JPS60121445A - Positive type photosensitive resin composition - Google Patents

Abstract

PURPOSE:To prevent precipitation of photosensitive agent crystals even during long term storage, to enhance sensitivity, resolution, and residual film rate, to improve developability, and to obtain excellent heat resistance by incorporating a specified compd. in an alkali-soluble resin. CONSTITUTION:A hundred pts.wt. of an alkali-soluble resin incorporates 5- 100pts.wt. of one kind of compds. represented by formulae I and II in which (a), (b) are each 3 or 4; (l), (m), (n), are each 0, 1, 2, or 3; (c) is 1-4; each of a-l, b-m and c-n is 1, 2, 3, or 4; R1, R5, R7 are each 1,2-naphthoquinonediazide-4-sulfonyl or 1,2-benzoquinonediazide-4-sulfonyl, or the like; R2, R6, R8, R11 are each H, halogen, alkyl, aryl, or the like; and R3, R4, R9, R10 are each H, alkyl, aryl, aralkyl, or the like, and each pair of R3 and R4, R9 and R10 may form a ring with c-c bonds or -O- bonds. As a result, the crystals of quinonediazide contained in the positive type photosensitive compsn. is prevented from precipitating during storage, and said compsn. can be enhanced in sensitivity, resolution, and residual film rate, and improved in developability and heat resistance, and therefore, it can be used for manufacture of integrated circuits, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a positive-working photosensitive resin composition, and more specifically, the present invention relates to a positive photosensitive resin composition, and more specifically, a crystal of a 1°2-quinonediazide compound prepared by blending an alkali-soluble resin with a specific 1,2-quinonediazide compound. (2) A positive photosensitive photoresist suitable for use as a photoresist that does not cause precipitation, has high sensitivity, high resolution, and high residual film rate, has excellent developability, and has heat resistance for integrated circuit production. The present invention relates to a resin composition.

Conventionally, as a photoresist for manufacturing integrated circuits, a negative photoresist in which a bisazide compound is blended with cyclized isoprene rubber is known.

However, this negative type photoresist has a limitation in resolution, and therefore has the disadvantage that it cannot sufficiently respond to higher integration of integrated circuits. On the other hand, in contrast to the negative photoresist, the positive photoresist has superior resolution and is therefore considered to be fully compatible with the increasing integration density of integrated circuits.

Currently, the positive photoresists commonly used in this field are 1,2-
Contains a quinonediazide compound.

However, conventional positive photoresists are 1.2-
Crystals of the quinonediazide compound are precipitated, and satisfactory results are not necessarily obtained in terms of various performances such as sensitivity, resolution (3) degree, residual film rate, etc. as a positive photoresist.

The purpose of the present invention is to eliminate the drawbacks of the prior art described in 1.
An object of the present invention is to provide a positive photosensitive resin composition that does not precipitate crystals of a 2-quinonediazide compound, has high sensitivity, high resolution, and high residual film rate, and has excellent developability and heat resistance. .

In order to achieve this objective, the present inventors have conducted extensive research and found that alkali-soluble resins with specific 1. The present invention was achieved by discovering that the above drawbacks can be improved by incorporating a 2-quinonediazide compound.

The positive photosensitive resin composition of the present invention has the following general formula (1) or the following general formula (II) (4) (wherein a and b are the same or different, 3 or an integer of 4, l and m are the same or different, 0 or 1-3
C is an integer of 1 to 4, n is an integer of 0 or 1 to 3, and (a-12), (b-m) and (c-
n) are all integers of 1 or more, R+, Rs and R7
are the same or different, 1,2-naphthoquinonediazide-
4-sulfonyl group, 1,2-naphthoquinonediazide-5
-Sulfonyl group or 1,2-benzoquinonediazide-
4-sulfonyl group, R2, R,, Re and R1+ are the same or different, and each has 1 to 1 carbon atoms, such as a halogen atom such as a hydrogen atom, a chlorine atom, or a bromine atom, or an alkyl group, preferably a methyl group, an ethyl group, or a propyl group. 4 alkyl groups, aryl groups such as phenyl groups and naphthyl groups, aralkyl groups such as benzyl groups, alkoxy groups, preferably alkoxy groups having 1 to 7 carbon atoms such as methoxy groups, phenoxy groups, and benzyloxy groups, cyano groups, or The nitro group, R3, R4, R2 and RjO are the same or different, and are a hydrogen atom, an alkyl group, preferably a methyl group, an ethyl group, a propyl group, (5) an alkyl group having 1 to 6 carbon atoms such as a hexyl group, phenyl or an aryl group without a substituent such as a naphthyl group, or an aryl group having a substituent such as a nitro group, an alkyl group having 1 to 3 carbon atoms, a methoxy group, an aralkyl group, preferably a hensyl group, etc. , R3 and R4 and R2
and RIO is characterized in that it contains 5 to 100 parts by weight of at least one compound represented by (a ring can be formed by a carbon-carbon bond or an ether bond).

In the composition of the present invention, the compound represented by the general formula (1) or (II) used as a photosensitizer can be obtained by, for example, condensing the phenolic hydroxyl group of a specific compound with 1,2-quinonediazide sulfonyl chloride. Manufactured.

