JP2021081643A - Positive type photosensitive resin composition, pattern cured film and method for producing the same, semiconductor element, and electronic device - Google Patents

Abstract

To provide a positive type photosensitive resin composition which has a low dielectric loss tangent, has good resolution after curing and is free from white turbidness of appearance and residues, a pattern cured film using the same and a method for producing the same, a semiconductor element having the pattern cured film as an interlayer insulating layer or a surface protective layer, and an electronic device having the semiconductor element.SOLUTION: A positive type photosensitive resin composition contains (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound generating an acid with light, (C) a heat crosslinking agent, and (D) an acrylic resin component having a structural unit represented by the following general formula (1). The phenol component in the component (A) is within a range of 29-42 mass% based on the whole photosensitive resin composition, and a weight average molecular weight of (D) the acrylic resin component is 31,000 or more and 47,000 or less.SELECTED DRAWING: None

Description

The present invention relates to a positive photosensitive resin composition, a pattern cured film and a method for producing the same, a semiconductor element, and an electronic device.

In recent years, with the increasing integration and miniaturization of semiconductor devices, the surface protective layer and interlayer insulating layer of semiconductor devices have become more excellent in electrical characteristics (dielectric modulus, etc.), heat resistance (thermal expansion coefficient, glass transition temperature, etc.), and so on. It is required to have mechanical properties (elastic modulus, elongation at break, etc.). In particular, low dielectric loss tangent and low dielectric constant are required for electrical characteristics in the future.
As a material for forming a surface protective layer and an interlayer insulating layer having such characteristics, a photosensitive resin composition containing an alkali-soluble resin having a phenolic hydroxyl group has been developed (for example, Patent Document 1, Patent Document 1, See 2 and 3). A patterned resin film (patterned resin film) is obtained by applying and drying these photosensitive resin compositions on a substrate to form a resin film, and exposing and developing the resin film. Then, the pattern-cured film (pattern-formed cured film) can be formed by heat-curing the pattern resin film, and the pattern-cured film can be used as a surface protective layer and an interlayer insulating layer.
Moreover, the low dielectric loss tangent and the low dielectric constant have the advantage of improving the cut-off property.

Japanese Unexamined Patent Publication No. 2008-3098885 Japanese Unexamined Patent Publication No. 2007-57595 International Publication No. 2010/073948

In order to make the resin have a low dielectric loss tangent, it is mainly necessary to reduce the hydroxyl group component (phenol component) having a high dielectric loss tangent value. However, when the phenol component is reduced, the ratio of other low molecular weight components is increased, which may deteriorate the solubility of the resin in an alkaline developer, the resolution after curing, and the heat resistance.
By the way, in the photosensitive resin composition, when the compatibility of each component such as the resin and the photosensitive agent is poor, the photosensitive resin composition tends to become cloudy, and the pattern cured film formed on the substrate tends to become cloudy. There is. If the pattern-cured film becomes cloudy, it becomes difficult to recognize the alignment mark on the substrate in the manufacturing process of the semiconductor element after the pattern-cured film is formed, which makes the work difficult.

With the conventional photosensitive resin composition, it is difficult to satisfy all the conditions of excellent post-curing resolution and appearance while maintaining low dielectric loss tangent.

Therefore, an object of the present invention is to provide a positive photosensitive resin composition that maintains low dielectric loss tangent and has no resolution after curing, white turbidity in appearance, and no residue. Another object of the present invention is to provide a method for producing a pattern cured film using the positive photosensitive resin composition, a semiconductor element having the pattern cured film as an interlayer insulating layer or a surface protective layer, and an electronic device having the semiconductor element. And.

The present invention relates to the following.
<1> (A) An alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that generates an acid by light, (C) a thermal cross-linking agent, and (D) a structure represented by the following general formula (1). It contains an acrylic resin component having a unit, the phenol component in the component (A) is in the range of 29 to 42% by mass of the entire photosensitive resin composition, and the weight average molecular weight of the acrylic resin component in (D) is. A positive photosensitive resin composition having a value of 31,000 or more and 47,000 or less.

［一般式（１）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は４〜２０のアルキル基を示す。］
＜２＞ （Ｄ）のアクリル樹脂成分が、下記一般式（２）で表される構造単位を有することを特徴とする上記＜１＞に記載のポジ型感光性樹脂組成物

[In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group of 4 to 20. ]
<2> The positive photosensitive resin composition according to <1> above, wherein the acrylic resin component of (D) has a structural unit represented by the following general formula (2).

［一般式（２）中、Ｒ^３は水素原子又はメチル基を示し、Ｒ^４は１級、２級又は、３級アミノ基を有する１価の有機基を示す。］
＜３＞ （Ｃ）熱架橋剤は、２つ以上のエポキシ基を有する化合物からなる上記＜１＞又は＜２＞に記載のポジ型感光性樹脂組成物。
＜４＞ （Ｃ）熱架橋剤は、下記一般式（３）で表される化合物を含有する上記＜１＞〜＜３＞のいずれか一項に記載のポジ型感光性樹脂組成物。

[In the general formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group having a primary, secondary or tertiary amino group. ]
<3> The positive photosensitive resin composition according to <1> or <2> above, wherein the (C) thermal cross-linking agent comprises a compound having two or more epoxy groups.
<4> The positive photosensitive resin composition according to any one of <1> to <3> above, wherein the (C) thermal cross-linking agent contains a compound represented by the following general formula (3).

［一般式（３）中、Ｒ^７〜Ｒ^１２は、それぞれ独立に炭素数１〜１０のアルキル基を示す。］
＜５＞ （Ｂ）成分がｏ−キノンジアジド化合物である、上記＜１＞〜＜４＞のいずれか一項に記載のポジ型感光性樹脂組成物。
＜６＞ パターンを有し、前記パターンが上記＜１＞〜＜５＞のいずれか一項に記載のポジ型感光性樹脂組成物からなる樹脂膜の硬化物を含む、パターン硬化膜。
＜７＞ 上記＜１＞〜＜６＞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の一部又は全面に塗布及び乾燥し樹脂膜を形成する工程と、樹脂膜の一部又は全面を露光する工程と、露光後の樹脂膜をアルカリ水溶液により現像してパターン樹脂膜を形成する工程と、パターン樹脂膜を加熱する工程とを有する、パターン硬化膜の製造方法。
＜８＞ 上記＜６＞に記載のパターン硬化膜を、層間絶縁層として有する半導体素子。
＜９＞ 上記＜６＞に記載のパターン硬化膜を、表面保護層として有する半導体素子。
＜１０＞ 上記＜８＞又は＜９＞に記載の半導体素子を有する電子デバイス。

[In the general formula (3), R ^{7 to} R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms. ]
<5> The positive photosensitive resin composition according to any one of <1> to <4> above, wherein the component (B) is an o-quinone diazide compound.
<6> A pattern cured film comprising a cured product of a resin film having a pattern and the pattern comprising the positive photosensitive resin composition according to any one of <1> to <5>.
<7> A step of applying and drying the positive photosensitive resin composition according to any one of <1> to <6> to a part or the entire surface of a substrate to form a resin film, and one of the resin films. A method for producing a pattern cured film, which comprises a step of exposing a part or the entire surface, a step of developing the exposed resin film with an alkaline aqueous solution to form a pattern resin film, and a step of heating the pattern resin film.
<8> A semiconductor device having the pattern cured film according to <6> above as an interlayer insulating layer.
<9> A semiconductor device having the pattern cured film according to <6> above as a surface protective layer.
<10> An electronic device having the semiconductor element according to the above <8> or <9>.

According to the present invention, it is possible to provide a positive photosensitive resin composition having a high resolution of the pattern cured film formed, which can sufficiently suppress the resolution and the residue after curing while maintaining a low dielectric loss tangent. Further, it is possible to provide a method for producing a pattern cured film using the positive photosensitive resin composition, a semiconductor element having the pattern cured film as an interlayer insulating layer and a surface protective layer, and an electronic device having the semiconductor element. ..

