JP5239446B2 - Positive photosensitive resin composition, method for producing resist pattern, and electronic component - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a resist pattern manufacturing method, and an electronic component.

  In recent years, semiconductor devices have been highly integrated and increased in size, and there has been a demand for thinner and smaller sealing resin packages. Along with this, it is required to form the surface protective layer and interlayer insulating film of the semiconductor element and the rewiring layer of the semiconductor package with materials having more excellent electrical characteristics, heat resistance, mechanical characteristics, and the like. Polyimide resin is one of the materials that can satisfy such required characteristics. For example, use of photosensitive polyimide obtained by imparting photosensitive characteristics to polyimide resin has been studied. When photosensitive polyimide is used, there is an advantage that a pattern forming process is simplified and a complicated manufacturing process can be shortened (for example, refer to Patent Documents 1 and 2).

  The polyimide resin film is generally formed by thinning a solution of a polyimide precursor (polyamic acid) obtained by reacting tetracarboxylic dianhydride and diamine (so-called varnish) by a method such as spin coating, and thermally dehydrating and ring-closing. (For example, refer nonpatent literature 1). The polyimide resin is cured through this dehydration ring closure process. However, in the case of a polyimide resin using a polyimide precursor, there is a problem that volume shrinkage due to dehydration (imidization) occurs during curing, resulting in a loss of film thickness and a decrease in dimensional accuracy. In addition, recently, a film formation process at a low temperature is desired, and a polyimide resin that can perform dehydration and ring closure at a low temperature but has properties comparable to those obtained by dehydration and ring closure at high temperatures. Is required. However, when the polyimide precursor is cured at a low temperature, imidization is incomplete, so that the formed cured film becomes brittle and the physical properties thereof are lowered.

In order to solve the drawbacks of the polyimide resin described above, studies have been made to increase the sensitivity, heat resistance, and mechanical properties of polymers that do not undergo dehydration and ring closure. For example, Non-Patent Document 2 and Patent Documents 3 to 6 discuss alicyclic polymers. In addition, a phenol resin having relatively excellent heat resistance, electrical insulation, and mechanical properties has been studied (for example, Patent Document 7).
Japan Polyimide Study Group, “Latest Polyimide: Basics and Applications”, 2002 J. et al. Photopolym. Sci. Technol. 18: 2005, p. 321-325 JP-A-49-115541 JP 59-108031 A International Publication No. 2004/006020 Pamphlet JP 2006-106214 A JP 2004-2754 A JP 2003-368530 A Japanese Patent No. 3812654

  However, with respect to the polymer that does not undergo dehydration and ring closure, similar to the photosensitive polyimide, further reduction in curing temperature, higher heat resistance, and higher mechanical properties have been demanded. In addition, since it is excellent in reducing the environmental load, there has been a demand for a shift to a positive photosensitive heat-resistant resin that can be developed with an aqueous alkaline solution, as in the case of semiconductor resist materials.

  Accordingly, an object of the present invention is to further improve the adhesion, heat resistance and mechanical properties after development in a positive photosensitive resin composition that can be developed with an aqueous alkaline solution. The present invention also provides a method of forming a resist pattern having good adhesion, heat resistance and mechanical properties using a positive photosensitive resin composition, and an electronic component having a resist pattern formed by such a method. The purpose is to provide.

  The positive photosensitive resin composition of the present invention contains (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that generates an acid by light, (C) a core-shell polymer, and (D) a solvent.

  Such a positive photosensitive resin composition can be developed with an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH). Further, according to the positive photosensitive resin composition of the present invention, it is possible to further improve the adhesion, heat resistance and mechanical properties during development.

  The component (A) is preferably a phenol resin because of its low cost and small volume shrinkage during curing. The component (A) is also preferably a vinyl polymer containing a monomer unit having a phenolic hydroxyl group because of excellent electrical characteristics (insulating properties) and small volume shrinkage during curing.

  In the positive photosensitive resin composition of the present invention, since the resolution at the time of forming a resist pattern is further improved, 1 to 50 parts by weight of component (C) with respect to 100 parts by weight of component (A). It is preferable to contain.

  The component (B) is preferably an o-quinonediazide compound because sensitivity at the time of forming a resist pattern is further improved.

  The positive photosensitive resin composition of the present invention preferably further contains (E) a thermal crosslinking agent that crosslinks the component (A) by heating. According to this, when the photosensitive resin film is heated, the reaction with the component (A), that is, the thermal crosslinking reaction is promoted, and the heat resistance of the cured film is improved.

  Further, the method for producing a resist pattern of the present invention comprises applying the above-described positive photosensitive resin composition on a support substrate, removing the solvent from the applied positive photosensitive resin composition, and forming a photosensitive resin film. A step of forming, a step of exposing the photosensitive resin film, a step of developing and patterning the exposed photosensitive resin film with an alkaline aqueous solution, and a step of heating the patterned photosensitive resin film. . According to such a manufacturing method, since the positive photosensitive resin composition described above is used, a resist pattern having a good shape with excellent sufficiently high adhesion at the time of development, heat resistance, and mechanical properties. Can be formed.

  In the method for producing a resist pattern of the present invention, the patterned photosensitive resin film is preferably heated to 200 ° C. or lower. Thereby, the damage by the heat with respect to an electronic component can fully be prevented.

  The electronic component of the present invention may have a resist pattern formed by the above-described manufacturing method as an interlayer insulating film and / or a surface protective layer. The electronic component of the present invention may have a resist pattern formed by the above-described manufacturing method as a cover coat layer. The electronic component of the present invention may have a resist pattern formed by the above-described manufacturing method as a core for the rewiring layer. The electronic component of the present invention may have a resist pattern formed by the above-described manufacturing method as a collar for holding conductive balls that are external connection terminals. The electronic component of the present invention may have a resist pattern formed by the above-described resist pattern manufacturing method as an underfill. Since such an electronic component has a resist pattern formed from the above-described positive photosensitive resin composition, it has high reliability.

  ADVANTAGE OF THE INVENTION According to this invention, in the positive photosensitive resin composition which can be developed with alkaline aqueous solution, the further improvement of the adhesiveness after development, heat resistance, and a mechanical characteristic can be aimed at. Further, the positive photosensitive resin composition according to the present invention can form a resist pattern having a good shape. In particular, by using a core-shell polymer, the flexibility (flexibility) of the cured film can be imparted. Moreover, since the positive photosensitive resin composition of the present invention can be developed with a TMAH aqueous solution, it is low in cost and has a low load on the global environment. According to the positive photosensitive resin composition of the present invention, since a resist pattern can be formed by a low-temperature heating process of 200 ° C. or lower, damage to an electronic device due to heat can be prevented, and the reliability is high. Electronic components can be provided with high yield.

  Since the positive photosensitive resin composition according to the present invention is excellent in stress relaxation properties, adhesiveness, and the like, it can be suitably used as various structural materials in packages having various structures developed in recent years. Furthermore, since the glass transition temperature of the cured film obtained by curing the positive photosensitive resin composition film is high, it can withstand heating processes such as sealing and solder reflow when mounting electronic parts having a cured film. There is an effect that can be.

  In addition, according to the method for producing a resist pattern according to the present invention, a resist pattern having sufficiently high adhesion, heat resistance, and mechanical properties can be formed with good sensitivity and resolution. The resist pattern formed by the method of the present invention has a good shape and characteristics, and has a small dimensional stability because of a small volume shrinkage during curing.

  Hereinafter, an embodiment of a positive photosensitive resin composition, a resist pattern manufacturing method, and an electronic component according to the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by the following embodiment.

[Positive photosensitive resin composition]
The positive photosensitive resin composition of this embodiment contains (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that generates an acid by light, (C) a core-shell polymer, and (D) a solvent. . Hereinafter, each component contained in the positive photosensitive resin composition will be described.

[(A) component: alkali-soluble resin having a phenolic hydroxyl group]
The component (A) is a resin having a phenolic hydroxyl group in the molecule and soluble in alkali. Specific examples thereof include a vinyl polymer containing a monomer unit having a phenolic hydroxyl group such as poly (hydroxystyrene), a phenol resin, a polybenzoxazole precursor such as poly (hydroxyamide), poly (hydroxyphenylene) ether, poly Naphthol.

