JPH10268522A - Pattern forming method and positive photoresist composition used for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a forming method for a pattern, in particular a pattern in which a fine pattern with 10 μm line/10 μm space such as a liquid crystal panel is required, to obtain excellent reproducibility while preventing discontinuity in lines and a short circuit, and to provide a positive photoresist compsn. for electroless plating having excellent adhesion property with a substrate and good plating resistance to be used for the pattern forming method above described. SOLUTION: A positive photoresist compsn. containing one or more kinds of specified sulfur-contg. org. compds. (such as thiourea, thiophene, thiazole, thionalide and diphenylcarbazide) is applied on a substrate 1, dried, selectively exposed through a mask pattern 3, and developed to remove the exposed part to form a photoresist pattern 4. Then the pattern is subjected to electroless plating to form a conductive pattern 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a pattern using a positive photoresist composition which is sensitive to actinic rays such as far ultraviolet rays including ultraviolet rays and excimer lasers, and a positive photoresist composition used for the same. More specifically, when forming a fine wiring pattern (conductive pattern) by an electroless plating method such as a TFT type liquid crystal panel, a photoresist pattern having excellent adhesion to a substrate, good plating resistance, and a good pattern shape is used. The present invention relates to a method for forming a pattern using a photoresist composition that can be formed, and a positive photoresist composition used for the method.

[0002]

2. Description of the Related Art In the manufacture of printed wiring boards and liquid crystal panels, a photoresist composition is applied onto a substrate provided with a copper wiring pattern or a transparent conductive pattern such as ITO, and dried to form a photoresist layer. The layer is selectively irradiated with actinic light through a positive mask and exposed,
The exposed portion of the photoresist layer is selectively removed with an aqueous alkali solution, and a part or all of the exposed substrate is subjected to electroless plating to form a conductor wiring (conductive pattern), and an alignment film is formed thereon. A way to do that has been proposed.
In particular, in forming conductor wiring on an ITO pattern such as a TFT liquid crystal panel, a positive photoresist composition is preferably used because of high resolution.

However, when a conventional photoresist composition is used, there has been a problem that the adhesion between the substrate and the photoresist pattern is generally insufficient, and a short circuit of the conductor wiring occurs. In addition, since the conductor layer is formed on the photoresist pattern during the electroless plating process, it is necessary to peel off the conductor layer portion formed on the photoresist pattern together with the photoresist pattern in forming the conductive pattern. There is a problem in that the conductor wiring is easily broken, and the conductor wiring is disconnected or short-circuited. In addition, in the case of a photoresist pattern using a positive photoresist composition, during development, the upper layer portion of the unirradiated portion of the actinic ray is thinly peeled off in a plate shape, floats in the developing solution, and re-adheres to the exposed substrate. There is a problem that it may cause a short circuit or the like of the conductor wiring. Regarding this, JP-A-4-31860, JP-A-6-43637, and JP-A-6-348
Although the technology described in Japanese Patent Application Publication No. 017 is proposed, there is a problem that a development residue is generated. In particular, in the case of pattern formation by an electroless plating method requiring a fine pattern of about 10 μm line / 10 μm space, such as a TFT type liquid crystal panel, a photoresist composition which can sufficiently satisfy these requirements has not been developed yet. Had not been found.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to solve the drawbacks of the conventional electroless plating method using a photoresist composition. In forming a pattern requiring a fine pattern of about 10 μm line / 10 μm space of a liquid crystal panel or the like, a method of forming a photoresist pattern having a good pattern shape, a method of forming a conductive pattern free from disconnection, short circuit, etc., and these patterns An object of the present invention is to provide a positive photoresist composition for electroless plating, which is applied to the formation and has excellent adhesion to a substrate and good plating resistance.

[0005]

That is, the present invention relates to thiourea, thiophene, thiazole, thionalide, diphenylcarbazide, thiazoline, tetramethylthiourea, mercaptobenzothiazole, mercaptobenzotriazole, dibenzothiazyldisulfide, N-tert-
A positive photoresist composition containing one or more sulfur-containing organic compounds selected from butyl-2-benzothiazolylsulfenamide and tetramethylthiuram disulfide is coated on a substrate and dried. The present invention relates to a method for forming a photoresist pattern, wherein a photoresist pattern is formed by selectively exposing through a mask pattern, and then developing and removing the exposed portion.

[0006] The present invention also relates to a method of forming a conductive pattern, wherein an electroless plating process is performed on a substrate on which a photoresist pattern has been formed by the above method, thereby forming a conductive pattern on an exposed substrate.

The present invention further provides a positive photoresist composition used in the above-mentioned method for forming a photoresist pattern and a method for forming a conductive pattern, wherein (a) an alkali-soluble resin, (b) a quinonediazide group-containing compound, and (c)
Thiourea, thiophene, thiazole, thionalide, diphenylcarbazide, thiazoline, tetramethylthiourea, mercaptobenzothiazole, mercaptobenzotriazole, dibenzothiazyl disulfide, N-te
The present invention relates to a positive photoresist composition comprising rt-butyl-2-benzothiazolylsulfenamide and one or more sulfur-containing organic compounds selected from tetramethylthiuram disulfide.

In the above, it is most preferred that the sulfur-containing organic compound is mercaptobenzothiazole.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The positive photoresist composition used in the pattern forming method of the present invention includes thiourea, thiophene, thiazole, thionalide, diphenylcarbazide, thiazoline, tetramethylthiourea, mercaptobenzothiazole, mercaptobenzotriazole, dibenzothiazyldisulfide. , N-tert-butyl-2-benzothiazolylsulfenamide, and one or more sulfur-containing organic compounds selected from tetramethylthiuram disulfide (referred to as component (c)).

When each of the above sulfur-containing organic compounds has isomers, these isomers are also included in the scope of the present invention.

In the present invention, in particular, in addition to the component (c),
Further, a composition containing the following components (a) and (b) (a) an alkali-soluble resin and (b) a compound containing a quinonediazide group,
A positive photoresist composition containing the component (c) is most preferably used.

Here, examples of the alkali-soluble resin as the component (a) include a novolak resin, an acetone-pyrogallol resin, a polyhydroxystyrene resin, and an acrylic resin.