It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is a schematic sectional drawing which shows one Embodiment of a semiconductor element. It is a schematic sectional drawing which shows one Embodiment of a semiconductor element.

[Positive Photosensitive Resin Composition]
The positive photosensitive resin composition of the present embodiment includes (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that generates an acid by light, (C) a thermal cross-linking agent, and (D). It contains an acrylic resin having a structural unit represented by the general formula (1). The phenol component in the component (A) is in the range of 29 to 42% by mass of the entire photosensitive resin composition, and the weight average molecular weight of the acrylic resin component in (D) is 25,000 or more and 47,000 or less. It is characterized by being.
First, each component contained in the positive photosensitive resin composition will be described.

<Ingredient (A)>
The component (A) is an alkali-soluble resin having a phenolic hydroxyl group (soluble in an alkaline aqueous solution). Here, one criterion for the solubility of the component (A) of the present invention in an alkaline aqueous solution will be described below. A substrate such as a silicon wafer is obtained by applying a resin solution obtained from the component (A) alone, an arbitrary solvent or the component (A), and the components (B), (C) and (D) described below in order. A resin film having a film thickness of about 5 μm is formed by spin coating on the film. 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 the resin film can be dissolved as a uniform solution, it is determined that the component (A) used is soluble in an alkaline aqueous solution.

The alkali-soluble resin as the component (A) has a structural unit represented by the following general formula (4).

［一般式（４）中、Ｒ^１３は水素原子又はメチル基を示し、Ｒ^１４は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜１０のアルコキシ基を示し、ａは０〜３の整数を示し、ｂは１〜３の整数を示す。ａとｂの合計は５以下である。］
（Ａ）アルカリ可溶性樹脂は一般式（４）で表される構造単位を与えるモノマ等を重合させることで得られる。

[In the general formula (4), R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. , A represent an integer of 0 to 3, and b represents an integer of 1 to 3. The total of a and b is 5 or less. ]
The alkali-soluble resin (A) can be obtained by polymerizing a monoma or the like giving a structural unit represented by the general formula (4).

In the general formula (4), the alkyl group having 1 to 10 carbon atoms represented by R ^14, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl Examples include groups and decyl groups. These groups may be linear or branched. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, a nonoxy group and a decoxy group. These groups may be linear or branched.

Examples of the monoma giving the structural unit represented by the general formula (4) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol and o-isopropenyl. Phenol can be mentioned. Each of these monomas can be used alone or in combination of two or more.

The method for obtaining the (A) alkali-soluble resin is not particularly limited. For example, the hydroxyl group of the polymer giving the structural unit represented by the general formula (4) is protected by a t-butyl group, an acetyl group, or the like to protect the hydroxyl group. A polymer is obtained by polymerizing a monoma having a protected hydroxyl group, and the obtained polymer is deprotected under an acid catalyst and converted into a hydroxystyrene-based structural unit. ) To deprotect.

The component (A) may be a polymer or a copolymer consisting only of a monoma giving a structural unit represented by the general formula (4), and may be a polymer or a copolymer giving a structural unit represented by the general formula (4). It may be a copolymer with other monomas. When the component (A) is a copolymer, the ratio of the structural unit represented by the general formula (4) in the copolymer is 100 mol of the component (A) from the viewpoint of solubility in the alkaline developer of the exposed part. With respect to%, 10 to 100 mol% is preferable, 20 to 97 mol% is more preferable, 30 to 95 mol% is further preferable, and 50 to 95 mol% is particularly preferable.

The component (A) is preferably an alkali-soluble resin having a structural unit represented by the following general formula (5) from the viewpoint of further improving the dissolution inhibitory property of the unexposed portion in the alkaline developer.

［一般式（５）中、Ｒ^１５は水素原子又はメチル基を示し、Ｒ^１６は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜１０のアルコキシ基を示し、ｃは０〜３の整数を示す。］

[In the general formula (5), R ¹⁵ represents a hydrogen atom or a methyl group, and R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. , C represent an integer of 0 to 3. ]

Examples of the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the alkoxy group having 1 to 10 carbon atoms represented by R ¹⁶ are the same as those of ^{R 14.}

The alkali-soluble resin having the structural unit represented by the general formula (5) can be obtained by using a monoma giving the structural unit represented by the general formula (5). Examples of the monomer giving the structural unit represented by the general formula (5) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, and m-methoxystyrene. And aromatic vinyl compounds such as p-methoxystyrene. Each of these monomas can be used alone or in combination of two or more.

When the component (A) is an alkali-soluble resin having a structural unit represented by the general formula (5), the general formula (5) is obtained from the viewpoint of inhibition of dissolution of the unexposed portion in the alkaline developer and mechanical properties of the pattern cured film. ) Is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, further preferably 5 to 70 mol%, and 5 to 50 mol% with respect to 100 mol% of the component (A). Is particularly preferable.

Further, the component (A) is preferably an alkali-soluble resin having a structural unit represented by the following general formula (6) from the viewpoint of lowering the elastic modulus.

［一般式（６）中、Ｒ^１７は水素原子又はメチル基を示し、Ｒ^１８は炭素数１〜１０のアルキル基又は炭素数１〜１０のヒドロキシアルキル基を示す。］

[In the general formula (6), R ¹⁷ represents a hydrogen atom or a methyl group, and R ¹⁸ represents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms. ]

The alkali-soluble resin having the structural unit represented by the general formula (6) can be obtained by using a monoma giving the structural unit represented by the general formula (6). Examples of the monoma giving the structural unit represented by the general formula (6) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth). Pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, (meth) Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, (meth) acrylate Examples include hydroxyoctyl, hydroxynonyl (meth) acrylate and hydroxydecyl (meth) acrylate. Each of these monomas can be used alone or in combination of two or more.

When the component (A) is an alkali-soluble resin having a structural unit represented by the general formula (6), the general formula (6) is obtained from the viewpoint of inhibition of dissolution of the final exposed portion in an alkaline developer and mechanical properties of the pattern cured film. ) Is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, further preferably 5 to 70 mol%, and 5 to 50 mol% with respect to 100 mol% of the component (A). Is particularly preferable.

The component (A) is a structural unit represented by the general formula (4) and a structural unit represented by the general formula (5) from the viewpoint of the solubility inhibitory property of the final exposed portion in the alkaline developer and the mechanical properties of the pattern cured film. An alkali-soluble resin having the above, an alkali-soluble resin having a structural unit represented by the general formula (4) and a structural unit represented by the general formula (6), a structural unit represented by the general formula (4) and a general An alkali-soluble resin having a structural unit represented by the formula (5) and a structural unit represented by the general formula (6) is preferable. From the viewpoint of further exhibiting the effects of the present invention, it is more preferable that the alkali-soluble resin has a structural unit represented by the general formula (4) and a structural unit represented by the general formula (5) or (6). ..

The molecular weight of the component (A) is preferably 1,000 to 500,000 in terms of weight average molecular weight, considering the balance between solubility in an alkaline aqueous solution, photosensitive properties, and mechanical properties of the pattern cured film, and 2,000 to 200,000. Is more preferable, and 2,000 to 100,000 is even more preferable. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting from a standard polystyrene calibration curve.

<Ingredient (B)>
The compound (B) that generates (generates) an acid by light (by receiving light), which is a component, functions as a photosensitive agent in the photosensitive resin composition. The component (B) has a function of generating an acid by receiving light irradiation and increasing the solubility of the light-irradiated portion in an alkaline aqueous solution. As the component (B), a compound generally called a photoacid generator can be used. Specific examples of the component (B) include an o-quinone diazonium compound, an aryldiazonium salt, a diallyliodonium salt, and a triarylsulfonium salt. The component (B) may be composed of only one of these compounds, or may be composed of two or more of them. Among these, the o-quinone diazide compound is preferable because of its high sensitivity.