  Among these, a phenol resin is preferable and a novolac type phenol resin is particularly preferable because of low cost and small volume shrinkage at the time of curing. In addition, a vinyl polymer containing a monomer unit having a phenolic hydroxyl group, particularly poly (hydroxystyrene) is also preferred because of excellent electrical characteristics (insulating properties) and small volume shrinkage during curing.

(Phenolic resin)
As a phenol resin, what is obtained by condensing (reaction) a phenol derivative and aldehydes in presence of catalysts, such as an acid or a base, can be used, for example. Among these, a phenol resin obtained when an acid catalyst is used is particularly referred to as a novolac type phenol resin. Specific examples of novolak resins include phenol / formaldehyde novolak resins, cresol / formaldehyde novolak resins, xylylenol / formaldehyde novolak resins, resorcinol / formaldehyde novolak resins, and phenol-naphthol / formaldehyde novolak resins.

  Examples of the phenol derivative used for obtaining the phenol resin include phenol; o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, and 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, Alkylphenols such as 3,4,5-trimethylphenol; alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol; alkenylphenols such as vinylphenol and allylphenol; aralkylphenols such as benzylphenol; Alkoxycarbonylphenols such as toxylcarbonylphenol; Arylcarbonylphenols such as benzoyloxyphenol; Halogenated phenols such as chlorophenol; Polyhydroxybenzenes such as catechol, resorcinol and pyrogallol; Bisphenols such as bisphenol A and bisphenol F; α- or β A naphthol derivative such as naphthol; a hydroxyalkylphenol such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol; a hydroxyalkylcresol such as hydroxyethylcresol; Ethylene oxide adducts; alcoholic hydroxyl group-containing phenols such as bisphenol monopropylene oxide adducts Carboxyl derivatives such as p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, diphenolic acid, etc. And group-containing phenol derivatives. Further, methylolated products of the above phenol derivatives such as bishydroxymethyl-p-cresol may be used as the phenol derivative.

  Furthermore, the phenol resin may be a condensation polymerization product of the above-described phenol derivative and a compound other than phenol such as m-xylene. In this case, the molar ratio of the compound other than phenol to the phenol derivative used for the condensation polymerization is preferably less than 0.5.

  Compounds other than the above-described phenol derivatives and phenol compounds are used singly or in combination of two or more.

  The aldehydes used to obtain the phenol resin include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, glyceraldehyde, Glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formyl acetic acid, methyl formyl acetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, repric acid, 4-acetylbutyric acid, acetone dicarboxylic acid Acid and 3,3′-4,4′-benzophenone tetracarboxylic acid And the like. In addition, a formaldehyde precursor such as paraformaldehyde or trioxane may be used in the reaction. These are used singly or in combination of two or more.

  Further, as the component (A), a novolac resin modified with a drying oil or an elastomer can be used. Use of such a novolak resin modified with a drying oil or an elastomer is preferable in that the flexibility (flexibility) of the cured film can be imparted.

  Dry oil is an ester of glycerin and unsaturated fatty acids, and has an iodine value of 130 or more. Specific examples of the drying oil include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia oil, coconut oil, and the like. Examples of the elastomer include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers.

  The drying oil and elastomer modification of the novolak resin is usually preferably performed at 50 to 130 ° C., and p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst as necessary.

(Poly (hydroxystyrene))
As poly (hydroxystyrene), for example, the ethylenically unsaturated double bond of hydroxystyrene introduced with a protecting group is polymerized (vinyl polymerization) in the presence of a catalyst (radical initiator) and further deprotected. What is obtained by this can be used. Further, branch type poly (hydroxystyrene) such as PHS-B (trade name of DuPont) may be used.

  Here, as the protective group for hydroxystyrene, conventionally known ones such as an alkyl group and a silyl group can be used. Further, styrene, (meth) acrylic acid ester, and the like can be copolymerized with hydroxystyrene having a protective group introduced.

  An alkali-soluble resin having a phenolic hydroxyl group obtained by reacting a part of the phenolic hydroxyl group of the component (A) with a polybasic acid anhydride can also be used as the component (A). By reacting the polybasic acid anhydride, the solubility of the component (A) in the alkaline aqueous solution (developer) is improved.

  As the polybasic acid anhydride, an acid anhydride of a polybasic carboxylic acid can be used. 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 acid, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, biphenyl Tetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetraca Aliphatic, such as carbon dianhydride, an aromatic tetracarboxylic acid dianhydride and the like.

  The reaction between the alkali-soluble resin having a phenolic hydroxyl group and the polybasic acid anhydride is carried out at 50 to 130 ° C., and the polybasic acid anhydride is 0.10 to 0.80 mole per mole of the phenolic hydroxyl group. The reaction is preferably carried out, more preferably from 0.15 to 0.60 mol, and further preferably from 0.20 to 0.40 mol. If the polybasic acid anhydride to be reacted is less than 0.10 mol, the polybasic acid anhydride to be reacted tends to be inferior in developability compared to the above range. When it exceeds, it exists in the tendency for the alkali resistance of an unexposed part to be inferior compared with the case where it exists in the said range.

  The molecular weight of the component (A) is preferably 1,000 to 500,000, and more preferably 2,000 to 200,000 in terms of weight average molecular weight in consideration of solubility in an aqueous alkali solution and balance between the photosensitive properties and the cured film properties. 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.

[Component (B): Compound that generates acid by light]
(B) The compound which produces | generates an acid by the light of a component is used as a photosensitive agent. Such a component (B) has a function of generating an acid by light irradiation and increasing the solubility of the irradiated portion in an alkaline aqueous solution. As the component (B), a compound generally called a photoacid generator can be used. Specific examples of the component (B) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. 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- And sulfonyl chloride.

  Examples of the hydroxy compound used in the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4- Trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3 , 4,3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethyli De Bruno [2,1-a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, and the like.

  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-hydroxypheny ) Hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, and the like.

  Examples of the dehydrochlorination 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 blending amount of the component (B) is preferably 3 to 100 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of the difference in dissolution rate between the exposed part and the unexposed part and the allowable width of sensitivity. 5 to 50 parts by weight is more preferable, and 5 to 30 parts by weight is most preferable.

[(C) component: core-shell polymer]
The core-shell polymer of component (C) is a polymer particle having a spherical core part and a shell part covering the core part. The core part is preferably formed from a polymer mainly composed of an elastomer and / or a rubbery polymer. The shell part is preferably formed from a polymer component graft polymerized to the core part.

(Core part)
The polymer that forms the core part is preferably one that does not inhibit grafting with the shell part. Examples of such polymers include diene rubber polymers such as butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber; butyl acrylate rubber, butadiene-butyl acrylate rubber, 2-ethylhexyl acrylate-butyl acrylate rubber, methacryl Acrylic rubber polymers such as 2-ethylhexyl acrylate-butyl acrylate rubber, stearyl acrylate-butyl acrylate rubber, dimethylsiloxane-butyl acrylate rubber, and silicon / butyl acrylate composite rubber; ethylene-propylene rubber, ethylene-propylene-diene rubber Examples thereof include olefin rubber polymers such as silicone rubber polymers such as polydimethylsiloxane, and these may be used alone or in admixture of two or more. Among these, styrene-butadiene rubber, acrylonitrile-butadiene rubber, 2-ethylhexyl acrylate-butyl acrylate rubber, and the like are preferable.

  The glass transition temperature of the core part is preferably 0 ° C. or lower, more preferably −10 ° C. or lower. When the glass transition temperature of the core part exceeds 0 ° C., the thermal expansion coefficient of the cured film of the positive photosensitive resin composition tends to increase. The glass transition temperature of the core part can be measured by a differential scanning calorimetry (DSC method).

(Shell part)
The polymer that forms the shell portion of the core-shell polymer is preferably bonded to the polymer that forms the core portion by graft polymerization or the like. The polymer forming the shell part preferably has a substituent selected from a carboxyl group, a hydroxyl group and an aromatic ring. Of these, the carboxyl group is preferably bonded to the polymer main chain via a side chain having 3 or more atoms. The number of atoms in the side chain interposed between the polymer main chain and the substituent is preferably 3 to 18, more preferably 6 to 12. When the number of atoms of this side chain is less than 3, the pot life of the positive photosensitive resin composition obtained by mixing with the component (A) or the component (B) is short, and the aggregates increase. There is a tendency for appearance and performance deterioration.

