JP2001281861A - Positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition developable with an alkaline aqueous solution, having high sensitivity and capable of easily forming a patterned thin film excellent in various characteristics such as flatness, resolution, developability, heat and chemical resistances, adhesion to a substrate, transparency and insulating property, and to provide a photosensitive resin composition capable of easily forming a patterned thin film excellent in low dielectric property as well as in the above various characteristics and a pattern forming method using the composition. SOLUTION: Each of the photosensitive resin compositions is a positive type photosensitive resin composition containing at least an alkali-soluble acrylic resin having an unsaturated ethylene group, a 1,2-naphthoquinonediazido- containing compound, a crosslinker and a silane coupling agent. In the pattern forming method in which the positive type photosensitive resin composition is successively subjected to application, 1st exposure, development, 2nd exposure and heating, the quantity of light in the 2nd exposure is 2-15 times that in the 1st exposure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition capable of forming a micropattern structure, and more particularly, to a semiconductor integrated circuit (IC) and a liquid crystal display (LCD). As a positive resist for forming a mask for manufacturing a circuit such as a thin film transistor (TFT) circuit, and an interlayer insulating film such as a liquid crystal display element, an integrated circuit element, and a solid-state imaging element, and a microlens such as a solid-state imaging element. The present invention relates to a positive photosensitive resin composition which is also suitable as a material for forming a permanent film and a pattern forming method using the same.

[0002]

2. Description of the Related Art Generally, liquid crystal display devices, integrated circuit devices,
In the manufacture of electronic components such as solid-state imaging devices, a protective film for preventing deterioration and damage, a flattening film for flattening the device surface, an insulating film for maintaining electrical insulation, and the like are provided. I have. In a TFT type liquid crystal display or an integrated circuit device, an interlayer insulating film is used to insulate between wirings arranged in layers. Generally, TFT for LCD,
In the manufacture of electronic components such as ICs, there is a strong demand for resists having high resolution of submicron or less and high sensitivity.

For example, a resist pattern formed on an IC silicon wafer by a wet etching method is required to have adhesiveness to a substrate and chemical resistance not to be affected by an etchant. If an ion implantation process is added,
Heat resistance that can withstand high-temperature heating is required. Further TFT
In order to use it as an insulating material, transparency is also required. However, there is a drawback that since the color is changed by performing the heat treatment, it cannot be used for an optical material such as a protective film of a liquid crystal color filter or a micro lens.

The formation of an interlayer insulating film requires a large number of steps, and various characteristics required for the interlayer insulating film, namely, flatness,
It is difficult to ensure good high resolution, developability, heat resistance, chemical resistance, adhesion to the substrate, transparency, insulation, etc., and a photosensitive resin composition that satisfies all these characteristics There was no. In addition, low dielectric properties are required for interlayer insulating films in order to suppress the occurrence of crosstalk with the increase in device density, but conventional photosensitive resin compositions have various properties and low dielectric properties. It was not fully satisfactory in terms of compatibility with sex.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to develop an alkaline aqueous solution, to have high sensitivity, and to obtain flatness, high resolution, developability, heat resistance, chemical resistance, and adhesion to a substrate. Resin composition that can easily form a patterned thin film having excellent properties such as transparency, transparency, and insulating properties. An object of the present invention is to provide a photosensitive resin composition capable of easily forming a patterned thin film having excellent dielectric properties and a pattern forming method using the same.

[0006]

According to the present invention, a photosensitive resin composition having the following constitution and a pattern forming method using the same are provided, and the above object of the present invention is achieved. (1) A positive photosensitive resin composition comprising at least an alkali-soluble acrylic resin having an unsaturated ethylene group, a compound containing a 1,2-naphthoquinonediazide group, a crosslinking agent, and a silane coupling agent. (2) The positive photosensitive resin composition according to the above (1), further comprising a fluorine-based surfactant. (3) The positive photosensitive resin composition as described in (1) or (2) above, wherein an alkali-soluble acrylic resin having no unsaturated ethylene group is used in combination. (4) The positive photosensitive resin composition according to any one of the above (1) to (3), wherein the crosslinking agent is a melamine-based compound. (5) The positive photosensitive resin composition according to any one of the above (1) to (4), wherein the crosslinking agent is an epoxy compound. (6) The positive photosensitive resin composition according to any one of the above (1) to (5), which contains a fluorine compound. (7) The positive photosensitive resin composition according to the above (6), wherein the fluorine compound is an epoxy compound. (8) In the step of sequentially performing the application, the first exposure, the development, the second exposure, and the heat treatment with the positive photosensitive resin composition according to any one of the above (1) to (7), A pattern forming method, wherein the amount of exposure light is 2 to 15 times that of the first exposure.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive resin composition of the present invention will be described in detail. First, each component blended in the photosensitive resin composition of the present invention will be described. [I] An alkali-soluble acrylic resin having an unsaturated ethylene group (hereinafter, also referred to as “acrylic resin (A)”)