As the o-quinone diazide compound, for example, a compound obtained by condensing an o-quinone diazidosulfonyl chloride with a hydroxy compound and / or an amino compound in the presence of a dehydrochloric acid agent can be used.

Examples of the o-quinone diazidosulfonyl chloride used in the reaction include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride and naphthoquinone-1,2-diazide-6-. Sulfonyl chloride can be mentioned.

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

Examples of the amino compound used in the reaction include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'. -Diaminodiphenylsulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone , Bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane.

Among these, 1,1-bis (4-hydroxyphenyl) -1- from the viewpoint of reactivity when synthesizing an o-quinone diazide compound and from the viewpoint of an appropriate absorption wavelength range when exposing a resin film. [4- {1- (4-Hydroxyphenyl) -1-methylethyl} phenyl] Tris (4-hydroxy) obtained by condensing ethane with 1-naphthoquinone-2-diazide-5-sulfonyl chloride. It is preferable to use a compound obtained by condensing phenyl) methane or tris (4-hydroxyphenyl) ethane with 1-naphthoquinone-2-diazide-5-sulfonyl chloride.

Examples of the dehydrochloric acid agent used in the reaction include sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine and pyridine. As the reaction solvent, for example, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether and N-methylpyrrolidone are used.

The combination of the o-quinonediazide sulfonyl chloride and the hydroxy compound and / or the amino compound results in a total of 0.5 to 1 mol of the number of moles of the hydroxy group and the amino group with respect to 1 mol of the o-quinone diazidosulfonyl chloride. It is preferable that they are blended in such a manner. The preferred blending ratio of the dehydrochloric acid agent and o-quinonediazidosulfonyl chloride is in the range of 0.95 / 1 mol to 1 / 0.95 mol equivalent.

The preferable reaction temperature of the above reaction is 0 to 40 ° C., and the preferable reaction time is 1 to 10 hours.

The content of the component (B) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the difference in dissolution rate between the exposed part and the unexposed part becomes large and the sensitivity becomes better. It is more preferably 5 to 50 parts by mass, further preferably 5 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass.

<(C) component)>
The thermal cross-linking agent as the component (C) is a compound having a structure capable of forming a bridging structure by reacting with the component (A) when the patterned resin film is heated and cured. This makes it possible to prevent brittleness of the film and melting of the film. Examples of the component (C) include a compound having a phenolic hydroxyl group, a compound having an alkoxymethylamino group, and a compound having an epoxy group.

The "compound having a phenolic hydroxyl group" here does not include (A) an alkali-soluble resin and a phenolic low molecular weight compound. The compound having a phenolic hydroxyl group as a thermal cross-linking agent can increase the dissolution rate of the exposed portion when developing with an alkaline aqueous solution and improve the sensitivity as well as the thermal cross-linking agent. The weight average molecular weight of such a compound having a phenolic hydroxyl group is preferably 2,000 or less, preferably 94 to 2,000, in consideration of the balance of solubility in an alkaline aqueous solution, photosensitive characteristics, and mechanical properties. More preferably, it is more preferably 108 to 2,000, and particularly preferably 108 to 1,500.

As the compound having a phenolic hydroxyl group, a conventionally known compound can be used, but since it has an excellent balance between the effect of promoting dissolution of the exposed portion and the effect of preventing melting of the photosensitive resin film during curing, it has an alkoxymethyl group. And a compound having a phenolic hydroxyl group is preferable, and a compound represented by the following general formula (7) is more preferable.

［一般式（７）中、Ｘは単結合又は２価の有機基を示し、Ｒ^１９、Ｒ^２Ｏ、Ｒ^１６及びＲ^２２はそれぞれ独立に水素原子又は１価の有機基を示し、ｓ及びｔはそれぞれ独立に１〜３の整数を示し、ｕ及びｖはそれぞれ独立に０〜３の整数を示す。］

[In the general formula (7), X represents a single bond or a divalent organic group, and R ¹⁹ , R ^2O , R ¹⁶ and R ²² each independently represent a hydrogen atom or a monovalent organic group, and s and t. Independently indicate an integer of 1 to 3, and u and v independently indicate an integer of 0 to 3. ]

In the general formula (7), the compound in which X is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by X include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, and a phenylene group. An arylene group having 6 to 30 carbon atoms, a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond and an amide bond. Can be mentioned. Further, ^{examples of the monovalent organic group represented by R 19} , R ^2O , R ¹⁶ and R ²² include carbons such as an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group, and a vinyl group. Examples thereof include an aryl group having 6 to 30 carbon atoms such as an alkenyl group having a number of 2 to 10 and a phenyl group, and a group in which a part or all of the hydrogen atoms of these hydrocarbon groups are replaced with a halogen atom such as a fluorine atom.
Examples of the compound represented by the above general formula (7) include 1,1-bis {3,5-bis (methoxymethyl) -4-hydroxyphenyl} methane (manufactured by Honshu Chemical Industry Co., Ltd., trade name "TMOM-pp"). -BPF ") can be used.

Compounds having an alkoxymethylamino group include, for example, (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluryl, (poly) (N-hydroxymethyl) benzoguanamine and (poly) (. Examples thereof include nitrogen-containing compounds in which all or part of an active methylol group such as N-hydroxymethyl) urea is alkyl etherified. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group and a butyl group, and may contain an oligomer component partially self-condensed. Specific examples of the compound having an alkoxymethylamino group include hexax (methoxymethyl) melamine, hexax (butoxymethyl) melamine, tetrax (methoxymethyl) glycoluryl, tetrax (butoxymethyl) glycoluryl and tetrax (methoxymethyl) urea. Can be mentioned.
Moreover, it is preferable to contain the compound represented by the general formula (3).

［一般式（３）中、Ｒ^７〜Ｒ^１２は、それぞれ独立に炭素数１〜１０のアルキル基を示す。］
炭素数１〜１０のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基及びデシル基が挙げられる。これらの基は直鎖状であっても、分岐鎖状であってもよい。

[In the general formula (3), R ^{7 to} R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms. ]
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. These groups may be linear or branched.

As the compound having an epoxy group, conventionally known compounds can be used. Specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, glycidyl amine, heterocyclic epoxy resin and polyalkylene glycol diglycidyl. Epoxy can be mentioned.

In addition to the above-mentioned compounds, the component (C) includes, for example, bis [3,4-bis (hydroxymethyl) phenyl] ether, 1,3,5-tris (1-hydroxy-1-methylethyl) benzene and the like. Aromatic compounds having a hydroxymethyl group, compounds having a maleimide group such as bis (4-maleimidephenyl) methane, 2,2-bis [4- (4'-maleimidephenoxy) phenyl] propane, compounds having a norbornene skeleton, Polyfunctional acrylate compounds, compounds having an oxetanyl group, compounds having a vinyl group and blocked isocyanate compounds can also be used.

Among the above-mentioned components (C), from the viewpoint of further improving sensitivity and heat resistance, it is preferable to use a compound having an alkoxymethyl group and a phenolic hydroxyl group or a compound having an alkoxymethylamino group, and it is preferable to use a compound having a resolution and a coating film. A compound having an alkoxymethylamino group is more preferable, and a compound having an alkoxymethylamino group obtained by alkyl etherifying all or part of the hydroxymethylamino group is more preferable, and all of the hydroxymethylamino groups are preferable from the viewpoint that the elongation can be further improved. A compound having an alkoxymethylamino group obtained by alkyl etherifying the above is particularly preferable.
Among the compounds having an alkoxymethylamino group obtained by alkyl etherifying all of the hydroxymethylamino groups, the compound represented by the following general formula (8) is preferable.

［一般式（８）中、Ｒ^２３〜Ｒ^２８は、それぞれ独立に炭素数１〜１０のアルキル基を示す。］

[In the general formula (8), R ^{23 to} R ²⁸ each independently represent an alkyl group having 1 to 10 carbon atoms. ]

In the general formula (8) ^{, examples of the alkyl group having 1 to 10 carbon atoms represented by R 23 to} R ²⁸ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Examples include an octyl group, a nonyl group and a decyl group. These groups may be linear or branched.

