WO2013121821A1 - Copolymère, procédé de fabrication de copolymère, composition de résine durcissable contenant le copolymère et produit durci obtenu en durcissant la composition de résine durcissable contenant le copolymère - Google Patents

Copolymère, procédé de fabrication de copolymère, composition de résine durcissable contenant le copolymère et produit durci obtenu en durcissant la composition de résine durcissable contenant le copolymère Download PDF

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WO2013121821A1
WO2013121821A1 PCT/JP2013/050721 JP2013050721W WO2013121821A1 WO 2013121821 A1 WO2013121821 A1 WO 2013121821A1 JP 2013050721 W JP2013050721 W JP 2013050721W WO 2013121821 A1 WO2013121821 A1 WO 2013121821A1
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copolymer
meth
curable resin
acrylate
resin composition
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PCT/JP2013/050721
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English (en)
Japanese (ja)
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寺西直史
高脇浩一
圓尾且也
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株式会社ダイセル
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals

Definitions

  • the present invention relates to lithography using actinic rays such as far ultraviolet rays, electron beams, ion beams, and X-rays in semiconductor processes, insulating films provided on electronic components such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, and protection.
  • actinic rays such as far ultraviolet rays, electron beams, ion beams, and X-rays
  • insulating films provided on electronic components such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, and protection.
  • Forms radiation sensitive resins and liquid crystal display materials photo spacers for liquid crystal displays, rib forming materials for liquid crystal displays, overcoats, color resists for forming color filters, TFT insulating films, etc.
  • the present invention relates to a curable resin composition used as a liquid crystal resist material, a paint, a coating agent, an adhesive, and the like, a production method thereof, and a cured product thereof.
  • curable resin compositions are conventionally known, and a curable resin composition made of an appropriate copolymer is selected and used in consideration of applicability, pattern formation characteristics, and the like.
  • curable resin composition excellent in various properties such as coating properties and pattern forming properties, for example, those comprising a copolymer containing a monomer unit derived from an alicyclic epoxy group-containing unsaturated compound are known. (Patent Documents 1 to 3).
  • curable resin compositions have a problem that the coating film when cured is hard. Therefore, there is a need for a curable resin composition that is excellent in various properties such as applicability and pattern formation characteristics and that has a flexible coating film when formed into a cured product.
  • an object of the present invention is to provide a copolymer capable of producing a curable resin composition that is excellent in various properties such as coating properties and pattern-forming properties and has a flexible coating film when cured. It is in providing the curable resin composition containing this copolymer, and the hardened
  • the present invention Including one or more monomer units (A) derived from an alicyclic epoxy group-containing unsaturated compound represented by the following general formula (I), and a monomer unit (B) containing an alkali-soluble group A copolymer is provided.
  • R is a hydrogen atom or a methyl group, and n is an integer of 1 to 10.
  • the present invention also provides: One or more of the alicyclic epoxy group-containing unsaturated compounds represented by the following general formula (I), A polymerizable unsaturated compound containing an alkali-soluble group, A method for producing a copolymer is provided.
  • R is a hydrogen atom or a methyl group, and n is an integer of 1 to 10.
  • the present invention also provides a curable resin composition containing the copolymer.
  • the present invention also provides a cured product obtained by curing the curable resin composition.
  • the copolymer of the present invention is excellent in various properties such as coatability and pattern formation characteristics, and can produce a curable resin composition having a flexible coating film when cured, so that the coating film is hardened. Products can be obtained, and it has become possible to develop flexible applications.
  • the copolymer of the present invention is Including one or more monomer units (A) derived from an alicyclic epoxy group-containing unsaturated compound represented by the following general formula (I), and a monomer unit (B) containing an alkali-soluble group It is out.
  • R is a hydrogen atom or a methyl group
  • n is an integer of 1 to 10.
  • the monomer unit (A) can be introduced into the copolymer by subjecting the corresponding alicyclic epoxy group-containing polymerizable unsaturated compound to copolymerization.
