WO2008029706A1 - Composition de résine pour former des films à effet d'aplatissement élevé - Google Patents

Composition de résine pour former des films à effet d'aplatissement élevé Download PDF

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Publication number
WO2008029706A1
WO2008029706A1 PCT/JP2007/066895 JP2007066895W WO2008029706A1 WO 2008029706 A1 WO2008029706 A1 WO 2008029706A1 JP 2007066895 W JP2007066895 W JP 2007066895W WO 2008029706 A1 WO2008029706 A1 WO 2008029706A1
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Prior art keywords
component
resin composition
film
compound
forming
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PCT/JP2007/066895
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English (en)
Japanese (ja)
Inventor
Tadashi Hatanaka
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Nissan Chemical Industries, Ltd.
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Application filed by Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to KR1020097006061A priority Critical patent/KR101411294B1/ko
Priority to JP2008533126A priority patent/JP5488779B2/ja
Publication of WO2008029706A1 publication Critical patent/WO2008029706A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C08F222/402—Alkyl substituted imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones

Definitions

  • the present invention relates to a planarizing film-forming resin composition excellent in planarization and a planarized film obtained by using the resin composition. More specifically, the present invention relates to a resin composition for forming a flattened film having high flatness when a step portion is coated, a hardened flattened film, and various materials using the cured film.
  • This flattening film-forming resin composition excellent in flattening is particularly suitable for an overcoat agent such as an interlayer insulating film or a color filter in a liquid crystal display or EL display.
  • a protective film is provided to prevent the element surface from being exposed to a solvent or heat during the manufacturing process.
  • a protective film requires not only high adhesion to the substrate to be protected and high solvent resistance but also performance such as transparency and heat resistance.
  • the color filter that is a base substrate or a black matrix resin is flattened. That is, the performance as a planarizing film is required.
  • the planarizing film as the protective film also needs high transparency.
  • acrylic resin with high transparency is used in such applications.
  • acrylic resins have the property of imparting heat resistance and solvent resistance by thermosetting or photocuring. ing.
  • thermosetting method a method of adding a methylol-based crosslinking agent and an acid catalyst to an acrylic resin having a hydroxy group, and a method of adding an epoxy-based crosslinking agent to an acrylic resin containing a carboxyl group are well known. It has been.
  • a method of thermosetting by introducing an epoxy group and a carboxyl group into an acrylic resin see Patent Document 1
  • a thermal radical initiator and a compound having two or more unsaturated double bonds in one molecule A method using a compound (see Patent Document 2) has also been proposed!
  • a method of adding a compound having two or more unsaturated double bonds and a photoradical initiator in one molecule to an acrylic resin, and a methylol-based acrylic resin containing a hydroxy group is known.
  • Patent Document 1 JP 2000-103937
  • Patent Document 2 JP 2000-119472 A
  • the present invention has been made based on the above circumstances, and is suitable for a flattening film for electrodes and color filters used in liquid crystal display elements, organic EL display elements, and the like. It is an object of the present invention to provide a resin composition that achieves excellent transparency and high flatness with high properties!
  • a planarizing film-forming resin composition comprising the following component (A), component (B), component (C), component (D), and solvent (E):
  • component an attalinole polymer having a functional group capable of causing a crosslinking reaction with component (D) and having a number average molecular weight of 2,000 to 25,000,
  • Component (B) Compound having two or more unsaturated double bonds in one molecule
  • Component (C) a compound that generates an acid by heat
  • Component (D) Thermally crosslinkable compound (excluding those that crosslink using the acid generated from component (C) as a catalyst)
  • the planarizing film forming resin composition according to the first aspect wherein the component (A) is an acrylic polymer having a structure of the formula (1).
  • R 1 represents an organic group having 1 to 12 carbon atoms.
  • planarizing film-forming resin composition according to the first aspect or the second aspect, wherein the component (B) is a compound having an ethylenically unsaturated group as an unsaturated double bond.
  • planarizing film-forming resin composition according to any one of the first aspect to the third aspect, which is (C) component strength S sulfonic acid esters.
  • the planarization film according to any one of the first to fourth aspects, wherein the component (D) is a thermally crosslinkable compound having two or more block isocyanate groups in one molecule.
  • Resin composition for forming is a thermally crosslinkable compound having two or more block isocyanate groups in one molecule.
