JP2003075997A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-developable positive-type photosensitive resin composition. SOLUTION: The positive-type photosensitive resin composition comprises (a) an alkali-soluble polymer, (b) a compound having a phenolic hydroxyl group, (c) an esterified quinonediazido compound and (d) inorganic particles of 1 to 30 nm particle diameter selected from aluminum compounds, silicon compounds, tin compounds, titanium compounds and zirconium compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type suitable for optical waveguides and lenses for optical elements which are required to have high transparency and a high refractive index, in which a portion exposed to ultraviolet rays is dissolved in an alkaline aqueous solution. It relates to a photosensitive resin composition.

[0002]

2. Description of the Related Art As a positive photosensitive resin composition in which an exposed portion is dissolved by alkali development, a positive resist composition, a positive photosensitive polyimide precursor composition, and a positive photosensitive poly A benzoxazole precursor composition has already been developed. These are used as masks in the silicon oxide film dry etching process for semiconductors and as heat resistant resins by heating or a suitable catalyst, and are used as surface protective films for semiconductors, interlayer insulating films, insulating layers for organic electroluminescent elements, etc. It is used. However, when applied to a lens for an optical element or the like, this resin composition has problems in transparency and refractive index of the film.

[0003]

The present invention is a composition in which inorganic particles having a specific particle size are added to an alkali-soluble polymer, a compound having a phenolic hydroxyl group, and a naphthoquinonediazide compound, and alkali development is performed before exposure. Almost insoluble in the solution, it can be easily dissolved in an alkaline developer when exposed to light, and fine patterns can be resolved.
Further, it has a high transparency and a high refractive index that can be used for an optical element.

[0004]

That is, the present invention is as follows.
(A) an alkali-soluble polymer, (b) a compound having a phenolic hydroxyl group, (c) an esterified quinonediazide compound, and (d) at least one selected from an aluminum compound, a silicon compound, a tin compound, a titanium compound, and a zirconium compound. Selected particle size 1nm to 30n
A positive-type photosensitive resin precursor composition containing m inorganic particles.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) in the present invention is required to be soluble in an alkali aqueous solution used as a developing solution, and any general alkali-soluble polymer that has been used so far can be used. It can be one.
As the alkali-soluble polymer, a novolac resin, a resole resin, a radical polymerizable polymer having a phenolic hydroxyl group or a carboxyl group, a polyimide precursor,
It is a polymer selected from polyimide and polybenzoxazole precursors. It is desirable that these polymers have an alkali-soluble group in the molecule.

Examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group.

The novolak resin and resol resin of the present invention can be obtained by polycondensing various phenols alone or a mixture of plural kinds thereof with aldehydes such as formalin by a known method.

Examples of the phenols constituting the novolac resin and the resole resin include phenol and p-
Cresol, m-cresol, o-cresol, 2,3
-Dimethylphenol, 2,4-dimethylphenol,
2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,
3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebisp-cresol,
Resorcin, catechol, 2-methylresorcin, 4-
Methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol,
2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol,
β-naphthol and the like can be mentioned, and these can be used alone or as a mixture of a plurality thereof.

The aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like, and these can be used alone or as a mixture of a plurality of them.

A homopolymer polymer of a radical-polymerizable monomer having a phenolic hydroxyl group or a carboxyl group of the present invention and / or a copolymer of the radical-polymerizable monomer and another radical-polymerizable monomer. The polymer can be obtained by polymerizing by a known method using a radical polymerization initiator.

Examples of the radically polymerizable monomer having a phenolic hydroxyl group or a carboxyl group include, for example, o
-Hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and alkyls thereof,
Alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester, carboxy substituents; polyhydroxyvinylphenols such as vinylhydroquinone, 5-vinylpyrogallol, 6-vinylpyrogallol, 1-vinylfluoroglycol O-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid, and their alkyl, alkoxy, halogen, nitro, cyano, amide, ester substituents, methacrylic acid and acrylic acid, and their α- Substituted haloalkyl, alkoxy, halogen, nitro, cyano compounds; divalent non-valent compounds such as maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid and 1,4-cyclohexenedicarboxylic acid. Saturated carboxylic acids and their methyls, Chill, propyl, i- propyl, n- butyl, sec- butyl, ter-butyl, phenyl, o-, m-, p-Toruiruha - Fuesuteru and ha - Fuamido may be mentioned as being preferred for. Among these, o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and their alkyl and alkoxy substitution products, sensitivity during patterning, residual film rate after resolution development, heat distortion resistance, solvent resistance It is preferably used from the standpoints of adhesion to the substrate, storage stability of the solution, and the like. These can be used alone or in combination of two or more.

Examples of the above-mentioned other radically polymerizable monomers include, for example, styrene and α-of styrene.
-, O-, m-, or p-position alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester substituents; diolefins such as butadiene, isoprene, chloroprene; methacrylic acid or acrylic acid Methyl, ethyl, n-propyl, i-propyl,
n-butyl, sec-butyl, ter-butyl, pentyl, neopentyl, isoamylhexyl, cyclohexyl, adamantyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, anthraquinonyl, piperonyl, salicyl, cyclohexyl, benzyl, phenesyl, cresyl, glycidyl, 1 , 1,1-Trifluoroethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, triphenylmethyl, tricyclo [5.2.1.0 ^2,6 ] decane-8 -Yl (as the trivial name in the art "dicyclopentanyl")
It is said that. ), Cumyl, 3- (N, N-dimethylamino) propyl, 3- (N, N-dimethylamino) ethyl, furyl, furfuryl esterification products Anilides of methacrylic acid or acrylic acid, amides, or N, N- Dimethyl, N, N-diethyl, N, N-dipropyl, N, N-diisopropyl, anthranilamide, acrylonitrile, acrolein, methacrylonitrile,
Vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, N-phenylmaleinimide, N- (4-hydroxyphenyl) maleinimide, N-methacryloylphthalimide, N-acryloyl Phthalimide or the like can be used. These may be used alone or in combination of two or more. Of these, styrene, and α-position, o-position, m-position, p-position alkyl, alkoxy, halogen, haloalkyl substitution product of styrene; butadiene, isoprene; methacrylic acid, or methyl acrylate,
Ethyl, n-propyl, N-butyl, glycidyl, and tricyclo [5.2.1.02,6] decan-8-yl ester were used to detect sensitivity during patterning, residual film rate after resolution development, It is particularly preferably used from the viewpoints of heat distortion resistance, solvent resistance, adhesion to a substrate, storage stability of a solution, and the like. When a copolymer of a radical-polymerizable monomer having a phenolic hydroxyl group and another radical-polymerizable monomer other than that is used as the alkali-soluble resin, a preferable copolymerization ratio of the other radical-polymerizable monomer is pheno- The amount is preferably 30% by weight or less, particularly preferably 5 to 20% by weight, based on the total amount of the radically polymerizable monomer having a hydroxyl group and another radically polymerizable monomer. Further, when a copolymer of a radically polymerizable monomer having a carboxyl group and another radically polymerizable monomer other than that is used as the alkali-soluble resin, a preferable copolymerization ratio of the other radically polymerizable monomer is Based on the total amount of the radical-polymerizable monomer having a group and the other radical-polymerizable monomer, preferably 90% by weight or less,
Particularly preferably, it is 10 to 80% by weight. If the proportion of these radical-polymerizable monomers exceeds the above-mentioned proportion with respect to the radical-polymerizable monomers having a phenolic hydroxyl group or a carboxyl group, alkali development may be difficult.

