JPH04296755A - Positive type photoresist composition - Google Patents

Abstract

PURPOSE:To obtain a high sensitivity and to improve a resolving power, developability and heat resistance by incorporating a specific alkali-soluble novolak resin, specific arom. polyhydroxy compd. and quinonediazide compd. into the above-mentioned compsn. CONSTITUTION:This compsn. contains at least the following three components: The one thereof is the alkali-soluble novolak resin consisting of 5 to 95mol% m-cresol and 2 to 6% dimer content obtd. by condensation of 5 to 95mol% compd. expressed by formula I and aldehydes in area ratio of gel permeation chromatograph patterns. In the formula I, R1 to R3 denote a hydrogen atom, 1 to 4C alkyl group or alkoxy geoup, provided that the case all of R1 to R3 are a hydrogen atom is excluded. The two thereof is the arom. polyhydroxy compd. having 3 to 9 pieces of hydroxyl groups in one molecule, provided that polyhydroxyl benzophenone is excluded. The three thereof is the 1,2- quinonediazide compd. The photoresist compsn. is obtd. by incorporating the above-mentioned compd. therein.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a positive photoresist composition that is sensitive to radiation, and in particular to a photoresist composition for microfabrication that has high resolution and sensitivity, as well as a good pattern cross-sectional shape. It is something. The positive photoresist according to the present invention can be applied to semiconductor wafers,
It is applied to a thickness of 0.5 to 3 μm onto a substrate such as glass, ceramics, or metal by spin coating or roller coating. Thereafter, it is heated and dried, and a circuit pattern and the like are printed by irradiation with ultraviolet rays through an exposure mask and developed to form a positive image. Further, by etching this positive image as a mask, a pattern can be processed on the substrate. Typical application fields include IC
There are semiconductor manufacturing processes such as, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photoablation processes.

0002

[Prior Art] As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin and a naphthoquinone diazide compound as a photosensitive material is used. For example, USP-3,666,473 as "Novolak type phenolic resin/naphthoquinone diazide substituted compound"
No., USP-4,115,128 and USP-4,1
No. 73,470, etc., and as the most typical composition.
An example of "novolac resin consisting of cresol-formaldehyde/trihydroxybenzophenone-1,2 naphthoquinonediazide sulfonic acid ester" is Thompson
"Introduction to Microlithography" (L.F. Thompson "Intro-du Microlithography")
ction to Microlitho-gra
phy”) (ACS Publishing, No. 219, P112~
121). Novolac resins as binders are particularly useful in this application because they can be dissolved in aqueous alkaline solutions without swelling and also provide high resistance to plasma etching, especially when the resulting image is used as an etching mask. It is. In addition, the naphthoquinonediazide compound used in photosensitive materials itself acts as a dissolution inhibitor that reduces the alkali solubility of novolak resin, but when it decomposes upon exposure to light, it produces alkali-soluble substances and rather reduces the alkali solubility of novolak resin. It is unique in that it acts as a light enhancer, and because of its large change in properties with respect to light, it is particularly useful as a photosensitive material for positive photoresists. From this point of view, many positive photoresists containing novolac resins and naphthoquinone diazide photosensitive materials have been developed and put into practical use.
Sufficient results have been achieved in line width processing of approximately 5 μm to 2 μm.

However, the degree of integration of integrated circuits is increasing more and more, and in the production of semiconductor substrates such as VLSIs, 1
It has become necessary to process ultra-fine patterns having line widths of μm or less. In such applications, a photoresist is particularly required that has high resolution, high pattern shape reproduction accuracy to accurately copy the shape of the exposure mask, and high sensitivity from the viewpoint of high productivity. In addition, in order to increase the degree of integration of integrated circuits, the etching method has shifted from the conventional wet etching method to the dry etching method. To prevent this from happening, resists are required to have high heat resistance.

In order to improve the heat resistance of the resist, it is necessary to use a resin that does not contain components with a weight average molecular weight of 2000 or less (Japanese Patent Laid-Open No. 60-97347), and to use a resin whose total content from monomer to trimer is 10% by weight or less. A technique using resin (Japanese Unexamined Patent Publication No. 189739/1983) has been disclosed. However, when the above-mentioned resins in which low molecular weight components are removed or reduced are used, there are problems in that the sensitivity usually decreases and the throughput in device manufacturing decreases. Attempts have also been made to improve the sensitivity and developability of resists by incorporating specific compounds into resist compositions. For example, JP-A-61-141441 discloses a positive photoresist composition containing trihydroxybenzophenone. Although the sensitivity and developability of positive photoresists containing trihydroxybenzophenone are improved, there is a problem in that the addition of trihydroxybenzophenone deteriorates heat resistance.

[0005] Also, JP-A-64-44439, JP-A-1
-177032, 1-280748, 2-1035
0 shows an idea to increase sensitivity without deteriorating heat resistance by adding an aromatic polyhydroxy compound other than trihydroxybenzophenone, but it is not necessarily sufficient to improve developability. I can not say.

[0006]

SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to provide a positive photoresist composition that can provide a resist pattern with high sensitivity, excellent resolution, developability, and heat resistance, especially in the production of semiconductor devices. It's about providing things.

[0007]

[Means for Solving the Problems] As a result of careful consideration and careful consideration of the above-mentioned characteristics, the present inventors have achieved the above-mentioned properties by using a specific alkali-soluble resin, a quinonediazide compound, and a polyhydroxy compound having a specific structural formula. It was discovered that the object could be achieved, and based on this knowledge, the present invention was completed. That is, the object of the present invention is to contain at least 5 to 95 mol% of m-cresol and 5 to 9 mol% of a compound represented by the following general formula (I) (excluding m-cresol).
An alkali-soluble novolac resin obtained by condensing 5 mol% and aldehydes, the dimer content is 2 to 2 in area ratio of gel permeation chromatographic pattern.
an alkali-soluble novolak resin in the range of 6%;

0
008]

[Case 2]

[0009] Here, R1 to R3: may be the same or different, and are hydrogen atoms,
an alkyl group or alkoxy group having 1 to 4 carbon atoms,
However, the case where all of R1 to R3 are hydrogen atoms is excluded. represents. A positive photoresist characterized by containing (1) an aromatic polyhydroxy compound having 3 to 9 hydroxyl groups in one molecule (excluding polyhydroxybenzophenone), (2) a 1,2-quinonediazide compound. achieved by the composition.

