JPH0342656B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a positive photosensitive resin composition, and more particularly, the present invention relates to a positive photosensitive resin composition, and more specifically, an alkali-soluble resin and a specific 1, 2
- A positive photosensitive resin composition containing a quinonediazide compound, which is suitable as a photoresist that has high sensitivity, high resolution, and high residual film rate, has excellent developability, and has heat resistance for producing integrated circuits. relating to things.

Conventionally, as a photoresist for producing 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, compared to this negative photoresist, a positive photoresist made by blending a 1,2-quinonediazide compound with an alkali-soluble resin has superior resolution and is expected to be able to respond to the high integration of integrated circuits. ing.

However, conventional positive photoresists
Satisfactory results have not always been obtained in various performances such as sensitivity, resolution, and residual film rate.

Furthermore, with conventional positive photoresists, the pattern tends to deform due to temperature rise during the post-bake or dry etching process.Therefore, a positive photoresist that is less deformed due to temperature rise, that is, a positive photoresist with excellent heat resistance, is required. There is.

An object of the present invention is to eliminate the drawbacks of the above-mentioned conventional techniques, and to provide a positive photosensitive resin composition that has high sensitivity, high resolution, high residual film rate, and has excellent developability and heat resistance. It is in.

As a result of intensive research to achieve this objective, the present inventors found that alkali-soluble resins with specific 1 and 2
- By blending a quinonediazide compound,
The present invention has been achieved by discovering that the above drawbacks can be improved.

That is, the present invention provides an alkali-soluble resin;
In a positive photosensitive resin composition comprising a 1,2-quinonediazide compound, the 1,2-quinonediazide compound contains an α-pyrone natural dye having a hydroxyl group, a γ-pyrone natural dye having a hydroxyl group, and a hydroxyl group-containing natural dye. A compound selected from the group consisting of a diazine natural dye having a hydroxyl group and a quinone natural dye having a hydroxyl group, preferably at least one 1,2-quinonediazide sulfonic acid ester of a γ-pyrone natural dye having a hydroxyl group, 1,2-quinonediazide sulfonic acid ester is the alkali-soluble resin
The object of the present invention is to provide a positive photosensitive resin composition characterized in that 5 to 100 parts by weight are blended with respect to 100 parts by weight.

The 1,2-quinonediazide sulfonic acid ester used in the composition of the present invention is, for example, the α-pyrone natural pigment having a hydroxyl group, the γ-pyrone natural pigment having a hydroxyl group, or the diazine natural pigment having a hydroxyl group. and 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1 , 2-benzoquinonediazide-4-sulfonyl chloride, etc.
It can be obtained by subjecting 2-quinonediazide sulfonyl chloride and preferably 1,2-naphthoquinonediazide-5-sulfonyl chloride to a condensation reaction in the presence of a basic catalyst, followed by purification.

Examples of the α-pyrone natural pigments having a hydroxyl group include hispidine, 2',3'-dioxy-dibenz-α-pyrone, ellagic acid, gluverdine, and osporaftone. Examples of the γ-pyrone natural pigments having a hydroxyl group include eugenin, brazilin, hematoxylin, euxanthone, gentimin, chrysin, tringin which is a glycoside of chrysin, primethin, apigenin, apiin which is a glycoside of apigenin, Luteolin, quercetin, quercitrin, a glycoside of quercetin, isoquercitrin, quercimeritrin, rutin, hyperin, carangin, kaempferol, fuisetin, morin, rhamnetin, myricetin, cycadoflavone, naringenin, naringin, a glycoside of naringenin, sakranetin , hesperitin, alpinone, catechin, daidzein, prunetin, prunitrin which is a glycoside of prunetin, irigenin, iridine which is a glycoside of irigenin, osazine, pelargonidin, cyanidin, leucodelphinidin and the like. Examples of the diazine natural pigments having a hydroxyl group include xanthopterin, leucopterin, entropterin, chrysopterin, and iodinine. Examples of the quinone natural pigments having a hydroxyl group include polypolic acid, atromentin, leucomelone, muscarfine, osporein, juglone, echinochrome A, spinone A, spinochrome N, alizarin, purpurin, emodin, carminic acid, kermesic acid, and skylin. , pyromycin, and the like.