The acrylic resin (A) comprises a polymer or copolymer of at least one of acrylic acid and methacrylic acid (hereinafter referred to as (meth) acrylic acid) and a functional group having an unsaturated ethylene group. It can be synthesized by a reaction with a compound via a carboxyl group of (meth) acrylic acid. The acrylic resin (A) is made of (meth) acrylic acid and any monomer copolymerizable therewith, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate , N-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate,
tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate,
Benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate,
At least the carboxyl group of (meth) acrylic acid between a copolymer of at least one of isobornyl methacrylate, glycidyl acrylate, glycidyl methacrylate, styrene, acrylamide, methacrylamide, and acrylonitrile and a functional compound having an unsaturated ethylene group Through the reaction, an unsaturated ethylene group can be introduced into the copolymer. Here, the functional compound may be bonded to a functional group bonded to a monomer copolymerizable with (meth) acrylic acid, for example, a carboxyl group, a hydroxyl group, an amino group, or the like. Here, the unsaturated ethylene group means a CH ₂ ＣＨCH— group or a group in which one or more of its bonded hydrogen atoms is substituted with a substituent such as an alkyl group. The functional compound having an unsaturated ethylene group is preferably CH ₂ ＣＨCH (CH ₂ ) _n R (R
Is a functional group such as a hydroxyl group, an amino group and an epoxy group. n is an integer of 1 to 5, preferably 1 or 2. ). The acrylic resin (A) preferably has an unsaturated ethylene group in the range of 1 to 70 mol% based on the monomer unit constituting the acrylic resin (A). The acrylic resin (A) is a monomer having an unsaturated ethylene group copolymerizable with at least one of acrylic acid and methacrylic acid, and other copolymerizable monomers such as methyl acrylate. Can also be synthesized by copolymerization with a monomer or the like. This acrylic resin (A)
The mass average molecular weight is preferably from 1,000 to 100,000, more preferably from 3000 to 70,000.
It is. If the weight average molecular weight is too low, the film-forming ability is poor, and the film will be very thin during development. On the other hand, if the weight average molecular weight is too high, the development time will be long, which may adversely affect the substrate.

The amount of the acrylic resin (A) is from 35 to 95 parts by weight based on 100 parts by weight of the total of the acrylic resin (A), the 1,2-naphthoquinonediazide group-containing compound, and the crosslinking agent. It is preferable to mix them, more preferably 4
5 to 85 parts by mass. If the amount is too low, the transparency, insulating properties and coating properties deteriorate, while if the amount is too high, the sensitivity decreases and curing failure occurs, which is not preferable. In the photosensitive resin composition of the present invention, an alkali-soluble acrylic resin having no unsaturated ethylene group in the acrylic resin (A) can be used in combination. The resin that can be used in combination is also referred to as an acrylic resin (a). Examples of the acrylic resin (a) include the above-mentioned acrylic resin which is reacted with a functional compound having an unsaturated ethylene group to produce the acrylic resin (A), an ester thereof, and the like. The acrylic resin (a) is usually 0% relative to the acrylic resin (A).
To 50% by mass, preferably 0 to 30% by mass.

[II] 1,2-Naphthoquinonediazide group-containing compound As the 1,2-naphthoquinonediazide group-containing compound used in the present invention, 1,2-naphthoquinonediazidesulfonic acid ester is used. As this ester, a compound in which all or a part of the hydroxyl groups of the polyhydric phenol is esterified with 1,2-naphthoquinonediazidosulfonic acid can be used.
Compounds in which 化合物 100% are esterified with 1,2-naphthoquinonediazidosulfonic acid can be used. Examples of the 1,2-naphthoquinonediazide group-containing compound include, for example,
2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4, 1,2 of trihydroxybenzophenone such as 6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester -Naphthoquinonediazidosulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazido-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1, Two
-Naphthoquinonediazide-5-sulfonic acid ester, 2,3,
4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2, 3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4 '-Tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquino Tetrahydroxy benzophenone, such as diazide-5-sulfonic acid ester 1,2
Naphthoquinonediazidesulfonic acid ester, 2,3,4,2 ',
6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 1,2-Naphthoquinonediazidosulfonic acid ester of pentahydroxybenzophenone, 2,4,6,3 ', 4'5'-hexahydroxybenzophenone
-1,2-naphthoquinonediazide-4-sulfonic acid ester,
2,4,6,3 ', 4'5'-hexahydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,
3 ', 4'5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3', 4 '
1,2-naphthoquinonediazidosulfonic acid ester of hexahydroxybenzophenone, such as 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,4'-dihydroxyphenyl) methane-1,2 -Naphthoquinonediazide-4-sulfonic acid ester, bis (2,4'-dihydroxyphenyl) methane-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, bis (p
-Hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane- 1,2
-Naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2 -Naphthoquinonediazide-4-
Sulfonate, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonate, bis (2,3,4-trihydroxyphenyl) methane-1,2- Naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2
-Naphthoquinonediazide-5-sulfonic acid ester, 2,2-
Bis (2,3,4-trihydroxyphenyl) propane-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2, 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3- Phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-
Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-
Sulfonate, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate, bis (2,5-dimethyl-4-hydroxyphenyl)-
2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-
(Hydroxyphenyl) -2-hydroxyphenylmethane-
1,2-naphthoquinonediazide-5-sulfonic acid ester,
3,3,3 ', 3'-tetramethyl-1,1'-spiroindene-5,6,7,
5 ', 6', 7'-Hexanol-1,2-naphthoquinonediazide-4-
Sulfonate, 3,3,3 ', 3'-tetramethyl-1,1'-
Spiroindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-tri Hydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester 1,2-naphthoquinonediazidosulfonic acid esters of (polyhydroxyphenyl) alkanes.

These 1,2-naphthoquinonediazide group-containing compounds can be used alone or in combination of two or more. The compound containing a 1,2-naphthoquinonediazide group as described above can be prepared, for example, by reacting a halide of 1,2-naphthoquinonediazidesulfonic acid with a corresponding polyhydric phenol (polyhydric hydroxy compound) in the presence of a base catalyst.
By esterification with In such an esterification reaction, it is desirable that the halide of 1,2-naphthoquinonediazidosulfonic acid is usually used in an amount of 1.0 to 1.2 mol per 1 mol of the hydroxyl group of the hydroxy compound.

