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
  • C08F290/02—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 end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/064—Polymers containing more than one epoxy group per molecule
• • 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
  • C08F290/02—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 end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • 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
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

• the present invention relates to a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, a polymerizable unsaturated group-containing alkali-soluble resin, a photosensitive resin composition containing the same as an essential component, and a cured film obtained by curing the composition.
• the photosensitive resin composition containing the specific polymerizable unsaturated group-containing alkali-soluble resin of the present invention and its cured product are a solder resist layer, a plated resist layer, a resist layer such as an etching resist layer, and layers such as a multilayer printed wiring board.
• a film for a gas barrier a sealing material for semiconductor light emitting elements such as lenses and light emitting diodes (LEDs), a top coat for paints and inks, a hard coat for plastics, and a rust preventive film for metals.
• the electronic components used there are required to be smaller and higher in density. Further, in terms of workability of the insulating materials used for them, miniaturization and optimization of the cross-sectional shape of the processed pattern are required.
• a method of patterning by exposure and development is known as an effective means for microfabrication of an insulating material, and a photosensitive resin composition has been used there. Many properties such as heat resistance and chemical resistance are required.
• various studies have been conducted on the use of an organic insulating material in a gate insulating film for an organic TFT, but it is necessary to reduce the operating voltage of the organic TFT by thinning the gate insulating film, and the withstand voltage is generally high. For organic insulating materials of about 1 MV / cm, the application of a thin film of about 0.2 ⁇ m is being studied.
• the conventional insulating material made of a photosensitive resin composition utilizes a photocuring reaction by a reaction between a photoreactive alkali-soluble resin and a photopolymerization initiator, and is mainly used as an exposure wavelength for photocuring.
• the i-line (365 nm), which is one of the line spectra of the above, is used.
• this i-ray is absorbed by the photosensitive resin itself or the colorant, and the degree of photocurability is lowered.
• the amount of absorption increases.
• a photosensitive resin composition in such an application contains a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photopolymerization initiator and the like.
• the photosensitive resin composition disclosed in the art as an application as a material for a color filter can be applied.
• Patent Document 1 and Patent Document 2 disclose a copolymer containing a predetermined unsaturated organic acid ester and an unsaturated organic acid as constituents as a binder resin.
• Patent Document 3 discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule is effective for forming a negative pattern such as a color filter. ..
• Patent Document 4 Patent Document 5
• Patent Document 6 and Patent Document 7 disclose a liquid resin using a reaction product of an epoxy (meth) acrylate having a bisphenol fluorene structure and an acid anhydride.
• the copolymer disclosed in Patent Document 1 and Patent Document 2 is a random copolymer, the alkali dissolution rate is distributed in the light-irradiated portion and the light-non-irradiated portion, and the development operation is performed.
• the time margin is narrow, and it is difficult to obtain sharp-angled pattern shapes and fine patterns.
• the exposure sensitivity is significantly lowered, and a fine negative pattern cannot be obtained.
• the alkali-soluble unsaturated compound described in Patent Document 3 is insolubilized by light irradiation, it is expected that the sensitivity will be higher than that of the above-mentioned combination of the binder resin and the polyfunctional polymerizable monomer.
• the compound exemplified here is obtained by arbitrarily adding acrylic acid, which is a polymerizable unsaturated group, and an acid anhydride to the hydroxyl group of the phenol oligomer, and even in the case of such a proposal, each molecule Since the molecular weight and the amount of the carboxyl group can be widely distributed, the distribution of the alkali dissolution rate of the alkali-soluble resin becomes wide, and it is difficult to form a fine negative pattern.
• Patent Document 4 the resins exemplified in Patent Document 4, Patent Document 5, Patent Document 6 and Patent Document 7 have a small molecular weight because they are reaction products of epoxy (meth) acrylate and acid anhydride. Therefore, it is difficult to increase the difference in alkali solubility between the exposed portion and the unexposed portion, and it is not possible to form a fine pattern.
• a photolithography method using various photosensitive resin compositions is used as a microfabrication method for an insulating material, but the insulating film formed after the pattern can be miniaturized and the shape can be optimized.
• many properties such as adhesion to a substrate, reliability, heat resistance, and chemical resistance are required.
• it may be necessary to have resistance to breakage, and to provide a material having excellent chemical resistance required in an electrode processing process after forming an insulating film. Is becoming necessary.