  • the alicyclic epoxy group-containing polymerizable unsaturated compound corresponding to the monomer unit (A) is:
  • n 3 to 10.
  • the content of the monomer unit (A) is not particularly limited. For example, although it varies depending on the type of monomer used and the type of resist (negative or positive type), it is based on the total monomer units constituting the copolymer. It is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and further preferably 25 to 75% by weight. When the content of the monomer unit (A) is too small, there may be a problem that the flexibility of the coating film becomes insufficient. When the content of the monomer unit (A) is too large, the coating film There may be a problem that the curability of the resin is insufficient.
  • the lower limit of the content of the monomer unit (A1) when the monomer unit (A1) is contained in the copolymer is not particularly limited, for example, it may be 10% by weight of the whole monomer unit (A). Preferably, it is 20% by weight, more preferably 25% by weight.
  • flexibility may arise.
  • the alicyclic epoxy group-containing polymerizable unsaturated compound corresponding to the monomer unit (A) can be used alone or in combination of two or more, but the alicyclic epoxy group-containing polymerizable unsaturated compound can be used.
  • the average number of added moles of caprolactone units in the compound is not particularly limited, but is, for example, 0.3 or more, preferably 0.5 or more, and more preferably 0.7 or more.
  • the average number of moles added of caprolactone units is the average number of moles of lactone units in formula (I).
  • n is an integer of 1 to 10, but when calculating the average number of added moles of caprolactone units, an alicyclic epoxy in which the number of added moles of caprolactone units is 0.
  • n is an integer, but since the monomer unit (A) may be contained in two or more types, the average added mole number of the caprolactone unit is not necessarily an integer.
  • the monomer unit containing an alkali-soluble group has a function of imparting alkali solubility to the polymer.
  • the polymer is dissolved in an alkaline aqueous solution (developer) during development.
  • the monomer unit containing an alkali-soluble group can be introduced into a polymer by subjecting a polymerizable unsaturated compound containing an alkali-soluble group to copolymerization.
  • a group usually used in the resist field can be used, and examples thereof include a carboxyl group and a phenolic hydroxyl group.
  • Representative examples of the polymerizable unsaturated compound containing an alkali-soluble group include, but are not limited to, an unsaturated carboxylic acid or an acid anhydride thereof, hydroxystyrene or a derivative thereof. Among these, unsaturated carboxylic acid or its acid anhydride is particularly preferable.
  • unsaturated carboxylic acid or its acid anhydride for example, ⁇ , ⁇ -unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and the acid anhydride thereof (maleic anhydride, An itaconic anhydride, etc.).
  • acrylic acid and methacrylic acid are particularly preferable.
  • the polymerizable unsaturated compound containing an alkali-soluble group can be used alone or in combination of two or more.
  • the proportion of monomer units containing alkali-soluble groups in the copolymer varies depending on the type of monomer used and the type of resist (negative type or positive type).
  • the content is 5 to 50% by weight, preferably 5 to 40% by weight, and more preferably 5 to 30% by weight. If this ratio is too small, it may be difficult to dissolve in an alkali developer, and developability may be deteriorated. Conversely, if it is too large, etching resistance after development may be deteriorated.
  • the copolymer contained in the alicyclic epoxy group-containing curable resin composition of the present invention can contain a monomer unit (C) other than the monomer unit (A) and the monomer unit (B).
  • the monomer unit (C) can be introduced into the polymer by subjecting the corresponding polymerizable unsaturated compound to copolymerization.
  • the monomer unit (C) is roughly classified as follows: Monomer unit (C1): a monomer unit corresponding to an alicyclic epoxy group-containing polymerizable unsaturated compound other than the monomer unit (A), Monomer unit (C2): a monomer unit corresponding to an epoxy group-free alicyclic polymerizable unsaturated compound, Monomer unit (C3): Other monomer units.