The 1,2-naphthoquinonediazide group-containing compound is usually used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the acrylic resin (A) in the photosensitive resin composition according to the present invention.
Preferably, it is contained in an amount of 10 to 50 parts by weight. When the amount is less than 5 parts by weight, the amount of acid generated by exposure is small, so that a coating film formed from the composition has a small difference in solubility in a developing solution between an exposed portion and an unexposed portion, so that patterning becomes difficult. On the other hand, if it exceeds 100 parts by weight, the 1,2-naphthoquinonediazide group-containing compound remains without being sufficiently decomposed by short-time light irradiation,
The sensitivity may decrease.

[III] Crosslinking agent The crosslinking agent used in the present invention is the acrylic resin (A)
It is not particularly limited as long as it has a function of reacting with a functional group such as a carboxyl group by heating and crosslinking, but preferably includes a melamine compound represented by the following formula (I). Can be

[0014]

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In the formula (I), R^FiveIs -NR⁵¹R⁵²｛R⁵¹, R
⁵²Is hydrogen or -CH_TwoOR⁵³(R⁵³Is hydrogen or charcoal
Represents an alkyl group or a cycloalkyl group having a prime number of 1 to 6
You. ). ｝ Or a phenyl group;¹, R^Two, R
^Three, R^FourIs hydrogen or -CH _TwoOR⁵³(R⁵³Is hydrogen or
Represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group.
Show. ). R above⁵³An alkyl group or cycloa
As the alkyl group, a methyl group, an ethyl group, n-propyl
Group, isopropyl group, n-butyl group, isobutyl group, t
-Butyl group, n-amyl group, isoamyl group, n-hexyl
And a cyclohexyl group. Used in the present invention
Specific examples of the crosslinking agent represented by the formula (I) used include,
For example, hexamethylolmelamine (R¹, R^Two, R^Three,
R^Four, R⁵¹, R⁵²Is -CH_TwoOH) and alkylation
Hexamethylolmelamine (R¹, R^Two, R^Three, R^Four,
R⁵¹, R⁵²Is -CH_TwoOR⁵³And R⁵³Is preferred
Or 1 to 3 carbon atoms), partially methylolated melamine
(R¹, R^Two, R^Three, R^Four, R⁵¹, R⁵²1 to be selected from
Five are -CH_TwoOH and unselected is hydrogen) and its al
Killed product (preferably R⁵³Is carbon number 1-3), tetrame
Tyrol benzoguanamine (R¹, R^Two, R^Three, R^FourAre each
-CH_TwoOH, R^FiveIs a phenyl group) and alkylated tet
Lamethylol benzoguanamine (preferably R⁵³Is carbon
Formulas 1-3), partially methylolated benzoguanamine
(R ¹, R^Two, R^Three, R^Four1 to 3 selected from -CH
_TwoOH and unselected is hydrogen) and its alkylated form (preferred)
Preferably R⁵³Is a group having 1 to 3 carbon atoms, or
Oligomer (preferably 2 to 5 monomers) and the like
be able to. As other crosslinking agents used in the present invention
Means epoxy compound, phenol compound, azo compound
Compounds, isocyanate compounds, etc.
Xy compounds are preferred. For example, with epoxy curing agent
Have an average of one or more epoxy groups in the molecule
Compounds, for example, n-butyl glycidyl ether
, 2-ethoxyhexyl glycidyl ether, phenyl
Luglycidyl ether, allyl glycidyl ether, d
Tylene glycol diglycidyl ether, propylene glycol
Recall diglycidyl ether, neopentyl glycol
Rudiglycidyl ether, glycerol polyglycidyl
Ethers, sorbitol polyglycidyl ether, etc.
Lysidyl ether, adipic acid diglycidyl ester,
Glycidyl S such as o-phthalic acid diglycidyl ester
Ter, 3,4-epoxycyclohexylmethyl (3,4
-Epoxycyclohexane) carboxylate, 3,4
-Epoxy-6-methylcyclohexylmethyl (3,4
-Epoxy-6-methylcyclohexane) carboxyle
, Bis (3,4-epoxy-6-methylcyclohexene)
Silmethyl) adipate, dicyclopentanedienoxy
Side, bis (2,3-epoxycyclopentyl) A
An alicyclic epoxy such as ter may be used. The crosslinking agent is
Distribute in the range of 2 to 50 parts by mass with respect to the acrylic resin (A).
And more preferably 4 to 40 parts by mass.
is there. If the compounding amount is too small, the sensitivity decreases, and
May occur, on the other hand, if the amount is too large, transparency,
Insulation and coating properties may deteriorate. [IV] Silane coupling agent The photosensitive resin composition of the present invention comprises a silane coupling agent.
Inclusion improves the adhesion to the substrate
You. The silane coupling agent is preferably a functional
Silane coupling agents and the like. Sensuality sila
Examples of the coupling agent include the following:
However, among them, S3 and S4 are preferable. S1. Vinyltriethoxysilane: CH_Two= CHSi
(OC_TwoH_Five)_Three S2. Vinyl tris (β-methoxyethoxy) silane:
CH_Two= CHSi (OCH_TwoH_FourOCH_Three)_Three S3. γ-glycidoxypropyltrimethoxysilane:

[0016]

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S4. γ-methacryloxypropyltrimethoxysilane:

[0018]

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S5. γ-mercaptopropyltrimethoxysilane: The HSC ₃ H ₆ Si (OCH ₃ ) ₃ silane coupling agent is preferably used in an amount of 0.01 to 5 parts by mass based on the acrylic resin (A).