Novolak resins include, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol,
3,4-xylenol, 3,5-xylenol, 3,6
-Xylenol, 2,3,4-trimethylphenol,
3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol,
-Tert-butylphenol, resorcinol, 2-
Methyl resorcinol, catechol, 4-methyl catechol, 3-methoxy phenol, methyl gallate, ethyl gallate, 4-ethyl phenol, 4-propyl phenol, 4-isopropyl phenol, o-methyl phenol, m-methyl phenol, p- It can be obtained by addition polymerization of phenols such as methylphenol with formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde and the like. Above all, a novolak resin containing m-cresol and p-cresol can be preferably used because it has excellent performance in terms of sensitivity, developability, and storage stability.

As the acetone-pyrogallol resin, a mixture of an acetone-pyrogallol resin having a molecular weight of about 2,000 and an acetone-pyrogallol resin having a molecular weight of about 3,000 is preferably used.

Examples of the polyhydroxystyrene resin include polyhydroxystyrene and polyhydroxymethylstyrene.

Examples of the acrylic resin include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, 2-ethylacrylic acid, and 3-ethylacrylic acid.
Propylacrylic acid, 3-isopropylacrylic acid, monohydroxyethyl succinate acrylate, monohydroxyethyl acrylate phthalate, monohydroxyethyl acrylate dihydrophthalate, monohydroxyethyl acrylate tetrahydrophthalate, monohydroxyethyl acrylate hexahydrophthalate, acrylic Acid dimer, monomer having a carboxyl group such as acrylic acid trimer, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
n-butyl acrylate, n-butyl methacrylate,
Isobutyl acrylate, isobutyl methacrylate,
2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, ethylene glycol monomethyl ether monoacrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol (mono) acrylate, glycerol (Mono) methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, etc. Polymerized ones That. When using acrylic resin,
The acid value is preferably about 20 to 250 mgKOH / g, and more preferably about 50 to 150 mgKOH / g.
If the acid value is too low, development with an aqueous alkali solution becomes difficult, while if the acid value is too high, coating properties and dispersibility deteriorate.

The alkali-soluble resin preferably has a weight average molecular weight of about 2,000 to 200,000.
More preferably, it is about 5,000 to 150,000. If the weight-average molecular weight is too low, the film-forming ability is poor and the film is greatly reduced during development, which is not preferable. On the other hand, if the weight-average molecular weight is too high, the development time becomes longer or the development becomes impossible, which is not preferable.

The alkali-soluble resin is preferably blended in the range of 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, per 100 parts by weight of the total of components (a) to (c). If the amount is too low, the transparency, insulating properties and coating properties deteriorate, while if the amount is too high, the sensitivity decreases and curing failure occurs, which is not preferable.