The present invention will be explained in detail below. Resin (1) used in the present invention is m-cresol 5 to 95 mol%
is obtained by addition condensation of 5 to 95 mol % of the compound represented by the general formula (I), excluding m-cresol, and an aldehyde under an acidic catalyst. Compounds other than m-cresol represented by the general formula (I) include, for example, cresols such as o-cresol and p-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol, 2,4-xylenol,
Xylenol such as 2,6-xylenol, alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, p-methoxyphenol, m-methoxyphenol, 3,5 -dimethoxyphenol, 2-methoxy-4
- Alkoxyphenols such as methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxyphenol, bis such as 2-methyl-4-isopropylphenol Alkylphenols and the like can be used alone or in combination of two or more, but are not limited to these.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenyl acetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, and p-phenylpropylaldehyde. -Hydroxybenzaldehyde, o-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, chloroacetaldehyde, and their acetals, such as chloroacetaldehyde diethyl acetal, can be used, but among these, formaldehyde is preferred. preferable. These aldehydes may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, etc. can be used. The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 2,000 to 30,000. When it is less than 2,000, film loss in unexposed areas after development is large, and when it exceeds 30,000, the development speed becomes low. Especially suitable is 6000-2000
It is in the range of 0. Here, the weight average molecular weight is defined as a polystyrene equivalent value determined by gel permeation chromatography.

[0012] As a method for adjusting the dimer component of the novolac resin used in the present invention, for example, JP-A-60
-97347, 60-189739, 60-452
38, JP-A-2-275955, after synthesizing a novolac resin according to a conventional method, it is dissolved in a polar solvent such as methanol, ethanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and then water or water-polar One method is to precipitate the resin by placing it in a solvent mixture. Other methods include, for example, JP-A-1-
276131, when synthesizing an alkali-soluble resin, after a predetermined period of reaction, usually 150 to 20
Whereas water, unreacted monomers, formaldehyde, and oxalic acid were removed by distillation under reduced pressure at 0°C, at 230°C,
Preferably, by performing distillation under reduced pressure of 10 mmHg or less at 250° C. or higher, the dimer component can be efficiently distilled off. Furthermore, JP-A-64-14229, JP-A-2-6091
The method disclosed in No. 5 may also be used. The dimer content of the novolac resin used in the present invention is 2 to 6
% (gel permeation chromatograph (GPC) area ratio), the dimer component of the novolac resin can be adjusted by the above operation. Alternatively, a dimer represented by general formula (II) may be added to adjust the total dimer amount to 2 to 6% by weight.

[0013]

[Chemical formula 3]

Here, R4, R5: may be the same or different, hydrogen atom, halogen atom, alkyl group or alkoxy group, R6, R
7: may be the same or different, hydrogen atom or alkyl group, a, b, c, d: each an integer of 1 to 3, a+c
=b+d=5, represents.

Specific examples of the compound represented by the general formula (II) include 2,2'-methylenebis(4-methylphenol), 2,2'-methylenebis(4-methoxyphenol), methylenebis(3-methyl phenol), methylenebis(2-methylphenol), 4,4'-ethylidenebisphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4'-ethylidenebisphenol, 4,4'-methylenebis( 2,6-dimethylphenol), 2,2'-methylenebis(4-chlorophenol), 2,2'-methylenebis(3,4-dimethylphenol), 4,4'-(1-methylethylidene)bis(
2,6-dimethylphenol), 2,2'-methylenebis(4-tert-butylphenol), 4,4'-methylenebis(2-tert-butyl-6-methylphenol), and the like.

[0016] Used in the present invention: ■ 3 to 9 in one molecule
As the aromatic polyhydroxy compound having hydroxyl groups (excluding polyhydroxybenzophenone), for example, compounds represented by the following general formulas (III) to (XIII) can be used, but are limited to these. It is not something that will be done.

[0017]

[C4]

Y: alkylene group or residue of aromatic compound, Z: alkylene group or oxaalkylene group, R10
, R11: When R8 and/or R9 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group or a nitro group, an alkyl group having 5 or more carbon atoms, a hydroxyl group, an aryl group, an aralkyl group or an acyl group and can form a ring with a carbon bond or an ether bond. These groups may have a substituent. R8 and/or R
When 9 is a carboxyl group, aryl group, aralkyl group, acyl group, alkoxycarbonyl group, alkyloxy group, or aryloyloxy group, a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group. represents an acyl group, and can form a ring with a carbon bond or an ether bond. These groups may have a substituent. e, f: integers from 1 to 3, 3≦a+b, g, h: 1 to 4
is an integer representing a+c=b+d=5.