• the present invention is capable of patterning with excellent resolution by alkaline development, and also has excellent chemical resistance when it is necessary to go through a processing process such as electrode formation after forming an insulating film in a touch panel manufacturing process or the like. It is an object of the present invention to provide a photosensitive resin composition which is an excellent photosensitive resin composition and can be applied to an insulating film or the like which is also excellent in reliability such as bending resistance. Other purposes are a method for producing a polymerizable unsaturated group-containing alkali-soluble resin used in this photosensitive resin composition, a polymerizable unsaturated group-containing alkali-soluble resin produced by this production method, and this photosensitive resin. It is an object of the present invention to provide a cured film obtained by curing a composition.
• the present inventors have found that it is effective to use a photosensitive resin composition using a polymerizable unsaturated group-containing alkali-soluble resin having a specific alicyclic structure in order to solve the above problems. Completed the invention.
• the present invention relates to an epoxy (meth) acrylate resin represented by the following general formula (1) with respect to (a) a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid thereof.
• the present invention relates to a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, which comprises reacting an anhydride.
• R 1 independently represents an alkyl group, a phenyl group or an allyl group having 1 to 8 carbon atoms.
• R 2 is independently a hydrogen atom, a dicyclopentenyl group, one or more is a dicyclopentenyl group.
• R 3 represents a hydrogen atom or a methyl group.
• another embodiment of the present invention is a polymerizable unsaturated group-containing alkali-soluble resin obtained by the above-mentioned production method, which has a structure represented by the general formula (2) and is soluble in a polymerizable unsaturated group-containing alkali.
• resin has a structure represented by the general formula (2) and is soluble in a polymerizable unsaturated group-containing alkali.
• X indicates a tetravalent carboxylic acid residue
• Y represents a carboxyl group-containing group or a hydrogen atom represented by the above formula (3)
• Z indicates the structure represented by the above formula (2a).
• m is a number having an average value of 1 to 20.
• R 1 represents an alkyl group, a phenyl group or an allyl group having 1 to 8 carbon atoms.
• R 2 is independently a hydrogen atom, a dicyclopentenyl group, one or more is a dicyclopentenyl group.
• R 3 represents a hydrogen atom or a methyl group.
• M indicates a p + 1 valent carboxylic acid residue, and p is 1 or 2.
• the present invention relates to a photosensitive resin composition
• a photosensitive resin composition comprising (C) a photopolymerization initiator and (D) a solvent as essential components.
• Another embodiment of the present invention relates to a cured product obtained by curing the above-mentioned photosensitive resin composition.
• the photosensitive resin composition using the polymerizable unsaturated group-containing alkali-soluble resin having a specific alicyclic structure of the present invention can be patterned by alkaline development, and the cured product has a low elastic modulus and excellent bending characteristics.
• a processing process such as electrode formation after forming an insulating film in a touch panel manufacturing process or the like, a cured product pattern having excellent chemical resistance can be obtained.
• the present invention relates to a method for producing a polymerizable unsaturated group-containing alkali-soluble resin by reacting the acid dianhydride, and a polymerizable unsaturated group-containing alkali-soluble resin produced by the method.
• R 1 independently represents an alkyl group, a phenyl group or an allyl group having 1 to 8 carbon atoms.
• the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group or a hexyl. Examples include, but are not limited to, a group, a cyclohexyl group, a methylcyclohexyl group, and the like. Among these substituents, a phenyl group and a methyl group are preferable, and a methyl group is particularly preferable, from the viewpoint of easy availability and reactivity when prepared as a cured product.
• R 2 is independently a hydrogen atom, a dicyclopentenyl group, one or more is a dicyclopentenyl group.
• the dicyclopentenyl group is a group derived from dicyclopentadiene and is represented by the following formula (1 réelle) or formula (1b).
• the raw material of the epoxy (meth) acrylate resin is obtained by the reaction of a dicyclopentadiene type epoxy resin with (meth) acrylic acid (acrylic acid, methacrylic acid or both).
• This epoxy resin can be obtained by reacting a diphenol compound represented by the following general formula (4) with epichlorohydrin such as epichlorohydrin to epoxidize it.
• This diphenol compound can be obtained by reacting a 2,6-di-substituted phenol compound with dicyclopentadiene in the presence of a catalyst such as boron trifluoride / ether complex.
• R 1 and R 2 are synonymous with the definitions in the above general formula (1), respectively.
