JP2003076006A - Positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type 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, high resolution, developability, heat and chemical resistances, adhesion to a substrate, transparency and insulating property, to further provide a positive type 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 to provide a pattern forming method using the composition. SOLUTION: The positive type photosensitive resin composition comprises at least an alkali-soluble resin comprising a copolymer having at least styrenes, acrylic acid or methacrylic acid and a hydroxyalkyl ester as constitutional units, a compound containing a 1,2-naphthoquinonediazido group and a crosslinker. In the pattern forming method, the positive type photosensitive resin composition is applied and subjected to first exposure, development, second exposure and heating in order, and it is characterized in that the quantity of light in the second exposure is 2-15 times that in the first exposure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-soluble resin and a photosensitive resin composition containing the same, and more particularly to a photosensitive resin composition capable of forming a microscopic pattern structure, more specifically a semiconductor integrated circuit. (IC),
Thin film transistor (TF) for liquid crystal display (LCD)
T) As a positive resist for forming a mask for manufacturing a circuit such as a circuit, further, an interlayer insulating film such as a liquid crystal display device, an integrated circuit device, a solid-state imaging device or a permanent film such as a microlens such as a solid-state imaging device. The present invention relates to a positive photosensitive resin composition which is also suitable as a forming material 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 production of electronic components such as solid-state imaging devices, a protective film for preventing deterioration and damage thereof, a flattening film for flattening the device surface, an insulating film for maintaining electrical insulation, etc. are provided. There is. Further, in a TFT type liquid crystal display or an integrated circuit element, an interlayer insulating film is used to insulate between wirings arranged in layers. Generally, TFT for LCD,
In the manufacture of electronic parts 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 by a wet etching method of an IC silicon wafer is required to have adhesiveness with a substrate and chemical resistance that is not attacked by an etching solution. 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 it cannot be used as an optical material such as a protective film of a liquid crystal color filter or a microlens because the color changes due to heat treatment.

The formation of the interlayer insulating film requires a large number of steps, and various characteristics required for the interlayer insulating film, that is, flatness,
It is difficult to secure good resolution, developability, heat resistance, chemical resistance, adhesion to a substrate, transparency, insulation, etc., and a photosensitive resin composition satisfying all of these characteristics. There was no In addition, with respect to the interlayer insulating film, a low dielectric property is required in order to suppress the occurrence of crosstalk with the increase in device density. However, in the conventional photosensitive resin composition, various characteristics and a low dielectric property are required. It was not completely satisfactory in terms of compatibility with sex.

Further, JP-A-6-242599 and JP-A-6-242599
Japanese Patent No. 321890 discloses a radiation-sensitive resin composition comprising a 4- (4-hydroxyphenyl) cyclohexanone phenolic compound and an alkali-soluble resin,
The pattern formation characteristics such as heat resistance were not sufficiently satisfactory.

On the other hand, in order to improve various characteristics of the photosensitive resin composition and the radiation sensitive resin composition, many proposals have been made so far regarding the alkali-soluble resin and the composition containing the same. For example, in JP-A-6-18702, an alkali-soluble polymer composed of a copolymer of hydroxystyrenes and styrene, 1,2-naphthoquinonediazide sulfonic acid ester, and a compound having at least two epoxy groups in the molecule are disclosed. A photosensitive resin composition for a lens containing is disclosed. JP-A-6-136239 discloses an alkali-soluble resin, a 1,2-naphthoquinonediazide compound, a compound containing two or more epoxy groups in the molecule,
A radiation-sensitive resin composition for microlenses containing melamines and trihalomethyltriazines or onium salts is disclosed. Japanese Patent Laid-Open No. 10-307388 discloses a radiation-sensitive resin composition containing an alkali-soluble cyclic polyolefin resin, a 1,2-naphthoquinonediazide compound and a crosslinking agent. JP-A No. 11-52560 discloses an unsaturated carboxylic acid, an alkali-soluble resin composed of a copolymer of an epoxy group-containing radically polymerizable compound and other olefinic unsaturated compounds, and a 1,2-naphthoquinonediazide compound. A radiation-sensitive resin composition containing a nitrogen-containing crosslinking agent is disclosed. JP 2000-3
27877 discloses a radiation-sensitive microlens containing a 1,2-naphthoquinonediazide compound and a copolymer of an unsaturated carboxylic acid, an epoxy group-containing (meth) acrylate and another olefinic unsaturated compound. Resin compositions are disclosed.

However, in the conventional resin composition, various characteristics required for the positive type photosensitive resin composition, that is, high sensitivity, flatness, high resolution, developability, heat resistance, chemical resistance, substrate No composition was obtained that was satisfactory in terms of adhesion, transparency, insulation, etc.