In the present invention, a surfactant is used to improve the coatability of the photosensitive resin composition, for example, to prevent striation (after coating streaks), to improve the developability of the coating film, and to further improve the flatness. Can also be blended. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, and polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Nonionic surfactants such as polyoxyethylene dialkyl esters such as oxyethylene aryl ethers, polyoxyethylene dilaurate, and polyoxyethylene distearate; F-Top EF301, 303, and 352 (Shin-Akita Chemical Co., Ltd.)
Manufactured), Mega Fac F171, F172, F17
3, F177 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S
-382, SC-101, SC-102, SC-
103, SC-104, SC-105, SC-1
06 (manufactured by Asahi Glass Co., Ltd.), a fluorine-based surfactant, organosiloxane polymer KP3
41 (manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth) acrylic acid-based copolymer polyflow Nos. 57 and 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK). Among these surfactants, fluorine surfactants are preferred.

These can be used in combination of two or more. Such a surfactant is used in an amount of 1 in the photosensitive resin composition.
When the amount is 00 parts by mass, it may be contained in an amount of 2 parts by mass or less, preferably 1 part by mass or less. The photosensitive resin composition of the present invention preferably contains 3% by mass or more of fluorine atoms in the solid content of the photosensitive resin composition of the present invention so that the cured film contains fluorine atoms, more preferably By containing 5 to 30% by mass, it is possible to more easily form a patterned thin film having excellent low dielectric properties in addition to other properties. The fluorine compound of the present invention is used as a fluorine atom source capable of providing such a patterned thin film having excellent low dielectric properties. The fluorine compound in the present invention,
At the time of exposure or heating, it may be bonded to a carboxyl group contained in the acrylic resin (A), or may be bonded to a cross-linking agent. It may be present as a mixture of a photosensitive resin composition without performing. Typical examples of the fluorine compound are compounds having a fluorinated group shown in the following (1) to (8).

(1) F (CF ₂ ) _n − (2) (CF ₃ ) ₂ CF (CF ₂ ) _n −2 (3) H (CF ₂ ) _n − (4) CF ₃ CHFCF ₂ − (5) _{) (CF 3) 2 CH- (} 6) - (CF 2 CClF) -

[0023]

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Here, n is usually 1 to 10, preferably 5
~ 8. In formulas (7) and (8), hydrogen on the benzene ring may be substituted with fluorine or another substituent, or the benzene ring may be alicyclic.

Examples of the fluorine compound include alcohols, carboxylic acids, epoxy compounds, olefins, halogenated compounds, acrylates, methacrylates, esters, ethers, amines and the like.
Among them, epoxy compounds, acrylates, methacrylates, and amines are preferred.

Specific examples of the epoxy compounds, acrylates, methacrylates, and amines containing an epoxy group include the groups shown in Table 1 below and the above (1) to (1).
Compounds in which the fluorine-containing group shown in (8) is bonded can be mentioned.

[0027]

[Table 1]

In the frame of Table 1 above, for example, groups containing epoxy are described as epoxy compounds. The epoxy compounds are defined by the groups and the above (1) to (8).
And various epoxy compounds formed by bonding with a fluorine-containing group or the like. The same applies to other compounds. As the fluorine compound, epoxy compounds and amines are particularly preferable. Particularly, a fluorinated aromatic epoxy compound having an aromatic fluorine-containing group such as the above (7) and (8), and a fat such as the above (1) Fluoroaliphatic compounds having a group III fluorine-containing group are preferred. Preferred examples of the fluorinated aromatic epoxy compound include:

[0029]

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2,2 '-[1,3-phenylenebis
[[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] oxymethylene]] bis-oxirane

[0031]

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2,2-bis [4- (2,3-epoxypropoxy) phenyl] hexafluoropropane is mentioned, and a preferred example of the fluorinated aliphatic compound is

[0033]

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And the like.

Examples of the photopolymerization initiator that can be used in the present invention include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoamine generator.

Examples of the photoradical polymerization agent include α-diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, thioxanthone, Thioxanthones such as 4-diethylthioxanthone and thioxanthone-4-sulfonic acid, benzophenones such as benzophenone and 4,4′-bis (dimethylamino) benzophenone, benzophenones such as 4,4′-bis (diethylamino) benzophenone, Michler's ketones and acetophenone; 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone Non, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl]
-2-morpholino-1-propanone, 2-benzyl-
Acetophenones such as 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, quinones such as anthraquinone and 1,4-naphthoquinone, phenacyl chloride, trihalomethylphenylsulfone, tris (trihalomethyl) ) -Halogen compounds such as -s-triazine, acylphosphine oxides, peroxides such as di-t-butyl peroxide and the like.

As a photoradical polymerization agent, for example, IR
GACURE-184, 261, 369, 500, 6
51, 907 (manufactured by Ciba-Geigy), Darocur-1
173, 1116, 2959, 1664, 40
43 (Merck Japan), KAYACURE-DETX, MB
P, DMBI, EPA, OA (Nippon Kayaku Co., Ltd.), V
ICURE-10, 55 (STAUFFER Co. LTD), TRIGONA
LP1 (AKZO Co. LTD), SANDORAY 1000 (SANDOZ Co.
LTD), DEAP (APJOHN Co. LTD), QUANTACURE-PD
Commercial products such as O, ITX, and EPD (manufactured by WARD BLEKINSOP Co. LTD) can also be used.

