Classifications

• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • 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
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays
  • H10K59/122—Pixel-defining structures or layers, e.g. banks

Definitions

• the present invention relates to a novel reactive polycarboxylic acid compound (A), an active energy ray-curable resin composition containing the compound, and a cured product thereof.
• A novel reactive polycarboxylic acid compound
• the present invention relates to a novel reactive polycarboxylic acid compound suitable as a resist material that can also be used as a material for display devices such as organic EL display elements, an active energy ray-curable resin composition containing the compound, and a cured product thereof.
• Organic EL display elements which utilize the electroluminescence of organic compounds, have many features, such as being self-luminous and not dependent on viewing angle, having a fast response speed, and being able to be made thin and lightweight, and are being actively developed for use in image display devices.
• Photolithographic pattern formation technology is used to fabricate the components of display devices such as organic electroluminescence displays, such as partition walls and planarizing layers, and active energy ray-curable resin compositions are used.
• the present invention aims to provide an active energy ray-curable resin composition and its cured product that can be patterned by photolithography and have low outgassing. More specifically, the present invention aims to provide an active energy ray-curable resin material with low outgassing per acid value.
• the inventors conducted extensive research to solve the above problems, and discovered that a resin and resin composition using a reaction product of a specific epoxy resin with an unsaturated group-containing carboxylic acid and a specific polybasic acid anhydride solves the above problems, thus arriving at the present invention.
• n represents an average value and is a number from 0 to 10.
• P and R each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group, and multiple Ps and Rs may be the same or different.
• G represents a glycidyl group.
• the reactive polycarboxylic acid compound (A) of the present invention can be obtained by reacting an epoxy resin (a) having a structure represented by the following formula (1) or (2) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule to obtain a reactive epoxy carboxylate compound (c), and then reacting the resulting compound with a polybasic acid anhydride (d) represented by the following formula (3).
• n indicates the average value and is a number between 0 and 10.
• n indicates the average value and is a number between 0 and 10.
• P and R each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and multiple P's and R's may be the same or different.
• the alkyl group having 1 to 8 carbon atoms may be any of linear, branched, and cyclic alkyl groups, and specific examples thereof include methyl, cyclohexylmethyl, ethyl, 2-cyclopentylethyl, propyl, 2-methylpropyl, 2,2-dimethylpropyl, 3-cyclopropylpropyl, isopropyl, cyclopropyl, butyl, 2-methylbutyl, 3-methylbutyl, 2-butyl, 3-methylbutan-2-yl, tert-butyl, cyclobutyl, pentyl, 2-methylpentyl, 3-ethylpentyl, 2,4-dimethylpentyl, 2-pentyl, 2-methylpent
• the epoxy resin (a) used in the present invention is an epoxy resin represented by the above formula (1) or (2).
• Epoxy resins represented by the above formula (1) are generally available under various trade names, such as EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 manufactured by Nippon Kayaku Co., Ltd., Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-690, Epicron N-695, Epicron N-665-EXP, and Epicron N-672-EXP manufactured by DIC Corporation, and YDCN-700-7, YDCN-700-10, YDCN-704, and YDCN-704A manufactured by Nippon Steel Chemical & Material Co., Ltd.
• Epoxy resins represented by formula (2) are generally available under various trade names, such as NC-3000, NC-3100, NC-3000-L, NC-3000-H, NC-3000-LC, and NC-3000-LLC, manufactured by Nippon Kayaku Co., Ltd.
• Examples of the carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule include (meth)acrylic acids, crotonic acid, ⁇ -cyanocinnamic acid, cinnamic acid, or reaction products of saturated or unsaturated dibasic acids with unsaturated group-containing monoglycidyl compounds.