[0008]

The object of the present invention is to develop with an alkaline aqueous solution and to have high sensitivity, and further, flatness, high resolution, developability, heat resistance, chemical resistance, and adhesion to a substrate. Of an alkali-soluble resin capable of easily forming a patterned thin film having excellent properties such as transparency, transparency, and insulation, and a photosensitive resin composition containing the same, as well as the conventional properties described above. It is an object of the present invention to provide a photosensitive resin composition capable of easily forming a patterned thin film having excellent low dielectric properties, which was difficult to achieve, and a pattern forming method using the same.

[0009]

According to the present invention, the above-mentioned object of the present invention is achieved by providing a photosensitive resin composition having the following constitution and a pattern forming method using the same.

(1) at least styrene, acrylic acid or methacrylic acid, and an alkali-soluble resin comprising a copolymer having a hydroxyalkyl ester as a constitutional unit, a 1,2-naphthoquinonediazide group-containing compound, and a crosslinking agent A positive photosensitive resin composition comprising:

(2) The positive photosensitive resin composition as described in (1) above, wherein the 1,2-naphthoquinonediazide group-containing compound is a cyclohexane derivative.

(3) The positive photosensitive resin composition as described in (1) or (2) above, wherein the crosslinking agent is a melamine compound.

(4) The positive photosensitive resin composition as described in any one of (1) to (3) above, wherein the crosslinking agent is an epoxy compound.

(5) In the step of successively applying, first exposing, developing, second exposing, and heat treating the positive photosensitive resin composition according to any one of (1) to (4) above. , Second
The pattern formation method, wherein the light amount of the exposure is 2 to 15 times that of the first exposure.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention will be described in detail below. First, each component to be added to the photosensitive resin composition of the present invention will be described. [I] An alkali-soluble resin comprising a copolymer having at least styrenes, acrylic acid or methacrylic acid, and a hydroxyalkyl ester as a constituent unit. (Hereinafter, also referred to as "resin (A)")

The resin (A) of the present invention represents a copolymer having at least styrenes, acrylic acid or methacrylic acid, and a hydroxyalkyl ester as a constituent unit. Examples of styrenes include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene,
Examples thereof include p-methylstyrene, p-vinyltoluene, p-methoxystyrene and the like. As the hydroxyalkyl ester, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl methacrylate and the like can be mentioned.

The resin (A) of the present invention may contain other copolymerization component as a constituent unit in addition to styrenes, acrylic acid or methacrylic acid, and hydroxyalkyl ester. Other copolymerizable components include acrylic acid alkyl esters (eg, methyl acrylate, isopropyl acrylate, etc.), methacrylic acid alkyl esters (eg, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-).
Butyl methacrylate, tert-butyl methacrylate, etc.), methacrylic acid cyclic alkyl ester (for example,
Cyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate,
Isoboronyl methacrylate, etc.), Acrylic acid cyclic alkyl ester (eg, dicyclopentanyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isobornyl acrylate, etc.), Methacrylic acid aryl ester (eg, phenyl) Methacrylate, benzyl methacrylate, etc.), acrylic acid aryl esters (phenyl acrylate, benzyl acrylate, etc.), dicarboxylic acid diesters (diethyl maleate, diethyl fumarate, diethyl itaconate, etc.) and the like. This resin (A) is
The mass average molecular weight is preferably 1,000 to 100,000, and more preferably 3,000 to 70,000.
It is 0. If the mass average molecular weight is too low, the film forming ability is poor and the film slippage becomes severe during development. On the other hand, if it is too high, the development time becomes long and the substrate may be adversely affected.

The blending amount of the resin (A) is such that the resin (A),
The amount of 1,2-naphthoquinonediazide group-containing compound and the cross-linking agent is preferably in the range of 35 to 95 parts by weight, more preferably 45 to 85 parts by weight, based on 100 parts by weight. If the blending amount is too low, the transparency, insulating property and coating property are deteriorated, while if the blending amount is too large, the sensitivity is lowered and curing failure is caused, which is not preferable. In the photosensitive resin composition of the present invention, another alkali-soluble resin can be used in combination with the above alkali-soluble resin (A). This resin which can be used together is also referred to as a resin (a). Examples of the resin (a) include those disclosed in JP-A-10-
Alkali-soluble cyclic polyolefin-based resin described in JP-A No. 307388, JP-A-2000-327877.
Copolymers with unsaturated carboxylic acids, epoxy group-containing (meth) acrylates and other olefinic unsaturated compounds described in Japanese Patent Application No. 2001-15898.
1, an acrylic resin having a polymerizable group,
Examples thereof include a copolymer of styrene and (meth) acrylic acid, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid, and the like. These resins (a) that can be used in combination are
The acid value is preferably in the range of 50 to 150. Also,
The molecular weight is 1,000 to 100,000, more preferably 3,000 to 70,000. The resin (a) is usually 0 to 50% by mass, preferably 0, relative to the resin (A).
~ 30 mass% is used.