The quinonediazide group-containing compound as the component (b) is not particularly limited as long as it can be used as a photosensitive component. Examples thereof include naphthoquinone-1,2-diazide-4-sulfonic acid, Naphthoquinone-
Naphthoquinone such as 1,2-diazide-5-sulfonic acid
An esterified product of 1,2-diazidosulfonyl halide and a hydroxy compound is preferably used. Specifically, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,3,4-trihydroxybenzophenone, naphthoquinone-1,2-diazide-5-sulfone of 2,3,4-trihydroxybenzophenone Acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,4,6-trihydroxybenzophenone, naphthoquinone-1,2-diazide-5-sulfonic acid ester of 2,4,6-trihydroxybenzophenone Trihydroxybenzophenone and naphthoquinone-
Ester compound with 1,2-diazidosulfonic acid; 2,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2 ′, 4,4′-tetrahydroxybenzophenone, naphthoquinone-1,2-diazide-5-of 2,2 ′, 4,4′-tetrahydroxybenzophenone Sulfonate, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,3,4,3'-tetrahydroxybenzophenone, naphthoquinone-1,2- of 2,3,4,3'-tetrahydroxybenzophenone Diazide
5-sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,3,4,4′-tetrahydroxybenzophenone, naphthoquinone-1,2,3,4,4′-tetrahydroxybenzophenone 2
-Diazido-5-sulfonic acid ester, 2,3,4
Naphthoquinone-1,2-diazido-4-sulfonic acid ester of 2′-tetrahydroxybenzophenone, 2,
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 3,4,2'-tetrahydroxybenzophenone, naphthoquinone-1,2-diazide of 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone Ester compounds of tetrahydroxybenzophenone and naphthoquinone-1,2-diazidosulfonic acid, such as -5-sulfonic acid ester; naphthoquinone-1,2 of 2,3,4,2 ′, 4′-pentahydroxybenzophenone -Diazido-4-sulfonic acid ester, 2,3,4,2 ',
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 4′-pentahydroxybenzophenone, 2,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 3,4,2 ', 6'-pentahydroxybenzophenone, naphthoquinone-1,2- of 2,3,4,2', 6'-pentahydroxybenzophenone Diazide-5
Ester compounds of pentahydroxybenzophenone and naphthoquinone-1,2-diazidosulfonic acid, such as sulfonic acid esters; naphthoquinone-1,2- of 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone
Diazide-4-sulfonic acid ester, 2,4,6
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 3 ′, 4 ′, 5′-hexahydroxybenzophenone, naphthoquinone-1,3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone 2-diazide-
4-sulfonic acid ester, 3,4,5,3 ', 4',
Hexahydroxybenzophenone such as naphthoquinone-1,2-diazide-5-sulfonic acid ester of 5′-hexahydroxybenzophenone;
Ester compound with 2-diazidosulfonic acid; 2,2 ′
Naphthoquinone-1, dihydroxydiphenylmethane,
2-diazide-4-sulfonic acid ester, naphthoquinone-1,2- of 2,2'-dihydroxydiphenylmethane
Diazide-5-sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,4′-dihydroxydiphenylmethane, naphthoquinone-1,2-diazide-5-sulfonic acid of 2,4′-dihydroxydiphenylmethane Ester, naphthoquinone-1,2-diazide-4 of 4,4'-dihydroxydiphenylmethane
Ester compounds of dihydroxydiphenylmethane with naphthoquinone-1,2-diazidosulfonic acid, such as -sulfonic acid ester, naphthoquinone-1,2-diazide-5-sulfonic acid ester of 4,4′-dihydroxydiphenylmethane; 1- ( 2-hydroxyphenyl) -1-
Naphthoquinone of (2′-hydroxyphenyl) ethane
1,2-diazide-4-sulfonic acid ester, 1- (2
-Hydroxyphenyl) -1- (2'-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-5
Sulfonic acid ester, 1- (2-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of -1- (4′-hydroxyphenyl) ethane;
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-(2-hydroxyphenyl) -1- (4'-hydroxyphenyl) ethane, 1- (4-hydroxyphenyl) -1- (4'-hydroxyphenyl ) Naphthoquinone-1,2-diazide-4-sulfonic acid ester of ethane, naphthoquinone-1,2-diazide-5-sulfonic acid ester of 1- (4-hydroxyphenyl) -1- (4′-hydroxyphenyl) ethane , 1-phenyl-1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2,4-dihydroxyphenyl) ethane, 1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenyl-1- (2,4-dihydroxyphenyl) ethane, naphthoquinone-1,2- of 1-phenyl-1- (2,6-dihydroxyphenyl) ethane Diazide
4-sulfonic acid ester, 1-phenyl-1- (2,6
-Dihydroxyphenyl) ethane naphthoquinone-1,
2-diazido-5-sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 1- (2-hydroxyphenyl) -2- (2′-hydroxyphenyl) ethane, 1- (2-hydroxy Phenyl)-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 2- (2'-hydroxyphenyl) ethane, 1-
Naphthoquinone-1,2-diazide of (2-hydroxyphenyl) -2- (4′-hydroxyphenyl) ethane
4-sulfonic acid ester, naphthoquinone-1,2-diazide-5-sulfonic acid ester of 1- (2-hydroxyphenyl) -2- (4′-hydroxyphenyl) ethane, 1- (4-hydroxyphenyl) -2 -Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (4'-hydroxyphenyl) ethane, naphthoquinone-1,2- of 1- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) ethane Diazide-5-sulfonic acid ester, naphthoquinone-1,2-diazide-of 1-phenyl-2- (2,4-dihydroxyphenyl) ethane
4-sulfonic acid ester, 1-phenyl-2- (2,4
-Dihydroxyphenyl) ethane naphthoquinone-1,
2-diazido-5-sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 1-phenyl-2- (2,6-dihydroxyphenyl) ethane, 1-phenyl-2- (2,6 Ester compounds of diphenylhydroxyethane and naphthoquinone-1,2-diazidesulfonic acid, such as naphthoquinone-1,2-diazido-5-sulfonic acid ester of -dihydroxyphenyl) ethane; 1- (2-hydroxyphenyl)- 1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2′-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2-hydroxyphenyl) -1- (2'-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -1- (4'-hydroxyphenyl) Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 1- (2-hydroxyphenyl) -1- (4'-
Naphthoquinone-1,2 of hydroxyphenyl) propane
-Diazido-5-sulfonic acid ester, 1- (4-hydroxyphenyl) -1- (4'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 1- (4-hydroxyphenyl) -1
-Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-(4'-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of phenyl-1- (2,4-dihydroxyphenyl) propane, naphthoquinone-1,2- of 1-phenyl-1- (2,4-dihydroxyphenyl) propane Diazide-5-sulfonic acid ester, 1-phenyl-1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2,6-dihydroxyphenyl) propane, 1
Naphthoquinone-1,2-diazido-5-sulfonic acid ester of -phenyl-1- (2,6-dihydroxyphenyl) propane, 1- (2-hydroxyphenyl) -2-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2′-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2-hydroxyphenyl) -2- (2'-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -2- (4'-hydroxyphenyl) Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 1- (2-hydroxyphenyl) -2- (4'-
Naphthoquinone-1,2 of hydroxyphenyl) propane
-Diazido-5-sulfonic acid ester, 2- (2-hydroxyphenyl) -1- (4'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 2- (2-hydroxyphenyl) -1
-Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-(4'-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 1- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) Naphthoquinone-1,2-diazide-5-sulfonic acid ester of propane, naphthoquinone-1,2-diazide-4 of 1-phenyl-2- (2,4-dihydroxyphenyl) propane
-Sulfonic acid ester, 1-phenyl-2- (2,4-
Dihydroxyphenyl) propane naphthoquinone-1,
2-diazido-5-sulfonic acid ester, naphthoquinone-1,2-diazido-4-sulfonic acid ester of 2-phenyl-1- (2,4-dihydroxyphenyl) propane, 2-phenyl-1- (2,4 -Dihydroxyphenyl) propane naphthoquinone-1,2-diazide-5
Sulfonic acid ester, naphthoquinone-1,2-phenyl-2- (2,6-dihydroxyphenyl) propane
-Diazido-4-sulfonic acid ester, 1-phenyl-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 2- (2,6-dihydroxyphenyl) propane, naphthoquinone-1,2-diazide of 2-phenyl-1- (2,6-dihydroxyphenyl) propane 4-
Sulfonic acid ester, naphthoquinone-1,2-phenyl-1- (2,6-dihydroxyphenyl) propane
-Diazido-5-sulfonic acid ester, 2- (2-hydroxyphenyl) -2- (2'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 2- (2-hydroxyphenyl) -2
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-(2′-hydroxyphenyl) propane, 2-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2-hydroxyphenyl) -2- (4'-hydroxyphenyl) Naphthoquinone-1,2-diazide-5-sulfonic acid ester of propane, 2- (4-hydroxyphenyl) -2- (4'-
Naphthoquinone-1,2 of hydroxyphenyl) propane
-Diazido-4-sulfonic acid ester, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of propane, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2-phenyl-2- (2,4-dihydroxyphenyl) propane, 2-phenyl- 2-
Naphthoquinone-1,2-diazido-5-sulfonic acid ester of (2,4-dihydroxyphenyl) propane, 2
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of phenyl-2- (2,6-dihydroxyphenyl) propane, naphthoquinone-1,2 of 2-phenyl-2- (2,6-dihydroxyphenyl) propane -Diazido-5-sulfonic acid ester, naphthoquinone-1,2-diazido-4-sulfonic acid ester of 1- (2-hydroxyphenyl) -3- (2'-hydroxyphenyl) propane, 1- (2-hydroxyphenyl ) -3-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2′-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2-hydroxyphenyl) -3- (4′-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -3- (4′-hydroxyphenyl) Naphthoquinone-1,2-diazide-5-sulfonic acid ester of propane, 1- (4-hydroxyphenyl) -3- (4'-