• Examples of the (meth)acrylic acids mentioned above include monocarboxylic acid compounds containing one carboxy group in one molecule, such as (meth)acrylic acid, ⁇ -styrylacrylic acid, ⁇ -furfurylacrylic acid, (meth)acrylic acid dimer, half esters which are equimolar reaction products of saturated or unsaturated dibasic acid anhydrides and (meth)acrylate derivatives having one hydroxyl group in one molecule, and half esters which are equimolar reaction products of saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives, as well as polycarboxylic acid compounds having multiple carboxy groups in one molecule, such as half esters which are equimolar reaction products of saturated or unsaturated dibasic acid anhydrides and (meth)acrylate derivatives having multiple hydroxyl groups in one molecule, and half esters which are equimolar reaction products of saturated or unsaturated dibasic acids and glycidyl
• the carboxylic acid compound (b) is preferably a monocarboxylic acid, and even when a monocarboxylic acid and a polycarboxylic acid are used in combination, the value represented by the molar amount of monocarboxylic acid/the molar amount of polycarboxylic acid is preferably 15 or more.
• the value represented by the molar amount of monocarboxylic acid/the molar amount of polycarboxylic acid is preferably 15 or more.
• (meth)acrylic acid, a reaction product of (meth)acrylic acid and ⁇ -caprolactone, and cinnamic acid in terms of sensitivity when made into an active energy ray-curable resin composition are preferred.
• the total amount of carboxylic acid compound (b) is preferably 20-90 equivalent percent per equivalent of epoxy resin (a). Outside this range, the effect of the composite hardening will be weak. Of course, in this case, sufficient care must be taken to prevent gelling during the reaction and the stability of the reactive epoxy carboxylate compound (c) over time.
• the carboxylation reaction can be carried out without a solvent, or diluted with a solvent.
• a solvent or diluted with a solvent.
• the solvent that can be used here, as long as it is an inert solvent for the carboxylation reaction.
• the amount of solvent used should be adjusted appropriately depending on the viscosity and use of the resulting resin, but it is preferably used so that the solids content is 90 to 20% by mass, and more preferably 80 to 30% by mass.
• Ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as gamma-butyrolactone; mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and butylene glycol monomethyl ether acetate; and polycarboxylic acid alkyl esters such as dialkyl glutarate, dialkyl succinate, and dialkyl adipate.
• alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate
• cyclic esters such as
• Ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.
• alkyl ethers such as diethyl ether and ethyl butyl ether
• glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether
• cyclic ethers such as tetrahydrofuran.
• Ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, isophorone, etc.
• reaction can be carried out in a single or mixed organic solvent using a reactive compound (B) other than the reactive polycarboxylic acid compound (A) described below (hereinafter also referred to simply as "reactive compound (B)").
• a reactive compound (B) other than the reactive polycarboxylic acid compound (A) described below
• reactive compound (B) when used as a curable resin composition, it can be used directly as a composition, which is preferable.
• catalysts that can be used include known general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and zirconium octanoate.
• known general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and zirconium octanoate.
• thermal polymerization inhibitor can be used.
• the thermal polymerization inhibitor it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, etc.
• the toughness of the cured product will not be sufficient, and if it is larger than this, the viscosity will be too high, making coating, etc. difficult.
• the acid addition step is carried out for the purpose of introducing a carboxy group, if necessary, into the reactive epoxy carboxylate compound (c) obtained in the previous step, to obtain a reactive polycarboxylic acid compound (A). That is, the hydroxyl group generated by the carboxylation reaction is subjected to an addition reaction with the polybasic acid anhydride (d) represented by the above formula (2) (hereinafter also simply referred to as “polybasic acid anhydride (d)”), thereby introducing a carboxy group via an ester bond.
• polybasic acid anhydride (d) represented by the above formula (2)
• the polybasic acid anhydride (d) is preferably a compound represented by the following formula (3):
• the amount of polybasic acid anhydride (d) added is preferably calculated so that the solid content acid value (based on JIS K5601-2-1:1999) of the finally obtained reactive polycarboxylic acid compound (A) is preferably 10 to 110 mgKOH/g, more preferably 20 to 100 mgKOH/g.