• the dicyclopentadiene is preferably 0.28 to 2.0 mol, more preferably 0.28 to 1.0 mol, and even more preferably 0.28 to 2.0 mol of dicyclopentadiene with respect to 1 mol of the 2,6-disubstituted phenol compound. It can be obtained by adding 0.3 to 0.5 mol and reacting in the presence of a catalyst.
• Examples of the 2,6-di-substituted phenol compound include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, and 2,6-di (n-butyl).
• Phenol, 2,6-di (t-butyl) phenol, 2,6-dihexylphenol, 2,6-dicyclohexylphenol, 2,6-diphenylphenol and the like which are easily available and cured. From the viewpoint of reactivity at the time, 2,6-dimethylphenol is preferable.
• the acid catalyst used when reacting the 2,6-di-substituted phenol compound with dicyclopentadiene is Lewis acid, specifically, boron trifluoride, boron trifluoride / phenol complex, and boron trifluoride.
• -Boron trifluoride compounds such as ether complexes, metal chlorides such as aluminum chloride, tin chloride, zinc chloride, titanium tetrachloride and iron chloride, and organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid and propanesulfonic acid.
• boron trifluoride / ether complex is preferable because of its ease of handling.
• the amount of the acid catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of dicyclopentadiene.
• reaction method a method in which a 2,6-di-substituted phenol compound and a catalyst are charged in a reactor and dicyclopentadiene is added dropwise over 1 to 10 hours is preferable.
• the reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 180 ° C, still more preferably 120 to 160 ° C.
• the reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, still more preferably 4 to 8 hours.
• an alkali such as sodium hydroxide or potassium hydroxide is added to inactivate the catalyst, and then the unreacted 2,6-di-substituted phenol compound is recovered under reduced pressure.
• a solvent such as toluene, xylene, methyl ethyl ketone, or methyl isobutyl ketone is added to dissolve the reaction product, washed with water, and then the solvent and the unreacted raw material are recovered under reduced pressure.
• a diphenol compound can be obtained.
• a solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether may be used as necessary for adjusting the viscosity.
• Mass spectrometry and FT-IR measurement can be used as a method for confirming that the dicyclopentenyl group has been introduced into the diphenol compound.
• an electrospray mass spectrometry method ESI-MS
• FD-MS field decomposition method
• the dicyclopentenyl group has been introduced by subjecting a sample obtained by separating components having different numbers of nuclei by mass spectrometry to GPC or the like.
• a sample dissolved in an organic solvent such as tetrahydrofuran is applied onto the KRS-5 cell, and the cell with a sample thin film obtained by drying the organic solvent is measured by FT-IR.
• the peak derived from the C—O stretching vibration in the phenol nucleus appears near 1210 cm -1
• the peak derived from the CH stretching vibration of the olefin moiety of the dicyclopentadiene skeleton is 3040 cm only when the dicyclopentadiene group is introduced. Appears near -1.
• the amount of dicyclopentenyl group introduced can be quantified by the ratio (A 3040 / A 1210 ) of the peak (A 1210) in the vicinity. It has been confirmed that the larger the ratio, the better the physical property value, and the preferable ratio (A 3040 / A 1210 ) for satisfying the desired physical property is 0.05 or more, more preferably 0.1 or more.
• a dicyclopentadiene type epoxy resin By reacting the diphenol compound obtained by the above method with epihalohydrin, a dicyclopentadiene type epoxy resin can be obtained. This reaction is carried out according to a conventionally known method.
• an alkali metal hydroxide such as sodium hydroxide is added as a solid or concentrated aqueous solution to a mixture of a diphenol compound and epihalohydrin having an excess molar amount with respect to the hydroxyl group of the diphenol compound, and the reaction temperature is 30 to 120 ° C. It can be obtained by reacting for 0.5 to 10 hours, or by adding a quaternary ammonium salt such as tetraethylammonium chloride to a diphenol compound and an excess amount of epihalohydrin as a catalyst and reacting at a temperature of 50 to 150 ° C. for 1 to 5 hours. It can be obtained by adding an alkali metal hydroxide such as sodium hydroxide to polyhalohydrin ether as a solid or concentrated aqueous solution and reacting at a temperature of 30 to 120 ° C. for 1 to 10 hours.
• the amount of epihalohydrin used is 1 to 10 times the molar amount, preferably 2 to 5 times the molar amount of the hydroxyl group of the diphenol compound, and the amount of the alkali metal hydroxide used is the amount of the diphenol compound. It is in the range of 0.85 to 1.1 times the molar amount with respect to the hydroxyl group.