Naphthoquinone-1,2 of hydroxyphenyl) propane
-Diazido-4-sulfonic acid ester, 1- (4-hydroxyphenyl) -3- (4'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of propane, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 1-phenyl-3- (2,4-dihydroxyphenyl) propane, 1-phenyl- 3-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2,4-dihydroxyphenyl) propane, 1
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of -phenyl-3- (2,6-dihydroxyphenyl) propane, naphthoquinone-1,2 of 1-phenyl-3- (2,6-dihydroxyphenyl) propane Ester compounds of dihydroxyphenylpropane and naphthoquinone-1,2-diazidosulfonic acid, such as diazide-5-sulfonic acid ester; naphthoquinone-1,2 of 2,2 ′, 2 ″ -trihydroxytriphenylmethane -Diazido-4-sulfonic acid ester, 2,2 ', 2''-
Naphthoquinone of trihydroxytriphenylmethane
1,2-diazide-5-sulfonic acid ester, 2,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2 ′, 4 ″ -trihydroxytriphenylmethane, naphthoquinone-1,2-diazide of 2,2 ′, 4 ″ -trihydroxytriphenylmethane 5-sulfonic acid ester, naphthoquinone-1,2-diazide-4- of 2,4 ′, 4 ″ -trihydroxytriphenylmethane
Sulfonic acid ester, naphthoquinone-1,4-diazide-5-sulfonic acid ester of 2,4 ′, 4 ″ -trihydroxytriphenylmethane, naphthoquinone of 4,4 ′, 4 ″ -trihydroxytriphenylmethane 1,2
-Diazido-4-sulfonic acid ester, 4,4 ',
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 4 ''-trihydroxytriphenylmethane,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,2 ′, 2 ″ -trihydroxytriphenylethane, naphthoquinone-1,2- of 2,2 ′, 2 ″ -trihydroxytriphenylethane Diazido-5-sulfonic acid ester, naphthoquinone-1,2-diazide of 2,2 ′, 4 ″ -trihydroxytriphenylethane
4-sulfonic acid ester, naphthoquinone-1,2-diazide-5-sulfonic acid ester of 2,2 ′, 4 ″ -trihydroxytriphenylethane, 2,4 ′, 4 ″-
Naphthoquinone of trihydroxytriphenylethane
1,2-diazide-4-sulfonic acid ester, 2,
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 4 ′, 4 ″ -trihydroxytriphenylethane, naphthoquinone-1,2-diazide of 4,4 ′, 4 ″ -trihydroxytriphenylethane 4-sulfonic acid ester, naphthoquinone-1,2-diazide-5 of 4,4 ′, 4 ″ -trihydroxytriphenylethane
Sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,2 ′, 2 ″ -trihydroxytriphenylpropane, naphthoquinone of 2,2 ′, 2 ″ -trihydroxytriphenylpropane-
1,2-diazide-5-sulfonic acid ester, 2,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2 ′, 4 ″ -trihydroxytriphenylpropane, naphthoquinone-1,2-diazide of 2,2 ′, 4 ″ -trihydroxytriphenylpropane 5-sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,4 ′, 4 ″ -trihydroxytriphenylpropane, 2,4 ′, 4 ″ -trihydroxytriphenylpropane Naphthoquinone-1,2
-Diazido-5-sulfonic acid ester, 4,4 ',
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 4 ″ -trihydroxytriphenylpropane,
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 4,4 ′, 4 ″ -trihydroxytriphenylpropane, 4- [1,1-dimethyl-1- (o-hydroxymethyl) phenyl] -bis Naphthoquinone-1,2-diazido-4-sulfonic acid ester of (o-hydroxyphenyl) methane, 4- [1,1-dimethyl-1- (o
-Hydroxymethyl) phenyl] -bis (o-hydroxyphenyl) methane naphthoquinone-1,2-diazido-5-sulfonic acid ester, 4- [1,1-dimethyl-
1- (o-hydroxymethyl) phenyl] -bis (p-
Naphthoquinone-1,2- of hydroxyphenyl) methane
Diazido-4-sulfonic acid ester, naphthoquinone of 4- [1,1-dimethyl-1- (o-hydroxymethyl) phenyl] -bis (p-hydroxyphenyl) methane
1,2-diazide-5-sulfonic acid ester, 4-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of [1,1-dimethyl-1- (p-hydroxymethyl) phenyl] -bis (o-hydroxyphenyl) methane, 4- [1,1-dimethyl- Naphthoquinone-1,2-diazido-5-sulfonic acid ester of 1- (p-hydroxymethyl) phenyl] -bis (o-hydroxyphenyl) methane, 4- [1,1-dimethyl-1- (p-hydroxymethyl) ) Phenyl] -bis (p-hydroxyphenyl) methane naphthoquinone-1,2-diazide-4-
Sulfonate, 4- [1,1-dimethyl-1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (p-hydroxymethyl) phenyl] -bis (p-hydroxyphenyl) methane, [4- (o-hydroxyphenylmethyl) phenyl] -bis (o-hydroxy Naphthoquinone-1,2-diazide of phenyl) methane
4-sulfonic acid ester, naphthoquinone-1,2-diazide-5-sulfonic acid ester of [4- (o-hydroxyphenylmethyl) phenyl] -bis (o-hydroxyphenyl) methane, [4- (o-hydroxyphenyl) Methyl) phenyl] -bis (p-hydroxyphenyl) methane naphthoquinone-1,2-diazide-4-sulfonic acid ester, [4- (o-hydroxyphenylmethyl)
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenyl] -bis (p-hydroxyphenyl) methane, naphthoquinone of [4- (p-hydroxyphenylmethyl) phenyl] -bis (o-hydroxyphenyl) methane 1,2-diazide-4-sulfonic acid ester,
[4- (p-hydroxyphenylmethyl) phenyl]-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of bis (o-hydroxyphenyl) methane, [4-
(P-hydroxyphenylmethyl) phenyl] -naphthoquinone of bis (p-hydroxyphenyl) methane
1,2-diazide-4-sulfonic acid ester, [4-
(P-hydroxyphenylmethyl) phenyl] -naphthoquinone of bis (p-hydroxyphenyl) methane
1,2-diazide-5-sulfonic acid ester, 1- {4
-Naphthoquinone-1,2-diazido-4-sulfonic acid ester of-[1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane, 1- {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-5-sulfonic acid ester, 1- {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane naphthoquinone-
1,2-diazide-4-sulfonic acid ester, 1- {4
Diazide-5-sulfonic acid ester of-[1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane-1,2-naphthoquinone, 1- {Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane; 1- {4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane naphthoquinone-
1,2-diazide-5-sulfonic acid ester, 1- {4
-Naphthoquinone-1,2-diazide-4-sulfonic acid ester of-[1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane, 1- {Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane; 1- [4- (o-hydroxyphenylmethyl)
Phenyl] -1,1-bis (o-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of ethane, naphthoquinone-1,2- of 1- [4- (o-hydroxyphenylmethyl) phenyl] -1,1-bis (o-hydroxyphenyl) ethane Diazide-5
Sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 1- [4- (o-hydroxyphenylmethyl) phenyl] -1,1-bis (p-hydroxyphenyl) ethane, 1- [4 -(O-Hydroxyphenylmethyl) phenyl] -1,1-bis (p-hydroxyphenyl) ethane naphthoquinone-1,2-diazido-5-sulfonic acid ester, 1- [4- (p-hydroxyphenylmethyl) Phenyl] -1,1-bis (o-hydroxyphenyl) ethane naphthoquinone-
1,2-diazide-4-sulfonic acid ester, 1- [4
-(P-hydroxyphenylmethyl) phenyl] -1,
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 1-bis (o-hydroxyphenyl) ethane, 1
-[4- (p-hydroxyphenylmethyl) phenyl]
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of -1,1-bis (p-hydroxyphenyl) ethane, 1- [4- (p-hydroxyphenylmethyl) phenyl] -1,1-bis (p -Hydroxyphenyl) ethane naphthoquinone-1,2-diazido-5-sulfonic acid ester, 1- {4- [1,1-dimethyl-1- (o-
(Hydroxyphenyl) methyl] phenyl} -2,2-bis (o-hydroxyphenyl) ethane naphthoquinone-
1,2-diazide-4-sulfonic acid ester, 1- {4
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-[1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -2,2-bis (o-hydroxyphenyl) ethane, 1- {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -2,2-bis (p-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-4-sulfonic acid ester, 1- {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -2,2-bis (p-hydroxyphenyl) ethane naphthoquinone-
1,2-diazide-5-sulfonic acid ester, 1- {4
-Naphthoquinone-1,2-diazide-4-sulfonic acid ester of-[1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -2,2-bis (o-hydroxyphenyl) ethane, 1- {4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -2,2-bis (o-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-5-sulfonic acid ester, 1- {4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -2,2-bis (p-hydroxyphenyl) ethane naphthoquinone-
1,2-diazide-4-sulfonic acid ester, 1- {4
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-[1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -2,2-bis (p-hydroxyphenyl) ethane, 1- Naphthoquinone-1,2-diazido-4-sulfonic acid ester of [4- (o-hydroxyphenylmethyl) phenyl] -2,2-bis (o-hydroxyphenyl) ethane, 1- [4- (o-hydroxyphenyl) Methyl) phenyl] -2,2-bis (o-hydroxyphenyl) ethane naphthoquinone-
1,2-diazide-5-sulfonic acid ester, 1- [4
-(O-hydroxyphenylmethyl) phenyl] -2,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2-bis (p-hydroxyphenyl) ethane;
-[4- (o-hydroxyphenylmethyl) phenyl]
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of -2,2-bis (p-hydroxyphenyl) ethane, 1- [4- (p-hydroxyphenylmethyl) phenyl] -2,2-bis (o Naphthoquinone-1,2-diazide-4-sulfonic acid ester of -hydroxyphenyl) ethane, naphthoquinone of 1- [4- (p-hydroxyphenylmethyl) phenyl] -2,2-bis (o-hydroxyphenyl) ethane- 1,2-diazido-5-sulfonic acid ester, naphthoquinone-1,2-diazide of 1- [4- (p-hydroxyphenylmethyl) phenyl] -2,2-bis (p-hydroxyphenyl) ethane
4-sulfonic acid ester, naphthoquinone-1,2-diazide-5-sulfonic acid ester of 1- [4- (p-hydroxyphenylmethyl) phenyl] -2,2-bis (p-hydroxyphenyl) ethane and the like. Can be

