heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocycle and having 3 to 20 carbon atoms as the substituent substituting a hydrogen atom in the groups represented by R I4 to R I9 include the heterocyclic groups having 2 to 10 carbon atoms and the group containing a heterocycle and having 3 to 20 carbon atoms explained for R 13 etc. in formula (II).
  • hydrocarbon groups having 1 to 20 carbon atoms, heterocyclic groups having 2 to 10 carbon atoms, and heterocyclic-containing groups having 3 to 20 carbon atoms represented by R I4 to R I9 , as well as the hydrocarbon groups having 1 to 20 carbon atoms or the heterocyclic-containing groups having 3 to 20 carbon atoms in which some or all of the methylene groups have been substituted with -O- or -CO-, may further have a substituent or may be unsubstituted.
  • the substituent is substituted, it is preferably selected from the above-mentioned substituent group 2, and more preferably a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a heterocyclic group having 2 to 10 carbon atoms, or a heterocyclic-containing group having 3 to 20 carbon atoms.
  • Preferred examples of the polymerization initiator (I) include compounds No. I1 to No. I15 shown below, and examples of the compound represented by formula (VII) above include compounds No. I1 and No. I3 to No. I15 shown below.
  • the polymerization initiator (I) used in the present invention is not limited to the following compounds.
  • those having a carbazole structure are particularly preferred due to their high sensitivity, and those having both a carbazole structure and a nitro group are particularly preferred.
  • R I3 has 10 or less, particularly 5 or less, carbon atoms in terms of ease of availability of the polymerization initiator and sensitivity.
  • R I3 is preferably a phenyl group, an alkyl group, or an alkenyl group, which may be substituted with a substituent.
  • R I1 is preferably a linear or cyclic alkyl group, an aryl group, or an arylalkyl group, or a group in which some or all of the methylene groups in these groups have been substituted with -O-, from the viewpoint of sensitivity and ease of production, a group in which some or all of the methylene groups in the aryl group have been substituted with -O-, and a group in which some or all of the methylene groups in the alkyl group in a phenyl group substituted with an alkyl group have been substituted with -O-.
  • R I1 preferably has 20 or less carbon atoms, more preferably 8 to 20, and particularly preferably 9 to 15.
  • R I2 has 10 or less carbon atoms, particularly 7 or less, and particularly 3 or less carbon atoms are preferred in terms of ease of production.
  • R I2 is preferably a substituted or unsubstituted chain alkyl or phenyl group in terms of sensitivity and ease of production, and more preferably a chain alkyl group.
  • compounds I9 to I15 are preferred in terms of sensitivity and ease of production, and are more preferred than compounds I9 and I11, with the compound represented by compound I9 being particularly preferred.
  • radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and titanocene compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyr-1-yl)]titanium.
  • radical polymerization initiators include ADEKA Optomer N-1414, N-1717, N-1919, ADEKA Arcles NCI-831, and NCI-930 (all manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, and IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by Tronly); and others.
  • Thermal radical polymerization initiators are not particularly limited as long as they generate radicals upon heating, and conventionally known compounds can be used. Preferred examples include azo compounds, peroxides, and persulfates.
  • Azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane).
  • Peroxides include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di(4-t-butylcyclohexyl) peroxydicarbonate.
  • persulfates examples include ammonium persulfate, sodium persulfate, and potassium persulfate.
  • the above-mentioned polymerization initiator (I) can be used alone or in combination of two or more of the above-mentioned types.
  • the content of the polymerization initiator (I) is preferably 0.5 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, and particularly preferably 1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the total amount of the colorant (A), alkali-developable resin (B), epoxy compound (C), compound having active hydrogen capable of reacting with the epoxy compound (D), and tertiary amine compound or a salt thereof (E).
  • the content of the polymerization initiator (I) is preferably 0.5 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, and particularly preferably 1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the solid content of the composition.
  • the solid content referred to in this invention refers to the content excluding the aforementioned solvent.