  • planarizing film-forming resin composition based on 100 parts by mass of component (A), 3 to 60 parts by mass of component (B), 0.1 to 10 parts by mass of component (C) and 1 to 50 parts by mass of component (D)
  • the planarizing film-forming resin composition according to any one of the first to fifth aspects, comprising:
  • planarization film formed from the planarization film-forming resin composition according to any one of the first aspect to the sixth aspect.
  • the fat composition for flattening film formation excellent in flattening of the present invention has only high solvent resistance for the flattening film of electrodes and color filters used in liquid crystal display elements, organic EL display elements, and the like. It can be formed while maintaining high transparency and high flatness.
  • the resin composition for flattening film formation excellent in flattening of the present invention comprises (A) an acrylic polymer, (B) a compound having an unsaturated double bond, and (C) the heat of component.
  • the “planarizing film” includes a protective film for protecting the element surface.
  • the component (A) of the present invention is an acrylic polymer having a functional group for allowing a crosslinking reaction with the component (D) and having a number average molecular weight of 2,000 to 25,000.
  • the “acrylic polymer” refers to homopolymers and copolymers of monomers having an acrylic group, and copolymers of monomers having an acrylic group and other monomers.
  • Functional groups that can undergo a thermal crosslinking reaction with the thermally crosslinkable compound of component (D) contained in the structure of the acrylic polymer of component (A) are a carboxyl group, a hydroxy group, an activity Desirably, it is at least one selected from an amino group having hydrogen.
  • the amino group having active hydrogen means a primary or secondary amino group having high reaction activity and capable of releasing a proton. Therefore, the amide group does not have an active hydrogen, and therefore does not correspond to an amino group having an active hydrogen.
  • At least one selected from a carboxyl group and a hydroxy group is preferable because the effects of the present invention can be easily obtained.
  • the glass transition temperature of the acrylic polymer as the component (A) is 50 ° C or higher! /. If the glass transition temperature (Tg) is 50 ° C or less, the coated film after pre-beta may be tacked.
  • an acrylic polymer having a structure represented by the following formula (1) is particularly preferred!
  • R 1 represents an organic group having 1 to 12 carbon atoms
  • R 1 examples include methyl group, ethyl group, propyl group, butyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, dimethylphenyl group, jetylphenol group, hydroxyphenyl group. Group, carboxyphenyl group, naphthyl group, tolyl group and the like.
  • the acrylic polymer of component (A) is a monomer having a functional group for allowing a thermal crosslinking reaction with the thermally crosslinkable compound of component (D), and has the formula (1)
  • the polymer obtained by using a monomer containing maleimides is particularly preferred because it achieves high res, transparency and high res, and Tg.
  • the acrylic polymer of the component (A) is not particularly limited as long as it is an acrylic polymer having such a structure, and other skeletons and side chain types of the polymer constituting the acrylic polymer are particularly limited. Not.
  • the acrylic polymer as the component (A) has a number average molecular weight in the range of 2,000 to 25,000. If the number average molecular weight exceeds 25,000 and is too large, the flatness of the step will decrease, while if the number average molecular weight is less than 2,000 and it is too small, curing will be insufficient during thermal crosslinking. Solvent resistance may be reduced.
  • an acrylic polymer comprising a copolymer obtained by polymerizing plural types of monomers (hereinafter referred to as a specific copolymer) is used as the component (A). It can also be used.
  • the acrylic polymer of component (A) may be a blend of a plurality of types of specific copolymers.
  • the specific copolymer is an acrylic polymer obtained by copolymerizing at least one or more monomers appropriately selected from the group of monomers having a functional group for the thermal crosslinking reaction. At least one or more monomers suitably selected from the group of monomers having a functional group for the thermal crosslinking reaction and a monomer containing a maleimide represented by the above formula (1) were formed as essential structural units. It is a copolymer.
  • the number average molecular weight is more preferably 2,000 to 25,000.
  • such a specific copolymer is preferably used as the component (A).
  • component (A) such a specific copolymer is preferably used as the component (A).
  • Specific examples of the monomer having a functional group for the crosslinking reaction are given below, but the invention is not limited thereto.
