JP2010145604A - Positive photosensitive resin composition and method of manufacturing bump using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition that forms a uniform photosensitive resin film even when the film thickness is 10 μm or longer, has high resolution property, high adhesiveness, sufficient developing speed to alkali developing solution, high plating liquid resistance, reduces cracking and chipping of the photosensitive resin film in a plating process, and is suitable for thick film formation suitable as a material for forming a bump having high peeling property, and a method of manufacturing a bump using them. <P>SOLUTION: This positive photosensitive resin composition includes (A) alkali soluble novolak resin, (B) phenol resin denaturalized with compound having unsaturated 4-100C hydrocarbon group machine, and (C) compound for generating acid with light. The content of the (B) component is 5 to 50 mass% to the total content of the (A) component and the (B) component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition and a method for producing a bump using the same. More specifically, it is suitable for photofabrication performed when a circuit board is manufactured and an electronic component is mounted on the circuit board, and a positive-type photosensitive resin composition for a thick film capable of alkali development, and the photosensitive resin composition The present invention relates to a photosensitive resin film made of a material and a bump forming method using the same.

In recent years, with the downsizing of electronic equipment, the high integration of LSI and the ASIC are rapidly progressing. For this reason, multi-pin thin film mounting for mounting LSI on electronic devices is required, and bare chip mounting by TAB method or flip chip method is adopted. In such multi-pin mounting, bump electrodes called bumps need to be arranged on the substrate with high precision as connection terminals, and bumps are made highly accurate and narrow in response to further miniaturization of LSIs. There is a growing need for pitching.
The photosensitive resin composition used when forming the bumps can form a uniform photosensitive resin film having a thickness of 10 μm or more, the patterned film has adhesion to the substrate, and has excellent resolution. In addition, it is required to have plating resistance when performing plating for forming bumps, to reproduce the patterning shape of the plating shape, and to be easily peeled off by a peeling solution after plating.
In addition, it is required that no cracks occur in the photosensitive resin film during or after water washing or drying treatment during plating. If cracks occur during plating, the plating deposits at an undesired location such as plating, which causes a short circuit. If cracks occur after plating, when the plating is performed again because of insufficient plating thickness, the plating is likely to be deposited on the crack portion, and the correct shape of the plating may not be obtained. Therefore, the photosensitive resin composition for forming a plating is particularly required to suppress the occurrence of cracks during or after plating.
However, a photosensitive resin composition comprising a novolak resin, a naphthoquinonediazide group-containing compound and other additives conventionally used as bump forming materials has not been satisfactory in generating cracks. That is, there is a problem in that the formed photosensitive resin film is fragile and thus easily cracks.
For example, Patent Documents 1 and 2 disclose a photosensitive resin composition that does not generate cracks during development even when used as a dry film using a poly-p-hydroxystyrene-based resist. There was a problem that the contrast was lowered.
Patent Document 3 discloses a photosensitive resin composition for bump formation that includes an alkali-soluble copolymer containing a carboxyl group or a phenolic hydroxyl group and can be used as a dry film. The metal layer swells and a good pattern cannot be obtained, and cracks are generated during the plating process.
Patent Document 4 discloses a photosensitive resin film containing an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride. As in Patent Document 3, a metal layer obtained by plating treatment swells and has a good pattern. Cannot be obtained, and cracks are generated during the plating process.
Patent Document 5 discloses a photosensitive resin composition for bump formation containing a novolak resin and an alcoholic hydroxyl group, a carboxyl group, and / or a phenolic hydroxyl group. However, the contrast as the photosensitive resin composition is lowered. was there.
Patent Document 6 discloses a positive photoresist composition to which poly (vinyl lower alkyl ether) is added for the purpose of improving plating resistance. However, since the solubility of vinyl lower alkyl ethers in an alkaline developer is low, it is necessary to add a polynuclear phenol compound, and the resistance to plating tends to decrease.

JP-A-5-107756 Japanese Patent Laid-Open No. 5-107757 Japanese Patent No. 3832099 Japanese Patent No. 3633179 JP 2000-250208 A JP 2000-250210 A

  An object of the present invention is to form a positive photosensitive resin composition that can form a highly uniform photosensitive resin film even with a thick film of 10 μm or more, and is excellent in resolution, plating solution resistance and peelability, and bumps using the same. It is to provide a manufacturing method.