  • ⁇ Monomer unit (C1) Monomer unit corresponding to an alicyclic epoxy group-containing polymerizable unsaturated compound other than the monomer unit (A)>
  • the monomer unit (C1) can be introduced into the copolymer by subjecting the corresponding alicyclic epoxy group-containing polymerizable unsaturated compound to copolymerization.
  • Examples of the alicyclic epoxy group-containing polymerizable unsaturated compound include 3,4-epoxycyclohexyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, and 2- (3,4).
  • Examples of the alicyclic epoxy group-containing polymerizable unsaturated compound include polymerizable unsaturated compounds containing an epoxy group-containing alicyclic carbocycle such as 3,4-epoxycyclohexane ring ((meth) acrylic acid ester derivatives, etc.). Among them, 3,4-epoxycyclohexyl (meth) acrylate, epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5.2.1.0 2,6 ] decan-9-yl ( More preferred are (meth) acrylates, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, or mixtures thereof].
  • an epoxy group-containing alicyclic carbocycle such as 3,4-epoxycyclohexane ring ((meth) acrylic acid ester derivatives, etc.).
  • the upper limit of the content of the monomer unit (C1) when the monomer unit (C1) is contained in the copolymer is not particularly limited, for example, 60% by weight with respect to all the monomer units constituting the copolymer %, More preferably 50% by weight, and even more preferably 40% by weight.
  • hardenability of a coating film may fall may arise.
  • ⁇ Monomer unit (C2) Monomer unit corresponding to an epoxy group-free alicyclic polymerizable unsaturated compound>
  • the monomer unit (C2) can be introduced into the copolymer by subjecting the corresponding epoxy group-free alicyclic polymerizable unsaturated compound to copolymerization.
  • Examples of the alicyclic ring contained in the epoxy group-free alicyclic polymerizable unsaturated compound include alicyclic hydrocarbon rings having 5 to 20 carbon atoms. It may be a polycyclic ring or the like.
  • Typical alicyclic hydrocarbon rings include, for example, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring, norbornene ring, bornane ring, isobornane ring, perhydroindene ring, decalin ring, perhydrofluorene ring.
  • the alicyclic hydrocarbon ring includes an alkyl group such as a methyl group (for example, a C 1-4 alkyl group), a halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group optionally protected by a protecting group, oxo And a substituent such as a carboxyl group which may be protected with a protecting group.
  • the alicyclic ring is preferably, for example, a polycyclic alicyclic hydrocarbon ring (bridged hydrocarbon ring) such as a tricyclo [5.2.1.0 2,6 ] decane ring or an adamantane ring.
  • Epoxy group-free alicyclic polymerizable unsaturated compounds include, for example, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, 2- (cyclohexyl) ethyl (meth) acrylate, 2- (cyclohexylmethyloxy) ethyl (Polmerizable unsaturated compounds containing a cyclohexane ring such as (meth) acrylate and 3- (cyclohexylmethyloxy) propyl (meth) acrylate (such as (meth) acrylate derivatives); 2-bicyclo [2.2.1] heptyl ( Polymerizable unsaturated compounds containing a 2-bicyclo [2.2.1] heptane ring such as (meth) acrylate (eg (meth) acrylate derivatives); Polymerizability containing an adamantane ring such as 1-adamantyl (meth) acrylate Unsaturated
  • a polymerizable unsaturated compound containing a tricyclo [5.2.1.0 2,6 ] decane ring or an adamantane ring is preferable, and among them, tricyclo [5.2 .1.0 2,6] decan-8-yl (meth) acrylate.
  • ⁇ Monomer unit (C3) Other monomer units>
  • the monomer unit (C3) can be introduced into the polymer by subjecting the corresponding polymerizable unsaturated compound to copolymerization.
  • Examples of the polymerizable unsaturated compound corresponding to the monomer unit (C3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( (Meth) acrylic acid alkyl esters such as (meth) acrylate [for example, (meth) acrylic acid C 1-10 alkyl ester, etc.]; (meth) acrylic acid having an aromatic cyclic structure in the molecule such as benzyl (meth) acrylate Ester; Styrenic compounds such as styrene, vinyl toluene, ⁇ -methylstyrene vinyl naphthalene; and vinyl ether compounds such as methyl vinyl ether, butyl vinyl ether, and phenyl vinyl ether.