That is, the compound represented by the general formula (1) has the following general formula (III) (6) (where m and n are the same or different, an integer of 3 or 4, R+2 and R13 are the same or different, a hydrogen atom, Alkyl group, aryl group or aralkyl group, RI4
and Rls are the same or different and mean a hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, cyano group or nitro group).
1,2-quinonediazide sulfonyl chloride such as 2-nara 1-quinonediazide-4-sulfonyl chloride, 1,2-naph I.quinonediazide-5-sulfonyl chloride, 1,2-benzoquinonediazide-4-sulfonyl chloride, etc., is treated with a base. It can be obtained by carrying out a condensation reaction in the presence of a neutral catalyst and then purifying it.

The amount of 1,2-quinonediazide sulfonyl chloride to be used with respect to the compound represented by general formula (II[) in the condensation reaction is the amount of the compound represented by general formula (I[I) to be condensed with 1,2-quinonediazide sulfonyl chloride. It can be adjusted as appropriate depending on the number of hydroxyl groups, and usually 1 mole of 1°(7)2-quinonediazide sulfonyl chloride is used per equivalent of the number of hydroxyl groups.

Examples of the basic catalyst used in the condensation reaction include inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and organic amines such as diethylamine and triethylamine. The amount of these basic catalysts used is usually 1 to 2 times the mole, preferably 1 to 2 times the mole of 1,2-quinonediazide sulfonyl chloride used.
It is 1.3 times the mole. The condensation reaction is usually carried out in the presence of a solvent, and examples of the solvent include water, dioxane, diethyl ether, tetrahydrofuran, acetone, and methyl ethyl ketone. Usually 100-1
000 parts by weight are used.

The condensation reaction temperature varies depending on the solvent used, but is generally -20 to 60°C, preferably 0 to 40°C.

Examples of the compound represented by the general formula (T11) include 2,3,4.2', 3', 4'-hexahy(8) droxy-diphenylmethane, and 2,3,4.2'.

3',4'-hexahydroxy-diphenylethane-(
1,1), 2,3,4.2',3',4'-hexahydroxy-diphenylpropane-(1°1), 2.3,4
．． 2″, 3′, 4′-hexahydroxy-diphenylpropane-(2,2), 2°3.4.2′, 3′, 4′
-hexahydroxy-diphenyl-n-butane-(1,
1), 2,3°4.2',3',4'-hegizahydroxy-diphenyl-n-pentane-(1,1),2.
3,4°2',3',4'-hexahydroxy-diphenylcyclohexane-(1,1), 2.3.4.2'.

3', 4', -hexahydroxy-diphenyl-4-oxacyclohexane-(1,1), 2,3°4.2'
, 3',4'-hexahydroxy-triphenylmethane, 2,4.6.2',4',6'-hexahydroxy-
diphenylmethane, 2. 4゜6.2', 4', 6'-
Hexahydroxy-diphenylethane-(1,l), 2
．． 4. 6. 2'.

4',6'-hexahydroxy-diphenylpropane-(9) Pan-(1,1),2,4,6.2',4',6'-hexahydroxy-diphenylpropane-(2゜2) ,2
．． 4,6.2', 4', 6'-hexahydroxy-diphenyl-n-butane-(1,1), 2.4,6.2',
4',6'-hexahydroxy-diphenyl-n-pentane-(1,1), 2゜4.6.2',4',6'-
hexahydroxy-diphenylcyclohexane-(1,
1) , 2,4°6.2', 4', 6'-hexahydroxy-triphenylmethane, 2,3,4.2', 3',
4'-hexahydroxy-5,51-dibromo-diphenylmethane, 2,3,4.2',3',4'-hexahydroxy-5,51-dibromo-diphenylbroban-(2,2), 2, 4,6.2'.

4',6'-hexahydroxy-3,31-dibromo-
Diphenylmethane, 2.4,6.2',4'.

61-hexahydroxy-3,3'-dibromo-diphenylpropane-(2,2), 2. 3. 4°2',
3',4'-hexahydroxy-5,51-dichloro-
Diphenylpropane (2,2), 2° (10) 4.6.2',4',6'-hexahydroxy-3,3
1-dichloro-diphenylpropane-(2゜2), 2
,3,4.2',3',4''-hexahydroxy-5,
51-dimethyl-diphenylpropane-(2,2), 2
,4,6.2',4',6''-hexahydroxy-3,
3'-dimethyl-diphenylpropane-(2,2),
2, 3, 4.2'.

3',4'-hexahydroxy-5,5'-dimethoxy-diphenylpropane-(2,2), 2°4.6.2
',4',6'-hexahydroxy-3,3'-dimethoxy-diphenylpropane-(2,2), 2.3. 4
．． 2', 3', 4'-hexahydroxy-5,51
-dicyano-diphenylpropane-(2,2), 2,4
, 6.2', 4'.

6'-hexahydroxy-3,31-dicyano-diphenylpropane-(2,2), 2. 3. 4°2',
3',4'-hexahydroxy-5,51-dinitro-
diphenylpropane-(2,2), 2.4,6.2',
4',6'-hexahydroxy-3+ 3'-dinitro-diphenylpropane-(2,2), 2. 3. 4
．． 5. 2', 3', 4'.

51-octahydroxy-diphenylmethane, 2°3.
4,5.2',3',4',5'-octahydroxy-
Diphenylpropane-(2,2), 2°3.4,6.
2', 3', 4', 6'-octahydroxy-diphenylmethane, 2. 3. 4. 6゜2', 3', 4',
6'-octahydroxy-diphenylpropane-(2,
2) etc.

