WO2009119622A1 - 感光性樹脂およびこれを利用した感光性樹脂組成物 - Google Patents
感光性樹脂およびこれを利用した感光性樹脂組成物 Download PDFInfo
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- WO2009119622A1 WO2009119622A1 PCT/JP2009/055877 JP2009055877W WO2009119622A1 WO 2009119622 A1 WO2009119622 A1 WO 2009119622A1 JP 2009055877 W JP2009055877 W JP 2009055877W WO 2009119622 A1 WO2009119622 A1 WO 2009119622A1
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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
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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
- C08G63/66—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
- G03F7/004—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
- G03F7/027—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 having a fluorene skeleton and a photosensitive resin composition using the same. More specifically, the photosensitive resin has various excellent properties and can be easily produced at low cost. Resin and interlayer insulating films and protective films (for example, interlayer filters and protective films used for color filters, liquid crystal display elements, integrated circuit elements, solid-state image sensors, etc.) in liquid crystal displays and electronic parts, etc.
- the present invention relates to a photosensitive resin composition useful for preparation.
- a polymer compound having a fluorene skeleton has excellent physical properties such as high heat resistance, high transparency, high refractive index, and low linear expansion coefficient. Utilizing this property, a polymer compound having a fluorene skeleton in which a radical polymerizable unsaturated bond structure (vinyl group) is introduced into the molecule is used as an optical overcoat agent, hard coat agent, antireflection film. In addition, studies on optical materials such as spectacle lenses, optical fibers, optical waveguides, and holograms are underway.
- a plastic lens material a compound obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with (meth) acrylic acid chloride, or 9,9-bis (4-hydroxyphenyl) fluorene with ethylene oxide or propylene oxide
- Patent Document 1 a copolymer containing as a main component a compound obtained by adding (meth) acrylic acid after the addition of is disclosed.
- the compounds disclosed in this patent document have the disadvantages that the molecular weight is low, the structure is flexible, the refractive index is not sufficient, and the strength of the cured product is low because the crosslinking density is low. is there.
- polymer compounds having a fluorene skeleton are also applied to so-called photoresists such as liquid crystal color filters, black matrices, solder resists, etc., due to their excellent heat resistance and chemical resistance (Patent Documents). 2 and 3).
- Photosensitive resins based on these technologies can obtain a high crosslinking density and can obtain a cured product having excellent strength, heat resistance, and chemical resistance, but the synthesis takes a very long time. For this reason, the cost is high and it is difficult to say that it is widely used. Further, since coloring occurs due to the manufacturing method, it is difficult to apply to optical components that require transparency, and it cannot be said that the characteristics of the fluorene skeleton are fully utilized.
- JP-A-4-325508 Japanese Patent No. 3673321 JP 2007-264433 A
- an object of the present invention is to provide such a photosensitive resin and a photosensitive resin composition using the photosensitive resin.
- the present inventors have conducted extensive research to solve the above problems, and as a result, have obtained a polymer compound obtained by reacting a compound having a specific fluorene skeleton with tetrabasic dianhydride.
- a photosensitive resin obtained by adding a specific carboxylic acid-reactive (meth) acrylate compound can be easily produced at low cost, provides high strength at a high crosslinking density, and has high heat resistance and high transparency.
- the present inventors have found that it exhibits excellent characteristics such as a high refractive index and a low linear expansion coefficient, and has completed the present invention.
- the present invention provides a polymer compound obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with a tetrabasic acid dianhydride to a carboxylic acid represented by the following general formula (2). It is a photosensitive resin obtained by adding an acid-reactive (meth) acrylate compound.
- ring Z 1 and ring Z 2 represent a monocyclic or condensed polycyclic hydrocarbon ring
- R 1a and R 1b represent a hydrogen atom or a substituent
- R 2a and R 2b represent other than a hydrogen atom.
- R 3a and R 3b represent a hydrogen atom or a methyl group
- k1 and k2 are the same or different and represent an integer of 0 to 4
- m1 and m2 are the same or different and represent an integer of 0 to 3
- N1 and n2 are the same or different and represent an integer of 0 to 10
- p1 and p2 are the same or different and represent an integer of 0 to 4, provided that ring Z 1 and ring Z 2 are monocyclic hydrocarbon rings.