Examples of the cationic photopolymerization initiator include diazonium salts, triphenylsulfonium salts, metallocene compounds, diaryliodonium salts, nitrobenzylsulfonates, α-sulfonyloxyketones,
Diphenyldisulfones and imidylsulfonates. As a cationic photopolymerization initiator, ADEKA ULTRASET PP-33, OPTMER SP-150, and 170 (manufactured by Asahi Denka Kogyo KK) (diazonium salt),
OPTOMER SP-150, 170 (manufactured by Asahi Denka Kogyo Co., Ltd.) (sulfonium salt), IRGACURE 2
61 (manufactured by Ciba-Geigy) (metallocene compound)
And other commercially available products.

Examples of the photoamine generator include nitrobenzicarbamimates and iminosulfonates.
These photopolymerization initiators are appropriately selected and used depending on the exposure conditions (for example, under an oxygen atmosphere or under an oxygen-free atmosphere). These photopolymerization initiators,
Two or more kinds can be used in combination.

The photopolymerization initiator is preferably added in an amount of 0 to 5 parts by mass, more preferably 0 to 2 parts by mass, based on 100 parts by mass of the solid content of the photosensitive resin composition of the present invention.
When the amount of the photopolymerization initiator exceeds 5 parts by mass, the photopolymerization initiator may bleed out from the surface of the coating film formed from the photosensitive resin composition of the present invention, or the heat treatment may be reduced. . Further, the positive photosensitive resin composition of the present invention,
It can contain a photopolymerizable monomer and can be used as a means for adjusting the physical properties of a positive image by selecting its amount and type. The photopolymerizable monomer is a component that is polymerized by exposure. Specifically, a monofunctional or polyfunctional methacrylate or acrylate (hereinafter, referred to as (meth) acrylate) is preferably exemplified. Further, the photopolymerizable monomer may contain fluorine.

As monofunctional (meth) acrylates,
For example, Aronix M-101, M-111, M
-114 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYARA
DTC-110S, TC-120S (Nippon Kayaku Co., Ltd.)
V-158, V-2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (commercially available).

As the bifunctional (meth) acrylate,
For example, Aronix M-210, M-240, M
-6200 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYAR
And DD260, HX-220, R-604 (manufactured by Nippon Kayaku Co., Ltd.), V260, V312, V335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (commercially available).

Examples of (meth) acrylates having three or more functionalities include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., and specifically, Aronix M-309,
M-400, M-405, M-450, M-7
100, M-8030, M-8060 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYARAD DPHA, TM
PTA, DPCA-20, -30, -60,-
120 (manufactured by Nippon Kayaku Co., Ltd.), V-295, -30
0, -360, -GPT, -3PA, -400
Commercial products such as (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and PPZ (manufactured by Idemitsu Petrochemical Co., Ltd.) are exemplified.

Of these, Aronix M-400,
Polyfunctional (meth) acrylates having three or more functionalities such as KAYARAD DPHA are preferably used. These monomers can be used in combination of two or more kinds.

The photopolymerizable monomer is an acrylic resin (A) 1
The amount is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass with respect to 00 parts by mass.

The photosensitive resin composition of the present invention comprises an acrylic resin (A), a compound containing a 1,2-naphthoquinonediazide group,
Crosslinking agent and silane coupling agent, besides, surfactant,
It is prepared by dissolving a fluorine compound or the like in a solvent.

Solvents for dissolving the photosensitive resin composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether. , Ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, B propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3
-Methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate,
3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, Diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate,
Ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate Nate, ethyl-3
-Ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-
Methyl 3-methylbutanoate, methyl acetate, ethyl acetate,
Propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl Ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol,
Examples thereof include propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin.

Further, in order to improve the heat resistance of the photosensitive resin composition and the adhesion to the substrate, the photosensitive resin composition may contain a compound having at least two epoxy groups in the molecule. Such epoxy group-containing compounds include, for example, Epicoat 1001, 1002, 1003, 100
4, 1007, 1009, 1010, 828
Bisphenol A type epoxy resin such as (trade name; Yuka Shell Epoxy Co., Ltd.), bisphenol F type epoxy resin such as Epicoat 807 (trade name; Yuka Shell Epoxy Co., Ltd.), Epicoat 152, 154 ( Product name: Yuka Shell Epoxy Co., Ltd.), EPPN20
Phenol novolak type epoxy resin such as 1, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.), EOCN102, 103S, 104S, 1020, 1025, 1027
(Trade name; manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S7
Cresol novolak type epoxy resin such as 5 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), CY-175, 1
77, 179, Aldarite CY-182, 19
2, 184 (trade name; manufactured by Ciba-Geigy Corporation), ER
L-4234, 4299, 4221, 4206 (trade name; manufactured by UCC), Shodyne 509 (trade name;
Showa Denko Co., Ltd.), Epicron 200, 400 (trade name; manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (trade name: Yuka Shell Epoxy Co., Ltd.), ED
Cyclic aliphatic epoxy resins such as -5661 and 5662 (trade names; manufactured by Celanese Coatings Co., Ltd.), Epolite 100MF (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), and Epiol TMP (manufactured by Nippon Yushi Co., Ltd.) And aliphatic polyglycidyl ether.

Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic polyglycidyl ether and the like are preferably used.

The molecular weight of the epoxy group-containing compound as described above is not particularly limited, and may be a high molecular weight or a low molecular weight such as glycidyl ether of bisphenol A (or F). Good.

The epoxy group-containing compound as an optional component is 5 to 5 parts by mass based on 100 parts by mass of the acrylic resin (A).
It is used as needed in an amount of 0 parts by mass. Further, in the photosensitive resin composition of the present invention, if necessary, an antistatic agent, a storage stabilizer, an antihalation agent, an antifoaming agent, a pigment and the like can be added.