1,2 for the natural dye in the condensation reaction
- The amount of quinonediazide sulfonyl chloride to be used can be appropriately adjusted depending on the number of hydroxyl groups in the natural dye, and usually 1,2- One mole of quinonediazide sulfonyl chloride is used.

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 1.3 times the mole of 1,2-quinonediazide sulfonyl chloride used.

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 to 1000 parts by weight is used per 100 parts by weight.

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

Specific examples of the 1,2-quinonediazide sulfonic acid ester used in the composition of the present invention obtained in this way include the following compounds.

Hispidine-1,2-naphthoquinonediazide-
5-sulfonic acid diester, hispidine-1,2-naphthoquinone diazide
5-sulfonic acid monoester, 2'3'-dioxy-dibenz-α-pyrone-1,
2-naphthoquinonediazide-5-sulfonic acid diester, ellagic acid-1,2-naphthoquinonediazide-5
-sulfonic acid tetraester, ellagic acid-1,2-naphthoquinonediazide-5
-sulfonic acid triester, gluterdine-1,2-naphthoquinonediazide-5-sulfonic acid monoester, osporactone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, eugenin-1,2-naphthoquinonediazide-
5-sulfonic acid monoester, Brazilin-1,2-naphthoquinonediazide-
5-sulfonic acid triester, hematoxylin-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, hematoxylin-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, hematoxylin-1,2-naphthoquinonediazide-5- Sulfonic acid triester, hematoxylin-1,2-naphthoquinonediazide-5-sulfonic acid diester, oixanthone-1,2-naphthoquinonediazide-5-sulfonic acid diester, gentimine-1,2-naphthoquinonediazide-
5-sulfonic acid diester, chrysin-1,2-naphthoquinonediazide-5
-Sulfonic acid diester, Tringin-1,2-naphthoquinone diazide-
5-sulfonic acid diester, primethine-1,2-naphthoquinone diazide
5-sulfonic acid diester, apigenin-1,2-naphthoquinonediazide-
5-sulfonic acid triester, apiin-1,2-naphthoquinonediazide-5
-Sulfonic acid triester, luteolin-1,2-naphthoquinonediazide-
5-sulfonic acid triester, quercetin-1,2-naphthoquinone diazide
5-sulfonic acid pentaester, quercetin-1,2-naphthoquinone diazide
5-sulfonic acid tetraester, quercetin-1,2-naphthoquinone diazide
5-sulfonic acid triester, quercetin-1,2-naphthoquinone diazide
5-sulfonic acid diester, quercetin-1,2-naphthoquinone diazide
5-sulfonic acid monoester, quercetin-1,2-naphthoquinone diazide
4-sulfonic acid tetraester, quercetin-1,2-benzoquinone diazide
4-sulfonic acid tetraester, quercitrin-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, isoquercitrin-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, quercimeritrin-1,2-naphthoquinonediazide- 5-sulfonic acid tetraester, rutin-1,2-naphthoquinonediazide-5-
Sulfonic acid diester, hyperin-1,2-naphthoquinone diazide-5
-Sulfonic acid tetraester, carangin-1,2-naphthoquinonediazide-
5-sulfonic acid triester, kaempferol-1,2-naphthoquinonediazide-5-sulfonic acid triester, fisetin-1,2-naphthoquinonediazide-
5-sulfonic acid triester, morin-1,2-naphthoquinonediazide-5-
Sulfonic acid tetraester, morin-1,2-naphthoquinonediazide-5-
Sulfonic acid pentaester, rhamnetin-1,2-naphthoquinone diazide
5-sulfonic acid triester, myricetin-1,2-naphthoquinone diazide
5-sulfonic acid pentaester, cycadflavone-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, naringenin-1,2-naphthoquinonediazide-5-sulfonic acid triester, naringin-1,2-naphthoquinonediazide-
5-sulfonic acid diester, Sakuranetin-1,2-naphthoquinonediazide-5-sulfonic acid diester, Hesperitin-1,2-naphthoquinonediazide-5-sulfonic acid diester, Alpinone-1,2-naphthoquinonediazide-
5-sulfonic acid diester, catechin-1,2-naphthoquinonediazide-5
-Sulfonic acid tetraester, daidzein-1,2-naphthoquinone diazide-
5-sulfonic acid monoester, planetin-1,2-naphthoquinone diazide
5-sulfonic acid diester, prunitrin-1,2-naphthoquinonediazide-5-sulfonic acid diester, irigenin-1,2-naphthoquinonediazide-
5-sulfonic acid diester, iridine-1,2-naphthoquinonediazide-5
-sulfonic acid diester, osazine-1,2-naphthoquinonediazide-5
-sulfonic acid diester, pelargonidin-1,2-naphthoquinonediazide-5-sulfonic acid triester, cyanidin-1,2-naphthoquinonediazide-
5-sulfonic acid tetraester, leucodelphinidin-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, xanthopterin-1,2-naphthoquinonediazide-5-sulfonic acid diester, leucopterin-1,2-naphtho Quinonediazide-5-sulfonic acid triester, Entropterin-1,2-naphthoquinonediazide-5-sulfonic acid triester, Chrysopterin-1,2-naphthoquinonediazide-5-sulfonic acid diester, Iodinine-1,2-naphthoquinonediazide −
5-sulfonic acid diester, polypolic acid-1,2-naphthoquinonediazide-5-sulfonic acid diester, atromentin-1,2-naphthoquinonediazide-5-sulfonic acid triester, leucomelone-1,2-naphthoquinonediazide-5-sulfone acid triester, muscarfine-1,2-naphthoquinonediazide-5-sulfonic acid triester, osporein-1,2-naphthoquinonediazide-5-sulfonic acid triester, juglone-1,2-naphthoquinonediazide-5
-Sulfonic acid monoester, Echinochrome A-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, Spinone A-1,2-naphthoquinonediazide-
5-sulfonic acid tetraester, spinochrome N-1,2-naphthoquinonediazide-5-sulfonic acid triester, alizarin-1,2-naphthoquinonediazide-
5-sulfonic acid diester, purpurin-1,2-naphthoquinone diazide
5-sulfonic acid diester, emodin-1,2-naphthoquinonediazide-5
-Sulfonic acid diester, carminic acid-1,2-naphthoquinonediazide-
5-sulfonic acid triester, kermesic acid-1,2-naphthoquinone diazide
5-sulfonic acid triester, Skylin-1,2-naphthoquinone diazide
5-sulfonic acid hexaester, pyromycin-1,2-naphthoquinonediazide-5-sulfonic acid triester, and these 1,2-quinonediazide sulfonic acid esters may be used alone or in combination of two or more in the composition of the present invention. It can be used for things.