These compounds represented by general formula (III) can be obtained in good yields, for example, by reacting the corresponding polyhydroxybenzene with aldehydes or ketones in the presence of an acidic catalyst such as hydrochloric acid.

The compound represented by the general formula (III) thus obtained can be purified by crystallization in an organic solvent such as alcohol, acetone, acetic acid, benzene, toluene, chlorobenzene, or a mixed solvent thereof. .

Further, the compound represented by the general formula (Iff) can be efficiently halogenated by reacting it with a halogen such as chlorine or bromine in a solvent, for example, acetic acid or water. In addition, this halide can be replaced with sodium alkoxide,
By reacting with sodium nitrite, potassium cyanide, etc., it can be alkoxylated, nitrated, or cyanated and polyhydroxylated. Other methods can also be used to introduce various substituents into the compound represented by the general formula (I[).

In addition, the compound represented by the general formula (II) is a compound represented by the following general formula (IV) (where n is an integer of 1 to 4, RI6 and RI7 are the same or different, and a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group) groups, R+8 and RU are the same or different;
hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, cyano group or nitro group) (13).
naphthoquinonediazide-4-sulfonyl chloride, 1.
2-naphthoquinonediazide-5-sulfonyl chloride,
It is obtained by subjecting 1.2-benzoquinonediazide-4-sulfonyl chloride to a condensation reaction in the presence of a basic catalyst and then purifying it.

The condensation reaction conditions in this case are the same as those for the compound represented by general formula (III) and 1,2-quinonediazide sulfonyl chloride.

Examples of the compound represented by the general formula (IV) used in this case include 2,3.4-)lihydroxydiphenylmethane, 2,4.6-trihydroxydiphenylmethane, and 2,3.4-)lihydroxydiphenylmethane. 5-bromo diphenylmethane, 2. 4゜6-Dolihydroxy-3-bromo-diphenylmethane, 2,3.4-)dihydroxy-5-chloro-diphenylmethane, 2,4.6-trihydroxy-3-chloro-diphenylmethane, 2,3.
4-trihydroxy-5-methyl-diphenylmeth (1
4) 2,4.6-dolihydroxy-3-methyl-diphenylmethane, 2,3.4-)dihydroxy-5-methoxy-diphenylmethane, 2,4.6-dolihydroxy-3-methoxy-diphenylmethane, 2 , 3.4-)dihydroxy-5-cyano-diphenylmethane, 2,4.6
-Dolihydroxy-3-cyano-diphenylmethane, 2
．． 3.4=trihydroxy-5-nitro-diphenylmethane, 2,4. ．． 6-Dolihydroxy-3-nitro-diphenylmethane, 2,3.4-)dihydroxy-4'-
Methyl-diphenylmethane, 2,4.6-trihydroxy-41-methyl-diphenylmethane, 2,3.4-trihydroxy-41-butyl-diphenylmethane, 2
, 3.4-) IJ hydroxy-41-mo-butyl-diphenylmethane, 2, 3. 4. , 5-tetrahydroxy-diphenylmethane, 2. 3. 4. 6-titrahydroxy-diphenylmethane, 2,5-dihydroxy-diphenylmethane, 213-dihydroxy-diphenylmethane-2,4-dihydroxy-3-methyl-diphenylmethane, 2,5-dihydroxy-41-methyl-
diphenylmethane, 2,5-dihydroxy-41-t-
Butyl-diphenylmethane, 2゜4-dihydroxy-3
, 4'-dimethyl-diphenylmethane, 2,4-dihydroxy-3-methyl-4'-t-butyl-diphenylmethane, 2,3゜4-trihydroxy-diphenylethane-(1゜1), 2,4.6 -trihydroxy-diphenylethane-(1,1), 2,3.4-trihydroxy-diphenylpropane-(1,1), 2,4゜6-
Trihydroxydiphenylpropane (1°1), 2
．． 5-dihydroxy-diphenylethane-(1,1),
2,5-dihydroxy-diphenylpropane-(1,1
), 2,3-dihydroxy-diphenylethane-(1
, 1), 2,3-dihydroxy-diphenylpropane-(1,1)l<.

These compounds represented by the general formula (IV) can be prepared, for example, by reacting the corresponding benzyl chloride with polyhydroxybenzene or a derivative thereof in the presence of a Lewis acid catalyst, or by reacting the benzyl chloride with polyhydroxybenzene or a derivative thereof. Alternatively, the resulting polyalkoxy compound can be further treated with aluminum chloride, sodium hydroxide, hydrochloric acid-pyridine, hydrogen iodide water,
Obtained by treatment with boron tribromide, aqueous hydrogen bromide, etc. The compound represented by the general formula (IV) obtained in this way can be synthesized by halogenated, alkoxylated, nitrated or cyanated by a method similar to the method for synthesizing the derivative of the compound represented by the general formula (■). It can be a hydroxy compound.

Specific examples of the compound represented by the general formula (I) thus obtained include the following compounds.

2.3,4.2',3',4'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-4-
Sulfonic acid hexaester, 2. 3゜4.2', 3'
, 4'-hexahydroxy-diphenylmethane-1,2
-naphthoquinone diazide-5-sulfonic acid hexaester, 2. 3. 4. 2'.

