WO2009119623A1 - Photosensitive resin and photosensitive resin composition comprising the same - Google Patents
Photosensitive resin and photosensitive resin composition comprising the same Download PDFInfo
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- WO2009119623A1 WO2009119623A1 PCT/JP2009/055878 JP2009055878W WO2009119623A1 WO 2009119623 A1 WO2009119623 A1 WO 2009119623A1 JP 2009055878 W JP2009055878 W JP 2009055878W WO 2009119623 A1 WO2009119623 A1 WO 2009119623A1
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- WIPO (PCT)
- Prior art keywords
- photosensitive resin
- general formula
- compound
- group
- carboxylic acid
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- NZNDDHPULQNYEA-UHFFFAOYSA-N O=C(CC1C(CCC(O2)=O)C2=O)OC1=O Chemical compound O=C(CC1C(CCC(O2)=O)C2=O)OC1=O NZNDDHPULQNYEA-UHFFFAOYSA-N 0.000 description 2
Classifications
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- 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
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- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
Definitions
- the present invention relates to a photosensitive resin and a photosensitive resin composition using the same, and more specifically, can be easily produced at low cost, has high sensitivity, and is particularly used for negative photolithography.
- the present invention relates to a photosensitive resin and a photosensitive resin composition that exhibit good patterning properties.
- High molecular compounds with radically polymerizable unsaturated bond structure (vinyl group) in the molecule are used in various fields as photosensitive compositions and thermosetting compositions by utilizing the crosslinking reaction by polymerization of vinyl groups. Yes.
- photosensitive resins having a bisphenol-type aromatic polyester structure in the main chain are excellent in heat resistance and chemical resistance, so many have been proposed so far, such as liquid crystal color filters, black matrices, It is applied to a photoresist such as a solder resist (Patent Documents 1 to 3).
- An object of the present invention is to provide such a photosensitive resin and a photosensitive resin composition using the same.
- the present inventors have conducted extensive research to solve the above problems, and as a result, the polymer compound obtained by reacting a specific bisphenol with an acid dianhydride has an ethylenically unsaturated group.
- a photosensitive resin obtained by adding a carboxylic acid-reactive compound having a group can be easily produced at low cost, and it is easy to adjust a crosslinking density and an acid value, and has high sensitivity and excellent patternability. As a result, the present invention has been completed.
- the present invention provides a carboxylic acid reactivity having an ethylenically unsaturated group to a polymer compound obtained by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2). It is a photosensitive resin obtained by adding a compound.
- Y is —CO—, —SO 2 —, —C (CF 3 ) 2 —, —Si (CH 3 ) 2 —, —CH 2 —, —C (CH 3 ) 2 —, —O— ,
- R 1 and R 2 independently represent a hydrogen atom or a methyl group, and n and m independently represent a number of 0 to 4.
- X represents a tetravalent carboxylic acid residue.
- the present invention also provides a photosensitive resin composition
- a photosensitive resin composition comprising the above photosensitive resin and a photopolymerization initiator and / or a photosensitizer.
- the photosensitive resin of the present invention is excellent in chemical resistance and heat resistance, has high storage stability, can be easily produced at low cost, has excellent productivity, and is easy to adjust the crosslinking density and acid value. Applicable to a wide range of applications. Moreover, the photosensitive resin composition using this photosensitive resin has high sensitivity and good patternability.
- the polymer compound constituting the photosensitive resin of the present invention is obtained by reacting a compound represented by the following general formula (1) and a compound represented by the following general formula (2).
- Y represents —CO—, —SO 2 —, —C (CF 3 ) 2 —, —Si (CH 3 ) 2 —, —CH 2 —, —C (CH 3 ) 2 —, —O—, A cyclohexyl group, a 9,9-fluorenyl group or a direct bond;
- R 1 and R 2 independently represent a hydrogen atom or a methyl group; and n and m independently represent a number of 0 to 4.
- compound (1) Specific examples of the compound represented by the general formula (1) (hereinafter sometimes referred to as “compound (1)”) include bisphenol A, ethoxylated bisphenol A, bisphenol F, ethoxylated bisphenol F, 4, 4'-biphenol, 3,3'-biphenol, ethoxylated 4,4'-biphenol, ethoxylated 3,3'-biphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, ethoxylated 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybenzophenone, ethoxylated 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfone, ethoxylated bis (4-hydroxyphenyl) sulfone, 2,2- Bis (4-hydroxyphenyl) hexafluoropropane, Etoxy 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4
- Y in the general formula (1) is a 9,9-fluorenyl group
- Y in the general formula (1) is a 9,9-fluorenyl group
- 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] Fluorene is preferred, and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is most preferred.
- the method for synthesizing the ethoxylated compound is not particularly limited. Even if the compound is synthesized by adding ethylene oxide to a phenolic compound, phenoxyethanol is added to the corresponding ketone or carboxylic acid by Friedel. -Although it may be added by a Crafts reaction, a method of adding phenoxyethanol is preferable because the chain length of ethylene glycol is not distributed and the physical properties can be easily designed.
- compound (2) a compound represented by the following general formula (2) (hereinafter sometimes referred to as “compound (2)”) is used.
- compound (2) a compound represented by the following general formula (2) (hereinafter sometimes referred to as “compound (2)”) is used.
- X represents a tetravalent carboxylic acid residue.