- 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 has high storage stability, can be easily produced at low cost, has excellent productivity, and has excellent characteristics such as high heat resistance, high transparency, high refractive index, and low linear expansion coefficient. It is what you have.
- the photosensitive resin composition of the present invention using this photosensitive resin has high sensitivity and can provide a cured product having excellent strength and the like.
- the polymer compound constituting the photosensitive resin of the present invention is obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) and a tetrabasic acid dianhydride described later.
- ring Z 1 and ring Z 2 represent a monocyclic or condensed polycyclic hydrocarbon ring
- R 1a and R 1b represent a hydrogen atom or a substituent
- R 2a and R 2b represent other than a hydrogen atom.
- R 3a and R 3b represent a hydrogen atom or a methyl group
- k1 and k2 are the same or different and represent an integer of 0 to 4
- m1 and m2 are the same or different and represent an integer of 0 to 3
- N1 and n2 are the same or different and represent an integer of 0 to 10
- p1 and p2 are the same or different and represent an integer of 0 to 4, provided that ring Z 1 and ring Z 2 are monocyclic hydrocarbon rings.
- the hydrocarbon corresponding to the hydrocarbon ring represented by the ring Z 1 and the ring Z 2 is monocyclic or condensed polycyclic, for example, monocyclic carbonization such as benzene.
- Hydrogen, condensed bicyclic hydrocarbons for example, C 8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C 10-16 condensed bicyclic hydrocarbons
- condensed tricyclic hydrocarbons anthracene
- condensed 2- to 4-cyclic hydrocarbons such as phenanthrene.
- benzene is preferred in applications that require particularly high solubility, compatibility, and low solution viscosity.
- Ring Z 1 and ring Z 2 may be the same or different rings, and may usually be the same ring.
- the substituent represented by R 1a and R 1b is not particularly limited, but is usually an alkyl group.
- the alkyl group include C 1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C 1-4 alkyl group, particularly a methyl group).
- the groups R 1a and R 1b may be different from each other or the same. When k1 (or k2) is 2 or more, the groups R 1a (or R 1b ) may be different or the same in the same benzene ring.
- substitution position of the group R 1a (or R 1b ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited.
- Preferred substitution numbers k1 and k2 are 0 or 1, in particular 0.
- the substitution numbers k1 and k2 may be different but are usually the same.
- Examples of the substituents R 2a and R 2b substituted on the ring Z 1 and the ring Z 2 include alkyl groups (methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, s-butyl groups, t-butyl groups and the like).
- cycloalkyl group (cyclopentyl group, cyclohexyl group etc.) C 5-10 cycloalkyl group, preferably C 5-8 cycloalkyl group, more preferably C 5-6 cycloalkyl group, etc.), aryl group [phenyl group, alkylphenyl group (methylphenyl group (tolyl group), dimethylphenyl group (xylyl group), etc.), etc.
- C 6-10 aryl group preferably C 6-8 aryl group, especially phenyl group
- aralkyl group C 6-10 aryl-C 1-4 alkyl group such as benzyl group, phenethyl group, etc.
- Hydrocarbon groups such as alkoxy groups (C 1-4 alkoxy groups such as methoxy groups); acyl groups (C 1-6 acyl groups such as acetyl groups); alkoxycarbonyl groups (C 1- such as methoxycarbonyl groups) 4 alkoxycarbonyl group etc.); halogen atom (fluorine atom, chlorine atom etc.); nitro group; cyano group etc.
- Preferred substituents R 2a are an alkyl group (C 1-6 alkyl group), a cycloalkyl group (C 5-8 cycloalkyl group), an aryl group (C 6-10 aryl group), an aralkyl group ( C 6-8 aryl-C 1-2 alkyl group), and C 1-4 alkyl group, C 1-4 alkoxy group, and C 6-8 aryl group are particularly preferable.
- the substituent R 2a (or R 2b ) may be substituted on the benzene ring alone or in combination of two or more.
- the groups R 2a and R 2b may be the same or different from each other, but are usually the same. When m1 (or m2) is 2 or more, the groups R 2a (or R 2b ) may be different or the same in the same hydrocarbon ring.
- the substitution position of the substituent R 2a is not particularly limited, and depends on the substitution position of a hydroxyl group or a hydroxy (poly) alkyleneoxy group (hereinafter sometimes referred to as a hydroxyl group-containing group). Thus, it can be substituted at the 2-6 positions (for example, the 2-position, 5-position, 2,5-position, etc.) of the phenyl group constituting the phenol skeleton.