[II] 1,2-naphthoquinonediazide group-containing compound The 1,2-naphthoquinonediazide group-containing compound used in the composition of the present invention is, for example, 1,2 represented by the following general formula (1): Examples include cyclohexane derivatives containing a naphthoquinonediazide group.

[0020]

[Chemical 1]

In the general formula (1), X _{1 to} X ₁₅ may be the same or different and each is a hydrogen atom, an alkyl group, an alkoxy group or a group represented by --OD (wherein D has a hydrogen atom or a quinonediazide skeleton). Is an organic group), provided that at least one of X _{1 to} X ₁₅ is an -OD group. And, at least one, preferably 1 to 5, and more preferably 2 to 5 of D existing in the general formula (1) is an organic group having a quinonediazide skeleton. Further, in the general formula (1), at least one of X _{1 to} X ₅ and at least one of X _{6 to} X ₁₀ are preferably —OD groups.

In X _{1 to} X ₁₅ , the alkyl group preferably has 1 to 4 carbon atoms, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group and n.
Examples thereof include -butyl group and t-butyl group. The alkoxy group preferably has 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group.

The quinonediazide skeleton in D of the -OD group is preferably the following general formula (4) or the following general formula (5).
Alternatively, the skeleton is represented by the general formula (6).

[0024]

[Chemical 2]

Examples of the organic group having such a quinonediazide skeleton include 1,2-benzoquinonediazide-
4-sulfonyl group, 1,2-naphthoquinonediazide-4
-Sulfonyl group, 1,2-naphthoquinonediazide-5-
A sulfonyl group, a 1,2-quinonediazide-6-sulfonyl group, a 2,1-naphthoquinonediazide-4-sulfonyl group, a 2,1-naphthoquinonediazide-5-sulfonyl group and the like are shown. Of these, a 1,2-naphthoquinonediazide-4-sulfonyl group and a 1,2-naphthoquinonediazide-5-sulfonyl group are particularly preferable.

In the general formula (1), the compound corresponding to the case where all D are hydrogen atoms, that is, the compound corresponding to the case where the group represented by -OD is a hydroxyl group is the compound represented by the general formula (1). [Hereinafter, the precursor of the general formula (1) is referred to as "compound (a)"].

Specific examples of the compound "(a)" include compounds represented by the following formulas (a-1) to (a-18).

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

The compound (a) is, for example, a phenol compound and a ketone compound represented by the following general formula.

[0033]

[Chemical 7]

(Wherein X _{31 to} X ₃₅ are the same or different and each is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. Is shown) and is reacted in the presence of an acidic catalyst.

The phenols include phenol,
o-cresol, m-cresol, p-cresol,
2,5-xylenol, 3,4-xylenol, resorcinol, catechol, hydroquinone, methylhydroquinone, phloroglucinol, pyrogallol, p-monomethoxyhydroquinone, m-monomethoxyresorcinol, o-monomethoxycatechol and the like are preferable.

Specific examples of the ketone compound represented by the above general formula include the following general formulas.

[0037]

[Chemical 8]

Examples thereof include compounds represented by:

As the compound represented by the general formula (1), 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester of the above-mentioned compound (a), 1,2 2-naphthoquinonediazide-6-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, 1,2
There may be mentioned 1,2-quinonediazidesulfonic acid esters such as benzoquinonediazide-4-sulfonic acid ester. Of these, preferred compounds are 1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 1,
2-naphthoquinonediazide-5-sulfonic acid ester and the like.

The compound represented by the general formula (1) can be obtained, for example, by esterifying the compound (a) with 1,2-quinonediazidesulfonyl halide in the presence of a basic catalyst. In this case, the reaction ratio between the compound (a) and 1,2-quinonediazidesulfonyl halide is 0.2 to 1 mol of 1,2-quinonediazidesulfonyl halide per 1 gram equivalent of the phenolic hydroxyl group of the compound (a). Is preferred, and particularly preferred is 0.
It is 4-1 mol.

The average esterification rate of the compound represented by the general formula (1) is preferably 30 to 100%. If the average esterification rate is less than 30%, the resolution may be deteriorated or the pattern shape may be deteriorated.

In addition, 1,2-naphthoquinonediazide sulfonic acid ester can also be used as the 1,2-naphthoquinonediazide group-containing compound used in the present invention.
As this ester, a compound obtained by esterifying all or part of the hydroxyl groups of the polyhydric phenol with 1,2-naphthoquinonediazide sulfonic acid can be used. Specifically, 20 to 100% of the hydroxyl groups of the polyhydric phenol can be used. A compound esterified with 1,2-naphthoquinonediazide sulfonic acid can be used.

