JP2005173528A - Positive photosensitive resin composition, method for producing relief pattern and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition excellent in adhesiveness to a copper substrate and excellent also in heat resistance and properties of a cured film; a method for producing a relief pattern using the same and having good adhesiveness to a substrate; and electronic components having an interlayer insulation film or a surface protection film and constituting a semiconductor device or a multilayer wiring board with high reliability. <P>SOLUTION: The positive photosensitive resin composition contains (A) a polybenzoxazole precursor represented by formula (1), (B) a compound which generates an acid upon irradiation with an actinic ray, (C) a divalent organo-transition-metal compound represented by formula (2) and (D) a solvent. The method for producing the relief pattern and the electronic components use the same. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a positive photosensitive resin composition, and more specifically, a positive type that becomes a polybenzoxazole-based heat-resistant polymer that can be applied as a surface protective film, an interlayer insulating film or the like of an electronic component such as a semiconductor element by heat treatment. The present invention relates to a photosensitive resin composition, a method for producing a relief pattern using the same, and an electronic component.

Polybenzoxazole resin is widely used as a surface protection film and interlayer insulation film for semiconductor elements because it has excellent heat resistance, electrical properties and mechanical properties, as well as polyimide resin, and it can be easily formed and the surface can be flattened. Has been.
When polybenzoxazole resin or polyimide resin is used as a surface protective film or an interlayer insulating film, a method is generally used in which a precursor resin is applied on a substrate in the form of a solution and thermally dried to form a film ( Japanese Patent No. 1891307). In recent years, copper has been used as a wiring metal in order to cope with higher speed and higher integration of semiconductor elements. Further, as the package form shifts to the CSP structure, a copper rewiring is formed on the outermost surface of the chip. With these trends, polybenzoxazole resin or polyimide resin as a surface protective film comes into contact with copper wiring, and adhesion between the resin and copper wiring is required. However, the conventional polybenzoxazole resin or polyimide resin has a problem of weak adhesiveness with copper.

Japanese Patent No. 1891307

The present invention provides a positive photosensitive resin composition that overcomes the above-described problems and that provides sufficient adhesion to copper wiring.
In addition to the above-mentioned problems, the present invention provides a positive photosensitive resin composition having excellent heat resistance.
In addition, the present invention provides a method for manufacturing a relief pattern that has a high resolution and a pattern having a good shape.
In addition, the present invention provides a highly reliable electronic component by having a relief pattern with a good shape.

(1) The present invention comprises (A) a polybenzoxazole precursor represented by the general formula (1), (B) a compound that generates an acid upon irradiation with active actinic radiation, (C) two compounds represented by the general formula (2) The present invention relates to a positive photosensitive resin composition comprising a valent organic transition metal compound and (D) a solvent.

（式中、Ｒ^１は１個の芳香環を含む基又は２〜３個の芳香環が単結合、エーテル結合、２,２−ヘキサフルオロプロピレン結合、２,２−プロピレン結合、スルホン結合、メチレン結合及びカルボニル結合の中から選ばれた少なくとも一種の結合を介して結合した化学構造を持つ二価の有機基を示し、Ｒ^２は１個の芳香環を含む基又は２〜３個の芳香環が単結合、エーテル結合、２,２−ヘキサフルオロプロピレン結合、２,２−プロピレン結合、メチレン結合及びスルホン結合の中から選ばれた少なくとも一種の結合を介して結合した化学構造を有する四価の有機基を示す）

(Wherein R ¹ is a group containing one aromatic ring or 2 to 3 aromatic rings are a single bond, ether bond, 2,2-hexafluoropropylene bond, 2,2-propylene bond, sulfone bond, methylene) A divalent organic group having a chemical structure bonded via at least one bond selected from a bond and a carbonyl bond, wherein R ² is a group containing one aromatic ring or two to three aromatic rings Having a chemical structure in which is bonded through at least one bond selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a 2,2-propylene bond, a methylene bond, and a sulfone bond. (Indicates organic group)