Specific examples of the compound represented by the general formula (III) include p-bis(2,3,4-trihydroxybenzoyl)benzene, p-bis(2,4,6-trihydroxybenzoyl)benzene , m-bis (2,
3,4-trihydroxybenzoyl)benzene, m-bis(2,4,6-trihydroxybenzoyl)benzene, p-bis(2,5-dihydroxy-3-brombenzoyl)benzene, p-bis(2,3 , 4-trihydroxy-5-methylbenzoyl)benzene, p-bis (2,3,4-trihydroxy-5-methoxybenzoyl)benzene, p-bis (2,3,4-trihydroxy-5-nitrobenzoyl) ) Benzene, p-bis (
2,3,4-trihydroxy-5-cyanobenzoyl)
Benzene, 1,3,5-tris (2,5-dihydroxybenzoyl)benzene, 1,3,5-tris (2,
3,4-trihydroxybenzoyl)benzene, 1,2
, 3-tris (2,3,4-trihydroxybenzoyl)benzene, 1,2,4-tris (2,3,4-trihydroxybenzoyl)benzene, 1,2,4,5-
Tetrakis (2,3,4-trihydroxybenzoyl)benzene, α,α'-bis (2,3,4-trihydroxybenzoyl)-p-xylene, α, α', α'
-Tris (2,3,4-trihydroxybenzoyl)
Mesitylene, bis(2,5-dihydroxybenzoyl)
Methane, bis(2,3,5-trihydroxybenzoyl)methane, ethylene glycol-di(2-hydroxybenzoate), ethylene glycol-di(3-hydroxybenzoate), ethylene glycol-di(
4-hydroxybenzoate), ethylene glycol-
Di(2,3-dihydroxybenzoate), ethylene glycol-di(2,6-dihydroxybenzoate)
ethylene glycol-di(3,5-dihydroxybenzoate), ethylene glycol-di(3,5-dihydroxybenzoate), ethylene glycol-di(3,5-dihydroxybenzoate),
, 4,5-trihydroxybenzoate), ethylene glycol-di (2-nitro-3,4,5-trihydroxybenzoate), ethylene glycol-di (2-
cyano-3,4,5-trihydroxybenzoate),
Ethylene glycol di(2,4,6-trihydroxybenzoate), diethylene glycol di(2,
3-dihydroxybenzoate), 1,3-propanediol-di(3,4,5-trihydroxybenzoate), polytetrahydrofuran glycol-di(3,
4,5-trihydroxybenzoate), neopentyl glycol di(3,4,5-trihydroxybenzoate), 1,2-benzenedimethanol di(3
, 4,5-trihydroxybenzoate), 1,3-benzenedimethanol-di(3,4,5-trihydroxybenzoate), 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'-hexahydroxytriphenylmethane, 2,4,6,2',4',
6'-hexahydroxy-diphenyl-n-butane, 2
,4,6,2',4',6'-hexahydroxy-diphenyl-n-pentane,2,4,6,2',4',6
'-hexahydroxydiphenylcyclohexane- (
1,1), 2,4, 6,2',4',6'-hexahydroxy-triphenylmethane, nordihydroguaiaretic acid, bis(3-benzoyl-4,5,6-trihydroxyphenyl)methane, Bis (3-acetyl-4,5,6-trihydroxyphenyl)methane, bis (3-propionyl-4,5,6-trihydroxyphenyl)methane, bis (3-butyryl-4,5,6-
trihydroxyphenyl)methane, bis(3-hexanoyl-4,5,6-trihydroxyphenyl)methane, bis(3-heptanoyl-4,5,6-trihydroxyphenyl)methane, bis(3-decanoyl) -4,
5,6-trihydroxyphenyl)methane, bis(3
-octadecanoyl-4,5,6-trihydroxyphenyl)methane, 1,10-bis-(2,4-dihydroxyphenyl)-decane-1,10-dione, 1,14
-bis- (2,4-dihydroxyphenyl)-tetradecane-1,14-dione, 1,8-bis- (2,
4-dihydroxyphenyl)-octane-1,8-dione, 1,10-bis-(2,3,4-trihydroxyphenyl)-decane-1,10-dione, 1,12-
Bis-(2,4-dihydroxyphenyl)-dodecane-1,12-dione, 1,4-bis-(2,4-
dihydroxyphenyl)-butane-1,4-dione, 1
,1-(5,5'-diacetyl-2,3,4,2'
,3',4'-hexahydroxy)diphenylethane,
1,1- (5-acetyl-2,3,4,2',3',
4'-hexahydroxy)diphenyl-2-methoxyethane, 1,1-(5-acetyl-2,3,4,2',
4',6'-hexahydroxy)diphenyl-2-hydroxyethane, 1,1-(2,4,6,2',4'-
Pentahydroxy-3-propanoyl)diphenylethanol, 4,4',3",4"-tetrahydroxy-3
, 5,3',5'-tetramethyltriphenyl methane, 4,4',2",3",4"-pentahydroxy-3
, 5,3',5'-tetramethyltriphenylmethane, 2,4,6,2',4',6'-hexahydroxy-
5,5'-dipropionyltriphenylmethane, 2,
3,4,2',3',4',3",4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,
4,6,2',4',6',2",3",4"-nonahydroxy-5,5'-dipropionyltriphenylmethane, 2,4,2',4',2",3 Examples include ",4"-heptahydroxytriphenylmethane, phenyl 2,3,4-trihydroxybenzoate, and phenyl 3,4,5-trihydroxybenzoate.

[0020]

[C5]

Here, R12: hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, acyl group, alkoxycarbonyl group, alkyloxy group,
aryloyloxy group, cyano group or nitro group,
R13, R14: may be the same or different, hydrogen atom, alkyl group or aryl group, Y: single bond or -O-CH2- group, i, j: 1-3
An integer of , i+j=4, k: an integer of 3 to 8.

Specific examples of the compound represented by the general formula (IV) include 10,15-dihydro-2,3,7,8,1
2,13-hexahydroxy-5H-tribenzo [a
, d, g] cyclononene, 10,15-dihydro-3,
8,13-trimethoxy-2,7,12-tris (methoxyd3)-5H-tribenzo [a,d,g]cyclononene, 10,15-dihydro-1,6,11-trihydroxy-2,7,12 -trimethoxy-4,9,1
4-trimethyl-5H-tribenzo [a, d, g] cyclononene, 10,15-dihydro-1,6,11-trihydroxy-2,7,12-trimethoxy-4,9,
14-tripropyl-5H-tribenzo [a, d, g
] Cyclononene, 2,8,14,20-tetramethylpentacyclo [19.3.1.13, 7.19, 13.
115,19] Octacosa-1 (25), 3, 5, 7
(28), 9, 11, 13 (27), 15, 17,
19 (26),21,23-dodecaene-4,6,1
Examples include 0,12,16,18,22,24-octole.

[0023]

[C6]

Here, R15, R16: may be the same or different, hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, amino group, monoalkylamino group, dialkylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, carboxyl group, cyano group, nitro group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group or acyloxy group, and these groups have a substituent. R17 to R19: a lower alkyl group which may be the same or different and may have a hydrogen atom or a substituent,
l, m, n, o: each an integer from 1 to 3, l+n=4
, m+o=5, represents.