- substitution numbers m1 and m2 of the substituents R 2a and R 2b are preferably 0 to 2, more preferably 0 to 1 (particularly 0), depending on the number of substitutions of the hydroxyl group-containing group.
- the substitution numbers m1 and m2 may be different but are usually the same in many cases.
- R 3a and R 3b of the hydroxyl group-containing group is hydrogen or a methyl group.
- R 3a and R 3b may be the same or different from each other, but are usually the same.
- n1 and n2 of the (poly) alkyleneoxy group are the same or different and can be selected from the range of 0 to 10, preferably 0 to 8 (for example, 1 to 8), more preferably 0 to 6 (for example, 1 to 6), particularly about 0 to 4 (for example, 1 to 4).
- the sum of n1 and n2 (n1 + n2) can be selected from the range of 0 to 20, preferably 0 to 16 (eg 2 to 12), more preferably 0 to 12 (eg 2 to 12), especially 0. It may be about 8 to 8 (for example, 2 to 8).
- the (poly) alkyleneoxy group may be composed of the same alkoxy group, and different types of alkoxy groups (for example, ethoxy group and propyleneoxy group) are mixed. Usually, it is often composed of the same alkoxy group.
- the number of substitutions p1 and p2 of the hydroxyl group-containing group is in the range of 0 to 4, preferably 1 to 4, particularly preferably 1 to 2.
- p1 and p2 are 1 to 3
- ring Z 1 and ring Z 2 are condensed polycyclic hydrocarbon rings
- ring Z 1 p2 sum included in the sum and ring Z 2 of p1 contained is 1 or more, respectively.
- the sum of p1 and p2 (p1 + p2) is preferably 2 to 8, and more preferably 2 to 4.
- p1 and p2 are preferably 2 to 3 in applications in which the crosslink density of the cured product is required.
- substitution numbers p1 and p2 may be different but are usually the same in many cases.
- the substitution position of the hydroxyl group-containing group is not particularly limited, and can be selected from the 2 to 6 positions of the phenyl group substituted at the 9 position of fluorene according to the number of p1 (or p2), and p1 (or p2) is 2 In this case, for example, it may be 3,4-position, 3,5-position, etc.
- One hydroxyl group-containing group may be generally substituted at the 4-position.
- the plurality of hydroxyl group-containing groups constituting the same phenol skeleton may be the same or different.
- R 1a and R 1b represent a hydrogen atom or a substituent
- R 2a , R 2b , R 6b and R 6b represent a substituent other than a hydrogen atom
- R 3a and R 3b represent a hydrogen atom or a methyl group.
- K1 and k2 are the same or different and represent an integer of 0 to 4
- m1, m2, m3 and m4 are the same or different and represent an integer of 0 to 3
- n1, n2, n3 and n4 are the same or different
- p1 and p2 are the same or different and represent an integer of 1 to 4
- p3 and p4 are the same or different and represent an integer of 0 to 3)
- R 1a and R 1b , R 2a and R 2b , R 3a and R 3b , k1 and k2, m1 and m2, n1 and n2 are the same as described above.
- R 6b and R 6b correspond to R 2a and R 2b
- m3 and m4 correspond to m1 and m2
- n3 and n4 correspond to n1 and n2, respectively, and have the same meaning.
- p1 and p2 are the same as described above, but 1 to 4 is preferable.
- p3 and p4 correspond to p1 and p2, and are preferably 0 to 3.
- a compound in which p1 + p2 + p3 + p4 is 2 in the general formula (3) such as 9,9-bis (hydroxyalkoxynaphthyl) fluorenes and 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes;
- Examples thereof include compounds in which p1 + p2 + p3 + p4 is 2 or more in the general formula (3) such as -bis (polyhydroxyalkoxynaphthyl) fluorenes and 9,9-bis (polyhydroxypolyalkoxynaphthyl) fluorenes.
- 9,9-bis (hydroxyalkoxynaphthyl) fluorenes include 9,9-bis (hydroxyalkoxynaphthyl) fluorene ⁇ for example, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] Fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [ And 9,9-bis (hydroxyC 2-4 alkoxynaphthyl) fluorene etc. such as 5- (2-hydroxypropoxy) -1-naphthyl] fluorene ⁇ .