（一般式(２)中、Ｒ^３は、水素または一価の有機基、Ｍは二価の有機遷移金属を表わす）
（２） また、本発明は、さらに、（Ｅ）酸触媒反応によりアルカリ水溶液に対する溶解性が増加される酸分解性基を有する化合物を含有してなる前記（１）に記載のポジ型感光性樹脂組成物に関する。
（３） また、本発明は、前記（１）又は（２）記載のポジ型感光性樹脂組成物を支持基板上に塗布し、乾燥する工程、露光する工程、加熱する工程、現像する工程及び加熱処理する工程を含むレリーフパターンの製造方法に関する。
（４） また、本発明は、前記（３）記載の製造方法により得られるレリーフパターンの層を有してなる電子部品に関する。

(In general formula (2), R ³ represents hydrogen or a monovalent organic group, and M represents a divalent organic transition metal)
(2) The present invention further includes (E) a positive photosensitive resin as described in (1) above, which further comprises (E) a compound having an acid-decomposable group whose solubility in an alkaline aqueous solution is increased by an acid-catalyzed reaction. The present invention relates to a resin composition.
(3) Moreover, this invention apply | coats the positive photosensitive resin composition of the said (1) or (2) on a support substrate, and the process of drying, the process of exposing, the process of heating, the process of developing, The present invention relates to a method for manufacturing a relief pattern including a step of heat treatment.
(4) Moreover, this invention relates to the electronic component which has a layer of the relief pattern obtained by the manufacturing method of the said (3) description.

  The positive photosensitive resin composition of the present invention has excellent adhesion to a copper substrate. Further, according to the method for producing a relief pattern of the present invention, since it is excellent in adhesiveness with a copper substrate, it is possible to easily produce a surface protective film such as a semiconductor element, an interlayer insulating film, and the like that exhibit good characteristics. Furthermore, the electronic component of the present invention is a highly reliable semiconductor device having an interlayer insulating film or a surface protective film with good adhesion to a copper substrate.

  The component (A) used in the present invention is a polybenzoxazole precursor. After exposure to active actinic radiation and heat treatment after irradiation with active actinic radiation, the exposed part is improved in solubility in an alkaline aqueous solution due to the change in component (B), and the dissolution rate differs from the unexposed part, so that a relief pattern can be formed. . The alkaline aqueous solution is an aqueous solution exhibiting alkalinity in which tetramethylammonium hydroxide, metal hydroxide, amine and the like are dissolved in water. The polybenzoxazole precursor becomes a resin film having excellent heat resistance by curing reaction after formation of the relief pattern.

  Examples of the polybenzoxazole precursor of component (A) include polyhydroxy polyamides generally obtained using dicarboxylic acid and dihydroxydiamine as raw materials. Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4′-biphenyldicarboxylic acid, 4,4′-dicarboxydiphenyl ether, 4,4 ′. -Dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5 -Aromatic dicarboxylic acids such as chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid And aliphatic dicarboxylic acids such as succinic acid. Alone or in combination of two or more can be used. Of these, aromatic dicarboxylic acids are preferred from the viewpoint of heat resistance.

  Examples of the dihydroxydiamine include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, and bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexa Fluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, 4,6-diaminoresorcinol 4,5-diaminoresorcinol, bis (4-amino 3-carboxyphenyl) aromatic diamines, such as methane, it can be mentioned as preferred. By using an aromatic diamine, a polybenzoxazole precursor having good heat resistance is obtained.

In the present invention, the polybenzoxazole precursor includes, for example, dicarboxylic acid dihalide (chloride, bromide) and dihydroxydiamine as shown in Polymer Letter., Vol. 2, pp655-659 (1964). In this case, the reaction is preferably carried out in the presence of a dehalogenation acid catalyst in an organic solvent. Dicarboxylic acid dichloride can be obtained by reacting dicarboxylic acid with thionyl chloride.
The polyhydroxyamide is prepared by, for example, dissolving the dihydroxydiamine compound and a dehydrochlorination catalyst such as pyridine in an organic solvent, dropping and reacting the dicarboxylic acid dichloride dissolved in the organic solvent, and then adding it to a poor solvent such as water. The precipitate can be obtained by filtration and drying. Examples of the organic solvent used in the reaction include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, and γ-butyrolactone. These aprotic polar solvents are used alone or in combination of two or more.

Further, in the present invention, the polybenzoxazole precursor passes through a dicarboxylic acid derivative obtained by reacting 1-hydroxybenzotriazole with a dicarboxylic acid as disclosed in, for example, JP-A-9-183848. It can be obtained by reacting this with dihydroxydiamine.
A preferred ratio (molar ratio) between the dihydroxydiamine compound and the dicarboxylic acid is in the range of 0.6 / 1 to 1 / 0.6 in the former / the latter. A preferred reaction temperature is -30 to 40 ° C, and a preferred reaction time is 5 minutes to 10 hours.