Examples of the 1,2-naphthoquinonediazide group-containing compound include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone- 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4
-Sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and other trihydroxybenzophenone 1,2-naphthoquinonediazidesulfonic 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 -Naphthoquinonediazide-4-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonate, 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-naphthoquinonediazide-5-sulfonic acid ester, etc. 1,2-naphthoquinonediazide sulfonic acid ester of tetrahydroxybenzophenone, 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 such as pentahydroxybenzophenone 1,2-naphthoquinonediazide sulfonate, 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', 4'5 ' -Hexahydroxybenzophenone-
1,2-Naphthoquinonediazide-5-sulfonic acid ester and other hexahydroxybenzophenones 1,2-naphthoquinonediazidesulfonic 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-sulfone 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-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-sulfonate, 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-methyl Ethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonate, 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 ester,
Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-
Sulfonate, 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'-Trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1,2-naphthoquinonediazide 1,2- of (polyhydroxyphenyl) alkanes such as -5-sulfonic acid ester
Examples include naphthoquinone diazide sulfonic acid ester.

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

The 1,2-naphthoquinonediazide group-containing compound is used as the resin (A) 10 in the photosensitive resin composition according to the present invention.
It is desirable that the amount is usually 5 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 0 parts by mass. When the amount is less than 5 parts by mass, the amount of acid generated by exposure is small, so that the coating film formed from the composition has a small difference in solubility between the exposed part and the unexposed part in a developing solution, which makes patterning difficult. On the other hand, when it exceeds 100 parts by mass, the 1,2-naphthoquinonediazide group-containing compound is not sufficiently decomposed and remains in the light irradiation for a short time, so that the sensitivity may be lowered.

As the 1,2-naphthoquinonediazide group-containing compound used in the composition of the present invention, the cyclohexane derivative represented by the above general formula (1) is particularly preferable.

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

[0048]

[Chemical 9]

In the formula (I), R^FiveIs -NR⁵¹R⁵²{R⁵¹, R
⁵²Are each hydrogen or -CH₂OR⁵³(R⁵³Is hydrogen or charcoal
Indicates an alkyl group or cycloalkyl group having a prime number of 1 to 6
You ) Is shown. } Or a phenyl group, and R¹, R², R
³, R^FourAre each hydrogen or -CH ₂OR⁵³(R⁵³Is hydrogen or
Is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group
Show. ) Is shown. R above⁵³Alkyl group or cyclo
As the alkyl group, methyl group, ethyl group, n-propyl group
Group, isopropyl group, n-butyl group, isobutyl group, t
-Butyl group, n-amyl group, isoamyl group, n-hexyl
And a cyclohexyl group.

Crosslinking represented by the formula (I) used in the present invention
Specific examples of the agent include, for example, hexamethylol melami
(R¹, R², R³, R^Four, R⁵¹, R⁵²Are each -CH₂
OH) and alkylated hexamethylol melamine
(R¹, R², R³, R^Four, R⁵¹, R⁵²Are each -CH₂O
R⁵³, And R⁵³Preferably has 1 to 3 carbon atoms, partial methyl
Rolled melamine (R¹, R², R³, R^Four, R⁵¹, R⁵²Or
1 to 5 selected from -CH₂OH and non-selection is water
Element) and its alkylated form (preferably R)⁵³Has 1 carbon
~ 3), tetramethylol benzoguanamine (R¹，
R², R³, R^FourAre each -CH₂OH, R^FiveIs phenyl
Group) and alkylated tetramethylol benzoguanamine
(Preferably R⁵³Has 1 to 3 carbon atoms, partial methylolation
Benzoguanamine (R ¹, R², R³, R^FourSelected from
1 to 3 are -CH₂OH and non-selective hydrogen) and its
Alkylation (preferably R⁵³Has 1 to 3 carbon atoms,
Or an oligomer of the above compound (preferably, monomer 2 to
5) and the like.

Other cross-linking agents used in the present invention include:
Examples thereof include epoxy compounds, phenol compounds, azo compounds, isocyanate compounds, and the like, of which epoxy compounds are preferable. For example, the epoxy curing agent is a compound having one or more epoxy groups on average in the molecule, for example, n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, Glycidyl ethers such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester,
Glycidyl esters such as 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, alicyclic epoxies such as bis (2,3-epoxycyclopentyl) ether, etc. Is mentioned.

The cross-linking agent is preferably blended in the range of 2 to 50 parts by mass with respect to the resin (A), more preferably 4 parts by mass.
~ 40 parts by mass. If the blending amount is too small, the sensitivity may be lowered to cause poor development, whereas if the blending amount is too large, the transparency, insulating property or coating property may be deteriorated.