- 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes include, for example, 9,9-bis (hydroxydialkoxynaphthyl) fluorene [eg, 9,9-bis ⁇ 6- [2- (2-hydroxy Ethoxy) ethoxy] -2-naphthyl ⁇ fluorene, 9,9-bis ⁇ 6- [2- (2-hydroxypropoxy) propoxy] -2-naphthyl ⁇ fluorene, 9,9-bis ⁇ 5- [2- (2 9,9-bis (hydroxydi-C 2 ) such as -hydroxyethoxy) ethoxy] -1-naphthyl ⁇ fluorene, 9,9-bis ⁇ 5- [2- (2-hydroxypropoxy) propoxy] -1-naphthyl ⁇ fluorene -4 alkoxy naphthyl) fluorene] 9,9-bis (hydroxymethyl dialkoxy naphthyl) fluorene such as
- the 9,9-bis (polyhydroxyalkoxynaphthyl) fluorenes correspond to the 9,9-bis (hydroxyalkoxynaphthyl) fluorenes, and compounds having p1 + p2 + p3 + p4 of 2 or more, for example, 9,9-bis (di or di) Trihydroxyalkoxynaphthyl) fluorene [eg, 9,9-bis [di (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [di (2-hydroxypropoxy) -2-naphthyl] fluorene, etc. 9,9-bis (polyhydroxyalkoxynaphthyl) fluorene such as 9,9-bis (di- or trihydroxyC 2-4 alkoxynaphthyl) fluorene and the like].
- the 9,9-bis (polyhydroxypolyalkoxynaphthyl) fluorenes correspond to the 9,9-bis (hydroxyalkoxynaphthyl) fluorenes, and n1, n2, n3, n4 are 2 or more and p1 + p2 + p3 + p4 is 2 or more.
- a compound such as 9,9-bis (di or trihydroxydialkoxynaphthyl) fluorene eg, 9,9-bis ⁇ di [2- (2-hydroxyethoxy) ethoxy] -2-naphthyl ⁇ fluorene, 9 bis 9,9-bis (di or trihydroxy dialkoxy naphthyl) fluorene such as (di or trihydroxy-di C 2-4 alkoxy-naphthyl) fluorene, etc.]; corresponding to these compounds, the formula (formula 3 ) In which n1, n2, n3 and n4 are 3 or more.
- R 1a and R 1b represent a hydrogen atom or a substituent
- R 2a , R 2b , R 7b and R 7b represent a substituent other than a hydrogen atom
- R 3a and R 3b represent a hydrogen atom or a methyl group.
- K1 and k2 are the same or different and represent an integer of 0 to 4
- n1 and n2 are the same or different and represent an integer of 0 to 10
- p1 and p2 are the same or different and represent an integer of 1 to 3 .
- R 1a and R 1b , R 2a and R 2b , R 3a and R 3b , k1 and k2, m1 and m2, n1 and n2 are the same as described above.
- R 7b and R 7b correspond to R 3a and R 3b and have the same meaning.
- p1 and p2 are the same as described above, but 1 to 3 are preferable.
- 9,9-bis (hydroxyalkoxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorenes ⁇ eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2 -Hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) Phenoxyethanol] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenoxyethanol] fluorene 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene
- 9,9-bis (hydroxyalkoxyalkylphenyl) fluorene preferably 9,9-bis (hydroxy-branched C 3-4 such as 9,9-bis (2-hydroxypropoxy-diC 1-4 alkylphenyl) fluorene Alkoxy-dialkylphenyl) fluorenes ⁇ .
- 9,9-bis (hydroxypolyalkoxyphenyl) fluorenes include compounds in which n1 and n2 are 2 or more, such as 9,9-bis (hydroxydialkoxyphenyl) fluorenes ⁇ eg, 9,9-bis [ 4- (2-hydroxydiethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3- Methylphenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3,5-dimethylphenyl Fluorene, 9,9-bis [4- (2-hydroxydiethoxy) phenoxyethanol] fluorene, 9,9-bis [4- (2- Droxydipropoxy) phenoxyethanol] fluorene, 9,9-bis [4-
- 9,9-bis (hydroxyethoxyphenyl) fluorene 9,9-bis (hydroxyethoxy-3-methylphenyl) fluorene, 9,9-bis (hydroxyethoxy-3,5dimethylphenyl) fluorene, 9 , 9-bis (hydroxyethoxy-2-phenoxyethanol) fluorene is preferred.