By using the photosensitive resin composition of the present invention, a pattern can be formed, for example, as follows. First, each component, for example, having a solid content of 5%
The solution is dissolved in a solvent so as to have a concentration of about 60% by mass, and the solution is filtered through a filter having a pore size of about 0.2 to 10 μm to prepare a photosensitive resin composition solution of the present invention. And
The photosensitive resin composition solution of the present invention is applied to the surface of a substrate such as a silicon wafer and the like, and the solvent is removed by pre-baking to form a coating film of the photosensitive resin composition. Next, after performing a radiation irradiation process (first exposure) such as a light irradiation process on the formed coating film, a positive pattern is formed by performing a development process to remove a portion irradiated with the radiation. Solvent resistance of the pattern obtained by development,
Further exposure (second exposure) may be performed to improve various properties such as film strength and heat resistance, and the pattern may be heated before, during or after exposure to further enhance the effect of the exposure. May be. This heat treatment is preferably performed after the exposure, and the light amount of the second exposure is preferably 2 to 15 times that of the first exposure. In the method of the present invention, it is preferable that the second exposure amount is ² to 15 times the exposure amount of the first exposure, which is 20 to 150 mJ / cm ² . In addition, the heat treatment is performed in
0 ° C., preferably 3 to 60 minutes.

As a method of applying the photosensitive resin composition solution of the present invention to a substrate, various methods such as a spin coating method, a flow coating method, and a roll coating method can be adopted. Prebaking conditions are, for example, a heating temperature of 50 to 150 ° C. and a heating time of 30 to 600 seconds. The radiation used for the radiation irradiation treatment is ultraviolet light from an ultra-high pressure mercury lamp or the like, i-line having a wavelength of 365 nm, h-line having a wavelength of 405 nm,
Charged particle beams such as X-rays such as g-line at 436 nm, KrF excimer laser having a wavelength of 248 nm, and ArF excimer laser having a wavelength of 193 nm, synchrotron radiation, and X-rays or electron beams.

The developing solution used in the developing treatment is preferably, for example, sodium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n- Propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline,
Pyrrole, piperidine, 1,8-diazabicyclo [5.
4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane and the like. Also, in this alkaline aqueous solution, etc.,
A water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a solvent to which an appropriate amount of a surfactant is added can also be used. The development processing time is, for example, 10 to
It is 300 seconds, and as a developing method, a liquid puddle method, a dipping method, a rocking dipping method, or the like can be used. After the alkali development, a rinsing treatment by washing with running water is performed. As the rinsing treatment, it is preferable to wash with water using an ultra-high pressure micro jet.

In the ultrahigh-pressure microjet, water is injected from a high-pressure injection device. The applied pressure of the ultra-high pressure microjet is usually 20 to 350 kgf / cm ² (2.9 to 3 kgf / cm ² ).
4.3 MPa), preferably 30 to 250 kgf / cm
² (4.9 to 24.5 MPa). The applied pressure is selected depending on the shape of the nozzle. In the present invention, a cat-eye type nozzle (having a concave lens-shaped cross section) is preferable. The jet angle of the ultra-high pressure micro jet has a great effect on the water washing action. The washing effect is strongest when it is perpendicular to the surface of the photosensitive resin composition. On the other hand, the removal of the composition in the non-photosensitive portion is not sufficient simply by a strong rinsing action, and the unnecessary composition must be removed from the substrate by mechanical water impact. The direction perpendicular to the substrate is the best, but the angle between the perpendicular direction and the direction of ejection to the substrate may be about ± 0 to about 20 degrees, and the ejection may be performed forward or backward with respect to the traveling direction of the substrate. .

As an economical embodiment of the present invention, it is practical to employ continuous water washing. In this case, the fan is provided so that water is evenly distributed in the width direction of the photosensitive resin composition layer. A single or multiple spray nozzles that spray with the mold spread are arranged in the fan spreading direction, and the photosensitive resin composition moves at a constant speed in the direction perpendicular to the fan-shaped spray direction and passes through the water spray part. It is preferable to carry out a continuous washing treatment by using a method of performing the above.

According to this method, since it can be effectively removed even in the deep portion of the non-exposed portion layer, it can be used for a composition having a large layer thickness and which is generally difficult to remove, and a pattern having a good profile can be formed. Can be done.

An ultra-high pressure jet precision cleaning system AF series (Asahi Sunac Co., Ltd.) is a particularly preferred high-pressure injection device having a function for satisfying the above-mentioned injection pressure, impact angle, water flow spreading shape and the like. Can be Among them, AF5400S is suitable for relatively high pressure injection, and AF2800II is suitable for relatively low pressure injection. However, as long as the apparatus has the above-described injection applied pressure, impact angle, water flow spreading shape, etc., it is not limited to this model, and can be applied to the washing means after development in the pattern forming method of the present invention.

In this method, since the effect of the ultrahigh-pressure microjet is strong and extends deep, the non-pattern portion is substantially removed by washing with water.

After the above-mentioned water washing treatment, the patterned resin composition is air-dried with, for example, compressed air or compressed nitrogen, and subjected to the second exposure and heat treatment to form a cured patterned thin film on the substrate. You. The resulting patterned thin film has high resolution, flatness, high resolution, developability, heat resistance,
Excellent physical properties such as chemical resistance, adhesion to substrates, transparency, and insulation. Further, in the photosensitive resin composition, those further containing a fluorine compound have a relative dielectric constant of 3 or less, preferably 2.8 or less, in addition to the above characteristics. Therefore, the photosensitive resin composition of the present invention is useful for a protective film, a flattening film, an interlayer insulating film, and the like of an electronic component.
It is useful for microlenses such as solid-state imaging devices.