[IV] Other Additives In addition to the above components, the positive photosensitive resin composition of the present invention comprises
A photopolymerization initiator may be contained to accelerate curing. 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 radical photopolymerization 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, and 2,2. 4-diethylthioxanthone, thioxanthones such as thioxanthone-4-sulfonic acid, benzophenone, benzophenones such as 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, Michler's ketones, acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophene 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, trihalomethylphenyl sulfone, tris (trihalomethyl) ) -S-Triazine and other halogen compounds, acylphosphine oxides, di-t-butyl peroxide and other peroxides, and the like.

Further, as a radical photopolymerization agent, for example, IR
GACURE-184, 261, 369, 500, 6
51, the same 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 (manufactured by AKZO Co.LTD), SANDORAY 1000 (SANDOZ Co.
LTD), DEAP (APJOHN Co.LTD), QUANTACURE-PD
Commercially available products such as O, ITX, EPD (manufactured by WARD BLEKINSOP Co.LTD) can also be used.

As the photocationic polymerization initiator, diazonium salts, triphenylsulfonium salts, metallocene compounds, diaryl iodonium salts, nitrobenzyl sulfonates, α-sulfonyloxyketones,
Examples include diphenyldisulfones and imidyl sulfonates. As a photocationic polymerization initiator, Adeka Ultraset PP-33, OPTMER SP-150, and 170 (manufactured by Asahi Denka Co., Ltd.) (diazonium salt),
OPTOMER SP-150, 170 (manufactured by Asahi Denka Co., Ltd.) (sulfonium salt), IRGACURE 2
61 (manufactured by Ciba-Geigy Co., Ltd.) (metallocene compound)
It is also possible to use a commercially available product such as.

Examples of the photoamine generator include nitrobenzicarbamates and iminosulfonates.
These photopolymerization initiators are appropriately selected and used depending on the exposure conditions (for example, oxygen atmosphere or oxygen-free atmosphere). Further, these photopolymerization initiators,
It is also possible to use two or more types in combination.

The photopolymerization initiator is added in an amount of preferably 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 decrease. .

The positive type photosensitive resin composition of the present invention may contain a photopolymerizable monomer, and can be used as a means for adjusting the physical properties of a positive image by selecting the amount and type of the photopolymerizable monomer. . The photopolymerizable monomer is a component that is polymerized by exposure. Specifically, monofunctional or polyfunctional methacrylates or acrylates (hereinafter referred to as (meth) acrylates) are preferable. Further, the photopolymerizable monomer may contain fluorine.

As the monofunctional (meth) acrylate,
For example, Aronix M-101, M-111, M
-114 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARA
DTC-110S, TC-120S (Nippon Kayaku Co., Ltd.)
Manufactured by Osaka Organic Chemical Industry Co., Ltd. (commercially available), and the like.

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

Examples of tri- or higher functional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are mentioned, and specifically, Aronix M-309,
Same M-400, Same M-405, Same M-450, Same M-7
100, the same M-8030, the same M-8060 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD DPHA, the same TM
PTA, DPCA-20, -30, -60, and-
120 (manufactured by Nippon Kayaku Co., Ltd.), V-295, and -30.
0, same-360, same-GPT, same-3PA, same-400
Commercial products such as (produced by Osaka Organic Chemical Industry Co., Ltd.) and PPZ (produced by Idemitsu Petrochemical Co., Ltd.) can be mentioned.

Of these, Aronix M-400,
Trifunctional or higher polyfunctional (meth) acrylates such as KAYARAD DPHA are preferably used. These monomers can be used in combination of two or more.

The photopolymerizable monomer is blended in an amount of preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). Further, the photosensitive resin composition according to the present invention can improve the adhesiveness with the substrate by including the silane coupling agent. The silane coupling agent preferably includes a functional silane coupling agent. Examples of the functional silane coupling agent are shown below, and among them, 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:

[0065]

[Chemical 10]

S4. γ-methacryloxypropyltrimethoxysilane:

[0067]

[Chemical 11]

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 with respect to the alkali-soluble resin (A). Two or more of these may be used. Such a 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 in the photosensitive resin composition is 100 parts by mass.

The photosensitive resin composition of the present invention preferably contains 3% by mass of fluorine atoms in the solid content of the photosensitive resin composition of the present invention so that the cured film contains fluorine atoms.
As described above, by more preferably containing 5 to 30% by mass, a patterned thin film having excellent low dielectric properties in addition to other properties can be more easily formed. A fluorine compound is used as a fluorine atom source capable of providing such a patterned thin film having an excellent low dielectric property. The fluorine compound used in the present invention is a resin (A) when exposed to light or heated.
May be bonded to a carboxyl group contained in, or may be bonded to a cross-linking agent, and further may be polymerized between fluorine compounds, as a mixture of the photosensitive resin composition without reacting with these It may exist.
Typical examples of the fluorine compound are compounds to which the fluorine-containing groups shown in the following (1) to (8) are bound.