- Compound (2) is an acid dianhydride, specifically, butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclohexane Pentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, cycloheptanetetracarboxylic dianhydride, norbornanetetracarboxylic dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyl Tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride,
- the above compound (1) is subjected to an addition reaction with the compound (2) to obtain a polymer compound constituting the photosensitive resin of the present invention.
- the ratio of compound (2) to 100 mol parts of compound (1) is preferably in the range of 110 to 200 mol parts, more preferably 120 to 160 mol parts.
- the amount is less than 110 parts by mole, the addition amount of the carboxylic acid-reactive compound having an ethylenically unsaturated group that contributes to the photosensitive performance cannot be increased, and sufficient photosensitive performance may not be obtained.
- the amount exceeds 200 parts by mole synthesis is difficult because the solubility of the raw materials is low, and the molecular weight necessary to form a coating film may not be obtained.
- a catalyst may be used.
- the catalyst to be used is not particularly limited as long as it promotes the reaction. Examples thereof include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N , N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, , 5-diazabicyclo [4,3,0] nonene-5, etc., quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, Fins, trip
- the amount of the catalyst used is not particularly limited, but is preferably in the range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of compound (1). If the amount of the catalyst is more than 2.0 parts by mass, the electrical characteristics and storage stability of the photosensitive resin may be adversely affected.
- a solvent may be used for the purpose of dissolving the reaction raw materials and reducing the viscosity.
- the type of solvent is not particularly limited as long as it does not inhibit the reaction, but examples include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate.
- Glycol ether acetates such as, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol ethers such as propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ete
- Propylene glycol ether acetates such as acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, dimethyl
- Examples include sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.
- the amount of the solvent to be used is not particularly limited, but is preferably in the range of 25 to 150 parts by mass with respect to 100 parts by mass in total of the compound (1) and the compound (2). If it is less than 25 parts by mass, the viscosity may not be sufficiently reduced. On the other hand, when the amount exceeds 150 parts by mass, the reaction concentration may decrease too much and the reaction rate may decrease.
- the above compound (1) and compound (2) are subjected to an addition reaction by adding a solvent or a catalyst as necessary.
- the reaction is preferably heated, and the raw material is dissolved by heating, and the reaction rate is also accelerated.
- the heating temperature can be appropriately set according to the types of the compound (1) and compound (2) and the apparatus used, but is preferably in the range of about 60 to 220 ° C. More preferably, it is in the range of 90 to 160 ° C.
- the reaction temperature is lower than 60 ° C., it may take time to complete the reaction.
- the reaction temperature is higher than 220 ° C., side reactions such as coloring may occur, or the reaction rate may decrease due to an equilibrium in which the acid anhydride is closed.
- the photosensitive resin of the present invention can be obtained by reacting the polymer compound obtained as described above with a carboxylic acid reactive compound having an ethylenically unsaturated group.
- the carboxylic acid-reactive compound having an ethylenically unsaturated group (hereinafter sometimes simply referred to as “carboxylic acid-reactive compound”) has an ethylenically unsaturated group and easily reacts with carboxylic acid. If there is, it can be used without particular limitation, and specific examples include an epoxy compound having an ethylenically unsaturated group, an isocyanate compound, a vinyl ether compound, and a methylol compound.
- epoxy compound examples include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, and a compound represented by the following general formula (4). .
- R 3 represents a hydrogen atom or a methyl group
- R 4 represents a group represented by the following general formula (5)
- r, s, and t each independently represent an integer of 0 to 9. However, r, s, and t are not 0 at the same time.
- Examples of the compound represented by the general formula (4) include 4-hydroxybutyl (meth) acrylate glycidyl ether, polyethylene glycol-polypropylene glycol (meth) acrylate glycidyl ether, and the like.
- isocyanate compounds include 2- (meth) acryloyloxyethyl isocyanate
- vinyl ether compounds include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate as methylol compounds. N-methylol (meth) acrylamide and the like.
- epoxy compounds are preferable, and vinylbenzyl glycidyl ether and 4-hydroxybutyl (meth) acrylate glycidyl ether are particularly preferable.
- Vinyl benzyl glycidyl ether is a compound represented by the following general formula (3), and can improve heat resistance and chemical resistance.
- 4-hydroxybutyl (meth) acrylate glycidyl ether is preferably used because of its high sensitivity.
- Such a carboxylic acid reactive compound is subjected to an addition reaction with the above polymer compound.
- the ratio of the carboxylic acid-reactive compound in the photosensitive resin of the present invention varies depending on the use and cannot be generally specified.
- the acid value of the resin solid content is 30 to 150 mgKOH. It is preferable to adjust so that it exists in the range of / g. If the acid value is lower than 30 KOH / g, the development speed may be reduced and a required pattern may not be obtained. On the other hand, when the acid value is higher than 150 mgKOH / g, the pattern is likely to be peeled off due to excessive development, and the electrical characteristics and the like may be deteriorated.
- the acid value of the resin solid content is a measured value based on JIS-K0070.
- a catalyst may be used for the purpose of promoting the reaction.
- the type of catalyst varies depending on the type of the carboxylic acid reactive compound and cannot be generally specified. Examples of the catalyst include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, and N-ethylmorpholine.
- the amount of the catalyst used is not particularly limited, but is preferably in the range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of compound (1). If the amount of the catalyst is too large, the electrical properties and storage stability of the photosensitive resin may be adversely affected.
- a polymerization inhibitor in reacting the carboxylic acid reactive compound, it is preferable to add a polymerization inhibitor.