The content of the component (C) is 0.5 to 50 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the difference in dissolution rate between the exposed part and the final exposed part becomes large and the sensitivity becomes better. Preferably, 1 to 40 parts by mass is more preferable, and 2 to 30 parts by mass is further preferable.

<Ingredient (D)>
The acrylic resin as the component (D) has a structural unit represented by the following general formula (9).

［一般式（９）中、Ｒ^２９は水素原子又はメチル基を示し、Ｒ^３０は炭素数２〜２０のヒドロキシアルキル基を示す。］

[In the general formula (9), R ²⁹ represents a hydrogen atom or a methyl group, and R ³⁰ represents a hydroxyalkyl group having 2 to 20 carbon atoms. ]

By containing the component (D) having the structural unit represented by the general formula (9), the photosensitive resin composition of the present embodiment sufficiently suppresses the white turbidity of the photosensitive resin composition and forms a pattern cured film. The haze value can be lowered. Further, by containing the component (D), the photosensitive characteristics and the thermal shock resistance (the rate of change of the mechanical characteristics after being left at a high temperature and after a cold impact test is small) can be further improved. The component (D) may be composed of only one kind of acrylic resin, or may contain two or more kinds of acrylic resins.

By including the structural unit represented by the above general formula (9) in the component (D), the interaction between the component (D) and the component (A) is improved and the compatibility is improved. Adhesion to the substrate, mechanical properties and thermal shock resistance can be further improved.

In the general formula (9), (A) from viewpoint of further improving the compatibility and thermal shock resistance of the components, preferably R ³⁰ is hydroxyalkyl group of 2 to 15 carbon atoms, hydroxyalkyl group having 2 to 10 carbon atoms Is more preferable, and a hydroxyalkyl group having 2 to 8 carbon atoms is particularly preferable.
The hydroxyalkyl group having 2 to 20 carbon atoms represented by R ^30, for example, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyheptyl group, hydroxyoctyl group, hydroxy nonyl group , Hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group (sometimes referred to as hydroxylauryl group), hydroxytridecyl group, hydroxytetradecyl group, hydroxypentadecyl group, hydroxyhexadecyl group, hydroxyheptadecyl group, hydroxy Examples thereof include an octadecyl group, a hydroxynonadecil group and a hydroxyeicosyl group. These groups may be linear or branched.

Examples of the monoma that gives the acrylic resin having the structural unit represented by the general formula (9) include hydroxyalkyl (meth) acrylate.

Examples of such hydroxyalkyl (meth) acrylate include compounds represented by the following general formula (10).
CH ₂ = C (R ³¹ ) -COOR ³² ... (10)
[In the general formula (10), R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents a hydroxyalkyl group having 2 to 20 carbon atoms. ]

From the viewpoint that the effects of the present invention can be exhibited to a higher degree, it is desirable to add an acrylic resin having a structural unit represented by the general formula (9) as a polymer.

Examples of the monoma compound represented by the general formula (10) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and (meth). ) Hydroxyhexyl acrylate, (meth) hydroxyheptyl acrylate, (meth) hydroxyoctyl acrylate, (meth) hydroxynonyl acrylate, (meth) hydroxydecyl acrylate, (meth) hydroxyundecyl acrylate, (meth) Hydroxydodecyl acrylate (sometimes referred to as hydroxylauryl (meth) acrylate), hydroxytridecyl (meth) acrylate, hydroxytetradecyl (meth) acrylate, hydroxypentadecyl (meth) acrylate, (meth) acrylic Examples thereof include hydroxyhexadecyl acrylate, hydroxyheptadecyl (meth) acrylate, hydroxyoctadecyl (meth) acrylate, hydroxynonadecil (meth) acrylate and hydroxyeicosyl (meth) acrylate. These monomas are used alone or in combination of two or more. Among these, from the viewpoint of further improving compatibility with the component (A) and elongation at break, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic Hydroxypentyl acid, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxy (meth) acrylate It is preferable to use undecyl or hydroxydodecyl (meth) acrylate.

The component (D) may be an acrylic resin composed of only the structural units represented by the general formula (9), or an acrylic resin having a structural unit other than the structural units represented by the general formula (9). May be good. In the case of an acrylic resin having a structural unit other than the structural unit represented by the general formula (9), the ratio of the structural unit represented by the general formula (9) in the acrylic resin is the ratio of the structural unit represented by the general formula (9) to the total amount of the component (D). It is preferably 0.1 to 30 mol%, more preferably 0.3 to 20 mol%, and even more preferably 0.5 to 10 mol%. When the composition ratio of the structural unit represented by the general formula (9) is 0.1 to 30 mol%, the compatibility with the component (A) and the thermal shock resistance of the pattern cured film can be further improved. it can.

The component (D) is preferably an acrylic resin having a structural unit represented by the following general formula (11).

［一般式（１１）中、Ｒ^３３は水素原子又はメチル基を示し、Ｒ^３４は１級、２級又は３級アミノ基を有する１価の有機基を示す。］
（Ｄ）成分が一般式（１１）で表される構造単位を有することで、未露光部の現像液に対する溶解阻害性をより向上できる。

[In the general formula (11), R ³³ represents a hydrogen atom or a methyl group, and R ³⁴ represents a monovalent organic group having a primary, secondary or tertiary amino group. ]
When the component (D) has a structural unit represented by the general formula (11), the solubility inhibitory property of the unexposed portion in the developing solution can be further improved.

Examples of the monoma for giving the acrylic resin having the structural unit represented by the general formula (11) include aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, and N, N-dimethylaminoethyl (meth). Acrylate, N-ethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Acrylate, N-ethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, piperidine-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylicate, 2, 2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) ) Acrylate and 2- (piperidin-4-yl) ethyl (meth) acrylate. These monomas are used alone or in combination of two or more. Among these, from the viewpoint of further improving the adhesion of the pattern cured film to the substrate, mechanical properties and thermal shock resistance, R ³⁴ in the general formula (11) has a monovalent value represented by the following general formula (12). It is preferably an organic group.

［一般式（１２）中、Ｙは炭素数１〜５のアルキレン基を示し、Ｒ^３５〜Ｒ^３９は各々独立に水素原子又は炭素数１〜２０のアルキル基を示し、ｎは０〜１０の整数を示す。］

[In the general formula (12), Y represents an alkylene group having 1 to 5 carbon atoms, R ^{35 to} R ³⁹ independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n is 0 to 10. Indicates an integer. ]

In the general formula (11) ^{, examples of the polymerizable monomer in which R 34} gives a structural unit represented by a monovalent organic group represented by the general formula (12) include piperidine-4-yl (meth). Acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4 -Il (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate and 2- (piperidin-4-yl) ethyl (meth) acrylate can be mentioned. Among these, 1,2,2,6,6-pentamethylpiperidine-4-ylmethacrylate was designated as FA-711MM, and 2,2,6,6-tetramethylpiperidine-4-ylmethacrylate was designated as FA-712HM. (Both are manufactured by Hitachi Kasei Co., Ltd.), which are preferable because they are commercially available.

When the acrylic resin (D) has a structural unit represented by the general formula (11), the ratio of the structural unit represented by the general formula (11) is compatibility with the component (A) and solubility in a developing solution. From the above point, it is preferably 0.3 to 10 mol%, more preferably 0.4 to 6 mol%, and 0.5 to 5 mol% with respect to the total amount of the component (D). Is even more preferable.

The component (D) is preferably an acrylic resin having a structural unit represented by the following general formula (13).