The present invention includes [1] (A) an alkali-soluble novolak resin, (B) a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms, (C) a compound that generates an acid by light, A positive photosensitive resin composition containing 5 to 50% by mass of the component (B) with respect to the total amount of the component (A) and the component (B). It is in providing a conductive resin composition.
The present invention also relates to [2] the positive photosensitive resin composition according to the above [1], wherein the component (C) is an o-quinonediazide compound. Since the sensitivity at the time of forming a resist pattern further improves, it is preferable that it is an o-quinonediazide compound.
The present invention also provides the positive type according to [1] or [2], wherein the content of the component [3] (C) is 3 to 100 parts by mass with respect to 100 parts by mass of the component (A). The present invention relates to a photosensitive resin composition.
Thereby, the resolution at the time of forming a resist pattern further improves.
According to such a positive photosensitive resin composition, a uniform coating film having a film thickness of 10 μm or more can be formed, and a resist pattern having sufficiently high sensitivity and resolution, excellent adhesion, and good plating solution resistance can be formed. Is possible.
[4] The method for producing a bump of the present invention is a method in which the positive photosensitive resin composition according to any one of the above [1] to [3] is formed on a substrate with a film thickness of 10 to 100 μm. A step of forming a film, a step of exposing the photosensitive resin film with ultraviolet rays, a step of developing and patterning with an alkaline aqueous solution after the exposure, a step of plating after the patterning, and a resist pattern after the plating treatment And a peeling step. According to such a manufacturing method, since the positive photosensitive resin composition described above is used, a good plating pattern can be formed with sufficiently high sensitivity and resolution.

  According to the present invention, a positive-type photosensitive resin composition that can form a highly uniform photosensitive resin film even with a thick film of 10 μm or more and is excellent in resolution, plating solution resistance and peelability, and these are used. A bump manufacturing method (forming method) can be provided.

Hereinafter, preferred embodiments of the present invention will be described in detail. In this specification, “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto.
[Positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention comprises (A) an alkali-soluble novolak resin, (B) a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms, and (C) an acid by light. Containing a compound that produces Hereinafter, each component contained in the positive photosensitive resin composition will be described.

<(A) component>
The alkali-soluble novolak resin as component (A) can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst.
Examples of phenols used at this time include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4 , 5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like. .
Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.
The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and the like are used as the acid catalyst.
(A) Although the weight average molecular weight of alkali-soluble novolak resin is not specifically limited, 10000-50000 are preferable.
The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) (in terms of standard polystyrene).

<(B) component>
The phenol resin modified with the component (B) compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is a compound having a phenol derivative and an unsaturated hydrocarbon group having 4 to 100 carbon atoms. It can be obtained by subjecting a reaction product with an "unsaturated hydrocarbon group-containing compound") (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivative") and an aldehyde to a condensation polymerization reaction.
Examples of the phenol derivative include phenol; o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl Alkylphenols such as phenol; alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol; alkenylphenols such as vinylphenol and allylphenol; aralkylphenols such as benzylphenol; Cooxycarbonylphenol; arylcarbonylphenol such as benzoyloxyphenol; halogenated phenol such as chlorophenol; polyhydroxybenzene such as catechol, resorcinol, pyrogallol; bisphenol such as bisphenol A and bisphenol F; α- or β-naphthol, etc. Naphthol derivatives; hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol; hydroxyalkylcresols such as hydroxyethylcresol; monoethylene oxide adduct of bisphenol Alcoholic hydroxyl group-containing phenol derivatives such as monopropylene oxide adducts of bisphenol; p-hydroxypheny Acid, p- hydroxy phenylpropionic acid, p- hydroxyphenyl butanoic acid, p- hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenyl benzoate, hydroxyphenoxy benzoate, carboxyl group-containing phenol derivatives such as di-phenolic acids. Further, methylolated products of the above phenol derivatives such as bishydroxymethyl-p-cresol may be used as the phenol derivative. A phenol derivative is used individually by 1 type or in combination of 2 or more types.

The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated bonds from the viewpoint of adhesion of the resist pattern and thermal shock resistance, and storage stability of the positive photosensitive resin composition From the viewpoint of safety, the unsaturated bond is preferably 30 or less. Moreover, from the viewpoint of compatibility when the resin composition is used and the flexibility of the cured film, the unsaturated hydrocarbon group preferably has 8 to 80 carbon atoms, more preferably 10 to 60 carbon atoms.
Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbon having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acid and unsaturated fatty acid ester. is there. Suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidone Examples include acids, arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, an ester of an unsaturated fatty acid having 8 to 30 carbon atoms and a monovalent to trivalent alcohol having 1 to 10 carbon atoms is more preferable, and an unsaturated fatty acid having 8 to 30 carbon atoms and a trivalent alcohol are preferable. Especially preferred are esters with glycerin.
Esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerin are commercially available as vegetable oils. Vegetable oils include non-drying oils with an iodine value of 100 or less, semi-drying oils with more than 100 and less than 130, or 130 or more drying oils. Non-drying oils include, for example, olive oil, Asa seed oil, cashew oil, potato oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include paulownia oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia oil and coconut oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.
From the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the resist pattern, it is preferable to use a drying oil, and more preferable are tung oil and linseed oil.
These unsaturated hydrocarbon group-containing compounds are used singly or in combination of two or more.