The polymer having the structural unit represented by the general formula (1) as a main component of the present invention is a polymer which can be a polymer having an imide ring, an oxazole ring or other cyclic structure by heating or a suitable catalyst. is there. By forming a ring structure, heat resistance and solvent resistance are dramatically improved.

The above general formula (1) represents a polyamic acid having a hydroxyl group, and due to the presence of the hydroxyl group, the solubility in an aqueous alkaline solution is better than that of a polyamic acid having no hydroxyl group. Particularly, among the hydroxyl groups, phenolic hydroxyl groups are more preferable than the solubility in the alkaline aqueous solution. Further, by having 10 wt% or more of a fluorine atom in the general formula (1), when developing with an alkaline aqueous solution,
Since water repellency is appropriately exerted at the interface of the film, bleeding at the interface can be suppressed. However, if the content of fluorine atoms exceeds 20% by weight, the solubility in an alkaline aqueous solution decreases, the organic solvent resistance of the polymer having a cyclic structure by heat treatment decreases, and the solubility in fuming nitric acid decreases. Not good for Thus, it is preferable that the fluorine atom is contained in an amount of 10% by weight or more and 20% by weight or less.

R ^{1 in the} above general formula (1) represents a structural component of an acid dianhydride, which contains an aromatic ring and has 1 to 4 hydroxyl groups. A divalent to octavalent organic group having at least two carbon atoms is preferable, and a trivalent or tetravalent organic group having 6 to 30 carbon atoms is more preferable.

Specifically, those having a structure represented by the general formula (2) are preferable, and in this case, R ⁴ and R ⁶ are divalent to tetravalent organic groups selected from 2 to 20 carbon atoms. Although shown, those containing an aromatic ring are preferable in view of the heat resistance of the obtained polymer, and among them, particularly preferable structures include those such as trimellitic acid, trimesic acid, and naphthalenetricarboxylic acid residues. Further, R ⁵ is preferably a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. Furthermore, the hydroxyl group is preferably located adjacent to the amide bond. As such an example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane containing a fluorine atom, bis (3-
Hydroxy-4-aminophenyl) hexafluoropropane, fluorine-free, bis (3-amino-4-)
Hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, 2, 4-diamino-phenol, 2,5-diaminophenol,
The thing which the amino group of 1,4-diamino-2,5-dihydroxybenzene couple | bonded etc. can be mentioned.

Further, R ⁷ and R ^{8 in} the general formula (2) are preferably hydrogen and / or an organic group having 1 to 20 carbon atoms. If it has more than 20 carbon atoms, the solubility in an alkaline developer decreases.

In the general formula (2), o and s represent integers of 0 to 2, and r represents integers of 1 to 4. r
When the value is 5 or more, the properties of the resulting heat resistant resin film deteriorate.

R ¹ (COOR ³ ) m (O of the general formula (1)
Among the compounds represented by formula (2) in which H) p is represented by the general formula (2), examples of preferable compounds include those having the structures shown below, but are not limited thereto.

[0020]

[Chemical 6]

Further, it may be modified with a tetracarboxylic acid or a dicarboxylic acid having no hydroxyl group as long as the solubility in alkali, the photosensitivity and the heat resistance are not impaired. Examples of this include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid, and the two carboxyl groups thereof being methyl groups or ethyl groups. Aliphatic tetracarboxylic acids such as diester compounds, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and diester compounds having two carboxyl groups as methyl groups or ethyl groups, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids and aliphatic dicarboxylic acids such as adipic acid. These are preferably modified by 50 mol% or less of the acid component, more preferably 30 mol% or less. If it is modified by 50 mol% or more, the solubility in alkali and the photosensitivity may be impaired.

R ² in the above general formula (1) represents a structural component of diamine. Among them, preferred examples of R ² include those having an aromatic group and a hydroxyl group due to the heat resistance of the obtained polymer, and specific examples thereof include a bis (amino-hydroxy group) having a fluorine atom. -Phenyl) hexafluoropropane, no fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine,
Examples thereof include compounds such as diaminophenol and dihydroxybenzidine and those having the structures represented by the general formulas (3), (4) and (5).

Among these, R ⁹ , R ¹¹ in the general formula (3),
R ¹³ in the general formula (4) and R ¹⁶ in the general formula (5) are preferably an aromatic ring or an organic group having a hydroxyl group in view of the heat resistance of the obtained polymer. R ¹⁰ in the general formula (3), the general formula (4)
R ¹² and R ^{14 in} the formula and R ¹⁵ in the general formula (5) are preferably an organic group having an aromatic ring in view of the heat resistance of the obtained polymer. Further, t and u in the general formula (3) represent integers of 1 or 2, v in the general formula (4) and w in the general formula (5) represent integers from 1 to 4.

Specific examples of R ² (OH) q in the general formula (1) represented by the general formula (3) are shown below.

[0025]

[Chemical 7]

Specific examples of R ² (OH) q in the general formula (1) represented by the general formula (4) are shown below.

[0027]

[Chemical 8]

Specific examples of R ² (OH) q in the general formula (1) represented by the general formula (5) are shown below.

[0029]

[Chemical 9]

In the general formula (3), R ⁹ and R ¹¹ each represent a trivalent to tetravalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and the aromatic group is selected from the heat resistance of the resulting polymer. Those having a ring are preferable. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used. R ¹⁰ has 2 carbon atoms
It represents a divalent organic group up to -30. An aromatic divalent group is preferable to the heat resistance of the obtained polymer, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. Other than these, an aliphatic cyclohexyl group and the like can also be used.