  The polyhydroxyamide used for the component (A) can introduce an alkenyl group or an alkynyl group at the molecular structure terminal. By introducing such a compound having a double bond to the resin end, control of the dissolution rate in an aqueous alkali solution, cured film properties such as film elongation and tensile strength due to cross-linking of the resin end introduction group by heat curing treatment The shelf life can be improved by the improvement and the resin end group suppressing side reactions. Introduction of an alkenyl group, an alkynyl group, or the like into the resin terminal can be easily performed by reacting the terminal group with the monomer in advance, or by reacting the terminal group after resin synthesis.

  (A) As molecular weight of a component, 3000-200000 are preferable at a weight average molecular weight, and 5000-100000 are more preferable. Moreover, 1-4 are preferable and, as for the dispersion degree which remove | divided the weight average molecular weight by the number average molecular weight, 1-3 are more preferable. The molecular weight of the component (A) is measured by a gel permeation chromatography method and can be converted using a standard polystyrene calibration curve.

The compound that generates an acid upon irradiation with active actinic radiation, which is the component (B) used in the present invention, has a function of generating an acid upon exposure and increasing the solubility of the exposed portion in an alkaline aqueous solution. As the component (B), onium salts, halogen-containing compounds, quinonediazide compounds, sulfonic acid ester compounds, and the like are used.
Examples of onium salts include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like, and preferably diaryl iodonium salts, triaryl sulfonium salts, trialkylsulfonium salts (the carbon number of the alkyl group is 1). ~ 8). As the counter anion of the onium salt, for example, tetrafluoroboric acid, hexafluoroantimonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid and the like are preferable.
Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like, and preferably trichloromethyltriazine, bromoacetylbenzene, and the like.
Examples of the quinonediazide compound include a diazobenzoquinone compound and a diazonaphthoquinone compound.
Examples of the sulfonic acid ester compound include esters of an aromatic compound having a phenolic hydroxyl group and an alkyl sulfonic acid or an aromatic sulfonic acid. For example, aromatic compounds having a phenolic hydroxyl group include phenol, resorcinol, pyrogallol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene and the like. Examples of the alkyl sulfonic acid include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butyl sulfonic acid, and camphor sulfonic acid. Examples of the aromatic sulfonic acid include benzenesulfonic acid and naphthylsulfonic acid.
The component (B) is preferably used in an amount of 0.5 to 100 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the component (A) in terms of film thickness after development and sensitivity.

  Examples of the divalent organic transition metal compound (C) used in the present invention include 2,4-pentanedione copper, 2,2,6,6-tetramethyl-3,5-heptanedione copper, 2 , 4-pentanedione chromium, 2,2,6,6-tetramethyl-3,5-heptanedione chromium, 2,4-pentanedione nickel, 2,2,6,6-tetramethyl-3,5-heptane Although dione nickel etc. are mentioned, it is not restricted to this range. The amount of the component (D) is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of improving adhesion to the substrate, but 0.5 to 0.5 from the viewpoint of film properties after curing. 10 parts by weight is more preferable.

The solvent of the component (D) used in the present invention is not particularly limited as long as it can dissolve the components (A) to (C) well and dissolve them uniformly. For example, N-methyl -2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, cyclohexanone, cyclopentanone, ethyl lactate, propylene glycol monomethyl ether, Aprotic polar solvents such as propylene glycol monomethyl ether acetate are used alone or in combination of two or more.
The component (D) is preferably used in an amount of 50 to 700 parts by weight, more preferably 80 to 500 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of the coating film thickness.

