JP6919746B2 - Positive type photosensitive resin composition, manufacturing method of pattern cured film, cured product, interlayer insulating film, cover coat layer, surface protective film and electronic components - Google Patents

Description

The present invention relates to a positive photosensitive resin composition, a method for producing a pattern cured film using the same, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.

Conventionally, polyimide or polybenzoxazole having excellent heat resistance, electrical properties, mechanical properties, etc. has been used as a surface protective film and an interlayer insulating film of a semiconductor element. In recent years, a photosensitive polyimide having a photosensitive property imparted to the polyimide itself has been used, and when this is used, the manufacturing process of the pattern cured film can be simplified and the complicated manufacturing process can be shortened.

In the production of the pattern cured film, an organic solvent such as N-methylpyrrolidone has been used for development. However, in consideration of the environment, a method of mixing a naphthoquinone diazide compound as a photosensitizer with polyimide or a polyimide precursor is used. A resin composition that can be developed with an alkaline aqueous solution has been proposed (see, for example, Patent Document 1 or 2).

As a resin composition that can be developed with an alkaline aqueous solution, a resin composition containing a polybenzoxazole, a polybenzoxazole precursor, or a novolak resin has been proposed (see, for example, Patent Document 3).

On the other hand, in recent years, the integration and miniaturization of semiconductor elements have progressed, and there are demands for thinning and miniaturization of package substrates and cost reduction. Therefore, a package structure that does not use the underbump metal (UBM) layer used to improve the reliability of the semiconductor element has been proposed (see Non-Patent Documents 1 and 2).

JP-A-64-60630 U.S. Pat. No. 4,395,482 Japanese Unexamined Patent Publication No. 2009-265520

"ADVANCES IN WLCSP TECHNOLOGIES FOR GROWING MARKET NEEDS", Abstracts of 6th Annual International Wafer Level Packaging Convention, [2009-10-27] "TECHNOLOGY SOLUTIONS FOR A DYNAMIC AND DIVERSE WLCSP MARKET", Abstracts of 7th Annual International Wafer Label Packing Conference, 2010-11-14 Hiroshi Ito et al. , Assessment of Onium Salt Chemical Photoinitiator as Novel Dissolution Inhibitor for Novolac Resin, J. Mol. Electrochem. Soc. 2222-2327 (1988)

In the package structure from which the under bump metal (UBM) layer is removed, a positive photosensitive resin composition is used for the design in which the pattern cured film provided on the outermost layer reinforces the bumps to ensure reliability. It is preferable to increase the thickness of the pattern cured film from the conventional film thickness (10 μm or less).
However, when a thick film is formed by a positive photosensitive resin composition using a conventional naphthoquinone diazide compound, there is a problem that the transmittance at the photosensitive wavelength becomes low, the sensitivity deteriorates, and the development time becomes long. On the other hand, in the resin composition having high sensitivity, although the developing time is short, there is a problem that the unexposed portion is also developed.

Further, as an alkali positive photosensitive resin composition that does not use a naphthoquinone diazide compound, a dissolution-suppressing positive photosensitive resin composition has been proposed (see Non-Patent Document 3). However, it is technically difficult to apply a thick film to the above-mentioned dissolution-suppressing positive photosensitive resin composition.

An object of the present invention is a positive photosensitive resin composition having a practically good dissolution contrast between an exposed portion and an unexposed portion when forming a thick pattern cured film, and a pattern cured film using the same. The present invention is to provide an interlayer insulating film, a cover coat layer, a surface protective film and an electronic component.

The present inventors have attempted to form a thick film using a positive photosensitive resin composition in which an alkali-soluble resin and a naphthoquinone diazide compound are combined. However, the transmittance of the coating film at the photosensitive wavelength became low, a sufficient alkali dissolution rate could not be obtained in the exposed portion, and an opening could not be obtained in the development time within the practical range. In addition, it has been found that the longer the developing time, the more the developing solution permeates the unexposed portion, resulting in a decrease in resolution.

Therefore, as a result of further studies in view of the above problems, the present inventors have combined an alkali-soluble resin and an onium salt that generates an acid by i-ray exposure (hereinafter, also referred to as an onium salt having i-ray sensitivity). It has been found that by using the positive photosensitive resin composition, it is possible to develop a practical dissolution contrast even when forming a thick pattern cured film.

（式中、Ｘは対陰イオンである。また、芳香環には置換基を有していてもよい。）
＜７＞前記（ｂ）成分が、下記式（ｂ―２）で表される化合物である１〜６のいずれか一項に記載のポジ型感光性樹脂組成物。

（式中、Ｍｅはメチル基である。）
＜８＞層間絶縁膜、カバーコート層又は表面保護膜の形成に用いられる１〜７のいずれか一項に記載のポジ型感光性樹脂組成物。
＜９＞ＵＢＭフリー構造を有する半導体装置の層間絶縁膜、カバーコート層又は表面保護膜の形成に用いられる１〜７のいずれか一項に記載のポジ型感光性樹脂組成物。
＜１０＞１〜９のいずれか一項に記載のポジ型感光性樹脂組成物を基板上に塗布、乾燥し、感光性樹脂膜を形成する工程と、
得られた感光性樹脂膜を所定のパターンに露光する工程と、
露光した樹脂膜を、アルカリ水溶液を用いて現像して、パターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程と、
を含むパターン硬化膜の製造方法。
＜１１＞前記加熱処理の温度が２５０℃以下である１０に記載のパターン硬化膜の製造方法。
＜１２＞１〜９のいずれか一項に記載のポジ型感光性樹脂組成物の硬化物。
＜１３＞１２に記載の硬化物を用いた層間絶縁膜、カバーコート層又は表面保護膜。
＜１４＞１３に記載の層間絶縁膜、カバーコート層又は表面保護膜を有する電子部品。 According to the present invention, the following positive photosensitive resin compositions and the like are provided.
<1> A positive photosensitive resin composition containing (a) an alkali-soluble resin, (b) an onium salt that generates an acid by i-ray exposure, (c) a solvent, and (d) a cross-linking agent. c) A positive photosensitive resin composition in which the total of the components (a), (b) and (d) is 88% by mass or more with respect to the total mass of the positive photosensitive resin composition excluding the solvent.
<2> A positive photosensitive resin composition containing (a) an alkali-soluble resin, (b) an onium salt that generates an acid by i-ray exposure, and (c) a solvent, wherein the component (a) is 100 parts by mass. On the other hand, a positive photosensitive resin composition containing 0 to 100 ppm of a naphthoquinone diazide compound or an acid-reactive protecting group-containing compound.
<3> The positive photosensitive resin composition according to 2, which further contains (d) a cross-linking agent.
<4> The positive photosensitive property according to any one of 1 to 3, wherein the component (a) contains a polyimide, a polyimide precursor, a polybenzoxazole, a polybenzoxazole precursor, a novolak resin, or a polyhydroxystyrene. Resin composition.
<5> The component (b) is a compound that inhibits the dissolution of the component (a) in an alkaline aqueous solution before i-ray exposure and does not inhibit the dissolution of the component (a) in an alkaline aqueous solution after i-ray exposure. The positive photosensitive resin composition according to any one of 1 to 4.
<6> The positive photosensitive resin composition according to any one of 1 to 5, wherein the component (b) is a compound represented by the following general formula (b-1).