  • the polymerizable unsaturated compound corresponding to the monomer unit (C3) includes a radical polymerizable monomer having a hydrophilic group.
  • the hydrophilic group include a hydroxyl group (excluding phenolic groups), a quaternary ammonium group, an amino group, a heterocyclic group, and the like.
  • Specific examples of the radical polymerizable monomer having a hydrophilic group include, for example, (meth) acrylic having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
  • Acid esters alkoxypolyalkylene glycols such as methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate ( (Meth) acrylate; (meth) acrylic acid ester having an amino group such as 2-aminoethyl (meth) acrylate; vinylid such as 2-vinylpyrrolidone And heterocyclic compounds having a group (a nitrogen-containing heterocyclic compounds, etc.) can be mentioned.
  • alkoxypolyalkylene glycols such as methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, methoxytriethylene
  • the method for producing the copolymer of the present invention comprises: One or more of the alicyclic epoxy group-containing unsaturated compounds represented by the general formula (I); A polymerizable unsaturated compound containing an alkali-soluble group, There is no particular limitation as long as it is a method for producing a copolymer characterized by copolymerization. Moreover, the manufacturing method of the copolymer of this invention may attach
  • a normal radical initiator can be used as the polymerization initiator used for polymerization.
  • a normal radical initiator can be used.
  • a redox initiator may be combined with a reducing agent.
  • azo compounds are preferred, and in particular, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyric acid) dimethyl. Is preferred.
  • the amount of the polymerization initiator used can be appropriately selected within a range that does not impair smooth copolymerization, but is usually about 0.1 to 10% by weight based on the total amount of all monomer components and polymerization initiator, Preferably, it is about 0.5 to 8% by weight.
  • a chain transfer agent generally used in radical polymerization may be used in combination.
  • Specific examples include thiols (n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan, etc.), thiolic acids ( Mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, thiomalic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), ⁇ -methylstyrene dimer , Terbinolene, myrcene, limonene, ⁇ -pinene, ⁇ -pinene
  • Polymerization can be carried out by conventional methods such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, etc. Among these, solution polymerization is preferable.
  • the monomer and the polymerization initiator may be supplied all at once to the reaction system, or a part or all of them may be dropped into the reaction system.
  • a method in which a solution obtained by dissolving a polymerization initiator in a polymerization solvent is dropped into a mixed solution of a monomer and a polymerization solvent kept at a constant temperature for polymerization, or a monomer and a polymerization initiator are previously used as a polymerization solvent.
  • a method in which the dissolved solution is dropped into a polymerization solvent maintained at a constant temperature for polymerization can be employed.
  • the polymerization temperature can be appropriately selected, for example, in the range of about 30 to 150 ° C.
  • the polymerization solvent can be appropriately selected depending on the monomer composition and the like.
  • a solvent containing 30% by weight or more (more preferably 50% by weight or more, particularly 80% by weight or more) of a solvent described later as a solvent contained in the curable resin composition of the present invention is preferable.
  • processing such as solvent replacement can be omitted at the time of producing the curable resin composition, and the production process can be further simplified.
  • the copolymer of the present invention is produced by the above method.
  • the weight average molecular weight of the copolymer is, for example, about 500 to 100,000, preferably about 1,000 to 40,000, and more preferably about 2,000 to 30,000.
  • the degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer is about 1 to 3.
  • the curable resin composition of the present invention includes the copolymer of the present invention.
  • the curable resin composition of the present invention may contain a solvent.