- the type of the polymerization inhibitor is not particularly limited as long as it suppresses the unsaturated bond reaction. Examples thereof include hydroquinone, hydroquinone monomethyl ether, t-butyl hydroquinone, t-butyl catechol, N-methyl-N-nitroso.
- N-nitrosophenylhydroxylamine / ammonium salt (Wako Pure Chemical Industries, Ltd .: Q-1300), N-nitrosophenylhydroxylamine / aluminum salt (Wako Pure Chemical Industries, Ltd .: Q-1301), 2, Examples include 2,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl.
- N-nitrosophenylhydroxylamine aluminum salt and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl are preferable.
- the amount of the polymerization inhibitor varies depending on the type and reaction conditions, and cannot be generally stated, but is preferably in the range of 5 to 2000 ppm with respect to the entire photosensitive resin. If it is less than this range, unsaturated bonds may react during production to cause gelation, and if it is more than this range, the sensitivity may be lowered, which is not preferable.
- the heating temperature can be appropriately set depending on the type and apparatus of the carboxylic acid reactive compound, but is preferably in the range of 60 to 150 ° C. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, if the reaction temperature is higher than 150 ° C., side reactions such as coloring may occur, or unsaturated bonds may react to cause gelation.
- the polymer compound obtained by reacting the compound (1) with the compound (2) has an excess of compound (2) with respect to compound (1) when the mixing ratio is as described above. It has a structure of things.
- an epoxy compound having an ethylenically unsaturated group is applied as the carboxylic acid reactive compound, an acid anhydride may react with the —OH group generated by the opening of the epoxy ring, resulting in an increase in molecular weight.
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents a group represented by the following general formula (7).
- l, p and q each independently represent an integer of 0 to 9. However, l, p and q are not 0 simultaneously.
- This reaction may be performed prior to or simultaneously with the addition of the epoxy compound having an ethylenically unsaturated group, but considering the reproducibility of the reaction, the reaction is performed prior to the reaction of the epoxy compound having an ethylenically unsaturated group. Is more preferable.
- compound (6) Specific examples of the compound represented by the general formula (6) (hereinafter sometimes referred to as “compound (6)”) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Examples include 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, etc. Among these, crosslinking reactivity and cost Therefore, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate are preferably used.
- a catalyst may be used when reacting the compound (6) or water.
- the kind of the catalyst is the same as that which can be used at the time of the reaction of the compound (1) and the compound (2).
- the catalyst used in this reaction may be used as it is, or the same one may be added or another Different types of catalysts may be added separately.
- the reaction temperature is preferably in the range of 60 to 150 ° C. If the reaction temperature is too low, it may take time to complete the reaction. If the reaction temperature is too high, side reactions such as coloring may occur, or unsaturated bonds may react to cause gelation.
- the photosensitive resin prepared as described above can be taken out as a solid by spray drying, film drying, dropping into a poor solvent, reprecipitation, etc. for the purpose of purification, storage, solvent change, and the like.
- the molecular weight of the photosensitive resin of the present invention is not particularly limited, but is preferably 1,500 to 100,000, more preferably 2,000 to 20,000. Within this range, a good balance between coating film strength and developability is preferable.
- the molecular weight of the photosensitive resin is a weight average molecular weight in terms of styrene by GPC under the conditions described in the examples.
- the photosensitive resin composition of the present invention contains the photosensitive resin and a photopolymerization initiator and / or a photosensitizer as essential components.
- the photopolymerization initiator and / or photosensitizer may be mixed in a state dissolved or dispersed in a solvent, or chemically bonded to the photosensitive resin.
- the photopolymerization initiator and / or photosensitizer used in the present invention is not particularly limited.
- benzophenone, 4-hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, bis-N Benzophenones such as N, diethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, ethyl anthraquinone, benzanthraquinone Anthraquinones such as aminoanthraquinone, chloroanthraquinone, anthraquinone-2-sulfonate, anthraquinone-2,6-disulfonate, acetophenone
- Accelerators can also be added to the photosensitive resin of the present invention.
- the accelerator include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine and the like.
- a polymerizable monomer having one or more unsaturated groups in the molecule (hereinafter sometimes simply referred to as “polymerizable monomer”) can be used.
- Polymerizable monomer Chemical resistance, heat resistance and mechanical strength can be improved.
- the polymerizable monomer any monomer having at least one unsaturated bond in the molecule can be used without particular limitation, and an appropriate monomer may be selected depending on the intended use and purpose.
- polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups
- trimethylolpropane di (meth) acrylate trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate
- Trimethylolpropane propoxytri (meth) acrylate tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate
- polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups
- dipenta Erythritol penta (meth) acrylate dipentaerythritol hexa (meth) acrylate
- bisphenol A polyoxyethylene di (meth) acrylate bisphenol A dioxyethylene Di (meth) acrylate
- bisphenol A trioxyethylene di (meth) acrylate bisphenol A decaoxyethylene
- a colorant can be added to the photosensitive resin composition of the present invention for the purposes of design, visibility, and prevention of halation of the photoresist.
- the kind of colorant to be added can be appropriately selected depending on the purpose of coloring.
- Anthraquinone pigments, azo pigments, quinacridone pigments, coumarin pigments, triphenylmethane pigments and the like can be exemplified, and one or more of these can be used.
- the photosensitive resin composition of the present invention can be in the form of a solution or a paste, and therefore can contain a solvent.
- the type of solvent used is not particularly limited, but examples include water, ethylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, and diethylene glycol.