(In the formula, X is a counter anion. Further, the aromatic ring may have a substituent.)
<7> The positive photosensitive resin composition according to any one of 1 to 6, wherein the component (b) is a compound represented by the following formula (b-2).

(In the formula, Me is a methyl group.)
<8> The positive photosensitive resin composition according to any one of 1 to 7, which is used for forming an interlayer insulating film, a cover coat layer or a surface protective film.
<9> The positive photosensitive resin composition according to any one of 1 to 7, which is used for forming an interlayer insulating film, a cover coat layer or a surface protective film of a semiconductor device having a UBM-free structure.
<10> A step of applying the positive photosensitive resin composition according to any one of 1 to 9 onto a substrate and drying it to form a photosensitive resin film.
A step of exposing the obtained photosensitive resin film to a predetermined pattern, and
The process of developing the exposed resin film with an alkaline aqueous solution to obtain a patterned resin film,
The step of heat-treating the pattern resin film and
A method for producing a pattern cured film including.
<11> The method for producing a pattern cured film according to 10, wherein the temperature of the heat treatment is 250 ° C. or lower.
<12> A cured product of the positive photosensitive resin composition according to any one of 1 to 9.
<13> An interlayer insulating film, a cover coat layer, or a surface protective film using the cured product according to 12.
An electronic component having the interlayer insulating film, cover coat layer, or surface protective film according to <14> 13.

According to the present invention, a positive photosensitive resin composition capable of realizing a practical dissolution contrast even when forming a thick pattern cured film, a method for producing a pattern cured film using the same, a cured product, and interlayer insulation. A film, a cover coat layer, a surface protective film and an electronic component can be provided.

It is a schematic cross-sectional view which shows the manufacturing method of the package structure which does not provide a UBM layer. It is schematic cross-sectional view of the semiconductor device which has the rewiring structure which is one Embodiment of the electronic component of this invention.

Hereinafter, the first and second positive photosensitive resin compositions of the present invention, a method for producing a pattern cured film using the same, and embodiments of electronic components will be described in detail. The present invention is not limited to the following embodiments.
As used herein, the term "A or B" may include either A or B, or both. Further, as for the materials exemplified below, unless otherwise specified, one kind may be used alone, or two or more kinds may be used in combination. Further, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means quantity.
The first and second positive photosensitive resin compositions may be collectively referred to as "the positive photosensitive resin composition (resin composition) of the present invention".

[First positive photosensitive resin composition]
The first aspect of the first positive photosensitive resin composition of the present invention is (a) an alkali-soluble resin, (b) an onium salt that generates an acid by i-ray exposure, (c) a solvent, and (d) cross-linking. The components (a), (b), and (d) of the positive photosensitive resin composition containing the agent with respect to the total mass of the positive photosensitive resin composition excluding the solvent (c). The total of is 88% by mass or more. The total of the components (a), (b), and (d) is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and may be 100% by mass.
The second aspect of the first positive photosensitive resin composition of the present invention is (a) an alkali-soluble resin, (b) an onium salt that generates an acid by i-ray exposure, (c) a solvent, and (d). ) A cross-linking agent is contained, and the amount of the naphthoquinone diazide compound is 0 or more and less than 100 ppm with respect to 100 parts by mass of the component (a). In the second aspect, the total of the components (a), (b), and (d) is 88% by mass or more with respect to the total mass of the positive photosensitive resin composition excluding the solvent (c). It is preferable, 90% by mass or more is more preferable, 95% by mass or more is further preferable, 98% by mass or more is further preferable, and 100% by mass may be used.
It may be simply referred to as a component (a), a component (b), a component (c) and a component (d), respectively. The first aspect and the second aspect are collectively referred to as the first positive photosensitive resin composition of the present invention. Hereinafter, each component will be described.

((A) component: alkali-soluble resin)
The alkali-soluble resin is not particularly limited, but a resin having high electrical insulation is preferable. For example, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, polyamide-imide, polyhydroxystyrene, novolak resin, norbornene resin, epoxy resin and acrylic resin can be mentioned.

In particular, from the viewpoint of achieving both insulating properties and mechanical properties, it is preferable to use polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, novolak resin or polyhydroxystyrene.

The alkali-soluble resin is usually developed with an aqueous alkaline solution. Therefore, it is preferably soluble in an alkaline aqueous solution.
Examples of the alkaline aqueous solution include an organic ammonium aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, and an organic amine aqueous solution. Generally, it is preferable to use a TMAH aqueous solution having a concentration of 2.38% by weight. Therefore, the component (a) is preferably soluble in the TMAH aqueous solution.