In the general formula (4), R ¹² and R ¹⁴ represent a divalent organic group having 2 to 20 carbon atoms. An aromatic divalent group is preferable to the heat resistance of the obtained polymer. Examples of such groups include a phenyl group, a biphenyl group,
Examples thereof include a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group, but in addition to these, an aliphatic cyclohexyl group can also be used. R ¹³ is
A trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms is shown, and one having an aromatic ring is preferable from the heat resistance of the obtained polymer. Specifically, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis (hydroxyphenyl) propane group, a bis ( Hydroxyphenyl)
It represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, or the like. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used.

In the general formula (5), R ¹⁵ has 2 to 2 carbon atoms.
It represents a divalent organic group selected from 0. Due to the heat resistance of the obtained polymer, an aromatic divalent group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group and a diphenylsulfone group. However, other than this, an aliphatic cyclohexyl group or the like can also be used. R ¹⁶ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and one having an aromatic ring is preferable from the heat resistance of the resulting polymer. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used.

It is also possible to modify with another diamine component in the range of 1 to 40 mol%. Examples of these are phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or aromatic compounds thereof. Examples thereof include compounds in which the group ring is substituted with an alkyl group or a halogen atom. Examples of such compounds include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or aromatic compounds thereof. Examples thereof include compounds in which the group ring is substituted with an alkyl group or a halogen atom, such as aliphatic cyclohexyldiamine and methylenebiscyclohexylamine. When 40 mol% or more of such a diamine component is copolymerized, the heat resistance of the obtained polymer decreases.

R ^{3 in the} general formula (1) represents hydrogen or an organic group having 1 to 20 carbon atoms. From the viewpoint of stability of the resulting positive photosensitive resin composition solution, R ³ is preferably an organic group, but hydrogen is preferable from the viewpoint of solubility in an alkaline aqueous solution. In the present invention, hydrogen atoms and alkyl groups can be mixed. By controlling the amounts of hydrogen and organic groups of R ^3, the dissolution rate in the alkaline aqueous solution changes, and therefore, by this adjustment, a positive photosensitive resin composition having an appropriate dissolution rate can be obtained. A preferable range is that 10% to 90% of R ³ is a hydrogen atom. If R ³ has more than 20 carbon atoms, it will not dissolve in the alkaline aqueous solution. From the above, it is preferable that R ³ contains at least one hydrocarbon group having 1 to 16 carbon atoms and the other is a hydrogen atom.

Further, m in the general formula (1) represents the number of carboxyl groups, and represents an integer from 0 to 2. N in the general formula (1) represents the number of repeating structural units of the polymer of the present invention, and is preferably in the range of 10 to 100,000.

Polyhydroxyamide may be used in place of polyamic acid as a heat-resistant polymer precursor similar to polyamic acid. A method for producing such a polyhydroxyamide can be obtained by subjecting a bisaminophenol compound and a dicarboxylic acid to a condensation reaction. Specifically, dicyclohexylcarbodiimide (D
CC) such as a dehydration condensing agent and an acid are reacted, and a bisaminophenol compound is added thereto, or a solution of dicarboxylic acid dichloride is added dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. is there.

In the case of using polyhydroxyamide, a positive type photosensitive resin composition in which a portion exposed to ultraviolet rays can be removed with an aqueous alkaline solution by adding a photosensitizer such as naphthoquinone diazide sulfonate to a solution of polyhydroxyamide You can get things.

Further, in order to improve the adhesiveness to the substrate, R ¹ of the general formula (1), in the range that does not lower the heat resistance,
An aliphatic group having a siloxane structure may be copolymerized with R ² . Specifically, as the diamine component, bis (3-
Aminopropyl) tetramethyldisiloxane, bis (p
-Amino-phenyl) octamethylpentasiloxane and the like copolymerized with 1 to 10 mol% thereof may be included in the polymer represented by the general formula (1) of the present invention It may be a copolymer or a blend with another structural unit. At that time, it is preferable that the structural unit represented by the general formula (1) is contained in an amount of 90 mol% or more. The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

The polymer represented by the general formula (1) of the present invention can be obtained by, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature, or a diester is obtained from the tetracarboxylic acid dianhydride and an alcohol. Then, it can be synthesized by a method of reacting with an amine in the presence of a condensing agent, a method of obtaining a diester with tetracarboxylic acid dianhydride and an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting with an amine. .

Examples of the compound (b) having a phenolic hydroxyl group used in the present invention include Bis-
Z, BisOC-Z, BisOPP-Z, BisP-C
P, Bis26X-Z, BisOTBP-Z, BisO
CHP-Z, BisOCR-CP, BisP-MZ, B
isP-EZ, Bis26X-CP, BisP-PZ,
BisP-IPZ, BisCR-IPZ, BisOCP
-IPZ, BisOIPP-CP, Bis26X-IP
Z, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, T
risP-PA, BisOFP-Z, BisRS-2
P, BisPG-26X, BisRS-3P, BisO
C-OCHP, BisPC-OCHP, Bis25X-
OCHP, Bis26X-OCHP, BisOCHP-
OC, Bis236T-OCHP, methylenetris-F
R-CR, BisRS-26X, BisRS-OCHP
(Above, brand name, Honshu Chemical Industry Co., Ltd.), BIR-O
C, BIP-PC, BIR-PC, BIR-PTBP,
BIR-PCHP, BIP-BIOC-F, 4PC, B
IR-BIPC-F, TEP-BIP-A (above, a brand name, Asahi Organic Material Industry Co., Ltd. product) are mentioned.

Of these, preferred compounds having a phenolic hydroxyl group are, for example, Bis-Z and B.
isP-EZ, TekP-4HBPA, TrisP-H
AP, TrisP-PA, BisOCHP-Z, Bis
P-MZ, BisP-PZ, BisP-IPZ, Bis
OCP-IPZ, BisP-CP, BisRS-2P,
BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, BIP-PC,
BIR-PC, BIR-PTBP, BIR-BIPC-
F etc. are mentioned. Of these, particularly preferable compounds having a phenolic hydroxyl group include, for example, Bi
s-Z, TekP-4HBPA, TrisP-HAP,
TrisP-PA, BisRS-2P, BisRS-3
P, BIR-PC, BIR-PTBP, BIR-BIP
C-F. By adding this compound having a phenolic hydroxyl group, the resin composition obtained is hardly dissolved in an alkali developing solution before exposure and easily dissolved in an alkali developing solution after exposure, so that film loss due to development is reduced. Development is facilitated in a short time in a small amount.

The amount of such a compound having a phenolic hydroxyl group added is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, based on 100 parts by weight of the polymer.