The shell part containing as a main component a polymer having a substituent selected from a carboxyl group, a hydroxyl group and an aromatic ring can be formed, for example, by polymerizing the following monomers.
(C1) one or more monomers selected from the group consisting of a half ester of dicarboxylic acid and hydroxyalkyl (meth) acrylic acid, a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having an aromatic ring;
(C2) a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule;
(C3) Other copolymerizable monomers.
Or
(C1) one or more monomers selected from the group consisting of a half ester of dicarboxylic acid and hydroxyalkyl (meth) acrylic acid, a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having an aromatic ring;
(C2) A monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule.

(Halfester of dicarboxylic acid and hydroxyalkyl (meth) acrylic acid)
The half ester of dicarboxylic acid and hydroxyalkyl (meth) acrylic acid is, for example, 2-hydroxyethyl acrylate and dicarboxylic anhydride such as succinic anhydride, phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, and the like It is obtained by reacting. Specific examples of such half esters include 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl. And hexahydrophthalic acid. You may use these individually or in mixture of 2 or more types. Among these, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid and the like are preferable.

  The dicarboxylic acid constituting the half ester is preferably one in which two carboxyl groups are bonded via an alkylene chain having 2 or more carbon atoms. A core-shell polymer obtained by using a half ester of dicarboxylic acid in which two carboxyl groups are bonded via methylene (1 carbon atom) or directly bonded is mixed with component (A) or component (B) The pot life of the subsequent positive photosensitive resin composition is short, and the aggregates tend to increase, causing problems such as appearance and performance deterioration.

((Meth) acrylate having hydroxyl group)
A polymer obtained by polymerizing a (meth) acrylate having a hydroxyl group is preferable in terms of excellent compatibility with the component (A), the component (B), and the like. Examples of the (meth) acrylate having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. These may be used alone or in admixture of two or more.

((Meth) acrylate with aromatic ring)
A polymer obtained by polymerizing a (meth) acrylate having an aromatic ring is preferable in that it has high compatibility with the component (A) and the component (B) and has excellent heat resistance. Examples of the (meth) acrylate having an aromatic ring include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) ) Acrylate, nonylphenol (meth) acrylate, nonylphenol ethylene oxide adduct (meth) acrylate, naphthyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, neopentyl glycol (meth) acrylic acid benzoate, Examples include 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid and 2- (meth) acryloyloxyethyl-2-hydroxypropyl-phthalic acid. These may be used alone or in combination of two or more. Of these, benzyl acrylate, phenoxyethyl acrylate, and neopentyl glycol acrylic acid benzoate are preferred.

(Monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule)
The polymer forming the shell part is obtained by polymerizing the monomer of the component (c1) listed above and a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule. Such a polymer is excellent in that the core-shell polymer can be a crosslinked particle. Examples of the monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,4-butane. Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acryl modified polydi Monomers having two or more (meth) acryloyl groups in the molecule such as tilsiloxane; Monomers having two or more vinyl groups in the molecule such as divinylbenzene; It can use individually or in combination of 2 or more types. Among these, 1,6-hexanediol diacrylate, diethylene glycol diacrylate and the like are preferable.

  The amount of the monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule is preferably 1 part by mass or more with respect to 100 parts by mass of all monomers forming the shell part, and 2 parts by mass or more. It is more preferable that When the amount of the monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule is less than 1 part by mass, crosslinking tends to be insufficient.

(Other copolymerizable monomers)
As the polymer that forms the shell portion, the monomer of the component (c1) listed above, a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule, and a copolymerizable monomer are polymerized. The resulting polymer can be used. Such a polymer is preferable from the viewpoint that both good graft polymerizability and improved affinity for the component (A) and the component (B) can be achieved. Examples of the copolymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, ( T-butyl (meth) acrylate, pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, ( (Meth) acrylates such as octadecyl (meth) acrylate, butoxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, glycidyl (meth) acrylate Α-methylstyrene, α-ethylstyrene, α-fluorostyrene, α-chlorostyrene, α-bromo Aromatic vinyl compounds such as styrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, methoxystyrene; (meth) acrylamides such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide ; Unsaturation of (meth) acrylic acid metal salts such as calcium (meth) acrylate, barium (meth) acrylate, lead (meth) acrylate, tin (meth) acrylate acrylate, zinc (meth) acrylate Fatty acids; vinyl cyanide compounds such as (meth) acrylonitrile, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, (Meta) a Norbornyl methyl rillate, cyanonorbornyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fentil (meth) acrylate, (meth) acrylic acid Adamantyl, dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] dec-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2, (meth) acrylate ⁶ ] Deca-4-methyl, (meth) acrylic acid ester having an alicyclic hydrocarbon group such as cyclodecyl (meth) acrylate; N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Ni- Propyl maleimide, N-butyl maleimide, Ni-butyl maleimide, Nt-butyl maleimide, N-lauryl maleimide N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (4-bromophenyl) phenylmaleimide, N- (2-methyl Phenyl) maleimide, N- (2-ethylphenylmaleimide, N- (2-methoxyphenyl) maleimide, N- (2,4,6-trimethylphenyl) maleimide, N- (4-benzylphenyl) maleimide, N- ( N-substituted maleimides such as 2,4,6-tribromophenyl) maleimide; and the like. Moreover, you may use these by 1 type (s) or 2 or more types. Among these, n-butyl acrylate, 2-ethylhexyl acrylate and the like are preferable.

  The amount of other copolymerizable monomer used is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of all monomers forming the shell part.

The theoretical glass transition temperature of the shell part is preferably 20 ° C. or less, more preferably 10 ° C. or less, and particularly preferably 0 ° C. or less. The theoretical glass transition temperature of the shell part can be calculated from the following equation. 1 / Tg = W ₁ / T ₁ + W ₂ / T ₂ +... W _n / T _{n In the} formula, W ₁ , W ₂ ... W _n is the mass% of each monomer (= (the amount of each monomer) / Total monomer mass) × 100), and T ₁ , T ₂ ... T _n are the glass transition temperatures (absolute temperatures) of the homopolymer of each monomer.

  The mass ratio of the core part / shell part in the core-shell polymer is preferably in the range of 30/70 to 90/10, and more preferably in the range of 40/60 to 80/20. When the mass ratio of the core part / shell part exceeds 30/70 (the ratio of the core part is less than 30), the toughness of the photosensitive resin cured film tends to decrease. When the mass ratio of the core part / shell part exceeds 90/10 (the ratio of the shell part is less than 10), the core-shell polymer tends to aggregate and tends to cause a problem in operability.

  The particle diameter of the core-shell polymer is preferably 30 to 500 nm, more preferably 40 to 200 nm, and particularly preferably 45 to 150 nm. When the particle size is less than 30 nm, it is difficult to obtain a core having a particle size smaller than 30 nm, and this tends to be unfavorable from the viewpoint of mass productivity. When the particle size exceeds 500 nm, the heat resistance of the resulting cured cured photosensitive resin film Tend to decrease the mechanical properties and mechanical properties.

  The particle diameter of the core-shell polymer can be measured using an ultrafine particle size distribution meter (MICROTRAC UPA150 manufactured by Lees & Northrup). The method for controlling the particle size of the core-shell polymer is not particularly limited. For example, when the core-shell polymer is synthesized by emulsion polymerization, the particle size is controlled by controlling the number of micelles during emulsion polymerization according to the amount of emulsifier used. be able to.

  In addition to the core-shell polymer listed in this embodiment, the core-shell polymers described in US Pat. No. 3,322,852 and US Pat. No. 3,496,250 can also be suitably exemplified as the core-shell polymer of the present invention. .

  (C) The compounding quantity of the core shell polymer which is a component is 1-50 mass parts with respect to 100 mass parts of alkali-soluble resin which has the phenolic hydroxyl group which is (A) component, Preferably it is 5-30 mass parts. When the blending amount of the core-shell polymer is less than 1 part by mass, the mechanical properties of the obtained cured film tend to deteriorate. If it exceeds 50 parts by mass, the resolution and the heat resistance of the cured film obtained will tend to decrease, and the compatibility and dispersibility with other components will tend to decrease.

[(D) component: solvent]
Component (D) is a solvent. Specific examples thereof 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 glycol Examples thereof include monobutyl ether and dipropylene glycol monomethyl ether.