- R 2a And R 2b is preferably a phenyl group.
- 9,9-bis (hydroxyalkoxyarylphenyl) fluorenes include 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9-bis [4- (2-hydroxypropoxy) 9,9-bis (hydroxyalkoxyarylphenyl) fluorene, such as -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-tolylphenyl] fluorene, preferably 9,9- Bis (2-hydroxyethoxyarylphenyl) fluorene ⁇ and the like.
- 9,9-bis (hydroxypolyalkoxyarylphenyl) fluorenes include 9,9-bis (hydroxydialkoxyarylphenyl) fluorenes ⁇ eg, 9,9-bis ⁇ 4- [2- (2-hydroxyethoxy 9,9-bis (hydroxydialkoxyarylphenyl) fluorene such as ethoxy] -3-phenylphenyl ⁇ fluorene, preferably 9,9-bis [2- (2-hydroxyethoxy) ethoxyarylphenyl] fluorene ⁇ included.
- Tetrabasic acid dianhydride is used as the compound to be reacted with the compound having the fluorene skeleton.
- tetrabasic dianhydride examples include butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic Acid dianhydride, cyclohexane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, norbornane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic acid Dianhydride, biphenyl ether tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicar
- pyromellitic dianhydride 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride
- benzophenone tetracarboxylic dianhydride Biphenyltetracarboxylic dianhydride is preferred.
- a polymer compound constituting the photosensitive resin of the present invention is obtained by addition reaction of a tetrabasic acid dianhydride with the compound having the fluorene skeleton.
- the ratio of tetrabasic dianhydride to 1 mol of the compound having a fluorene skeleton is preferably 0.5 mol to 1.5 mol, and more preferably 0.65 mol to 1.25 mol.
- the ratio of tetrabasic acid dianhydride is less than 0.5 mol and exceeds 1.5 mol, sufficient molecular weight may not be obtained.
- a catalyst may be used in the addition reaction of a compound having a fluorene skeleton and a tetrabasic acid dianhydride.
- 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, trimethylbenzylam
- the amount of the catalyst to be 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 in total of the compound having a fluorene skeleton and the tetrabasic dianhydride. 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 and cyclohexanone, acetate esters such as ethyl acetate and 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 a range of 25 to 150 parts by mass is preferable with respect to 100 parts by mass in total of the compound having a fluorene skeleton and the tetrabasic dianhydride. 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 heating temperature can be appropriately set according to the type of the compound having a fluorene skeleton and the tetrabasic acid dianhydride and the apparatus to be used, but it is generally preferably in the range of 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 adding a carboxylic acid reactive (meth) acrylate compound represented by the following general formula (2) to the polymer compound obtained as described above.
- R 4 represents a hydrogen atom or a methyl group
- R 5 represents a group represented by the following general formula (5)
- q, r, and s each independently represent an integer of 0 to 9. However, q, r, and s are not 0 simultaneously.
- carboxylic acid reactive (meth) acrylate represented by the general formula (2) examples include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3- Examples thereof include hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, and polyethylene glycol-polypropylene glycol (meth) acrylate glycidyl ether.
- Such a carboxylic acid reactive (meth) acrylate compound is subjected to an addition reaction with the above polymer compound.
- the proportion of the carboxylic acid-reactive (meth) acrylate compound in the photosensitive resin of the present invention is not unclear because it varies depending on the application, but when used for a photocurable coating agent or an optical material, the acid value of the photosensitive resin It may be added until becomes zero.
- 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 differs depending on the type of carboxylic acid-reactive (meth) acrylate compound, and cannot be generally stated.
- Examples 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, 1,5-diazabicyclo [4,3,0] nonene-5, and other amines, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide Quaternary ammonium compounds, tributylphosphine, triphenylphosphine and the like and mixtures thereof.
- 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 the compound having the fluorene skeleton. 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 (meth) acrylate 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 decrease, which is not preferable.