In addition, one criterion that the component (a) is soluble in an alkaline aqueous solution will be described below. (A) The component is dissolved in an arbitrary solvent to prepare a solution, and then spin-coated on a substrate such as a silicon wafer to form a resin film having a film thickness of about 5 μm. This is immersed in any one of a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, and an organic amine aqueous solution at 20 to 25 ° C. As a result, when it is dissolved to form a solution, it is determined that the component (a) used is soluble in an alkaline aqueous solution.

The polyimide precursor preferably has a structure represented by the formula (1).

式（１）中、Ａは下記式（２ａ）〜（２ｅ）で表される４価の有機基のいずれかであり、Ｂは下記式（３）で表される２価の有機基である。Ｒ^１及びＲ^２は各々独立に水素原子又は１価の有機基である。

In the formula (1), A is any of the tetravalent organic groups represented by the following formulas (2a) to (2e), and B is a divalent organic group represented by the following formula (3). .. R ¹ and R ² are independently hydrogen atoms or monovalent organic groups.

上記式（２ｄ）中、Ｘ及びＹは、各々独立に、各々が結合するベンゼン環と共役しない２価の基又は単結合を示す。式（２ｅ）中、Ｚは酸素原子又は硫黄原子を示す。

In the above formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugate with the benzene ring to which they are bonded. In formula (2e), Z represents an oxygen atom or a sulfur atom.

式（３）中、Ｒ^３〜Ｒ^１０は、各々独立に水素原子、フッ素原子又は１価の有機基を表し、Ｒ^３〜Ｒ^１０の少なくとも１つはフッ素原子、メチル基又はトリフルオロメチル基を表す。

In formula (3), R ^{3 to} R ¹⁰ independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and ^{at least one of R 3 to} R ¹⁰ is a fluorine atom, a methyl group or a trifluoromethyl group. Represents.

^{The monovalent organic groups of R 1} and R ^{2 in} the above formula (1) include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 carbon atoms). 6) Fluoroalkyl groups and the like can be mentioned.

In X and Y in the above formula (2d), the divalent groups that are not conjugated to the benzene ring include an oxygen atom, a dimethylmethylene group, a bis (trifluoromethyl) methylene group, a dimethylsilylene group, and a methyltrifluoromethylmethylene group. And so on.

B in the formula (1) is a structure derived from a diamine used as a raw material, and is a divalent organic group represented by the formula (3).
Examples of the monovalent organic group of R ^{3 to R 10} include a methyl group and a trifluoromethyl group. From the viewpoint of good i-ray transmittance and low stress, it is preferable that two or more are methyl groups or trifluoromethyl groups.

Examples of the polyimide include a polyimide formed from the above-mentioned polyimide precursor.

（式（４）中、Ｕは単結合又は２価の基であり、Ｗは２価の基である。） The polybenzoxazole precursor is a precursor having a structural unit represented by the following formula (4).

(In formula (4), U is a single bond or a divalent group and W is a divalent group.)

（式（ＵＶ１）中、Ｒ^１１及びＲ^１２は各々独立に水素原子、フッ素原子、炭素数１〜６のアルキル基又は炭素数１〜６のフッ素化アルキル基であり、ａは１〜３０の整数である。） The divalent group of U in the formula (4) is preferably a group containing an aliphatic chain structure having 1 to 30 carbon atoms, and is a group containing a structure represented by the following formula (UV1). Is more preferable.

(In the formula (UV1), R ¹¹ and R ¹² are independently hydrogen atoms, fluorine atoms, alkyl groups having 1 to 6 carbon atoms or fluorinated alkyl groups having 1 to 6 carbon atoms, and a is 1 to 30. It is an integer.)

^{R 11} and R ¹² in the formula (UV1) are preferably a methyl group or a trifluoromethyl group, and more preferably a trifluoromethyl group, from the viewpoint of polymer transparency.
a is preferably an integer of 1-5.

The divalent group of W preferably has a structure derived from a dicarboxylic acid, and examples of such a raw material dicarboxylic acid include dodecanedioic acid, isophthalic acid, terephthalic acid, and 2,2-bis (4-carboxyphenyl). -1,1,1,3,3,3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 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-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid Examples include acid.

Examples of the polybenzoxazole include polybenzoxazole formed from the above-mentioned polybenzoxazole precursor.

Examples of the novolak resin include aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol and hydroquinone, and phenols which are at least one selected from these alkyl-substituted or halogen-substituted aromatic compounds such as formaldehyde, acetaldehyde and benzaldehyde. Those obtained by polycondensation with an aldehyde compound are preferable, and examples thereof include phenol and formaldehyde resin, cresol and formaldehyde resin, phenol, cresol and formaldehyde cocondensation resin.

The molecular weight of the polymer of the component (a) is preferably a weight average molecular weight of 1000 to 100,000 in terms of polystyrene, more preferably 1500 to 100,000, and even more preferably 2000 to 85,000. If the weight average molecular weight is less than 10000, the solubility in an alkaline developer may become too high, and if it is larger than 100,000, the solubility in a solvent decreases or the viscosity of the solution increases, resulting in poor handleability. There is a risk of doing so.
The weight average molecular weight can be measured by the gel permeation chromatograph method and can be determined by conversion using a standard polystyrene calibration curve.

(Component (b): Onium salt having i-ray sensitivity)
The component (b) can be used without particular limitation as long as it is an onium salt having i-ray sensitivity, but a compound having an iodonium structure or a sulfonium structure is preferable. From the viewpoint of high contrast, a compound having an iodonium structure is more preferable.
The component (b) differs in the solubility of the exposed portion and the unexposed portion in the developing solution in response to the light when, for example, the resin composition is applied onto the substrate and the formed resin film is irradiated with light. It has a function of imparting.
The component (b) is preferably one having high compatibility with the component (a).

The component (b) is preferably a compound that does not inhibit the dissolution of the component (a) in the alkaline aqueous solution before the i-ray exposure and does not inhibit the dissolution of the component (a) in the alkaline aqueous solution after the i-ray exposure. By releasing the dissolution inhibition in the exposed portion after i-line exposure, when a thick pattern cured film is formed using the resin composition of the present invention, patterning can be performed with a sensitivity and development time within a practical range. ..

