KR20010095268A - Positive photosensitive resist composition - Google Patents

Abstract

PURPOSE: 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. CONSTITUTION: 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

Positive photosensitive resin composition {POSITIVE PHOTOSENSITIVE RESIST COMPOSITION}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a photosensitive resin composition, and in particular, to a photosensitive resin composition capable of forming a micro pattern structure, and more particularly, to a thin film transistor (TFT) circuit for a semiconductor integrated circuit (IC) and a liquid crystal display (LCD). Positive photosensitive resin composition suitable as a positive photosensitive resin composition for making the mask for circuit manufacturing, and also as a permanent film forming material, such as interlayer insulation films, such as a liquid crystal display element, an integrated circuit element, and a solid-state image sensor, and microlenses, such as a solid-state image sensor, etc. And a pattern forming method using the same.

In general, in the manufacture of electronic components such as liquid crystal display devices, integrated circuit devices, and solid state imaging devices, a protective film for preventing the deterioration or damage, a flattening film for flattening the surface of the device, an insulating film for maintaining electrical insulation, and the like. Is installed. In a TFT type liquid crystal display or an integrated circuit device, an interlayer insulating film for insulating between wirings arranged in layers is used.

In general, in the production of electronic components such as LCD TFTs and ICs, there is a strong demand for a resist having a high sensitivity of submicron or less and having high sensitivity.

For example, the resist pattern formed by the wet etching method of IC silicon wafer requires the adhesiveness with a board | substrate or the chemical-resistance which does not interfere with an etching liquid. In addition, when an ion infra process is applied, heat resistance that withstands high temperature heating is required. In addition, transparency is also required for use as the insulating material of the TFT. However, since it discolors by performing heat processing, there is a drawback that it cannot be used as an optical material such as a protective film or a microlens of a liquid crystal color filter.

In addition, the formation of the interlayer insulating film requires a large number of processes, and it is difficult to ensure good characteristics such as flatness, high resolution, developability, heat resistance, chemical resistance, adhesion to the substrate, transparency, and insulation properties required for the interlayer insulating film. There was no photosensitive resin composition which satisfies all these properties.

Further, as for the interlayer insulating film, low dielectric constant for controlling the generation of crosstalk is desired as the device becomes higher, but conventional photosensitive resin compositions are not sufficiently satisfactory in terms of achieving both these characteristics and low dielectric constant. It was.

An object of the present invention can be formed in an alkaline aqueous solution, it is highly sensitive, and easy to form a patterned thin film having excellent properties such as flatness, high resolution, developability, heat resistance, chemical resistance, adhesion to the substrate, transparency, insulation, etc. To provide a photosensitive resin composition which can be formed, and also a photosensitive resin composition which can easily form an excellent patterned thin film having low dielectric properties, which has been difficult to realize simultaneously with the above-described characteristics, and a pattern forming method using the same. have.

In this invention, the photosensitive resin composition of the following structure and the pattern formation method using the same are provided, and the said objective of this invention is achieved.

(1) A positive photosensitive resin composition comprising at least an alkali-soluble acrylic resin having an unsaturated ethylene group, a 1,2-naphthoquinone diazide group-containing compound, a crosslinking agent, and a silane binder.

(2) The positive photosensitive resin composition as described in said (1) containing fluorine-type surfactant.

(3) The positive photosensitive resin composition as described in said (1) or (2) characterized by using together alkali-soluble acrylic resin which does not have unsaturated ethylene group.

(4) The positive photosensitive resin composition according to any one of (1) to (3), wherein the crosslinking agent is a melamine-based compound.

(5) The positive photosensitive resin composition according to any one of (1) to (4), wherein the crosslinking agent is an epoxy compound.

(6) The positive photosensitive resin composition as described in any one of said (1)-(5) containing fluorine compound.

(7) The positive photosensitive resin composition according to the above (6), wherein the fluorine compound is an epoxy compound.

(8) The amount of light of the second exposure in the step of applying the positive photosensitive resin composition according to any one of (1) to (7), and sequentially performing the first exposure, the development, the second exposure, and the heat treatment. It is 2 to 15 times of this 1st exposure, The pattern formation method characterized by the above-mentioned.

Hereinafter, the photosensitive resin composition of this invention is explained in full detail.

First, each component mix | blended with the photosensitive resin composition of this invention is demonstrated.

[I] Alkali-soluble acrylic resin which has unsaturated ethylene group (henceforth "acrylic resin (A)")

The acrylic resin (A) is a polymer or copolymer of any one or more of acrylic acid and methacrylic acid (hereinafter referred to as (meth) acrylic acid) and a carboxyl group of (meth) acrylic acid of a functional compound having an unsaturated ethylene group. Can be synthesized by reaction through. In addition, acrylic resin (A) is (meth) acrylic acid and any monomer copolymerizable with this, 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-hydroxy Ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobor One kind of yl methacrylate, glycidyl acrylate, glycidyl methacrylate, styrene, acrylamide, methacrylamide, acrylonitrile An unsaturated ethylene group can be introduced into this copolymer by reaction with the copolymer of the above and the carboxyl group of the (meth) acrylic acid at least of the functional compound which has an unsaturated ethylene group. Here, this functional compound can also be combined with the functional group couple | bonded with the monomer copolymerizable with (meth) acrylic acid, for example, a carboxyl group, a hydroxyl group, an amino group, etc.