In the composition of the present invention, the alkali-soluble resin to which the 1,2-quinonediazide sulfonic acid ester is added is not particularly limited, but includes, for example, phenols such as phenol, cresol, xylenol, and phenylphenol, formaldehyde, and paraformaldehyde. , novolak resins obtained from aldehydes such as furfural, acetaldehyde, and benzaldehyde, hydroxystyrene polymers, aminostyrene polymers, monoolefin compounds, and copolymers of ethylenically unsaturated carboxylic acids.

The amount of the 1,2-quinonediazide sulfonic acid ester in the composition of the present invention 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 resolution of the resulting composition will be poor, the residual film rate after development will be insufficient, and the pattern obtained will be deformed by heat due to poor heat resistance. It becomes easier. On the other hand, if this amount exceeds 100 parts by weight, a composition with high sensitivity cannot be obtained.

The composition of the present invention preferably contains a 1,2-quinonediazide compound other than the 1,2-quinonediazide sulfonic acid ester, for example, at most 100 parts by weight, preferably at most 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. can be blended in a proportion of 20 parts by weight or less. These 1,2-quinonediazide compounds include, for example, the following general formula () ■■■ Turtle shell [0028] ■■■ (where n is an integer of 1 to 3, R ₅ is an alkyl group,
1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, or 1,2-naphthoquinonediazide-5-sulfonyl chloride, Examples include compounds obtained by condensation reaction of -benzoquinone diazide-4-sulfonyl chloride and the like. Specific examples of the compound represented by the general formula () include 2,3,4-trihydroxyphenylmethylketone, 2,3,4-trihydroxyphenylethylketone, and 2,3,4-trihydroxyphenylmethylketone. enylbutylketone, 2,3,4-trihydroxyphenyl-n-hexylketone, 3,4,5-trihydroxyphenylmethylketone, 3,4,5-
trihydroxyphenylethyl ketone, 3,4,
5-trihydroxyphenylbutyl ketone, 3,
4,5-trihydroxyphenyl-n-hexyl ketone, 2,4,6-trihydroxyphenylmethyl ketone, 2,4,6-trihydroxyphenylethyl ketone, 2,4,6-trihydroxyphenyl Butyl ketone, 2,4,6-trihydroxyphenyl-n-hexyl ketone, 2,3,4-
Trihydroxyphenyldecyl ketone, 2,3,
4-trihydroxyphenyl dodecyl ketone,
2,3,4-trihydroxybenzophenone,
2,4,6-trihydroxybenzophenone,
Examples include 2,3,4-trihydroxyphenylbenzyl ketone, 3,4,5-trihydroxybenzyl ketone, 2,4,6-trihydroxyphenylbenzyl ketone (US Pat. No. 3046118 and Japanese Patent Publication No. 37 −18015 specification).