• the target epoxy resin can be obtained by removing it by a method such as filtration.
• the epoxy resin thus obtained is a dicyclopentadiene type epoxy resin and is represented by the following general formula (5).
• R 1 and R 2 are synonymous with the definitions in the above general formula (1), respectively.
• n is the number of repetitions, and represents a number from 0 to 5 on average.
• the epoxy equivalent (g / eq.) Of the epoxy resin is preferably 244 to 3700, more preferably 260 to 2000, more than 270, and even more preferably less than 700.
• the molecular weight distribution of the obtained epoxy resin can be changed by changing the charging ratio of the diphenol compound and epihalohydrin in the epoxidation reaction, and the amount of epihalohydrin used can be brought closer to the equimolar mass with respect to the hydroxyl group of the diphenol compound.
• n is an average value in the range of 0 to 5, preferably in the range of 0 to 2, more preferably in the range of 0 to 1, and in the range of 0 to 0.5. It is particularly preferable to have. Within this range, it becomes easy to suppress an excessive increase in molecular weight due to the addition of acid dianhydride.
• the epoxy resin is reacted with (meth) acrylic acid to obtain an epoxy (meth) acrylate resin having a polymerizable unsaturated group.
• the epoxy resin and (meth) acrylic acid can be reacted by a known method. For example, an equimolar (meth) acrylic acid is used for 1 mol of the epoxy group of the above epoxy resin, but since the (meth) acrylic acid is reacted with all the epoxy groups, the equimolar of the epoxy group and the calciuml group is used. You may also use a slight excess of (meth) acrylic acid.
• an epoxy (meth) acrylate resin in which the glycidyl group is replaced with the group represented by the following formula (6) in the general formula (5) is obtained.
• R 3 has the same meaning as the definition in the above general formula (1).
• the solvent and catalyst used in this reaction and other reaction conditions are not particularly limited.
• the solvent it is preferable to use a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature.
• solvents include cellosolvent solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, and high boiling ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate.
• ketone solvents such as cyclohexanone and diisobutyl ketone.
• the catalysts include ammonium salts containing tetraethylammonium bromide, triethylbenzylammonium chloride and the like, and known catalysts such as phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine.
• an epoxy (meth) acrylate resin represented by the general formula (1) can be obtained.
• This epoxy (meth) acrylate resin contains by-products derived from side reactions and by-products derived from by-products contained during the synthesis of raw materials, but these may be purified and removed before use. As long as it does not affect the quality or use of the product, it may be used with some by-products remaining.
• a polymerizable unsaturated group-containing alkali-soluble resin can be obtained by reacting the epoxy (meth) acrylate resin with carboxylic acids.
• carboxylic acids As the carboxylic acids, (a) dicarboxylic acids or tricarboxylic acids and (b) tetracarboxylic acids are used.
• the dicarboxylic acid or tricarboxylic acid may be a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, but an acid anhydride is suitable in terms of reactivity.
• the tetracarboxylic acids may be tetracarboxylic acids or acid dianhydrides thereof, but acid dianhydrides are suitable in terms of reactivity.
• Examples of (a) dicarboxylic acid, tricarboxylic acid or acid anhydrides thereof include saturated chain hydrocarbon dicarboxylic acid or tricarboxylic acid or acid anhydrides thereof, saturated ring hydrocarbon dicarboxylic acid or tricarboxylic acid or these. Includes acid anhydrides, unsaturated hydrocarbon dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof.
• the hydrocarbon residues (structure excluding the carboxyl group) of these dicarboxylic acids or tricarboxylic acids or their acid anhydrides are further substituted with substituents such as alkyl groups, cycloalkyl groups and aromatic groups. May be.
• saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citraalinic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimeric acid, sebacic acid. , Sveric acid, diglycolic acid and the like.
• saturated cyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornandicarboxylic acid, hexahydrotrimellitic acid and the like.
• unsaturated hydrocarbon dicarboxylic acids or tricarboxylic acids include maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid and the like.
• aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include phthalic acids, trimellitic acids and the like.
• Acid anhydrides of these dicarboxylic acids or tricarboxylic acids can also be used.
• succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid or their anhydrides are preferable, and succinic acid, itaconic acid and tetrahydrophthalic acid or their acid anhydrides are preferable. Is more preferable.