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N -(Carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
  • Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
  • Examples of monomers having a hydroxy group other than the phenolic hydroxy group include 2 xyloxy 6-hydroxynorbornene 1-carboxyl-6-latatane, 2-hydroxyethyl methacrylate, 2 hydroxypropyl methacrylate, 5 methacryloyl And oxy 6-hydroxynorbornene 2 carboxy 6-latathone.
  • examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
  • the specific copolymer may be a copolymer formed with a monomer other than a monomer having a functional group for thermal crosslinking reaction (hereinafter referred to as other monomer) as a structural unit. Good.
  • the other monomer only needs to be copolymerizable with a monomer having at least one of a carboxyl group, a hydroxy group, and an amino group having an active hydrogen, and (A) There is no particular limitation as long as the properties of the components are not impaired.
  • monomers containing maleimides include monomers containing maleimides, acrylic ester compounds, methacrylic ester compounds, acrylonitrile, maleic anhydride, styrene compounds, and bull compounds.
  • Examples of monomers containing maleimides include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • acrylate compound examples include methyl acrylate and ethyl acrylate. , Isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2, 2, 2-trifluoroethyl acrylate, tert butyl acrylate, cyclohexyl acrylate, isobol 2-rutalylate, 2-methoxyethyl atylate, methoxytriethylene glycol acrylate, 2 ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3 methoxy butyl acrylate, 2-methyl-2-adamantyl acrylate And 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl 8-tricyclodecyl acrylate and the like.
  • methacrylic acid ester compounds examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthrinole methacrylate, nonlinole methacrylate methacrylate.
  • Examples include methyl 8-tricyclodecyl metatalylate and 8-ethyl 8-tricyclodecyl methacrylate.
  • Examples of the bur compound include methyl butyl ether, benzyl butyl ether, vinyleno naphthalene, vinyl oleanthracene, vinino decanole basole, 2-hydroxy ethino levenyl ether, vinyl vinyl ether, and propyl butyl.
  • Examples include ether.
  • styrene compound examples include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
  • a polymer obtained by using a monomer containing maleimides is particularly preferable because it achieves high transparency and high Tg.
  • the method for obtaining the acrylic polymer as component (A) used in the present invention is not particularly limited. Therefore, the method for obtaining the specific copolymer used in the present invention is not particularly limited.
  • the above-mentioned one or more monomers can be obtained by subjecting a polymerization initiator or the like to a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent as required.
  • the solvent used is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. Specific examples include the solvents described in (E) Solvent described later.
  • the specific copolymer thus obtained is usually in a solution state in which the specific copolymer is dissolved in a solvent.
  • the solution of the specific copolymer obtained as described above is re-precipitated by adding it under stirring with jetyl ether, water, etc., and the generated precipitate is filtered and washed,
  • the powder of the specific copolymer can be obtained by drying at normal temperature or heat under pressure or reduced pressure. By such an operation, it is possible to remove the polymerization initiator and unreacted monomer coexisting with the specific copolymer, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification is not possible with a single operation, the obtained powder may be redissolved in a solvent and the above operation repeated.
  • the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (E) described later and used as a solution.
  • the component (B) of the present invention is a compound having two or more unsaturated double bonds per molecule.
  • the “compound having two or more unsaturated double bonds in one molecule” preferably refers to a compound having two or more ethylenically unsaturated groups in one molecule, and more preferably a terminal. This refers to a compound having two or more bur groups, attalylate groups or metatalylate groups.
  • a polyfunctional acrylate compound having two or more unsaturated double bonds per molecule is preferred.
  • the compound having two or more unsaturated double bonds per molecule as the component (B) is a phase with each component in the solution of the planarizing film-forming resin composition excellent in planarization of the present invention. If solubility is favorable, it will not specifically limit.
  • the above polyfunctional acrylate The compounds are readily available as commercial products. Specific examples include KYARAD T-1420, DPHA, DPHA-2C, D310, D-330, DPCA-20, and DPCA. — 30, DPCA — 60, same DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620, R-551, R-712 , Same R -604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (above, manufactured by Nippon Kayaku Co., Ltd.) ), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M
  • the ratio of the compound having two or more unsaturated double bonds in one molecule as the component (B) used in the present invention is 3 to 100 parts by mass with respect to 100 parts by mass of the acrylic polymer as the component (A).