  These solvents can be used alone or in combination of two or more. Moreover, the compounding quantity of (D) component is although it does not specifically limit, It is preferable to adjust so that the ratio of the solvent in a positive type photosensitive resin composition may be 20 to 90 weight%.

[(E) component: thermal crosslinking agent]
In the positive photosensitive resin composition of the present invention, in addition to the components (A) to (D), a thermal crosslinking agent can be used as the component (E). The thermal crosslinking agent reacts with the component (A) by heating at the time of curing of the film after pattern formation, that is, bridges. Thereby, the brittleness of the film and the melting of the film can be prevented. A compound having a phenolic hydroxyl group is preferable because it has not only an effect as a thermal crosslinking agent but also an effect of increasing the dissolution rate of the exposed area and increasing the sensitivity when developing with an alkaline aqueous solution by blending. As such a thermal crosslinking agent, specifically, a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, a compound having an epoxy group, or the like can be used.

(Compound having phenolic hydroxyl group)
The molecular weight of the compound having a phenolic hydroxyl group is preferably 2000 or less. Considering the balance between the solubility in an aqueous alkali solution and the photosensitive property, the number average molecular weight is preferably 94 to 2000, more preferably 108 to 2000, and most preferably 108 to 1500.

  Moreover, as a compound having a phenolic hydroxyl group, a conventionally known compound can be used, but the compound represented by the following general formula (I) prevents dissolution at the time of curing of the film and the effect of promoting the dissolution of the exposed area. It is particularly preferred because of its excellent balance of effects.

（Ｉ）

(I)

In formula (I), X represents a single bond or a divalent organic group, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent organic group, and s and t are each Independently represents an integer of 1 to 3, and u and v each independently represent an integer of 0 to 4.

  In general formula (I), the compound in which X is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by X include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group and propylene group, alkylidene groups having 2 to 10 carbon atoms such as ethylidene group, and phenylene groups. Arylene groups having 6 to 30 carbon atoms, such as groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, sulfone groups, carbonyl groups, ether bonds, thioether bonds, amide bonds Etc. Among these, a divalent organic group represented by the following general formula (II) is preferable.

（ＩＩ）

(II)

  In the formula (II), X ′ is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), or one of these hydrogen atoms. A group, a sulfone group, a carbonyl group, an oxy group, a thio group, or an amide group, part or all of which are substituted with a halogen atom, R ″ represents a hydrogen atom, a hydroxy group, an alkyl group, or a haloalkyl group; 10 represents an integer, and a plurality of R ″ may be the same as or different from each other.

(Compound having a hydroxymethylamino group)
Compounds having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N-hydroxy It is a nitrogen-containing compound obtained by alkyl etherifying all or part of an active methylol group such as methyl) urea. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like.

(Compound having an epoxy group)
The compound having an epoxy group is not particularly limited, but bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, glycidylamine, heterocyclic epoxy, polyalkylene Examples include glycol diglycidyl ether.

  In addition to this, as the thermal crosslinking agent as component (E), bis {3,4-bis (hydroxymethyl) phenyl} ether, 1,3,5-tris (1-hydroxy-1-methylethyl) benzene and the like Aromatic compounds having a hydroxymethyl group; compounds having a maleimide group such as bis (4-maleimidophenyl) methane and 2,2-bis {4- (4′-maleimidophenoxy) phenyl} propane; compounds having a norbornene skeleton; A polyfunctional acrylate compound; a compound having an oxetanyl group; a compound having a vinyl group; a blocked isocyanate compound and the like can be used.

  The component (E) is preferably a compound having a phenolic hydroxyl group and / or a compound having a hydroxymethylamino group from the viewpoint of improving sensitivity and heat resistance.

  In the case where such component (E) is blended, the blending amount is based on the development time, the allowable width of the unexposed part remaining film ratio, and the characteristics of the cured film with respect to 100 parts by weight of component (A) 1 to 50 parts by mass is preferable, 2 to 30 parts by mass is more preferable, and 3 to 25 parts by mass is most preferable. Moreover, (E) component is used individually by these 1 type or in combination of 2 or more types.

  In addition to the components (A) to (D) and (E), the positive photosensitive resin composition described above includes (1) a compound that generates an acid by heating, (2) a dissolution accelerator, and (3) dissolution. You may mix | blend components, such as an inhibitor, (4) coupling agent, and (5) surfactant or a leveling agent.

[(1) Compound that generates acid by heating]
By using a compound that generates an acid by heating separately from the component (B), it becomes possible to generate an acid at the time of heating, and the reaction between the component (A) and the component (E), that is, the thermal crosslinking reaction is promoted. . This improves the heat resistance of the cured film. In addition, some compounds that generate an acid upon heating generate an acid even when irradiated with light. In this case, the solubility of an exposed portion in an alkaline aqueous solution increases. Therefore, the difference in solubility in the alkaline aqueous solution between the unexposed area and the exposed area is increased, and the resolution is improved.

  It is preferable that the compound which produces | generates an acid by such a heating is what produces | generates an acid by heating to 50-250 degreeC, for example. Specific examples include onium salts, pyridinium salts, imide sulfonates, and the like.

  Examples of the onium salt include diaryliodonium salts such as aryldiazonium salts and diphenyliodonium salts; diaryliodonium salts and di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; trimethylsulfonium salts and the like. A trialkylsulfonium salt; a dialkylmonoarylsulfonium salt such as dimethylphenylsulfonium salt; a diarylmonoalkyliodonium salt such as diphenylmethylsulfonium salt; and a triarylsulfonium salt. Among these, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid, di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid Phenylsulfonium salt, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di (t-butylphenyl) iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, benzenesulfonic acid Dimethylphenylsulfonium salt and diphenylmethylsulfonium salt of toluenesulfonic acid are preferred.

  Further, as a compound that generates an acid by heating, a salt formed from a strong acid other than an onium salt and a base, more specifically, a pyridinium salt can be used. Examples of the strong acid include aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid; methanesulfonic acid and ethane Examples thereof include alkylsulfonic acids such as sulfonic acid and butanesulfonic acid. As the base, pyridine, alkylpyridine such as 2,4,6-trimethylpyridine; N-alkylpyridine such as 2-chloro-N-methylpyridine; halogenated-N-alkylpyridine and the like are desirable.

  As the imide sulfonate, for example, naphthoyl imide sulfonate or phthalimide sulfonate can be used.

In addition to the compounds described above, a compound having a structure represented by the following general formula (III) or a compound having a sulfonamide structure represented by the following general formula (IV) is used as a compound that generates an acid by heating. You can also.

R ⁵ R ⁶ C═N—O—SO ₂ —R ⁷ (III)

—HN—SO ₂ —R ⁸ (IV)

In formula (III), R ⁵ is, for example, a cyano group, and R ⁶ is, for example, a methoxyphenyl group, a phenyl group, or the like. R ⁷ is, for example, an aryl group such as p-methylphenyl group or phenyl group, an alkyl group such as methyl group, ethyl group or isopropyl group, or a perfluoroalkyl group such as trifluoromethyl group or nonafluorobutyl group. is there.

In the formula (IV), R ⁸ is, for example, an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a methylphenyl group or a phenyl group, a perfluoroalkyl group such as a trifluoromethyl group or nonafluorobutyl. It is. Examples of the group bonded to the N atom of the sulfonamide structure represented by the general formula (IV) include 2,2′-bis (4-hydroxyphenyl) hexafluoropropane and 2,2′-bis (4-hydroxy). Phenyl) propane and di (4-hydroxyphenyl) ether.

  0.1-30 mass parts is preferable with respect to 100 mass parts of (A) component, as for the compounding quantity of the compound which produces | generates an acid by heating, 0.2-20 mass parts is more preferable, 0.5-10 mass parts Is more preferable.

[(2) Dissolution promoter]
By adding a dissolution accelerator to the positive photosensitive resin described above, the dissolution rate of the exposed area when developing with an alkaline aqueous solution is increased, and the sensitivity and resolution are improved, as in the case of component (A). be able to. 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.

  When such a dissolution accelerator is blended, the blending amount can be determined by the dissolution rate with respect to the alkaline aqueous solution, for example, 0.01 to 30 parts by weight with respect to 100 parts by weight of component (A). be able to.