In preparing the component (B), first, the phenol derivative and the unsaturated hydrocarbon group-containing compound are reacted to produce an unsaturated hydrocarbon group-modified phenol derivative. The above reaction is usually preferably carried out at 50 to 130 ° C. The reaction ratio between the phenol derivative and the unsaturated hydrocarbon group-containing compound is 1 to 100 parts by mass of the unsaturated hydrocarbon group-containing compound with respect to 100 parts by mass of the phenol derivative from the viewpoint of improving the flexibility of the cured film. It is preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst, if necessary.
Next, the unsaturated hydrocarbon group-modified phenol derivative is reacted with an aldehyde to produce a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. Examples of the aldehydes include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, and glyceraldehyde. Examples of aldehydes include glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, repric acid. 4-acetylbutyric acid, acetone dicarboxylic acid and 3,3 ′, 4,4′-benzophenone tetracarboxylic acid. Further, a formaldehyde precursor such as paraformaldehyde or trioxane may be used. These aldehydes are used alone or in combination of two or more.

The reaction between the aldehydes and the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and conventionally known synthesis conditions for phenol resins can be used. The reaction is preferably performed in the presence of a catalyst such as an acid or a base, and an acid catalyst is more preferably used. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.
The above reaction is preferably carried out usually at a reaction temperature of 100 to 120 ° C. Moreover, although reaction time changes with kinds and quantity of a catalyst to be used, it is 1 to 50 hours normally. After completion of the reaction, the reaction product is dehydrated under reduced pressure at a temperature of 200 ° C. or lower to obtain a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms.
In the reaction, a solvent such as toluene, xylene, or methanol can be used.
In addition, a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is obtained by reacting the above-described phenol derivative with an unsaturated hydrocarbon group-containing compound, and m-xylene. It can also be obtained by combining such compounds other than phenol and polycondensing with aldehydes. In this case, the molar ratio of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.

The phenol resin modified with the compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms thus obtained is further reacted with a polybasic acid anhydride to use the acid-modified phenol resin as the component (B). be able to. By acid-modifying with a polybasic acid anhydride, the solubility of the component (B) in an alkaline aqueous solution (developer) is further improved.
The polybasic acid anhydride is not particularly limited as long as it has a plurality of carboxylic acids and has a form (acid anhydride) obtained by dehydration condensation of the carboxylic acid. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Dibasic acid anhydrides such as methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, biphenyltetra Carboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracar Aliphatic, such as phosphate dianhydride, an aromatic tetracarboxylic acid dianhydride. You may use these individually by 1 type or in combination of 2 or more types.
Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride. For example, the polybasic acid anhydride is preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. preferable. In this case, there is an advantage that a resist pattern having a good shape can be formed.
The above reaction can be carried out at 50 to 130 ° C. In the above reaction, the polybasic acid anhydride is preferably reacted with 0.10 to 0.80 mol, more preferably 0.15 to 0.60 mol with respect to 1 mol of the phenolic hydroxyl group. More preferably, the reaction is performed at 20 to 0.40 mol. If the polybasic acid anhydride is less than 0.10 mol, the developability tends to decrease, and if it exceeds 0.80 mol, the alkali resistance of the unexposed area tends to decrease.
In addition, you may contain a catalyst in the said reaction as needed from a viewpoint of performing reaction rapidly. Examples of the catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine.

The component (A) can also be obtained by reacting a phenol resin and an unsaturated hydrocarbon group-containing compound. The phenol resin is a polycondensation reaction product of a phenol derivative and an aldehyde. In this case, as a phenol derivative and aldehydes, the thing similar to the phenol derivative and aldehyde mentioned above can be used, and a phenol resin can be synthesize | combined on the conventionally well-known conditions as mentioned above.
Specific examples of phenol resins obtained from such phenol derivatives and aldehydes include phenol / formaldehyde novolak resins, cresol / formaldehyde novolak resins, xylylenol / formaldehyde novolak resins, resorcinol / formaldehyde novolak resins, phenol-naphthol / formaldehyde novolak resins. Is mentioned.
Next, the phenol resin and the unsaturated hydrocarbon group-containing compound are reacted to produce a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms.
The reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably performed at 50 to 130 ° C. Moreover, the reaction rate of a phenol derivative and an unsaturated hydrocarbon group containing compound is 1-100 mass parts of unsaturated hydrocarbon group containing compounds with respect to 100 mass parts of phenol resins from a viewpoint of improving the flexibility of a cured film. It is preferable that it is 5-50 mass parts, and it is especially preferable that it is 10-30 mass parts. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst. In addition, solvents, such as toluene, xylene, methanol, tetrahydrofuran, can be used for reaction.
Further, a polybasic acid anhydride is further reacted with the phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms, which is a reaction product of the phenol resin and the unsaturated hydrocarbon group-containing compound. An acid-modified phenol resin may be used as the component (B). By acid-modifying with a polybasic acid anhydride, the solubility of the component (B) in an alkaline aqueous solution (developer) is further improved. For the reaction with the polybasic acid anhydride, the same conditions as those described above can be used. As a polybasic acid anhydride, the thing similar to the polybasic acid anhydride mentioned above can be illustrated.