- Glycol ethers such as dimethyl ether, glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol, propylene glycol monomethyl ether Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether and other propylene glycol ethers, propylene glycol monomethyl ether acetate , Propylene glycol ether acetates such as propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate
- photosensitive resin composition of the present invention conventionally known components such as a polymerization inhibitor, a plasticizer, an antifoaming agent, and a coupling agent can be further blended as necessary.
- the photosensitive resin composition of the present invention can be obtained by mixing the above essential components and, if necessary, a solvent and other optional components according to a conventional method.
- the photosensitive resin composition of the present invention obtained as described above can be used for photoresist applications such as liquid crystal color filters, black matrices, and solder resists.
- the photosensitive resin composition of the present invention is applied on a substrate as a solution or a paste.
- the coating method is not particularly limited, and screen printing, curtain coating, blade coating, spin coating, spray coating, dip coating, slit coating, and the like are applied.
- the applied solution or paste is exposed with UV or electron beam through a predetermined mask. When apply
- the developing method can be any of a spray method, a paddle method, an immersion method, and the like, but a spray method with few residues is preferable. Ultrasonic waves or the like can be irradiated as necessary.
- weak alkaline water is preferably used as the developer.
- an organic solvent, a surfactant, an antifoaming agent, etc. can be added.
- Example 1 In a 1000 ml flask equipped with a stirrer and a condenser, 67.5 g of pyromellitic dianhydride (Daicel product: PMDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical) 82.5 g (manufactured by BPEF) and 100 g of propylene glycol monomethyl ether acetate were added and heated in an oil bath at 155 ° C. for 4 hours while stirring under a nitrogen stream.
- PMDA pyromellitic dianhydride
- 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene Osaka Gas Chemical
- the obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 420 mPa ⁇ s / 25 ° C., styrene-converted weight average molecular weight by GPC was 5,330, and solid content acid value was 52. 0.0 mg KOH / g.
- mold viscosity meter was used for the viscosity measurement.
- GPC was measured using TSKgel G7000HXL, TSKgel GMHXL, TSKgel G2500HXL manufactured by Tosoh Corporation, and THF eluent at 40 ° C. and a flow rate of 0.5 ml / min.
- the acid value was measured according to the neutralization titration method described in JIS-K0070.
- Example 2 Photosensitivity of a light yellow transparent viscous liquid in the same manner as in Example 1 except that 75.0 g of 4-vinylbenzyl glycidyl ether was replaced with 81.0 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE). Resin (A2) solution was obtained. When this solution was analyzed in the same manner as in Example 1, the viscosity was 330 mPa ⁇ s / 25 ° C., the weight average molecular weight was 4,920 in terms of styrene by GPC, and the acid value was 54.8 mgKOH / g.
- Example 3 In a 1000 ml flask equipped with a stirrer and a condenser tube, 67.5 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product: BPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka) Gas Chemical Co., Ltd. (BPEF) 82.5 g, 4-dimethylaminopyridine 0.9 g, and propylene glycol monomethyl ether acetate 100 g were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream.
- BPDA biphenyltetracarboxylic dianhydride
- BPEF 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene
- Example 4 The reaction was conducted under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzyl glycidyl ether was replaced with 45.0 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE).
- this solution obtained as a liquid photosensitive resin (A4) solution was analyzed in the same manner as in Example 1, the viscosity was 990 mPa ⁇ s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 6,200, and the solid content acid value was 64. 0.5 mg KOH / g.
- Example 5 In a 1000 ml flask equipped with a stirrer and a condenser tube, 75 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product: BPDA), 75 g of ethylene oxide-added bisphenol A (Nippon Emulsifier Co., Ltd .: BA2 glycol), 4-dimethylaminopyridine 0 0.9 g and 100 g of propylene glycol monomethyl ether acetate were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream.
- BPDA biphenyltetracarboxylic dianhydride
- BA2 glycol ethylene oxide-added bisphenol A
- 4-dimethylaminopyridine 0 0.9 g and 100 g of propylene glycol monomethyl ether acetate were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream.
- Example 6 The reaction was conducted under the same conditions as in Example 5 except that 51 g of 4-vinylbenzyl glycidyl ether was replaced with 54 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE). A photosensitive resin (A6) solution was obtained. This solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 1,430 mPa ⁇ s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 14,200, and the solid content acid value was 68.5 mgKOH / g.
- Comparative Example 3 The reaction was carried out under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzyl glycidyl ether was replaced with 18.0 g of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd .: GMA), and a light yellow transparent viscous liquid photosensitive resin was used. (A9) A solution was obtained. The solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 8,100 mPa ⁇ s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 5,200, and the solid content acid value was 86.5 mgKOH / g.
- Comparative Example 4 The reaction was carried out under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzylglycidyl ether was replaced with 21.1 g of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd .: GMA), and a light yellow transparent viscous liquid photosensitive resin was used. (A10) A solution was obtained. This solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 7,800 mPa ⁇ s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 6,500, and the solid content acid value was 75.6 mgKOH / g.
- Test example 1 For the photosensitive resins of Examples 1 to 6 and Comparative Examples 1 and 2, the weight average molecular weight in terms of polystyrene was measured by GPC immediately after production and one month after storage at room temperature, and the rate of change was examined. The results are shown in Table 1.