  • composition of the present invention may further contain conventional additives such as dispersants, organic polymers, inorganic compounds, coupling agents other than the silane coupling agent (G), chain transfer agents, sensitizers, surfactants, leveling agents, melamine compounds, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; plasticizers; adhesion promoters; fillers; defoamers; surface conditioners; antioxidants; ultraviolet absorbers; dispersing aids; anti-agglomeration agents; catalysts; curing accelerators; crosslinking agents; and thickeners.
  • additives such as dispersants, organic polymers, inorganic compounds, coupling agents other than the silane coupling agent (G), chain transfer agents, sensitizers, surfactants, leveling agents, melamine compounds, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butyl
  • the dispersant can be anything that can disperse and stabilize colorant (A), and polymer dispersants made of polyester, polyether, or polyurethane that have amine and/or a quaternary salt thereof as a basic functional group and have an amine value of 1 to 100 mgKOH/g are suitable.
  • Commercially available dispersants that can be used include, for example, the BYK series manufactured by BYK Chemie.
  • organic polymer examples include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, etc.
  • the properties of the cured product can also be improved by using the organic polymer together with the compound (B).
  • the inorganic compounds include, for example, metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt-based compounds, manganese-based compounds, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, and copper; of these, titanium oxide, silica, layered clay minerals, and silver are preferred.
  • metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina
  • layered clay minerals Milori blue, calcium carbonate, magnesium carbonate, cobalt-based compounds, manganese-based compounds, glass powder, mica, talc, kaolin, ferrocyanide, various metal
  • Silane coupling agents other than the above-mentioned silane coupling agent (G) include various silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. Among these, silane coupling agents having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403, are preferred.
  • the surfactants that can be used include anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; cationic surfactants such as higher amine halogen salts and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; and silicone surfactants.
  • the leveling agents can be broadly divided into silicone-based leveling agents, acrylic-based leveling agents, fluorine-based leveling agents, and vinyl-based leveling agents.
  • fluorine-based leveling agents include leveling agents with a fluoroaliphatic hydrocarbon skeleton and leveling agents with a polyfluoroalkylene ether skeleton, which is a repeating unit formed via ether bonds.
  • the inclusion of a leveling agent is preferable because it allows for the production of a uniform cured product.
  • leveling agents such as Megafac RS-56, RS-72-A, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-78, and RS-90 (manufactured by DIC Corporation).
  • the amount be 0.01 to 20 parts by mass per 100 parts by mass of the solids in the composition, as this enhances the above-mentioned effects of including the leveling agent, and more preferably 0.01 to 15 parts by mass.
  • the content of optional components other than the above-mentioned (A) to (I) may be appropriately selected depending on the intended use, and is not particularly limited as long as it does not impair the effects of the present invention. However, it is preferably 20 parts by mass or less in total per 100 parts by mass of the above-mentioned components (A) to (I).
  • composition of the present invention and its cured product can be used in a wide range of applications, including curable paints, varnishes, curable adhesives, printed circuit boards, color filters for display devices (specifically, color liquid crystal display panels for color televisions, PC monitors, personal digital assistants, digital cameras, etc.); color filters for CCD image sensors; touch panels, electroluminescent display devices, plasma display panels, and black partition walls for organic EL display devices), powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in the manufacturing process of LCDs, compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, microcrystalline cellulose esters, and the like.
  • color filters for display devices specifically, color liquid crystal display panels for color televisions, PC monitors, personal digital assistants, digital cameras, etc.
  • color filters for CCD image sensors touch panels,
  • the cured product of the present invention is a cured product of the above-mentioned composition.
  • the cured product of the present invention has excellent light-shielding properties, adhesion, and pattern perpendicularity.
  • the manufacturing method of the present invention includes a step of curing the above-described composition.
  • the method for curing the composition in the curing step of the present invention includes commonly used methods, such as irradiating the composition with light and heating the composition.
  • Examples of light sources used for curing the composition include electromagnetic wave energy having a wavelength of 200 nm to 700 nm obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, and the like, and high-energy rays such as electron beams, X-rays, and radioactive rays are preferred.
  • Ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, and the like that emit light with a wavelength of 300 to 450 nm are preferred.
  • the composition can be heated, for example, at a temperature of approximately 80 to 120°C.
  • the curing method is a method of irradiating the composition with light, that is, the curing step includes a step of irradiating the composition with light, because this shortens the process time and enables patterning by light.
  • the curing step includes a step of irradiating the composition with light, because this shortens the process time and enables patterning by light.
  • the heating temperature is preferably 100°C or higher and 300°C or lower, particularly preferably 150°C or higher and 250°C or lower.
  • the method for producing a cured product of the present invention may include other steps, if necessary, in addition to the curing step.
  • the other steps include a development step in which unpolymerized portions in the coating film of the composition are removed after the curing step to obtain a patterned cured product, a pre-baking step in which the composition is heat-treated to remove the solvent in the composition before the curing step, and a step in which a coating film of the composition is formed before the curing step.
  • a crosslinking agent or the like when a crosslinking agent or the like is included, a reaction step with each agent may be included in addition to the above steps.
  • the curing conditions may be appropriately set depending on the components used.
  • the cured product of the present invention can be suitably used as a black matrix, with excellent light-blocking properties, adhesion, and pattern perpendicularity.
  • the black matrix is preferably formed by the steps of (1) forming a coating film of the composition (particularly a colored alkali-developable photosensitive composition) on a substrate, (2) irradiating the coating film with actinic light through a mask having a predetermined pattern, (3) developing the exposed coating film with a developer (particularly an alkali developer), and (4) heating the developed coating.
  • the composition is also useful as a coloring composition for inkjet and transfer printing methods that do not require a development step.
  • Color filters for use in liquid crystal display panels and the like can be manufactured by repeating steps (1) to (4) above using the composition to form a pattern of the three colors RGB.
  • the composition can be used to form a coating film on substrates such as soda glass, quartz glass, semiconductor substrates, metals, paper, and plastics using known methods such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, and dipping. Furthermore, once a coating film has been formed on a substrate such as a film, it can also be transferred to another substrate; there are no limitations on the method used.
  • the display device of the present invention has the same configuration as conventionally known display devices, except that it is equipped with the cured product of the present invention.
  • the display device may be equipped with a color filter for a display element, which has a colored layer and/or a light-shielding layer (black matrix) on a substrate, and at least one of the colored layer and the light-shielding layer is a cured product of the polymerizable composition, but is not limited to this.
  • Carbon Black Dispersion No. 1 25 g of Carbon Black No. 1, 7.5 g of Alkali-Developable Resin B-1 described below, 2 g of DISPERBYK-161 (dispersant, manufactured by BYK-Chemie), and 65.5 g of PGMEA were weighed out, combined, and processed in a bead mill to obtain Carbon Black Dispersion No. 1.
  • the resulting reaction solution was cooled to room temperature (25°C), and 160 g of PGMEA, 59 g of biphthalic anhydride, and 0.24 g of tetra-n-butylammonium bromide were added to the cooled reaction solution.
  • the mixture was stirred at 120°C for 4 hours, and then 20 g of tetrahydrophthalic anhydride was added.
  • the mixture was stirred at 120°C for 4 hours, at 100°C for 3 hours, at 80°C for 4 hours, at 60°C for 6 hours, and at 40°C for 11 hours.
  • Examples 1 to 5 and Comparative Examples 1 to 5 Preparation of Compositions
  • Compositions (Examples 1 to 5 and Comparative Examples 1 to 5) were obtained by mixing the components according to the formulations in Tables 1 and 2 below.
  • the numerical values for the formulations in the tables represent parts by mass.
  • the symbols for each component in the tables represent the following components.