The molecular weight of the component (B) is preferably 1,000 to 500,000, more preferably 2,000 to 200,000, and more preferably 2,000 to 100,000, considering the solubility in an aqueous alkali solution and the balance between the photosensitive properties and the cured film properties. It is more preferable that it is 5,000 to 50,000. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.
The content of the phenol resin modified with the compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms as the component (B) is 5 to 50 with respect to the total amount of the component (A) and the component (B). Although it is mass%, it is more preferable that it is 5-40 mass% from a viewpoint of development speed and resolution, and it is especially preferable that it is 10-30 mass%.

<(C) component>
The compound which produces | generates an acid with the light which is (C) component is used as a photosensitive agent. Such a component (C) has a function of generating an acid by irradiation with light and increasing the solubility of the irradiated portion in an alkaline aqueous solution. As the component (C), a compound generally called a photoacid generator can be used. Specific examples of the component (C) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts and the like. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.
As the o-quinonediazide compound, for example, a compound obtained by subjecting o-quinonediazidesulfonyl chloride to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent can be used.
Examples of the o-quinonediazidesulfonyl chloride used in the reaction include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4- A sulfonyl chloride is mentioned.

  Examples of the hydroxy compound used in the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- ( 4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetra Hydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ′, 4 ′, 5′-hexahydroxy Benzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxy) Enyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, And tris (4-hydroxyphenyl) ethane.

  Examples of the amino compound used in the reaction include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4 ′. -Diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) Sulfone, bis (3-amino-4-hydroxyphenyl) hexa Ruoropuropan, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like.

Examples of the dehydrochlorinating agent used in the reaction include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like. Moreover, as a reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone, or the like is used.
o-quinonediazidosulfonyl chloride and hydroxy compound and / or amino compound are blended so that the total number of moles of hydroxy group and amino group is 0.5 to 1 per mole of o-quinonediazidesulfonyl chloride. It is preferred that A preferred blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 molar equivalent to 1 / 0.95 molar equivalent.
In addition, the preferable reaction temperature of the above-mentioned reaction is 0-40 degreeC, and preferable reaction time is 1 to 10 hours.
The content of the component (C) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of the difference in dissolution rate between the exposed part and the unexposed part and the allowable range of sensitivity. 5-50 mass parts is more preferable, and 5-30 mass parts is especially preferable.

<(D) component>
(D) A solvent can also be contained as a component. When the positive photosensitive resin composition of the present invention contains a solvent, a more uniform coating film can be produced and the film thickness can be easily adjusted. Specific examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene Examples include glycol monobutyl ether and dipropylene glycol monomethyl ether.
These solvents can be used alone or in combination of two or more. Moreover, although content of (D) component is not specifically limited, It is preferable to adjust so that the ratio of the solvent in positive type photosensitive resin composition may be 20-90 mass%.

<Other ingredients>
In addition to the above components (A) to (D), the positive photosensitive resin composition described above contains components such as an elastomer, a dissolution accelerator, a dissolution inhibitor, a coupling agent, and a surfactant or leveling agent. Furthermore, you may contain.

(Elastomer)
The positive photosensitive resin composition of the present invention preferably further contains an elastomer of component (E) in order to impart flexibility to the cured product of the positive photosensitive resin composition. A conventionally known elastomer can be used as the elastomer, but the glass transition temperature (Tg) of the polymer constituting the elastomer is preferably 20 ° C. or lower.
Examples of such elastomers include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the styrenic elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, and styrene-butadiene-methacrylate block. Examples thereof include polymers. As a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used in addition to styrene.

  Specific examples of styrenic elastomers include Tufrene, Solprene T, Asaprene T, Tuftec (above, manufactured by Asahi Kasei Corporation), Elastomer AR (produced by Aron Kasei Co., Ltd.), Kraton G, Califlex (above, Shell Japan Co., Ltd.) Manufactured), JSR-TR, TSR-SIS, Dynalon (above, manufactured by JSR Corporation), Denka STR (manufactured by Electrochemical Co., Ltd.), Quintac (manufactured by Nippon Zeon Co., Ltd.), TPE-SB series (Sumitomo Chemical Co., Ltd.) ), Lavalon (Mitsubishi Chemical Co., Ltd.), Septon, Hibler (above, Kuraray Co., Ltd.), Sumiflex (Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (above, Riken Vinyl Industry Co., Ltd.), Paraloid EXL series (made by Rohm and Haas) can be mentioned.