• Examples of the above (b) tetracarboxylic acid or its acid dianhydride include chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, and aromatic polyvalent.
• a carboxylic acid or an acid dianhydride thereof and the like are included. Even if each hydrocarbon residue (structure excluding the carboxyl group) of these tetracarboxylic acids or their acid dianhydrides is further substituted with a substituent such as an alkyl group, a cycloalkyl group or an aromatic group. good.
• tetracarboxylic acid examples include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid and the like as examples of the chain hydrocarbon tetracarboxylic acid.
• alicyclic tetracarboxylic acid examples include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid and the like.
• aromatic polyvalent carboxylic acids examples include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid and the like. Acid dianhydrides of these tetracarboxylic acid compounds can also be used.
• the molar ratio (a) / (b) with the carboxyl group of the substance (acid anhydride group is calculated as 2 mol of carboxyl group) is preferably 0.01 to 0.5, more preferably 0.02 to 0.3. It is preferable, and more preferably 0.03 or more and less than 0.1.
• each component (c): (a): (b) 1: 0.2 to 1.0: 0.01 to 1.0, preferably 1: 0.2 to 0.4: 0.4 to It is desirable to react quantitatively so as to be 0.8. In this case, the reaction may be carried out quantitatively so that the molar ratio (c) / [(a) / 2+ (b)] of the total amount of the acid component to the epoxy (meth) acrylate resin is 0.5 to 1.0. desirable.
• the carboxyl group (acid anhydride group is 2 mol) of the carboxylic acid component [(a) + (b)] with respect to 1 mol of the hydroxyl group of the epoxy (meth) acrylate resin (c).
• the reaction is carried out quantitatively so that the total amount of the carboxyl group (calculated) is 0.1 to 1.0 mol, preferably 0.5 to 1.0 mol.
• reaction with (a) a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof can be carried out with a catalyst such as triethylamine, tetraethylammonium bromide and triphenylphosphine. In the presence, it can be heated at 90-130 ° C. and stirred to react.
• a catalyst such as triethylamine, tetraethylammonium bromide and triphenylphosphine.
• the polymerizable unsaturated group-containing alkali-soluble resin produced by the above-mentioned production method preferably has an acid value of 30 to 200 mgKOH / g, and more preferably 50 to 150 mgKOH / g. If the oxidation is less than 30 mgKOH / g, a residue is likely to remain during alkaline development, and if it exceeds 200 mgKOH / g, the penetration of the alkaline developer becomes too fast and peeling development may occur.
• the polymerizable unsaturated group-containing alkali-soluble resin produced by the above-mentioned production method preferably has a hydrolyzable halogen content of 0.2% by mass or less.
• a hydrolyzable halogen content 0.2% by mass or less, the curing reaction is less likely to be hindered by the hydrolyzable halogen, and the physical properties of the cured product, particularly the insulation reliability, are less likely to deteriorate. Preferred for use.
• the hydrolyzable halogen content is preferably 0.1% by mass or less, more preferably 0.05% by mass or less.
• the epoxy (meth) acrylate resin represented by the general formula (1) is obtained, and further represented by the general formula (2).
• a polymerizable unsaturated group-containing alkaline availability resin having a structure is produced.
• the polymerizable unsaturated group-containing alkaline availability resin of the present invention includes not only the resin having the structure represented by the general formula (2) but also the resin having a different degree of polymerization generated at each stage of the above-mentioned production method or a resin derived from the resin. It can also be a contained resin.
• m is a number of 1 to 20, but the average value is preferably in the range of 1.5 to 10 and more preferably in the range of 2 to 5.
• the polymerizable unsaturated group-containing alkaline availability resin is represented by the following formula (7).
• R 3 has the same meaning as the definition in the above general formula (1).
• X and Z are synonymous with the definitions in the above general formula (2), respectively.
• n has the same meaning as the definition in the above general formula (5).
• L 1 and L 2 are independently hydrogen atoms, either of the above formulas (7a) or (3), but not all of them are hydrogen atoms. Equation (3) is the same as that in the above equation (2).
• L 3 binds as L 1 or L 2 of another molecule.
• the photosensitive resin composition of the present invention contains the following components (A) to (D).
• Examples of the photopolymerizable monomer having at least two polymerizable unsaturated groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol.
• vinyl benzyl ether compounds of polyvalent phenols such as phenol novolac
• addition polymers of divinyl compounds such as divinylbenzene.