  • A-1 Carbon black dispersion No. 1
  • B-1 Alkaline developable resin PGMEA solution
  • C-1 Compound represented by the following formula (c1) (molecular weight: 1,000 to 1,500, epoxy equivalent: 280 q/eq)
  • D-1 Compound represented by the following formula (d1)
  • E-1 Compound represented by the following formula (e1)
  • F-1 Propylene glycol monomethyl ether acetate (PGMEA)
  • F-2 Methoxybutyl acetate (MBA)
  • G-1 Silane coupling agent
  • G-1 G-2: KRM-403 (Shin-Etsu Chemical Co., Ltd.)
  • H-1 Dipentaerythritol hexaacrylate
  • I-1 Compound No. I9
  • J-1 Propylene glycol monomethyl ether acetate dispersed silica sol (30% by mass SiO 2 )
  • J-2 BYK-323 (manufactured by BYK-Chemie)
  • compositions obtained in the examples and comparative examples were applied to a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 100°C for 60 seconds to obtain a coating film with a thickness of 1.0 ⁇ m.
  • the resulting coating film was exposed to light through a 5 ⁇ m mask at an exposure dose of 50 mJ/ cm2 .
  • a Proximity Liner (product name: TME-150R, manufactured by Topcon Corporation) was used as the light source. After exposure, the coating film was immersed in an aqueous solution of 0.4% by mass of potassium hydroxide at 25°C for 60 seconds for development, and thoroughly rinsed with water.
  • a pattern line width of 4 ⁇ m or more and less than 7 ⁇ m was evaluated as A
  • a pattern line width of 3 ⁇ m or more and less than 4 ⁇ m or 7 ⁇ m or more and less than 8 ⁇ m was evaluated as B
  • a pattern line width of less than 3 ⁇ m or 8 ⁇ m or more was evaluated as C. The results are shown in Tables 1 and 2.
  • ⁇ Pattern perpendicularity> A pattern was prepared in the same manner as in ⁇ Patterning characteristics>, and the junction angle (taper angle) between the pattern and the substrate was measured using a scanning electron microscope. This taper angle corresponds to the angle ⁇ in Figure 1. The measured taper angles are shown in Tables 1 and 2. A taper angle of 70° or more indicates excellent pattern perpendicularity.
  • ⁇ Volume resistivity> The compositions obtained in the examples and comparative examples were applied using a spin coater to a glass substrate (100 mm x 100 mm) on which aluminum had been vapor-deposited for electrodes, and heated at 230°C for 180 minutes to obtain a coating film with a thickness of 3 ⁇ m.
  • Aluminum for electrodes with an area of 0.5 cm2 was vapor-deposited onto the obtained cured coating film, and a sample was prepared in which the black coating film was sandwiched between aluminum electrodes.
  • the volume resistivity of the coating film at an applied voltage of 10 V was measured using a microcurrent meter (Advantest Co., Ltd., Model R8340A). A value of 8 x 10 ⁇ cm or more is within the acceptable range, and a value of 1 x 10 ⁇ cm or more indicates an excellent volume resistivity.
  • ⁇ OD value> The compositions obtained in the examples and comparative examples were applied to a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 100°C for 60 seconds to obtain a coating film with a thickness of 1 ⁇ m.
  • the obtained coating film was exposed to light at a dose of 50 mJ/cm2 using a Proximity Aliner (product name: TME-150R, manufactured by Topcon Corporation) and then baked at 230°C for 30 minutes to obtain a cured film.
  • the OD value of the obtained cured film was measured using a Macbeth transmission densitometer, and the OD value was divided by the film thickness after post-baking to calculate the OD value per film thickness (/ ⁇ m).
  • the higher the OD value the better the light-blocking properties, and an OD value of 3.7 or higher indicates excellent light-blocking properties.
  • ⁇ Storage stability> The compositions obtained in the Examples and Comparative Examples were blended and then stored at 5°C, and the change in development time was evaluated. After 3 months of storage, the development time (the time it takes for the coating film to dissolve) per 1 ⁇ m of film thickness was evaluated using a 0.4% by mass aqueous solution of potassium hydroxide. Those whose development time was more than 10% but not more than 20% of the time immediately after production were rated C, those whose development time was more than 5% but not more than 10% were rated B, and those whose development time was 5% or less were rated A. If stability is poor, the components will react in the system, polymerizing and becoming less soluble, resulting in a longer development time.