Specific examples of the compound represented by the general formula (V) include 1-(4-hydroxyphenyl)-1,3
, 3-trimethyl-5,6-dihydroxyindan, 1
- (3,4-dihydroxyphenyl)-1,3,3-
Trimethyl-6-hydroxyindan, 1-(3,4
-dihydroxyphenyl)-1,3,3-trimethyl-
5,6-dihydroxyindan, 1-(3-hydroxyphenyl)-1,3,3-trimethyl-6-dihydroxyindan, 1-(2,3-dihydroxyphenyl)-1,3,3-trimethyl- 4,5-dihydroxyindan, 1-(2,3-dihydroxyphenyl)-1
,3,3-trimethyl-6,7-dihydroxyindan, 1-(2,4-dihydroxyphenyl)-1,3,
3-trimethyl-4,6-dihydroxyindan, 1-
(2,4-dihydroxyphenyl)-1,3,3-trimethyl-5,7-dihydroxyindan, 1- (3
,5-dihydroxyphenyl)-1,3,3-trimethyl-4,6-dihydroxyindan, 1-(3,5
-dihydroxyphenyl)-1,3,3-trimethyl-
5,7-dihydroxyindan, 1-(2,3,4-
trihydroxyphenyl)-1,3,3-trimethyl-4,5,6-trihydroxyindan, 1-(2,
3,4-trihydroxyphenyl)-1,3,3-trimethyl-5,6,7-trihydroxyindan, 1-
(2,4,5-trihydroxyphenyl) -1,3
, 3-trimethyl-4,6,7-trihydroxyindan, 1-(2,4,5-trihydroxyphenyl)-
1,3,3-trimethyl-4,5,7-trihydroxyindan, 1-(2,4,6-trihydroxyphenyl)-1,3,3-trimethyl-4,5,6-trihydroxyindan , 1-(2,3,4-trihydroxyphenyl)-1,3,3-triethyl-4,5,6-trihydroxyindan, 1-(2,3,4-trihydroxyphenyl)-1 ,3,3-triethyl-5,6,
7-trihydroxyindan, 1-(3-methyl-4
-hydroxyphenyl)-1,3,3-trimethyl-5
, 6,7-trihydroxyindan, 1-(4-aminophenyl)-1,3,3-trimethyl-5,6,7-
Trihydroxyindane, 1-(2,4-dihydroxyphenyl)-1,3,3-trimethyl-4,6-dihydroxyindane, 1-(2,4-dihydroxyphenyl)-1,3,3- Examples include trimethyl-5,7-dihydroxyindan.

[0026]

[C7]

R22, R23: may be the same or different, hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloxy group, aryloyl represents an oxy group, a cyano group or a nitro group, and these groups may have a substituent, p, r
: May be the same or different, integer from 1 to 3, q, s
: May be the same or different, an integer from 1 to 4, and
p+q=4, r+s=5, represents.

Specific examples of the compound represented by the general formula (VI) include 2-(3,4-dihydroxyphenyl)-
3,5,7-trihydroxybenzopyran, 2-(3
, 4,5-trihydroxyphenyl)-3,5,7-trihydroxybenzopyran, 2-(3,4-dihydroxyphenyl)-3-(3,4,5-trihydroxybenzoyloxy)-5 , 7-dihydroxybenzopyran, 2-(3,4,5-trihydroxyphenyl)-
Examples include 3-(3,4,5-trihydroxybenzoyloxy)-5,7-dihydroxybenzopyran.

[0029]

[Chemical formula 8]

[0030] Here, X': single bond, lower alkylene group or -CH2Y'
- group, Y': sulfur atom or oxygen atom, R24 to R26: may be the same or different, alkyl group, alkoxy group, hydrogen atom, hydroxyl group, or halogen atom, R27 to R29: may be the same or different, halogen atom , an alkyl group or an alkoxy group, t, u, v: an integer of 1 to 3 w, x, y: an integer of 2 to 4.

Specific examples of the compound represented by the general formula (VII) include α,α',α''-tris(3,5-dimethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene. , α,α',α"-tris(3,5-diethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(3,5
-di-n-propyl-4-hydroxyphenyl)1,3,
5-triisopropylbenzene, α, α', α''-tris(3,5-diisopropyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α',
α”-tris(3,5-di-n-butyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α
, α', α''-Tris(3-methyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,
α',α''-tris(3-methoxy-4-hydroxyphenyl)1,3,5-triisopropylbenzene, 1,
3,5-tris(3,5-dimethyl-4-hydroxyphenyl)benzene, 1,3,5-tris(5-methyl-
Examples include 2-hydroxyphenyl)benzene, 2,4,6-tris(3,5-dimethyl-4-hydroxyphenylthiomethyl)mesitylene, and the like.

[0032]

[Chemical formula 9]

[0033] Here, X'': single bond or lower alkylene group, R30 to R3
2: which may be the same or different, alkyl group, alkoxy group, hydrogen atom or halogen atom, R33: hydrogen atom or alkyl group, a', b', c': integers from 1 to 3 d', e', f ': Represents an integer from 2 to 4.

Specific examples of the compound represented by the general formula (VIII) include 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(4 ”
-hydroxyphenyl)ethyl]benzene, 1-[α-
Methyl-α-(4'-hydroxyphenyl)ethyl]-
3-[α,α'-bis(4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3,5'-
dimethyl-4'-hydroxyphenyl)ethyl]-4-
[α,α'-bis(3'',5''-dimethyl-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3'-methyl-4'-hydroxyphenyl)ethyl ]-4-[α,α'-bis(3"-methyl-4"-
hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3'-methoxy-4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(3"-methoxy-4") -hydroxyphenyl)ethyl]benzene, 1-
[α-Methyl-α-(2′,4′-hydroxyphenyl)ethyl]-4-[α,α′-bis(4”-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α −
(2',4'-dihydroxyphenyl)ethyl]-3-
Examples include [α,α'-bis(4''-hydroxyphenyl)ethyl]benzene.

[0035]

[Chemical formula 10]

Specific examples of the compound represented by the general formula (IX) include tris-(3-methyl-4-hydroxybenzyl)isocyanurate, tris-(3-t-butyl-
4-Hydroxybenzyl)isocyanurate, tris-
(3,5-dimethyl-4-hydroxybenzyl)isocyanurate, bis-(3-methyl-4-hydroxybenzyl)isocyanurate, tris-(2,4-dihydroxybenzyl)isocyanurate, tris-(2,3,
Examples include 4-trihydroxybenzyl) isocyanurate and bis-(2,4-dihydroxybenzyl) isocyanurate.

[0037]

[Chemical formula 11]

Here, Y': lower alkylene group, R36: hydrogen atom, halogen atom, alkyl group or alkoxy group, i': an integer of 2 to 4, j': an integer of 1 to 3, k': 2 or 3. represents.

Specific examples of the compound represented by the general formula (X) include 2,6-bis-(2,4-dihydroxybenzyl)cyclohexanone, 2,6-bis-(2,4-dihydroxybenzyl)cyclo Pentanone, 2,6-bis-
Examples include (3,4,5-trihydroxybenzyl)cyclohexanone and 2,6-bis-(3,4,5-trihydroxybenzyl)cyclopentanone.