Herein, the unsaturated ethylene group means a group in which at least one CH ₂ = CH- group or a bonded hydrogen atom thereof is substituted with a substituent such as an alkyl group.

A functional compound having an unsaturated ethylene is preferably _{CH 2 = CH (CH 2)} n R (R is a functional group of a hydroxyl group, an amino group, an epoxy group, etc. are exemplified. N is an integer 1 to 5, preferably It is an integer of 1-2.

It is preferable that acrylic resin (A) has an unsaturated ethylene group in 1 to 70 mol% with respect to an acrylic resin (A) constituent monomer unit.

The acrylic resin (A) may also be synthesized by copolymerization with any one or more of acrylic acid and methacrylic acid, a monomer having an unsaturated ethylene group copolymerizable, and other copolymerizable monomers such as methyl acrylate. have.

The acrylic resin (A) preferably has a mass average molecular weight of 1,000 to 100,000, more preferably 3000 to 70,000. If the mass average molecular weight is too low, the film-forming ability is insufficient, and film peeling is extremely severe at the time of development. On the other hand, if the mass average molecular weight is too high, the development time is prolonged, which may adversely affect the substrate.

It is preferable to mix | blend the compounding quantity of this acrylic resin (A) in 35-95 weight part in 100 mass parts of total amounts of an acrylic resin (A), a 1, 2- naphthoquinone diazide group containing compound, and a crosslinking agent, More preferably, it is 45-85 mass parts. If the blending amount is too low, transparency, insulation, and coating film properties decrease. On the other hand, if the blending amount is too large, the sensitivity is lowered and curing failure is not preferable.

The photosensitive resin composition of this invention can use together alkali-soluble acrylic resin which does not hold the unsaturated ethylene group in this acrylic resin (A). This resin which can be used together is also described as acrylic resin (a).

As acrylic resin (a), the said acrylic resin, its ester body, etc. which make it react with the functional compound which has an unsaturated ethylene group in order to manufacture acrylic resin (A) are mentioned.

Acrylic resin (a) is 0-50 mass% normally with respect to acrylic resin (A), Preferably 0-30 mass% is used.

[II] 1,2-naphthoquinone diazide group-containing compound

As the 1,2-naphthoquinone diazide group-containing compound used in the present invention, 1,2-naphthoquinone diazide sulfonic acid ester is used. As this ester, the compound in which all or part of the hydroxyl group of polyhydric phenol is 1,2-naphthoquinone diazide sulfonic-acid diesterized can be used, Specifically, 20-100% of the hydroxyl group of polyhydric phenol is 1,2-naph. Toquinone diazide sulfonic acid diesterized compounds can be used.

Examples of the 1,2-naphthoquinone diazide group-containing compound include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4- Trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2, 1,2-naphthoquinone diazide sulfonic acid ester of trihydroxy benzophenone, such as 4, 6- trihydroxy benzophenone 1, 2- naphthoquinone diazide-5- sulfonic acid ester, 2, 2 ', 4 , 4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide -5-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoqui Nondiazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydride Hydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4 1,2-naphnoquinone diazide sulfonic acid ester of tetrahydroxy benzophenone, such as a 4'- tetrahydroxy-3'- methoxy benzophenone- 1, 2- naphthoquinone diazide-5- sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxy benzophenone, such as -1, 2- naphthoquinone diazide-5- sulfonic acid ester, 2, 4, 6, 3 ', 4', 5'- Heck Hydroxybenzophenone-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-naphthoquinone diazide-4-sulfonic acid ester, 3,4,5,3 ', 4 1,2-naphthoquinone diazide sulfonic acid ester, bis (2,4) of hexahydroxy benzophenone, such as a ", 5" -hexahydroxy benzophenone 1, 2- naphthoquinone diazide-5- sulfonic acid ester '-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- Ftoquinone diazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,1,1-tri (p -Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 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] ratio Sphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4 Sulfonic acid esters, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid esters, 3,3,3 ', 3' Tetramethyl-l, l'-spiroindene-5,6,7,5 ', 6', 7'-hexanol-l, 2-naphthoquinone diazide-4-sulfonic acid ester, 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'-trihydroxyflavan-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2' , 4'-trihydroxyflavan-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavane And 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as -1,2-naphthoquinone diazide-5-sulfonic acid ester.

In addition, these 1,2-naphthoquinone diazide group containing compounds can also be used individually or in combination of 2 or more types. Such a 1,2-naphthoquinone diazide group-containing compound is, for example, a halide of 1,2-naphthoquinone diazide sulfonic acid as a corresponding polyhydric phenol (polyhydric hydroxy compound) in the presence of a base catalyst. Obtained by esterification. In such an esterification reaction, the halide of 1,2-naphthoquinonediazidesulfonic acid is preferably used in an amount of 1.0 to 1.2 moles with respect to 1 mole of hydroxyl groups of the hydroxy compound.

The 1,2-naphthoquinone diazide group-containing compound is usually 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the acrylic resin (A) in the photosensitive resin composition according to the present invention. It is desirable to do it. If the amount is less than 5 parts by weight, the amount of acid produced by the exposure is small, so that the coating film formed from this composition may have a small difference in solubility with respect to the developing solution of the exposed portion and the unexposed portion, which may make patterning difficult, while 100 parts by weight When exceeding, since a 1,2-naphthoquinone diazide group containing compound will not fully decompose | disassemble by a short time light irradiation, a sensitivity may fall.