As the esterified quinonediazide compound (c) added to the present invention, a compound in which a sulfonic acid of naphthoquinonediazide is bound with an ester to a compound having a phenolic hydroxyl group is preferable. The compound having a phenolic hydroxyl group used here may be the same as or different from the compound having a phenolic hydroxyl group of (b). Examples of such compounds include Bis-Z and B
isP-EZ, TekP-4HBPA, TrisP-H
AP, TrisP-PA, BisOCHP-Z, Bis
P-MZ, BisP-PZ, BisP-IPZ, Bis
OCP-IPZ, BisP-CP, BisRS-2P,
BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC,
BIR-PC, BIR-PTBP, BIR-PCHP,
BIP-BIOC-F, 4PC, BIR-BIPC-
F, TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, methylenebisphenol, BisP-AP (trade name, Honshu Chemical Industry) Compounds of 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid introduced into a compound (such as manufactured by Co., Ltd.) by an ester bond can be exemplified as preferable compounds, but other compounds can also be used. .

When the molecular weight of the naphthoquinonediazide compound used in the present invention is more than 1000, the naphthoquinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the obtained film is lowered.
Problems such as deterioration of mechanical properties and adhesion may occur. From this point of view, the preferable molecular weight of the naphthoquinonediazide compound is 300 to 1
It is 000. More preferably, it is 350 to 800. The addition amount of such a naphthoquinonediazide compound is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polymer.

The inorganic particles of component (d) added to the present invention include, for example, aluminum complex, aluminum oxide particles, tin oxide-aluminum oxide composite particles, silicon oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles. Particles, tin oxide-silicon oxide composite particles, zirconium oxide-silicon oxide composite particles, tin complex, tin oxide particles, zirconium oxide-tin oxide composite particles, titanium complex, titanium oxide particles, tin oxide-titanium oxide composite particles, Silicon oxide-titanium oxide composite particles,
Examples thereof include zirconium oxide-titanium oxide composite particles, zirconium complex, zirconium oxide particles and the like. Of these, preferably, tin oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles,
Zirconium oxide-silicon oxide composite particles, etc., tin oxide particles, zirconium oxide-tin oxide composite particles, etc., titanium oxide particles, tin oxide-titanium oxide composite particles, silicon oxide-
Examples thereof include titanium oxide composite particles, zirconium oxide-titanium oxide composite particles, zirconium oxide particles and the like. Particularly preferred are tin oxide-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, titanium oxide particles, zirconium oxide-tin oxide composite particles, zirconium oxide-silicon oxide composite particles, and zirconium oxide particles.

The particle size of these inorganic particles is preferably 1 nm to 30 nm, particularly preferably 1 nm to 15 nm.
nm. When the particle size is from 1 nm to 30 nm, a predetermined pattern can be resolved by exposure and the composition has photosensitivity. On the other hand, when the thickness exceeds 30 nm, the light used for exposure is diffusely reflected by the particles, and a predetermined pattern cannot be resolved, resulting in no photosensitivity. The addition amount of these inorganic particles is preferably 50 to 500 parts by weight, and particularly preferably 60 to 300 parts by weight with respect to 100 parts by weight of the polymer. It is confirmed that when the addition amount is 50 parts by weight to 500 parts by weight with respect to 100 parts by weight of the polymer, both the refractive index and the transmittance (particularly 400 nm) are improved. On the other hand, if it is less than 50 parts by weight, both transparency and refractive index will not rise, and if it exceeds 500 parts by weight, both transparency and refractive index will be improved, but pattern processing will be difficult at all and it will not have photosensitivity.

These inorganic particles, even as simple particles,
It can also be used as composite particles. Furthermore, these inorganic particles can also be used as a mixture of one or more kinds.

Examples of commercially available compounds include "Optraque TR-50" which is a tin oxide-titanium oxide composite particle.
2 "," Optlake TR-504 ", silicon oxide-titanium oxide composite particles" Optlake TR-503 ", titanium oxide particles" Optlake TR-505 "((above, trade name, Catalysis Chemicals Co., Ltd. )), Zirconium oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particle sol (manufactured by Catalysts & Chemicals Co., Ltd.),
Examples thereof include tin oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.).

If necessary, a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate, an alcohol such as ethanol, or the like for the purpose of improving the wettability between the photosensitive resin composition and the substrate. Ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, other inorganic particles,
Alternatively, polyimide powder or the like can be added.

Further, in order to improve the adhesiveness to a base substrate such as a silicon wafer, a silane coupling agent or the like is added to the varnish of the photosensitive resin composition in an amount of 0.5 to 10% by weight, or the base substrate is used in such a manner. It can also be pretreated with a chemical solution.

When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane and an aluminum chelating agent are added in an amount of 0.5 to 10% by weight based on the polymer in the varnish. .

When the substrate is treated, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. The solution of 5 to 20% by weight is surface-treated by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, then 50 to 300 degrees Celsius
The reaction between the substrate and the above coupling agent proceeds by applying the temperature up to.

Next, a method for forming a resin pattern using the photosensitive resin composition of the present invention will be described.

The photosensitive resin composition is applied onto the substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but the substrate is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The coating thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but the coating thickness after drying is usually 0.1 to 150.
It is applied to have a thickness of μm.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably carried out using an oven, a hot plate, infrared rays or the like in the range of 50 to 150 ° C. for 1 minute to several hours.

Next, the photosensitive resin composition film is exposed to actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays, but in the present invention, i rays (365 nm), h rays (405 nm), and g rays (43 nm) of a mercury lamp are used.
6 nm) is preferably used.

Formation of the pattern of the photosensitive resin is accomplished by removing the exposed portion with a developing solution after the exposure. As the developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl Aqueous solutions of compounds showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred. Further, in some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolaclone, or dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination of several kinds. Good. After development, rinse with water. Also here, rinse treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water. (A)
The component is a homopolymer polymer of a radically polymerizable monomer having a phenolic hydroxyl group or a carboxyl group, a copolymer polymer of the radically polymerizable monomer and other radically polymerizable monomers, a novolak resin, In the case of a resole resin, after development, a temperature of 170 to 300 ° C. is applied to convert it into a heat resistant resin film with improved heat resistance for use. On the other hand, when the component (a) is a polymer whose main component is the structural unit represented by the general formula (1), 20
It is used after being converted to a heat resistant resin film by applying a temperature of 0 to 500 degrees.

When a titanium compound is contained in the heat-resistant resin film for conversion, ultraviolet rays are applied to the unexposed area of 100 mJ / cm ² to 400 after development and before applying temperature.
When irradiated with 0 mJ / cm ² and then converted into a heat-resistant resin film by applying a temperature, the irradiated heat-resistant resin film has an increased transparency in the range of 400 nm to 500 nm, as compared with the case of no irradiation of ultraviolet rays. This improvement in transparency is due to the photocatalytic reaction of the contained titanium oxide.