[(3) Dissolution inhibitor]
A dissolution inhibitor is a compound that inhibits the solubility of the component (A) in an alkaline aqueous solution, and can be contained in the positive photosensitive resin composition. Specific examples of the dissolution inhibitor include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like. These are useful for controlling the remaining film thickness, development time and contrast. In the case where a dissolution inhibitor is blended, the blending amount is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of component (A), in terms of sensitivity and an allowable range of development time, and 0.01 to 15 Mass parts are more preferable, and 0.05 to 10 parts by mass are even more preferable.

[(4) 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-butylsiphenylsilanediol, 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 (dipropyldroxysilyl) benzene, 1,4-bis (dibutylhydroxy) And silyl) benzene.

  0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for the compounding quantity in the case of using such a coupling agent, 0.5-10 mass parts is more preferable.

[(5) Surfactant or leveling agent]
By adding the surfactant or leveling agent to the positive photosensitive resin composition, it is possible to prevent coatability, for example, striation (thickness unevenness) or improve developability. Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like, and Megafax F171 is a commercially available product. F173, R-08 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (trade name, Sumitomo 3M), organosiloxane polymers KP341, KBM303, KBM403, KBM803 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) ) And the like.

  In the case of using such a surfactant or leveling agent, the total blending amount is preferably 0.001 to 5 parts by mass, and 0.01 to 3 parts by mass with respect to 100 parts by mass of the component (A). More preferred.

  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 is possible to form a pattern with a good shape having a sufficiently high sensitivity and resolution and having good adhesion and heat resistance.

[Method for producing resist pattern]
Next, an embodiment of a resist pattern manufacturing method will be described. In the method for producing a resist pattern according to the present embodiment, the above-described positive photosensitive resin composition is applied onto a support substrate, and the solvent is removed from the applied positive photosensitive resin composition by drying to provide a photosensitive resin. A drying process for forming a film; an exposure process for exposing the photosensitive resin film; a developing process for developing the exposed photosensitive resin film with an alkaline aqueous solution to form a resist pattern; and a photosensitive resin film after development. A heating step of heating. Hereinafter, each step will be described.

(Coating / drying (film formation) process)
First, in the step of applying and drying a positive photosensitive resin composition on a support substrate, on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO _2, etc.), silicon nitride, The above-described positive photosensitive resin composition is spin-coated using a spinner or the like, and then the support substrate is dried using a hot plate, an oven, or the like. As a result, a film of the positive photosensitive resin composition is formed on the support substrate.

(Exposure process)
Next, in the exposure step, the photosensitive resin composition (photosensitive resin film) formed as a film on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In the present invention, the alkaline aqueous solution-soluble polymer of the photosensitive resin composition has high transparency to i-line, and therefore, i-line irradiation can be suitably used. It should be noted that after exposure, post-exposure heating (PEB) may be performed as necessary, and then the development process may be performed. The post-exposure heating temperature is preferably 70 ° C. to 140 ° C., and the post-exposure heating time is preferably 1 minute to 5 minutes.

(Development process)
In the development step, a resist pattern is obtained by removing the exposed portion of the photosensitive resin film exposed to actinic rays with a developer. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH). 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.

(Heating process)
Next, in the heating step, the formed resist pattern is heated. The resist pattern is cured by this heating. The heating temperature is 250 ° C. or less, desirably 225 ° C. or less, and more desirably 140 to 200 ° C.

  Heating can be performed using an oven such as a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the process under nitrogen because the oxidation of the photosensitive resin film can be prevented. Since the above-described heating temperature range is lower than the conventional heating temperature, damage to the support substrate and the device can be reduced. Therefore, by using the resist pattern manufacturing method of the present invention, electronic components can be manufactured with high yield. It also leads to energy savings in the process. Furthermore, according to the positive photosensitive resin composition of the present invention, since the volume shrinkage (curing shrinkage) in the heat treatment step found in photosensitive polyimide or the like is small, it is possible to prevent a reduction in dimensional accuracy.

  The heating time in the heating step may be a time sufficient for the positive photosensitive resin composition to cure, but is preferably approximately 5 hours or less in view of work efficiency.

(Microwave curing)
In the heating step, a microwave curing device or a variable frequency microwave curing device can be used in addition to the above-described nitrogen-substituted oven. By using these, it is possible to effectively heat only the photosensitive resin film while keeping the temperature of the substrate or device at, for example, 200 ° C. or lower.

  In the variable frequency microwave curing apparatus, the microwave is irradiated in pulses while changing its frequency, so that standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when a metal wiring is included as an electronic component to be described later as a substrate, the occurrence of discharge from the metal can be prevented by irradiating microwaves in a pulsed manner while changing the frequency, and the electronic component is protected from destruction. It is preferable in that it can be performed. Furthermore, heating using a frequency-variable microwave is preferable because the cured film properties do not deteriorate even when the curing temperature is lowered as compared to an oven (see J. Photopolym. Sci. Technol., 18, 327-332 (2005)). .

  The frequency of the frequency variable microwave is in the range of 0.5 to 20 GHz, but is practically preferably in the range of 1 to 10 GHz, and more preferably in the range of 2 to 9 GHz. In addition, it is desirable to continuously change the frequency of the microwave to be irradiated, but actually the irradiation is performed by changing the frequency stepwise. At that time, the shorter the time for irradiating a single-frequency microwave, the less likely it is to generate a standing wave or a metal discharge. Therefore, the irradiation time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

  The output of the microwave to be irradiated varies depending on the size of the apparatus and the amount of the object to be heated, but is generally in the range of 10 to 2000 W, practically preferably 100 to 1000 W, more preferably 100 to 700 W, further preferably 100 to 700 W. 500 W is most preferred. If the output is 10 W or less, it is difficult to heat the object to be heated in a short time, and if it is 2000 W or more, a rapid temperature rise tends to occur.

  Moreover, it is preferable to irradiate the microwave by turning it on / off in a pulsed manner. By irradiating the microwaves in a pulsed manner, it is preferable in that the set heating temperature can be maintained and damage to the cured film and the substrate can be avoided. Although the time for irradiating the pulsed microwave at one time varies depending on the conditions, it is preferably about 10 seconds or less.

According to the method for producing a resist pattern as described above, a resist pattern having good heat resistance can be obtained with sufficiently high sensitivity and resolution.

[Semiconductor device manufacturing process]
Next, as an example of the resist pattern manufacturing method of the present invention, a semiconductor device manufacturing process will be described with reference to the drawings. 1 to 5 are schematic sectional views showing an embodiment of a manufacturing process of a semiconductor device having a multilayer wiring structure.

  First, the structure 100 shown in FIG. 1 is prepared. The structure 100 includes a semiconductor substrate 1 such as an Si substrate having circuit elements, a protective film 2 such as a silicon oxide film covering the semiconductor substrate 1 having a predetermined pattern from which the circuit elements are exposed, and on the exposed circuit elements. And the interlayer insulating film 4 made of a polyimide resin or the like formed on the protective film 2 and the first conductor layer 3 by a spin coating method or the like.

  Next, by forming the photosensitive resin layer 5 having the window portion 6A on the interlayer insulating film 4, the structure 200 shown in FIG. 2 is obtained. The photosensitive resin layer 5 is formed, for example, by applying a photosensitive resin such as chlorinated rubber, phenol novolac, polyhydroxystyrene, or polyacrylate ester by a spin coating method. The window portion 6A is formed so that a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique.

  After the interlayer insulating film 4 is etched to form the window 6B, the photosensitive resin layer 5 is removed to obtain a structure 300 shown in FIG. For etching the interlayer insulating film 4, dry etching means using a gas such as oxygen or carbon tetrafluoride can be used. By this etching, the portion of the interlayer insulating film 4 corresponding to the window portion 6A is selectively removed, and the interlayer insulating film 4 provided with the window portion 6B so that the first conductor layer 3 is exposed is obtained. Next, the photosensitive resin layer 5 is removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.

  Furthermore, the 2nd conductor layer 7 is formed in the part corresponding to the window part 6B, and the structure 400 shown in FIG. 4 is obtained. A known photolithography technique can be used to form the second conductor layer 7. As a result, the second conductor layer 7 and the first conductor layer 3 are electrically connected.