  • the solvent include ether [diethyl ether; ethylene glycol mono- or dialkyl ether, diethylene glycol mono- or dialkyl ether (such as diethylene glycol dialkyl ether such as diethylene glycol methyl ethyl ether), propylene glycol mono- or dialkyl ether, propylene glycol mono- or diaryl ether, Dipropylene glycol mono or dialkyl ether (dipropylene glycol di-C 1-4 alkyl ether such as dipropylene glycol dimethyl ether and dipropylene glycol methyl n-propyl ether), tripropylene glycol mono or dialkyl ether, 1,3-propanediol Mono- or dialkyl ether, 1,3-butanediol mono- or dialky Chain ethers such as glycol ethers such as ether, 1,4-butanediol mono or dialky
  • diethylene glycol ethyl methyl ether EDM
  • dipropylene glycol dimethyl ether DPMNP
  • propylene glycol monomethyl ether acetate MMC
  • 3-methoxybutyl acetate MAA
  • Particularly preferred are 1-methoxy-2-propanol (MMPG), 3-methoxy-1-butanol (MB) and the like.
  • the solvent content with respect to the entire curable resin composition is not particularly limited, but can be, for example, 40 to 90% by weight, preferably 45 to 85% by weight, from the viewpoint of the polymer production conditions and the viscosity of the blended composition. %, More preferably 50 to 80% by weight.
  • the manufacturing method of the curable resin composition of this invention should just be a manufacturing method of the curable resin composition containing the said copolymer, and is not restrict
  • a curing catalyst thermal acid generator (thermal curing catalyst, thermal cationic polymerization initiator), photoacid generator (photocuring catalyst, photocationic polymerization start), if necessary. Agent)] photo radical initiator, curing agent, curing accelerator, radiation sensitive component, reactive diluent, additive (crosslinking agent, filler, coloring pigment, polymerization inhibitor, adhesion promoter, antifoaming) Agents, flame retardants, antioxidants, UV absorbers, stress reducing agents, flexibility imparting agents, waxes, resins, crosslinking agents, halogen trapping agents, leveling agents, wetting improvers, etc.) .
  • polymerization can be refine
  • a curable resin composition can also be obtained by melt
  • the solvent of the said illustration can be used as a solvent which comprises curable resin composition as needed.
  • the thermal acid generator is not particularly limited, and examples thereof include Sun-Aid SI-45, Same as left SI-47, Same as left SI-60, Same as left SI-60L, Same as left SI-80, Same as left SI-80L, SI-100, left SI-100L, left SI-145, left SI-150, left SI-160, left SI-110L, left SI-180L (Sanshin Chemical Co., Ltd., product name), CI- 2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2638, CI-2064 (Nippon Soda Co., Ltd., product name), CP-66, CP-77 (Asahi Denka Kogyo Co., Ltd.
  • Oxonium salts, ammonium salts and the like can be used.
  • the photoacid generator is not particularly limited.
  • Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (trade name, manufactured by Union Carbide, USA), Irgacure 261 (Ciba) ⁇ Specialty Chemicals, trade name), SP-150, SP-151, SP-170, Optomer SP-171 (above, trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), CG-24-61 (Ciba Specialty) Chemicals, trade name), DAICATII (Daicel, trade name), UVAC1591 (Daicel Cytec, trade name), CI-2064, CI-2638, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758 ( Top, Nippon Soda Co., Ltd., trade name), PI-2074 (Rhone-Poulenc, trade name,
  • benzophenones such as benzophenone; acetophenone benzyl, benzyl dimethyl ketone; benzoins, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; dimethoxyacetophenone, dimethoxyphenyl Acetophenones such as acetophenone and diethoxyacetophenone; diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate [Nippon Kayaku Co., Ltd.
  • a photosensitizer can be added.
  • the polymerization initiator is not particularly limited, but is preferably blended in the cur
  • the addition amount of the curing catalyst is not particularly limited. For example, it is 0.05 to 10% by weight, preferably 0.5 to 5% by weight, based on the copolymer (resin content) in the curable resin composition. It is.
  • a curing catalyst can be used individually or in combination of 2 or more types.
  • the cross-linking agent is not particularly limited, and for example, polyfunctional alcohol compounds and polyfunctional thiol compounds can be used.
  • the polyfunctional alcohol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups.