(17) 3',4'-hexahydroxy-diphenylmethane-1
, 2-benzoquinonediazide-4-sulfonic acid hexaester, 2.3,4.2',3'.

41-hexahydroxy-diphenylmethane-1゜2-
Naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4.2',3',4'-hexahydroxy-
diphenylmethane-1,2-naphthoquinone diazide-5
-sulfonic acid tetraester, 2,3,4.2',3'
, 4'-hexahydroxy-diphenylmethane-1,2
-Naphthoquinonediazide-5-sulfonic acid triester, 2°3.4.2',3',4'-hexahydroxy-
diphenylmethane-1,2-naphthoquinone diazide-5
-Sulfonic acid diester, 2,3.4.2'.

3',4'-hexahydroxy-diphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid monoester, 2,3,4.2',3'',4'-hexahydroxy-diphenylethane-(1°1)-1,2-naphthoquinonediazide-5-sulfone acid pentaester, 2,3
．． 4.2', 3'.

(18) 4'-hexahydroxy-diphenylpropane-(1,
1) -1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4.2'.

3',4'-1,xahydroxydiphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4°2',3',4
'-hexahydroxy-diphenyl-n-bukun-(1
, 1) -1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2.3,4.2',3',4'-
hexahydroxy-diphenyl-n-pentane-(1,
1) -1゜2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4.2',3'',41-hexahydroxy-diphenylcyclohexane-(1,1
) -1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4.2'.

3',4'-hexahydroxy-diphenyl-4-oxacyclohexane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4
．． 2',3',4'-hexahydroxy-triphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6.2',4',6'-hexahydroxy-diphenylmethane -1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2゜4
．． 6.2',4',6'-hexahydroxy-diphenylethane-(1,1>-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2.4,6.2'
, 4',6'-hexahydroxy-diphenylpropane-(1,1>-1,2-naphthoquinonediazide-5-
Sulfonic acid pentaester, 2.4.6.2', 4',
6'-hexahydroxydiphenylpropane-(2,
2) -1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2. 4. 6. 2', 4', 6'
-hexahydroxydiphenyl-n-butane-(1,
1) -1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2. 4. 6. 2'.

4',6'-hexahydroxy-diphenyl-n-pentane-(1,1)-1,2-naphthoquinonediazide-5
-Sulfonic acid pentaester, 2°4.6.2', 4'
, 6'-hexahydroxy-diphenylcyclohexane-(1,1)-1,2-naphthoquinonediazide-5-
Sulfonic acid pentaester, 2,4.6.2',4',
6'-hexahydroxy-triphenylmethane-1,2
-Naphthoquinonediazide-5-sulfonic acid pentaester, 2.3,4.2',3',4'-hexahydroxy-5,51-dibromo-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester ester,
2, 3, 4. 2', 3'.

41-Hexahydroxy-5,51-dibromo-diphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6.2
',4',6'-hexahydroxy-3,3'-dibromo-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6.2',
4',6'-hexahydroxy-3,31-dibromo-
diphenylpropane-(2,2)-1,2-naphthoki(
21) Nondiazide-5-sulfonic acid pentaester, 2.3
,4.2',3',4'-hexahydroxy-5,51
-dichloro-diphenylpropane-(2,2)-1,2
-Naphthoquinonediazide-5-sulfonic acid pentaester, 2,4.6.2'.

4',6'-hexahydroxy-3,3'-dichloro-
diphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2.
3. 4. 2',3',4'-hexahydroxy-5
,5”-dimethyl-diphenylpropane-(2,2)-
1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2. 4゜6.2',4',6'-hexahydroxy-3゜31-dimethyl-diphenylpropane-
(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4.2',3'.

4'-hexahydroxy-5,5'-dimethoxy-diphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6.
2',4',6'-hexahy(22) droxy-3,3'-dimethoxy-diphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2. 3゜4.2', 3',
4'-Hexahydroxy-5゜5'-dicyano-diphenylpropane-(2,21-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4.6.2
',4''.

6'-hexahydroxy-3,31-dicyano-diphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2.3,4.2
',3',4'-hexahydroxy-5,5'-dinitro-diphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,
4,6゜2',4',6'-hexahydroxy-3,3
'-dinitro-diphenylpropane-(2,2) -1
, 2-naphthoquinonediazide-5-sulfonic acid pentaester, 2. 3. 4. 5. 2', 3'.

4',5'-octahydroxy-diphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid octaester, 2. 3. 4. 5. 2', 3''.

4″,5′-octahydroxy-diphenylmethane-1
, 2-naphthoquinonediacid-5-sulfonic acid hebutaester, 2,3,4,5.2',3'.

4',5'-octahydroxy-diphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid hexaester, 2,3,4,5.2',3''.

4',5'-octahydroxy-diphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid pentaester, 2. 3. 4. , 5. 2', 3'.

4',5'-octahydroxy-diphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid tetraester, 2,3.4', 5,2°, 3'.

4',5'-octahydroxy-diphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid triester, 2,3,4,5.2',3'.

4',5'-octahydroxy-diphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.4,5.2',3'.

4',5'-octahydroxy-diphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid monoester, 2,3,4,5.2',3'.