- the heating temperature can be appropriately set depending on the type and apparatus of the carboxylic acid reactive (meth) acrylate compound, but is generally 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 molecular weight of the photosensitive resin of the present invention is not particularly limited, but is preferably 1,000 to 200,000, more preferably 2,500 from the viewpoint of coating film strength, film forming property, or developability. ⁇ 50,000 is preferred.
- 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 paste mixed with a solution or a filler, and for that purpose can also 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 is used as a photoresist, it 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.
- coating using a solvent you may pass through a drying process.
- a pattern can be formed by developing the exposed coating film wet.
- 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.
- As the developer weak alkaline water is preferably used. For the purpose of assisting developability, 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, pyromellitic dianhydride (Daicel product: PMDA) 64 g, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd.) : BPEF) 136 g and propylene glycol monomethyl ether acetate 134 g were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream.
- PMDA pyromellitic dianhydride
- BPEF 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene
- the obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 2900 mPa ⁇ s / 25 ° C., styrene-converted weight average molecular weight 12,523 by GPC, solid content acid value 2 0.2 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 In a 1000 ml flask equipped with a stirrer and a condenser, 72 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product: BPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical) (Product: BPEF) 128 g, 4-dimethylaminopyridine 1 g and propylene glycol monomethyl ether acetate 134 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
- the obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 4200 mPa ⁇ s / 25 ° C., styrene-converted weight average molecular weight 7,243 by GPC, solid content acid value 2 0.5 mg KOH / g.
- photosensitive compositions having the compositions shown in Table 1 were prepared.
- This photosensitive composition was applied to a 1.1 mm thick soda lime glass substrate with a bar coater to a dry film thickness of 6 ⁇ m, dried for 10 minutes with a hot air dryer at 80 ° C., and then cooled to room temperature. Subsequently, ultraviolet rays with an integrated light amount of 300 mJ / cm 2 were irradiated with an ultra-high pressure mercury lamp UV irradiator.
- the cured coating film was subjected to pencil hardness and crosscut-tape peel tests according to JIS-K5400 to evaluate the strength of the coating film.
- the photosensitive composition using the photosensitive resin of Comparative Example 1 has a low molecular weight and thus has a weak coating film forming ability and could not be evaluated without adding other resin components.
- the photosensitive compositions using the photosensitive resins of Examples 1 and 2 gave a smooth film and had good hardness and adhesion.
- Example 7 In a 1000 ml flask equipped with a stirrer and a condenser, pyromellitic dianhydride (Daicel product: PMDA) 76 g, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd.) : BPEF) and propylene glycol monomethyl ether acetate (134 g) were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream.
- PMDA pyromellitic dianhydride
- PMDA 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene
- BPEF propylene glycol monomethyl ether acetate
- the obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 4800 mPa ⁇ s / 25 ° C., styrene-converted weight average molecular weight by GPC was 23,169, and solid content acid value was 75. 0.2 mg KOH / g.
- Example 8 In a 1000 ml flask equipped with a stirrer and a condenser tube, 90 g of biphenyltetracarboxylic dianhydride (product of Ube Industries, Ltd .: BPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical) 110 g of BPEF, 134 g of propylene glycol monomethyl ether acetate, and 1 g of 4-dimethylaminopyridine were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream.
- BPDA biphenyltetracarboxylic 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 6600 mPa ⁇ s / 25 ° C., styrene-converted weight average molecular weight 18,230 by GPC, solid content acid value 71 0.6 mg KOH / g.
- a photosensitive resin (A6) was obtained according to Synthesis Example 1 and Example 1 described in Japanese Patent No. 3813244 using a bisphenolfluorene type epoxy resin having an epoxy equivalent of 257 (product of Osaka Gas Chemical Co., Ltd .: BPFG). The synthesis took 20 hours or more, and the productivity was extremely low as compared with Examples 1 to 4 of the present invention.
- a photosensitive resin (A7) was obtained according to Synthesis Example 1 and Example 2 described in Japanese Patent No. 3813244 using a bisphenolfluorene type epoxy resin (Osaka Gas Chemical Co., Ltd. product: BPFG) having an epoxy equivalent of 257.
- the synthesis took 21 hours or more, and the productivity was remarkably low as compared with Examples 7 and 8 of the present invention.
- Comparative Example 6 A reaction was conducted in the same manner as in Example 8 except that 80 g of 4-hydroxybutyl acrylate glycidyl ether was changed to 60 g of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd .: GMA) to obtain a photosensitive resin solution (A8).