Also, for example, 2,4,2',4'-tetrahydroxy-6,6'-dimethyl-diphenylmethane, 2,
6,2′,6′-tetrahydroxy-3,5,3′,
5'-tetrachloro-diphenylmethane, 2,2'-
Dihydroxy-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,
4'-dimethoxy-triphenylmethane, 2,2'-
Dihydroxy-dinaphthylmethane, 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',4'-tetrahydroxy-6,
6′-dicarbomethoxy-diphenylmethane, 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',4'-tetrahydroxy-diphenylcyclohexane-(1,1), 2,2'-dihydroxy-4,
4'-dimethoxy-diphenylmethane, 2,4,
2',4'-tetrahydroxy-diphenylpentane-(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-4-sulfonyl chloride or 1,2-benzo 1,2 obtained by condensation reaction with quinonediazide-4-sulfonyl chloride etc.
- Quinonediazide sulfonic acid ester
-1953) can also be blended.

Furthermore, Special Publication No. 37-3627, No. 37-13109
Publication No. 40-26126, Publication No. 40-3801,
Publication No. 45-5604, Publication No. 45-27345, Publication No. 51-
Publication No. 13013, Japanese Unexamined Patent Publication No. 48-96575, Publication No. 48-
Publication No. 63802, Publication No. 48-63803, Publication No. 58-75149
1,2-quinonediazide compounds described in Japanese Patent Publication No. 1, etc. can also be used.

Furthermore, the following general formula (), ■■■ Tortoise shell [0029] ■■■ The following general formula (), ■■■ Tortoise shell [0030] ■■■ (In the general formulas () and (), a and b are the same or different , an integer of 3 or 4, l
and m are the same or different, 0 or an integer of 1 to 3, c is an integer of 1 to 4, n is 0 or an integer of 1 to 3, and (a-l), (b-m) and ( c-n) are all integers of 1 or more; R ₁ , R ₅ and R ₇ are the same or different; 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group or 1 ,2
-benzoquinonediazide-4-sulfonyl group,
R ₂ , R ₆ , R ₈ and R ₁₁ are the same or different, and are hydrogen atoms, halogen atoms, alkyl groups, aryl groups,
Aralkyl group, alkoxy group, cyano group or nitro group, R ₃ , R ₄ , R ₉ and R ₁₀ are the same or different and mean a hydrogen atom, alkyl group, aryl group or aralkyl group, R ₃ and R ₄ and R ₉ and R ₁₀ can form a ring with a carbon-carbon bond or an ether bond) The following general formula (), ■■■ Turtle shell [0031] ■■■ (In the general formula (), n is 2 to 4 integer,
l is 0 or an integer of 1 to 3, m is an integer of 1 to 4,
k is an integer from 1 to 4, and k+l+m=5,
R ₁ is 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-
Sulfonyl group or 1,2-benzoquinonediazide-4-sulfonyl group, _R2 is a hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, cyano group or nitro group, Z
means a residue of methane or an aromatic compound), the following general formula (), ■■■ Turtle Shell [0032] ■■■ or the following general formula (), ■■■ Turtle Shell [0033] ■■■ (General formula In () and (), a, b
and c is an integer of 1 to 4, a and b are the same or different, l, m and n are 0 or integers of 1 to 3, l and m are the same or different, (a-
l), (b-m) and (c-n) are integers of 1 or more, R ₁ , R ₂ and R ₅ are 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5- a sulfonyl group or a 1,2-benzoquinonediazide-4-sulfonyl group;
R ₁ and R ₂ are the same or different, R ₃ , R ₄ and R ₅ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a cyano group or a nitro group, and R ₃ and R ₄ are the same or different,
_R7 means an alkyl group, an aryl group or an aralkyl group, Z means an alkylene group or an oxaalkylene group with or without a substituent)
A 1,2-quinonediazide compound represented by can also be used.