Examples of the olefin elastomer include copolymers of α-olefins having 2 to 20 carbon atoms (for example, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM)), and carbon number 2 Copolymer of ~ 20 dienes and α-olefin, carboxy-modified NBR obtained by copolymerizing epoxidized polybutadienebutadiene-acrylonitrile copolymer with methacrylic acid, ethylene-α-olefin copolymer rubber, ethylene-α-olefin -Diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer rubber, and the like. Specific examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. Specific examples of the dienes having 2 to 20 carbon atoms Includes dicyclopentadiene, 1,4-hexadiene, cyclooctanediene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene.
Specific examples of olefin elastomers include milastoma (Mitsui Petrochemical Co., Ltd.), EXACT (Exxon Chemical Co., Ltd.), ENGAGE (Dow Chemical Co., Ltd.), Nipol series (Nihon Zeon Co., Ltd.), hydrogenated styrene. -Butadiene rubber DYNABON HSBR (manufactured by JSR Corp.), butadiene-acrylonitrile copolymer NBR series (manufactured by JSR Corp.), XER series (both terminal carboxyl group-modified butadiene-acrylonitrile copolymers having a crosslinking point (manufactured by JSR Corp.) ), BF-1000 (manufactured by Nippon Soda Co., Ltd.) of partially epoxidized polybutadiene, and liquid butadiene-acrylonitrile copolymer HYCAR series (manufactured by Ube Industries, Ltd.).

Urethane elastomers are composed of structural units of a hard segment composed of low molecular (short chain) diol and diisocyanate and a soft segment composed of high molecular (long chain) diol and diisocyanate. Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, and poly (1,6-hexene). Xylene carbonate), poly (1,6-hexylene-neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. Examples of the low molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48 to 500.
Specific examples of the urethane-based elastomer include PANDEX T-2185, T-2983N (manufactured by Dainippon Ink & Chemicals, Inc.), sylactolan E790, and the Hitaroid series (manufactured by Hitachi Chemical Co., Ltd.).

The polyester elastomer is obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic rings are substituted with a methyl group, an ethyl group, a phenyl group, and the like, Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more.
Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol; Examples include alicyclic diol, bisphenol A, bis- (4-hydroxyphenyl) -methane, bis- (4-hydroxy-3-methylphenyl) -propane, resorcin and the like. These compounds can be used individually by 1 type or in combination of 2 or more types.
In addition, a multi-block copolymer having an aromatic polyester (eg, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (eg, polytetramethylene glycol) portion as a soft segment component is used as a polyester elastomer. You can also. Polyester elastomers are available in various grades depending on the types and ratios of hard segments and soft segments, and the difference in molecular weight.
Specific examples of the polyester elastomer include Hytrel (DuPont-Toray Industries, Inc.), Perprene (Toyobo Co., Ltd.), Espel (Hitachi Chemical Industries, Ltd.) and the like.

Polyamide elastomers are composed of hard segments made of polyamide and soft segments made of polyether or polyester, and are roughly divided into two types: polyether block amide type and polyether ester block amide type. The Examples of the polyamide include polyamide 6, polyamide 11, and polyamide 12. Examples of the polyether include polyoxyethylene, polyoxypropylene, polytetramethylene glycol and the like.
Specific examples of the polyamide-based elastomer include UBE polyamide elastomer (manufactured by Ube Industries), Daiamide (manufactured by Daicel Huls Co., Ltd.), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MMS Japan Co., Ltd.), Novamid ( Mitsubishi Chemical Co., Ltd.), Glais (Dainippon Ink Chemical Co., Ltd.) and the like.

Acrylic elastomers are acrylic esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, monomers having an epoxy group such as glycidyl methacrylate, allyl glycidyl ether, and / or vinyls such as acrylonitrile and ethylene. It is obtained by copolymerizing with a monomer.
Examples of such acrylic elastomers include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

Silicone elastomers are mainly composed of organopolysiloxane, and are classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Further, a part of organopolysiloxane modified with a vinyl group, an alkoxy group or the like may be used.
Specific examples of such silicone elastomers include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

  In addition to the above-described elastomer, a rubber-modified epoxy resin can also be used. The rubber-modified epoxy resin includes, for example, a part or all of epoxy groups such as bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin, or cresol novolac type epoxy resin, It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber or the like.