[III] crosslinking agent

The crosslinking agent used in the present invention is not particularly limited as long as the crosslinking agent reacts with a functional group such as a carboxyl group of the acrylic resin (A) by heating and has a function of crosslinking, but preferably the following formula (I) The melamine type compound shown by these is mentioned.

Equation (Ⅰ) of, R ⁵ is ^{-NR 51 R 52 {R 51,} R 52 are each an H or -CH ₂ OR ⁵³ (R ⁵³ represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms or hydrogen.) .} Or a phenyl group, and R ¹ , R ² , R ³ , and R ⁴ each represent hydrogen or —CH ₂ OR ⁵³ (R ⁵³ represents hydrogen or an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group.).

As said alkyl group or cycloalkyl group of R <^53> , 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-hex Real group, cyclohexyl group, etc. are mentioned.

Specific examples of the crosslinking agent represented by the formula (Ⅰ) used in the present invention include, for example, hexamethyl melamine ^{(R 1, R 2, R} 3, R 4, R 51, R 52 are each -CH ₂ OH) and alkylated Hexamethylol melamine (R ¹ , R ² , R ³ , R ⁴ , R ⁵¹ , R ⁵² are each -CH ₂ OR ⁵³ _, R ⁵³ is preferably 1 to 3 carbon atoms), partially methylolated melamine (R ¹ , 1 to 5 selected from R ² , R ³ , R ⁴ , R ⁵¹ , and R ⁵² are -CH ₂ OH and non-selective hydrogen; and their alkylates (preferably R ⁵³ has 1 to 3 carbon atoms) , Tetramethylolbenzoguanamine (R ¹ , R ² , R ³ , R ⁴ are each -CH ₂ OH, R ⁵ is a phenyl group) and alkylated tetramethylolbenzoguanamine (preferably R ⁵³ has 1 carbon atom). 3), partially methylolated benzoguanamine ( ¹ to 3 selected from R ¹ , R ² , R ³ , and R ⁴ are -CH ₂ OH and non-selective hydrogen) and their alkylates (preferably R ⁵³ is 1 to 3 carbon atoms, or an oligomer of the compound (preferably, 2 to 5 dimers), and the like.

As another crosslinking agent used by this invention, an epoxy type compound, a phenol type compound, an azo type compound, an isocyanate type compound, etc. are mentioned, Among these, an epoxy type compound is preferable.

For example, as an epoxy-type hardening | curing agent, it is a compound which has an average of 1 or more epoxy groups in a molecule | numerator, For example, n-butylglycidyl ether, 2-ethoxyhexyl glycidyl ether, phenylglycidyl ether, allyl glycy Glycidyl ethers, such as dil ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether Glycidyl esters such as acid diglycidyl ester and o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3,4-epoxy-6- Methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2,3 -Alicyclic epoxy such as epoxycyclopentyl) ether It is listed.

It is preferable to mix | blend a crosslinking agent in 2-50 mass parts with respect to acrylic resin (A), More preferably, it is 4-40 mass parts. When the compounding amount is slightly exceeded, the sensitivity may be lowered and developing defects may be caused. On the other hand, when the compounding amount is exceeded too much, transparency, insulation and coating properties may be deteriorated.

[IV] silane binder

The photosensitive resin composition of this invention can improve adhesiveness with a board | substrate by containing a silane binder. As a silane binder, Preferably a functional silane binder etc. are mentioned. Although the following are mentioned as a functional silane binder, Especially, S3 and S4 are preferable.

S1. Vinyltriethoxysilane: CH ₂ = CHSi (OC ₂ H ₅ ) ₃

S2. Vinyltris (β-methoxyethoxy) silane:

CH ₂ = CHSi (OCH ₂ H ₄ OCH ₃ ) ₃

S3. γ-glycidoxypropyltrimethoxysilane:

S4. γ-methacrylooxypropyltrimethoxysilane:

S5. γ-mercaptopropyltrimethoxysilane:

HSC ₃ H ₆ Si (OCH ₃ ) ₃

It is preferable that 0.01-5 mass parts of silane binders are used with respect to acrylic resin (A).

In the present invention, a surfactant may be blended to improve the coatability of the photosensitive resin composition, for example, to prevent striation (coating stripes) and to improve the developability of the coating film, and to further improve flatness. As surfactant, For example, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc. Nonionic surfactants, such as polyoxyethylene dialkyl esters, such as polyoxyethylene aryl ether, polyoxyethylene dilaurate, and polyoxyethylene distearate, F-top EF301, copper 303, copper 352 (Niakita Chemical property) Mega Park F171, East F172, East F173, East F177 (manufactured by Japan Nippon Ink Chemical Co., Ltd.), Floraard FC-430, East FC-431 (manufactured by Sumitomo Industries Co., Ltd.) Asahi Gaard AG710, Supron S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (made by Asahi Choza Co., Ltd.) Fluorine-based surfactant, organosiloxane polymer-KP341 (Shinwol Chemical Co., Ltd.) (Meth) acrylic-acid copolymer polypro-No.57, 95 (manufactured by Kogyo Oil and Chemicals Co., Ltd.), etc. are mentioned. Among these surfactants, fluorine-based surfactants are preferable.