4',5'-octahydroxy-diphenylpropane =
(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid hexaester, 2. 3. 4゜6.2', 3
',4',6'-octahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid hexaester, 2. 3゜4.6.2', 3', 4', 6
'-octahydroxy-diphenylpropane-(2,2
)-1,2-naphthoquinonediazide-5-sulfonic acid hexaester.

Further, specific examples of the compound represented by the general formula (]I) include the following compounds.

2.3.4-trihydroxy-diphenylmethane-1,
2-naphthoquinonediazide-4-sulfonic acid triester, 2,3.4-)lyhydroxydiphenylmethane-
1,2-naphthoquinonediazide-5-sulfonic acid triester, 2,3.4=trihydroxy-diphenylmethane-1,2-(25) benzoquinonediazide-4-sulfonic acid triester,
2, 3. ．． 4-) Lyhydroxydiphenylmethane-1
, 2-naphthoquinonediazide-5-sulfonic acid diester, 2. 3. 4--1-lihydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 2.4.6-trihydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.4--)rihydroxy-5
-Bromodiphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,4.6-dolihydroxy-3-bromo-diphenylmethane-1,2-
naphthoquinonediazide-5-sulfonic acid diester, 2
, 3.4-trihydroxy-5-chloro-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2.4°6-trihydroxy-3-chloro-diphenylmethane-1,2-naphthoquinonediazide-
5-sulfonic acid diester, 2,3,4-)dihydroxy-5-methyl-diphenylmethane-1,2-naf(2
6) Toquinone diazido 5-sulfonic acid diester, 2,4
．． 6-trihydroxy-3-methyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2. 3. 4-toIJhydroxy-5-methoxydiphenylmethane-1゜2-naphthoquinonediazide-5-sulfonic acid diester, 2,4.6-dolihydroxy-3-methoxy-diphenylmethane-1,2-
naphthoquinonediazide-5-sulfonic acid diester, 2
, 3゜4-trihydroxy-5-cyano-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,4.6-trihydroxy-3-cyano-diphenylmethane-1,2-naphthoquinonediazide-
5-sulfonic acid diester, 2.3.4-)dihydroxy-5-nitro-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2. 4.
6-1-dihydroxy-3-nitro-diphenylmethane-1゜2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.4-)dihydroxy-41-methyl-diphenylmethane-1,2-naphthoquinonediazide
5-sulfonic acid diester, 2,4°6-dolihydroxy-4″-methyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.
4-1-dihydroxy-4T t-butyl-diphenylmethane-1゜2-naphthoquinonediazide-5-sulfonic acid diester, 2,4.6-trihydroxy-4'-
t-Butyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2°3.4.5
-tetrahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, 2
,3,4.5-tetrahydroxy-diphenylmethane-
1,2-naphthoquinonediazide-5-sulfonic acid triester, 2゜3.4.5-tetrahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3,4. ．． 5-Tetrahydroxy-diphenylmethane-1,2-naphthoquinonediazide-
5-sulfonic acid monoester, 2.3゜4.6-tetrahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid triester, 2.5-dihydroxy-diphenylmethane-1,2-naphthoquinonediazide- 5-sulfonic acid diester, 2,3-dihydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,4-dihydroxy-3-methyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid Diester, 2,5-dihydroxy-4'-methyl-diphenylmethane-1,2-
naphthoquinonediazide-5-sulfonic acid diester, 2
,5-dihydroxy-41-t-butyl-diphenylmethane-1゜2-naphthoquinonediazide-5-sulfonic acid diester, 2,4-dihydroxy-3,41-dimethyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfone Acid diester, 2,4-dihydroxy-
3-Methyl-4+ t I-butyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.4-(29) trihydroxy-diphenylethane-(1,1)-1,
2-naphthoquinonediazide-4-sulfonic acid triester, 2. 3. 4-1-dihydroxy-diphenylethane-(1,1)-1,2-naphthoquinonediazide-5
-sulfonic acid triester, 2.3.4-1-dihydroxy-diphenylethane-(1,1)-1,2-benzoquinonediazide-4-sulfonic acid triester, 2,3
．． 4-)dihydroxy-diphenylethane-(1,1)
-1゜2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.4-)dihydroxy-diphenylethane-(1,1)-1,2-naphthoquinonediazide-5-
Sulfonic acid monoester, 2. 4゜6-trihydroxydiphenylethane-(1゜1)-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3.4
-) dihydroxy-diphenylpropane-(1,1)-
1,2-naphthoquinonediazide-5-sulfonic acid diester, 2, 4. 6-) Dihydroxy-diphenylpropane-(1,1)-1,2-naphthoquinone diazide (
30) -5-sulfonic acid diester, 2,5-dihydroxy-
Diphenylethane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,5-dihydroxy-diphenylpropane-(1,1)-1,2-
naphthoquinonediazide-5-sulfonic acid diester, 2
,3-dihydroxy-diphenylethane-(1,1)-
1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3-dihydroxy-diphenylpropane-(
1,1)-1,2-naphthoquinonediazide-5-sulfonic acid diester.

In the composition of the present invention, general formula (I) or (n)
Compounds represented by can be used in combination.

In the composition of the present invention, the alkali-soluble resin to which the compound represented by the general formula (1) and/or (II) is added is not particularly limited, but for example, a novolac resin obtained from phenol and formaldehyde, cresol and formaldehyde, hydroxystyrene polymers, aminostyrene polymers, copolymers of ethylenically unsaturated carboxylic acids and monoolefin compounds, and the like.