［一般式（１３）中、Ｒ^４０は水素原子又はメチル基を示し、Ｒ^４１は炭素数４〜２０のアルキル基を示す。］

[In the general formula (13), R ⁴⁰ represents a hydrogen atom or a methyl group, and R ⁴¹ represents an alkyl group having 4 to 20 carbon atoms. ]

When the component (D) has a structural unit represented by the general formula (13), the dissolution inhibitory property of the final exposed portion in the developing solution can be further improved.
In the general formula (13), the alkyl group having 4 to 20 carbon atoms represented by R ^41, for example, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Examples thereof include a group (sometimes referred to as a lauryl group), a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group and an eicosyl group. These groups may be linear or branched.

^{In the general formula (13), R 41} is preferably an alkyl group having 4 to 16 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms, from the viewpoint of further improving sensitivity, resolution and thermal shock. It is preferably an alkyl group having 4 carbon atoms (n-butyl group).

Examples of the monoma giving the structural unit represented by the general formula (13) include alkyl (meth) acrylate. Examples of the alkyl (meth) acrylate include a compound represented by the following general formula (14).
CH ₂ = C (R ⁴² ) -COOR ⁴³ ... (14)
[In the general formula (14), R ⁴² represents a hydrogen atom or a methyl group, and R ⁴³ represents an alkyl group having 4 to 20 carbon atoms. ]

Examples of the monoma represented by the general formula (14) include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and octyl (meth) acrylate. Nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (sometimes referred to as lauryl (meth) acrylate), tridecyl (meth) acrylate, (meth) ) Tetradecyl acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate and eicocil (meth) acrylate. These polymerizable monomers are used alone or in combination of two or more. Among these, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) from the viewpoint of further improving elongation at break and lowering the elasticity. It is preferable to use octyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate or dodecyl (meth) acrylate (also referred to as lauryl (meth) acrylate).

When the acrylic resin (D) has a structural unit represented by the general formula (13), the ratio of the structural unit represented by the general formula (13) is 50 to 93 mol with respect to the total amount of the component (D). %, More preferably 55-85 mol%, even more preferably 60-80 mol%. When the ratio of the structural unit represented by the general formula (13) is 50 to 93 mol%, the thermal shock resistance of the pattern cured film can be further improved.

The component (D) is preferably an acrylic resin having a structural unit represented by the following general formula (15).

［一般式（１５）中、Ｒ^４４は水素原子又はメチル基を示す。］
（Ｄ）成分が一般式（１５）で表される構造単位を有することで、感度をより向上することができる。

[In general formula (15), R ⁴⁴ represents a hydrogen atom or a methyl group. ]
When the component (D) has a structural unit represented by the general formula (15), the sensitivity can be further improved.

Examples of the monoma giving the structural unit represented by the general formula (15) include acrylic acid and methacrylic acid.

When the acrylic resin (D) has a structural unit represented by the general formula (15), the ratio of the structural unit represented by the general formula (15) is 5 to 35 mol with respect to the total amount of the component (D). %, More preferably 10 to 30 mol%, even more preferably 15 to 25 mol%. When the composition ratio of the structural unit represented by the general formula (15) is 5 to 35 mol%, the compatibility with the component (A) and the developability can be further improved.

The component (D) is, for example, a monomer giving a structural unit represented by the above general formula (9), and a structure represented by the general formulas (11), (13) and (15) added as needed. It is obtained by blending a monoma giving a unit, stirring in a solvent such as ethyl lactate, toluene, or isopropanol, and heating if necessary.

Further, the monoma used for synthesizing the (D) acrylic resin may further contain a monoma other than the monoma giving the structural units represented by the general formulas (9), (11), (13) and (15). Good.

Examples of such monomas include esters of vinyl alcohols such as benzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, acrylonitrile, and vinyl-n-butyl ether, tetrahydrofurfuryl (meth) acrylate, and the like. Glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromo (meth) acrylic acid, α-chloro ( Maleic acid monoesters such as meta) acrylic acid, β-frill (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic acid anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. Examples thereof include fumaric acid, silicic acid, α-cyanosilicic acid, itaconic acid, crotonic acid and propioleic acid. These monomas are used alone or in combination of two or more.

The weight average molecular weight of the component (D) is preferably 2,000 to 100,000, more preferably 10,000 to 50,000, and particularly preferably 31,000 to 47,000. .. When the weight average molecular weight is 2,000 or more, the thermal shock resistance of the cured film can be further improved, and when it is 100,000 or less, the compatibility with the component (A) and the developability can be further improved. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting from a standard polystyrene calibration curve.

The content of the component (D) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of the balance between sensitivity, resolution, adhesion, mechanical properties and thermal shock resistance, and is preferably 3 to 30 parts by mass. Parts are more preferable, and 5 to 20 parts by mass are further preferable.

<Other ingredients>
In addition to the above components (A) to (D), the positive photosensitive resin composition of the present embodiment includes a solvent, an elastomer, a compound that produces an acid by heating, a dissolution accelerator, a dissolution inhibitor, a coupling agent, and a coupling agent. , Surfactant, leveling agent and the like may be contained.

(solvent)
The positive photosensitive resin composition of the present embodiment has the effect of facilitating coating on a substrate and forming a coating film having a uniform thickness by containing a solvent. Examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypupionate, N-methyl-2-pyrrolidone, and N. , N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethylketone, diisobutylketone, methylamylketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol Examples thereof include monobutyl ether and dipropylene glycol monomethyl ether. These solvents may be used alone or in combination of two or more. Among these, ethyl lactate or propylene glycol monomethyl ether acetate is preferably used from the viewpoint of solubility and uniformity of the coating film.

(Elastomer)
As the elastomer, conventionally known elastomers can be used, but it is preferable that the glass transition temperature (Tg) of the polymer constituting the elastomer is 20 ° C. or lower.

Examples of such an elastomer include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and silicone-based elastomers. Further, the elastomer may be a fine particle elastomer. These elastomers may be used alone or in combination of two or more.

When an elastomer is used, the content is preferably 1 to 60 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).

(Compound that produces acid by heating)
By using a compound that produces an acid by heating, it becomes possible to generate an acid when the pattern resin film is heated, and the reaction between the component (A) and the component (C), that is, the thermal cross-linking reaction is promoted. The heat resistance of the pattern cured film is improved. Further, since the compound that produces an acid by heating also generates an acid by light irradiation, the solubility of the exposed portion in the alkaline aqueous solution is increased. Therefore, the difference in solubility between the final exposed portion and the exposed portion in the alkaline aqueous solution becomes larger, and the resolution is further improved.

The compound that produces an acid by such heating is preferably one that produces an acid by heating to, for example, 50 to 250 ° C. Specific examples of the compound that produces an acid by heating include imide sulfonate, a salt formed from a strong acid such as an onium salt and a base.

When a compound that produces an acid by heating is used, the content is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, and 0.5 by mass with respect to 100 parts by mass of the component (A). 10 parts by mass is more preferable.

(Dissolution accelerator)
By blending the dissolution accelerator with the above-mentioned positive photosensitive resin composition, the dissolution rate of the exposed portion when developing with an alkaline aqueous solution can be increased, and the sensitivity and resolution can be improved. As the dissolution accelerator, conventionally known ones can be used. Specific examples thereof include compounds having a carboxyl group, a sulfonic acid, and a sulfonamide group.

The content of such a dissolution accelerator can be determined by the dissolution rate in an alkaline aqueous solution, and can be, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (A). ..

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

(Coupling agent)
By blending the coupling agent with the positive photosensitive resin composition, the adhesiveness of the formed pattern curing film to the substrate can be further enhanced. Examples of the coupling agent include an organic silane compound and an aluminum chelate compound. Examples of the organic silane compound include ureapropyltriethoxysilane.

When a coupling agent is used, the content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A).