These can also be used 2 or more types. Such surfactant may be contained in an amount of 2 parts by mass or less, preferably 1 part by mass or less, when the total amount of the photosensitive resin composition is 100 parts by mass.

The photosensitive resin composition of the present invention preferably contains 3% by mass or more, more preferably 5 to 30% by mass of the fluorine atom in the solid content of the photosensitive resin composition of the present invention so that the fluorine atom is contained in the cured film. In addition to other properties, an excellent patterned thin film of low dielectric properties can be formed more easily.

As the fluorine source resource capable of providing such a patterned thin film having excellent low dielectric properties, the fluorine compound in the present invention is used.

The fluorine compound in the present invention may be bonded to the carboxyl group contained in the acrylic resin (A) at the time of photosensitive or heating, or may be bonded to a crosslinking agent, or the fluorine compounds may be polymerized with each other, and the photosensitive resin composition does not react with these. It may exist as a mixture of these.

Typical examples of the fluorine compound are compounds in which the fluorine-containing group shown in the following (1) to (8) is bonded.

(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)-

Here, n is 1-10 normally, Preferably it is 5-8. In addition, in Formula (7) and Formula (8), the hydrogen of a benzene ring may be substituted by substituents other than fluorine, and 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. Especially, epoxy compounds, acrylates, methacrylate, and amines are preferable.

As specific examples of the epoxy compounds, acrylates, methacrylates, and amines containing these epoxy groups, compounds in which the group shown in Table 1 below and the fluorine-containing group shown in the above (1) to (8) are combined can be enumerated. .

In Table 1, for example, a group containing an epoxy is described as the epoxy compound, but the epoxy compound is a group of various kinds formed by combining the group and the fluorine-containing group described in the above (1) to (8). It means an epoxy compound. The same applies to other compounds.

Especially as a fluorine compound, epoxy compounds and amines are preferable, Especially the fluorinated aromatic epoxy compound which has aromatic fluorine-containing groups, such as said (7) and (8), and aliphatic fluorine-containing groups, such as said (1) Preferred fluorinated aliphatic compounds are preferred.

Preferred examples of the fluorinated aromatic epoxy compound include

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

2,2-bis [4- (2,3-epoxypropoxy) phenyl] hexafluoropropane

Listed and preferred examples of fluorinated fatty compounds

This is listed.

As a photoinitiator which can be used by this invention, an optical radical polymerization initiator, a photocationic polymerization initiator, a photoamine generator, etc. are mentioned.

As an optical radical polymerizer, For example, (alpha)-diketones, such as benzyl and diacetyl, acyl phosphorus, such as benzoin, acyl phosphorus, such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, Thioxanthones such as oxanthone, 2,4-diethyl thioxanthone and thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (di Benzophenones, such as ethylamino) benzophenone, mycloketones, acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylamino acetophenone, (alpha), (alpha) '-dimethoxy acetone Methoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2- Acetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -phthalan-1-one, quinones such as anthraquinone and 1,4-naphthoquinone, phenacyl chloride, and trihalo Methylphenylsulfone, Tris ) -S- peroxides such as halogen compounds, acylphosphine oxy Drew, di -t- butyl peroxide, such as triazine are exemplified.

Moreover, as an optical radical polymerizer, for example, IRGACURE-184, copper 261, copper 369, copper 500, copper 651, copper 907 (made by Chiba-Geigi), Darocur-1173, copper 1116, copper 2959, copper 1664, copper 4043 ( Merck Japan Co., Ltd., KAYACURE-DETX, East MBP, East DMBI, East EPA, East OA (made by Nippon Kayaku Co., Ltd.), VICURE-10, East 55 (made by STAUFFER Co.LTD), TRIGONAL P1 (AKZO Co.LTD Commercially available products such as SANDORAY 1000 (manufactured by SANDORAY Co.LTD), DEAP (manufactured by APJOHN Co.LTD), QUANTACURE-PDO, copper ITX, and copper EPD (manufactured by WARD BLEKINSOP Co.LTD).

As photocationic polymerization initiators, diazonium salts, triphenylsulfonium salts, metallocene compounds, diaryl iodonium salts, nitrobenzylsulfonates, α-sulfonyloxyketones, diphenyl disulfones and imidyl sulfo Nates are listed.

As photocationic polymerization initiator, Adekaultrasset PP-33, OPTMER SP-150, East 170 (manufactured by Wook Tong Industry Co., Ltd.) (diazonium salt), OPTOMER SP-150, 170 (manufactured by Uk Tong Industry Co., Ltd.) Commercial products, such as (sulfonium salt) and IRGACURE 261 (made by Chiba-Geigi Co., Ltd.) (metarosene compound), can be used.

Examples of the photoamine generator include nitrobenzi carbamates and aminosulfonites. These photoinitiators are suitably selected and used according to exposure conditions (for example, in an oxygen atmosphere or an oxygen-free atmosphere). In addition, these photoinitiators can be used in combination of 2 or more type.

The photopolymerization initiator is preferably added in an amount of 0 to 5 parts by mass, and more preferably 0 to 2 parts by mass with respect to 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 on the surface of the coating film formed from the photosensitive resin composition of the present reaction, or the heat treatment may decrease.

Moreover, the positive photosensitive resin composition of this invention can contain a photopolymerizable monomer, and can be used as a means of adjusting the positive physical property by selecting the quantity and kind. The photopolymerizable monomer is a component which is polymerized by exposure. Specifically, monofunctional or polyfunctional methacrylate or acrylate (hereinafter, referred to as (meth) acrylate) is preferably listed. In addition, the photopolymerizable monomer may contain fluorine.