The elastomer may be in the form of fine particles (hereinafter also referred to as “elastomer particles”). The elastomer fine particles are elastomers dispersed in a fine particle state in a positive photosensitive resin composition, and include elastomers that are islands in a sea-island structure by phase separation in an incompatible system, elastomers that are so-called microdomains, and the like. Is.
The elastomer fine particles are obtained by copolymerizing a crosslinkable monomer having two or more unsaturated polymerizable groups and one or more other monomers selected so that the Tg of the elastomer fine particles is 20 ° C. or less (so-called cross-linking). Fine particles) are preferred. As the other monomer, it is preferable to use a monomer obtained by copolymerizing a monomer having a functional group other than the polymerizable group, for example, a functional group such as a carboxyl group, an epoxy group, an amino group, an isocyanate group, or a hydroxyl group.
Examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol di Examples thereof include compounds having a plurality of polymerizable unsaturated groups such as (meth) acrylate and polypropylene glycol di (meth) acrylate. Of these, divinylbenzene is preferred.
The crosslinkable monomer used in producing the elastomer fine particles is preferably used in an amount of 1 to 20% by mass, more preferably 2 to 10% by mass, based on all monomers used for copolymerization.
Examples of other monomers include diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene, and 1,3-pentadiene; (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α- Unsaturated nitrile compounds such as ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, and fumaric acid dinitrile; (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N, N '-Ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N Unsaturated amides such as N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylic acid esters such as butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; styrene, α-methylstyrene , O-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol and other aromatic vinyl compounds; bisphenol A diglycidyl ether, glycol diglycidyl ether and the like, (meth) acrylic acid, hydroxyalkyl (meth) acrylate Reaction with etc. Therefore, epoxy (meth) acrylate obtained; urethane (meth) acrylate obtained by reaction of hydroxyalkyl (meth) acrylate and polyisocyanate; epoxy group-containing non-residue such as glycidyl (meth) acrylate and (meth) allyl glycidyl ether Saturated compounds; (meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β- (meth) acryloxyethyl, hexahydro Unsaturated acid compounds such as phthalic acid-β- (meth) acryloxyethyl; Amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate; (meth) acrylamide, dimethyl (meth) acrylamide, etc. An amide group-containing unsaturated compound , Hydroxyl-containing unsaturated compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
Among these, butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, (meth) acrylic acid, hydroxyalkyl (Meth) acrylates and the like are preferably used.

(Dissolution promoter)
By blending the dissolution accelerator in the positive photosensitive resin composition described above, the dissolution rate of the exposed area when developing with an alkaline aqueous solution can be increased, and the sensitivity and resolution can be improved. A conventionally well-known thing can be used as a dissolution promoter. Specific examples thereof include compounds having a carboxyl group, a sulfonic acid, and a sulfonamide group.
The content when such a dissolution accelerator is blended can be determined by the dissolution rate with respect to the alkaline aqueous solution, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (A). be able to.

(Dissolution inhibitor)
The dissolution inhibitor is a compound that inhibits the solubility of the component (A) in an alkaline aqueous solution, and is used to control the remaining film thickness, development time, and contrast. Specific examples thereof include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like. When blending a dissolution inhibitor, the content is preferably 0.01 to 20 parts by weight, preferably 0.01 to 15 parts per 100 parts by weight of component (A), from the viewpoint of sensitivity and the allowable range of development time. Mass parts are more preferable, and 0.05 to 10 parts by mass are particularly preferable.

(Coupling agent)
By mix | blending a coupling agent with the above-mentioned positive photosensitive resin composition, the adhesiveness with the board | substrate of the cured film formed can be improved. Examples of the coupling agent include organic silane compounds and aluminum chelate compounds.
Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl-n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol , N-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (Ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldi) Droxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Benzene.
When using a coupling agent, the content is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A).

(Surfactant or leveling agent)
By blending a surfactant or a leveling agent into the above-mentioned positive photosensitive resin composition, coating properties such as striation (film thickness unevenness) can be prevented and developability can be improved. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Commercially available products include Megafax F171, F173, R-08 (Dainippon Ink Chemical Co., Ltd., trade name), Fluorad FC430, FC431 (Sumitomo 3M Limited, trade name), organosiloxane polymers KP341, KBM303, KBM403. , KBM803 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
When using surfactant or a leveling agent, 0.001-5 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for the total content, 0.01-3 mass parts is more preferable.

  The positive photosensitive resin composition described above can be developed using an aqueous alkaline solution such as tetramethylammonium hydroxide (TMAH). Furthermore, by using the above-mentioned positive photosensitive resin composition, it becomes possible to form a resist pattern having good adhesion and thermal shock resistance with sufficiently high sensitivity and resolution.

[Bump manufacturing method]
Next, a bump manufacturing method will be described. The method for producing a bump of the present invention comprises a step of forming a photosensitive resin film comprising the above positive photosensitive resin composition on a substrate with a film thickness of 10 to 100 μm, a step of exposing, and a photosensitive resin after exposure. A step of developing and patterning the film with an aqueous alkaline solution, a step of plating the patterned photosensitive resin film, and a step of peeling after plating are provided.
Hereinafter, each step will be described.

<Application process>
First, the positive photosensitive resin composition described above is applied onto a support substrate such as a semiconductor wafer and dried to form a photosensitive resin film. The positive photosensitive resin composition described above is spin-coated using a spinner or the like to form a photosensitive resin film. The support substrate on which the photosensitive resin film is formed is dried using a hot plate, an oven, or the like. Thereby, a photosensitive resin film is formed on the support substrate. By setting the film thickness to 10 to 100 μm, the thickness can sufficiently cover the bump height formed by the plating process.
<Exposure process>
Next, in the exposure step, the photosensitive resin film formed on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In the positive photosensitive resin composition described above, the component (A) is highly transparent to i-line, so i-line irradiation can be suitably used. In addition, after exposure, post-exposure heating (PEB) can be performed as necessary. The post-exposure heating temperature is preferably 70 to 140 ° C., and the post-exposure heating time is preferably 1 to 5 minutes.
<Development process>
In the development process, the photosensitive resin film is patterned by removing the exposed portion of the photosensitive resin film after the exposure process with a developer. As the developer, for example, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) is preferably used. The base concentration of these aqueous solutions is preferably 0.1 to 10% by mass. Furthermore, alcohols and surfactants can be added to the developer and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developer.
<Plating process>
The plating method is not particularly limited, and various conventionally known plating methods can be employed. For example, the plating solution includes a gold plating solution, a solder plating solution, a copper plating solution, and a silver plating solution. Electroless plating and electroplating can be performed alone or in combination.