General formula (1) and/or (
The compounding amount of the compound represented by II) is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin.

If this amount is less than 5 parts by weight, the residual film rate after development will be insufficient, the pattern obtained will be easily deformed by heat, and it will be impossible to obtain a photosensitive resin composition with high resolution. On the other hand, if this amount exceeds 100 parts by weight, a highly sensitive photosensitive resin composition cannot be obtained.

The composition of the present invention contains, for example, 100 parts by weight or less, preferably 1,2-quinonediazide compound other than the compound represented by the general formula (1) or (II), per 100 parts by weight of the alkali-soluble resin. can be blended in an amount of 50 parts by weight or less, particularly preferably 20 parts by weight or less. These 1゜2-quinonediazide compounds include, for example, the hydroxyl group of a compound represented by the following general formula (V) (where n is an integer of 1 to 3, and R11l means an alkyl group, an aryl group, or an aralkyl group). 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1.2 in all or part of the group
Examples include compounds obtained by condensation reaction of -naphthoquinonediazide-5-sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride.

Specific examples of the compound represented by this general formula (V) include 2.3.4-)lyhydroxyphenylmethylketone,
2,3.4-)lyhydroxyphenylethylketone, 2
, 3.4-1-lyhydroxyphenylbutyl ketone, 2
, 3.4-) Lihydroxyphenyl-n-hexyl ketone, 3,4.5-trihydroxyphenylmethyl ketone, '3.4.5-) Lihydroxyphenylethyl ketone, 3,4.5-(33) Trihydroxyphenylbutylketone, 3,4°5-trihydroxyphenyl-n-hexylketone, 2,4.
．． 61 hydroxyphenyl methyl ketone, 2,4.6
-) Lihydroxyphenylethyl ketone, 2,4.6-
Trihydroxyphenylbutylketone, 2,4.6-trihydroxyphenyl-n-hexylketone, 2,3.
4-) Lihydroxyphenyldecyl ketone, 2,3.4
-trihydroxyphenyldodecylketone, 2,3°4
-trihydroxybenzophenone, 2,4.6-trihydroxybenzophenone, 2,3.4-trihydroxyphenylbenzyl ketone, 3,4°5-)! J hydroxybenzyl ketone, 2.4.6-].lyhydroxyphenylbenzyl ketone, etc. (US Pat. No. 3,046,118 and Japanese Patent Publication No. 3'1-18015). Also, for example, 2°4.2', 4'-tetrahydroxy-6,6'-dimethyl-diphenylmethane, 2,6
．． 2',6'-tetrahydroxy-3,5,3',5'
-Tetrachloro-diphenylmethane, 2.21-dihyde (34) Waxy 4.4''-dimethyl-diphenylmethane-(1
, 1), 2.2'-dihydroxy-4,4'-dimethoxy-diphenylethane-(1,1), 2.4.2', 4
'-tetrahydroxy-diphenylethane-(1,1)
, 2,2'-dihydroxy-4,41-dimethoxy-triphenylmethane, 2,2'-dihydroxy-dinaphthyl-(l,1)-methane, 2,4.2',4'-tetrahydroxy-diphenyl sulfide ,2,4.2',4
'-tetrahydroxy-diphenyl sulfoxide, 2,
4. 2',4'-tetrahydroxy-6,6'-dimethyl-diphenylethane-(1,1), 2°4.2
″, 41-tetrahydroxy-6,6′-dicarbomethoxydiphenylmethane, 2,4°2′, 4′-tetrahydroxy-6,6′-dimethyl-triphenylmethane, 2,4.2′, 4 '-Tetrahydroxy-diphenylpropane-(1°1), 2,4.2', 4'-tetrahydroxy-diphenyl-n-butane-(1,1>, 2
, 4°2', 4'-pentahydroxy-triphenylmethane, 2. 4. 2″, 41-tetrahydroxy-diphenylcyclohexane-(1,1), 2,2′-dihydroxy-4,4′-dimethoxy-diphenylmethane,
2,4.2',4'-tetrahydroxy-diphenylpenkune-(1,1>,2,4゜2',4'-tetrahydroxy-diphenylpropane-(2,2),2.4
．． 2',4'tetrahydroxy-triphenylmethane, 2,2'-dihydroxy-5,5'-dibromo-diphenylmethane, 2,2'-dihydroxy-5,5''-dichloro-diphenylethane-(1,1) , 2.2'-
Dihydroxy-5,5'-dibromo-diphenylethane-(1,1) etc. to 1,2-naphthoquinonediazide-5-
Sulfonyl chloride, 1,2-naphthoquinonediazide-
1,2-quinonediazide sulfonic acid ester (Japanese Patent Publication No. 37-1953) obtained by condensation reaction with 4-sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride may also be blended.

Furthermore, the composition of the present invention may optionally contain a copolymer of styrene and maleic anhydride, a copolymer of styrene and maleic anhydride, a copolymer of styrene and maleic anhydride, a natural resin such as rosin or shellac, etc. Synthetic resins such as vinyl ether polymers, vinyl acetate polymers, vinyl alcohol polymers, vinyl pyrrolidone polymers, etc.
It can also be added in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight.