  • Polyhydric alcohols such as glycols, polyethylene glycols, polypropylene glycols, polybutylene glycols, polytetramethylene glycols and other polyalkylene glycols, polycaprolactone dio Le acids, polycaprolactone triols, and the like polycarbonate diols.
  • the polyfunctional thiol compound is not particularly limited as long as it is a compound having two or more thiol groups.
  • polyfunctional (meth) acrylate for example, polyfunctional (meth) acrylate, a polyfunctional epoxy compound, polyfunctional urethane (meth) acrylate, polyfunctional epoxy (meth) acrylate (on epoxy group) Acrylic acid added type) and the like.
  • a polyfunctional (meth) acrylate and a heat or radiation polymerization initiator, or a polyfunctional epoxy compound and a heat or radiation acid generator may be combined.
  • Each of these radiation-sensitive components, heat or radiation polymerization initiators, and heat or radiation acid generators may be used alone or in combination of two or more.
  • the polyfunctional (meth) acrylate is not particularly limited.
  • di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol
  • di (meth) acrylate of polyalkylene glycol such as polyethylene glycol and polypropylene glycol.
  • Di (meth) acrylates of hydroxylated polymers at both ends such as hydroxypolybutadiene at both ends, hydroxypolyisoprene at both ends, and hydroxypolycaprilactone at both ends, glycerin, 1,2,4, -butanetriol, trimethylolalkane
  • Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as tetramethylolalkane, pentaerythritol, dipentaerythritol, and polyalkylene trihydric polyhydric alcohols
  • Poly (meth) acrylates of coal adducts poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol, 1,4-benzenediols, polyester (meth) acrylate, epoxy (meth) acrylate, Examples include urethane (meth) acrylate, alkyd resin (meth) acrylate, silicon resin
  • the reactive diluent is not particularly limited as long as it can dissolve the copolymer.
  • a polymerizable vinyl monomer having one or more (meth) acryl groups can be used.
  • the reactive diluent can also function as the radiation-sensitive component.
  • alkyl or cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate Hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate; mono- or di (meth) acrylates of ethylene glycol, (meth) acrylates of methoxyethylene glycol, mono- or di (meth) acrylates of tetraethylene glycol, Mono or di (meth) acrylate of glycol such as mono or di (meth) acrylate of tripropylene glycol; 3,4-epoxycyclohexylmethyl (meth) acrylate, Epoxy group-containing (meth) acrylates such as dil (meth) acrylate;
  • the reactive diluent is not particularly limited, but for example, those having a flash point of 100 ° C. or higher are preferable from the viewpoint of ensuring safety in the production process.
  • the reactive diluent is not particularly limited, but for example, a polyol such as trimethylolpropane tri (meth) acrylate or a polyfunctional (meth) acrylate such as (meth) acrylate of an alkylene oxide adduct thereof is particularly preferable. .
  • the compounding amount of the reactive diluent is not particularly limited. For example, it is 1 to 1000 parts by weight, preferably 50 to 700 parts by weight, and more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the copolymer. Can be blended in proportions.
  • the filler added as necessary to the curable resin composition of the present invention is not particularly limited, and examples thereof include reactive resins such as epoxy resins, barium sulfate, silicon oxide, talc, clay, calcium carbonate, and the like. It is done.
  • the coloring pigment include phthalocyanine green, crystal violet, titanium oxide, and carbon black. Although it does not restrict
  • the curable resin composition thus obtained has a high adhesion to a substrate and a substrate by curing, is excellent in chemical resistance such as solvent resistance and alkali resistance, and has a flexible coating film.
  • a cured film or the like can be obtained. Therefore, in addition to liquid crystal resist materials, it is also useful as a component of paints, inks, coating agents, adhesives, etc., especially flexible materials such as display materials and protective films used in liquid crystals, organic EL, etc. Can be suitably used.
  • the cured product of the present invention is formed by, for example, applying the curable resin composition to various substrates or substrates by a method such as a spin coater or a slit coater to form a coating film, and then curing the coating film. Can be obtained.