  Finally, the surface protective layer 8 is formed on the interlayer insulating film 4 and the second conductor layer 7 to obtain the semiconductor device 500 shown in FIG. In the present embodiment, the surface protective layer 8 is formed as follows. First, the positive photosensitive resin composition according to the above-described embodiment is applied onto the interlayer insulating film 4 and the second conductor layer 7 by spin coating, and dried to form a photosensitive resin film. Next, after light irradiation through a mask on which a pattern corresponding to the window 6C is drawn at a predetermined portion, the photosensitive resin film is patterned by developing with an alkaline aqueous solution. Thereafter, the patterned photosensitive resin film (resist pattern) is cured by heating to form a film as the surface protective layer 8. The surface protective layer 8 protects the first conductor layer 3 and the second conductor layer 7 from external stress, α rays, and the like, and the obtained semiconductor device 500 is excellent in reliability.

  In the above-described embodiment, the method for manufacturing a semiconductor device having a two-layer wiring structure is shown. However, when a multilayer wiring structure having three or more layers is formed, the above steps are repeated to form each layer. Can do. That is, it is possible to form a multilayer pattern by repeating each step of forming the interlayer insulating film 4 and each step of forming the surface protective layer 8. In the above example, not only the surface protective layer 8 but also the interlayer insulating film 4 can be formed using the positive photosensitive resin composition of the present invention.

[Electronic parts]
Next, the electronic component of the present invention will be described. The electronic component of the present invention has a resist pattern formed by the above-described manufacturing method using the above-described positive photosensitive resin composition as an interlayer insulating film or a surface protective layer. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like. The resist pattern can be used specifically as a surface protective layer or an interlayer insulating film of a semiconductor device, an interlayer insulating film of a multilayer wiring board, or the like. The electronic component of the present invention is not particularly limited except that it has a surface protective layer and an interlayer insulating film formed using the above-described positive photosensitive resin composition, and can have various structures.

[Other structures]
Moreover, since the positive photosensitive resin composition of the present invention is excellent in stress relaxation property, adhesiveness, and the like, it can be used as various structural materials in packages having various structures developed in recent years. 6 and 7 show a cross-sectional structure of an example of such a semiconductor device.

  FIG. 6 is a schematic cross-sectional view showing a wiring structure as an embodiment of the semiconductor device. The semiconductor device 600 shown in FIG. 6 includes a silicon chip 23, an interlayer insulating film 11 provided on one surface side of the silicon chip 23, and an Al having a pattern including the pad portion 15 formed on the interlayer insulating film 11. A wiring layer 12, an insulating layer 13 (for example, a P-SiN layer) and a surface protective layer 14, which are sequentially stacked on the interlayer insulating film 11 and the Al wiring layer 12 while forming an opening on the pad portion 15, and a surface protective layer 14 in contact with the pad portion 15 in the openings of the insulating layer 13 and the surface protective layer 14 and the surface of the core 18 opposite to the surface protective layer 14. And a rewiring layer 16 extending on the surface protective layer 14. Further, the semiconductor device 600 is formed so as to cover the surface protective layer 14, the core 18, and the rewiring layer 16, and a cover coat layer 19 in which an opening is formed in a portion of the rewiring layer 16 on the core 18. The conductive ball 17 connected to the rewiring layer 16 with the barrier metal 20 interposed therebetween in the opening of the layer 19, the collar 21 that holds the conductive ball, and the cover coat layer 19 around the conductive ball 17 are provided. The underfill 22 is provided. The conductive ball 17 is used as an external connection terminal and is formed of solder, gold or the like. The underfill 22 is provided to relieve stress when the semiconductor device 600 is mounted.

  FIG. 7 is a schematic cross-sectional view showing a wiring structure as one embodiment of a semiconductor device. In the semiconductor device 700 of FIG. 7, an Al wiring layer (not shown) and the pad portion 15 of the Al wiring layer are formed on the silicon chip 23, and an opening is formed on the pad portion 15 in the upper part. An insulating layer 13 laminated on the Al wiring layer is formed, and a surface protective layer 14 of the element is further formed. A rewiring layer 16 is formed on the pad portion 15, and the rewiring layer 16 extends to an upper portion of the connection portion 24 with the conductive ball 17. Further, a cover coat layer 19 is formed on the surface protective layer 14. The rewiring layer 16 is connected to the conductive ball 17 through the barrier metal 20.

  6 and 7, the positive photosensitive resin composition described above includes not only the interlayer insulating layer 11 and the surface protective layer 14 but also the cover coat layer 19, the core 18, the collar 21, the underfill 22, and the like. It can be used as a material for forming. The cured body using the positive photosensitive resin composition described above is excellent in adhesion with a metal layer such as the Al wiring layer 12 and the rewiring layer 16 and a sealing agent, and has a high stress relaxation effect. A semiconductor device in which the body is used for the cover coat layer 19, the core 18, the collar 21 such as solder, the underfill 12 used in a flip chip or the like has extremely high reliability.

  As described above, by using the positive photosensitive resin composition described above, curing using low-temperature heating of 200 ° C. or lower is possible in the heat treatment step that conventionally required 300 ° C. or higher. . Furthermore, since the positive photosensitive resin composition of the present invention has a small volume shrinkage (curing shrinkage) in the heat treatment step found in photosensitive polyimide and the like, it can prevent a reduction in dimensional accuracy. The cured film of the positive photosensitive resin composition has a high glass transition temperature. Accordingly, the surface protective layer is excellent in heat resistance. As a result, an electronic component such as a semiconductor device having excellent reliability can be obtained with high yield and high yield.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

(Synthesis Example 1: Synthesis of polymer (A3) soluble in alkaline aqueous solution)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged. After cooling to 5 ° C., 12.64 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether tetracarboxylic acid chloride. Next, 87.50 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1, 18.30 g of 3,3,3-hexafluoropropane was added. After dissolving this with stirring, 8.53 g of pyridine was added. Then, while maintaining the temperature at 0 to 5 ° C., the above 4,4′-diphenyl ether dicarboxylic acid chloride solution was dropped over 30 minutes, and then stirring was continued for 30 minutes. The reaction solution was poured into 3 liters of water, and the precipitate was collected. The precipitate was washed three times with pure water and then dried under reduced pressure to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as “A3”). The weight-average molecular weight determined by GPC standard polystyrene conversion of A3 was 14600, and the degree of dispersion was 1.6.

(Synthesis Example 2: Synthesis of core-shell polymer (C2))
1360 g of pure water, 328 g of an aqueous solution obtained by diluting Emulgen 109P (nonionic surfactant, trade name, manufactured by Kao Corporation) to 30% by mass in advance (net nonionic surfactant: 98 g), and Nipol 1562 (acrylonitrile-butadiene rubber, 800 g of Nippon Zeon product name, glass transition temperature-20 ° C.) was placed in a 4 L glass container and mixed by stirring, and the inside of the container was purged with nitrogen. Thereafter, 280 g of butyl acrylate, 15 g of 1,6-hexanediol diacrylate, 31 g of 2-acryloyloxyethyl phthalic acid, and 4 g of cumene hydroperoxide as a polymerization initiator were added and stirred for 1 hour. The temperature was raised to ° C. After the temperature increase, an aqueous potassium persulfate solution in which 0.15 parts by weight of potassium persulfate was dissolved in 2 parts by weight of pure water was added, and the temperature was raised to 60 ° C. After the temperature rise, 6 g of sodium pyrophosphate and 0.008 g of iron (II) sulfate dissolved in 50 g of pure water were added and stirring was continued for 6 hours to obtain a polymer emulsion in which the core-shell polymer was dispersed. The reaction rate at this time was 95%. The weight ratio of the core part / shell part of the obtained core-shell polymer was 50/50. Moreover, the glass transition temperature (theoretical glass transition temperature) of the shell part was −51 ° C.

The average particle size of the core-shell polymer in the obtained polymer emulsion was measured in the state of the emulsion subjected to the following treatment using an ultrafine particle size distribution meter (MICROTRAC UPA150 manufactured by Lees & Northrup). The obtained polymer emulsion was diluted 100 times with pure water, and irradiated with ultrasonic waves for 3 minutes using an ultrasonic cleaner (LEO Ultrasonic LEO-80: frequency 46 Hz, output 80 W). The polymer was dispersed. The emulsion in which the core-shell polymer was dispersed was put in the particle size distribution meter, and the particle size was measured. The measurement time was 3 minutes.
Measurement condition light source: Diode laser (780 nm, 3 mW)
Measurement range: Full range (0.0032 to 6.5406 μm)
Particle properties: transparent, spherical particle dispersion medium: analysis of measurement data obtained by a program attached to water (MICROTRAC Data Handling System SD-UPA150-100, manufactured by Mountec). 50% average particle diameter of core-shell polymer Was 70 nm.