  • the force is preferably 60 parts by mass S, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 40 parts by mass. If this proportion is too low, reduces the flatness, the is too high if there coating film tack input Rukoto force s after solvent resistance is pre-beta lowered the flattening film cured .
  • Component (C) is a compound that generates an acid by heat. This is a substance that decomposes during post-beta to generate acids (sulfonic acids, carboxylic acids, etc.). If it has such properties, its type and structure are not particularly limited. .
  • Examples of the compound that generates acid by the heat of component (C) include, for example, sulfonic acid ester compounds, sulfonamide compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitro compounds.
  • sulfonic acid ester compounds for example, sulfonic acid ester compounds, sulfonamide compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitro compounds.
  • the compound (C) that generates an acid by heat may be used alone or in combination of two or more.
  • the component (C) is considered to contribute to improving the flatness of the coating film and the cured film, although the reason is not clear. In this sense, sulfonic acid ester R is preferred.
  • Compounds that generate an acid by heat can be used singly or in combination of two or more.
  • the amount introduced is selected in the range of 0.1 to 10 parts by mass, preferably 0.5 to 7 parts by mass, relative to 100 parts by mass of component (A). When this amount is less than 0.1 parts by mass, high flatness cannot be obtained, and when this amount is 10 parts by mass or more, the storage stability of the resin composition for forming a flattened film is poor.
  • Component (D) is a heat-crosslinkable compound, except for those that crosslink using the acid generated from component (C) as a catalyst.
  • the crosslinking proceeds rapidly at a low temperature, for example, at the time of pre-beta, so that a film having high flatness cannot be obtained. Therefore, the component (D) is assumed to start crosslinking at a temperature higher than the acid generation temperature of the component (C), and below the temperature at which the component (D) is crosslinked, the acid generated from the component (C) is affected. In the post-beta, the acid generated from the component (C) and the component (D) start to crosslink, and the resin composition for flattening film formation excellent in planarization according to the present invention starts to crosslink. And since film
  • Examples of the compound satisfying such conditions include compounds having two or more block isocyanate groups in one molecule.
  • This may be a compound having two or more block isocyanate groups in one molecule that can be thermally cured at a conventional post-beta temperature, for example, on a film made of the acrylic polymer of component (A).
  • a conventional post-beta temperature for example, on a film made of the acrylic polymer of component (A).
  • bayonet There is no particular limitation on the type and structure of the bayonet.
  • the compound of component (D) has two or more block isocyanate groups in which one or more isocyanate groups (—NCO) are blocked by an appropriate protecting group, and is heated at a high temperature during thermal curing.
  • the protecting group (block part) is thermally dissociated and removed, and the functional group (carboxyl group, hydroxy group) for thermosetting in the acrylic polymer of component (A) is released via the generated isocyanate group.
  • Group and an amino group having active hydrogen) a crosslinking reaction proceeds between, for example, formula (71)
  • the compound of the component (D) having two or more blocked isocyanate groups in one molecule may be prepared by, for example, allowing a suitable blocking agent to act on a compound having two or more isocyanate groups in one molecule. With the power S to get.
  • Examples of the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimethyl hexane methacrylate.
  • Examples thereof include diisocyanate and the like, or dimers, trimers thereof, or a reaction product of these with diols, triols, diamines, and triamines.
  • Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol.
  • alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol.
  • the thermal decomposition of the block portion occurs and the crosslinking reaction proceeds via the isocyanate group.
  • the temperature of the thermal dissociation of the block part is considerably higher than the prebeta temperature, for example, 150 ° C to 230 ° C (D) Especially preferred as a component compound!
  • Examples of the compound of component (D) include the following specific examples.
  • the isocyanate compound is derived from isophorone diisocyanate.
  • Examples of such compounds that the compound (D) is more preferred from the viewpoint of heat resistance and coating properties include the following.
  • R in the following formula represents an organic group.
  • the compound of component (D) may be used alone or in combination of two or more.
  • the compound of component (D) is used in an amount of 1 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the acrylic polymer of component (A).
  • the amount of the component (D) compound used is too small below the lower limit of the above range, the thermosetting is insufficient and a satisfactory hardened flattening film cannot be obtained. If the amount of the compound used exceeds the upper limit of the above range, the development is insufficient and a development residue is generated.