[0070] _{(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) -

[0071]

[Chemical 12]

Here, n is usually 1 to 10, preferably 5
~ 8. Further, in the formulas (7) and (8), hydrogen on the benzene ring may be substituted with a substituent such as fluorine, 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 and amines.
Of these, epoxy compounds, acrylates, methacrylates, and amines are preferable.

Specific examples of these fluorine-containing epoxy compounds, acrylates, methacrylates, and amines include the groups shown in Table 1 below and the above (1) to
The compound which the fluorine-containing group shown by (8) couple | bonded can be mentioned.

[0075]

[Table 1]

In the frame of Table 1 above, for example, a group containing epoxy as an epoxy compound is described. The epoxy compound means the group and the above (1) to (8).
It means various epoxy compounds formed by combining with the fluorine-containing group described in 1. The same applies to other compounds. As the fluorine compound, epoxy compounds and amines are preferable, and particularly, fluorinated aromatic epoxy compounds having an aromatic fluorine-containing group such as (7) and (8) above, and fats such as (1) above. Fluoroaliphatic compounds having a group-containing fluorine-containing group are preferred. Preferred examples of the fluorinated aromatic epoxy compound include:

[0077]

[Chemical 13]

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

[0079]

[Chemical 14]

2,2-bis [4- (2,3-epoxypropoxy) phenyl] hexafluoropropane can be mentioned, and preferable examples of the fluorinated aliphatic compound include:

[0081]

[Chemical 15]

And the like.

The photosensitive resin composition of the present invention comprises a resin (A), a 1,2-naphthoquinonediazide group-containing compound and a crosslinking agent, and optionally a photopolymerization initiator, a silane coupling agent, a fluorine compound and the like. Is dissolved in a solvent to prepare.

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 persobutyl 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, benzylmethyl 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, glycerin and the like.

Further, in the present invention, a surfactant may be added to improve the coatability of the photosensitive resin composition, for example, to prevent striation (coating streaks) and to improve the developability of the coating film. As the surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether,
Nonionic surfactants such as polyoxyethylene aryl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene dilaurate, polyoxyethylene dialkyl esters such as polyoxyethylene distearate, Ftop EF301, and 30
3, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFacque F
171, the same F172, the same F173, the same F177 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-430,
FC-431 (Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC-10
1, the same SC-102, the same SC-103, the same SC-10
4, the same SC-105, the same SC-106 (Asahi Glass Co., Ltd.
Fluorine-based surfactants marketed under the name
Organosiloxane polymer KP341 (produced by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based copolymer polyflow
No. 57 and 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like.

Two or more of these may be used. The amount of such a surfactant in the photosensitive resin composition is 1
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.

Further, in order to improve the heat resistance of the photosensitive resin composition and the adhesion to the substrate, a compound having at least two epoxy groups in the molecule may be contained. Examples of such epoxy group-containing compounds include Epicoat 1001, 1002, 1003, and 100.
4, same 1007, same 1009, same 1010, same 828
(Brand name: Yuka Shell Epoxy Co., Ltd.) and other bisphenol A type epoxy resins, Epicoat 807 (Brand name; Yuka Shell Epoxy Co., Ltd.) and other bisphenol F type epoxy resins, Epicoat 152, 154 ( Product name; Yuka Shell Epoxy Co., Ltd., EPPN20
1, phenol 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.) and other phenol novolac type epoxy resins, EOCN102, 103S, 104S, 1020, 1025, 1027.
(Trade name; manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S7
5 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.) and other cresol novolac type epoxy resins, CY-175 and 1
77, 179, Aldalite CY-182, 19
2,184 (trade name; manufactured by Ciba-Geigy Co., Ltd.), ER
L-4234, 4299, 4221, 4206 (trade name; manufactured by U.C.C. company), Shodyne 509 (trade name;
Showa Denko KK, Epicron 200, 400 (trade name; manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), ED
-5661, 5662 (trade name; manufactured by Celanese Coating Co., Ltd.) and other cycloaliphatic epoxy resins, Epolite 100MF (manufactured by Kyoeisha Yushi-Kagaku Kogyo Co., Ltd.), Epiol TMP (manufactured by NOF CORPORATION) Examples thereof include aliphatic polyglycidyl ether.

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

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

The epoxy group-containing compound as an optional component is optionally used in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of the resin (A). Furthermore, in the photosensitive resin composition of the present invention, an antistatic agent, a storage stabilizer, an antihalation agent, an antifoaming agent, a pigment and the like can be added, if necessary.