As monofunctional (meth) acrylate, for example, Alonics M-101, Copper M-111, Copper M-114 (made by Dong-A Synthetic Chemical Co., Ltd.), KAYARADTC-110S, and Copper TC-12OS (Japan Explosives Co., Ltd.) ), V-158, V-2311 (made by Osaka Organic Chemical Industry Co., Ltd.) (commercially available product), etc. are mentioned.

As a bifunctional (meth) acrylate, for example, Alonics M-210, Copper M-240, Copper M-6200 (made by Dong-A Synthetic Chemical Co., Ltd.), KAYARAD DDDA, Copper HX-220, Copper R-604 (Made by Nippon Kayaku Co., Ltd.), V260, V312, V335HP (made by Osaka Organic Chemical Industry Co., Ltd.) (commercially available product), etc. are mentioned.

As (meth) acrylate more than trifunctional, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a trisacryloyloxy ethyl phosphate, a pentaerythritol tetra (meth), for example Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and specific examples thereof include Alkonix M-309, Copper M-400, Copper M-405, and Copper. M-450, M-7100, M-8030, M-8060 (made by Dong-A Synthetic Chemical Co., Ltd.), KAYARAD DPHA, TMPTA, DDPCA-20, D-30, D-60, D- 120 (made by Nippon Kayaku Co., Ltd.), V-295, East-300, East-360, East-GPT, East-3PA, East-400 (made by Osaka Organic Chemical Industry Co., Ltd.), PPZ Note) Commercial items, such as (i), are listed.

Among these, trifunctional or higher polyfunctional (meth) acrylates such as Alonics M-400 and KAYARAD DPHA are preferably used.

These monomers can also be used in combination of 2 or more type.

The polymerizable monomer is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass with respect to 100 parts by mass of the acrylic resin (A).

The photosensitive resin composition of the present invention is prepared by dissolving an acrylic resin (A), a 1,2-naphthoquinone diazide group-containing compound, a crosslinking agent and a silane binder, a surfactant, a fluorine compound and the like in a solvent.

Examples of the solvent 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, and 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, 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, 2 Ethyl hydroxypropionate, 2-hydroxy-2-methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propionate Foxy propionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxy acetate, ethyl oxyacetate, 2-hydroxy-3-methylbutyrate, methyl acetate, Ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate , Methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyrivate, ethyl pyrrate, propyl pyrivate, butyl pyrvinate, methyl acetate, ethyl acetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, acetic acid Benzyl, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propinol, butanol, hexanol, cyclohexanol, ethylene glycol, di Ethylene glycol, glycerin, and the like.

Moreover, in order to improve the heat resistance of the photosensitive resin composition and adhesiveness with a board | substrate, you may contain the compound which has two or more epoxy groups in a molecule | numerator. As such an epoxy group containing compound, Bisphenol-A type, such as Epicoat 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (brand name; Emulsion Shell Epoxy Co., Ltd.) Bisphenol F type epoxy resins, such as epoxy resin and epicoat 807 (brand name; Emulsion Shell Epoxy Co., Ltd.), epicoat 152, copper 154 (brand name; Emulsion Shell Epoxy Co., Ltd.), EPPN 201, copper 202 (brand name) : Phenolic novolac-type epoxy resins, such as Nippon Kayaku Co., Ltd., EOCN 102, copper 103S, copper 104S, 1020, 1025, 1027 (brand name; Nippon Kayaku Co., Ltd.), Epicoat 180S75 (brand name; emulsion shell) Cresol novolak-type epoxy resins, such as epoxy (Co., Ltd. product), CY-175, copper 177, copper 179, Aldalite CY-182, copper 192, 184 (brand name; Chiba-Geigi Co., Ltd. product), ERL- 4234, 4299, 4221, 4206 (brand name; product made in UC C), Shodine 509 (brand name; product made by fire extinguishing company), epicron 200, copper 400 (brand name; product made in Japan Nippon Inks Corporation), epicoat 871 , 872 (trade name; oil painting Shell Epoxy Co., Ltd.) Cyclic aliphatic epoxy resins such as ED-5661 and B5662 (trade name; manufactured by Ceranis Coating Co., Ltd.); And aliphatic polyglycidyl ethers such as

Among these, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic polyglycidyl ethers, 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 high molecular weight, or may be low molecular weight such as glycidyl ether of bisphenol A (or F).

The epoxy group containing compound as an arbitrary component is used as needed in the quantity of 5-50 mass parts with respect to 100 mass parts of acrylic resin (A).

Moreover, in the photosensitive resin composition of this invention, an antistatic agent, a storage stabilizer, a halation inhibitor, an antifoamer, a pigment, etc. can also be added as needed.

By using the photosensitive resin composition of this invention, a pattern can be formed as follows, for example. First, the photosensitive resin composition solution of this invention is prepared by melt | dissolving each component in a solvent so that the density | concentration of the solid content may be 5-60 mass% and filtering this in a filter about 0.2-10 micrometers in diameter. And the photosensitive resin composition solution of this invention is apply | coated to the surface of board | substrates, such as a silicon wafer, and pre-bake is performed to remove a solvent and form the coating film of the photosensitive resin composition. Subsequently, a radiation pattern (first exposure) such as a light irradiation treatment is applied to the formed coating film, and then a development pattern is performed to remove the radiation portion, thereby forming a positive pattern.