  • the (E) solvent used in the present invention dissolves the (A) component to the (D) component and dissolves the (F) component to be added later if desired, and has such solubility. If it has a solvent, its type and structure are not particularly limited.
  • Such (E) solvents include, for example, ethylene glycol monomethyl ether, ethylenic glycolenolemonotinoreethenole, methinorecerosonolevacetate, ethenorecerosonolevate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl etherenole, propylene glycolate, propylene glycolenomonomethylenoateolate, propylene glycolenolemonomethylenoate acetate, propylene glycolenopropenoreatenoacetate, toluene, xylene, methyl ethyl ketone, cyclopenta Non, cyclohexanone, 2-heptanone, ⁇ -butyral rataton, 2-hydroxyethyl ethionate, 2-hydroxyethyl 2-methylpropionate, ethoxyethyl ethoxylate, hydroxy Ethyl acid, methyl 2-hydroxy
  • solvents propylene glycol monomethyl ether, propylene glycol monomethino ethenore acetate, 2-heptanone, propylene glycol monopropenoyl ether, propylene glycol propyl ether acetate, lactyl acetate, butyl lactate From the viewpoint of good coating properties and high safety.
  • solvents are generally used as solvents for photoresist materials.
  • Component (F) is a surfactant.
  • a surfactant may be further contained for the purpose of improving the coating property as long as the effect of the present invention is not impaired. it can.
  • the surfactant of the component (F) is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant.
  • a fluorine-based surfactant such as those manufactured by Sumitomo 3EM Co., Ltd., Dainippon Ink & Chemicals, Inc., or Asahi Glass Co., Ltd. can be used as this type of surfactant. These commercial products are convenient because they can be easily obtained.
  • F-top EF301 F-top EF301, EF 303, EF352 (manufactured by Gemco), MegaFuck F171, F173, F—475, F—482, R—08, R—30, BL—20 ( Dainippon Ink & Chemicals, Inc.), Florard FC430, FC4 31 (Sumitomo 3EM), Asahi Guard AG710, Surflon S-382, SC101, S C102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) )) And other fluorosurfactants.
  • the surfactant of component (F) can be used singly or in combination of two or more.
  • a surfactant When a surfactant is used, its content is usually 0.2% by mass or less, preferably 0.1% by mass or less, in 100% by mass of the resin composition for flattening film formation. . Even if the amount of the surfactant used for the component (F) is set to an amount exceeding 0.2% by mass, the effect of improving the coating property becomes dull and not economical.
  • the resin composition for flattening film formation excellent in the flattening of the present invention may include a rheology adjusting agent, an adhesion aid such as a silane coupling agent, a pigment, and the like, as long as the effects of the present invention are not impaired. It may contain dyes, storage stabilizers, antifoaming agents, or dissolution accelerators such as polyhydric phenols and polyhydric carboxylic acids.
  • the resin composition for flattening film formation excellent in flattening of the present invention comprises an acrylic polymer as component (A), a compound having an unsaturated double bond as component (B), and an acid generated by heat from component (C).
  • a composition comprising a compound, a thermally crosslinkable compound of component (D), and (F) a solvent, each of which may further contain one or more of surfactants of component (F) and other additives as desired. It is a thing.
  • planarizing film-forming resin composition excellent in planarization according to the present invention are as follows.
  • component (A) Based on 100 parts by weight of component (A), 3 to 60 parts by weight of component (B), 0.1 to 10 parts by weight of component (C) and 1 to 50 parts by weight of component (D) A resin composition for forming a flattened film.
  • [2] A planarizing film-forming resin composition further comprising 0.2% by mass or less of component (F) in the composition of [1] above.
  • the ratio of the solid content in the resin composition for flattening film formation excellent in flattening of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent. 80% by weight, for example 5 to 60% by weight, or 10 to 50% by weight.
  • solid content means what remove
  • the method for preparing the planarizing film-forming resin composition excellent in planarization according to the present invention is not particularly limited.
  • the preparation method include dissolving component (A) in (E) solvent.
  • the solution of the specific copolymer obtained by the polymerization reaction in the solvent (E) can be used as it is.