The 1,2-quinonediazide compound represented by the above general formula () is, for example, di(2,3,4-trihydroxyphenyl)methane, 1,1-di(2,
3,4-trihydroxyphenyl)propane,
2,2-di(2,3,4-trihydroxyphenyl)propane, 1,1-di(2,3,4-trihydroxyphenyl)butane, 1,1-di(2,
3,4-trihydroxycyclohexane, 1,1
-di(2,3,4-trihydroxy)-4-oxacyclohexane, di(2,4,6-trihydroxyphenyl)methane, 1,1-di(2,4,6
-trihydroxyphenyl)propane, 2,2-
Di(2,4,6-trihydroxyphenyl)propane, 1,1-di(2,4,6-trihydroxyphenyl)butane, 1,1-di(2,4,6-trihydroxyphenyl) ) Cyclohexane, 1,1
-di(2,4,6-trihydroxyphenyl)-
4-oxacyclohexane, di(2,3,4-trihydroxy-5-bromophenyl)methane,
2,2-di(2,4,6-trihydroxy-3-
chlorophenyl)propane, di(2,3,4-trihydroxy-5-methylphenyl)methane,
2,2-(2,4,6-trihydroxy-3-methyl)propane, di(2,3,4-trihydroxy-5-cyanophenyl)methane, 2,2-di(2,4,6-trihydroxy-3-methyl)propane, hydroxy-3-nitrophenyl)propane, di(1,2,3,4-tetrahydroxyphenyl)methane, 2,2-di(1,
Polyhydroxy compounds such as 2,3,5-tetrahydroxyphenyl)propane and 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2
It can be obtained by condensation with -naphthoquinonediazide-4-sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.125 to 1.

The 1,2-quinonediazide compound represented by the above general formula () is, for example, 2,3,4-trihydroxydiphenylmethane, 2,4,6-trihydroxydiphenylmethane, 2,3,4-trihydroxy- 5-chlorodiphenylmethane, 2,4,
6-trihydroxy-3-bromodiphenylmethane, 2,3,4-trihydroxy-5-methyldiphenylmethane, 2,4,6-trihydroxy-
3-cyanodiphenylmethane, 2,3,4-trihydroxy-5-nitrodiphenylmethane, 2,
3,4-trihydroxy-4'-methyldiphenylmethane, 2,4,6-trihydroxy-4'-methyldiphenylmethane, 2,3,4-trihydroxy-4'-t-butyldiphenylmethane ,2,3,
4,5-tetrahydroxydiphenylmethane,
2,3,4,6-tetrahydroxydiphenylmethane, 2,5-dihydroxydiphenylmethane,
2,4-dihydroxydiphenylmethane, 2,4
-dihydroxy-4′-methyldiphenylmethane,
2,5-dihydroxy-4'-t-butyldiphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-phenylpropane, 2-(2,4,
6-trihydroxyphenyl)-2-phenylpropane, 2-(2,3,4-trihydroxy-5
-chlorophenyl)-2-phenylpropane, 2
-(2,3,4-trihydroxy-5-methylphenyl)-2-phenylpropane, 2-(2,4,
6-trihydroxy-3-cyanophenyl)-2
-Phenylpropane, 2-(2,3,4-trihydroxy-5-nitrophenyl)-2-phenylpropane, 2-(2,3,4-trihydroxyphenyl)-2-(p-tolyl) Propane, 2-(2,
4,6-trihydroxyphenyl)-2-(4-t
-butylphenyl)propane, 2-(2,3,4,
5-tetrahydroxyphenyl)-2-phenylpropane, 2-(2,3,4,6-tetrahydroxy)-2-phenylpropane, 2-(2,5-dihydroxyphenyl)-2-phenylpropane enylpropane,
Polyhydroxy compounds such as 2-(2,4-dihydroxyphenyl)-2-phenylpropane and 2-(2,4-dihydroxyphenyl)-2-(p-tolyl)propane and 1,2-naphthoquinonediazide −
5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2
-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.25 to 1.