This heat treatment is carried out for 5 minutes to 5 hours while the temperature is selected and the temperature is raised stepwise or a certain temperature range is selected and the temperature is continuously raised. As an example, 130 degrees, 200
And heat treatment at 350 degrees for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.

The resin film formed from the photosensitive composition according to the present invention is used for a high refractive index interlayer film for optical elements, microlenses and the like.

[0061]

The present invention will be described below with reference to examples and techniques, but the present invention is not limited to these examples. In addition, the evaluation of the photosensitive resin composition in the examples was performed by the following methods.

Preparation of Photosensitive Resin Film A positive photosensitive resin composition (hereinafter referred to as varnish) was applied onto a 6-inch silicon wafer and a 6-inch glass substrate so that the film thickness after prebaking would be 1.6 μm. Then, hot plate (S manufactured by Dainippon Screen Mfg. Co., Ltd.)
CW-636) was used for prebaking at 120 ° C. for 3 minutes to obtain a photosensitive resin film.

Method of measuring film thickness Lambda Ace STM-6 manufactured by Dainippon Screen Mfg. Co., Ltd.
02 was used to measure the film thickness of the photosensitive resin film with a refractive index of 1.64.

Exposure exposure machine (i-line stepper NSR-175 manufactured by Nikon Corporation)
5-i7A), set the reticle with the pattern cut, and with an exposure dose of 300 mJ / cm ² (intensity of 365 nm).
i-line exposure was performed.

Development Using a developing device SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd., a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed at 50 rpm for 10 seconds. After that, leave still for 20 seconds at 0 rotation, rinse with water at 400 rotations,
It was shaken off at 3000 rpm for 10 seconds and dried.

Confirmation of Photosensitivity After exposure and development, the photosensitivity was confirmed by confirming that a 5 μm square was opened.

Preparation of Heat-Resistant Resin Film The positive photosensitive resin film on the exposed and developed 6-inch silicon wafer and 6-inch glass substrate was exposed using an exposure machine (Canon Co., Ltd. contact aligner PLA501F). UV intensity of 10 mW / cm ² (converted to 365 nm) for a predetermined time, UV full wavelength exposure (main wavelength: 33
0 nm, 365 nm, 405 nm, 436 nm) or without exposure, and then using a nitrogen atmosphere (oxygen concentration 300 ppm) in a clean oven (CLH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) If it is composed of radical polymer and novolac resin, it is heated and cured at 250 ° C for 30 minutes, otherwise, 170 ° C for 30 minutes, and further at 320 ° C for 60 minutes.
Minute heating and curing were performed to obtain a heat resistant resin film.

Method for measuring film thickness Lambda Ace STM-6 manufactured by Dainippon Screen Mfg. Co., Ltd.
02 was used to measure the film thickness of the heat resistant resin film with a refractive index of 1.78.

Calculation of transmittance Using a UV-visible spectrophotometer UV-260 (manufactured by Shimadzu Corporation) for a 1.0 μm heat-resistant resin film formed on a 6-inch glass substrate, 400 nm and 500 nm Membrane permeability was measured.

Measurement of Refractive Index A prism coupler (Metrico) was used for a 1.0 μm heat-resistant resin film formed on a 6-inch silicon wafer.
n (manufactured by N. Co., Ltd.), 633 nm (He-
The refractive index (TM) in the direction perpendicular to the film surface was measured using a Ne laser.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (a) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) under a stream of dry nitrogen.
18.3 g (0.05 mol) and allyl glycidyl ether 34.2 g (0.3 mol) were added to gamma butyrolactone 1
It was dissolved in 00 g and cooled to -15 ° C. 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma-butyrolactone was added dropwise thereto so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, 4 at 0 ℃
Reacted for hours. The solution was concentrated with a rotary evaporator and poured into 1 l of toluene to obtain an acid anhydride (a).

[0072]

[Chemical 10]

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 18.3 g (0.05 mol) BAHF was added to acetone 100
The solution was dissolved in 1 ml of propylene oxide (17.4 g, 0.3 mol) and cooled to -15 ° C. A solution of 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride dissolved in 100 ml of acetone was added dropwise thereto. After the dropping is completed,
The reaction was carried out at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and dried in vacuum at 50 ° C.

30 g of the solid was placed in a 300 ml stainless autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here by a balloon to carry out the reduction reaction at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and the mixture was concentrated with a rotary evaporator to obtain a diamine compound (b). The obtained solid was used for the reaction as it was.

[0075]

[Chemical 11]

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (c) 2-amino-4-nitrophenol 15.4 g (0.1
50 ml of acetone, 30 g of propylene oxide
It was dissolved in (0.34 mol) and cooled to -15 ° C. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic chloride in 60 ml of acetone was gradually added dropwise. After the dropping was completed, the reaction was carried out at -15 ° C for 4 hours. Then, the temperature was returned to room temperature and the generated precipitate was collected by filtration.

This precipitate was dissolved in 200 ml of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon containing hydrogen gas was attached to this, and stirring was continued at room temperature until the hydrogen gas balloon did not shrink further, and the mixture was further stirred for 2 hours with the hydrogen gas balloon attached. After the stirring was completed, the palladium compound was removed by filtration, and the solution was concentrated by a rotary evaporator until the volume became half. Ethanol is added here to perform recrystallization,
Crystals of the desired compound were obtained.

[0078]

[Chemical 12]

Synthesis Example 4 Synthesis of hydroxyl group-containing diamine (d) 2-amino-4-nitrophenol 15.4 g (0.1
Mol) acetone 100 ml, propylene oxide 1
It was dissolved in 7.4 g (0.3 mol) and cooled to -15 ° C. 20.4 g of 4-nitrobenzoyl chloride here
A solution of (0.11 mol) in 100 ml of acetone was gradually added dropwise. After the dropping was completed, the reaction was carried out at -15 ° C for 4 hours. Then, the temperature was returned to room temperature and the generated precipitate was collected by filtration. Then, crystals of the target compound were obtained in the same manner as in Synthesis Example 2.

[0080]

[Chemical 13]

Synthesis Example 5 Synthesis of Quinonediazide Compound (1) Under a dry nitrogen stream, 7.21 g (0.05
Mol) and 13.43 g (0.05 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature. Here, triethylamine 5.06 mixed with 50 g of 1,4-dioxane
Using g, a quinonediazide compound (1) was obtained in the same manner as in Synthesis Example 5.