[0040]

[Chemical formula 12]

[0041] Here, R37 to R44: may be the same or different, and are hydrogen atoms,
Hydroxyl group, halogen atom, alkyl group, alkoxy group, aralkyl group, aryl group, amino group, monoalkylamino group, dialkylamino group, acylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group group, carboxyl group, cyano group, nitro group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group or acyloxy group, provided that at least three are hydroxyl groups, R45 to R48: may be the same or different, hydrogen Represents an atom or a lower alkyl group, Y'': an oxygen atom or a single bond.

Specific examples of the compound represented by the general formula (XI) include 3,3,3',3'-tetramethyl-1,1
'-spirobiindane-4,6,7,4',6',7'
-hexol, 3,3,3',3'-tetramethyl-1
,1'-spirobiindane-5,6,7,5',6',
7'-hexol, 3,3,3',3'-tetramethyl 1,1'-spirobiindane-4,5,6,4',5'
, 6'-hexol, 3,3,3',3'-tetramethyl-1,1'-spirobiindane-4,5,6,5',
6',7'-hexol, 1,1'-spirobiindane-4,5,6,4',5',6'-hexol, 1,1
'-spirobiindane-5,6,7,5',6',7'
-hexol, 1,1'-spirobiindane-5,6,
5',6'-tetrol, 3,3,3',3'-tetramethyl-1,1'-spirobiindane-5,6,5',
6'-tetrol, 3,3,3',3'-tetramethyl-1,1'-spirobiindane-6,7,6',7'-
Tetrol, 5,5'-di-t-butyl-3,3,3'
,3'-tetramethyl-1,1'-spirobiindane-
6,7,6',7'-tetrol, 5-t-butyl-3
, 3,3',3'-tetramethyl-1,1'-spirobiindane-6,7,6',7'-tetrol, 3,3,
3',3'-tetramethyl-1,1'-spirobiindane-5,6,6'-triol, 4,4,4',4'-
Tetramethyl-2,2'-spirobi-chroman-6,7
, 6',7'-tetrol and the like.

[0043]

[Chemical formula 13]

Here, R49: may be the same or different, hydrogen atom, alkyl group, aryl group or aralkyl group, R50: may be the same or different, alkyl group, aryl group or aralkyl group, l', m' : An integer from 1 to 3, n': An integer from 2 to 4, where l'+m'=4 and l'+n'=5.

Specific examples of the compound represented by the general formula (XII) include 2,4,6,2',4',6'-hexahydroxy-5,5'-dipropionyltriphenylmethane, 2, 3,4,2',3',4',3",4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2',4',6',2", 3”, 4”
-nonahydroxy-5,5'-dipropionyltriphenylmethane, 2,4,6,2',4',6'-hexahydroxy-5,5'-dibutyryltriphenylmethane, and the like.

[0046]

[Chemical formula 14]

[0047] Here, Y''': lower alkylene group, R51 to R53: may be the same or different, hydrogen atom,
Halogen atom, alkyl group, alkoxy group, alkenyl group, alkoxycarbonyl group, alkyloxy group or acyl group, r', s', t': an integer of 1 to 3, o', p', q': 2 to represents an integer of 4.

Specific examples of the compound represented by the general formula (XIII) include 2,6-bis-(2'-hydroxy-3
',5'-dimethyl-benzyl)-p-cresol, 2
, 6-bis-(2'-hydroxy-5'-methyl-benzyl)-p-cresol, 2,6-bis-(2'-hydroxy-3',5'-di-t-butyl-benzyl)- p
-cresol, 2,6-bis-(2'-hydroxy-5
'-ethyl-benzyl)-p-cresol, 2,6-bis-(2',4'-dihydroxy-benzyl)-p-cresol, 2,6-bis-(2'-hydroxy-3'-
t-Butyl-5'-methyl-benzyl)-p-cresol, 2,6-bis-(2',3',4'-trihydroxy-5'-acetyl-benzyl)-p-cresol, 2
, 6-bis-(2',4',6'-trihydroxy-benzyl)-p-cresol, 2,6-bis-(2',3
',4'-trihydroxy-benzyl)-p-cresol, 2,6-bis-(2',3',4'-trihydroxy-benzyl)-3,5-dimethyl-phenol, 4,
6-bis-(4'-hydroxy-3',5'-dimethyl-benzyl)-pyrogallol, 4,6-bis-(4'-
Hydroxy-3',5'-dimethoxy-benzyl)-pyrogallol, 2,6-bis-(4'-hydroxy-3'
, 5'-dimethyl-benzyl)-1,3,4-trihydroxy-phenol, 4,6-bis-(2',4',6
'-trihydroxy-benzyl)-2,4-dimethyl-
Examples include phenol, 4,6-bis-(2',3',4'-trihydroxy-benzyl)-2,5-dimethyl-phenol, and the like. These polyhydroxy compounds may be used alone or in combination of two or more. The blending amount is usually 200 parts by weight or less, preferably 10 to 150 parts by weight, per 100 parts by weight of the quinonediazide compound. If the usage ratio is less than 10 parts by weight, no effect of increasing sensitivity can be obtained substantially, while if it exceeds 200 parts by weight, the residual film rate will drop significantly.