<Peeling process>
After the plating treatment, the resist pattern remaining on the substrate can be peeled by immersing the substrate in a stripping solution being stirred at room temperature (25 ° C.) to 80 ° C. for 1 to 10 minutes. Thereby, a plating pattern is obtained.
As the stripping solution, for example,
Ethylene glycol alkyl ethers: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc.
Ethylene glycol dialkyl ethers: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.
Ethylene glycol alkyl acetates: methyl cellosolve acetate, ethyl cellosolve acetate, etc.
Propylene glycol alkyl ether acetates: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.
Ketones: acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone Aromatic monohydrides: toluene, xylene, etc.
Cyclic ethers such as dioxane:
Esters: methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3- Examples thereof include, but are not limited to, methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These may be used alone or in combination of two or more.

According to the bump manufacturing method as described above, a uniform coating film having a film thickness of 10 μm or more can be formed, and a resist pattern having a sufficiently high sensitivity and resolution, excellent adhesion, and good plating solution resistance can be formed. And a good plating pattern can be formed.
As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.
The following A1 was prepared as the component (A).
Phenolic resin (Asahi Organic Materials Co., Ltd., trade name “EP4080G”)

As the component (B), the following B1 to B4 were prepared.
(Synthesis of (B1))
100 parts by weight of phenol, 20 parts by weight of linseed oil and 0.1 parts by weight of trifluoromethanesulfonic acid were mixed and stirred at 120 ° C. for 2 hours to obtain a compound a which is a dry oil-modified phenol derivative. Next, 101 g of the compound a, 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours to carry out a reaction. And after heating up to 120 degreeC and stirring under reduced pressure for 3 hours, the reaction liquid was cooled to room temperature (25 degreeC) under atmospheric pressure, and the dry oil modified phenol resin (B1) which is a reaction product was obtained.

(Synthesis of (B2))
100 parts by mass of phenol, 10 parts by mass of linseed oil and 0.1 part by mass of trifluoromethanesulfonic acid were mixed and stirred at 120 ° C. for 2 hours to obtain a compound b which is a dry oil-modified phenol derivative. Next, 130 g of the compound b, 16.3 g of paraformaldehyde, and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours to carry out a reaction. And after heating up to 120 degreeC and stirring under reduced pressure for 3 hours, the reaction liquid was cooled to room temperature under atmospheric pressure, and the dry oil modified phenol resin (B2) which is a reaction product was obtained.

(Synthesis of (B3))
100 parts by mass of phenol, 30 parts by mass of linseed oil and 0.1 part by mass of trifluoromethanesulfonic acid were mixed and stirred at 120 ° C. for 2 hours to obtain a compound c which is a dry oil-modified phenol derivative. Next, 130 g of the above compound c, 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and reacted at 90 ° C. for 3 hours to carry out a reaction. And after heating up to 120 degreeC and stirring under reduced pressure for 3 hours, the reaction liquid was cooled to room temperature under atmospheric pressure, and the dry oil modified phenol resin d which is a reaction product was obtained. 130 g of the above compound d, 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours to carry out a reaction. Subsequently, after heating up to 120 degreeC and stirring under reduced pressure for 3 hours, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and it stirred at 100 degreeC under atmospheric pressure for 1 hour. The reaction solution was cooled to room temperature to obtain a dry oil-modified phenol resin (B3) as a reaction product.

(Preparation of (B4))
Paravinylphenol resin (trade name “Maryl Linker CHM” manufactured by Maruzen Petrochemical Co., Ltd.)

The following C1 was prepared as the component (C).
C1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1-naphthoquinone-2-diazide-5-sulfonic acid Esters (Esterification rate of about 90%, manufactured by AZ Electronic Materials, trade name “TPPA528”)

The following D1 was prepared as the component (D).
D1: Propylene glycol monomethyl ether acetate

(Examples 1-5 and Comparative Examples 1-3)
The components (A) to (D) were blended at the predetermined ratios shown in Tables 1 and 2, and this solution was filtered using a 5 μm filter manufactured by Millipore Corporation. A positive photosensitive resin composition solution No. 3 was prepared.

表中、数値は質量部を示す。

In the table, numerical values indicate parts by mass.