(Surfactant or leveling agent)
By blending a surfactant or a leveling agent into the positive photosensitive resin composition, the coatability can be further improved. Specifically, for example, by containing a surfactant or a leveling agent, striation (unevenness of film thickness) can be further prevented and developability can be further improved. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and polyoxyethylene octylphenol ether. Examples of commercially available products include Megafax F171, F173, R-08 (manufactured by DIC Corporation, trade name), Florard FC430, FC431 (manufactured by Sumitomo 3M Ltd., trade name), Organosiloxane Polymer KP341, KBM303, KBM403 and KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) can be mentioned.

When a surfactant or a leveling agent is used, the content is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the component (A).

The positive photosensitive resin composition of the present embodiment can be developed using an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH). Further, by using the positive photosensitive resin composition of the present embodiment described above, it is possible to form a pattern cured film having good adhesion and thermal shock resistance with sufficiently high sensitivity and resolution.

"Manufacturing method of pattern cured film and pattern cured film]
The pattern cured film of the present invention can be obtained by heating a positive photosensitive resin composition.
Next, a method for producing the pattern cured film will be described. The method for producing a pattern cured film of the present embodiment is a step of applying and drying the positive photosensitive resin composition of the present embodiment on a part or the entire surface of a substrate to form a resin film (coating / drying (deposition) step). ), A step of exposing a part or the entire surface of the resin film (exposure step), a step of developing the exposed resin film with an alkaline aqueous solution to form a pattern resin film (development step), and heating the pattern resin film. It has a step (heat treatment step). Hereinafter, each step will be described.

<Applying / drying (deposition) process>
First, the positive photosensitive resin composition of the present embodiment is applied onto a substrate and dried to form a resin film. In this step, first, the positive photosensitive resin composition of the present embodiment is applied onto a substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ or SiO ₂ ), silicon nitride, or the like, and a spinner or the like is applied. Use to rotate and apply to form a coating. The thickness of the coating film is not particularly limited, but is preferably 0.1 to 40 μm. The substrate on which this coating film is formed is dried using a hot plate, an oven, or the like. The drying temperature and drying time are not particularly limited, but it is preferably carried out at 80 to 140 ° C. for 1 to 7 minutes. As a result, a photosensitive resin film is formed on the support substrate. The thickness of the photosensitive resin film is not particularly limited, but is preferably 0.1 to 40 μm.

<Exposure process>
Next, in the exposure step, the resin film formed on the substrate is irradiated with active rays such as ultraviolet rays, visible rays, and radiation through a mask. In the positive photosensitive resin composition of the present embodiment, since the component (A) is highly transparent to i-rays, i-ray irradiation can be preferably used. After exposure, post-exposure heating (PEB) can also be performed, if necessary, from the viewpoint of improving the dissolution rate. When heating after exposure, the temperature is preferably 70 ° C. to 140 ° C., and the time for post-exposure heating is preferably 1 minute to 5 minutes.

<Development process>
In the developing step, the exposed portion of the resin film after the exposure step is removed with a developing solution, so that the resin film is patterned and a patterned resin film is obtained. As the developing solution, for example, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine and tetramethylammonium hydroxide (TMAH) is preferably used. Be done. The base concentration of these aqueous solutions is preferably 0.1 to 10% by mass. Further, alcohols or surfactants can be added to the developer for use. Each of these can be blended in the range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developing solution. As a method of developing using a developing solution, for example, the developing solution is arranged on a positive photosensitive resin film by a method such as shower development, spray development, immersion development, paddle development, etc., and under the condition of 18 to 40 ° C. , Leave for 30-360 seconds. After leaving it to stand, it is washed with water and spin-dried to wash the pattern resin film.

<Heat treatment process>
Next, in the heat treatment step, the pattern cured film can be formed by heat-treating the pattern resin film. The heating temperature in the heat treatment step is preferably 250 ° C. or lower, more preferably 225 ° C. or lower, and further preferably 140 to 200 ° C. from the viewpoint of sufficiently preventing damage to the semiconductor device due to heat.

The heat treatment can be performed using, for example, an oven such as a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, or a microwave curing furnace. Further, either in the atmosphere or in an inert atmosphere such as nitrogen can be selected, but it is preferable to carry out under nitrogen because the pattern can be prevented from being oxidized. Since the above-mentioned preferable heating temperature range is lower than the conventional heating temperature, damage to the support substrate and the semiconductor device can be suppressed to a small extent. Therefore, by using the method for manufacturing the resist pattern of the present embodiment, the electronic device can be manufactured with a high yield. It also leads to energy saving of the process. Further, according to the positive photosensitive resin composition of the present embodiment, since the volume shrinkage (curing shrinkage) in the heat treatment step seen in the photosensitive polyimide or the like is small, it is possible to prevent a decrease in dimensional accuracy.

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

In addition to the oven described above, the heat treatment can also be performed using a microwave curing device or a frequency variable microwave curing device. By using these devices, it is possible to effectively heat only the photosensitive resin film while keeping the temperature of the substrate and the semiconductor device, for example, 200 ° C. or lower (J. Photopolym. Sci. Techno 1. 18,327-332 (2005)).

According to the method for producing a pattern-cured film of the present embodiment described above, a pattern-cured film having sufficiently high sensitivity and resolution and excellent adhesion and thermal shock resistance can be obtained.

[Interlayer insulation layer, surface protection layer]
The pattern-cured film obtained by the method for producing a pattern-cured film of the present embodiment can be used as an interlayer insulating layer or a surface protective layer of a semiconductor element.

[Semiconductor element]
Further, the semiconductor element of the present embodiment has an interlayer insulating layer or a surface protective layer of the present embodiment.
The semiconductor element of the present embodiment is not particularly limited, but refers to a memory, a package, or the like having a multi-layer wiring structure, a rewiring structure, or the like.
Here, an example of the manufacturing process of the semiconductor element will be described with reference to the drawings. 1 to 5 are a schematic perspective view and a schematic end view showing an embodiment of a manufacturing process of a semiconductor element having a multilayer wiring structure. In FIGS. 1 to 5, (a) is a schematic perspective view, and (b) is a schematic end view showing the Ib-Ib to Vb-Vb end faces in (a), respectively.

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

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

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

Further, the second conductor layer 7 is formed in the portion corresponding to the window portion 6B to obtain the structure 400 shown in FIG. A known photographic etching technique can be used to form the second conductor layer 7. As a result, the second conductor layer 7 and the first conductor layer 3 are electrically connected.

Finally, the surface protective layer 8 is formed on the interlayer insulating layer 4 and the second conductor layer 7, and the semiconductor element 500 shown in FIG. 5 is obtained. In the present embodiment, the surface protective layer 8 is formed as follows. First, the above-mentioned photosensitive resin composition is applied onto the interlayer insulating layer 4 and the second conductor layer 7 by a spin coating method, and dried to form a photosensitive resin film. Next, after irradiating a predetermined portion with light through a mask on which a pattern corresponding to the window portion 6C is drawn, the exposed resin film is developed with an alkaline aqueous solution to form a pattern resin film. After that, the pattern resin film is cured by heating to form a pattern cured film used as the surface protective layer 8. The surface protective layer 8 protects the first conductor layer 3 and the second conductor layer 7 from external stress, α rays, and the like, and the semiconductor element 500 using the surface protective layer 8 of the present embodiment is reliable. Excellent in sex.

In the above-described embodiment, a method for manufacturing a semiconductor element having a two-layer wiring structure is shown, but when forming a three-layer or more multi-layer wiring structure, the above steps are repeated to form each layer. Can be done. That is, it is possible to form a multi-layer pattern by repeating each step of forming the interlayer insulating layer 4 and each step of forming the surface protective layer 8. Further, in the above example, not only the surface protective layer 8 but also the interlayer insulating layer 4 can be formed by using the positive photosensitive resin composition of the present embodiment.
The electronic device of the present embodiment is not limited to the one having a surface protective layer, a cover coat layer or an interlayer insulating layer formed by using the above-mentioned positive photosensitive resin composition, and can have various structures.