These may be used alone or in combination of two or more. In the naphthoquinonediazidosulfonic acid ester of a hydroxy compound used in the present invention, the esterification rate is preferably about 30 to 100% by weight. The esterification rate is [(naphthoquinonediazidosulfonic acid ester mole number) /
(Molar number of hydroxy group before esterification of hydroxy compound)] × 100.

In the present invention, at the time of forming a positive image, the quinonediazide group-containing compound is irradiated with actinic light to
The molecular structure changes and becomes soluble in the developer. The quinonediazide group-containing compound is preferably blended in a range of 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin. If the compounding amount is too small, the sensitivity is lowered and poor development may be caused. On the other hand, if the compounding amount is too large, the transparency, insulation and coating properties deteriorate, which is not preferable.

As described above, the sulfur-containing organic compound (c) is thiourea, thiophene, thiazole, thionalide, diphenylcarbazide, thiazoline, tetramethylthiourea, mercaptobenzothiazole, mercaptobenzotriazole, dibenzothiazyl. One or more selected from disulfide, N-tert-butyl-2-benzothiazolylsulfenamide, and tetramethylthiuram disulfide are used. Of these, mercaptobenzothiazole is most preferred.

The positive photoresist composition of the present invention containing the above-mentioned sulfur-containing compound as the component (c) can improve the adhesion to the substrate, and can prevent the chipping or peeling of the pattern due to the penetration of the plating solution. Since this is prevented beforehand and acts as a catalyst poison, a conductive film does not adhere to the photoresist pattern during electroless plating. Further, at the time of exposure, irregular reflection of actinic rays can be suppressed, which has an effect as an antireflection agent, and at the time of peeling, peeled pieces do not adhere again to the substrate, so that in the production of multilayer wiring boards and liquid crystal panels, uniform An alignment film having a large thickness can be formed, and product quality can be improved.

The sulfur-containing compound is preferably added in an amount of 0.01 to 20 parts by weight, more preferably 0.1 to 8 parts by weight, per 100 parts by weight of the total of components (a) to (c). It is. If the amount is too small, it is difficult to sufficiently achieve the effects of the present invention. On the other hand, if the amount is too large, the sensitivity may decrease, which is not preferable.