In addition, in order to improve various properties such as solvent resistance, film strength, heat resistance, etc. of the pattern obtained by development, exposure may be performed again (second exposure), and in order to further increase the effect of exposure, before exposure, during exposure, or exposure. In any of the following, the pattern may be heated. It is preferable to perform this heat processing after exposure preferably, and it is preferable that the light amount of a 2nd exposure is 2-15 times of a 1st exposure.

In the method of this invention, it is preferable to make 2nd exposure amount into 2-15 times the exposure amount of a 1st exposure as 20-150mJ / cm <2>. Moreover, as for heat processing, 100-220 degreeC and 3 to 60 minutes are preferable.

As a method of apply | coating the photosensitive resin composition solution of this invention to a board | substrate, various methods, such as a rotary coating method, a flowchart coating method, and a roll coating method, can be employ | adopted. Pre-bake conditions are a heating temperature of 50-150 degreeC and a heating time for 30 second-600 second, for example. The radiation used in the irradiation treatment includes ultraviolet rays from ultra-high pressure mercury lamps, i-rays of wavelength 365 nm, h-rays of wavelength 405 nm, g-rays of 436 nm, KrF excimer laser of wavelength 248 nm, and ArF excimer laser of wavelength 193 nm. Charged particle beams, such as X-rays or an electron beam, such as an ultraviolet-ray and a syncrotron radiation, are mentioned.

As the developing solution used for the developing treatment, 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- The aqueous alkali solution which dissolves undecene, 1, 5- diazabicyclo [4.3.0] -5-nonane, etc. is mentioned. In addition, a water-soluble organic solvent such as methanol, ethanol, or the like to which an appropriate amount of a surfactant is added may be used. The developing treatment time is, for example, 10 to 300 seconds, and the developing method may be a liquid dipping method, a dipping method, a rocking dipping method, or the like.

After alkali development, the rinse treatment by running water washing is performed, but the rinse treatment is preferably washed with an ultra-high pressure microjet.

The ultra high pressure microjet is sprayed with water from a high pressure jet. The application pressure of the ultrahigh pressure microjet is usually 20 to 350 kgf / cm 2 (2.9 to 34.3 MPa), preferably 30 to 250 kgf / cm 2 (4.9 to 24.5 MPa). This applied pressure is selected according to the shape of the nozzle, and in the present invention, a cat-eye nozzle (cross section is preferably a concave lens shape) is preferable.

The spray angle of the ultra-high pressure microjet has a great influence on the flushing action. The vertical washing with respect to the surface of the photosensitive resin composition is the strongest washing action. On the other hand, the removal of the composition of the non-photosensitive portion is insufficient to be strong only in the washing action, and the unnecessary composition must be removed from the substrate by the impact of mechanical water. The angle between the vertical direction and the spraying direction to the substrate may be about 0 to 20 degrees so that the spraying may be sprayed forward or backward with respect to the traveling direction of the substrate.

In addition, although it is practical to employ continuous water washing as an economical embodiment of the present invention, in this case, a spray nozzle that maintains fan-shaped spreading and sprays so that water is spread evenly in the width direction of the photosensitive resin composition layer alone Alternatively, it is preferable to perform a continuous flushing treatment as a method of plural arrangements in the direction in which the fan is spread, and passing through the injection portion of water while moving the photosensitive resin composition at a constant speed in a direction perpendicular to the jet direction of the fan surface.

By this method, since it can remove effectively also in the deep part of a non-exposed part layer, it can also be used also for the composition which is difficult to remove by the thick general thickness, and can form a favorable pattern.

The high-pressure jetting device having a function for satisfying the injection pressure, impact angle, water flow spreading shape, and the like, which can be particularly preferably used, includes the ultra-high pressure jet precision cleaning system AF series (manufactured by Asahi Sanak Co., Ltd.). Of these, the AF5400S is suitable for relatively high pressure injection, and the AF2800II is suitable for relatively low pressure injection. However, as long as it is a device having the above-mentioned injection application pressure, impact angle, water flow spreading shape, and the like, it is not limited to this kind, and can be applied as a washing means after development in the pattern formation method of the present invention.

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

After the patterned resin composition is washed with water, the patterned thin film is dried on, 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.

The patterned thin film obtained in this way is excellent in physical properties, such as high resolution, flatness, high resolution, developability, heat resistance, chemical-resistance, adhesiveness with a board | substrate, transparency, and insulation. Further, in the photosensitive resin composition, in addition to the above characteristics, the relative dielectric constant of the photosensitive resin composition is lower than 3, preferably lower than 2.8. Therefore, the photosensitive resin composition of the present invention is useful for protective films, planarization films, interlayer insulating films, and the like of electronic components, and especially for microlenses such as interlayer insulating films of liquid crystal display devices, integrated circuit devices, and solid state imaging devices, and solid state imaging devices.

<Example>

Hereinafter, although the photosensitive resin composition of this invention is demonstrated based on an Example, this invention is not limited to these.