[0082]

[Chemical 14]

Synthesis Example 6 Synthesis of quinonediazide compound (2) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5 under a dry nitrogen stream.
-Naphthoquinone diazide sulfonyl chloride 40.2
8 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 1,4-dioxane 5
Using 15.18 g of triethylamine mixed with 0 g of quinonediazide compound (2) in the same manner as in Synthesis Example 5.
Got

[0084]

[Chemical 15]

Synthesis Example 7 Synthesis of quinonediazide compound (3) 4-isopropylphenol 6.81 under a stream of dry nitrogen.
g (0.05 mol) and 5-naphthoquinone diazide sulfonyl chloride 13.43 g (0.05 mol) 1,4
-Dissolved in 450 g dioxane and brought to room temperature. Here, 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane was used, and was used in the same manner as in Synthesis Example 5 to obtain a quinonediazide compound (3).

[0086]

[Chemical 16]

Synthesis Example 8 Synthesis of quinonediazide compound (4) 11.41 g of bisphenol A under a stream of dry nitrogen
(0.05 mol) and 5-naphthoquinone diazide sulfonyl chloride (26.86 g, 0.1 mol) were dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature. here,
Using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (4) was obtained in the same manner as in Synthesis Example 8.

[0088]

[Chemical 17]

Similarly, the compounds having a phenolic hydroxyl group used in Examples and Comparative Examples are shown below.

[0090]

[Chemical 18]

Example 1 4.1 g (0.0205 mol) of 4,4'-diaminodiphenyl ether and 1,3-bis (3-) under a stream of dry nitrogen.
Aminopropyl) tetramethyldisiloxane 1.24 g
(0.005 mol) of N-methyl-2-pyrrolidone (N
MP) was dissolved in 50 g. 21.4 g (0.03 mol) of hydroxy group-containing acid anhydride (a) was added to NMP14.
g, and reacted at 20 ° C. for 1 hour, then 5
The reaction was carried out at 0 ° C for 4 hours. Then, a solution prepared by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 50 ° C. for 3 hours.

In 40.0 g of the obtained solution, 2 g of the naphthoquinonediazide compound (1) shown above, 1 g of Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group, and a particle diameter of 5 nm were used. "Optlake TR-502" (trade name, manufactured by Catalysts & Chemicals Co., Ltd.) 26
g was added to obtain a varnish A of the positive photosensitive resin composition.
Using the obtained varnish, as described above, a positive type photosensitive resin film is prepared on a silicon wafer and a glass substrate, exposed, developed and thermally cured, and the varnish's photosensitivity, cured film transmittance and refractive index are obtained. Was evaluated.

Example 2 Diamine (b) 1 obtained in Synthesis Example 2 under a stream of dry nitrogen
3.6 g (0.0225 mol), 4 as an end-capping agent
-Ethynylaniline (trade name: P-APAC, manufactured by Fuji Photo Film Co., Ltd.) (0.29 g, 0.0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Hydroxy group-containing acid anhydride (a) 17.5
g (0.025 mol) was added together with 30 g of pyridine, and the mixture was reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 l of water, and the polymer solid precipitate was collected by filtration.
The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours.

10 g of the polymer solid thus obtained
2 g of the naphthoquinonediazide compound (2) shown above and BisRS-2P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 2 as a compound having a phenolic hydroxyl group
g, vinyltrimethoxysilane 1 g, and particle size 5 nm
50 g of "Optlake TR-502" (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) was dissolved in 30 g of gamma butyrolactone to obtain a varnish B of a positive photosensitive resin composition.
Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

Example 3 20.78 g (0.055 mol) of the diamine compound (c) obtained in Synthesis Example 3 under a stream of dry nitrogen, 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.
24 g (0.005 mol) was dissolved in 50 g NMP. Here, 13.95 g (0.045 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid anhydride
Was added together with 21 g of NMP and reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. After stirring at 50 ° C. for 2 hours, a solution prepared by diluting 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 50 ° C. for 3 hours.

1.6 g of the naphthoquinonediazide compound (3) shown above was added to 30 g of the obtained solution, and TrisP-PA (trade name, as a compound having a phenolic hydroxyl group).
Honshu Chemical Industry Co., Ltd.) 0.8g, particle size 10nm "
85 g of OPTRAY TR-505 "(trade name, manufactured by Catalysts & Chemicals Industry Co., Ltd.) was dissolved to obtain a varnish C of a positive type photosensitive resin composition. The varnish thus obtained was used to obtain silicon as described above. A positive photosensitive resin film was formed on a wafer and a glass substrate, exposed, developed and thermally cured, and the varnish's photosensitivity, the transmittance and the refractive index of the heat resistant resin film were evaluated.

Example 4 6.08 g (0.025 mol) of the diamine compound (d) obtained in Synthesis Example 4 and 4.21 g (0.021 mol) of 4,4'-diaminodiphenyl ether were obtained under a dry nitrogen stream. 0.806 g (0.00325 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was dissolved in 70 g of NMP. Hydroxyl group-containing acid anhydride (a) 24.99 g (0.035 mol), 3,3 ′,
4,4′-Biphenyltetracarboxylic acid dianhydride 4.4
1 g (0.015 mol) was added at room temperature together with 25 g of NMP, and the mixture was stirred at room temperature for 1 hour and then at 50 ° C. for 2 hours. Then, 17.6 g of glycidyl methyl ether
(0.2 mol) diluted with 10 g of NMP was added,
The mixture was stirred at 70 ° C for 6 hours.

In 40 g of this polymer solution, 2.5 g of the naphthoquinonediazide compound (4) shown above and BIR-PC (trade name, as a compound having a phenolic hydroxyl group)
Asahi Organic Materials Co., Ltd. 2g, particle size 8nm "Optrake TR-503" (trade name, Catalyst Kasei Co., Ltd.)
150 g) was dissolved to obtain a varnish D of a positive photosensitive resin composition. Using the varnish obtained, as described above,
A positive photosensitive resin film was formed on a silicon wafer and a glass substrate, exposed, developed and thermally cured, and the varnish's photosensitivity, the transmittance and the refractive index of the heat resistant resin film were evaluated.

Example 5 16.93 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a stream of dry nitrogen
(0.04625 mol) N-methyl-2-pyrrolidone (NMP) 50 g, glycidyl methyl ether 26.4
g (0.3 mol) and the temperature of the solution was cooled to -15 ° C. A solution prepared by dissolving 7.38 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride and 5.08 g (0.025 mol) of isophthalic acid dichloride in 25 g of gamma-butyrolactone had an internal temperature of 0 ° C.
It was dropped so that it would not exceed. 6 hours after completion of dropping
Stirring was continued at ° C.