- the photosensitive resins of Examples 1 to 6 showed almost no change, but the photosensitive resins of Comparative Examples 1 and 2 showed an increase in molecular weight of about 25% and were inferior in storage stability.
- Example 7 Using the photosensitive resin A1 obtained in Example 1, a photosensitive resin composition was prepared with the formulation shown in Table 2 below. This photosensitive resin composition was applied to a 1.1 mm thick soda lime glass substrate with a spin coater to a dry film thickness of 3 ⁇ m, dried on a hot plate at 100 ° C. for 90 seconds, and then cooled to room temperature.
- Examples 8 to 10 and Comparative Examples 5 to 8 A photosensitive resin composition was prepared in the same manner as in Example 7 except that the photosensitive resin A1 was replaced with the photosensitive resins A2 to A10, and the sensitivity and resolution were evaluated. The results are also shown in Table 2.
- the photosensitive compositions using the photosensitive resins of Comparative Examples 1 to 4 were highly sensitive and exhibited good resist characteristics.
- the photosensitive resin of the present invention is excellent in chemical resistance and heat resistance, has high productivity and excellent storage stability, and the photosensitive resin composition using the photosensitive resin has high sensitivity and good patternability. Therefore, it is suitably used for photoresist applications.
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Abstract
Description
攪拌機と冷却管を備えた1000mlのフラスコに、ピロメリット酸二無水物(ダイセル社製品:PMDA)67.5g、9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン(大阪ガスケミカル社製:BPEF)82.5g、プロピレングリコールモノメチルエーテルアセテート100gを入れ、窒素気流下で攪拌しながら155℃のオイルバスで4時間加熱した。続けて、120℃まで冷却した後、4-ジメチルアミノピリジン0.9g、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシル(ADEKA社製品:アデカスタブLA-7RD)0.03g、2-ヒドロキシエチルアクリレート30.0gを加え、120℃で4時間攪拌を続けた。更に4-ビニルベンジルグリシジルエーテル75.0gを加え、120℃で2時間攪拌した。次に室温まで冷却し、不揮発分が50質量%になるようプロピレングリコールモノメチルエーテルアセテートを加えて淡黄色透明粘稠性の感光性樹脂(A1)溶液を得た。 Example 1
In a 1000 ml flask equipped with a stirrer and a condenser, 67.5 g of pyromellitic dianhydride (Daicel product: PMDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical) 82.5 g (manufactured by BPEF) and 100 g of propylene glycol monomethyl ether acetate were added and heated in an oil bath at 155 ° C. for 4 hours while stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 0.9 g of 4-dimethylaminopyridine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (product of ADEKA: ADK STAB LA-7RD) 03 g and 2-hydroxyethyl acrylate 30.0 g were added, and stirring was continued at 120 ° C. for 4 hours. Further, 75.0 g of 4-vinylbenzyl glycidyl ether was added, and the mixture was stirred at 120 ° C. for 2 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous photosensitive resin (A1) solution.
4-ビニルベンジルグリシジルエーテル75.0gを4-ヒドロキシブチルアクリレートグリシジルエーテル(日本化成社製品:4HBAGE)81.0gに代えた以外は実施例1と同様にして、淡黄色透明粘稠性液体の感光性樹脂(A2)溶液を得た。この溶液を実施例1と同様にして分析したところ、粘度330mPa・s/25℃、GPCによるスチレン換算重量平均分子量4,920、固形分酸価54.8mgKOH/gであった。 Example 2
Photosensitivity of a light yellow transparent viscous liquid in the same manner as in Example 1 except that 75.0 g of 4-vinylbenzyl glycidyl ether was replaced with 81.0 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE). Resin (A2) solution was obtained. When this solution was analyzed in the same manner as in Example 1, the viscosity was 330 mPa · s / 25 ° C., the weight average molecular weight was 4,920 in terms of styrene by GPC, and the acid value was 54.8 mgKOH / g.
攪拌機と冷却管を備えた1000mlのフラスコに、ビフェニルテトラカルボン酸二無水物(宇部興産社製品:BPDA)67.5g、9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン(大阪ガスケミカル社製:BPEF)82.5g、4-ジメチルアミノピリジン0.9g、プロピレングリコールモノメチルエーテルアセテート100gを入れ、窒素気流下で攪拌しながら155℃のオイルバスで4時間加熱した。続けて、120℃まで冷却した後、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシル(ADEKA社製品:アデカスタブLA-7RD)0.03g、2-ヒドロキシエチルアクリレート12.0gを加え、120℃で4時間攪拌を続けた。更に4-ビニルベンジルグリシジルエーテル42.0gを加え、120℃で2時間攪拌した。次に室温まで冷却し、不揮発分が50質量%になるようプロピレングリコールモノメチルエーテルアセテートを加えて淡褐色透明粘稠性の感光性樹脂(A3)溶液を得た。この溶液を実施例1と同様にして分析したところ、粘度2860mPa・s/25℃、GPCによるスチレン換算重量平均分子量6,610、固形分酸価65.2mgKOH/gであった。 Example 3
In a 1000 ml flask equipped with a stirrer and a condenser tube, 67.5 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product: BPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka) Gas Chemical Co., Ltd. (BPEF) 82.5 g, 4-dimethylaminopyridine 0.9 g, and propylene glycol monomethyl ether acetate 100 g were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 0.03 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (product of ADEKA: Adeka Stab LA-7RD), 2-hydroxyethyl acrylate 12. 0 g was added and stirring was continued at 120 ° C. for 4 hours. Further, 42.0 g of 4-vinylbenzyl glycidyl ether was added and stirred at 120 ° C. for 2 hours. Next, it was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light brown transparent viscous photosensitive resin (A3) solution. When this solution was analyzed in the same manner as in Example 1, it was found that the viscosity was 2860 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 6,610, and the solid content acid value was 65.2 mgKOH / g.