The compound having an acid-decomposable group whose solubility in an alkaline aqueous solution is increased by the acid-catalyzed reaction which is the component (E) used in the present invention is catalyzed by the acid generated from the component (B) by active actinic radiation. It has a function of causing a decomposition reaction and increasing the solubility of the exposed portion in an alkaline aqueous solution. In addition, many of them also have the effect of inhibiting the solubility of unexposed areas. As the component (E), a compound having a phenolic hydroxyl group or carboxyl group in which part or all of the hydrogen atoms of the phenolic hydroxyl group or carboxyl group are substituted with an acid-decomposable group is preferable.
As the compound having a phenolic hydroxyl group or carboxyl group, a compound having 1 to 15 benzene rings and 1 to 20 phenolic hydroxyl groups or carboxyl groups in the molecule is preferable. In addition, these compounds may be resinous compounds such as phenol novolac resin and polyvinylphenol. Moreover, you may use the polybenzoxazole precursor which is (A) component. That is, polyhydroxyamide having a phenolic hydroxyl group or a carboxyl group may be used. Some or all of the hydrogen atoms of the phenolic hydroxyl group or carboxyl group of these compounds are substituted with an acid-decomposable group.
As the acid-decomposable group substituted by the hydrogen atom of the phenolic hydroxyl group or carboxyl group of the component (E), a substituent that is decomposed by an acid such as an acetal, ketal, silyl group, silyl ether group or the like is used. Examples of the acid-decomposable group include a t-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a t-butoxycarbonylmethyl group, and an ethyl vinyl ether group. , Methyl vinyl ether group, trimethylsilyl ether group and the like.
These substituents can be easily introduced, for example, by reacting a compound having a phenolic hydroxyl group or a carboxyl group with a vinyl ether compound in the presence of an acid catalyst. Moreover, it can introduce | transduce easily also by making the chloride of the substituent to introduce | transduce react under alkali catalysts, such as an amine.
Component (E) is preferably used in an amount of 2 to 500 parts by weight, more preferably 10 to 300 parts by weight, based on 100 parts by weight of component (A), from the viewpoint of the film thickness after development and sensitivity.

In addition, the positive photosensitive resin composition of the present invention can contain a suitable phenol compound or the like in order to adjust the solubility in an alkali developer.
As such a phenol compound, a compound containing 2 to 8 phenolic hydroxyl groups in the molecule can be used. For example, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl- (4-hydroxyphenyl) methane, 3,3′-methylenebis (2-hydroxy-5-methylbenzenemethanol, 2,2′-methylenebis (4- Methylphenol), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, tris (2-hydroxyphenyl) methane, tris ( 4-hydroxyphenyl) methane, bis (2-hydroxyphenyl)-(4-hydroxyphenyl) methane, bis (4-hydroxyphenyl)-(2-hydroxyphenyl) methane, 1,1,1-tris (2-hydroxy) Phenyl) ethane, 1,1-bis (2-hydroxyphenyl) -1- (4-hydride) Xylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-hydroxyphenyl) ethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy) Phenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1-bis (2-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) ) -Phenylmethane, bis (2-hydroxyphenyl) -phenylmethane, 4,4′-dihydroxy-3,3′-dimethyl-biphenyl, and the like.

  Further, the positive photosensitive resin composition of the present invention can contain a silane coupling agent in order to improve the adhesion to the silicon substrate. Examples of such silane coupling agents include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, Ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, 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 (methyl) Dihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, , 4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4 -Bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene and the like. These coupling agents may be provided in the form of a solution with an organic solvent such as alcohol. The amount of the silane coupling agent is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of improving adhesion to the silicon substrate, but 0.5 from the viewpoint of film properties after curing. More preferred is 10 parts by weight.

In addition, the positive photosensitive resin composition of the present invention may be added with an appropriate surfactant or leveling agent in order to prevent coating properties such as striation (film thickness unevenness) or improve developability. Can do. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Megafax F171 is a commercially available product. , F173, R-08 (Dainippon Ink Chemical Co., Ltd. product name), Florard FC430, FC431 (Sumitomo 3M Co., Ltd. product name), Organosiloxane polymer KP341, KBM303, KBM403, KBM803 (Shin-Etsu Chemical Co., Ltd. product) Name).
Furthermore, a storage stabilizer, a dissolution inhibitor, and the like can be blended with the positive photosensitive resin composition of the present invention as necessary.