（式中、Ｘは対陰イオンである。また、芳香環には置換基を有していてもよい。） As the component (b), for example, a compound represented by the following general formula (b-1) can be used.

(In the formula, X is a counter anion. Further, the aromatic ring may have a substituent.)

The substituent on the aromatic ring is not particularly limited as long as it does not interfere with the effect of the present invention. Specific examples thereof include an alkyl group, an alkenyl group, an alkoxy group, a trialkylsilyl group, a group in which a part or all of the hydrogen atom of each group is replaced with a fluorine atom, a chlorine atom, a bromine atom, a fluorine atom and the like. Be done. Moreover, the aromatic ring may have a plurality of substituents.

X ^- is the, p- toluenesulfonate ion, trifluoromethanesulfonate ion, hexafluoro boride ion, 9,10-dimethoxy-anthracene-2-sulfonate ion, 8-anilino naphthalene-1-sulfonic acid ion, methyl Examples thereof include sulfonic acid ion, sulfate ion, nitrate ion, trichloroacetate ion, chloride ion and the like.

Specific examples of compounds having an iodonium structure include diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate, diphenyliodonium-8-anilinonaphthalene-1-sulfonate, diphenyliodonium sulfonate, diphenyliodonium trifluoromethyl sulfonate, Diphenyliodonium nonafluorobutane sulfonate, diphenyliodonium toluenesulfonate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium hexafluorophosphate, 4-methoxyphenyliodonium nitrate, 4-methoxyphenyliodonium trifluoromethylsulfo Nate, 4,4'-di-t-butyldiphenyliodonium trifluoromethylsulfonate, phenyl (5-trifluoromethylsulfonyl-4-octen-4-yl) iodonium hexafluoroborate and the like can be mentioned.

（式中、Ｍｅはメチル基である。） Of these, from the viewpoint of high sensitivity and high dissolution contrast, it is preferable to use diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate, which is a compound represented by the following formula (b-2).

(In the formula, Me is a methyl group.)

Further, a compound represented by the following formula (b-3) is also preferable.

The content of the component (b) is preferably 2 to 50 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the component (a).

When the component (b) is in the above range, the dissolution inhibition of the component (a) is strongly caused in the unexposed portion, and the dissolution inhibition effect disappears in the exposed portion, so that the dissolution contrast between the unexposed portion and the exposed portion is lost. Can be raised. Since the dissolution contrast is high, it can be suitably used when forming a thick pattern cured film. Moreover, the development time can be shortened.

((C) component: solvent)
As the component (c), γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, Examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone and the like. Usually, there is no particular limitation as long as other components in the photosensitive resin composition can be sufficiently dissolved.
Among these, from the viewpoint of excellent solubility of each component and coating property at the time of resin film formation, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-Dimethylacetamide, dimethyl sulfoxide is preferably used.

The content of the component (c) is not particularly limited, but is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the component (a).

(Component (d): Cross-linking agent)
The component (d) can react with an alkali-soluble resin (crosslinking reaction) or the crosslinking agent itself can be polymerized in the step of heat-treating the patterned resin film after coating, exposing and developing the resin composition. Thereby, even when the resin composition is cured at a relatively low temperature, for example, 250 ° C. or lower, good mechanical properties, chemical resistance and flux resistance can be imparted.

The component (d) is not particularly limited as long as it is a compound that is crosslinked or polymerized in the heat treatment step, but is a compound having an alkoxyalkyl group such as a methylol group or an alkoxymethyl group, an epoxy group, an oxetanyl group or a vinyl ether group. Is preferable.
A compound in which these groups are bonded to a benzene ring, a melamine resin in which the N-position is substituted with a methylol group or an alkoxymethyl group, or a urea resin is preferable. Further, a compound in which these groups are bonded to a benzene ring having a phenolic hydroxyl group is more preferable because the dissolution rate of the exposed portion can be increased during development and the sensitivity can be improved.

Among them, two or more methylol groups or alkoxymethyl groups are used from the viewpoints of good sensitivity, varnish stability, and prevention of melting of the photosensitive resin film when the photosensitive resin film is cured after pattern formation. The compound having is preferable.

（式（５）中、Ｒ_１及びＲ_２は、それぞれ独立に炭素数１〜３０のアルキル基である。） As the component (d), a compound represented by the following formula (5) is preferable because a cured film having excellent chemical resistance can be obtained when the resin composition is cured at a low temperature of 250 ° C. or lower.

(In formula (5), R ₁ and R ₂ are independently alkyl groups having 1 to 30 carbon atoms.)

Moreover, it is also preferable to use the following compounds as the component (d).

The content of the component (d) is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the component (a).

In the first aspect of the first resin composition of the present invention, the amount of the naphthoquinone diazide compound is preferably 0 or more and less than 100 ppm with respect to 100 parts by mass of the component (a). In the first resin composition of the present invention, it is more preferably 0 to 50 ppm, further preferably 0 to 10 ppm, and particularly preferably not containing a naphthoquinone diazide compound (0 ppm).
When the naphthoquinone diazide compound is within the above range, the first resin composition of the present invention can maintain good photosensitive characteristics even in a thick film having a film thickness of 20 μm or more after coating.

Examples of the naphthoquinone diazide compound include a polyhydroxy compound and a reaction product of 1,2-naphthoquinone diazide-4-sulfonyl chloride or 1,2-naphthoquinone diazide-5-sulfonyl chloride.
Examples of the polyhydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, 2-hydroxyphenyl-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, 2- (4-hydroxyphenyl) -2- [4- [1,1-bis (4-hydroxyphenyl) ethyl] phenyl] propane, 4b, 5, 9b, 10 -Tetrahydro-1,3,6,8-Tetrahydroxy-5,10-dimethylindeno [2,1-a] inden, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy) Phyl) ethane and the like can be mentioned. Also, it is not necessarily limited to those listed here.