6 and 7 are schematic cross-sectional views showing an embodiment of a semiconductor device having a rewiring structure. Since the photosensitive resin composition of the present embodiment is also excellent in stress relaxation property, adhesiveness, etc., it can be used in a semiconductor device having a rewiring structure as shown in FIGS. 6 to 7 developed in recent years.

FIG. 6 is a schematic cross-sectional view showing a wiring structure as an embodiment of a semiconductor element. The semiconductor element 600 shown in FIG. 6 has an Al having a pattern including a silicon substrate 23, an interlayer insulating layer 11 provided on one surface side of the silicon substrate 23, and a pad portion 15 formed on the interlayer insulating layer 11. The wiring layer 12, the insulating layer 13 (for example, P-SiN layer) and the surface protective layer 14 which are sequentially laminated on the interlayer insulating layer 11 and the Al wiring layer 12 while forming an opening on the pad portion 15, and the surface protective layer. The island-shaped core 18 arranged in the vicinity of the opening on the 14 is in contact with the pad portion 15 in the opening of the insulating layer 13 and the surface protective layer 14, and is in contact with the surface of the core 18 opposite to the surface protective layer 14. Is provided with a rewiring layer 16 extending over the surface protective layer 14. Further, the semiconductor element 600 is formed by covering the surface protection layer 14, the core 18, and the rewiring layer 16, and the cover coat layer 19 and the cover coat layer 19 in which an opening is formed in the portion of the rewiring layer 16 on the core 18. A conductive ball 17 connected to the rewiring layer 16 with a barrier metal 20 sandwiched between the openings of the layer 19, a collar 21 for holding the conductive ball, and a cover coat layer 19 around the conductive ball 17 are provided. The underfill 22 is provided. The conductive ball 17 is used as an external connection terminal and is formed of solder, gold, or the like. The underfill 22 is provided to relieve stress when mounting the semiconductor element 600.

In the semiconductor element 700 of FIG. 7, an Al wiring layer (not shown) and a pad portion 15 of the Al wiring layer are formed on the silicon substrate 23, and an insulating layer 13 is formed on the pad portion 15 of the Al wiring layer. The surface protective layer 14 is formed. A rewiring layer 16 is formed on the pad portion 15, and the rewiring layer 16 extends to the upper part of the connecting portion 24 with the conductive ball 17. Further, a cover coat layer 19 is formed on the surface protective layer 14. The rewiring layer 16 is connected to the conductive ball 17 via the barrier metal 20.

In the semiconductor elements of FIGS. 6 and 7, the positive photosensitive resin composition forms not only the interlayer insulating layer 11 and the surface protective layer 14, but also the cover coat layer 19, the core 18, the collar 21, the underfill 22, and the like. Can be used as a material for. The pattern cured film using the positive photosensitive resin composition of the present embodiment has excellent adhesion to a metal layer such as the Al wiring layer 12 or the rewiring layer 16 or a sealing material, and has a high stress relaxation effect. The semiconductor element in which this pattern curing film is used for the interlayer insulating layer 11, the surface protective layer 14, the cover coat layer 19, the core 18, the collar 21 such as solder, the underfill 22 used for flip chips, etc. is extremely reliable. Will be excellent.

The positive photosensitive resin composition of the present embodiment is preferably used for the interlayer insulating layer 11, the surface protective layer 14 and / or the cover coat layer 19 of the semiconductor element having the rewiring layer 16 in FIGS. 6 and 7. ..

The film thickness of the interlayer insulating layer 11, the surface protective layer 14, and the cover coat layer 19 is preferably 3 to 20 μm, more preferably 5 to 15 μm.

[Electronic device]
The electronic device of this embodiment has the semiconductor element of this embodiment. The electronic device includes the above-mentioned semiconductor elements, and examples thereof include mobile phones, smartphones, tablet terminals, personal computers, and hard disk suspensions.

As described above, in the positive photosensitive resin composition of the present embodiment, white turbidity is sufficiently suppressed, so that the haze value of the pattern-cured film to be formed becomes small, and the semiconductor device after the pattern-cured film is formed is manufactured. Alignment becomes easier in the process. Further, the pattern cured film formed by the photosensitive resin composition of the present embodiment has excellent mechanical properties, and the rate of change in mechanical properties after being left at a high temperature and after a thermal shock test is small. Further, the photosensitive resin composition of the present embodiment can provide a semiconductor element and an electronic device having excellent reliability.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

The materials used in this example are shown below.
[(A) component]
A1: 4-Hydroxystyrene / styrene = 85/15 (molar ratio) copolymer (weight average molecular weight = 10,000, manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marcalinker CST")
A2: 4-Hydroxystyrene / methyl methacrylate = 70/30 (molar ratio) copolymer (weight average molecular weight = 12,000, manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marcalinker CMM")
A3: 4-Hydroxystyrene / methyl methacrylate = 70/30 (molar ratio) copolymer (weight average molecular weight = 30,000, manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marcalinker HPST-70 (30K)" )
The weight average molecular weight was determined by gel permeation chromatography (GPC) in terms of standard polystyrene.
Specifically, the weight average molecular weight was measured with the following devices and conditions.
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: L6000 manufactured by Hitachi, Ltd.
Data processing device: C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow velocity: 1.0 ml / min, Detector: UV270 nm
Measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of a sample.

[(B) component]
B1: Compound represented by the following formula (Y) (manufactured by Daito Chemix Co., Ltd., trade name "PA-28"

[Component (C)]
C1: Compound having an alkoxymethyl group and a phenolic hydroxyl group; 4,4'-[1- [4- [1- [4-hydroxy-3,5-bis (methoxymethyl) phenyl] -1-methylethyl] phenyl ] Echiliden] Bis [2,6-bis (methoxymethyl) phenol] ^{A compound in which R 7 to} R ¹² of the general formula (3) are all methyl groups (manufactured by Honshu Kagaku Kogyo Co., Ltd., trade name "HMOM-TPPA", Molecular weight 688.9)
C2: Trifunctional epoxy compound (triglycidyl isocyanurate, manufactured by Nissan Chemical Industries, Ltd., trade name "TEPIC-VL", molecular weight: 381.4)
C3: Compound represented by the following formula (Z) (manufactured by Neochemical Co., Ltd., trade name "Cyme1300""

[(D) component]
D1: 13 g of ethyl lactate was weighed in a 100 ml three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, and a separately weighed polymerizable monomer (49.5 g of n-butyl (BA) acrylate). Dodecyl Acrylic Acid (DDA) 0.12g, Acrylic Acid (AA) 5.24g, Hydroxybutyl Acrylic Acid (HBA) 3.5g and 1,2,2,6,6-Pentamethylpiperidin-4-ylmethacrylate (Commodity) Name: FA-711MM, manufactured by Hitachi Kasei Co., Ltd.) 0.12 g and 0.4 g of azobisisobutyronitrile (AIBN) were added. At room temperature (25 ° C.) at about 160 rpm. While stirring, nitrogen gas was flowed at a flow rate of 400 m1 / min for 30 minutes to remove dissolved oxygen. After that, the inflow of nitrogen gas was stopped, the flask was sealed, and the temperature was raised to 65 ° C. in about 25 minutes in a constant temperature water tank. The same temperature was maintained for 10 hours to carry out a polymerization reaction to obtain acrylic resin D1. The polymerization rate at this time was 99%.
The weight average molecular weight of the acrylic resin D1 was 25,000. The molar ratio of the polymerizable monomer in the acrylic resin is as follows.
BA / DDA / AA / HBA / FA-711MM = 80 / 0.1 / 15/5 / 0.1 / (mo1%)

D2 to D5: Acrylic resins D2 to D5 were prepared in the same manner as in the above D1 synthesis method, except that ethyl lactate and propylene glycol monomethyl ether acetate (PGMEA) were charged in a total amount of 13 g in the blending ratio shown in Table 1. Each was synthesized. Table 1 shows the weight average molecular weights of the synthesized acrylic resins D2 to D5.
The weight average molecular weight of the component (D) was determined by the same method as the measurement of the weight average molecular weight of the component (A).