The positive photosensitive resin composition of the present invention is formed on a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO _2, etc.), a support substrate such as silicon nitride, and a metal wiring formed thereon. By coating and drying, a film of a positive photosensitive resin composition can be obtained. After that, irradiation with actinic rays such as ultraviolet rays, visible rays, and radiation (irradiation with active actinic radiation, exposure) is performed through a mask, followed by heat treatment as necessary, and then removing the exposed portion with a developer to make positive. A relief pattern of the mold is obtained. Preferably, the positive photosensitive resin composition of the present invention is applied on a support substrate or a metal wiring formed thereon and dried to form a film of the positive photosensitive resin composition (applied and dried). Step), followed by irradiation with actinic rays (active actinic radiation, exposure step) such as ultraviolet rays, visible rays, and radiation through a mask, followed by heat treatment (heating step), and exposing the exposed portion to a developer. A positive type relief pattern can be produced by removing (developing) and further heat-treating.
Drying is usually performed using an oven or a hot plate. The drying conditions are appropriately determined depending on the components of the positive photosensitive resin composition. When a hot plate is used, the drying conditions are preferably 60 to 140 ° C. for 30 seconds to 10 minutes. If the drying temperature is low, the fine pattern tends to be peeled off during development. On the other hand, when the drying temperature is high, the dissolution rate of the exposed portion in the developer tends to decrease and the sensitivity tends to decrease.
Next, if necessary, a heat treatment is performed after the exposure and before the development in order to promote the decomposition reaction of the component (E) in the light irradiation part. The heating conditions are appropriately determined depending on the components of the positive photosensitive resin composition, but when a hot plate is used, it is preferably 60 to 140 ° C. for 30 seconds to 10 minutes. When the heating temperature is low, the compound having an acid-decomposable group whose solubility in an alkaline aqueous solution is increased by an acid-catalyzed reaction does not efficiently decompose, and the sensitivity tends to decrease. When the heating temperature is high, the dissolution rate of the exposed portion in the developer tends to decrease and the development time tends to be long.
Next, as the developer used in the development processing, an alkali developer is preferably used. For example, an aqueous solution of 5 wt% or less such as sodium hydroxide, potassium hydroxide, sodium silicate, tetramethylammonium hydroxide, choline, Preferably, a 1.5 to 3.0% by weight aqueous solution or the like is used, but a more preferred developer is a 1.5 to 3.0% by weight aqueous solution of tetramethylammonium hydroxide.
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 weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer.
Next, a relief pattern of a heat-resistant polymer having an oxazole ring or other cyclic group is obtained by subjecting the obtained relief pattern to a heat treatment at 150 to 450 ° C. The positive photosensitive resin composition of the present invention is suitable as a resin composition for forming a film thickness of a heat-resistant polymer of 4 μm or more.
This pattern can be used as an interlayer insulating film or surface protective film for electronic components such as semiconductor devices and multilayer wiring boards.
The electronic component of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

Hereinafter, the present invention will be specifically described by way of examples.
(Synthesis Example 1)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 21.69 g of 4,4′-diphenyl ether dicarboxylic acid and 123 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C., and then 9.99 g of thionyl chloride. Was added dropwise and reacted for 1 hour to obtain a solution (G1) of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 103 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer, a thermometer, and a Dimroth condenser, and 25.83 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After stirring and dissolving, 26.58 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride (G1) was added dropwise over 1 hour, followed by stirring for 1 hour. Continued. The solution was poured into 4 liters of water, and the precipitate was collected and washed, and then dried under reduced pressure to obtain polyhydroxyamide (hereinafter referred to as polymer A). The weight average molecular weight calculated | required by standard polystyrene conversion of the polymer A was 20000, and dispersion degree was 1.5.

(Synthesis Example 2)
In a 0.3 liter flask equipped with a stirrer and a thermometer, 10 g (0.034 mol) of tris (4-hydroxyphenyl) methane, 26.7 g of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride ( 0.099 mol) and 135 g of dioxane were charged and dissolved by stirring. The flask was cooled, and a mixture of 10.2 g (0.101 mol) of triethylamine and 10.2 g of dioxane was added dropwise while keeping the reaction temperature at 20 ° C. or lower. After the dropping, the reaction temperature was room temperature (25 ° C.) and the mixture was stirred for 1 hour. The reaction solution was poured into 1 liter of 0.1 wt% aqueous hydrochloric acid solution, and the precipitate was collected and washed, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain 30 g of naphthoquinone diazide sulfonyl ester (B). When this was measured by HPLC (high performance liquid chromatograph), the content of the triester was 91.8%.