• photopolymerizable monomer having three or more polymerizable unsaturated groups When it is necessary to form a crosslinked structure between molecules of a polymerizable unsaturated group-containing alkali-soluble resin, it is more preferable to use a photopolymerizable monomer having three or more polymerizable unsaturated groups. These photopolymerizable monomers may be used alone or in combination of two or more. (B) The photopolymerizable monomer having at least two polymerizable unsaturated groups does not have a free carboxy group.
• the blending ratio of the component (B) is preferably 5 to 400 parts by mass, preferably 10 to 150 parts by mass with respect to 100 parts by mass of the component (A). If the blending ratio of the component (B) is more than 400 parts by mass with respect to 100 parts by mass of the component (A), the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed part. There is a problem that the solubility in an alkaline developer is lowered and the pattern edge is not sharpened.
• the compounding ratio of the component (B) is less than 5 parts by mass with respect to 100 parts by mass of the component (A)
• the ratio of the photoreactive functional group in the resin is small and the formation of the crosslinked structure is not sufficient, and further. Since the acid value of the resin component is high, the solubility in the alkaline developer in the exposed area is high, so that the formed pattern becomes thinner than the target line width, and the pattern is likely to be missing. Problems may occur.
• Examples of the photopolymerization initiator (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone and the like.
• Acetphenones including, benzophenone, 2-chlorobenzophenone, and benzophenones including p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin ethers including benzoin isobutyl ether and the like, 2- (o-Chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5 -Biimidazole compounds including diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, etc., 2-trichloromethyl-5-styryl -1,3,4-oxadiazole
• Photopolymerization initiators include organic peroxides including oxides and the like, thiol compounds including 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and the like. These photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator referred to in the present invention is used in the sense of including a sensitizer.
• (C) a compound that does not act as a photopolymerization initiator or a sensitizer by itself as a photopolymerization initiator, but can increase the ability of the photopolymerization initiator or sensitizer when used in combination.
• Examples of such compounds include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.
• the blending ratio of the component (C) is preferably 0.1 to 30 parts by mass, preferably 1 to 25 parts by mass, based on a total of 100 parts by mass of the components (A) and (B). good.
• the compounding ratio of the component (C) is less than 0.1 parts by mass, the photopolymerization rate becomes slow and the sensitivity decreases, while when it exceeds 30 parts by mass, the sensitivity is too strong.
• the pattern line width becomes thicker than the pattern mask, and there may be a problem that the line width faithful to the mask cannot be reproduced or the pattern edge is not sharpened.
• Examples of the solvent (D) include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol.
• Alcohols including ⁇ - or ⁇ -terpineol and the like, ketones including acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone and the like, toluene, xylene, tetramethylbenzene and the like.
• Ethers ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate , Esters containing propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like are included. These solvents may be used alone or in combination of two or more in order to satisfy characteristics such as coatability.
• the above-mentioned photosensitive resin composition may be provided with a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, a coupling agent, a surfactant, and a coloring agent, if necessary.
• Additives such as agents can be added.
• the curing accelerator for example, known compounds known as curing accelerators, curing catalysts, latent curing agents and the like usually applied to epoxy resins can be used, and tertiary amines, quaternary ammonium salts, tertiary phosphines, and quaternary compounds can be used.
• Class phosphonium salts, borate esters, Lewis acids, organic metal compounds, imidazoles, diazabicyclo-based compounds and the like are included.
• thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, hindered phenolic compounds, phosphorus-based heat stabilizers and the like.
• plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like.
• fillers include glass fiber, silica, mica, alumina and the like.
• leveling agents and defoaming agents include silicone-based, fluorine-based, and acrylic-based compounds.
• coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane.
• 3-Aminopropyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-ureidopropyltriethoxysilane and other silane coupling agents and the like are included.
• the surfactant include a fluorine-based surfactant, a silicone-based surfactant and the like.
• colorant known pigments, dyes and the like can be used without limitation.
• an epoxy resin having two or more epoxy groups can be used in addition to (A) to (D).
• epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin.
• These components are preferably compounds having an epoxy equivalent of 100 to 300 g / eq and a number average molecular weight of 100 to 5000.
• the component (E) only one kind of compound may be used, or two or more kinds may be used in combination.
• a compound having at least two epoxy groups is preferable.