After completion of the reaction, the solution was poured into 3 l of water to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours.

Polymer powder 10 thus obtained
The naphthoquinonediazide compound (2)
2 g, Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 1
g, 250 g of "Optrake TR-504" (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 5 nm, 30 g of NMP
To obtain a varnish E of the positive photosensitive resin composition. Using the obtained varnish, as described above, a positive photosensitive resin film is produced on a silicon wafer and a glass substrate,
After exposure, development and heat curing, the photosensitivity of the varnish and the transmittance and refractive index of the heat resistant resin film were evaluated.

Example 6 Diamine (b) 1 obtained in Synthesis Example 2 under a stream of dry nitrogen
3.6 g (0.0225 mol), 4 as an end-capping agent
-(3-aminophenyl) -2-methyl-3-butyne-
2-Ol (trade name: M-APACB, manufactured by Fuji Photo Film Co., Ltd.) 0.44 g (0.0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP).
17.5 g of hydroxy group-containing acid anhydride (a)
(0.025 mol) with 30 g of pyridine,
The reaction was carried out at 60 ° C for 6 hours. After the reaction was completed, the solution was added with 2 l of water.
The polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours.

10 g of the polymer solid thus obtained
2 g of the naphthoquinonediazide compound (2) shown above, and 2 g of BIR-PC (trade name, manufactured by Asahi Organic Materials Co., Ltd.) as a compound having a phenolic hydroxyl group,
1 g of vinyltrimethoxysilane, 100.0 g of "Optlake TR-504" (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 5 nm, and 30 g of gammabutyrolactone.
To obtain a varnish F of the positive photosensitive resin composition. Using the obtained varnish, as described above, a positive photosensitive resin film is produced on a silicon wafer and a glass substrate,
After exposure, development and heat curing, the photosensitivity of the varnish and the transmittance and refractive index of the heat resistant resin film were evaluated.

Example 7 Varnish B of the positive type photosensitive resin composition obtained in Example 2
As described above, a photosensitive polyimide precursor film was prepared, exposed and developed on a silicon wafer and a glass substrate, and the unexposed area was irradiated with 300 mJ / cm ² (365 nm).
(Converted) and exposed to all wavelengths of ultraviolet rays, and then thermally cured, and evaluated for photosensitivity of varnish, transmittance and refractive index of heat-resistant resin film.

Example 8 Varnish F of the positive type photosensitive resin composition obtained in Example 6
As described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, and developed, and an unexposed portion is irradiated with 2000 mJ / cm ² (converted to 365 nm).
UV exposure was performed on all wavelengths, and then heat curing was performed to evaluate the photosensitivity of the varnish, the transmittance and the refractive index of the heat resistant resin film.

Example 9 "Optolaque TR-50 having a particle size of 5 nm in Example 2"
2 "(trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.)
Change from g to 300 g, and otherwise perform the same as in Example 2,
Varnish G of the positive type photosensitive resin composition was obtained. Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

Example 10 "Optlake TR-50 having a particle size of 5 nm in Example 2"
2 "(trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.)
The procedure of Example 2 was repeated except that the amount of g was changed to 10 g to obtain a varnish H of the positive photosensitive resin composition. Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

Example 11 "Optolaque TR-50 having a particle size of 5 nm in Example 1"
2 "(trade name, manufactured by Catalysts & Chemicals Co., Ltd.) with a particle size of 5 nm
Zirconium oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.)
In the same manner as in Example 1 except for the above, to obtain a varnish M of the positive photosensitive resin composition. Using the obtained varnish, as described above, a positive photosensitive resin film is produced on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the photosensitivity of the varnish, the transmittance of the heat-resistant resin film, and The refractive index was evaluated.

Example 12 "Optolaque TR-50 having a particle diameter of 10 nm obtained in Example 3"
5 "(trade name, manufactured by Catalysts & Chemicals Co., Ltd.) with a particle size of 25n
m was changed to the tin oxide-zirconium oxide composite particle sol (manufactured by Catalysts & Chemicals Industry Co., Ltd.), and otherwise the same as in Example 3 to obtain a varnish N of the positive photosensitive resin composition. Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

Example 13 "Optolaque TR-50 having a particle diameter of 5 nm of Example 2"
2 "(trade name, manufactured by Catalysts & Chemicals Co., Ltd.) with a particle size of 15n
In the same manner as in Example 2 except that the aluminum oxide-titanium oxide composite particle sol of m was changed, a varnish P of the positive photosensitive resin composition was obtained. Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

Example 14 16.93 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane obtained in Example 5 was added to 1 part.
Changed to 8.3g (0.05mol) and further particle size 5n
m "Optrake TR-504" (trade name, manufactured by Catalysts & Chemicals Co., Ltd.) was changed to tin oxide particles having a particle diameter of 10 nm (manufactured by Kojundo Chemical Laboratory Co., Ltd.). The same procedure as in 5 was performed to obtain a varnish Q of the positive photosensitive resin composition. Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

Example 15 57 g (0.6 mol) of meta-cresol, 38 g (0.4 mol) of para-cresol, 75.5 g of a 37% by weight formaldehyde aqueous solution (0.93 mol of formaldehyde), and oxalic acid diacid under a stream of dry nitrogen. Hydrate 0.63 g (0.
(005 mol) and 264 g of methyl isobutyl ketone were charged and then immersed in an oil bath to carry out polycondensation reaction for 4 hours while refluxing the reaction solution. Then, the temperature of the oil bath is raised over 3 hours, and then the pressure in the flask is set to 30 to 50.
Decompressed to mmHg to remove volatile matter and dissolved,
The resin was cooled to room temperature to obtain 85 g of an alkali-soluble novolak resin polymer solid.

10 g of the novolak resin thus obtained
2 g of the naphthoquinonediazide compound (2) shown above and BisRS-2P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 2 as a compound having a phenolic hydroxyl group
g, vinyltrimethoxysilane 1 g, and particle size 5 nm
50 g of "Optlake TR-502" (trade name, manufactured by Catalysts & Chemicals Industry Co., Ltd.) was dissolved in 30 g of gamma-butyrolactone to obtain a varnish R of a positive photosensitive resin composition.
Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

Example 16 Under a dry nitrogen stream, 5 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 25 g of para-hydroxy-α-methylstyrene, 40 g of acrylic acid, 30 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate was charged and dissolved, and the mixture was stirred and reacted at 70 ° C. for 4 hours. After completion of the reaction, the alkali-soluble radically polymerized polymer solution was added to 1000 g of hexane, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours.