[0061]

EXAMPLES Hereinafter, the photosensitive resin composition of the present invention will be described based on examples, but the present invention is not limited to these examples.

Example 1 As an acrylic resin (A), 60 parts by mass of a polymerized derivative of methacrylic acid (weight average molecular weight: about 20,000, allyl group: 40 mol% based on methacrylic acid monomer unit), 2,3,
15 parts by mass of 4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate (2S: two of three hydroxyl groups are substituted, one is H), 22 parts by mass of hexamethoxymethylolmelamine, A photosensitive resin composition was prepared by mixing and stirring and dissolving 30.05 parts by mass of a silane coupling agent S and 200 parts by mass of propylene glycol monomethyl ether acetate.

This was applied to a glass substrate (Corning 705).
9) After coating on the upper surface so that the film thickness becomes 5 μm, the film is dried in a warm air heater at 100 ° C. for 2 minutes to obtain an L / S pattern of 2 to 8 μm (lines and spaces are 2 μm and 3 μm).
m, 4 μm, 6 μm, and 8 μm. 100mJ / c using an ultra-high pressure mercury lamp through a mask
Exposure was performed with an exposure amount of m ² , and a 1.5% by mass alkali solution of tetramethylammonium hydroxide at 25 ° C.
After developing for 0 second, washing with water and drying, a fine pattern was obtained.
Thereafter, the second the entire substrate with an exposure amount of 400 mJ / cm ²
It was exposed to light and heat-treated at 120 ° C. for 10 minutes to cure.

The characteristics of the obtained patterned heat-cured film were evaluated by the following methods. (1) Measurement of relative permittivity: The relative permittivity of the heat-cured film obtained above was measured using a permittivity measuring device (manufactured by Hewlett-Packard) at room temperature and 1 MHz. The relative dielectric constant was 3.2. (2) Evaluation of Adhesion Adhesion at the time of development is good, and 2 μm, 3 μm, 4 μm, and 6 μm.
There is no peeling of any of the fine lines of m and 8 μm. (3) Evaluation of heat resistance After measuring the thickness of the heat-cured film, the film was further heated in an oven at 240 ° C for 30 minutes. Then, the film thickness after the heat treatment was measured, and the residual film ratio of the heat-cured film was obtained. There was almost no change in the residual film ratio due to heating. (4) Evaluation of solvent resistance A mixture of dimethyl sulfoxide and monoethanolamine at a temperature of 80.degree.
After immersion in water for 12 minutes, the film was washed with water and dried, and the film thickness was measured. There was almost no change in film thickness due to immersion. (5) Evaluation of flatness The surface roughness of the heat-cured film was measured using a contact-type film thickness measuring instrument. 15 angstrom Ra value ()
And the flatness was good. (6) Measurement of Transparency The above-mentioned heat-cured film was measured at a wavelength of 380 to 800 nm using a double beam type spectrophotometer to determine the transmittance. The film was transparent, had little absorption at long wavelengths, and had a transmittance of 400% at 400 nm even at short wavelengths. (7) Evaluation of heat-resistant discoloration The above heat-cured film was further placed in a 240 ° C. oven for 30 minutes.
After heating for one minute, the transmittance was measured in the same manner as described above. The change in the transmittance at 400 nm was 1%, and almost no change was observed.

Example 2 As an acrylic resin (A), a methacrylic acid-benzyl acrylate copolymer derivative (weight average molecular weight: about 2,000)
0, methacrylic acid: benzyl acrylate = 8: 2 (molar ratio), allyl group: 40 mol% with respect to methacrylic acid monomer unit) 60 parts by mass, 2,3,4,4'-tetrahydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid ester (3S: 3 of 4 hydroxyl groups are substituted,
One is H) 15 parts by mass, hexamethoxymethylol melamine 22 parts by mass, the silane coupling agent S30.
05 parts by mass and 200 parts by mass of propylene glycol monomethyl ether acetate were mixed and dissolved by stirring to prepare a photosensitive resin composition. Example 3 In Example 1, 2,3,4,4′-tetrahydroxybenzophenone was used in place of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester.
A photosensitive resin composition was prepared in the same manner as in Example 1, except that -1,2-naphthoquinonediazide-5-sulfonic acid ester was used. Example 4 In Example 1, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester was replaced with tri (p-hydroxyphenyl) methane-1,2-
Naphthoquinonediazide-5-sulfonic acid ester (2S:
A photosensitive resin composition was prepared in the same manner as in Example 1, except that two of the three hydroxyl groups were substituted and one was H). Example 5 In Example 1, 2,4,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester was replaced with 4,4 ′-[1- [4- [1- [4 -Hydroxyphenyl] -1-
Methylethyl] phenyl] ethylidene] bisphenol-1,
2-Naphthoquinonediazide-5-sulfonic acid ester (2
S: A photosensitive resin composition was prepared in the same manner as in Example 1, except that two of the three hydroxyl groups were substituted and one was H).

When the characteristics of the patterned heat-cured film obtained by treating the photosensitive resin compositions of Examples 2 to 5 in the same manner as in Example 1 were evaluated by the above method, the relative permittivity, adhesion, The heat resistance, solvent resistance, flatness, transparency, and heat discoloration were almost the same as in Example 1. However,
The transparency of Example 5 was 93%.

Example 6 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 0.01 part by mass of a fluorine-based surfactant Megafac F177 was further used. Example 7 In Example 6, instead of 60 parts by mass of the methacrylic acid polymer derivative, 50 parts by mass of the polymer derivative and 10 parts by mass of polyhydroxyethyl methacrylate (mass average molecular weight 15,000) as the acrylic resin (a) were used. except,
In the same manner as in Example 6, a photosensitive resin composition was prepared.