The composition of the present invention can be applied to a substrate to be microfabricated, and a pattern can be formed by partially irradiating the composition with actinic light, such as ultraviolet rays, and developing it.

The method of applying the composition of the present invention to a substrate includes dissolving the composition of the present invention in an appropriate solvent to a concentration of 5 to 50% by weight, and applying the composition by spin coating, flow coating, or roll coating. An example of this method is to apply the agent by, for example, Suitable solvents used in this case include, for example, ketones such as cyclopentanone, cyclohexa(37)non, diacetone alcohol, alcohols such as n-butanol, dioxane, ethylene glycol dimethyl ether, ethyl glycol diethyl ether, etc. Ethers, alcohol ethers such as ethyl glycol monomethyl ether and ethylene glycol monoethyl ether, butyl acetate, cellosolve acetate,
Esters such as methoxyethyl acetate, 1,1.2
- Halogenated hydrocarbons such as trichloroethylene, polar solvents such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, etc. are used alone or in combination.

Storage stabilizers, pigments, and the like may be added to the composition of the present invention, if necessary. Furthermore, in order to improve the adhesive strength between the composition of the present invention and a substrate, depending on the selected substrate, for example, hexamethylsilazane, chloromethylsilane, etc. may be applied as an adhesive to the substrate.

Examples of the developer used in the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate (38), sodium silicate, sodium metasilicate, trisodium phosphate, and sodium hydrogen phosphate. Aqueous solutions of n-propylamine, di-n-propylamine, di-n-butylamine, methyldiethylamine, pyrrole, 2゜5-dimethylvirol, β-picoline, collidine, piperidine, piperazine, triethylenediamine, and other amines. Examples include aqueous solutions of alcohol amines such as dimethylethanolamine, triethanolamine and diethylhydroxylamine, aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and aqueous ammonia.

Further, an appropriate amount of alcohol such as methanol or ethanol, a sulfite stabilizer, or a surfactant may be added to the liquid +1.

The composition of the present invention does not precipitate crystals of the 1,2-quinonediazide compound, has high sensitivity, high resolution, high residual film rate, and has excellent developability, and is suitable for integrated circuit production. It is particularly useful as a positive photoresist having heat resistance for use in applications, and is also useful as a positive photoresist for mask production.

EXAMPLES Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 (1) Synthesis of novolac resin After charging 75 g of m-cresol and 25 g of p-cresol into a 500 ml Mitsubishi collapsible flask,
66 ml of a 37% by weight aqueous formalin solution and 0.04 g of oxalic acid were added. While stirring, the separable flask was immersed in an oil bath to adjust the reaction temperature to 100°C.
Allowed time to react. After the reaction was completed, water was distilled off by reducing the pressure to 30 mHH, and the temperature of the inner hot water was further raised to 130°C to remove unreacted substances. Next, the molten alkali-soluble novolac resin, which was a reaction product, was returned to room temperature and collected.

(2) Synthesis of photosensitizer In a 500 ml O three-way separable flask, 63 g of pyrogallol, 20 g of acetone, and 100 ml of dioxane.
was charged, and 10 ml of hydrochloric acid water was added while stirring.

After reacting this solution at 60°C for 10 hours and then at room temperature for 48 hours, a 40% acetic acid aqueous solution was added for 17 hours. The product was precipitated by mixing with 2.
3,4°2',3',4'-hexahydroxy-diphenylpropane-(2,2) was obtained.

2. Into a 500 ml triple collapsible flask under light shielding.
3. 4. 2', 3', 4'-hexahydroxy-
Diphenylpropane-(2,2) 14.6g, 1.2
-naphthoquinonediazide-5-sulfonyl chloride 53
．． 7 g and 250 ml of dioxane were charged and dissolved. Add triethylamine 23 to this solution without stirring.
g was gradually added, and the mixture was allowed to react at room temperature for 2 hours. After the reaction was completed, the contents were dropped into a large amount of 1% by weight hydrochloric acid solution to precipitate the product, washed with water, and vacuum dried at 40°C for 20 hours to obtain 2,3
．． 2'.

3',4'-hexahydroxy-diphenylpropane (
2,2)-1,2-naphthoquinonediazide (41)-5-sulfonic acid tetraester (hereinafter referred to as photosensitizer A) was obtained.

(3) Preparation and evaluation of photosensitive resin composition 20 g of the alkali-soluble novolac resin obtained in (1) and 5 g of the photosensitizer A obtained in (2) were added to
g of cellosolve acetate and filtered through a membrane filter with a pore size of 0.2 μm to prepare a solution of the photosensitive resin composition. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

The obtained solution was applied onto a silicon oxide film wafer using a spinner, and then brebaked in an open environment at 90° C. for 25 minutes to obtain a 1 μm thick photosensitive resin composition film. A test pattern mask manufactured by Toppan Printing Co., Ltd. was placed in close contact with the wafer and irradiated with 12.6 mJ/cd of ultraviolet light (measured with a model 205 UV power meter manufactured by Optical Associates, Inc.), and tetramethylammonium hydroxide 2.0 When developed with a wt% aqueous solution at 20°C for 60 seconds, a pattern with a line width of 1.0 μm was resolved (
42) I was able to do it. It can be seen that the photosensitive resin composition of the present invention has excellent sensitivity and resolution. Furthermore, the residual film rate in the unexposed area was as high as 91%, and there was no development residue (the pattern was clear and the developability was extremely excellent).