(Synthesis Example 3)
In a 0.5 liter flask equipped with a stirrer and a thermometer, Marcalinker M (trade name, manufactured by Maruzen Chemical Industry Co., Ltd., polyvinylphenol, weight average molecular weight determined by polystyrene conversion is 5000, dispersity is 2.5. 20 g) and 200 g of ethyl acetate were added and dissolved by stirring, 50 g of 3,4-dihydro-2H-pyran was added, then 0.3 g of 12N hydrochloric acid was added, and the mixture was stirred at room temperature (25 ° C.) for 70 hours. Continued. Thereafter, the reaction solution was transferred to a separating funnel, and then neutralized with 150 g of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, and the organic layer was washed several times with 150 g of pure water. After removing the organic layer and concentrating the organic layer with an evaporator, the concentrated organic layer was poured into n-hexane, and the precipitated resinous material was recovered and dried under reduced pressure to protect the phenolic hydroxyl group with a tetrahydropyranyl group. Polyvinylphenol was obtained (hereinafter referred to as dissolution inhibitor I). When the protection rate of the tetrahydropyranyl group with respect to the phenolic hydroxyl group of the dissolution inhibitor I was measured by ¹ H-NMR, it was 95%.

(Example 1)
Polymer A synthesized in Synthesis Example 1 as a polybenzoxazole precursor of component (A), naphthoquinone diazide ester obtained in Synthesis Example 2 as a compound that generates an acid upon irradiation with active actinic radiation of component (B) (B ), 2,4-pentanedione copper as the divalent organic transition compound of the component (C), and γ-butyrolactone as the solvent of the component (D). ) And dissolved under stirring to obtain a uniform solution state. Then, this solution was pressure filtered using a 1 μm pore polytetrafluoroethylene filter to obtain a positive photosensitive resin composition.

(Comparative Example 1)
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that the component (C) was not blended.

  In order to evaluate adhesion, a substrate on which copper was sputtered after TiN was sputtered on a silicon substrate was used. The obtained positive photosensitive resin composition was spin-coated on a substrate with a spinner, and heat-dried at 90 ° C. for 2 minutes on a hot plate to obtain a 12 μm positive photosensitive resin composition film. Next, after heating and drying at 120 ° C. for 2 minutes on a hot plate, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used as a developing solution, paddle development was performed for 100 seconds, and washing with pure water was performed on a silicon wafer. A polybenzoxazole precursor film was obtained. Subsequently, this film was heat-treated at 300 ° C. for 1 hour under a nitrogen atmosphere, and a cured film of polybenzoxazole having a thickness of 7 μm was obtained on the entire surface of the substrate. Using the cured film on the obtained wafer, a Sebastian test was conducted and the results are shown in Table 2.

(Example 2)
The positive photosensitive resin composition of Example 1 was spin-coated on a silicon wafer using a spinner, and heated and dried at 90 ° C. for 2 minutes on a hot plate to obtain a 12 μm positive photosensitive resin composition. A membrane was obtained. In order to evaluate the photosensitive properties, the coating film was exposed to 1000 to 11000 J / m ² through a reticle using an i-line reduction projection exposure apparatus (PFA3000iw manufactured by Canon Inc.). Next, after heating and drying at 120 ° C. for 2 minutes on a hot plate, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used as a developing solution, paddle development was performed for 100 seconds, and the relief pattern was washed with pure water. Obtained. This pattern was heat-treated at 300 ° C. for 1 hour in a nitrogen atmosphere to obtain a cured relief pattern. After curing, the pattern was observed with a metallographic microscope.

  Like Example 1, 2, what added the bivalent organic transition metal compound of (C) component showed favorable adhesiveness on the copper substrate. On the other hand, as in Comparative Example 1, the one without the organic transition metal compound was inferior in adhesion to the copper substrate as compared with the additive. Further, as a result of observing the relief pattern after curing, a relief pattern having a favorable shape with a minimum processing dimension of 10 μm was obtained.