  • the base material or substrate include glass, ceramic, silicon wafer, metal, and plastic.
  • Coating with a spin coater, slit coater, or the like can be performed by a known method.
  • the cured product of the present invention is excellent in various physical properties such as substrate adhesion, solvent resistance, hardness, film thickness uniformity, line width uniformity, sensitivity, developability, and pattern characteristics to be formed, and the coating film is flexible. It is.
  • the coating film is cured by heating, irradiating with an active energy ray for exposure, or heating after exposure.
  • the heating temperature is in the range of 50 ° C to 260 ° C, preferably in the range of 80 ° C to 240 ° C.
  • light of various wavelengths, for example, ultraviolet rays, X-rays, g-rays, i-rays, excimer lasers, etc. are used for exposure.
  • the thickness of the cured coating film can be appropriately selected depending on the application, but is generally about 0.1 to 40 ⁇ m, preferably about 0.3 to 20 ⁇ m, more preferably about 0.5 to 10 ⁇ m.
  • a solution prepared by dissolving 20 g of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 260 g of diethylene glycol ethyl methyl ether was dropped over 3 hours using another dropping funnel.
  • a light and / or thermosetting resin solution was obtained by aging for 3 hours.
  • the temperature of the solution was kept at 65 ° C.
  • the obtained curable resin solution had a solid content of 33.9% by weight, a molecular weight of 12,200, a dispersity of 1.70, and an acid value of 67 mg-KOH / g (in terms of solid content).
  • the obtained curable resin solution had a solid content of 34.1% by weight, a molecular weight of 12,700, a dispersity of 1.81, and an acid value of 66 mg-KOH / g (in terms of solid content).
  • the obtained curable resin solution had a solid content of 34.6% by weight, a molecular weight of 11,600, a dispersity of 1.79, and an acid value of 70 mg-KOH / g (in terms of solid content).
  • the obtained curable resin solution had a solid content of 34.2% by weight, a molecular weight of 12,500, a dispersity of 1.77, and an acid value of 71 mg-KOH / g (in terms of solid content).
  • the obtained curable resin solution had a solid content of 34.0% by weight, a molecular weight of 12,200, a dispersity of 1.74, and an acid value of 66 mg-KOH / g (in terms of solid content).
  • thermosetting resin solution was obtained.
  • the resulting light and / or thermosetting resin solution had a solid content of 34.6% by weight, an acid value of 68 mg-KOH / g (in terms of solid content), a weight average molecular weight Mw of 13,000, and a dispersity of 1. 71.
  • Examples 1 to 5 To 58 parts by weight of the light and / or thermosetting resin solution produced in Synthesis Examples 1 to 5, 15 parts by weight of dipentaerythritol hexaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.), caprolactone-modified dipentaerythritol hexa 5 parts by weight of acrylate (“KAYARAD DPCA-120” manufactured by Nippon Kayaku Co., Ltd.), 5 parts by weight of a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd.), and 100 parts by weight of propylene glycol monomethyl ether acetate as a solvent
  • the curable resin compositions 1 to 5 were prepared by blending parts.
  • Example 3 Stability In each Example and Comparative Example, a copolymer solution stored at room temperature for 1 week was used, and an evaluation test piece made of a glass plate was made in the same manner as in (1) above. Compared with the test specimen for evaluation produced using the copolymer solution before storage [said (1)], if the coating film has a uniform film thickness of the same film thickness, the film thickness slightly changes. If it was an equivalent coating film, it was evaluated as ⁇ , if the film thickness greatly changed, ⁇ , and if a uniform coating film could not be formed, it was rated as x. Similar results were obtained when both the evaluation test piece made of glass plate and the evaluation test piece made of stainless steel plate were used.
  • the curable resin compositions of the examples and the cured coating films obtained from the resin compositions are only excellent in terms of stability, substrate adhesion, and solvent resistance. Not only that, but also in terms of flexibility.