Example 2 (1) Synthesis of photosensitizer 14.6 g of 2.3,4.2',3',4'-hexahydroxy-diphenylpropane-(2,2).

A reaction was carried out in the same manner as in Example 1 (2) using 67.3 g of 1.2-naphthoquinonediazide-5-sulfonyl chloride, 300 ml of dioxane, and 29 g of triethylamine to obtain 2,3,4.2',3'.

41-hexahydroxy-diphenylpropane-(2,
2) -1,2' naphthoquinone diazido 5-sulfonic acid pentaester (hereinafter referred to as photosensitizer B) was obtained.

(2) Preparation and evaluation of photosensitive resin composition Under light shielding, 20 g of the alkali-soluble novolak resin obtained in Example 1 (1) and 5 g of photosensitizer B were dissolved in 75 g of cellosolve acetate, and a membrane with a pore size of 0° and 2 μm was prepared. A solution of the photosensitive resin composition was prepared by filtration with a filter. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

When the obtained solution was evaluated in the same manner as in Example 1 (3), a pattern with a line width of 1.0 μm could be resolved with ultraviolet irradiation of 10.5 mJ/cJ. Further, the residual film ratio in the unexposed area was as high as 92%, and as in Example 1, the developability was also extremely excellent.

Example 3 (1) Synthesis of photosensitizer 2.3,4.2',3',4'-hexahydroxy-diphenylmethane 13.2g, 1.2-naphtoquinonediazide 5-sulfonyl chloride 67°3g , using 300 ml of dioxane and 29 g of triethylamine, reacted in the same manner as in Example 1 (2) to obtain 2,3,
4.2',3',4'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester (hereinafter referred to as photosensitizer C) was obtained.

(2) Preparation and evaluation of photosensitive resin composition Under light shielding, 20 g of the alkali-soluble novolak resin obtained in Example 1 (1) and 5 g of photosensitizer C were dissolved in 75 g of cellosolve acetate, and a membrane with a pore size of 0° and 2 μm was dissolved. A solution of the photosensitive resin composition was prepared by filtration with a filter. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

When the obtained solution was evaluated in the same manner as in Example 1 (3), a pattern with a line width of 1.0 μm could be resolved with ultraviolet irradiation of 13.1 mJ/cJ. Further, the residual film ratio in the unexposed area was as high as 89%, and as in Example 1, the developability was also extremely excellent.

Example 4 (1) Synthesis of photosensitizer 2.3.4-Trihydroxy-diphenylmethane 10.
(45) Using 13.4 g of 1.2-naphthoquinonediazide-5=sulfonyl chloride, 150 ml of dioxane, and 10 g of triethylamine, 2,3.4- Trihydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester (hereinafter referred to as photosensitizer) was obtained.

(2) Preparation and evaluation of photosensitive resin composition Photosensitive agent C was used instead of photosensitive agent C, and the other conditions were Example 3.
A solution of the photosensitive resin composition was prepared under the same conditions. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate. When the obtained solution was evaluated in the same manner as in Example 1 (3), a pattern with a line width of 1.0 μm could be resolved with 13.5 mJ/self of ultraviolet irradiation. Further, the residual film ratio in the unexposed area was as high as 87%, and as in Example 1, the developability was also extremely excellent.

Example 5 (1) Synthesis of photosensitizer 2.3.4-)rihydroxy-5-bromodiphenylmethane 14.8g, 1.2-naphthoquinonediazide-5
-Sulfonyl chloride 13.4g, dioxane 150m
1 and 10 (46) g of triethylamine were reacted in the same manner as in Example 1 (2) to obtain 2.
．． 3.4-trihydroxy-5-bromo-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester (hereinafter referred to as photosensitizer E) was obtained.

(2) Preparation and evaluation of photosensitive resin composition Using photosensitizer E instead of photosensitizer C, otherwise Example 3
A solution of the photosensitive resin composition was prepared under the same conditions. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate. When the obtained solution was evaluated in the same manner as in Example 1 (3), a pattern with a line width of 1.0 #m could be resolved by irradiating ultraviolet light at 12.5 mJ/cJ. In addition, the residual film rate in the non-hazy area showed a high value of 87%, and Example 1
Similarly, the developability was also extremely excellent.

Agent: Patent Attorney Kawakita Takecho (47) 331-

Claims (1)

[Claims] (1) For 100 parts by weight of alkali-soluble resin, the following general formula (1) or the following general formula (II) (where a and b are the same or different, an integer of 3 or 4, j! and m are the same or different, 0 or 1~
3, C is an integer of 1 to 4, n is 0 or an integer of 1 to 3, and (a-j, (b-m) and (c-
n) are all (1) integers greater than or equal to 1; R1, Rs and R7 are the same or different; 1.
2-naphthoquinonediazide-4-sulfonyl group, 1.2
-naphthoquinonediazide-5-sulfonyl group or 1,
2-benzoquinonediazide-4-sulfonyl group, R2,
R6, R8 and R1+ are the same or different and are hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, cyano group or nitro group, R3,
R4, R5 and RIO are the same or different and mean a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and R3 and R4 and R9 and R+o can form a ring with a carbon-carbon bond or an ether bond). 5 to 100 of at least one of the represented compounds
A positive photosensitive resin composition characterized in that it contains parts by weight.