As the solvent for dissolving the positive photoresist composition of the present invention, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether,
Propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, Ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate , Diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3
-Ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate,
4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-
Methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone ,
Methyl peroxybutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl , Methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-
3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-
Methyl 3-methylbutanoate, methyl acetate, ethyl acetate,
Propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl Ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol,
Examples thereof include propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin.

The solvent contains a total of 10 parts of components (a) to (c).
2000 parts by weight or less, preferably 10 parts by weight with respect to 0 parts by weight
It can be blended in a range of not more than 00 parts by weight.

The positive photoresist composition of the present invention includes:
Further, if necessary, a sensitizer, a plasticizer, a surfactant, an antifoaming agent, and other additives can be added.

As a sensitizer, specifically, eosin B
(CI No. 45400), Eosin J (CI.
No. 45380), alcohol-soluble eosin (C.
I. No. 45386), cyanosine (C.I. No.
45410), bengal rose, erythrosine (C.
I. No. 45430), 2,3,7-trihydroxy-9-phenylxanthen-6-one, and xanthene dyes such as rhodamine 6G; thionine (C.I.
52000), Azure A (CI No. 5200)
5) and thiazine dyes such as Azure C (CI No. 52002); pyronin B (CI No. 4500)
5), and pyronin GY (CI No. 4500)
5) and the like; and coumarin compounds such as 3-acetylcoumarin and 3-acetyl-7-diethylaminocoumarin.

As the plasticizer, dioctyl phthalate,
Didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like can be mentioned.

Examples of the surfactant include various activators such as anionic, cationic and nonionic surfactants.

Examples of the antifoaming agent include various silicone-based and fluorine-based antifoaming agents.

In addition to the above, a silane coupling agent may be added for improving the adhesion to the substrate.

Next, the pattern forming method of the present invention will be described with reference to FIG.

FIG. 1 shows an embodiment of the pattern forming method of the present invention.

First, a solution obtained by dissolving a positive photoresist composition in a solvent is applied on a substrate 1 using a spinner or the like, and dried to form a photoresist layer 2 (FIG. 1A).

Here, as the substrate 1, a glass substrate provided with a transparent conductive film such as an ITO film, a glass-epoxy resin laminate coated with a copper wiring pattern, or the like is used. In order to improve the adhesion between the substrate 1 and the photoresist composition, a silane coupling agent may be added to the composition or may be applied to the substrate 1 by a method such as coating.

The photoresist layer 2 is formed by thoroughly dissolving, dispersing, and kneading the components of the positive photoresist composition using a three-roll mill, a ball mill, a sand mill, etc., and then screen-printing the substrate 1, a bar coater, a roll coater, and a reverse coater. It is provided as a layer on the substrate 1 by applying a dry film thickness of about 1 to 50 μm by a conventionally known method such as a curtain flow coater or a spray coater.

After the application, the solvent is left at room temperature for several hours to several days or placed in a warm air heater or an infrared heater for several tens minutes to several hours to dry and remove the solvent.

Next, the photoresist layer 2 is selectively exposed to actinic rays through a predetermined mask pattern 3 (FIG. 1B). Exposure is performed with a low-pressure mercury lamp, high-pressure mercury lamp,
Irradiation is performed by using an ultra-high pressure mercury lamp, a chemical lamp, an excimer laser generator, or the like to an amount sufficient to form a positive image. As an active energy ray used for exposure, g-line (436n) which is a bright line of a high-pressure mercury lamp is used.
m) or i-line (365 nm) or K, which is a shorter wavelength source
An active energy ray such as an rF excimer laser (248 nm), an electron beam, or an X-ray is preferable. The irradiation energy dose varies slightly depending on the type of the photoresist composition used, but is preferably about 50 to 2000 mJ / cm ² .

After the exposure, development is performed by a dipping method, a spray method or the like using a developing solution. The developer is preferably water or an aqueous alkali solution. Examples of the alkali component used in the developer include hydroxides, carbonates, silicates, bicarbonates, phosphates, pyrophosphates of alkali metals such as sodium and potassium. Acid salts; primary amines such as benzylamine and butylamine; secondary amines such as dimethylamine, dibenzylamine and diethanolamine; tertiary amines such as trimethylamine, triethylamine and triethanolamine;
Cyclic amines such as morpholine, piperazine and pyridine; polyamines such as ethylenediamine and hexamethylenediamine; ammonium hydroxides such as tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylbenzylammonium hydroxide and choline; trimethylsulfonium hydroxide; Examples include sulfonium hydroxides such as diethylmethylsulfonium hydroxide and dimethylbenzylsulfonium hydroxide. As the developing solution, an aqueous solution thereof or a solution to which these buffers are added is used. The exposed portion of the photoresist layer is selectively dissolved and removed by the development, so that a positive photoresist pattern 4 faithful to the mask pattern 3 can be obtained.

The obtained photoresist pattern 4 has a thickness of 10
The post-baking treatment may be performed by leaving the substrate in a temperature range of 0 to 200 ° C. for several tens minutes to several hours.

Next, the substrate is sufficiently washed to remove an alkali component attached to the surface of the substrate, and then subjected to an electroless plating treatment as shown in FIG. The conductive pattern 5 is formed on the substrate.

The electroless plating method has an advantage that the preparation and supply of a plating solution can be easily performed. Alternatively, the conductive pattern 5 may be formed by applying or filling a required portion of the conductive paste composition by a screen printing method or the like. As an example of the electroless plating method, the substrate can be formed by immersing the substrate in an electroless plating bath composed of a copper sulfate / formaldehyde / EDTA / sodium hydroxide solution for about 10 minutes to 10 hours.

According to the present invention, since a specific sulfur-containing organic compound is contained in the photoresist composition, the adhesion between the substrate and the photoresist layer can be improved, and the pattern due to the penetration of the plating solution can be improved. Chipping or peeling can be prevented beforehand. Furthermore, since these specific sulfur-containing organic compounds act as catalyst poisons, during electroless plating,
The conductive pattern is not formed on the photoresist pattern, and the conductive pattern 5 is selectively formed only on the exposed substrate as shown in FIG. Therefore, when the photoresist pattern is peeled, there is no need to peel the photoresist pattern and the conductive layer portion formed on the pattern together as in the conventional example.
The conventional problem that the conductor wiring is disconnected or short-circuited does not occur. Further, even when an alignment film is provided, an alignment film having a uniform thickness can be formed without causing poor alignment.