  • the (B) component, (C) component, (D) component, etc. are added to the solution of the (A) component in the same manner as described above to obtain a uniform solution, (E) a solvent is further added for the purpose of concentration adjustment. Additional inputs may be made. At this time, even if the (E) solvent used in the process of forming the specific copolymer and the (E) solvent used for adjusting the concentration at the time of preparing the resin composition for forming a flat film are the same, It may be good or different.
  • the prepared solution of the resin composition for forming a flattened film is preferably used after being filtered using a filter having a pore diameter of about 0.2 m.
  • the resin composition for planarization film formation excellent in planarization of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, or a glass substrate. , Quartz substrate, ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven By doing so, a coating film can be formed. Thereafter, the coating film is heated to form a planarization film-forming resin film excellent in planarization.
  • a semiconductor substrate for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, or a glass substrate. , Quartz substrate, ITO substrate, etc.
  • a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C to 160 ° C and a time of 0.3 to 60 minutes are employed.
  • the heating temperature and heating time are preferably 80 ° C to 140 ° C and 0.5 to 10 minutes.
  • the film thickness of the planarizing film-forming resin film formed from the planarizing film-forming resin composition is, for example, 0.1 to 30 m, and for example, 0.2 to 10 m. Further, for example, 0.2 to 5 111, which can be appropriately selected in consideration of the step of the substrate to be used and optical and electrical properties.
  • the post beta is generally 5 to 30 minutes on the hot plate and 3 in the oven at a heating temperature selected from the range of 140 ° C to 250 ° C. If it is treated for 0 to 90 minutes!
  • planarization film forming resin composition excellent in planarization according to the present invention can sufficiently planarize the step of the substrate and form a cured planarization film having high transparency. wear.
  • the cured film obtained from the resin composition for forming a flattened film of the present invention is excellent in solvent resistance, for example, resistance to an organic solvent such as N-methylpyrrolidone.
  • the resin composition for flattening film formation excellent in flattening according to the present invention includes a protective film, a flattening film, a thin film transistor (TFT) type liquid crystal display element, and various displays such as an organic EL element, It is suitable as a material for forming a cured film such as an insulating film. In particular, it is also suitable as a material for forming an interlayer insulating film for TFT-type liquid crystal elements, a protective film for color filters, an insulating film for organic EL elements, and the like.
  • TFT thin film transistor
  • HPMA 2-Hydroxypropylmetatalylate
  • GBLMA ⁇ -Butyloraton metatarate
  • PGMEA Propylene glycol monomethyl ether acetate
  • DPHA KAYARAD DPHA (trade name) manufactured by Nippon Kayaku Co., Ltd. [Dipentaerythritol Penta / Hexaatalylate]
  • PVE1 1,4-cyclohexanedimethanol dibule ether
  • IRG Irgacure369 (trade name) manufactured by Chinoku 'Specialty' Chemicals Co., Ltd. [2 Benzyl Nore 1 2 Dimethylamino 1- (4 Morpholinophenyl) 1 Butane 1-one]
  • PTSAM N ethyl 4 toluenesulfonamide
  • NCOl Degussa AG VESTAGON (registered trademark) B 1065 (trade name) [compound represented by formula S-4]
  • NC02 Degussa AG VESTANAT (registered trademark) Bl 358 (trade name) [compound represented by formula S-11]
  • the number-average molecular weight and weight-average molecular weight of the specific copolymer and specific cross-linked product obtained according to the following synthesis examples are as follows: GPC apparatus (Shodex (registered trademark) columns KF8 03L and KF804U manufactured by JASCO Corporation) Tetrahydrofuran was measured at a flow rate of 1 ml / min and eluted through a column (column temperature: 40 ° C.) The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) Is expressed in terms of polystyrene.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • MAA 15.5 g, CHMI 35.3 g, HEMA 25.5 g, and MMA 23.7 g are used as monomer components constituting the specific copolymer, and AIBN 5 g is used as a radical polymerization initiator.
  • the solution of component (A) (specific copolymer) of Mn4, 100, Mw7, 600 (specific copolymer concentration: 27. 5% by weight) was obtained (Pl).
  • BzMA 34.0 g, HPMA 33.0 g and GBLMA 33 ⁇ Og were used as the monomer components constituting the specific copolymer, and AIBN 3 g was used as the radical polymerization initiator.
  • ° C ⁇ By polymerization reaction at 100 ° C, Mnl4, 200, Mw28,000 (A) component (specific copolymer) solution (specific copolymer concentration: 37.5 mass%) is obtained. (P3).