• the active energy ray curable resin composition of the present invention exhibits good alkaline aqueous solution developability. In other words, there is good patterning property, a wide control range for overdevelopment, and no excess acid anhydride remains.
• the amount of the catalyst used is 0.1 to 10 parts by mass based on the total amount of the reactants, i.e., the epoxy compound (a), the reactive epoxy carboxylate compound (c) obtained from the carboxylic acid compound (b), and the polybasic acid anhydride (d), and optionally the solvent and other reactants.
• the reaction temperature is 60 to 150°C, and the reaction time is preferably 5 to 60 hours.
• catalysts that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, zirconium octanoate, etc.
• This acid addition reaction can be carried out without a solvent or diluted with a solvent.
• a solvent that can be used here, so long as it is an inert solvent for the acid addition reaction.
• the product can be directly subjected to the next step, the acid addition reaction, without removing the solvent, provided that the solvent is inert for both reactions.
• the solvent that can be used may be the same as that used in the carboxylation reaction.
• the amount of solvent used should be adjusted appropriately depending on the viscosity and use of the resulting resin, but it is preferably used so that the amount is 70 to 30% by mass, more preferably 60 to 40% by mass, based on the solid content.
• the reactive compound (B) can be used alone or in a mixed organic solvent.
• the reactive compound (B) when used as a curable resin composition, it is preferable because it can be used directly as a composition.
• thermal polymerization inhibitors as those exemplified in the carboxylation reaction described above.
• This acid addition reaction is terminated when the acid value of the reactant reaches a range of plus or minus 10% of the set acid value while sampling appropriately.
• the preferred molecular weight range of the reactive polycarboxylic acid compound (A) thus obtained is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.
• the toughness of the cured product will not be sufficient, and if it is larger than this, the viscosity will be too high, making coating, etc. difficult.
• Borate-based photopolymerization initiators include NK-3876 and NK-3881 manufactured by Nippon Kanko Shikushiki Co., Ltd.
• other photoacid generators include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (Kurokane Kasei Co., Ltd. Biimidazole, etc.), 2,2-azobis(2-amino-propane) dihydrochloride (Wako Pure Chemical Industries, Ltd. V50, etc.), 2,2-azobis[2-(imidazolin-2yl)propane]dihydrochloride (Wako Pure Chemical Industries, Ltd.
• Examples of suitable bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridin-1-yl)phenyl]titanium include bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridin-1-yl)phenyl]dihydrochloride (e.g., VA044 manufactured by Wako Pure Chemical Industries, Ltd.), bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridin-1-yl)phenyl]benzene(II)hexafluorophosphonate (e.g., Irgacure 261 manufactured by Ciba Geigy), and titanium (e.
• Irgacure 261 manufactured by Ciba Geigy
• titanium e.
• azo-based initiators such as azobisisobutyronitrile
• heat-sensitive peroxide-based radical initiators such as benzoyl peroxide
• radical and cationic photopolymerization initiators may be used in combination.
• One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.
• radical photopolymerization initiators are particularly preferred, taking into consideration the properties of the reactive polycarboxylic acid compound (A) of the present invention.
• the active energy ray-curable resin composition of the present invention may contain other additives as necessary.
• additives include thermosetting catalysts such as melamine, thixotropy-imparting agents such as aerosil, silicone-based and fluorine-based leveling agents and defoamers, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, and antioxidants.
• resins that are not reactive to active energy rays can also be used, such as other epoxy resins, phenolic resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified versions of these. These are preferably used in amounts up to 40 parts by mass in the resin composition.
• the reactive polycarboxylic acid compound (A) when using the reactive polycarboxylic acid compound (A) for solder resist applications, it is preferable to use a known general epoxy resin as a resin that does not exhibit reactivity to active energy rays. This is because the carboxyl groups derived from the reactive polycarboxylic acid compound (A) remain even after reaction and curing with active energy rays, and as a result, the cured product has poor water resistance and hydrolysis resistance. Therefore, by using an epoxy resin, the remaining carboxyl groups are further carboxylated, forming an even stronger crosslinked structure.