- the obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 12,400 mPa ⁇ s / 25 ° C., GPC styrene-converted weight average molecular weight 16,100, solid content acid The value was 74.2 mgKOH / g.
- Test example 1 For the photosensitive resins of Examples 7 to 8 and Comparative Examples 4 to 5, 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 2.
- the photosensitive resins of Examples 7 to 8 showed almost no change, but the photosensitive resins of Comparative Examples 2 to 3 showed an increase in molecular weight of about 25% and were inferior in storage stability.
- Examples 9-12 and Comparative Examples 7-12 Using the photosensitive resins of Examples 7 to 8 and Comparative Examples 4 to 6, photosensitive compositions were prepared according to the formulations shown in Table 3 below. This photosensitive 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.
- the photosensitive compositions using the photosensitive resins of Examples 7 to 8 have higher sensitivity than the photosensitive compositions using the photosensitive resins (A6 to A8) of Comparative Examples 4 to 6. Good resist properties were shown.
- Example 13 In a 1000 ml flask equipped with a stirrer and a condenser tube, 71.8 g of 3,3′-4,4′biphenyltetracarboxylic anhydride (manufactured by Ube Industries, Ltd .: BPDA), 9,9-bis [4- (2-hydroxyethoxy) ) 3Phenylphenyl] fluorene (Osaka Gas Chemical Co., Ltd .: BOPPEF) 109.7g, propylene glycol monomethyl ether acetate 128g, 4-dimethylaminopyridine 0.25g was added and heated with a mantle heater at 120 ° C for 4 hours with stirring. .
- 3,3′-4,4′biphenyltetracarboxylic anhydride manufactured by Ube Industries, Ltd .: BPDA
- 9,9-bis [4- (2-hydroxyethoxy) ) 3Phenylphenyl] fluorene Osaka Gas Chemical Co.,
- the viscosity was 187100 mPa ⁇ s / 25 ° C.
- the styrene conversion weight average molecular weight by GPC was 4,170
- solid content It was 66.8%
- the solid content acid value was 85.4 mgKOH / g.
- Example 14 In a 1000 ml flask equipped with a stirrer and a condenser, 61.22 g of 3,3′-4,4′biphenyltetracarboxylic anhydride (manufactured by Ube Industries, Ltd .: BPDA), 9,9-bis [6- (2-hydroxyethoxy) ) Naphtyl] fluorene (Osaka Gas Chemical Co., Ltd .: BNFEO) 95.89 g, propylene glycol monomethyl ether acetate 125 g, 4-dimethylaminopyridine 0.25 g were added, and heated with a mantle heater at 120 ° C. for 4 hours with stirring.
- BPDA 3,3′-4,4′biphenyltetracarboxylic anhydride
- 9,9-bis [6- (2-hydroxyethoxy) ) Naphtyl] fluorene Osaka Gas Chemical Co., Ltd .: BNFEO
- Examples 15-16 A photosensitive composition was prepared using the photosensitive resin of Example 13 and the formulation shown in Table 4. This photosensitive composition was evaluated in the same manner as in Examples 9-12.
- All the photosensitive compositions had high sensitivity and good resist characteristics.
- the photosensitive resin of the present invention can be easily produced at a low cost, the adjustment of the crosslinking density and the acid value is easy, and excellent heat resistance, high transparency, high refractive index, low linear expansion coefficient, etc. It has characteristics. Therefore, the resin composition using the photosensitive resin is used for interlayer insulating films and protective films (for example, color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc.) in liquid crystal displays and electronic components. It is useful for preparing a film or a protective film.
- interlayer insulating films and protective films for example, color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc.