  • CHMI 40.0 g and MMA 60.0 g are used as monomer components constituting the copolymer, and AIBN 5 g is used as a radical polymerization initiator, and these are used at a temperature of 60 ° C to 100 ° C in 200 g of solvent PGMEA.
  • a copolymer solution (copolymer concentration: 37.5% by mass) of Mn5, 100 and Mw9,500 was obtained (P5).
  • component (B) component, (C) component, (D) component, (E) solvent, and (F) component are mixed in a predetermined ratio to the solution of component (A), By stirring at room temperature for 3 hours to obtain a uniform solution, a resin composition for forming a flattened film of each Example and each Comparative Example was prepared.
  • copolymer solutions (P4, P5) were used instead of the component (A) solution.
  • the flattening film-forming composition was applied onto a quartz substrate using a spin coater, and then pre-betaged on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 m.
  • This coating film was placed on a hot plate for 30 minutes at a temperature of 230 ° C and post-beta was performed to form a cured film.
  • the cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550, manufactured by Shimadzu Corporation).
  • the flattening film-forming composition was applied onto a silicon wafer using a spin coater, and then pre-betaged on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film with a film thickness of 2.5 111.
  • This coating film was post-baked on a hot plate at 230 ° C for 30 minutes to form a cured film having a thickness of 2.1 m.
  • This cured film was immersed in N-methylpyrrolidone heated to 40 ° C for 10 minutes, and then the N-methylpyrrolidone on the surface was washed away with acetone and further dried at 100 ° C for 30 seconds. The film thickness change was not observed, and the film thickness decreased was marked X.
  • Example 1 to 7 the obtained coating films were good and exhibited a high leveling property of 60% or more, a high degree of 90% or more, transmittance, and excellent solvent resistance.
  • Comparative Examples 1 to 6 had a high transmittance of 90% or more, but the flatness was as low as 60% or less.
  • the resin composition for flattening film formation excellent in flattening according to the present invention is used for curing protective films, flattening films, insulating films, etc. in various displays such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements. It is suitable as a material for forming a film, and is particularly suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an insulating film of an organic EL element, and the like.
  • TFT thin film transistor

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

[PROBLÈMES] Proposer une composition de résine pour former des films aplatissants qui ont une transparence élevée et un effet d'aplatissement élevé, et qui sont appropriés pour des films de protection et des films aplatissants pour l'électrode ou le filtre de couleur devant être utilisé dans des dispositifs d'affichage à cristaux liquides, des dispositifs d'affichage EL organiques, etc. ; ainsi que des films aplatissants durcis. [MOYENS POUR RÉSOUDRE LES PROBLÈMES] Ces moyens consistent en une composition de résine pour former des films aplatissants, qui comprend (A) un polymère acrylique ayant une masse moléculaire moyenne en nombre de 2 000 à 25 000, (B) un composé ayant deux doubles liaisons insaturatées ou plus dans une molécule, (C) un composé capable de générer un acide lors du chauffage, (D) un composé de réticulation par chaleur, à l'exception de ceux capables de réticulation par la catalyse de l'acide généré par le composant (C), et (E) un solvant ; ainsi que des films durcis faits à partir de la composition.