(1) As the 1,2-quinonediazide compound used in the present invention, the following esterified product of the polyhydroxy compound with 1,2-naphthoquinonediazide-5-(and/or -4-)sulfonyl chloride is used. be able to. Examples of polyhydroxy compounds include:
2,3,4-trihydroxybenzophenone, 2,4,
4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,
4'-tetrahydroxybenzophenone, 2,2',4
, 4'-tetrahydroxybenzophenone, 2,4,
6,3',4'-pentahydroxybenzophenone, 2
, 3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'- Hexahydroxybenzophenone, 2,3,4,3',4',5'
-Polyhydroxybenzophenones such as hexahydroxybenzophenone, 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenylpentyl ketone, 2,3,4-trihydroxyphenylene polyhydroxyphenyl alkyl ketones such as hexyl ketone, bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane,
bis(2,4-dihydroxyphenyl)propane-1,
Bis((2,3,4-trihydroxyphenyl)propane-1, nordihydroguaiaretic acid, etc.)
poly)hydroxyphenyl)alkanes, 3,4,5-
Polyhydroxybenzoic acid esters such as propyl trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate, bis(2,3,4-trihydroxybenzoyl)
Methane, bis(3-acetyl-4,5,6-trihydroxyphenyl)-methane, bis(2,3,4-trihydroxybenzoyl)benzene, bis(2,4,6-
Bis(polyhydroxybenzoyl)alkanes or bis(polyhydroxybenzoyl)aryls such as trihydroxybenzoyl)benzene, ethylene glycol-di(
3,5-dihydroxybenzoate), alkylene di(polyhydroxybenzoate) such as ethylene glycol di(3,4,5-trihydroxybenzoate)
2,3,4-biphenyltriol, 3,4,5-
Biphenyltriol, 3,5,3',5'-biphenyltetrol, 2,4,2',4'-biphenyltetrol, 2,4,6,3',5'-biphenylpentol, 2,4 , 6,2',4',6'-biphenylhexol, polyhydroxybiphenyls such as 2,3,4,2', 3',4'-biphenylhexol, 4,4'
-bis(polyhydroxy)sulfides such as thiobis(1,3-dihydroxy)benzene, 2,2',4,
Bis( such as 4'-tetrahydroxydiphenyl ether)
polyhydroxyphenyl) ethers, 2,2',4
, 4'-tetrahydroxydiphenyl sulfoxide, and other bis(polyhydroxyphenyl) sulfoxides; ',
3'',4''-tetrahydroxy-3,5,3',5
'-Tetramethyltriphenylmethane, 4,4',2'
',3'',4''-pentahydroxy-3,5,3'
, 5'-tetramethyltriphenylmethane, 2,3,4
,2',3',4'-hexahydroxy-5,5'-diacetyltriphenylmethane, 2,3,4,2',3'
,4',3'',4''-octahydroxy-5,5'
-Diacetyltriphenylmethane, 2,4,6,2',
Polyhydroxytriphenylmethanes such as 4',6'-hexahydroxy-5,5'-dipropionyltriphenylmethane, 3,3,3',3'-tetramethyl-1,
1'-spirobi-indane-5,6,5',6'-tetrol, 3,3,3',3'-tetramethyl-1,1'
-spirobi-indan-5,6,7,5',6',7'
-hexol, 3,3,3',3'-tetramethyl-
1,1'-spirobi-indan-4,5,6,4',5
',6'-hexol, 3,3,3',3'-tetramethyl-1,1'-spirobi-indan-4,5,6,
Polyhydroxyspirobi-indanes such as 5',6',7'-hexol, 3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-
trihydroxyphenyl)phthalide, 3',4',5'
,6'-tetrahydroxyspiro [phthalide-3,9
'-xanthene] and other polyhydroxyphthalides, 2-
(3,4-dihydroxyphenyl)-3,5,7-trihydroxybenzopyran, 2-(3,4,5-trihydroxyphenyl)-3,5,7-trihydroxybenzopyran, 2-( 3,4-dihydroxyphenyl)-3-
(3,4,5-trihydroxybenzoyloxy)-5
, 7-dihydroxybenzopyran, 2-(3,4,5-
Polyhydroxybenzopyrans such as (trihydroxyphenyl)-3-(3,4,5-trihydroxybenzoyloxy)-5,7-dihydroxybenzopyran, or flavonoid pigments such as morin, quercetin, and rutin are used. I can do things.

Furthermore, general formula (III) used in the present invention
) to (XIII) can also be used. These naphthoquinone diazide ester photosensitive materials of polyhydroxy compounds alone,
Or it is used in combination of two or more types. The ratio of the photosensitive material to the alkali-soluble resin is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the resin.
Parts by weight. If the usage ratio is less than 5 parts by weight, the residual film rate will drop significantly, while if it exceeds 100 parts by weight, sensitivity and solubility in solvents will drop.

The composition of the present invention may further contain other polyhydroxy compounds in order to promote dissolution in the developer. Preferred polyhydroxy compounds include:
Phenols, resorcinol, phloroglucinum, 2,3,
4-trihydroxybenzophenone, 2,3,4,4'
-tetrahydroxybenzophenone, 2,3,4,3'
, 4',5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, phloroglucide, 2,4
, 2',4'-biphenyltetrol, 4,4'-thiobis(1,3-dihydroxy)benzene, 2,2',4
, 4'-tetrahydroxydiphenyl ether, 2,2
Examples include ',4,4'-tetrahydroxydiphenyl sulfoxide and 2,2',4,4'-tetrahydroxydiphenyl sulfone. These polyhydroxy compounds are polyhydroxy compounds 10 of the present invention.
0 parts by weight, usually 50 parts by weight or less, preferably 3 parts by weight.
It can be blended in a proportion of 0 parts by weight or less.

Examples of the solvent for dissolving the photosensitive material and alkali-soluble novolac resin of the present invention include ketones such as methyl ethyl ketone and cyclohexanone, and 4-ethoxy-2
- Keto ethers such as butanone and 4-methoxy-4-methyl-2-pentanone, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethers such as dioxane and ethylene glycol dimethyl ether, methyl cellosolve acetate, ethyl Cellosolve esters such as cellosolve acetate, fatty acid esters such as butyl acetate, methyl lactate, ethyl lactate, halogenated hydrocarbons such as 1,1,2-trichloroethylene, dimethylacetamide, N
- Highly polar solvents such as methylpyrrolidone, dimethylformamide, and dimethylsulfoxide can be exemplified. These solvents can be used alone or in combination.

A surfactant may be added to the positive photoresist composition of the present invention in order to further improve coating properties such as striation. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and polyoxyethylene nonyl. Polyoxyethylene alkyl allyl ethers such as phenol ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristear Sorbitan fatty acid esters such as esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as ethylene sorbitan fatty acid esters, EFTOP EF3
01, EF303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.)
, Megafuck F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103,
Fluorine-based surfactants such as SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic acid (co)polymerized polyflow No. 7
5, No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). The blending amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the alkali-soluble resin and quinonediazide compound in the composition of the present invention. These surfactants may be added alone or in some combination.

The developing solution for the positive photoresist composition of the present invention includes sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, triethylamine, and methyldiethylamine. tertiary amines such as dimethylethanolamine, alcohol amines such as triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, cyclic amines such as pyrrole and piperidine, alkalis such as Aqueous solutions of the following types can be used. Furthermore, appropriate amounts of alcohols and surfactants may be added to the aqueous alkali solution.