  • compositions obtained in the examples and comparative examples were applied to a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 100°C for 60 seconds to obtain a coating film with a thickness of 1 ⁇ m.
  • the obtained coating film was exposed to light at an irradiation dose of 50 mJ/ cm2 using a Proximity Aliner (product name: TME-150R, manufactured by Topcon Corporation), and then baked at 230°C for 30 minutes to obtain a cured film.
  • the evaluation substrate was placed in a high-temperature, high-humidity chamber at 120°C, 2 atm, and 100% relative humidity for 5 hours.
  • compositions of each example which contain a colorant (A), an alkali-developable compound (B), an epoxy compound (C), a compound having an active hydrogen capable of reacting with an epoxy compound (D), a tertiary amine compound or a salt thereof (E), a solvent (F), and a silane coupling agent (G), have sufficiently high light-blocking properties while maintaining high adhesion, and are capable of forming patterns with excellent vertical patterning.

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Abstract

La présente composition polymérisable contient : un colorant (A) ; une résine développable en milieu alcalin (B) ; un composé époxy (C) ; un composé (D) contenant de l'hydrogène actif qui peut réagir avec le composé époxy ; un composé amine tertiaire ou un sel de celui-ci (E) ; un solvant (F) ; et un agent de couplage au silane (G) représenté par la formule générale (I). La quantité du composé amine tertiaire ou d'un sel de celui-ci (E) est de préférence de 0,01 à 0,5 partie en masse pour 100 parties en masse du colorant (A) ; la résine développable en milieu alcalin (B) ; le composé époxy (C) ; le composé (D) contenant de l'hydrogène actif qui peut réagir avec le composé époxy ; et le composé amine tertiaire ou un sel de celui-ci (E). (Pour les symboles dans la formule, voir la demande.)
PCT/JP2024/045794 2024-04-11 2024-12-24 Composition polymérisable, matrice noire, produit durci, procédé de production de produit durci et dispositif d'affichage Pending WO2025215889A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012181306A (ja) * 2011-03-01 2012-09-20 Shin Etsu Chem Co Ltd 化学増幅レジスト材料及びパターン形成方法
JP2016033201A (ja) * 2013-11-26 2016-03-10 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． 化合物および着色硬化性樹脂組成物
JP2019059957A (ja) * 2013-09-03 2019-04-18 三菱ケミカル株式会社 リソグラフィー用共重合体の製造方法、レジスト組成物の製造方法及びパターンが形成された基板の製造方法
WO2021246457A1 (fr) * 2020-06-03 2021-12-09 富士フイルム株式会社 Composition de résine durcissable, film durci ainsi que procédé de fabrication de celui-ci, stratifié, et dispositif à semi-conducteurs
WO2023132296A1 (fr) * 2022-01-07 2023-07-13 株式会社Adeka Composition, procédé de production de produit durci, produit durci, filtre coloré et composé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012181306A (ja) * 2011-03-01 2012-09-20 Shin Etsu Chem Co Ltd 化学増幅レジスト材料及びパターン形成方法
JP2019059957A (ja) * 2013-09-03 2019-04-18 三菱ケミカル株式会社 リソグラフィー用共重合体の製造方法、レジスト組成物の製造方法及びパターンが形成された基板の製造方法
JP2016033201A (ja) * 2013-11-26 2016-03-10 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． 化合物および着色硬化性樹脂組成物
WO2021246457A1 (fr) * 2020-06-03 2021-12-09 富士フイルム株式会社 Composition de résine durcissable, film durci ainsi que procédé de fabrication de celui-ci, stratifié, et dispositif à semi-conducteurs
WO2023132296A1 (fr) * 2022-01-07 2023-07-13 株式会社Adeka Composition, procédé de production de produit durci, produit durci, filtre coloré et composé

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