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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)64g、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)136g、プロピレングリコールモノメチルエーテルアセテート134g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1g、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)0.04g、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)106gを加え、120℃で4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。
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)72g、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)128g、4-ジメチルアミノピリジン1g、プロピレングリコールモノメチルエーテルアセテート134g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)0.04g、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)84gを加え、120℃で4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(A2)溶液を得た。得られた樹脂溶液について、粘度、GPCによるスチレン換算重量平均分子量および固形分酸価を測定したところ、粘度4200mPa・s/25℃、GPCによるスチレン換算重量平均分子量7,243、固形分酸価2.5mgKOH/gであった。
特開平4-325508号公報に記載の合成例1に従い感光性樹脂(A3)を得た。
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)76g、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)124g、プロピレングリコールモノメチルエーテルアセテート134g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1g、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)0.04g、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)106g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(A4)溶液を得た。
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)90g、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)110g、プロピレングリコールモノメチルエーテルアセテート134g、4-ジメチルアミノピリジン1g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)0.04g、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)80g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。
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、特許第3813244号公報に記載の合成例1および実施例1に従い感光性樹脂(A6)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。
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、特許第3813244号公報に記載の合成例1および実施例2に従い感光性樹脂(A7)を得た。合成には21時間以上を要し、本発明の実施例7および実施例8に較べて生産性は著しく低いものであった。
実施例8の4-ヒドロキシブチルアクリレートグリシジルエーテル80gをグリシジルメタクリレート(三菱レイヨン社製品:GMA)60gに変更した以外は同様に反応を行い、感光性樹脂溶液(A8)を得た。得られた樹脂溶液について、粘度、GPCによるスチレン換算重量平均分子量および固形分酸価を測定したところ、粘度12,400mPa・s/25℃、GPCによるスチレン換算重量平均分子量16,100、固形分酸価74.2mgKOH/gであった。
実施例7~8および比較例4~5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2に示す。
実施例7~8および比較例4~6の感光性樹脂を用い、下記表3の配合で感光性組成物を作成した。この感光性組成物を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3に併せて示す。
攪拌機と冷却管を備えた1000mlのフラスコに3,3’-4,4’ビフェニルテトラカルボン酸無水物(宇部興産製:BPDA)71.8g、9,9-ビス[4-(2-ヒドロキシエトキシ)3フェニルフェニル]フルオレン(大阪ガスケミカル社製:BOPPEF)109.7g、プロピレングリコールモノメチルエーテルアセテート128g、4-ジメチルアミノピリジン0.25gを入れ、攪拌しながら120℃のマントルヒーターで4時間加熱した。続けて、p-メトキシフェノール(東京化成製)0.1g、ヒドロキシエチルアクリレート(東京化成製)13.7gを入れ、120℃で4時間加熱した。更に、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)34.68gを加え、120℃で4時間加熱攪拌し、淡黄色透明粘稠性の感光性樹脂(A9)溶液を得た。
得られた樹脂溶液について、粘度、GPCによるスチレン換算重量平均分子量、固形分および固形分酸価を測定したところ、粘度187100mPa・s/25℃、GPCによるスチレン換算重量平均分子量4,170、固形分66.8%、固形分酸価85.4mgKOH/gであった。
攪拌機と冷却管を備えた1000mlのフラスコに3,3’-4,4’ビフェニルテトラカルボン酸無水物(宇部興産製:BPDA)61.22g、9,9-ビス[6-(2-ヒドロキシエトキシ)ナフチル]フルオレン(大阪ガスケミカル社製:BNFEO)95.89g、プロピレングリコールモノメチルエーテルアセテート125g、4-ジメチルアミノピリジン0.25gを入れ、攪拌しながら120℃のマントルヒーターで4時間加熱した。続けて、p-メトキシフェノール(東京化成製)0.1g、ヒドロキシエチルアクリレート(東京化成製)13.3gを入れ、120℃で4時間加熱した。更に、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)56gを加え、120℃で4時間加熱攪拌し淡黄色透明粘稠性の感光性樹脂(A10)溶液を得た。
得られた樹脂溶液について、粘度、GPCによるスチレン換算重量平均分子量、固形分および固形分酸価を測定したところ、粘度586700mPa・s/25℃、GPCによるスチレン換算重量平均分子量9,250、固形分59.0%、固形分酸価60.4mgKOH/gであった。
Claims (7)
- 下記一般式(1)で表されるフルオレン骨格を有する化合物と四塩基酸二無水物とを反応させて得られる高分子化合物に、下記一般式(2)で表されるカルボン酸反応性(メタ)アクリレート化合物を付加させて得られる感光性樹脂。
- 上記一般式中のR2aおよびR2bがフェニル基である請求項1ないし3のいずれかの項に記載の感光性樹脂。
- 酸価が30~150mgKOH/g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。
- 請求項1ないし5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。
- 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6に記載の感光性樹脂組成物。
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