Example 8 A photosensitive resin was prepared in the same manner as in Example 6, except that 18 parts by mass of hexamethoxymethylolmelamine and 4 parts by mass of 2-ethoxyhexylglycidyl ether of an epoxy compound were used. A composition was prepared. When the characteristics of the patterned heat-cured films obtained by treating the photosensitive resin compositions of Examples 6 to 8 in the same manner as in Example 1 were evaluated by the above method, the flatness was 5% in terms of Ra value. Met. Also, relative permittivity, adhesion, heat resistance, solvent resistance,
The transparency and heat discoloration were almost the same as in Example 1.

Example 9 To each of the photosensitive resin compositions of Examples 1 to 8, 110 parts by mass of a fluorine compound F was newly added, mixed and dissolved by stirring to prepare each of the photosensitive resin compositions. Example 1
When the characteristics of the patterned heat-cured film obtained by treating in the same manner as above were evaluated by the above method, the relative dielectric constant was determined in Examples 1 to 3.
Each was 0.3 lower than 8. In addition, adhesion, heat resistance, solvent resistance, flatness, transparency, heat discoloration,
All were almost the same as Examples 1-8.

Example 10 A photosensitive resin composition was prepared in the same manner as in Example 4 except that the silane coupling agent S2 was used instead of the silane coupling agent S3 in the photosensitive resin composition of Example 4. did. Example 11 A photosensitive resin composition was prepared in the same manner as in Example 4, except that the silane coupling agent S4 was used instead of the silane coupling agent S3 in the photosensitive resin composition of Example 4. Example 12 A photosensitive resin composition was prepared in the same manner as in Example 4 except that the silane coupling agent S5 was used instead of the silane coupling agent S3 in the photosensitive resin composition of Example 4. When the characteristics of the patterned heat-cured film obtained by treating the photosensitive resin compositions of Examples 10 to 12 in the same manner as in Example 1 were evaluated by the above method, the relative dielectric constant, adhesion,
The heat resistance, solvent resistance, flatness, transparency, and heat discoloration were all substantially the same as in Example 4.

Comparative Example 1 A photosensitive resin composition was prepared in the same manner as in Example 1 except that the silane coupling agent S3 was omitted from the photosensitive resin composition of Example 1. When the properties of the patterned heat-cured film obtained by the treatment were evaluated by the above method, the relative permittivity, heat resistance, solvent resistance, flatness, transparency, and heat discoloration were almost the same as those in Example 1. However, peeling was observed in the fine lines of 2 μm and 3 μm in adhesion.

[0072]

The photosensitive resin composition of the present invention can be developed with an alkaline aqueous solution, has high resolution and high sensitivity, and has various properties such as flatness, heat resistance, solvent resistance and transparency. Preferably, a patterned thin film having excellent low dielectric properties, which has been difficult to realize simultaneously with the above characteristics, can be easily formed, preferably by the pattern forming method of the present invention. Therefore, the photosensitive resin composition of the present invention can be used as a positive resist for forming a mask for manufacturing a circuit such as a semiconductor integrated circuit, a thin film for a liquid crystal display, and a transistor circuit, and further, an interlayer insulating film and a protective film for a color filter. It can also be suitably used as a material for forming a permanent film such as a film and a microlens.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/1515 C08K 5/1515 5/28 5/28 5/3477 5/3477 5/5425 5/5425 5/5435 5 / 5435 5/548 5/548 C08L 33/04 C08L 33/04 G03F 7/004 501 G03F 7/004 501 504 504 7/022 7/022 7/40 501 7/40 501 H01L 21/027 H01L 21/30 502R F-term (reference) 2H025 AA01 AA02 AA06 AA07 AA08 AA10 AA14 AA20 AB16 AB17 AD03 BC53 BC54 BC85 CB13 CB14 CB43 CB52 CC04 CC06 CC20 FA03 FA17 FA29 FA30 2H096 AA00 AA25 AA27 CD06 BD02 BA02 BA01 BA02 CD02 CH024 CP024 EL027 EQ036 EU187 EX018 EX068 EX088 FD143 FD147 FD206 FD208 FD314 GP03 4J011 AA05 PA35 PA43 PA47 PA66 PA69 PB30 PB40 PC02 PC08 4J027 AA01 AA02 BA01 BA07 BA17 BA26 BA28 CA03 CA10 CA25 CC29 CC10 CC09 CB09 CB09 CB09 CB09

Claims (8)

[Claims] 1. A positive photosensitive resin composition comprising at least an alkali-soluble acrylic resin having an unsaturated ethylene group, a compound containing a 1,2-naphthoquinonediazide group, a crosslinking agent, and a silane coupling agent. . 2. The positive photosensitive resin composition according to claim 1, further comprising a fluorine-based surfactant. 3. The positive photosensitive resin composition according to claim 1, wherein an alkali-soluble acrylic resin having no unsaturated ethylene group is used in combination. 4. The positive photosensitive resin composition according to claim 1, wherein the crosslinking agent is a melamine compound. 5. The positive photosensitive resin composition according to claim 1, wherein the crosslinking agent is an epoxy compound. 6. The positive photosensitive resin composition according to claim 1, further comprising a fluorine compound. 7. The positive photosensitive resin composition according to claim 6, wherein the fluorine compound is an epoxy compound. 8. The step of sequentially applying, positively exposing, developing, developing, exposing, and heating the positive photosensitive resin composition according to claim 1 in a second exposure step. Wherein the amount of light is 2 to 15 times that of the first exposure.