The positive photoresist composition of the present invention may contain dyes, plasticizers, and adhesion aids, if necessary. Specific examples include dyes such as methyl violet, crystal violet, and malachite green, stearic acid, acetal resin, phenoxy resin,
Plasticizers such as alkyd resins, hexamethyldisilazane,
There are adhesion aids such as chloromethylsilane.

The above composition for positive photoresist is coated onto a substrate (eg silicon/silicon dioxide coated) such as that used for manufacturing precision integrated circuit elements using an appropriate coating method such as a spinner or coater, and then coated in a predetermined manner. A good resist can be obtained by exposing the resist to light through a mask and developing it. Examples of the present invention will be shown below, but the present invention is not limited thereto. Note that % indicates weight % unless otherwise specified. Moreover, the weight average molecular weight and the content of monomer, dimer or trimer were measured as follows. TSKgel manufactured by Toyo Soda Kogyo
GMHXL, G4000 HXL, G3000 H
Using columns connected to one each of XL and G2000 HXL, 40°C, flow rate 1ml/min, THF
The weight average molecular weight was calculated using monodisperse polystyrene as a standard by gel permeation chromatography (GPC) using a solvent and a detection wavelength of 282 nm. The contents of monomer and trimer were also measured and calculated under the same conditions.

[0057]

[Example] (1) Synthesis of novolak resin a 45 g of m-cresol, 55 g of p-cresol, 53 g of a 37% formalin aqueous solution and 0.1 g of oxalic acid were placed in a three-necked flask, and the temperature was raised to 100°C while stirring. , and reacted for 15 hours. After that, increase the temperature to 200℃ and gradually increase the thickness by 5mm.
The pressure was reduced to Hg, and water, unreacted monomers, formaldehyde, oxalic acid, etc. were distilled off. The molten alkali-soluble novolak resin was then returned to room temperature and recovered. The obtained novolac resin a has a weight average molecular weight of 8300 (in terms of polystyrene), and the monomer, dimer, and trimer contents are 0.5%, 12.7%, and 7.1%, respectively (total 20%).
．． 3%).

(2) Synthesis of Novolak Resin B After completely dissolving 20 g of Novolak Resin A obtained in (1) in 60 g of methanol, 30 g of water was gradually added to the solution with stirring to precipitate the resin. The upper layer was removed by decantation and the precipitated resin was recovered, heated to 40°C and dried under reduced pressure for 24 hours to obtain alkali-soluble novolak resin b. The weight average molecular weight was 9100 (in terms of polystyrene), and the monomer, dimer, and trimer contents were 0%, 4.7%, and 6.3%, respectively (total 11.0%).

(3) Synthesis of novolac resin c 38 g of m-cresol, 62 g of p-cresol, 47 g of a 37% formalin aqueous solution and 0.1 g of oxalic acid were placed in a three-necked flask, and the temperature was raised to 100° C. while stirring. The reaction was allowed to proceed for 15 hours. After that, the temperature was increased to 250℃, and the temperature was gradually increased to 1m.
The pressure was reduced to mHg to distill off water, unreacted monomers, formaldehyde, oxalic acid, dimer components, and the like. The molten alkali-soluble novolak resin was then returned to room temperature and recovered. The obtained novolak resin c has a weight average molecular weight of 7200 (polystyrene equivalent), and contains monomers,
The contents of dimer and trimer are 0%, 4.1%, and 6.
It was 9% (total 11.0%).

(4) Synthesis of novolak resin d 25 g of m-cresol, 50 g of p-cresol, 28 g of 3,5-xylenol, 53 g of a 37% formalin aqueous solution and 0.1 g of oxalic acid were placed in a three-necked flask, and the mixture was stirred. 1
The temperature was raised to 00°C and the reaction was continued for 15 hours. After that, the temperature was raised to 250℃ and the pressure was gradually reduced to 1mmHg.
Water, unreacted monomers, formaldehyde, oxalic acid, dimer components, etc. were distilled off. The molten alkali-soluble novolak resin was then returned to room temperature and recovered. The obtained novolac resin d has a weight average molecular weight of 4700 (in terms of polystyrene), and the monomer, dimer, and trimer contents are 0.5%, 5.2%, and 8.9%, respectively (total 14.6%).
).

(5) Synthesis of novolak resin e 45 g of m-cresol, 58 g of 3,5-xylenol, 58 g of a 37% formalin aqueous solution and 0.1 g of oxalic acid were placed in a three-necked flask, and the temperature was raised to 100° C. while stirring. 13
Allowed time to react. Thereafter, the temperature was raised to 200° C., and the pressure was gradually reduced to 5 mmHg to distill off water, unreacted monomers, formaldehyde, oxalic acid, and the like. The molten alkali-soluble novolak resin was then returned to room temperature and recovered. The obtained novolak resin e has a weight average molecular weight of 630.
0 (polystyrene equivalent), monomer, dimer,
The content of trimer is 0.4%, 10.2%, 8.8% respectively.
(19.4% in total).

(6) Synthesis of novolac resin f 120 g of an ethyl cellosolve acetate solution (novolac resin content: 41.5%) of the novolac resin e obtained in (5) was charged into a 3-liter flask, and further 880 g of ethyl cellosolve acetate was added. Add 550g of normal heptane to 23
After stirring at ℃ for 30 minutes, the mixture was placed and separated. Normal heptane in the lower layer obtained by liquid separation was removed using an evaporator, and ethyl cellosolve acetate was added to obtain an ethyl cellosolve acetate solution of novolak resin (content: 3
5% by weight). The obtained novolac resin f has a weight average molecular weight of 8900 (polystyrene equivalent), and the monomer, dimer, and trimer contents are 0%, 4.1%, and 7.1%, respectively.
% (total 11.2%).

(7) Synthesis of novolak resin g 50 g of m-cresol, 55 g of 2,3,5-trimethylphenol
, 37% formalin aqueous solution 57g and oxalic acid 0.1g
was charged into a three-necked flask, heated to 100° C. with stirring, and reacted for 15 hours. Thereafter, the temperature was raised to 200° C., and the pressure was gradually reduced to 5 mmHg to distill off water, unreacted monomers, formaldehyde, oxalic acid, and the like. The molten alkali-soluble novolak resin was then returned to room temperature and recovered. The obtained novolak resin g has a weight average molecular weight of 6100 (polystyrene equivalent), and the monomer, dimer, and trimer contents are 0.3% and 9.4%, respectively.
, 8.6% (total 18.3%).