For details regarding the 1,2-quinonediazide compound represented by the above general formula () or (),
It is described in the applicant's application dated December 6, 1988.

The 1,2-quinonediazide compound represented by the above general formula () is, for example, p-bis(4-hydroxybenzoyl)benzene, p-bis(2,5
-dihydroxybenzoyl)benzene, p-bis(2,3,4-trihydroxybenzoyl)benzene, m-bis(2,4,6-trihydroxybenzoyl)benzene, p-bis(4-hydroxy-3-chlorobenzoyl) ) benzene, p-bis(2,3,4-trihydroxy-5-methylbenzoyl)benzene, p-bis(2,4,6-trihydroxy-3-nitrobenzoyl)benzene,
p-bis(2,3,4-trihydroxy-5-cyanobenzoyl)benzene, 1,3,5-tris(2,5-dihydroxybenzoyl)benzene,
1,2,3-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4-tris(2,4,6-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,
Polyhydroxy compounds such as 3,4-trihydroxybenzoyl)mesitylene, 1,2-bis(2,3,4-trihydroxybenzoyl)naphthalene, and 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphtho Quinonediazide
It can be obtained by condensing 4-sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.083 to 1.
(filed on December 23, 1958).

The 1,2-quinonediazide compound represented by the above general formula () is, for example, ethylene glycol di(2-hydroxybenzoate), diethylene glycol di(2,3-dihydroxybenzoate), triethylene glycol di(2,6
-dihydroxybenzoate), ethylene glycol-di(3,4,5-trihydroxybenzoate), diethylene glycol-di(2,4,6-trihydroxybenzoate),
-trihydroxybenzoate), triethylene glycol di(2-hydroxy-3-methylbenzoate), ethylene glycol di(4-chloro-2-hydroxybenzoate), polyethylene glycol di(5-bromo-2-hydroxybenzoate) ), propylene glycol di(3-chloro-4-hydroxybenzoate), styrene glycol di(2-hydroxy-3-methoxybenzoate), polypropylene glycol di(2-hydroxy-5-methoxybenzoate), poly-3 , 3-bischloromethyloxetaneglycol-di(3-hydroxy-4-methoxybenzoate), 1,3-propanediol-di(3,4,5-trihydroxybenzoate), 1,4-butanediol-di( Polyhydroxy compounds such as 3-hydroxybenzoate), polytetrahydrofuran glycol di(3,4,5-trihydroxybenzoate) and 1,2-
naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, or 1,2-benzoquinonediazide-4-sulfonyl chloride in an equivalent ratio of 0.17 to 1.
It can be obtained by condensation with

The 1,2-quinonediazide compound represented by the above general formula () is, for example, ethylene glycol-monomethyl-mono(3,4,5-trihydroxybenzoate), ethylene glycol-monoethyl-mono(2,4,6-trihydroxybenzoate), hydroxybenzoate), diethylene glycol monoethyl
Mono(2,3-dihydroxybenzoate), triethylene glycol-monoethyl-mono(3,
5-dihydroxybenzoate), ethylene glycol monophenyl mono(3,4,5-trihydroxybenzoate), 1,2-benzenedimethanol monoethyl mono(3,4,5-trihydroxybenzoate), etc. Obtained by condensing a compound with 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, or 1,2-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.3 to 1. be able to.

For details regarding the 1,2-quinonediazide compound represented by the above general formula () or (),
It is described in the applicant's application dated January 10, 1982.

Furthermore, the composition of the present invention may be used, if necessary, in order to improve developability, storage stability of the composition, etc.
For example, natural resins such as rosin and silk, copolymers of styrene and maleic anhydride, copolymers of styrene and acrylic acid, methacrylic acid or their alkyl esters, acrylic ester polymers, vinyl acetal polymers, vinyl ethers. A synthetic resin such as a vinyl acetate polymer, a vinyl alcohol polymer, or a vinyl pyrrolidone polymer is added in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of an alkali-soluble resin. It can also be mixed and contained.

The composition of the present invention can be applied onto 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 composition of the present invention can be applied to a substrate by 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, cyclohexanone, and diacetone alcohol;
-Alcohols such as butanol, ethers such as dioxane, ethylene glycol dimethyl ether, ethyl glycol diethyl ether, alcohol ethers such as ethyl glycol monomethyl ether, ethylene glycol monoethyl ether, esters such as butyl acetate, cellosolve acetate, methoxyethyl acetate, etc. Class, 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, hexamethyldisilazane, chloromethylsilane, etc. may be applied to the substrate as an adhesion aid.