• the amount added is preferably 10 to 40 parts by mass with respect to 100 parts by mass in total of the components (A) and (B).
• one purpose of adding the epoxy resin is to reduce the amount of carboxyl groups remaining when the cured film is formed after patterning in order to improve the reliability of the cured film.
• the amount of the epoxy resin added is less than 10 parts by mass, the moisture resistance reliability when used as an insulating film, for example, may not be ensured.
• the compounding amount of the epoxy resin is more than 40 parts by mass, the amount of the photosensitive group in the resin component in the photosensitive resin composition may decrease, and the sensitivity for patterning may not be sufficiently obtained. ..
• the photosensitive resin composition contains the components (A) to (D) or the components (A) to (E) as main components. It is desirable that the solid content contains 70% by mass, preferably 80% by mass or more of the components (A) to (C) and (E) in total.
• the amount of the solvent (D) varies depending on the target viscosity, but it is preferably contained in the photosensitive resin composition in the range of 60 to 90% by mass.
• the photosensitive resin composition is, for example, applied to a substrate or the like, dried, irradiated (exposed) with light (including ultraviolet rays, radiation, etc.), and cured to obtain a cured product (coating film).
• light including ultraviolet rays, radiation, etc.
• a photomask or the like is used to provide a portion exposed to light and a portion not exposed to light, only the portion exposed to light is cured, and the other portion is dissolved with an alkaline solution, a cured product having a desired pattern can be obtained. (Coating film) is obtained.
• any of known methods such as a solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coat machine, and a spinner machine are used. Can also be adopted.
• a film is formed by applying the photosensitive resin composition to a desired thickness and then removing the solvent (pre-baking).
• Pre-baking is performed by heating with an oven, a hot plate, etc., vacuum drying, and a combination thereof.
• the heating temperature and heating time in the prebake are appropriately selected depending on the solvent used, and are performed at a temperature of, for example, 80 to 120 ° C. for 1 to 10 minutes.
• Examples of radiation used for exposure include visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc., but radiation having a wavelength in the range of 250 to 450 nm is preferable.
• Alkaline development can be performed using, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like as a developing solution. These developers are selected according to the characteristics of the resin layer, but a surfactant may be added if necessary. Development is preferably carried out at a temperature of 20 to 35 ° C. By using a commercially available developing machine, ultrasonic cleaner, or the like, a fine image can be formed precisely. After alkaline development, it is usually washed with water. Examples of the developing method include a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (filling) developing method, and the like.
• post-baking After developing in this way, heat treatment (post-baking) is performed under the conditions of a temperature of 180 to 250 ° C. and 20 to 100 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned coating film and the substrate. Post-baking is performed by heating with an oven, a hot plate, or the like, similarly to pre-baking.
• the curing temperature at this time is preferably in the range of 160 to 250 ° C.
• the cured product is used for a solder resist layer, a plated resist layer, a resist layer such as an etching resist layer, an interlayer insulating layer such as a multilayer printed wiring board, a film for a gas barrier, a lens, and a semiconductor light emitting element such as a light emitting diode (LED). It can also be used as a sealing material, a top coat for paints and inks, a hard coat for plastics, a rust preventive film for metals, and the like.
• Solid content concentration 100 ⁇ (W2-W0) / (W1-W0)
• the resin solution is dissolved in dioxane and titrated with a 0.1N-KOH aqueous solution using a potentiometric titrator (COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.) to determine the amount of KOH required per 1 g of solid content.
• the acid value was used.
• IR A Fourier transform infrared spectrophotometer (manufactured by PerkinElmer Precision, Spectrum One FT-IR Spectrometer 1760X) was used, KRS-5 was used for the cell, and a sample dissolved in THF was applied onto the cell and dried. After that, the absorbance with a wave number of 650 to 4000 cm -1 was measured.
• Mass spectrometry was performed by using a mass spectrometer (LCMS-2020, manufactured by Shimadzu Corporation), using acetonitrile and water as mobile phases, and measuring a sample dissolved in acetonitrile.
• Synthesis example 1 970 parts of 2,6-xylenol and 14.5 parts of 47% BF 3 ether complex are charged in a reaction device consisting of a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a cooling tube. The mixture was heated to 70 ° C. with stirring. While maintaining the same temperature, 300 parts of dicyclopentadiene (0.29 times mol with respect to 2,6-xylenol) was added dropwise over 2 hours. Further, the reaction was carried out at a temperature of 125 to 135 ° C. for 6 hours, and 2.3 parts of calcium hydroxide was added.