By using the photosensitive resin composition of the present invention, a pattern can be formed, for example, as follows. First, each component, for example, its solid content concentration is 5
The photosensitive resin composition solution of the present invention is prepared by dissolving it in a solvent so that the concentration becomes ˜60% by mass, and filtering this with a filter having a pore size of about 0.2 to 10 μm. And
The photosensitive resin composition solution of the present invention is applied to the surface of a substrate such as a silicon wafer and prebaked to remove the solvent, thereby forming a coating film of the photosensitive resin composition. Then, the formed coating film is subjected to a radiation irradiation process (first exposure) such as a light irradiation process, and then a development process is performed to remove the radiation irradiation portion to form a positive pattern. The solvent resistance of the pattern obtained by development,
To improve various properties such as film strength and heat resistance, further exposure (second exposure) may be performed. To further enhance the effect of exposure, the pattern is heated before, during or after exposure. You may. 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, the second exposure amount is preferably 2 to 15 times the exposure amount of the first exposure with 20 to 150 mJ / cm ² . The heat treatment is 100 to 22.
0 degreeC and 3 to 60 minutes are preferable.

As a method for applying the photosensitive resin composition solution of the present invention to a substrate, various methods such as a spin coating method, a cast coating method and a roll coating method can be adopted. The prebaking conditions are, for example, a heating temperature of 50 to 150 ° C. and a heating time of 30 seconds to 600 seconds. The radiation used for the radiation irradiation treatment is ultraviolet rays 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,
Examples include far-ultraviolet rays such as g-line of 436 nm, KrF excimer laser of wavelength 248 nm and ArF excimer laser of wavelength 193 nm, X-rays such as synchrotron radiation, and charged particle beams such as electron beams.

The developer used in the developing treatment is preferably, for example, sodium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine or di-n-. Propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline,
Pyrrole, piperidine, 1,8-diazabicyclo [5.
An alkaline aqueous solution obtained by dissolving 4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane and the like can be mentioned. In addition, in this alkaline aqueous solution,
It is also possible to use a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, or those to which an appropriate amount of a surfactant is added. The development processing time is, for example, 10 to 10.
It takes 300 seconds, and as a developing method, a puddle method, a dipping method, a rocking dipping method or the like can be used. After the alkali development, a rinse treatment by washing with running water is carried out. As the rinse treatment, washing with an ultrahigh pressure micro jet is preferred.

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

Further, it is practical to employ continuous water washing as an economical embodiment of the present invention. In that case, the fan is so arranged that water is evenly distributed in the width direction of the photosensitive resin composition layer. A single spray nozzle for spraying with a mold spread or a plurality of spray nozzles arranged in a fan spread direction, and the photosensitive resin composition moves at a constant speed in a direction perpendicular to the fan-shaped spray direction and passes through a water spray portion. It is preferable to carry out the continuous water washing treatment according to the above method.

According to this method, even a deep portion of the non-exposed portion layer is effectively removed, and therefore it can be used for a composition having a large layer thickness and generally hard to be removed, and a pattern having a good profile is formed. Can be made.

The high-pressure jet device, which has a function of satisfying the above-mentioned jet pressure, impact angle, water flow spread shape, etc. and which can be particularly preferably used, includes the ultra-high pressure jet precision cleaning system AF series (Asahi Sunac Co., Ltd.). To be Among them, AF5400S is suitable for relatively high-pressure injection, and AF2800II is suitable for relatively low-pressure injection. However, the apparatus is not limited to this model as long as it has the above-mentioned jetting applied pressure, impact angle, water stream spreading shape, etc., 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 ultra-high pressure micro jet is strong and extends to a deep portion, the non-patterned portion is substantially removed by washing with water.

The patterned resin composition is, after the above-mentioned washing treatment, 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. It The patterned thin film thus obtained has high resolution, flatness, high resolution, developability, heat resistance,
Excellent physical properties such as chemical resistance, adhesion to substrates, transparency, and insulation. The photosensitive resin composition further containing a fluorine compound has a low 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 as a protective film for electronic parts, a flattening film, an interlayer insulating film, and the like, and in particular, a liquid crystal display device, an integrated circuit device and an interlayer insulating film of a solid-state imaging device,
It is useful for microlenses such as solid-state imaging devices.

[0100]

EXAMPLES The photosensitive resin composition of the present invention will be described below based on examples, but the present invention is not limited thereto.

Example 1 A terpolymer of styrene, methacrylic acid and 2-hydroxyethyl methacrylate (copolymerization ratio 48: 22: 3)
0; mass molecular weight of about 15,000) 60 parts by mass of the present invention
15 parts by mass of the above photosensitizer a-1 (2S: 2 of 3 hydroxyl groups are substituted), hexamethoxymethylol melamine 2
2 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.

A glass substrate (Corning 705)
9) After spin coating so that the film thickness becomes 3 μm,
Dry on a hot plate at 100 ℃ for 2 minutes, 4μ
Through an m-square pattern mask, an exposure of 100 mJ / cm ² was performed using an ultra-high pressure mercury lamp, and a developing solution manufactured by Fuji Film Arch Co., Ltd.
It was developed for 60 seconds at 25 ° C. with a developing solution diluted to 1, washed with water and dried to obtain a fine pattern. After that, the entire substrate is second-exposed with an exposure amount of 400 mJ / cm ² , and 200 ° C.
And heat treated for 2 minutes to cure.