4-ビニルベンジルグリシジルエーテル42.0gを4-ヒドロキシブチルアクリレートグリシジルエーテル(日本化成社製品:4HBAGE)45.0gに代えた以外は実施例3と同じ条件で反応を行い、淡黄色透明粘稠性液体の感光性樹脂(A4)溶液を得たこの溶液を実施例1と同様にして分析したところ、粘度990mPa・s/25℃、GPCによるスチレン換算重量平均分子量6,200、固形分酸価64.5mgKOH/gであった。 Example 4
The reaction was conducted under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzyl glycidyl ether was replaced with 45.0 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE). When this solution obtained as a liquid photosensitive resin (A4) solution was analyzed in the same manner as in Example 1, the viscosity was 990 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 6,200, and the solid content acid value was 64. 0.5 mg KOH / g.
攪拌機と冷却管を備えた1000mlのフラスコに、ビフェニルテトラカルボン酸二無水物(宇部興産社製品:BPDA)75g、エチレンオキシド付加ビスフェノールA(日本乳化剤社製:BA2グリコール)75g、4-ジメチルアミノピリジン0.9g、プロピレングリコールモノメチルエーテルアセテート100gを入れ、窒素気流下で攪拌しながら155℃のオイルバスで4時間加熱した。続けて、120℃まで冷却した後、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシル(ADEKA社製品:アデカスタブLA-7RD)0.03g、2-ヒドロキシエチルアクリレート6gを加え、120℃で4時間攪拌を続けた。更に4-ビニルベンジルグリシジルエーテル51gを加え、120℃で2時間攪拌した。次に室温まで冷却し、不揮発分が50質量%になるようプロピレングリコールモノメチルエーテルアセテートを加えて淡黄色透明粘稠性の感光性樹脂(A5)溶液を得た。この溶液を実施例1と同様にして分析したところ、粘度1960mPa・s/25℃、GPCによるスチレン換算重量平均分子量12,470、固形分酸価69mgKOH/gであった。 Example 5
In a 1000 ml flask equipped with a stirrer and a condenser tube, 75 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product: BPDA), 75 g of ethylene oxide-added bisphenol A (Nippon Emulsifier Co., Ltd .: BA2 glycol), 4-dimethylaminopyridine 0 0.9 g and 100 g of propylene glycol monomethyl ether acetate were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 0.03 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (ADEKA product: ADK STAB LA-7RD) and 6 g of 2-hydroxyethyl acrylate were added. In addition, stirring was continued at 120 ° C. for 4 hours. Further, 51 g of 4-vinylbenzyl glycidyl ether was added and stirred at 120 ° C. for 2 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous photosensitive resin (A5) solution. When this solution was analyzed in the same manner as in Example 1, the viscosity was 1960 mPa · s / 25 ° C., the weight-average molecular weight was 12,470 in terms of styrene by GPC, and the solid content acid value was 69 mgKOH / g.
4-ビニルベンジルグリシジルエーテル51gを4-ヒドロキシブチルアクリレートグリシジルエーテル(日本化成社製品:4HBAGE)54gに代えた以外は実施例5と同じ条件で反応を行い、淡黄色淡黄色透明粘稠性液体の感光性樹脂(A6)溶液を得た。この溶液を実施例1と同様にして分析したところ、粘度1430mPa・s/25℃、GPCによるスチレン換算重量平均分子量14,200、固形分酸価68.5mgKOH/gであった。 Example 6
The reaction was conducted under the same conditions as in Example 5 except that 51 g of 4-vinylbenzyl glycidyl ether was replaced with 54 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE). A photosensitive resin (A6) solution was obtained. This solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 1,430 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 14,200, and the solid content acid value was 68.5 mgKOH / g.
エポキシ当量257のビスフェノールフルオレン型エポキシ樹脂(大阪ガスケミカル社製品:BPFG)を用い、特許文献3(特開平9-325494号公報)の合成例1および実施例1に従い感光性樹脂(A7)を得た。合成には20時間以上を要し、本発明の実施例1~4に較べて生産性は著しく低いものであった。 Comparative Example 1
Using a bisphenolfluorene type epoxy resin having an epoxy equivalent of 257 (Osaka Gas Chemical Co., Ltd. product: BPFG), a photosensitive resin (A7) is obtained according to Synthesis Example 1 and Example 1 of Patent Document 3 (Japanese Patent Laid-Open No. 9-325494). It was. The synthesis took 20 hours or more, and the productivity was extremely low as compared with Examples 1 to 4 of the present invention.
エポキシ当量257のビスフェノールフルオレン型エポキシ樹脂(大阪ガスケミカル社製品:BPFG)を用い、特許文献3(特開平9-325494号公報)記載の合成例1および実施例2に従い感光性樹脂(A8)を得た。合成には21時間以上を要し、本発明の実施例1~4に較べて生産性は著しく低いものであった。 Comparative Example 2
Using a bisphenolfluorene type epoxy resin having an epoxy equivalent of 257 (Osaka Gas Chemical Co., Ltd. product: BPFG), the photosensitive resin (A8) was prepared according to Synthesis Example 1 and Example 2 described in Patent Document 3 (Japanese Patent Laid-Open No. 9-325494). Obtained. The synthesis took 21 hours or more, and the productivity was significantly lower than that of Examples 1 to 4 of the present invention.