• the known general epoxy resin can use the above-mentioned cation-reactive monomer.
• the active energy ray-curable resin composition of the present invention is easily cured by active energy rays.
• active energy rays include ultraviolet rays, visible light rays, infrared rays, electromagnetic waves such as X-rays, gamma rays, and laser beams, and particle rays such as alpha rays, beta rays, and electron beams.
• ultraviolet rays, laser beams, visible light, and electron beams are preferred.
• the display device material is a material used in display elements such as liquid crystal display devices, organic EL devices, and electronic paper. Specific applications include spacers, protective films, planarizing films, interlayer insulating films, and partition materials. Of these, it is preferable that the display device according to one embodiment of the present invention is an organic EL device.
• the present invention also includes a cured product obtained by irradiating the curable resin composition with active energy rays, and also includes a multi-layer material having a layer of the cured product.
• the unreacted reactive polycarboxylic acid compound (A) as an alkaline water developable resist material composition, taking advantage of the characteristic that the unreacted reactive polycarboxylic acid compound (A) is soluble in an alkaline aqueous solution.
• the active energy ray-curable resin composition which is the resist material composition of the present invention, can be applied to various materials that can be patterned, and is particularly useful as a solder resist material and an interlayer insulating material for build-up construction methods, and can also be used as an optical waveguide in printed wiring boards, optoelectronic boards, optical boards, and other electrical, electronic, and optical substrates.
• Particularly suitable applications include photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulation materials, hole filling resins, component embedding resins, color resists, color filters, black matrices, and a wide range of other applications requiring resin compositions.
• insulating resin sheets such as prepregs, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulation materials, hole filling resins, component embedding resins, color resists, color filters, black matrices, and a wide range of other applications requiring resin compositions.
• the resin composition can be suitably used for the insulating layer of a multilayer printed wiring board (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is used as an insulating layer), a resin composition for an interlayer insulating layer (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is used as an interlayer insulating layer), a resin composition for plating (a multilayer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition), etc.
• a multilayer printed wiring board a multilayer printed wiring board in which a cured product of a photosensitive resin composition is used as an insulating layer
• a resin composition for an interlayer insulating layer a multilayer printed wiring board in which a cured product of a photosensitive resin composition is used as an interlayer insulating layer
• a resin composition for plating a multilayer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition
• Patterning using the active energy ray curable resin composition of the present invention can be carried out, for example, as follows.
• the curable resin composition of the present invention is applied to a substrate in a thickness of 0.1 to 200 ⁇ m by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, or spin coating, and the coating is dried at a temperature of usually 50 to 110° C., preferably 60 to 100° C., to form a coating film.
• the coating film is directly or indirectly irradiated with high energy rays such as ultraviolet rays through a photomask on which an exposure pattern has been formed, usually at an intensity of about 10 to 2000 mJ/cm 2 , and a desired pattern can be obtained using a developing solution described later, for example, by spraying, vibration immersion, paddle, brushing, or the like.
• high energy rays such as ultraviolet rays
• a photomask on which an exposure pattern has been formed usually at an intensity of about 10 to 2000 mJ/cm 2
• a desired pattern can be obtained using a developing solution described later, for example, by spraying, vibration immersion, paddle, brushing, or the like.
• Synthesis Example 1 Synthesis of reactive epoxy carboxylate compound (c) 218 g of cresol novolac epoxy resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., softening point 92°C, epoxy equivalent 218 g/eq.) and 72.0 g of acrylic acid (AA) as carboxylic acid compound (b) were added. 1.25 g of triphenylphosphine as catalyst and propylene glycol monomethyl ether monoacetate as solvent were added so that the solid content was 70 mass%, and the mixture was reacted at 100°C for 24 hours to obtain a reactive epoxy carboxylate compound (c) solution.

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• 2025
  • 2025-01-10 TW TW114101091A patent/TW202528410A/zh unknown
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