PCT/JP2007/066895 2006-09-01 2007-08-30 Composition de résine pour former des films à effet d'aplatissement élevé WO2008029706A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8168371B2 (en) 2007-01-22 2012-05-01 Nissan Chemical Industries, Ltd. Positive photosensitive resin composition
US8828651B2 (en) 2005-07-25 2014-09-09 Nissan Chemical Industries, Ltd. Positive-type photosensitive resin composition and cured film manufactured therefrom
JPWO2016013344A1 (ja) * 2014-07-24 2017-04-27 日産化学工業株式会社 カラーフィルター下層膜形成用樹脂組成物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6348351A (ja) * 1986-08-15 1988-03-01 Nok Corp アクリルエラストマ−組成物
JPH1045849A (ja) * 1996-07-31 1998-02-17 Nippon Shokubai Co Ltd 耐熱性樹脂およびその製造方法
JPH10265649A (ja) * 1997-03-26 1998-10-06 Asahi Denka Kogyo Kk 硬化性組成物
JPH10292083A (ja) * 1997-04-18 1998-11-04 Asahi Denka Kogyo Kk 硬化性組成物
JP2001164072A (ja) * 1999-12-09 2001-06-19 Jsr Corp スペーサー用感放射線性樹脂組成物およびスペーサー
JP2002323771A (ja) * 2001-02-22 2002-11-08 Nissan Chem Ind Ltd リソグラフィー用反射防止膜形成組成物
JP2003064236A (ja) * 2001-08-28 2003-03-05 Canon Inc 着色樹脂組成物とこれを用いたカラーフィルタとその製造方法、該カラーフィルタを用いた液晶素子

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0798854B2 (ja) * 1988-12-28 1995-10-25 積水化学工業株式会社 熱硬化性シート
JPH02302403A (ja) * 1989-05-18 1990-12-14 Hitachi Chem Co Ltd 感光性樹脂組成物及びこれを用いた感光性フイルム
JPH07103245B2 (ja) * 1990-07-30 1995-11-08 積水化学工業株式会社 被覆物の製造方法
CA2048232A1 (fr) * 1990-09-05 1992-03-06 Jerry W. Williams Compositions auto-adhesives photopolymerisables
JPH09255755A (ja) * 1996-03-21 1997-09-30 Mitsubishi Rayon Co Ltd 架橋硬化型樹脂組成物及びその硬化方法
JPH10148938A (ja) * 1996-11-19 1998-06-02 Hitachi Chem Co Ltd 金属精密加工用感光性フィルム及びこれを用いたパターン製造方法
JP2001163940A (ja) * 1999-12-08 2001-06-19 Kansai Paint Co Ltd 硬化性組成物
JP4534341B2 (ja) 2000-11-07 2010-09-01 Ｊｓｒ株式会社 硬化性樹脂組成物および反射防止膜
DE10115505B4 (de) * 2001-03-29 2007-03-08 Basf Coatings Ag Thermisch und mit aktinischer Strahlung härtbare wäßrige Dispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
JP3935182B2 (ja) * 2004-09-14 2007-06-20 積水化学工業株式会社 カラムスペーサ用硬化性樹脂組成物、カラムスペーサ及び液晶表示素子

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6348351A (ja) * 1986-08-15 1988-03-01 Nok Corp アクリルエラストマ−組成物
JPH1045849A (ja) * 1996-07-31 1998-02-17 Nippon Shokubai Co Ltd 耐熱性樹脂およびその製造方法
JPH10265649A (ja) * 1997-03-26 1998-10-06 Asahi Denka Kogyo Kk 硬化性組成物
JPH10292083A (ja) * 1997-04-18 1998-11-04 Asahi Denka Kogyo Kk 硬化性組成物
JP2001164072A (ja) * 1999-12-09 2001-06-19 Jsr Corp スペーサー用感放射線性樹脂組成物およびスペーサー
JP2002323771A (ja) * 2001-02-22 2002-11-08 Nissan Chem Ind Ltd リソグラフィー用反射防止膜形成組成物
JP2003064236A (ja) * 2001-08-28 2003-03-05 Canon Inc 着色樹脂組成物とこれを用いたカラーフィルタとその製造方法、該カラーフィルタを用いた液晶素子

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8828651B2 (en) 2005-07-25 2014-09-09 Nissan Chemical Industries, Ltd. Positive-type photosensitive resin composition and cured film manufactured therefrom
US8168371B2 (en) 2007-01-22 2012-05-01 Nissan Chemical Industries, Ltd. Positive photosensitive resin composition
JPWO2016013344A1 (ja) * 2014-07-24 2017-04-27 日産化学工業株式会社 カラーフィルター下層膜形成用樹脂組成物
US20170227848A1 (en) * 2014-07-24 2017-08-10 Nissan Chemical Industries, Ltd. Resin composition for forming color filter underlayer film
US10634999B2 (en) * 2014-07-24 2020-04-28 Nissan Chemical Industries, Ltd. Resin composition for forming color filter underlayer film

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JP5488779B2 (ja) 2014-05-14
JPWO2008029706A1 (ja) 2010-01-21
TWI431061B (zh) 2014-03-21
KR20090071568A (ko) 2009-07-01
KR101411294B1 (ko) 2014-06-26

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