In the first resin composition of the present invention, the acid-reactive protecting group-containing compound is preferably 0 to 1000 ppm based on 100 parts by mass of the component (a). In the first resin composition of the present invention, it is more preferably 0 to 100 ppm, further preferably 0 to 10 ppm, and particularly preferably not containing an acid-reactive protecting group-containing compound (0 ppm).
Within the above range, a thick film pattern can be formed at a lower cost than a chemically amplified positive photosensitive resin composition in which a PEB (Post Exposure Bake) step is indispensable.

Examples of the acid-reactive protecting group-containing compound include compounds in which the hydrogen atom of a carboxylic acid is replaced with a 1-alkoxyalkyl group or the like. Examples of the carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 4-carboxyphthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 1,4. -Cyclohexanedicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 2,6-naphthalenedicarboxylic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4'-Dicarboxybiphenyl, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, cholic acid, deoxycholic acid, lithocole Acid is mentioned. Examples of the 1-alkoxyalkyl group include tertiary alkyl groups such as t-butyl group and t-amyl group, isobolonyl group, ethoxymethyl group, 1-ethoxyethyl group, 1-butoxyethyl group and 1-isobutoxyethyl group. And so on.

The first resin composition of the present invention may contain a coupling agent, a dissolution accelerator, a dissolution inhibitor, a surfactant, a leveling agent and the like, if necessary.

In the first photosensitive resin composition of the present invention, the components (a) to (d) are preferably 91% by mass or more, preferably 92% by mass or more, based on the entire composition. More preferably, it is 93% by mass or more.

[Second positive photosensitive resin composition]
The second positive photosensitive resin composition of the present invention contains (a) an alkali-soluble resin, (b) an onium salt that generates an acid by i-ray exposure, and (c) a solvent, and (a) component 100. It contains 0 to 100 ppm of a naphthoquinone diazide compound or an acid-reactive protecting group-containing compound with respect to parts by mass.
The components (a) to (c) are the same as those of the first positive photosensitive resin composition. The second positive photosensitive resin composition may or may not contain (d) a cross-linking agent. The component (d) is the same as that of the first positive photosensitive resin composition.

In the second resin composition, the content of the naphthoquinone diazide compound is 0 to 100 ppm with respect to 100 parts by mass of the component (a). Further, it is preferably 0 to 50 ppm, more preferably 0 to 10 ppm, and further preferably not containing the naphthoquinone diazide compound (0 ppm).
When the naphthoquinone diazide compound is within the above range, the second resin composition can maintain good photosensitive characteristics even if it is a thick film having a film thickness of 20 μm or more after coating.

In the second resin composition, the content of the acid-reactive protecting group-containing compound is 0 to 100 ppm with respect to 100 parts by mass of the component (a). Further, it is preferably 0 to 50 ppm, more preferably 0 to 10 ppm, and further preferably not containing an acid-reactive protecting group-containing compound (0 ppm).
Within the above range, a thick pattern cured film can be formed at a lower cost than a chemically amplified positive photosensitive resin composition in which a PEB (Post Exposure Bake) step is indispensable.

In the second photosensitive resin composition, the components (a) to (c) are preferably 91% by mass or more, more preferably 92% by mass or more, and 93% by mass, based on the entire composition. % Or more is more preferable, 94% by mass or more is particularly preferable, 95% by mass or more is extremely preferable, 96% by mass or more is extremely particularly preferable, and 97% by mass or more. Is most preferable, and 98% by mass or more is most particularly preferable.

The second positive photosensitive resin composition of the present invention is the same as the first positive photosensitive resin composition except for the above-mentioned matters.

[Manufacturing method of pattern cured film]
In the production method of the present invention, the above-mentioned resin composition is applied onto a substrate and dried to form a photosensitive resin film, and the obtained photosensitive resin film is exposed to a predetermined pattern. A pattern-cured film can be produced by including a step of developing the resin film with an alkaline aqueous solution to obtain a pattern resin film and a step of heat-treating the pattern resin film.

(Resin film forming process)
Examples of the substrate include glass, semiconductors, _{metal oxide insulators such as TiO 2} and SiO ₂ , silicon nitride, copper, and copper alloys.
The application is not particularly limited, but can be applied using a spinner or the like.

Drying can be performed using a hot plate, an oven, or the like. The heating temperature is preferably 100 to 150 ° C. The heating time is preferably 30 seconds to 5 minutes. As a result, a resin film obtained by forming the above-mentioned resin composition into a film can be obtained.
The film thickness of the resin film is preferably 5 to 100 μm, more preferably 8 to 50 μm, and even more preferably 10 to 40 μm.

(Exposure process)
In the exposure step, a predetermined pattern can be exposed through a mask. Examples of the active light beam to be irradiated include ultraviolet rays including i-rays, visible rays, radiation and the like, and i-rays are preferable. As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine and the like can be used.

(Development process)
By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a positive photosensitive resin composition is used, the exposed portion is removed with a developing solution.
Examples of the alkaline aqueous solution used as the developing solution include sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide and the like, and tetramethylammonium hydroxide is preferable.
The concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass.
The development time varies depending on the type of polymer used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and from the viewpoint of productivity, 30 seconds to 4 minutes. Is even more preferable.

Alcohols or surfactants may be added to the developer. The amount to be added is 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 developing solution.

(Heat treatment process)
By heat-treating the pattern resin film, a crosslinked structure can be formed between the functional groups of the component (a) or between the component (a) and the component (d), and a pattern cured film can be obtained. When the component (a) contains a polyimide precursor or a polybenzoxazole precursor, each precursor undergoes a dehydration ring closure reaction to obtain a corresponding polymer.

The heating temperature is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., and even more preferably 160 to 230 ° C.
Within the above range, damage to the substrate and the device can be suppressed to a small extent, the device can be produced with a high yield, and energy saving of the process can be realized.

The heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
Within the above range, the cross-linking reaction or the dehydration ring closure reaction can be sufficiently proceeded.
The atmosphere of the heat treatment may be the atmosphere or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the pattern resin film.

Examples of the apparatus used in the heat treatment step include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace and the like.