[(E) component: adhesion aid]
E: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-403")

[(F) component: adhesion aid]
F: 5-amino1H-tetrazole (manufactured by Masuda Chemical Industry Co., Ltd., trade name "5ATZ""

(Examples 1 to 4 and Comparative Examples 1 to 3)
The components (A) to (E) in the amounts shown in Table 2 and 120 parts by mass of ethyl lactate as a solvent were blended, and this was pressure-filtered using a 0.2 μm-well PTFE filter to carry out Examples 1 to 4. And the positive photosensitive resin compositions of Comparative Examples 1 to 3 were prepared.

<Evaluation of resin composition>
The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated as shown below. The results are shown in Table 2.

(Appearance evaluation)
The photosensitive resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were visually observed, and if the resin was transparent and had no residue, it was A, cloudy, and if there was no residue, it was B, which was transparent. If a residue is generated, it is C, and if it is cloudy and a residue is generated, it is D. When the white turbidity of the resin is A, the mark for alignment marked on the substrate when manufacturing the semiconductor device having the pattern cured film formed by using the resin can be recognized.

(Measurement of dielectric loss tangent)
The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were spin-coated on a 6-inch silicon substrate and heated at 120 ° C. for 3 minutes to prepare a resin film having a film thickness of about 12 to 14 μm. Then, the resin film was heat-treated by the following method (i) and cured to obtain a cured film having a film thickness of about 10 μm.
(I) Using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., trade name "μ-TF"), heat-treat the resin membrane in nitrogen at a temperature of 230 ° C. (heating time 1.5 hours) for 2 hours. did.

The obtained cured film was measured for dielectric loss tangent at a frequency of 10 GHz using an SPDR dielectric resonator (manufactured by Keysight Technologies, Inc.).
If the dielectric loss tangent value is 0.025 or less, A, if it is greater than 0.025 and greater than 0.03, B, if it is greater than 0.03 and greater than 0.035, C, 0.035. If it is larger than that, it is set as D.

As is clear from Table 1, the positive photosensitive resin compositions of Examples 1 to 4 have a good appearance after coating and development, and the value of dielectric loss tangent is C rank or higher when measured at 10 GHZ. can do.
On the other hand, in Comparative Example 1, the phenol component was large and the value of the dielectric loss tangent could not be C rank or higher. Further, the photosensitive resin compositions of Comparative Examples 2 and 3 were inferior in alkali solubility due to an excessively small amount of phenol component, and after development, a residue of the coating film and cloudiness were observed.

(Examples 5 to 7 and Comparative Examples 4 to 8)
Ethyl lactate was blended with each of the blending amounts of (A) to (C), (E) (F) and Table 1 (D) shown in Table 3 as a solvent. The obtained formulation was pressure-filtered using a 0.2 μm-well PTFE filter to prepare positive photosensitive resin compositions of Examples 5 to 7 and Comparative Examples 4 to 8.

<Evaluation of positive photosensitive resin composition>
The positive photosensitive resin compositions of Examples 5 to 7 and Comparative Examples 4 to 8 were evaluated as shown below. The results are shown in Table 3.

Sensitivity, post-development resolution, post-curing resolution, residual stress, residue, and Tg were evaluated by the following methods.

(Pattern openness, resolution)
The positive photosensitive resin compositions obtained in Examples 5 to 7 and Comparative Examples 4 to 8 were spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a film thickness of 11 to 13 μm. did. Then, using an i-line stepper (manufactured by Canon Inc., trade name "FPA-30001W"), reduced projection exposure with i-line (365 nm) through a mask having a square hole pattern from 1 μm × 1 μm to 100 μm × 100 μm. did. Exposure amount was carried out while changing to 100~1520mJ / cm ² by 20mJ / cm ^2. After the exposure, it was developed with a 2.38 mass% aqueous solution of TMAH and then rinsed with water to obtain a patterned resin film. The minimum exposure amount at which a 100 μm × 100 μm square hole pattern can be formed was defined as the sensitivity. Further, within the range of the above exposure amount, the smallest size (length of one side) of the open square hole patterns was used as an index of resolution. The smaller the sensitivity and resolution, the better.

(Residual stress)
The residual stress of the cured film obtained by the same method as the above evaluation was measured using a stress measuring device (FLX-2320 type manufactured by KLA Tencor Co., Ltd.). The smaller the value (25 MPa or less), the better the residual stress.

(Tg)
A cured film having a film thickness of about 10 μm obtained by the same method as the above evaluation was peeled from the silicon substrate, and the glass transition temperature (Tg) of the peeled cured film was measured by DMA. At the time of measurement, the width of the sample was 10 mm, the film thickness was about 10 μm, and the distance between the chucks was 20 mm. The heating rate was 5 ° C./min. The Tg is preferably high, more preferably 200 ° C. or higher, and even more preferably 230 ° C. or higher.

As is clear from Table 3, the higher the molecular weight of the component (D), the better the resolution after curing. However, as the molecular weight of the component (D) increases, the alkali developability tends to decrease and the appearance tends to deteriorate.

The positive photosensitive resin compositions of Examples 5 to 7 are excellent in the residual film ratio, sensitivity, and resolution after curing, and do not generate any residue. On the other hand, in Comparative Examples 4 to 8, the development residue was generated due to the influence of the high molecular weight component, or the low molecular weight component caused sagging after curing, resulting in deterioration of the resolution.
Further, when C3 was used as the cross-linking component, the stress became high and the Tg also became low.

1 ... semiconductor substrate, 2 ... protective film, 3 ... first conductor layer, 4 ... interlayer insulating layer, 5 ... photosensitive resin layer, 6A, 6B, 6C ... window, 7 ... second conductor layer, 8 ... surface protection Layers, 11 ... Interlayer insulation layer, 12 ... Wiring layer, 13 ... Insulation layer, 14 ... Surface protection layer, 15 ... Pad part, 16 ... Rewiring layer, 17 ... Conductive balls, 18 ... Core, 19 ... Cover coat layer , 20 ... Barrier metal, 21 ... Color, 22 ... Underfill, 23 ... Silicon substrate, 24 ... Connection, 100, 200, 300, 400 ... Structure, 500, 600, 700 ... Semiconductor element

Claims (10)

It has (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that generates an acid by light, (C) a thermal cross-linking agent, and (D) a structural unit represented by the following general formula (1). It contains an acrylic resin component, the phenol component in the component (A) is in the range of 29 to 42% by mass of the entire photosensitive resin composition, and the weight average molecular weight of the acrylic resin component in (D) is 31,000. A positive photosensitive resin composition having a value of 47,000 or less.

[In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group of 4 to 20. ] The positive photosensitive resin composition according to claim 1, wherein the acrylic resin component (D) has a structural unit represented by the following general formula (2).

[In the general formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group having a primary, secondary or tertiary amino group. ] (C) The positive photosensitive resin composition according to claim 1 or 2, wherein the heat cross-linking agent comprises a compound having two or more epoxy groups. (C) The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the heat cross-linking agent contains a compound represented by the following general formula (3).

[In the general formula (3), R ^{7 to} R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms. ] The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the component (B) is an o-quinone diazide compound. A pattern cured film having a pattern, wherein the pattern contains a cured product of a resin film comprising the positive photosensitive resin composition according to any one of claims 1 to 5. A step of applying and drying the positive photosensitive resin composition according to any one of claims 1 to 6 on a part or the entire surface of a substrate to form a resin film, and exposing a part or the entire surface of the resin film. A method for producing a pattern cured film, which comprises a step, a step of developing a resin film after exposure with an alkaline aqueous solution to form a pattern resin film, and a step of heating the pattern resin film. A semiconductor device having the pattern cured film according to claim 6 as an interlayer insulating layer. A semiconductor device having the pattern cured film according to claim 6 as a surface protective layer. An electronic device having the semiconductor device according to claim 8 or 9.

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