Example 1

As acrylic resin (A) 60 mass parts, methacrylic acid polymerization derivative (mass average molecular weight about 2000, allyl group: 40 mol% with respect to the methacrylic acid monomeric unit), 2,3,4- trihydroxy benzophenone-1, 15 parts by mass of 2-naphthoquinone diazide-5-sulfonic acid ester (2S: two of three hydroxyl groups are substituted, one is H), 22 parts by mass of hexamethoxymethylolmelamine, 0.05 parts by mass of the silane binder S3, 200 parts by mass of propylene glycol monomethyl ether acetate was mixed and dissolved in stirring to prepare a photosensitive resin composition.

This was applied onto a glass substrate (Corning 7059) so as to have a film thickness of 5 μm, and then dried in a warm air heater for 2 minutes at 100 ° C. to form an L / S pattern of 2 to 8 μm (line and space of 2 μm, Through a mask of 3 μm, 4 μm, 6 μm, and 8 μm), using an ultra-high pressure mercury lamp and exposing at an exposure dose of 100 mJ / cm 2, and 1.5% by mass of tetramethylammonium hydroxide alkali. The solution was developed at 25 ° C. for 20 seconds, washed with water and dried to obtain a fine pattern. Then, the whole board | substrate was exposed by 2nd exposure with the exposure amount of 400mJ / cm <2>, and it heat-processed at 120 degreeC for 10 minutes, and hardened | cured.

The characteristics of the obtained pattern type heat curing film were evaluated by the following method.

(1) Measurement of dielectric constant: The dielectric constant of the obtained heat-cured film was measured using a dielectric constant measuring apparatus (manufactured by Hewlett-Packard Co., Ltd.) at room temperature and 1 MHz.

The relative dielectric constant was 3.2.

(2) Evaluation of adhesiveness

The adhesiveness at the time of image development is also good, and there is no peeling of any fine wire of 2 micrometers, 3 micrometers, 4 micrometers, 6 micrometers, and 8 micrometers.

(3) evaluation of heat resistance

After measuring the film thickness of the said heat-cured film, it heated further in 30 degreeC oven. And the film thickness after heat processing was measured, and the residual film rate of the heat hardening film was calculated | required. There was almost no change of the residual film rate by heating.

(4) Evaluation of solvent resistance

The heat-cured film was immersed in a mixed solution (volume ratio 3: 7) of dimethyl sulfoxide and monoethanolamine at a temperature of 80 ° C. for 12 minutes, and then washed with water and dried to measure the film thickness. There was almost no change in film thickness due to deposition.

(5) Evaluation of flatness

The surface roughness of the heat-cured film was measured using a contact type film thickness gauge. The flatness was good at an Ra value of 15 Hz.

(6) measurement of transparency

The heat-curable film was measured at a wavelength of 380-800 nm using a double beam type spectrophotometer to obtain transmittance. The film was transparent and had almost no absorption at long wavelengths. The transmittance at 400 nm was 96% even at short wavelengths.

(7) Evaluation of heat discoloration

After further heating the said heat-cured film for 30 minutes in 240 degreeC oven, the transmittance | permeability was measured by the same method as the above. The change in transmittance at 400 nm was 1% and almost no change was observed.

Example 2

As acrylic resin (A) methacrylic acid-benzyl acrylate copolymer derivative (mass average molecular weight about 20000, methacrylic acid: benzyl acrylate = 8: 2 (molar ratio), 40 mol per allyl group: 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, 1 is H 15 mass parts, 22 mass parts of hexamethoxymethylol melamine, 0.05 mass part of said silane binders S3, and 200 mass parts of propylene glycol monomethyl ether acetates were mixed, stirred and dissolved, and the photosensitive resin composition was produced.

Example 3

2,3,4,4'-tetrahydroxybenzophenone- instead of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester in Example 1 A photosensitive resin composition was produced in the same manner as in Example 1 except that 1,2-naphthoquinonediazide-5-sulfonic acid ester was used.

Example 4

In Example 1, tri (p-hydroxyphenyl) methane-1,2-nap instead 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 toquinonediazide-5-sulfonic acid ester (2S: two of three hydroxyl groups were substituted and one was H).

Example 5

4,4 '-[1- [4- [1- [instead of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester in Example 1; 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester (2S: 2 of 3 hydroxyl groups are substituted, 1 is H) A photosensitive resin composition was prepared in the same manner as in Example 1 except for using.

When the photosensitive resin compositions of Examples 2 to 5 were treated in the same manner as in Example 1, the characteristics of the patterned heat cured film were evaluated by the above method, and the relative dielectric constant, adhesiveness, heat resistance, solvent resistance, flatness, transparency, and heat resistance were evaluated. As for color change, all of them were almost the same as in Example 1. However, the transparency of Example 5 was 93%.

Example 6

In Example 1, the photosensitive resin composition was prepared like Example 1 except having used 0.01 mass part of fluorine-type surfactant mega parks F177.

Example 7

In Example 6, 10 mass parts of polyhydroxyethyl methacrylate (mass average molecular weight 15000) which is 50 mass parts of this polymerization derivatives, and acrylic resin (a) was used instead of 60 mass parts of methacrylic acid polymerization derivatives. In the same manner as in Example 6, a photosensitive resin composition was prepared.

Example 8

A photosensitive resin composition in the same manner as in Example 6 except that 18 parts by mass of hexamethoxymethylol melamine was used and 4 parts by mass of 2-ethoxyhexyl glycidyl ether of the epoxy compound was used. It prepared.