Further, a microwave curing device or a frequency variable microwave curing device may be used for the heat treatment.
By using these, it is possible to effectively heat only the pattern resin film while keeping the temperature of the substrate or device, for example, 220 ° C. or lower (see, for example, Japanese Patent No. 2587148). When curing is performed using microwaves, standing waves can be prevented and the substrate surface can be uniformly heated by irradiating the microwaves in a pulse shape while changing the frequency.
When the substrate includes metal wiring like an electronic component, it is possible to prevent the generation of discharge from the metal by irradiating the microwave in a pulse shape while changing the frequency, and it is possible to protect the electronic component from destruction.
By irradiating the microwave in a pulse shape, the set heating temperature can be maintained, and damage to the pattern resin film and the substrate can be prevented.

[Cured product]
The cured product of the present invention is a cured product of the positive photosensitive resin composition of the present invention. As a method for obtaining a cured product, the above-mentioned heat treatment step can be adopted.
The cured product of the present invention may be the above-mentioned pattern cured film.

[Electronic components]
The pattern cured film and the cured product produced by the above method can be used as an interlayer insulating film, a cover coat layer or a surface protective film.
Highly reliable electronic components such as semiconductor devices, multilayer wiring boards, and various electronic devices can be manufactured by using the interlayer insulating film, cover coat layer, surface protective film, and the like.

[Manufacturing process of semiconductor devices]
Using the method of the present invention, a semiconductor device, particularly a device having a package structure without a UBM layer, can be manufactured.
In the package structure without the UBM layer, the solder bumps are mounted directly on the copper rewiring, and the resin composition of the outermost layer reinforces the bumps in order to relieve the stress applied to the bumps and ensure reliability. It has a structure to be used.

The manufacturing process is shown in FIG. The photosensitive resin composition is applied onto a substrate 10 having a rewiring layer 20 and dried to form a resin film (1-1), and the obtained resin film 30 is exposed to a predetermined pattern. The exposed resin film is developed with a developing solution (1-2), the pattern resin film obtained by the development is heat-treated, and then a conductive ball or a conductive bump 40 is mounted (1-). 3) It is possible to manufacture a package without a UBM layer.
In the above package, in order to ensure reliability by reinforcing the bumps with the pattern resin film of the outermost layer, it is preferable to increase the thickness of the pattern cured film from the conventional film thickness (10 μm or less).

FIG. 2 is a schematic cross-sectional view of a semiconductor device having a rewiring structure without a UBM layer. In the semiconductor device 100 of FIG. 2, a metal (aluminum or the like) wiring 120 is provided on the wafer 110, and the insulating layer 130 is laminated so as to cover both ends of the wafer 110 and the metal wiring 120. An interlayer insulating film 140 is provided on the insulating layer 130 so as to cover a part of the insulating layer 130 and the metal wiring 120, and covers all the remaining exposed portions of the metal wiring 120 and the interlayer insulating film 140. The rewiring layer 150 is laminated. The conductive balls 170 are provided in contact with the rewiring layer 150, and the cover coat layer 160 is laminated on the rewiring layer 150 so as to fill the gaps formed by the rewiring layer 150 and the conductive balls 170.
By forming the cover coat layer 160 into a thick film using the resin composition of the present invention, it is possible to manufacture a semiconductor device without providing a UBM layer having a complicated forming process.

The semiconductor device is an embodiment of the electronic component of the present invention, but the present invention is not limited to the above, and various structures can be adopted.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. The present invention is not limited to the following examples.

[Synthesis of polybenzoxazole precursor]
Synthesis example 1
60 g of N-methylpyrrolidone was charged in a 0.2 liter flask equipped with a stirrer and a thermometer, and 13.92 g (38 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. And stirred and dissolved. Subsequently, while maintaining the temperature at 0 to 5 ° C., 10.69 g (40 mmol) of dodecanedioic acid dichloride was added dropwise over 10 minutes, and then the solution in the flask was stirred for 60 minutes. The above solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then reduced under reduced pressure to obtain a polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as Polymer I). do). The weight average molecular weight of the polymer I, which was determined by gel permeation chromatography (GPC) standard polystyrene conversion, was 33,100, and the dispersity was 2.0.

The conditions for measuring the weight average molecular weight by the GPC method are as follows. The measurement was carried out using a solution of 1 ml of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.
Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: L6000 manufactured by Hitachi, Ltd.
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow velocity: 1.0 ml / min, Detector: UV270 nm

Synthesis example 2
60 g of N-methylpyrrolidone was charged in a 0.2 liter flask equipped with a stirrer and a thermometer, and 13.92 g (38 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. And stirred and dissolved. Subsequently, 11.86 g (40 mmol) of 4,4'-diphenyl ether dicarboxylic acid dichloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., the temperature was returned to room temperature, and the solution in the flask was stirred for 3 hours. The above solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then reduced under reduced pressure to obtain a polyhydroxyamide (hereinafter referred to as Polymer II). The weight average molecular weight of Polymer II was 22,400 and the dispersity was 3.2, which was determined by GPC method standard polystyrene conversion in the same manner as in Synthesis Example 1.

Synthesis example 3
Except for replacing 10.69 g (40 mmol) of dodecanedioic acid dichloride used in Synthesis Example 1 with 7.48 g (28 mmol) of dodecanedioic acid dichloride and 3.56 g (12 mmol) of 4,4'-diphenyl ether dicarboxylic acid dichloride. Synthesis was carried out in the same manner as in Synthesis Example 1 to obtain a polyhydroxyamide (hereinafter referred to as Polymer III). The weight average molecular weight of Polymer III, which was determined by standard polystyrene conversion in the same manner as in Synthesis Example 1, was 41,800 and the dispersity was 2.0.

[Synthesis of polyimide precursor]
Synthesis example 4
50 g of N-methylpyrrolidone was charged in a 0.2 liter flask equipped with a stirrer and a thermometer, and 13.82 g (18 mmol) of 4,4'-diamino-2,2'-dimethylbiphenyl was added and dissolved by stirring. bottom. Subsequently, while maintaining the temperature at 0 to 5 ° C., 6.20 g (20 mmol) of 4,4'-oxydiphthalic dianhydride was added dropwise over 10 minutes, the temperature was returned to room temperature, and the solution in the flask was stirred for 3 hours. The above solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then reduced under reduced pressure to obtain polyamic acid (hereinafter referred to as Polymer IV). The weight average molecular weight of the polymer IV was 39,000 and the dispersity was 4.5, which was determined by GPC method standard polystyrene conversion in the same manner as in Synthesis Example 1.