<Evaluation of positive photosensitive resin composition>
[Compatibility]
Stir the solutions of the positive photosensitive resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3, and visually observe the dissolved state immediately after stirring and after 1 to 2 hours after stirring. The solubility was determined according to the following evaluation criteria.
○: It can be confirmed that dissolution is uniform visually after 1 or 2 hours.
X: It can be confirmed that dissolution is not uniform immediately after dissolution or visually after 1, 2 hours.

[Applicability]
The positive photosensitive resin composition solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were spin-coated on a 5-inch gold sputtered silicon substrate, heated at 120 ° C. for 5 minutes, and a film thickness of 20 μm. A photosensitive resin film was formed. The formed coated surface was visually observed and the coating property was judged according to the following evaluation criteria.
○: There is no unevenness on the surface of the photosensitive resin film.
X: There is unevenness on the surface of the photosensitive resin film.

[Developer resistance]
The positive photosensitive resin composition solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were spin-coated on a 5-inch silicon substrate, heated at 120 ° C. for 5 minutes, and a photosensitive film having a thickness of 20 μm. A resin film was formed. The obtained coating film was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 5 minutes, the film thickness after immersion was measured, and the remaining film ratio with respect to the developer in the unexposed area was calculated. Judgment was made according to the following evaluation criteria.
○: Remaining film ratio 80-100%.
(Triangle | delta): 40-80% of remaining film rate.
X: The remaining film rate is 0 to 40% or it is dissolved but an accurate value cannot be measured.

[Development speed]
The positive photosensitive resin composition solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were spin-coated on a 5-inch silicon substrate, heated at 120 ° C. for 5 minutes, and a photosensitive film having a thickness of 20 μm. A resin film was formed. Next, using a proximity exposure machine (trade name “UX-1000SM-XJ01” manufactured by USHIO INC.), Exposure was performed to 1200 mJ / cm ² with i-line (365 nm). After the exposure, development was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), and the time until the exposed area was dissolved was measured. The faster the time until dissolution, the better.

[Resolution]
The positive photosensitive resin composition solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were spin-coated on a 5-inch gold sputtered silicon substrate, heated at 120 ° C. for 5 minutes, and a film thickness of 20 μm. A photosensitive resin film was formed. Next, using a proximity exposure machine (trade name “UX-1000SM-XJ01” manufactured by USHIO INC.), Exposure was performed at 1200 mJ / cm ² with i-line (365 nm) through a mask. After the exposure, development was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) until the exposed portion was dissolved, and then rinsed with water to obtain a patterned substrate. The value obtained for the finest pattern is shown.

[Plating solution resistance]
Using the sputtered gold substrate having the pattern obtained in the “resolution” as a test specimen, a current density of 36.8 mA at 60 ° C. for 40 minutes in a non-cyanide gold plating solution (“ECF88K” manufactured by NE Chemcat). Gold plating was performed at / dm ² . The plated substrate was washed with running water and purified water. This specimen was visually observed, and the plating solution resistance was judged according to the following evaluation criteria.
○: No crack was observed in the photosensitive resin film portion.
X: The crack was observed in the whole pattern in the photosensitive resin film part.

[Peelability]
The substrate obtained by the above “plating solution resistance” was used as a test specimen, immersed in a stripping solution (acetone) being stirred at room temperature for 5 minutes, washed with running water to peel off the pattern-like cured product, and visually observed. The evaluation was made according to the following criteria.
○: A pattern-like cured product is not recognized.
X: Patterned cured product is recognized.

As is clear from Table 1, the positive photosensitive resin compositions of Examples 1 to 5 had good compatibility, coating properties, developer resistance, development speed, resolution, plating solution resistance, and peelability. It was.
On the other hand, in Comparative Example 1 in which the amount of the dry oil-modified resin was large, the coating film was uneven, and development took 30 minutes or more.
Further, in Comparative Example 2 in which the resin was only a novolac resin, cracks occurred in the photosensitive resin portion during the plating process, and gold plating was observed.
Further, in Comparative Example 3 in which paravinylphenol resin was added, the coating film was uneven due to poor compatibility with the novolak resin, and the gold plating shape was poor due to low resistance to the developing solution in the unexposed area.

Claims (4)

(A) an alkali-soluble novolak resin,
(B) a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms,
(C) a compound that generates an acid by light,
A positive photosensitive resin composition containing 5 to 50% by mass of the component (B) with respect to the total amount of the component (A) and the component (B). Resin composition.   The positive photosensitive resin composition according to claim 1, wherein the component (C) is an o-quinonediazide compound.   The positive photosensitive resin composition according to claim 1 or 2, wherein the content of the component (C) is 3 to 100 parts by mass with respect to 100 parts by mass of the component (A). A step of forming a photosensitive resin film with a film thickness of 10 to 100 μm on the substrate, the positive photosensitive resin composition according to claim 1,
Exposing the photosensitive resin film with ultraviolet rays;
After the exposure, a step of developing and patterning with an alkaline aqueous solution,
A step of plating after the patterning;
And a step of stripping the resist pattern after the plating process.