• the hydroxyl group equivalent was 213, the softening point was 71 ° C., and the absorption ratio (A 3040 / A 1210 ) measured by FT-IR was 0.11.
• M- 253, 375, 507, 629 was confirmed.
• the absorption ratio and ESI-MS measurement of FT-IR measurement it is possible to confirm the introduction of a dicyclopentenyl group as R 2 in at least the general formula (4).
• DPXLEA Epoxy acrylate resin obtained in Synthesis Example 1
• BPAEA Epoxy equivalent of bisphenol A type epoxy resin (epoxy equivalent 182) and acrylic acid (equal equivalent reaction of epoxy group and carboxyl group)
• BPDA 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride
• THPA 1,2,3,6-tetrahydrophthalic acid anhydride
• TEAB tetraethylammonium bromide MIBK: methyl isobutyl ketone
• PGMEA propylene glycol monomethyl Ether acetate
• Example 1 450 parts of DPXLEA 50% PGMEA solution, 49 parts of BPDA, 25 parts of THPA, 0.69 parts of TEAB, PGMEA in a reaction vessel equipped with a stirrer, temperature controller, reflux condenser, and air introduction device.
• a stirrer 450 parts of DPXLEA 50% PGMEA solution, 49 parts of BPDA, 25 parts of THPA, 0.69 parts of TEAB, PGMEA in a reaction vessel equipped with a stirrer, temperature controller, reflux condenser, and air introduction device.
• the solid content concentration of the obtained resin was 55%
• the acid value in terms of solid content
• Mw molecular weight
• A1 Alkali-soluble resin obtained in Example 1 above HA1: Alkaline-soluble resin obtained in Comparative Example 1 HA2: 68.9% PGMEA solution of cresol novolac type acid-modified epoxy acrylate resin (CCR-1172, Japan) Made by Yaku Co., Ltd.)
• B Dipentaerythritol hexaacrylate
• C1 Irgacure 184 (manufactured by BASF)
• C2 4,4'-bis (dimethylamino) benzophenone (Michler ketone)
• D Propylene glycol monomethyl ether acetate
• E Cresol novolac type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., YDCN-700-3, epoxy equivalent 203 g / eq., Softening point 73 ° C.)
• the photosensitive resin composition shown in Table 1 is applied onto a glass substrate of 125 mm ⁇ 125 mm using a spin coater so that the film thickness after post-baking is 30 ⁇ m, and prebaked at 110 ° C. for 5 minutes to coat the coating plate. It was created. Then, ultraviolet rays having a wavelength of 365 nm were irradiated with a high-pressure mercury lamp of 500 W / cm 2 through a photomask for pattern formation, and a photocuring reaction of the exposed portion was carried out. Next, this exposed coating film was developed with a 0.8% aqueous solution of tetramethylammonium hydroxide (TMAH) in a shower at 23 ° C.
• TMAH tetramethylammonium hydroxide
• a glass substrate with a cured film is immersed in a solution maintained at 80 ° C. of a mixed solution of 30 parts by mass of 2-aminoethanol and 70 parts by mass of glycol ether, pulled up after 10 minutes, washed with pure water, dried, and immersed in chemicals. The sample was prepared and the adhesion was evaluated.
• the photosensitive resin composition shown in Table 1 was applied to a glass substrate to which a 125 mm ⁇ 125 mm release film was attached using a spin coater so that the film thickness after post-baking was 30 ⁇ m, and the film thickness was 110 ° C. for 5 minutes.
• a coating plate was prepared by prebaking. Then, ultraviolet rays having a wavelength of 365 nm were irradiated with a high-pressure mercury lamp of 500 W / cm 2 through a photomask for pattern formation, and a photocuring reaction of the exposed portion was carried out. Next, this exposed coating film was developed with a 0.8% aqueous solution of tetramethylammonium hydroxide (TMAH) in a shower at 23 ° C.
• TMAH tetramethylammonium hydroxide
• Example 2 From the results of Example 2 and Comparative Examples 2 to 3, when the photosensitive resin composition containing the polymerizable unsaturated group-containing alkali-soluble resin of the present invention is used, patterning with excellent resolution by alkaline development is possible, and the patterning resistance is high. It can be seen that a cured film having excellent chemical properties and excellent reliability such as resistance to folds can be produced.

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