When the photosensitive resin compositions of Examples 6 to 8 were treated in the same manner as in Example 1, the characteristics of the patterned heat-curable film were evaluated by the above method, and the flatness was 5 GPa in all Ra values. In addition, about dielectric constant, adhesiveness, heat resistance, solvent resistance, transparency, and heat discoloration, all were substantially the same as Example 1.

Example 9

In each of the photosensitive resin compositions of Examples 1 to 8, 10 parts by mass of a new fluorine compound F1 was added and mixed, stirred and dissolved to prepare a photosensitive resin composition, respectively.

When the characteristics of the patterned heat-curable film obtained by the same treatment as in Example 1 were evaluated by the above method, the specific dielectric constant was 0.3 lower than those in Examples 1 to 8, respectively. In addition, about adhesiveness, heat resistance, solvent resistance, flatness, transparency, and heat discoloration, all were substantially the same as Examples 1-8.

Example 10

In the photosensitive resin composition of Example 4, the photosensitive resin composition was prepared like Example 4 except having used the silane binder S2 instead of the silane binder S3.

Example 11

In the photosensitive resin composition of Example 4, the photosensitive resin composition was prepared like Example 4 except having used the silane binder S4 instead of the silane binder S3.

Example 12

In the photosensitive resin composition of Example 4, the photosensitive resin composition was prepared like Example 4 except having used the silane binder S5 instead of the silane binder S3.

When the photosensitive resin compositions of Examples 10 to 12 were treated in the same manner as in Example 1, the characteristics of the patterned heat cured film were evaluated by the above method, and the relative dielectric constant, adhesion, heat resistance, solvent resistance, flatness, transparency, and heat resistance were evaluated. As for color change, almost all of them were the same as in Example 4.

Comparative Example 1

In the photosensitive resin composition of Example 1, except that the silane binder S3 was removed, the photosensitive resin composition was prepared in the same manner as in Example 1, and the characteristics of the patterned heat cured film obtained by treating in the same manner as in Example 1 were used in the above method. As a result, the dielectric constant, heat resistance, solvent resistance, flatness, transparency, and heat discoloration were almost the same as in Example 1, but peeling was observed in the fine lines of 2 탆 and 3 탆 in adhesion.

The photosensitive resin composition of the present invention can be developed in an alkaline aqueous solution, has a high resolution, high sensitivity, and has a variety of properties such as flatness, heat resistance, solvent resistance, transparency, and the like, and it is difficult to realize simultaneously with these properties. Preferably, the patterned thin film having excellent characteristics can be easily formed by the pattern forming method of the present invention.

Therefore, the photosensitive resin composition of the present invention is a positive resist for producing a mask for manufacturing a circuit such as a semiconductor integrated circuit, a liquid crystal display coating film, a transistor circuit, and also forms a permanent film such as an interlayer insulating film, a protective film for a color filter, and a microlens. It can also use suitably as a material.

Claims (12)

(A) Positive photosensitive property containing alkali-soluble acrylic resin which has unsaturated ethylene group, (B) 1, 2- naphthoquinone diazide group containing compound, (C) crosslinking agent, and (D) silane binder. Resin composition. The compounding quantity of acrylic resin (A) is 100 mass parts of total amounts of acrylic resin (A), a 1, 2- naphthoquinone diazide group containing compound (B), and a crosslinking agent (C) in the said composition. It is 35-95 mass parts with respect to the positive photosensitive resin composition. The compounding quantity of 1,2-naphthoquinone diazide group containing compound (B) is 5-100 mass parts with respect to 100 mass parts of acrylic resin (A) in the said composition, The positive photosensitive property of Claim 1 characterized by the above-mentioned. Resin composition. The positive photosensitive resin compound according to claim 1, further comprising a fluorine-based surfactant. The positive photosensitive resin composition according to claim 1, wherein an alkali-soluble acrylic resin (a) having no unsaturated ethylene group is used in combination with the alkali-soluble acrylic resin (A) having an unsaturated ethylene group. A crosslinking agent (C) is a melamine type compound represented by following formula (I), The positive photosensitive resin composition characterized by the above-mentioned. Equation (Ⅰ) of, R ⁵ is ^{-NR 51 R 52 {R 51,} R 52 are each an H or -CH ₂ OR ⁵³ (R ⁵³ represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms or hydrogen.) .} Or a phenyl group, and R ¹ , R ² , R ³ , and R ⁴ each represent hydrogen or —CH ₂ OR ⁵³ (R ⁵³ represents hydrogen or an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group.). The positive photosensitive resin composition according to claim 1, wherein the crosslinking agent (C) is an epoxy compound. The positive photosensitive resin composition of Claim 1 whose compounding quantity of a crosslinking agent (C) is 2-50 mass parts with respect to acrylic resin (A). The positive photosensitive resin composition of Claim 1 whose compounding quantity of a silane binder (D) is 0.01-5 mass parts with respect to acrylic resin (A). The positive photosensitive resin composition according to claim 1, further comprising a fluorine compound. The positive photosensitive resin composition according to claim 10, wherein the fluorine compound is a fluorinated epoxy compound. The process of applying the positive photosensitive resin composition as described in any one of Claims 1-11, and performing a 1st exposure, image development, 2nd exposure, and heat processing sequentially, WHEREIN: The quantity of light of a 2nd exposure of a 1st exposure Pattern formation method characterized by 2 to 15 times.