4-ビニルベンジルグリシジルエーテル42.0gをグリシジルメタクリレート(三菱レイヨン社製品:GMA)18.0gに代えた以外は実施例3と同じ条件で反応を行い、淡黄色透明粘稠性液体の感光性樹脂(A9)溶液を得た。この溶液を実施例1と同様にして分析したところ、粘度8,100mPa・s/25℃、GPCによるスチレン換算重量平均分子量5,200、固形分酸価86.5mgKOH/gであった。 Comparative Example 3
The reaction was carried out under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzyl glycidyl ether was replaced with 18.0 g of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd .: GMA), and a light yellow transparent viscous liquid photosensitive resin was used. (A9) A solution was obtained. The solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 8,100 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 5,200, and the solid content acid value was 86.5 mgKOH / g.
4-ビニルベンジルグリシジルエーテル42.0gをグリシジルメタクリレート(三菱レイヨン社製品:GMA)21.1gに代えた以外は実施例3と同じ条件で反応を行い、淡黄色透明粘稠性液体の感光性樹脂(A10)溶液を得た。この溶液を実施例1と同様にして分析したところ、粘度7,800mPa・s/25℃、GPCによるスチレン換算重量平均分子量6,500、固形分酸価75.6mgKOH/gであった。 Comparative Example 4
The reaction was carried out under the same conditions as in Example 3 except that 42.0 g of 4-vinylbenzylglycidyl ether was replaced with 21.1 g of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd .: GMA), and a light yellow transparent viscous liquid photosensitive resin was used. (A10) A solution was obtained. This solution was analyzed in the same manner as in Example 1. As a result, the viscosity was 7,800 mPa · s / 25 ° C., the weight-average molecular weight in terms of styrene by GPC was 6,500, and the solid content acid value was 75.6 mgKOH / g.
実施例1~6および比較例1~2の感光性樹脂について、製造直後と室温保存1ヵ月後のGPCによるポリスチレン換算重量平均分子量を測定し、その変化率を調べた。結果を表1に示す。 Test example 1
For the photosensitive resins of Examples 1 to 6 and Comparative Examples 1 and 2, the weight average molecular weight in terms of polystyrene was measured by GPC immediately after production and one month after storage at room temperature, and the rate of change was examined. The results are shown in Table 1.
実施例1で得た感光性樹脂A1を用い、下記表2に示す配合で感光性樹脂組成物を調製した。この感光性樹脂組成物を1.1mm厚のソーダライムガラス基板にスピンコーターで乾燥膜厚3μmとなるよう塗布、100℃のホットプレートで90秒乾燥させた後、室温まで冷却した。続いて超高圧水銀灯露光機にて、紫外線照度15mW/cm2(365nm)、積算光量20mJ/cm2で、UGRA-OFFSET-TEST KAIL1982をマスクとしたソフトコンタクト露光を行った後、25℃の1%炭酸ナトリウム水に90秒間浸漬現像しパターンを形成し、残ったステップ段数で感度を、マイクロラインで解像度を評価した。結果を表2に併せて示す。 Example 7
Using the photosensitive resin A1 obtained in Example 1, a photosensitive resin composition was prepared with the formulation shown in Table 2 below. This photosensitive resin composition was applied to a 1.1 mm thick soda lime glass substrate with a spin coater to a dry film thickness of 3 μm, dried on a hot plate at 100 ° C. for 90 seconds, and then cooled to room temperature. Subsequently, after performing soft contact exposure using an UGRA-OFFSET-TEST KAIL 1982 as a mask at an ultraviolet illuminance of 15 mW / cm 2 (365 nm) and an integrated light quantity of 20 mJ / cm 2 with an ultra-high pressure mercury lamp exposure machine, A pattern was formed by immersing and developing in% sodium carbonate water for 90 seconds, and the sensitivity was evaluated by the number of remaining steps, and the resolution was evaluated by a microline. The results are also shown in Table 2.
感光性樹脂A1を感光性樹脂A2~A10に代えた以外は実施例7と同様にして感光性樹脂組成物を調製し、感度および解像度を評価した。結果を表2に併せて示す。 Examples 8 to 10 and Comparative Examples 5 to 8
A photosensitive resin composition was prepared in the same manner as in Example 7 except that the photosensitive resin A1 was replaced with the photosensitive resins A2 to A10, and the sensitivity and resolution were evaluated. The results are also shown in Table 2.
Claims (9)
- 下記一般式(1)で表される化合物と下記一般式(2)で表される化合物を反応させて得られる高分子化合物に、エチレン性不飽和基を有するカルボン酸反応性化合物を付加させて得られる感光性樹脂。
- 一般式(1)で表される化合物100モル部に対する一般式(2)で表される化合物の割合が110~200モル部の範囲である請求項1記載の感光性樹脂。 The photosensitive resin according to claim 1, wherein the ratio of the compound represented by the general formula (2) to the 100 mol parts of the compound represented by the general formula (1) is in the range of 110 to 200 mol parts.