By applying an aqueous dispersion in which a palladium colloid is dispersed before the electroless plating treatment, the surface of the substrate is more activated.
Adhesion with the substrate can be further improved. The palladium colloid is used in an amount of 0.01 to 1 to obtain good dispersibility.
The particle size is preferably about μm, and the concentration is 0.5 to
It is preferably about 10 g / l.

If desired, it can further contain at least one soluble metal compound (alloying metal compound) selected from silver, tin, indium, nickel, copper, gold, cobalt, zinc or cadmium; Among them, tin sulfide is particularly preferred. Further, a chelating agent for chelating a palladium colloid or a soluble metal compound may be added.

As the chelating agent, palladium chloride,
It is not particularly limited as long as it can chelate the alloyed metal compound.Specifically, for example, kelidamic acid, orotic acid, hydantoin carboxylic acid, succinimide carboxylic acid, 2-pyrrolidone-5-carboxylic acid, Carboxyhydroxypyridine, carboxycaprolactam, picolinic acid or dipicolinic acid, carboxyxanthine, quinolinecarboxylic or dicarboxylic acid, lignin, vanillin, 9-imidaziridone-4-carboxylic acid,
Bases such as ammonia, amines, amino acids, EDTA, sodium chloride, ammonium hydroxide and other hydroxylated compounds (eg, alkali hydroxides) are exemplified,
Among these, keridamic acid, orotic acid and 2-pyrrolidone-5-carboxylic acid are particularly preferred. These chelating agents are used alone or in combination of two or more.
The concentration of the chelating agent may be such that the colloidal palladium and the alloy metal compound can be maintained in a dispersed state.

The electrolyte is required to be alkaline enough to solubilize the chelating agent and the metal complex, and usually has a pH of about 8 to 14, but is preferably about 12 to 14.
~ 14.

The contact with the palladium colloid is 10 to 6
It can be carried out at about 0 ° C, preferably about 30 to 50 ° C. A contact time of about 5 to 10 minutes is sufficient to obtain a further effect of the present invention.

Thereafter, the photoresist pattern is peeled off with an aqueous alkali solution such as triethanolamine, sodium hydroxide or potassium hydroxide, preferably having a pH of about 13 or more, and then a polyimide film is formed on the conductive pattern and the substrate by a known method. By forming and performing a rubbing treatment, a uniform alignment film (not shown) can be formed.

[0052]

EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention is not limited thereto.

(Preparation Example 1) m-cresol and p-cresol were mixed at a weight ratio of 60:40, and formaldehyde was added thereto in the presence of an oxalic acid catalyst. 10 parts by weight of 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,
3 parts by weight of an esterification reaction product with 2 mol of 2-diazide-5-sulfonyl chloride, 2 parts by weight of mercaptobenzotriazole, and 150 parts by weight of ethylene glycol monomethyl ether acetate were added, and the mixture was stirred and mixed for 5 minutes with a mixer. A positive photoresist composition was prepared.

(Preparation Example 2) In Preparation Example 1, a cresol novolak resin (m-cresol: p-cresol =
60:40 (weight ratio)) Instead of 10 parts by weight, methacrylic acid / methyl methacrylate / benzyl methacrylate / 2-hydroxyethyl acrylate = 20/40/1
Except for using 10 parts by weight of an acrylic resin (weight average molecular weight of about 20,0000) consisting of 0/30 (weight ratio),
A positive photoresist composition was prepared in the same manner as in Preparation Example 1.

(Preparation Example 3) A positive photoresist composition was prepared in the same manner as in Preparation Example 1, except that 4 parts by weight of thiourea was used instead of 2 parts by weight of mercaptobenzothiazole.

(Preparation Example 4) In Preparation Example 1, thiophene 3 was used instead of 2 parts by weight of mercaptobenzothiazole.
A positive photoresist composition was prepared in the same manner as in Preparation Example 1 except that parts by weight were used.

(Preparation Example 5) A positive photoresist composition was prepared in the same manner as in Preparation Example 1, except that 3.5 parts by weight of thiazole was used instead of 2 parts by weight of mercaptobenzothiazole. .

Preparation Example 6 In Preparation Example 1, thionalide 5 was used instead of 2 parts by weight of mercaptobenzothiazole.
A positive photoresist composition was prepared in the same manner as in Preparation Example 1 except that parts by weight were used.

(Preparation Example 7) A positive photoresist composition was prepared in the same manner as in Preparation Example 1 except that 3 parts by weight of diphenylcarbazide was used instead of 2 parts by weight of mercaptobenzothiazole. .

(Preparation Example 8) In Preparation Example 1, thiazoline 5 was used instead of 2 parts by weight of mercaptobenzothiazole.
A positive photoresist composition was prepared in the same manner as in Preparation Example 1 except that parts by weight were used.

Preparation Example 9 A positive photoresist composition was prepared in the same manner as in Preparation Example 1, except that 3 parts by weight of tetramethylthiourea was used instead of 2 parts by weight of mercaptobenzothiazole. .

(Preparation Example 10) A positive photoresist composition was prepared in the same manner as in Preparation Example 1, except that dibenzothiazyl disulfide (5 parts by weight) was used instead of mercaptobenzothiazole (2 parts by weight). did.

(Preparation Example 11) In Preparation Example 1, instead of 2 parts by weight of mercaptobenzothiazole, N-ter
t-butyl-2-benzothiazolylsulfenamide 5
A positive photoresist composition was prepared in the same manner as in Preparation Example 1 except that parts by weight were used.

(Preparation Example 12) A positive photoresist composition was prepared in the same manner as in Preparation Example 1 except that 6 parts by weight of tetramethylthiuram disulfide was used instead of 2 parts by weight of mercaptobenzothiazole. did.

(Comparative Preparation Example 1) A positive photoresist composition was prepared in the same manner as in Preparation Example 1, except that 2 parts by weight of mercaptobenzothiazole was not used.