[Synthesis of component (b)]
Synthesis example 5
In a 0.5 liter flask equipped with a stirrer and a thermometer, 150 mL of ion-exchanged water was charged, 4.3 g (14 mmol) of diphenyliodonium chloride was added, and the mixture was stirred and dissolved while heating at 100 ° C. Separately, 300 mL of ion-exchanged water was placed in a 1.0-liter flask equipped with a stirrer and a thermometer, 4.7 g (14 mmol) of sodium 9,10-dimethoxyanthracene sulfonate was added, and the mixture was heated at 100 ° C. While stirring and dissolving. Subsequently, an aqueous solution of diphenyliodonium chloride was poured into an aqueous solution of sodium 9,10-dimethoxyanthracene sulfonate, and the mixture was stirred for 3 hours until the temperature returned to room temperature. The precipitate was recovered, washed with pure water three times, and then dried under reduced pressure to obtain diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate (b1).

Synthesis example 6
300 mL of ion-exchanged water was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, 10.0 g (32 mmol) of diphenyliodonium chloride was added, and the mixture was stirred and dissolved while heating at 100 ° C. Separately, 300 mL of ion-exchanged water was placed in a 1.0-liter flask equipped with a stirrer and a thermometer, 10.0 g (32 mmol) of ammonium 8-anilino-1-naphthalene sulfonate was added, and the temperature was 100 ° C. The mixture was stirred and dissolved while heating. Subsequently, an aqueous solution of diphenyliodonium chloride was poured into an aqueous solution of ammonium 8-anilino-1-naphthalene sulfonate, and the mixture was stirred for 3 hours until the temperature returned to room temperature. The precipitate was recovered, washed with pure water three times, and then dried under reduced pressure to obtain diphenyliodonium-8-anilinonaphthalene-1-sulfonate (b2).

[Synthesis of acid-reactive protecting group-containing compounds]
Synthesis example 7
4.54 g (17.6 mmol) of 4,4'-dicarboxydiphenyl ether was placed in a 100 mL three-necked flask and suspended in 30 g of N-methylpyrrolidone. While cooling with ice, 3.74 g (39.6 mmol) of chloromethyl ethyl ether was added, followed by 3.55 g (35.1 mmol) of triethylamine. After stirring in an ice bath for 3 hours, the precipitated crystals were removed by filtration. A few drops of saturated aqueous sodium hydrogen carbonate solution were added to the mother liquor to stop the reaction, and the organic layer extracted with ethyl acetate was washed in the order of saturated aqueous sodium hydrogen carbonate solution, water, and saturated brine, and dried over anhydrous sodium sulfate. .. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the mixture was dried to obtain an acid-reactive protecting group-containing compound (e1).

[Examples of First Positive Photosensitive Resin Composition]
Examples 1-19 and Comparative Examples 1-13
The photosensitive resin compositions of Examples 1 to 19 and Comparative Examples 1 to 13 were prepared with the components and blending amounts shown in Tables 1 to 4. The blending amounts in Tables 1 to 4 are the parts by mass of the components (b) to (d), (b'-1) and (e1) with respect to 100 parts by mass of each polymer which is the component (a).
The components used are as follows.

(A) Ingredient:
Polymer I: Polymer I obtained in Synthesis Example 1
Polymer II: Polymer II obtained in Synthesis Example 2
Polymer III: Polymer III obtained in Synthesis Example 3
Polymer IV: Polymer IV obtained in Synthesis Example 4
Polymer V: Cresol Novolac EP4020G (manufactured by Asahi Organic Materials Industry Co., Ltd.)

(B) Ingredient:
(B1): Diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate obtained in Synthesis Example 5 (b2): Diphenyliodonium-8-anilinonaphthalene-1-sulfonate obtained in Synthesis Example 6

(C) Ingredient:
BLO: γ-butyrolactone NMP: N-methylpyrrolidone EL: ethyl lactate

(D) Ingredient:
D1: 1,3,4,6-tetrakis (methoxymethyl) glycouryl having the following structure (manufactured by Sanwa Chemical Co., Ltd., trade name "MX-270")

D2: "Nikalac MX-280" with the following structure (manufactured by Sanwa Chemical Co., Ltd., product name)

The compounds used other than the components (a) to (d) are as follows.
(B'-1): 2- (4-Hydroxyphenyl) -2- [4- [1,1-bis (4-hydroxyphenyl) ethyl] phenyl] propane and naphthoquinone-1,2-diazide-5-sulfonyl A compound obtained by reacting chloride with a molar ratio of 1: 3.

e1: Acid-reactive protecting group-containing compound obtained in Synthesis Example 7.

[Evaluation of dissolution rate and dissolution contrast]
The photosensitive resin compositions of Examples 1 to 19 and Comparative Examples 1 to 13 were spin-coated on a silicon substrate and dried at 120 ° C. for 3 minutes to form a resin film having a film thickness of 10 or 25 μm after drying. bottom. The obtained resin film is exposed through an interference filter using an ultra-high pressure mercury lamp and a proximity exposure device UX-1000SM-XJ01 (manufactured by Ushio, Inc.), and an i-line of ^{400 mJ / cm 2 is specified.} The pattern was irradiated.
After exposure, develop with 2.38 mass% aqueous solution of TMAH at 23 ° C. until the silicon substrate of the exposed portion is exposed (the development time required in each example is defined as each development time), and then rinse with water. Then, a pattern resin film was obtained.