  The core-shell polymer in the polymer emulsion was extracted with a solvent (propylene glycol monomethyl ether acetate) to obtain a core-shell polymer C2.

(Synthesis Example 3: Synthesis of core-shell polymer (C3))
A core-shell polymer C3 was obtained in the same manner as in Example 2 except that 31 g of 2-acryloyloxyethylphthalic acid in Synthesis Example 2 was changed to 31 g of hydroxypropyl acrylate. In addition, when the average particle diameter of the core-shell polymer in the polymer emulsion was measured in the same manner as in Example 2, it was 70 nm. The theoretical glass transition temperature of the shell portion was -47 ° C.

(Synthesis Example 4: Synthesis of core-shell polymer (C4))
A core-shell polymer C4 was obtained in the same manner as in Example 2 except that 31 g of 2-acryloyloxyethylphthalic acid in Synthesis Example 2 was changed to 31 g of neopentyl glycol acrylate benzoate.
In addition, when the average particle diameter of the core-shell polymer in the polymer emulsion was measured in the same manner as in Example 2, it was 70 nm. The theoretical glass transition temperature of the shell part was -46 ° C.

<Preparation of positive photosensitive resin composition>
The following A1, A2, and A3 were prepared as the component (A).
A1: m-cresol / p-cresol = 60/40 (molar ratio) cresol novolac resin (polystyrene equivalent weight average molecular weight = 7000, trade name EP4050G manufactured by Asahi Organic Materials Co., Ltd.)
A2: 4-hydroxystyrene / methyl methacrylate = 50/50 (molar ratio) copolymer (polystyrene-converted weight average molecular weight = 10000, trade name Maruka Linker CMM manufactured by Maruzen Petrochemical Co., Ltd.)
A3: Polymer synthesized in Synthesis Example 1 above

The following B1 was prepared as the component (B).
B1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1-naphthoquinone-2-diazide-5-sulfonic acid Ester (Esterification rate of about 90%, trade name TPPA528 manufactured by AZ Electronic Materials)

As the component (C), the following C1, C2, and C3 were prepared.
C1: Core-shell polymer formed from a butadiene-styrene-methacrylate copolymer (Rohm and Haas product name Paraloid EXL2655)
C2: Core-shell polymer synthesized in Synthesis Example 2 C3: Core-shell polymer synthesized in Synthesis Example 3 C4: Core-shell polymer synthesized in Synthesis Example 4

As the component (D), the following E1 and E2 were prepared.
D1: Ethyl lactate D2: Mixture of γ-butyrolactone and propylene glycol monomethyl ether acetate (weight ratio 90/10)

As the component (E), the following D1 and D2 were prepared.
E1: Hexamethoxymethyl melamine (CYTEC company product name CYMEL300)
E2: 1,1-bis {3,5-bis (methoxymethyl) -4-hydroxyphenyl} methane (trade name TMOM-pp-BPF manufactured by Honshu Chemical Industry Co., Ltd.)

The following γ1 and γ2 were prepared as comparative compounds.
γ1: particulate modified acrylonitrile-butadiene copolymer (extracted from ZEON SX1503A solvent (propylene glycol monomethyl ether acetate))
γ2: Liquid butadiene-acrylonitrile copolymer (Ube Industries, Ltd. trade name HYCAR CTBNX-1300)

(Examples 1 to 10)
(A)-(E) component was mix | blended in the predetermined | prescribed ratio shown in Table 1, and also 2 weight part of 50% methanol solutions of urea propyltriethoxysilane were mix | blended as a coupling agent. This solution was pressure filtered using a 3 μm pore Teflon (registered trademark) filter to obtain positive type photosensitive resin composition solutions (M1 to M10) of Examples 1 to 10.

(Comparative Examples 1-3)
Components (A) to (E) and the compound for comparative example were blended in the prescribed proportions shown in Table 1, and 2 parts by weight of a 50% methanol solution of urea propyltriethoxysilane was blended as a coupling agent. This solution was subjected to pressure filtration using a 3 μm pore Teflon (registered trademark) filter to obtain positive type photosensitive resin composition solutions (M11 to M13) of Comparative Examples 1 to 3.

<Evaluation of positive photosensitive resin composition>
[Photosensitive characteristics]
The positive photosensitive resin composition solutions (M1 to M13) obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were spin coated on a silicon substrate, heated at 100 ° C. for 5 minutes, and a film thickness of 11 A coating of ˜13 μm was formed. Thereafter, reduction projection exposure was performed with i-line (365 nm) through a mask using an i-line stepper (FPA-3000iW manufactured by Canon). After the exposure, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH), and development was performed so that the remaining film thickness was about 70 to 95% of the initial film thickness. Thereafter, the substrate was rinsed with water, and the minimum exposure amount necessary for pattern formation and the size of the smallest open square hole pattern were determined. Table 2 shows the results of evaluation using the minimum exposure amount as sensitivity and the size of the smallest open square hole pattern as resolution.

[Patterning of cured film properties measurement sample]
The positive photosensitive resin composition solutions (M1 to M13) obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were spin-coated on a silicon substrate and heated at 100 ° C. for 5 minutes to obtain a film thickness of about A coating film of 12 to 14 μm was formed. Thereafter, the coating films of the resins M1 to M13 were exposed at all wavelengths through a mask using a proximity exposure machine (PLA-600FA manufactured by Canon). After exposure, development was performed with a 2.38% aqueous solution of TMAH to obtain a 10 mm wide rectangular pattern. Thereafter, the coating film was heat-treated (cured) by the following method (i), (ii) or (iii) to obtain a cured film having a thickness of about 10 μm. Table 3 shows the curing conditions and the shrinkage ratio of the film thickness before and after curing ((1−film thickness after curing) / film thickness before curing) × 100) [%].
(I) Using a vertical diffusion furnace (μ-TF manufactured by Koyo Thermo System), the coating film was heat-treated in nitrogen at a temperature of 180 ° C. (heating time: 1.5 hours) for 2 hours.
(Ii) Using a vertical diffusion furnace (μ-TF manufactured by Koyo Thermo Systems Co., Ltd.), the coating film was heat-treated in nitrogen at a temperature of 200 ° C. (temperature rising time: 1.5 hours) for 2 hours.
(Iii) Using a frequency-variable microwave curing furnace (Microcure 2100 manufactured by Lambda Technology), microwave output 450 W, microwave frequency 5.9 to 7.0 GHz, temperature 170 ° C. (temperature rising time 5 minutes), heating for 2 hours Processed.

[Hardened film properties]
The cured film having a thickness of about 10 μm obtained in the above-mentioned “patterning of cured film physical property measurement sample” was peeled off from the silicon substrate, and the glass transition temperature (Tg) of the peeled film was measured with TMA / SS600 manufactured by Seiko Instruments Inc. Note that the width of the sample is 2 mm, the film thickness is 9 to 11 μm, and the distance between chucks is 10 mm. The load is 10 g, and the rate of temperature increase is 5 ° C./min. Further, the average breaking elongation (EL) of the release film was measured by an autograph AGS-H100N manufactured by Shimadzu Corporation. The width of the sample is 10 mm, the film thickness is 9 to 11 μm, and the distance between chucks is 20 mm. The pulling speed is 5 mm / min, and the measurement temperature is about room temperature (20 ° C. to 25 ° C.). Here, let the average of five or more measured values be "average breaking elongation (EL)" about the cured film obtained on the same conditions. The measured Tg and EL are shown in Table 3.

[Dielectric constant measurement]
The positive photosensitive resin composition solutions (M1 to M13) obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were spin-coated on a low resistance silicon substrate and heated at 100 ° C. for 5 minutes to form a film. A coating film having a thickness of about 11 μm was formed. The coating film on the substrate was cured under the curing conditions shown in Table 3. Next, an aluminum electrode having a diameter of 2 mm was formed on the cured film using a vacuum deposition apparatus. Next, the charge capacity between the aluminum electrode and the silicon substrate was measured using a measuring device in which a dielectric fixture Yokogawa Electric test fixture HP16451 was connected to the LF impedance analyzer HP4192A manufactured by Yokogawa Electric Corporation. The measurement environment was room temperature (20 ° C. to 25 ° C.), the humidity was 40% to 50% RH, the measurement frequency was 10 kHz, and the bias voltage was −35V. The relative dielectric constant of the cured film was determined from the measured charge capacity value of the electrode and the film thickness value near the electrode. The results are shown in Table 3.