10 g of the polymer solid thus obtained
2 g of the naphthoquinonediazide compound (1) shown above, 1 g of Bis-Z (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) as a compound having a phenolic hydroxyl group, and "Optrake TR-505" having a particle diameter of 10 nm. 47 g (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) was added to obtain a varnish S of a positive photosensitive resin composition. Using the obtained varnish, as described above, a positive type photosensitive resin film is prepared on a silicon wafer and a glass substrate, exposed, developed and thermally cured, and the varnish's photosensitivity, cured film transmittance and refractive index are obtained. Was evaluated.

COMPARATIVE EXAMPLE 1 "Optrake TR-50 having a particle diameter of 5 nm of Example 1"
2 "(trade name, manufactured by Catalysts & Chemicals Industry Co., Ltd.) was used, and the same procedure as in Example 1 was carried out to obtain a varnish I of the positive photosensitive resin composition. As described above, a positive type photosensitive resin film was prepared on a silicon wafer and a glass substrate, exposed, developed and thermally cured, and the varnish's photosensitivity, the transmittance and the refractive index of the heat resistant resin film were evaluated.

COMPARATIVE EXAMPLE 2 "Optrake TR-50 having a particle diameter of 5 nm of Example 2"
2 ”(trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle size of 60 n
m “Optrake TR-506” (trade name, manufactured by Catalysts & Chemicals Co., Ltd.), and otherwise the same as in Example 2,
Varnish J of a positive type photosensitive resin composition was obtained. Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

COMPARATIVE EXAMPLE 3 "Optlake TR-50 having a particle diameter of 10 nm of Example 3"
5 "(trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 35n
m “Optrake TR-509” (trade name, manufactured by Catalysts & Chemicals Co., Ltd.), and otherwise the same as in Example 3,
Varnish K of the positive type photosensitive resin composition was obtained. Using the obtained varnish, as described above, a positive photosensitive resin film is formed on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity and heat-resistant resin film transmittance and The refractive index was evaluated.

Comparative Example 4 16.93 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane of Example 5 was used as 1 part.
Change to 8.3g (0.05mol), particle size 5nm "
A varnish L of a positive photosensitive resin composition was obtained in the same manner as in Example 5, except that OPTRAY TR-504 "(trade name, manufactured by Catalysts & Chemicals Co., Ltd.) was not used. As described above, a positive photosensitive resin film was prepared on a silicon wafer and a glass substrate, exposed, developed, and heat-cured, and the varnish's photosensitivity, the heat-resistant resin film's transmittance and refractive index were evaluated. I went.

The evaluation results of Examples 1 to 16 and Comparative Examples 1 to 4 are shown in Table 1.

[0121]

[Table 1]

[0122]

INDUSTRIAL APPLICABILITY According to the present invention, a positive photosensitive resin composition which can be developed with an aqueous alkali solution and is excellent in transparency and refractive index can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA02 AA03 AA04 AB14 AC01                       AD03 BE01 CB25 CB26 CB28                       CB29 CB43 CB45 CB55 CB56                       CC20 FA17                 4J001 DA01 DC05 DC08 DD01 DD04                       DD05 DD07 DD08 EB07 EB08                       EB14 EB34 EB36 EB37 EB46                       EB57 EB58 EB60 EB69 EC14                       EC24 EC27 EC33 EC36 EC44                       EC66 EC70 EC74 EC75 FA01                       FB03 FB06 FC03 JA01 JA20

Claims (10)

[Claims] 1. An (a) alkali-soluble polymer, and (b)
A compound having a phenolic hydroxyl group, (c) an esterified quinonediazide compound, and (d) at least one selected from an aluminum compound, a silicon compound, a tin compound, a titanium compound, and a zirconium compound.
A positive photosensitive resin composition comprising inorganic particles of m to 30 nm. 2. The positive photosensitive resin composition according to claim 1, wherein the component (a) is a novolac resin and / or a resole resin. 3. A component (a) is a homopolymer polymer of a radical-polymerizable monomer having a phenolic hydroxyl group or a carboxyl group and / or the radical-polymerizable monomer and other radical-polymerizable monomers other than the above. The positive photosensitive resin composition according to claim 1, which is a copolymer polymer of-. 4. The positive photosensitive resin composition according to claim 1, wherein the component (a) is a polymer containing a structural unit represented by the general formula (1) as a main component. [Chemical 1] (In the formula, R ¹ has 2 or more carbon atoms.
A divalent to octavalent organic group, R ² represents a divalent to hexavalent organic group having at least 2 carbon atoms, and R ³ represents hydrogen or an organic group having 1 to 20 carbon atoms. n is an integer from 10 to 100000, m is an integer from 0 to 2,
p and q are integers from 0 to 4. However, p + q> 0
Is. ) 5. R ¹ (COOR ³ ) m (O of the general formula (1)
H) p is represented by General formula (2), The positive photosensitive resin composition of Claim 4 characterized by the above-mentioned. [Chemical 2] (R ⁴ and R ⁶ represent a divalent to tetravalent organic group selected from 2 to 20 carbon atoms, and R ⁵ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. R ⁷ and R ^{8 each} represent hydrogen and / or an organic group having 1 to 20 carbon atoms, o and s each represent an integer of 0 to 2, and r represents an integer of 1 to 4.) 6. The positive photosensitive resin composition according to claim 4, wherein R ² (OH) q of the general formula (1) is represented by the general formula (3). [Chemical 3] (R ⁹ and R ¹¹ represent trivalent to tetravalent organic groups having a hydroxyl group selected from 2 to 20 carbon atoms, and R ¹⁰ represents 2 to 30 carbon atoms.
A divalent organic group selected from the following is shown. t and u are integers of 1 or 2. ) 7. The positive photosensitive resin composition according to claim 4, wherein R ² (OH) q of the general formula (1) is represented by the general formula (4). [Chemical 4] (.V R ^12, R ¹⁴ represents a divalent organic group of up to 20 carbon atoms, R ¹³ is showing a trivalent to hexavalent organic group having a hydroxyl group selected from 3-20C Represents an integer from 1 to 4.) 8. The positive photosensitive resin composition according to claim 4, wherein R ² (OH) q in the general formula (1) is represented by the general formula (5). [Chemical 5] (R ¹⁵ represents a divalent organic group selected from 2 to 20 carbon atoms, and R ¹⁶ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. W is 1 Indicates an integer of up to 4). 9. A relief pattern of a heat-resistant resin formed by irradiating the positive photosensitive resin composition according to claim 1 with ultraviolet rays and then heating. 10. An optical element comprising the positive photosensitive resin composition according to claim 1.