- エチレン性不飽和基を有するカルボン酸反応性化合物が、下記一般式(4)で表されるものである請求項1ないし3のいずれかの項に記載の感光性樹脂。
- 一般式(1)で表される化合物と一般式(2)で表される化合物を反応させて得られる高分子化合物に、さらに下記一般式(6)で表される化合物または水を付加させるものである請求項1ないし4のいずれかの項に記載の感光性樹脂。
- 一般式(1)におけるYが9,9-フルオレニル基である請求項1ないし5のいずれかの項に記載の感光性樹脂。 6. The photosensitive resin according to claim 1, wherein Y in the general formula (1) is a 9,9-fluorenyl group.
- 酸価が30~150mgKOH/gである請求項1ないし6のいずれかの項に記載の感光性樹脂。 7. The photosensitive resin according to claim 1, wherein the acid value is 30 to 150 mgKOH / g.
- 請求項1ないし7のいずれかの項に記載の感光性樹脂と、光重合開始剤および/または光増感剤とを含有することを特徴とする感光性樹脂組成物。 A photosensitive resin composition comprising the photosensitive resin according to any one of claims 1 to 7, and a photopolymerization initiator and / or a photosensitizer.
- さらに、分子中に1個以上の不飽和基を持つ重合性モノマーを含有するものである請求項8に記載の感光性樹脂組成物。 Furthermore, the photosensitive resin composition of Claim 8 which contains the polymerizable monomer which has a 1 or more unsaturated group in a molecule | numerator.
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---|---|---|---|---|
JP2011219661A (en) * | 2010-04-12 | 2011-11-04 | Osaka Gas Chem Kk | Polyester resin having fluorene skeleton and method for producing the same |
WO2013073157A1 (en) * | 2011-11-14 | 2013-05-23 | 新日鉄住金化学株式会社 | Photosensitive material, holographic medium and holographic recording method |
JP2017219838A (en) * | 2016-06-02 | 2017-12-14 | 大阪ガスケミカル株式会社 | Photosensitive resin composition |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN105301902B (en) * | 2015-11-10 | 2020-01-10 | 杭州福斯特应用材料股份有限公司 | Positive photosensitive polyimide resin composition with ester-linked fluorene unit and siloxane |
TWI651313B (en) * | 2018-03-07 | 2019-02-21 | 台虹科技股份有限公司 | Alkenylbenzene derivative |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005060685A (en) * | 2003-07-31 | 2005-03-10 | Fuji Photo Film Co Ltd | Polymerizable composition |
WO2006025236A1 (en) * | 2004-09-03 | 2006-03-09 | Toyo Boseki Kabushiki Kaisha | Active ray-curable hyperbranched polymer and active ray-curable resin composition using same |
WO2007123017A1 (en) * | 2006-04-11 | 2007-11-01 | Wako Pure Chemical Industries, Ltd. | Polymerizable unsaturated compound and method for producing the same |
JP2008185681A (en) * | 2007-01-29 | 2008-08-14 | Kao Corp | Polyester for toner |
JP2008214451A (en) * | 2007-03-02 | 2008-09-18 | Teijin Fibers Ltd | Aromatic copolyester |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3813244B2 (en) * | 1996-06-07 | 2006-08-23 | 新日鐵化学株式会社 | Alkali developable unsaturated resin composition and highly sensitive negative pattern forming material using the same |
-
2009
- 2009-03-25 CN CN2009801075549A patent/CN101970532A/en active Pending
- 2009-03-25 KR KR1020107021980A patent/KR101520763B1/en active IP Right Grant
- 2009-03-25 TW TW098109757A patent/TWI452427B/en active
- 2009-03-25 WO PCT/JP2009/055878 patent/WO2009119623A1/en active Application Filing
- 2009-03-25 JP JP2010505697A patent/JP5142161B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005060685A (en) * | 2003-07-31 | 2005-03-10 | Fuji Photo Film Co Ltd | Polymerizable composition |
WO2006025236A1 (en) * | 2004-09-03 | 2006-03-09 | Toyo Boseki Kabushiki Kaisha | Active ray-curable hyperbranched polymer and active ray-curable resin composition using same |
WO2007123017A1 (en) * | 2006-04-11 | 2007-11-01 | Wako Pure Chemical Industries, Ltd. | Polymerizable unsaturated compound and method for producing the same |
JP2008185681A (en) * | 2007-01-29 | 2008-08-14 | Kao Corp | Polyester for toner |
JP2008214451A (en) * | 2007-03-02 | 2008-09-18 | Teijin Fibers Ltd | Aromatic copolyester |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011219661A (en) * | 2010-04-12 | 2011-11-04 | Osaka Gas Chem Kk | Polyester resin having fluorene skeleton and method for producing the same |
WO2013073157A1 (en) * | 2011-11-14 | 2013-05-23 | 新日鉄住金化学株式会社 | Photosensitive material, holographic medium and holographic recording method |
JP2013103984A (en) * | 2011-11-14 | 2013-05-30 | Nippon Steel & Sumikin Chemical Co Ltd | Photosensitive material, holographic recording medium and holographic recording method |
JP2017219838A (en) * | 2016-06-02 | 2017-12-14 | 大阪ガスケミカル株式会社 | Photosensitive resin composition |
Also Published As
Publication number | Publication date |
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TWI452427B (en) | 2014-09-11 |
CN101970532A (en) | 2011-02-09 |
TW200949444A (en) | 2009-12-01 |
JPWO2009119623A1 (en) | 2011-07-28 |
KR20110013361A (en) | 2011-02-09 |
KR101520763B1 (en) | 2015-05-15 |
JP5142161B2 (en) | 2013-02-13 |
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