[Stud pull test]
The positive type photosensitive resin composition solutions (M1 to M13) obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were placed on a substrate (after sputtering TiN on a silicon substrate and further sputtered with copper). And heated at 100 ° C. for 5 minutes to form a coating film having a thickness of about 12 to 14 μm. The coating film was cured under the curing conditions shown in Table 4 to obtain a cured film having a thickness of about 10 μm. The cured film is cut into small pieces together with the substrate, and the aluminum stud and the cured film are joined via an epoxy resin layer. Next, the stud was pulled and the load at the time of peeling was measured. The results are shown in Table 4.

[Temperature cycle test]
The positive photosensitive resin composition solutions (M1 to M13) obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were spin-coated on the substrate on which the rewiring was formed, and heated at 100 ° C. for 5 minutes. Then, a coating film having a film thickness of about 20 μm was formed. This coating film was exposed (1000 mJ / cm ² ) at all wavelengths through a mask using a proximity exposure machine (PLA-600FA manufactured by Canon). After exposure, development was performed with a 2.38% aqueous solution of TMAH to form 200 μm square via holes. The coating film was cured under the curing conditions shown in Table 4 to obtain a cover coat film. After forming an under barrier metal in the opening, solder balls were bumped to create a test part as shown in FIG. Furthermore, a test part was mounted and sealed to obtain a test sample. The test sample was subjected to a temperature cycle test (−55 ° C. to 125 ° C., 1000 cycles and 1500 cycles), and observed for defects such as cracks and peeling. The results are shown in Table 4.

  As is clear from Table 2, the sensitivity and resolution of the positive photosensitive resin compositions M1 to M10 of Examples 1 to 10 are not inferior to the positive photosensitive resin compositions of Comparative Examples 1 to 3, I understand that it is expensive. Further, as apparent from Table 3, the cured films formed from the positive photosensitive resin compositions M1 to M9 of Examples 1 to 9 all exhibited a low shrinkage of about 10%. The cured film of the positive photosensitive resin composition M10 of Example 10 using poly (hydroxyamide) as the component (A) has a shrinkage of 16% due to the elimination of water due to the ring-closing reaction during curing. Met.

  Further, as is apparent from Table 3, the positive photosensitive resin compositions M1 to M9 of Examples 1 to 9 have good Tg (180 ° C. or higher) and EL (5% or higher) even when cured at 180 ° C. showed that. Further, the positive photosensitive resin composition M10 of Example 10 was cured at 200 ° C., but showed good Tg and EL. Furthermore, when the positive photosensitive resin composition M1 of Example 1 was microwave-cured (curing condition iii) at 170 ° C., Tg and EL were higher than when it was thermally cured (curing condition i) at 180 ° C. Improved.

  Further, as is clear from Table 3, in the case of the positive photosensitive resin compositions M8 and M9 of Examples 8 and 9 using poly (hydroxystyrene) as the component (A), the dielectric constant of the cured film The rate was as good as 3 or less. On the other hand, in the case of the positive photosensitive resin compositions M11 and M12 of Comparative Example 1 and Comparative Example 2 using a single layer polymer as the component (C), the EL of the cured film was 5% or less. Furthermore, in the case of the positive photosensitive resin composition M13 of Comparative Example 3 that does not contain the component (C), the cured film was brittle and Tg and EL could not be measured.

The results of the stud pull test and the temperature cycle test are shown in Table 4. The cured films of the positive photosensitive resin compositions M1 to M10 of Examples 1 to 10 have high adhesion (adhesion) to copper (300 kgf / cm ² or more). Furthermore, since the thermal shock resistance is also high, defects such as cracks and peeling did not occur in the test sample after the temperature cycle test. On the other hand, in the case of the positive photosensitive resin compositions M11 and M12 of Comparative Example 1 and Comparative Example 2 using a single layer polymer as the component (C), the adhesiveness to copper is low, and in 1500 temperature cycle tests A defect occurred. Furthermore, in the case of the positive photosensitive resin composition M13 of Comparative Example 3 not containing the component (C), the adhesion to copper was low and the thermal shock resistance was also low.

It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing which shows one Embodiment of an electronic component (semiconductor device). It is a schematic sectional drawing which shows one Embodiment of an electronic component (semiconductor device).

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... 1st conductor layer, 4 ... Interlayer insulation film, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window part, 7 ... 2nd conductor layer, 8 ... Surface protection 11 ... Interlayer insulating layer, 12 ... Wiring layer, 12 ... Underfill, 13 ... Insulating layer, 14 ... Surface protective layer, 15 ... Pad part, 16 ... Rewiring layer, 17 ... Conductive ball, 18 ... Core, DESCRIPTION OF SYMBOLS 19 ... Cover coat layer, 20 ... Barrier metal, 21 ... Color, 22 ... Underfill, 23 ... Silicon chip, 24 ... Connection part, 100, 200, 300, 400 ... Structure, 500 ... Semiconductor device, 600 ... Semiconductor device 700: Semiconductor device.

Claims (16)

(A) an alkali-soluble resin having a phenolic hydroxyl group,
(B) a compound that generates an acid by light,
(C) a core-shell polymer, and (D) a solvent ,
(C) A positive photosensitive resin composition having a theoretical glass transition temperature of 20 ° C. or lower at the shell portion of the core-shell polymer .   The positive photosensitive resin composition according to claim 1, wherein the component (A) is a phenol resin.   The positive photosensitive resin composition according to claim 1, wherein the component (A) is a vinyl polymer containing a monomer unit having a phenolic hydroxyl group.   The positive photosensitive resin composition as described in any one of Claims 1-3 which contains 1-50 weight part of said (C) component with respect to 100 weight part of said (A) component.   The positive photosensitive resin composition as described in any one of Claims 1-4 whose said (B) component is an o-quinonediazide compound.   (E) The positive photosensitive resin composition as described in any one of Claims 1-5 which further contains the thermal crosslinking agent which bridge | crosslinks the said (A) component by heating. (C) The positive photosensitive resin composition as described in any one of Claims 1-6 whose glass transition temperature of the core part of a core-shell polymer is 0 degrees C or less. (C) The positive photosensitive resin composition as described in any one of Claims 1-6 whose core part of a core shell polymer is an acrylonitrile butadiene rubber. (C) The shell part of the core-shell polymer is
(C1) one or more monomers selected from the group consisting of a half ester of dicarboxylic acid and hydroxyalkyl (meth) acrylic acid, a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having an aromatic ring;
(C2) a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule;
(C3) is formed by polymerizing with other copolymerizable monomers,
Or
(C1) one or more monomers selected from the group consisting of a half ester of dicarboxylic acid and hydroxyalkyl (meth) acrylic acid, a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having an aromatic ring;
(C2) The positive photosensitive resin according to any one of claims 1 to 8, which is formed by polymerizing a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule. Resin composition. The positive photosensitive resin composition according to any one of claims 1 to 9 coated on a support substrate, a photosensitive resin film from the coated the positive photosensitive resin composition and removing the solvent Forming a step;
Exposing the photosensitive resin film;
Developing the photosensitive resin film after exposure with an alkaline aqueous solution to form a resist pattern;
Heating the resist pattern;
A method for producing a resist pattern comprising: The method for producing a resist pattern according to claim 10 , wherein the resist pattern is heated to 200 ° C. or lower. The electronic component which has a resist pattern formed by the manufacturing method of the resist pattern of Claim 10 or 11 as an interlayer insulation film and / or a surface protective layer. The electronic component which has a resist pattern formed by the manufacturing method of the resist pattern of Claim 10 or 11 as a cover coat layer. The electronic component which has the resist pattern formed by the manufacturing method of the resist pattern of Claim 10 or 11 as a core for rewiring layers. An electronic component having a resist pattern formed by the method for producing a resist pattern according to claim 10 or 11 as a collar for holding conductive balls as external connection terminals. The electronic component which has a resist pattern formed by the manufacturing method of the resist pattern of Claim 10 or 11 as an underfill.

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