(8) Synthesis of novolac resin h 200 g of ethyl cellosolve acetate solution (novolac resin content 50%) of novolac resin g obtained in (7) was added to 1 liter.
300 g of ion-exchanged water and 80 g of methanol were added thereto, and the mixture was stirred at 23° C. for 30 minutes, then set aside to separate into a resin solution layer and an aqueous solution layer. Furthermore, methanol and water in the obtained resin solution layer were distilled off under reduced pressure, and ethyl cellosolve acetate was added to reduce the novolac resin content to 3.
A 5% by weight solution was obtained. The obtained novolac resin h has a weight average molecular weight of 7900 (polystyrene equivalent), and the monomer, dimer, and trimer contents are 0% and 4.3%, respectively.
, 6.8% (total 11.1%).

(9) Synthesis of photosensitive material A 11.5 g of 2,3,4-trihydroxybenzophenone
, 30.2 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 300 ml of acetone were charged into a three-necked flask and uniformly dissolved. Next, a mixed solution of triethylamine/acetone=11.4 g/50 ml was gradually added dropwise, and the mixture was reacted at 25° C. for 3 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered, washed with water and dried (40°C) to obtain 1,2-naphthoquinonediazide of 2,3,4-trihydroxybenzophenone. 29.8 g of -5-sulfonic acid ester was obtained.

(10) Synthesis of photosensitive material B 2,3,4,4'-tetrahydroxybenzophenone 1
2.3 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 300 ml of acetone were charged into a three-necked flask and uniformly dissolved. Next, a mixture of triethylamine/acetone (15.2 g/50 ml) was gradually added dropwise, and the mixture was reacted at 25° C. for 3 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, the resulting precipitate was filtered off, washed with water and dried (40°C), and 2, 3, 4,
39.7 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of 4'-tetrahydroxybenzophenone
I got it.

(11) Synthesis of Photosensitive Material C 42 g of pyrogallol, 33 g of acetone, 80 ml of acetic acid and 64 ml of concentrated hydrochloric acid were placed in a three-necked flask and uniformly dissolved under stirring. After heating in a water bath and refluxing for 24 hours, the mixture was cooled to room temperature. After cooling, the reaction solution was heated to 200 ml.
The mixture was added dropwise to 0 ml of distilled water, and the product was precipitated, filtered, and dried under reduced pressure. The obtained 3,3,3',3'-tetramethyl-1,1'-spirobi-indan-5,6,7,5'
, 4 g of ,6',7'-hexol, 13 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 300 ml of acetone were placed in a three-necked flask and uniformly dissolved under stirring. Then, triethylamine/acetone = 4
．． A mixed solution of 9 g/30 ml was gradually added dropwise and reacted at room temperature for 3 hours. After the reaction was completed, the contents were added dropwise to a 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered off and dried under reduced pressure to obtain photosensitive material C.

(12) Synthesis of photosensitive material D 2,4,6,3',5'-biphenylpentol (Ph
10 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 500 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then triethylamine/acetone=15.2
A mixture of g/50 ml was gradually added dropwise, and the mixture was reacted at 25° C. for 3 hours. Add the reaction mixture to 2500 ml of 1% aqueous hydrochloric acid solution.
The precipitate formed was filtered out, washed with water and dried (40°C).
) to obtain 38.7 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of 2,4,6,3',5'-biphenylpentol (Phloroglucide).

(13) Preparation and evaluation of positive photoresist composition Cresol novolak resins a to h obtained in the above (1) to (8), photosensitive materials obtained in the above (9) to (12) A~
D and additives A to W shown in Tables 1 and 2 in Tables 3 and 4.
Dissolved in ethyl cellosolve acetate in the proportion shown in 0
．． A photoresist composition was prepared by filtration using a 2 μm microfilter. This photoresist composition was applied to a silicon wafer using a spinner and dried at 90°C for 30 minutes in a convection oven under a nitrogen atmosphere to a film thickness of 1.
．． A 2 μm resist film was obtained. Next, it was exposed to light through a test chart mask using a reduction projection exposure apparatus FPA-1550 manufactured by Canon Inc., developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, washed with water for 30 seconds, and dried.

The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope and the resist was evaluated. The results are shown in Tables 5 and 6. The sensitivity was defined as the reciprocal of the exposure amount for reproducing a 0.70 μm mask pattern, and was expressed as a relative value to the sensitivity of Comparative Example 1. The residual film rate was expressed as a percentage of the ratio of the unexposed area before and after development. The resolution represents the limit resolution at an exposure dose that reproduces a 0.70 μm mask pattern. Heat resistance was determined by baking a silicon wafer on which a resist pattern was formed for 30 minutes in a convection oven, and showing the temperature at which the pattern did not deform. The shape of the resist is 0.70μm
It is expressed as the angle (Θ) between the resist wall surface and the plane of the silicon wafer in the cross section of the resist pattern. Regarding developability, the case where no surface layer peeling or film residue was observed was good was expressed as ◯, the case where much was observed was expressed as ×, and the case where a little was observed was expressed as △. As can be seen, the resist composition of the present invention was excellent in sensitivity, residual film rate, resolution, heat resistance, resist shape, and developability.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

[Table 5]

[0076]

[Table 6]

[0077]

Effects of the Invention The positive photoresist of the present invention has excellent resolution, sensitivity, developability, and heat resistance, and is suitably used as a photoresist for microfabrication.

Claims (1)

[Claims] 1. A positive photoresist composition comprising at least the following three components. ■m-cresol 5-95 mol%, compound represented by the following general formula (I) (excluding m-cresol) 5-9
An alkali-soluble novolac resin obtained by condensing 5 mol% and aldehydes, the dimer content is 2 to 2 in area ratio of gel permeation chromatographic pattern.
Alkali-soluble novolac resin having a content of 6%, [Formula 1] Here, R1 to R3: may be the same or different, and a hydrogen atom,
an alkyl group or alkoxy group having 1 to 4 carbon atoms,
However, the case where all of R1 to R3 are hydrogen atoms is excluded. represents. (1) Aromatic polyhydroxy compounds having 3 to 9 hydroxyl groups in one molecule (excluding polyhydroxybenzophenone); (2) 1,2-quinonediazide compounds.