The characteristics of the obtained patterned thermosetting 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 Co.) at room temperature and 1 MHz. The relative dielectric constant was 3.4.

(2) Evaluation of heat resistance After measuring the film thickness of the above heat-cured film, it was further heated in an oven at 200 ° C. for 30 minutes. Then, the film thickness after the heat treatment was measured. There was almost no change in the film thickness due to heating.

(3) Evaluation of solvent resistance The above-mentioned heat-cured film was immersed in an NMP solution at room temperature for 10 minutes, washed with water and dried to measure the film thickness. There was almost no change in film thickness due to immersion.

(4) Measurement of Transparency The above heat-cured film was measured with a double beam type spectrophotometer at a wavelength of 380 to 700 nm to determine the transmittance. The film was transparent and hardly absorbed at long wavelengths, and the transmittance at 400 nm was 96% even at short wavelengths.

(5) Evaluation of heat discoloration resistance The above heat-cured film was further subjected to 30 ° C. in an oven at 230 ° C.
After heating for a minute, the transmittance was measured by the same method as above. The change in transmittance at 400 nm was 3%, and almost no color change was observed.

Comparative Example In Example 1, instead of the copolymer of the present invention, a copolymer of styrene and methacrylic acid (copolymerization ratio 78: 2
2; A photosensitive resin composition was prepared in the same manner as in Example 1 except that a mass average molecular weight of about 15,000) was used. The obtained resin composition was exposed and developed through a mask in the same manner as in Example 1, but the residual film rate was low and the pattern film thickness was thin, probably because of its high solubility in an alkali developing solution.
No good pattern was obtained.

Example 2 In Example 1, a-1 used as the photosensitizer was replaced with a
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition was changed to -9.

Example 3 In Example 1, a-1 used as the photosensitizer was replaced with a
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the photosensitive resin composition was changed to -17.

Example 4 In Example 1, a-1 used as the photosensitizer was replaced with a
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the photosensitive resin composition was changed to -18.

Example 5 In Example 1, a-1 used as a photosensitizer was replaced with a
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition was changed to -8.

Example 6 In Example 1, a-1 used as a photosensitizer was replaced with 4,
4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester
A photosensitive resin composition was prepared in the same manner as in Example 1.

Example 7 Instead of the terpolymer used in Example 1, a terpolymer of styrene, methacrylic acid, 2-hydroxyethyl methacrylate and dicyclopentanyl acrylate (copolymerization ratio 40: 22: 30: 8; A photosensitive resin composition was prepared in the same manner as in Example 1 except that a mass average molecular weight of about 15,000 was used.

Example 8 Instead of the terpolymer used in Example 1, a terpolymer of styrene, methacrylic acid, 2-hydroxyethyl methacrylate and cyclohexyl methacrylate (copolymerization ratio 40:22:30) was used. : 8; A photosensitive resin composition was prepared in the same manner as in Example 1 except that a mass average molecular weight of about 15,000) was used.

The characteristics of the patterned thermosetting films obtained by treating the photosensitive resin compositions of Examples 2 to 8 in the same manner as in Example 1 were evaluated by the above-mentioned methods. The solvent resistance, transparency and heat discoloration resistance were almost the same as in Example 1 except for Example 6. In addition, Example 6
Also, in the heat-resistant discoloration evaluation as well, the change in transmittance was 5%, but there was no problem in practical use.

[0118]

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 characteristics such as heat resistance, solvent resistance, transparency and heat discoloration resistance. It is possible to easily form a patterned thin film having an excellent low dielectric property, which has been difficult to realize simultaneously with these properties, preferably by the pattern forming method of the present invention. Therefore, the photosensitive resin composition of the present invention is used as a positive resist for preparing 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 or a microlens.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 21/30 502C

Claims (5)

[Claims] 1. An alkali-soluble resin comprising at least styrene, acrylic acid or methacrylic acid, and a copolymer having a hydroxyalkyl ester as a constituent unit, a 1,2-naphthoquinonediazide group-containing compound, and a crosslinking agent. A positive photosensitive resin composition characterized by the above. 2. The positive photosensitive resin composition according to claim 1, wherein the 1,2-naphthoquinonediazide group-containing compound is a cyclohexane derivative. 3. The positive photosensitive resin composition according to claim 1, wherein the crosslinking agent is a melamine compound. 4. The positive photosensitive resin composition according to claim 1, wherein the crosslinking agent is an epoxy compound. 5. The second exposure in the step of sequentially applying, positively exposing, developing, secondly exposing, and heat treating the positive photosensitive resin composition according to claim 1. The amount of light is 2 to 15 times that of the first exposure.