The photoresist composition obtained in each of the above preparation examples was applied to a glass substrate (10 cm × 10 cm × 0.3) in which an ITO film having a thickness of 0.5 μm was formed in advance.
mm) using a spin coater so as to have a dry film thickness of 2 μm, and dried at 80 ° C. for 1 minute. Then 10
Exposure is performed by irradiating with 200 mJ / cm ² ultraviolet light from a super-high pressure mercury lamp capable of emitting g-line having a wavelength of 436 nm through a mask capable of reproducing μm line / 10 μm space, and triethanolamine 2% by weight. It was immersed in an aqueous solution at 23 ° C. for 60 seconds and developed. At this time, the substrate on which the photoresist pattern was obtained was A-1 (Preparation Example 1).
Example 1), A-2 (using Preparation Example 2; Example 2), A-3 (using Preparation Example 3; Example 3), A-4
(Using Preparation Example 4; Example 4), A-5 (Using Preparation Example 5; Example 5), A-6 (Using Preparation Example 6; Example 6), A-7 (Using Preparation Example 7) Use; Example 7), A-8
(Using Preparation Example 8; Example 8), A-9 (Using Preparation Example 9; Example 9), A-10 (Using Preparation Example 10; Example 10), A-11 (Using Preparation Example 11) Use; Example 11),
A-12 (Using Preparation Example 12; Example 12), B-1
(Comparative Preparation Example 1 was used; Comparative Example 1), and the obtained substrate was observed with an SEM (scanning electron microscope) to observe chipping and peeling of the photoresist pattern. Table 1 shows the results.

Next, the substrates A-1 to A-12 and B-1
The substrate exposed with the ITO film was subjected to a palladium colloid aqueous solution (colloid particle size 0.05 μm, concentration 2 g / l).
For 10 minutes, and then as an electroless plating solution, copper sulfate / formaldehyde / EDTA / sodium hydroxide (1
0: 5: 1: 2 by weight) in a 20% aqueous solution.
Copper was selectively deposited on the ITO film by immersion for a time to form a wiring pattern. No copper wiring pattern was formed on the photoresist pattern. Thereafter, the photoresist pattern was peeled off with a 4% aqueous solution of sodium hydroxide to form a conductive pattern of copper on the glass substrate. Disconnection and short circuit at the top of the obtained copper pattern were observed. Table 1 shows the results.

Thereafter, a polyimide precursor solution was applied as an alignment film by a spinner so as to have a thickness of 2 μm after drying, dried and cured at a temperature of 140 ° C., and subjected to a rubbing treatment. The quality of the obtained alignment film was observed. Table 1 shows the results.

[0069]

[Table 1] Table 1 [Evaluation Method of Chipping / Peeling of Photoresist Pattern] The states of the photoresist layer before development and the photoresist pattern after development were observed by SEM.

：: A photoresist pattern was formed faithfully to the mask pattern. X: A part of the photoresist pattern was chipped or peeled. [Evaluation method of disconnection and short circuit] Copper wiring pattern obtained after peeling the photoresist pattern And a continuity test was performed.

Disconnection ：: No disconnection was observed X: Disconnection was partially observed Short circuit 短 絡: Short circuit was not observed ×: Short circuit was observed partially [Good / bad alignment film] was obtained. The state of the alignment film was observed by SEM.

：: An alignment film having a uniform film thickness was obtained, and no defective alignment was observed. X: A portion where the film thickness was uneven was observed, and a defective alignment was observed in a part.

[0073]

As described in detail above, the adhesiveness to the substrate is excellent, the disconnection of the substrate due to the peeling of the photoresist pattern can be prevented beforehand, the chemical solution does not peel off during the electroless plating treatment, and the plating resistance is improved. Provided are a pattern forming method using a good photoresist composition and a positive photoresist composition used for the method. Thereby, it is possible to form a fine pattern of about 10 μm line / 10 μm space with higher reproducibility by the electroless plating process, and to achieve better quality improvement in the production of multilayer wiring boards, liquid crystal panels, and the like. Can be.

[Brief description of the drawings]

FIG. 1 is a conceptual illustration of the steps of the pattern forming method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Photoresist layer 3 Mask pattern 4 Photoresist pattern 5 Conductive pattern

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H05K 3/18 H01L 21/30 502R

Claims (8)

[Claims] 1. Thiourea, thiophene, thiazole, thionalide, diphenylcarbazide, thiazoline, tetramethylthiourea, mercaptobenzothiazole, mercaptobenzotriazole, dibenzothiazyl disulfide, N-tert-butyl-2-benzothiazolylsulfene A positive photoresist composition containing one or more sulfur-containing organic compounds selected from amide and tetramethylthiuram disulfide is coated on a substrate, dried, and selectively exposed through a mask pattern. Forming a photoresist pattern by developing and then removing the exposed portions. 2. The method according to claim 1, wherein the sulfur-containing organic compound is mercaptobenzothiazole. 3. A conductive pattern is formed on an exposed substrate by performing an electroless plating process on the substrate on which the photoresist pattern has been formed by the method according to claim 1 or 2.
A method for forming a conductive pattern. 4. The method according to claim 3, wherein the sulfur-containing organic compound is mercaptobenzothiazole. 5. A positive photoresist composition used in the method for forming a photoresist pattern according to claim 1, wherein (a) an alkali-soluble resin, (b) a quinonediazide group-containing compound, and (c) thiourea. Thiophene, thiazole, thionalide, diphenylcarbazide,
One or more selected from thiazoline, tetramethylthiourea, mercaptobenzothiazole, mercaptobenzotriazole, dibenzothiazyl disulfide, N-tert-butyl-2-benzothiazolylsulfenamide, and tetramethylthiuram disulfide And a sulfur-containing organic compound. 6. The positive photoresist composition according to claim 5, wherein the sulfur-containing organic compound is mercaptobenzothiazole. 7. A positive photoresist composition used in the method for forming a conductive pattern according to claim 3, wherein (a) an alkali-soluble resin, (b) a quinonediazide group-containing compound, and (c) thiourea. Thiophene, thiazole, thionalide, diphenylcarbazide, thiazoline, tetramethylthiourea, mercaptobenzothiazole, mercaptobenzotriazole, dibenzothiazyl disulfide, N-tert-butyl-2-benzothiazolylsulfenamide, and tetramethylthiuram disulfide A positive photoresist composition comprising one or more sulfur-containing organic compounds selected from the group consisting of: 8. The positive photoresist composition according to claim 7, wherein the sulfur-containing organic compound is mercaptobenzothiazole.