  • the curable resin composition of the comparative example and the cured coating film obtained from the resin composition were particularly inferior in terms of flexibility.
  • a copolymer capable of producing a curable resin composition having excellent properties such as applicability and pattern formation properties and having a flexible coating film when formed into a cured product can be obtained. Therefore, the coating film obtained by curing this curable resin composition can be suitably used for flexible applications such as display materials used in liquid crystals, organic EL, and protective films.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne : un copolymère qui est apte à fabriquer une composition de résine durcissable qui a d'excellentes caractéristiques telles que des caractéristiques de capacité de revêtement et de formation de motif et qui fournit un film de revêtement doux quand elle est durcie ; un procédé de fabrication du copolymère ; une composition de résine durcissable qui contient le copolymère ; et un produit durci qui est obtenu en durcissant la composition de résine durcissable. L'invention concerne un copolymère qui contient (A) une ou plusieurs unités monomériques issues d'un composé insaturé contenant un groupe époxy alicyclique représenté par la formule générale (I) et (B) une unité monomérique contenant un groupe soluble dans les alcalins. (Dans la formule (I), R représente un atome d'hydrogène ou un groupe méthyle et n est un entier de 1-10).
PCT/JP2013/050721 2012-02-17 2013-01-17 Copolymère, procédé de fabrication de copolymère, composition de résine durcissable contenant le copolymère et produit durci obtenu en durcissant la composition de résine durcissable contenant le copolymère WO2013121821A1 (fr)

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JP2012-032339 2012-02-17
JP2012032339 2012-02-17

Publications (1)

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WO2013121821A1 true WO2013121821A1 (fr) 2013-08-22

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JP (1) JPWO2013121821A1 (fr)
TW (1) TW201336875A (fr)
WO (1) WO2013121821A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190044540A (ko) * 2017-10-20 2019-04-30 동우 화인켐 주식회사 착색 감광성 수지 조성물, 상기 수지 조성물을 사용하여 제조된 패턴층, 상기 패턴층을 포함하는 컬러필터, 및 상기 컬러필터를 포함하는 표시장치

Citations (2)

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JPH04117471A (ja) * 1990-09-06 1992-04-17 Mazda Motor Corp 塗料組成物
JP2006328322A (ja) * 2005-05-30 2006-12-07 Sekisui Chem Co Ltd 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

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Publication number Priority date Publication date Assignee Title
JP4389583B2 (ja) * 2003-12-26 2009-12-24 住友化学株式会社 感放射線性樹脂組成物

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Publication number Priority date Publication date Assignee Title
JPH04117471A (ja) * 1990-09-06 1992-04-17 Mazda Motor Corp 塗料組成物
JP2006328322A (ja) * 2005-05-30 2006-12-07 Sekisui Chem Co Ltd 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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190044540A (ko) * 2017-10-20 2019-04-30 동우 화인켐 주식회사 착색 감광성 수지 조성물, 상기 수지 조성물을 사용하여 제조된 패턴층, 상기 패턴층을 포함하는 컬러필터, 및 상기 컬러필터를 포함하는 표시장치
KR20200072461A (ko) * 2017-10-20 2020-06-22 동우 화인켐 주식회사 착색 감광성 수지 조성물, 상기 수지 조성물을 사용하여 제조된 패턴층, 상기 패턴층을 포함하는 컬러필터, 및 상기 컬러필터를 포함하는 표시장치
KR102129040B1 (ko) 2017-10-20 2020-07-02 동우 화인켐 주식회사 착색 감광성 수지 조성물, 상기 수지 조성물을 사용하여 제조된 패턴층, 상기 패턴층을 포함하는 컬러필터, 및 상기 컬러필터를 포함하는 표시장치
KR102243166B1 (ko) 2017-10-20 2021-04-22 동우 화인켐 주식회사 착색 감광성 수지 조성물, 상기 수지 조성물을 사용하여 제조된 패턴층, 상기 패턴층을 포함하는 컬러필터, 및 상기 컬러필터를 포함하는 표시장치

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