The developer used in the composition of the present invention includes:
For example, aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, trisodium phosphate, sodium hydrogen phosphate, n-propylamine, di-n-propylamine, di- -n-butylamine, methyldiethylamine, pyrrole,
Aqueous solutions of amines such as 2,2-dimethylpyrrole, β-picoline, collidine, piperidine, piperazine, and triethylenediamine, aqueous solutions of alcohol amines such as dimethylethanolamine, triethanolamine, and diethylhydroxylamine, and tetramethylammonium hydroxide. , aqueous solutions of quaternary ammonium salts such as tetraethylammonium hydroxide, aqueous ammonia, and the like.

Further, an appropriate amount of alcohols such as methanol and ethanol, sulfite stabilizers, or surfactants may be added to the developer.

The composition of the present invention does not precipitate crystals of 1,2-quinonediazide compound, has high sensitivity, high resolution, high residual film rate, and has excellent developability, and is suitable for producing integrated circuits. It is particularly useful as a positive photoresist having a heat resistance of 100%, 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 A 500 ml three-neck separable flask was charged with 75 g of m-cresol and 25 g of p-cresol, and then 66 ml of a 37% by weight formalin aqueous 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, and the reaction was allowed to proceed for 10 hours. After the reaction was completed, water was distilled off by reducing the pressure to 30 mmHg, and the internal temperature was further raised to 130°C to remove unreacted substances. The reaction product, molten alkali-soluble novolac resin, was then returned to room temperature and recovered.

(2) Synthesis of photosensitizer In a three-necked separable flask under light shielding,
15.11 g of morin, 67.17 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 800 ml of dioxane were charged and dissolved. While stirring this solution, 30.36 g of triethylamine was gradually added, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, 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 morine-1,2-naphthoquinonediazide-5-sulfonic acid pentaester. (hereinafter abbreviated 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 mixed under light shielding.
Dissolved in 75g dimethylformamide, pore size
A solution of the photosensitive resin composition was prepared by filtration with a 0.2 μm membrane filter.

The obtained solution was applied onto a silicon oxide film wafer using a spinner, and then heated in an oven at 90°C.
This was prebaked 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 11.6 mJ/cm ² of ultraviolet light (measured with a model 205 UV power meter manufactured by Optical Associates, Inc.) to remove tetramethylammonium hydroxide.
When developed with a 2.0% aqueous solution at 20°C for 60 seconds,
We were able to resolve patterns with a line width of 1.0 μm.
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. Further, the developed pattern was post-baked in an oven at 160°C for 30 minutes, but no pattern collapse was observed, and it had high heat resistance.

Examples 2 to 8 (1) Synthesis of photosensitizer A photosensitizer was synthesized by condensing the natural dyes shown in Table 1 and 1,2-quinonediazide sulfonyl chloride in the same manner as in Example 1(2). did.

■■■ Turtle shell [0007] ■■■ (2) Preparation and evaluation of photosensitive resin composition 20 g of the alkali-soluble novolak resin obtained in Example 1 (1), 5 g of the photosensitizer shown in Table 2, and 75 g of dimethyl sulfoxide were added. A solution of the photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 (3). Table 2 shows the results. It can be seen from Table 2 that the photosensitive resin composition of the present invention is excellent in sensitivity, resolution, and film retention rate. Also, all of the photosensitive resin compositions had excellent developability and heat resistance, similar to those of Example 1.

■■■ Turtle shell [0008] ■■■

Claims (1)

[Claims] 1 In a positive photosensitive resin composition consisting of an alkali-soluble resin and a 1,2-quinonediazide compound, the 1,2-quinonediazide compound is an α-pyrone natural dye having a hydroxyl group, a γ-pyrone type natural dye having a hydroxyl group Containing at least one 1,2-quinonediazide sulfonic acid ester of a compound selected from the group consisting of natural pigments, diazine natural pigments having a hydroxyl group, and quinone natural pigments having a hydroxyl group, the 1,
A positive photosensitive resin composition, characterized in that 5 to 100 parts by weight of 2-quinonediazide sulfonic acid ester is blended with respect to 100 parts by weight of the alkali-soluble resin.