The value obtained by dividing the film thickness after drying by the developing time was defined as the dissolution rate of the exposed portion.
Exposure part dissolution rate (nm / s) = film thickness after drying / development time

Further, the film thickness of the unexposed portion after development was measured, and the thickness obtained by subtracting the film thickness of the unexposed portion after development from the film thickness after drying was divided by the development time to obtain the dissolution rate of the unexposed portion.
Unexposed part dissolution rate (nm / s) = (film thickness after drying-film thickness of unexposed part after development) / development time

The dissolution contrast was determined by dividing the dissolution rate of the exposed portion by the dissolution rate of the unexposed portion.
Dissolution Contrast = Exposed Area Dissolution Rate / Unexposed Area Dissolution Rate The results are shown in Tables 1 to 4.

When each of the above pattern resin films was heat-treated at 200 ° C. for 1 hour, a good pattern cured film was obtained.

Examples 20-28 and Comparative Examples 14-15
The photosensitive resin compositions of Examples 20 to 28 and Comparative Examples 14 to 15 were prepared with the components and blending amounts shown in Table 5. The blending amounts in Table 5 are the same as those in Tables 1 to 4.

[Evaluation of pattern formation]
A pattern resin film was formed in the same manner as in Examples 1 to 19 and Comparative Examples 1 to 13, except that the film thickness after drying was 10 to 30 μm, the exposure amount was 800 mJ / cm ^{2, and the developing time was 150 seconds.}

In the above pattern resin film, a line and space pattern having a line width of 20 μm was observed with a microscope and a digital microscope VHX-100F (manufactured by KEYENCE Co., Ltd.) to confirm the presence or absence of scum. The case where patterning was possible without scum was designated as A, and the case with scum was designated as B. The results are shown in Table 5.

When each of the above pattern resin films was heat-treated at 200 ° C. for 1 hour, a good pattern cured film was obtained.

[Examples of Second Positive Photosensitive Resin Composition]
Examples 29-44 and Comparative Examples 16-28
The photosensitive resin compositions of Examples 29 to 44 and Comparative Examples 16 to 28 were prepared with the components and blending amounts shown in Tables 6 to 8. The blending amounts in Tables 6 to 8 are the parts by mass of the components (b) to (d) and the component (b') with respect to 100 parts by mass of each polymer which is the component (a).
The component (b') is as follows.
(B'1): Acid-reactive protecting group-containing compound obtained in Synthesis Example 7 ((e1) in Examples 1-28 and Comparative Examples 1-15)
(b'2): Compound represented by the following structural formula (TPPA528 (trade name) manufactured by Daito Chemix Co., Ltd., naphthoquinone diazide compound)

[Evaluation of dissolution rate and dissolution contrast]
The dissolution rate and dissolution contrast were evaluated in the same manner as in Examples 1 to 19 and Comparative Examples 1 to 13. In Examples 29 to 44 and Comparative Examples 16 to 28, the following evaluation criteria were used.
The case where the dissolution rate of the exposed portion was 150 nm / s or more was designated as A, the case where it was 50 or more and 150 nm / s was designated as B, and the case where it was slower than 50 nm / s was designated as C.
The case where the unexposed portion dissolution rate was 30 nm / s or less was designated as A, the case where it was 30 or more and 100 nm / s was designated as B, and the case where it was faster than 100 nm / s was designated as C.
The case where the dissolution contrast is 6 or more is A, the case where the dissolution contrast is 4 or more and less than 6 is B, the case where the dissolution contrast is 2 or more and less than 4 is C, and the case where the dissolution contrast is less than 2 is D.
The results are shown in Tables 6 and 7.

When each of the above pattern resin films was heat-treated at 200 ° C. for 1 hour, a good pattern cured film was obtained.

Examples 45-49 and Comparative Examples 29, 30
The photosensitive resin compositions of Examples 45 to 49 and Comparative Examples 29 and 30 were prepared with the components and blending amounts shown in Table 8.

[Evaluation of pattern formation]
The pattern forming property was evaluated in the same manner as in Examples 20 to 28 and Comparative Examples 14 and 15. The results are shown in Table 8.

When each of the above pattern resin films was heat-treated at 200 ° C. for 1 hour, a good pattern cured film was obtained.

The photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices, multilayer wiring boards, and various electronic devices.

Claims (11)

Positive photosensitive containing (a) a polybenzoxazole precursor having a structural unit represented by the following formula (4), (b) a compound represented by the following general formula (b-1), and (c) a solvent. It is a sex resin composition
Contains no naphthoquinone diazide compounds
A positive photosensitive resin composition containing no acid-reactive protecting group-containing compound.

(In formula (4), U is a single bond or a divalent group and W is a divalent group.)

(In the formula, X is a counter anion. Further, the aromatic ring may have a substituent.) The positive photosensitive resin composition according to claim 1, further comprising (d) a cross-linking agent. Claim 1 in which the component (b) is a compound that inhibits the dissolution of the component (a) in an alkaline aqueous solution before i-ray exposure and does not inhibit the dissolution of the component (a) in an alkaline aqueous solution after i-ray exposure. Alternatively, the positive photosensitive resin composition according to 2. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the component (b) is a compound represented by the following formula (b-2).

(In the formula, Me is a methyl group.) The positive photosensitive resin composition according to any one of claims 1 to 4, which is used for forming an interlayer insulating film, a cover coat layer or a surface protective film. The positive photosensitive resin composition according to any one of claims 1 to 4, which is used for forming an interlayer insulating film, a cover coat layer or a surface protective film of a semiconductor device having a UBM-free structure. A step of applying the positive photosensitive resin composition according to any one of claims 1 to 6 onto a substrate and drying it to form a photosensitive resin film.
A step of exposing the obtained photosensitive resin film to a predetermined pattern, and
The process of developing the exposed resin film with an alkaline aqueous solution to obtain a patterned resin film,
The step of heat-treating the pattern resin film and
A method for producing a pattern cured film including. The method for producing a pattern cured film according to claim 7, wherein the temperature of the heat treatment is 250 ° C. or lower. The cured product of the positive photosensitive resin composition according to any one of claims 1 to 6. An interlayer insulating film, a cover coat layer or a surface protective film using the cured product according to claim 9. An electronic component having the interlayer insulating film, cover coat layer or surface protective film according to claim 10.

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