(Examples 3 and 4)
Polymer A obtained in Synthesis Example 1 as the polybenzoxazole precursor of component (A), NAI-105 (trade name, manufactured by Midori Chemical Co., Ltd.) as a compound that generates an acid upon irradiation with active actinic radiation of component (B) N- (trifluoromethanesulfonyloxy) naphthalimide), NAI-106 (trade name, N- (camphorsulfonyloxy) naphthalimide manufactured by Midori Chemical Co., Ltd.), (C) as a divalent organic transition compound of 2, 4-pentanedione copper, γ-butyrolactone as a solvent for component (D), and compound having an acid-decomposable group whose solubility in an alkaline aqueous solution is increased by an acid-catalyzed reaction of component (E), synthesized in Synthesis Example 3 above Using the dissolved inhibitor I, these were combined and blended into a flask, and stirred and dissolved at room temperature (25 ° C.) to obtain a uniform solution. Deliberately it was. Then, this solution was pressure filtered using a 1 μm pore polytetrafluoroethylene filter to obtain a positive photosensitive resin composition. For the components (A) to (E), a positive photosensitive resin composition was prepared with the formulation shown in Table 3.

(Comparative Example 2)
Table 3 shows the composition of Comparative Example 2.

  In order to evaluate adhesion, a substrate on which copper was sputtered after TiN was sputtered on a silicon substrate was used. The obtained positive photosensitive composition was spin-coated on a substrate with a spinner and heat-dried at 90 ° C. for 2 minutes on a hot plate to obtain a 12 μm positive photosensitive resin composition film. Next, after heating and drying at 120 ° C. for 2 minutes on a hot plate, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used as a developing solution, paddle development was performed for 100 seconds, and washing with pure water was performed on a silicon wafer. A polybenzoxazole precursor film was obtained. Subsequently, this film was heat-treated at 300 ° C. for 1 hour under a nitrogen atmosphere, and a cured film of polybenzoxazole having a thickness of 7 μm was obtained on the entire surface of the substrate. A Sebastian test was performed using the cured film on the obtained wafer. Table 4 shows the test results.

The composition of Example 4 was spin-coated on a silicon wafer using a spinner, and was heat-dried on a hot plate at 90 ° C. for 2 minutes to obtain a 12 μm positive photosensitive resin composition film. In order to evaluate the photosensitive properties, the coating film was exposed to 1000 to 11000 J / m ² through a reticle using an i-line reduction projection exposure apparatus (PFA3000iw manufactured by Canon Inc.). Next, after heating and drying at 120 ° C. for 2 minutes on a hot plate, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used as a developing solution, paddle development was performed for 100 seconds, and the relief pattern was washed with pure water. Obtained. This pattern was heat-treated at 300 ° C. for 1 hour in a nitrogen atmosphere to obtain a cured relief pattern. After curing, the pattern was observed with a metallographic microscope.
As confirmed in Examples 3 and 4, the material to which the organic transition metal compound was added exhibited good adhesion on the copper substrate. On the other hand, as in Comparative Example 2, the one without the organic transition metal compound was inferior in adhesion to the copper substrate as compared with the additive. Further, as a result of observation of the relief pattern after curing, a relief pattern having a favorable shape with a minimum processing dimension of 10 μm was obtained.
The positive photosensitive resin compositions of Examples 3 and 4 of the present invention have excellent adhesion to a copper substrate, excellent adhesion to a copper substrate when a relief pattern is formed, and easily exhibit good characteristics. A surface protective film, an interlayer insulating film, and the like can be manufactured.

Claims (4)

(A) a polybenzoxazole precursor represented by the general formula (1), (B) a compound that generates an acid upon irradiation with active actinic radiation, (C) a divalent organic transition metal compound represented by the general formula (2), And (D) a positive photosensitive resin composition comprising a solvent.

(Wherein R ¹ is a group containing one aromatic ring or 2 to 3 aromatic rings are a single bond, ether bond, 2,2-hexafluoropropylene bond, 2,2-propylene bond, sulfone bond, methylene) A divalent organic group having a chemical structure bonded via at least one bond selected from a bond and a carbonyl bond, wherein R ² is a group containing one aromatic ring or two to three aromatic rings Having a chemical structure in which is bonded through at least one bond selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a 2,2-propylene bond, a methylene bond, and a sulfone bond. (Indicates organic group)

(In general formula (2), R ³ represents hydrogen or a monovalent organic group, and M represents a divalent organic transition metal) The positive photosensitive resin composition according to claim 1, further comprising (E) a compound having an acid-decomposable group whose solubility in an alkaline aqueous solution is increased by an acid-catalyzed reaction. A relief pattern comprising a step of applying the positive photosensitive resin composition according to claim 1 or 2 onto a support substrate, drying, exposing, heating, developing, and heat-treating. Production method. An electronic component comprising a relief pattern layer obtained by the manufacturing method according to claim 3.