JP2017111382A - Positive photosensitive resin composition, cured film, protective film, insulating film, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition excellent in balance of processability, mechanical strength, and residual stress after curing.SOLUTION: The positive photosensitive resin composition of the present invention contains (A) an alkali-soluble resin containing structural units a1) and a2), (B) a photoacid generator, and (C) a phenol compound. (In the formulae, R, R, Rand Reach independently represent a hydrogen atom, a hydroxyl group, or a 1-30C organic group; Rrepresents a hydrogen atom or a 1-30C organic group; and nand nare each an integer of 0-2.)SELECTED DRAWING: Figure 1

Description

  The present invention relates to a positive photosensitive resin composition, a cured film, a protective film, an insulating film, and an electronic device.

  In order to form a resin film constituting a photoresist or the like, a photosensitive resin composition that can be exposed and developed is used. Examples of the technique relating to the photosensitive resin composition include those described in Patent Document 1. Patent Document 1 describes a technique related to a photosensitive resin composition containing a resin having a phenolic hydroxyl group and a crosslinking agent.

  Patent Document 2 describes a technique related to a radiation-sensitive composition containing a polymer containing an epoxy group and a crosslinking agent containing a polyfunctional epoxy compound.

JP 2014-186300 A International Publication No. 2005/096100 Pamphlet

  About the photosensitive resin composition, showing sufficient sclerosis | hardenability by the heat processing at low temperature may be calculated | required. However, when the curing temperature of the photosensitive resin composition is set to a low temperature, the crosslinking agent for improving the heat resistance is not sufficiently crosslinked, and there is a concern that the residual stress after curing is increased by the remaining crosslinking group. Is done. Against this background, there is a need in the present technical field for a positive photosensitive resin composition having an excellent balance of workability, mechanical strength, and residual stress after curing.

  Then, this invention makes it a subject to provide the positive photosensitive resin composition excellent in workability, mechanical strength, and the balance of the residual stress after hardening.

According to the present invention,
(A) an alkali-soluble resin containing the following structural units a1) and a2);
(B) a photoacid generator;
(C) a phenol compound;
A positive photosensitive resin composition is provided.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４はそれぞれ独立して水素原子、水酸基又は炭素原子数１〜３０の有機基を表し、Ｒ_５は水素原子又は炭素原子数１〜３０の有機基を表し、ｎ_１及びｎ_２はそれぞれ０〜２の整数である。）

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom, a hydroxyl group or an organic group having 1 to 30 carbon atoms, and R ₅ is a hydrogen atom or having 1 to 30 carbon atoms. Represents an organic group, and n ₁ and n ₂ are each an integer of 0 to _2. )

  Moreover, according to this invention, the cured film comprised with the hardened | cured material of said positive photosensitive resin composition is provided.

  Moreover, according to this invention, the protective film comprised with said cured film is provided.

  Moreover, according to this invention, the insulating film comprised with said cured film is provided.

  Furthermore, according to this invention, an electronic apparatus provided with said cured film is provided.

  According to the present invention, it is possible to provide a positive photosensitive resin composition capable of forming a positive pattern with high sensitivity and improving the balance between mechanical strength and residual stress when formed into a cured film.

It is sectional drawing which shows an example of the electronic device which concerns on this embodiment. It is sectional drawing which shows an example of the electronic device which concerns on this embodiment.

  Hereinafter, embodiments will be described with reference to the drawings as appropriate. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate. In addition, unless otherwise specified, “to” represents the following.

[Positive photosensitive resin composition]
The positive photosensitive resin composition according to this embodiment includes the following components.
(A) Alkali-soluble resin containing structural units a1) and a2) (B) Photoacid generator (C) Phenol compound

  By adopting such a configuration, it is possible to form a positive pattern with high sensitivity, and even when cured at low temperature for use as a surface protective film and an interlayer insulating film, a balance between mechanical strength and residual stress is achieved. A positive photosensitive resin composition having characteristics can be provided.

In addition, the protective film and the insulating film according to the present embodiment are formed of a cured film that is a cured product of the photosensitive resin composition.
In addition, an electronic device such as a semiconductor device or a display device according to the present embodiment is configured by the cured film.

  Below, each component of the positive photosensitive resin composition which concerns on this embodiment is demonstrated in detail. The following is an example, and the present invention is not limited to the following.

((A) alkali-soluble resin)
The (A) alkali-soluble resin used in the present embodiment includes the following structural units a1) and a2).

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４はそれぞれ独立して水素原子、水酸基又は炭素原子数１〜３０の有機基を表し、Ｒ_５は水素原子又は炭素原子数１〜３０の有機基を表し、ｎ_１及びｎ_２はそれぞれ０〜２の整数である。）

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom, a hydroxyl group or an organic group having 1 to 30 carbon atoms, and R ₅ is a hydrogen atom or having 1 to 30 carbon atoms. Represents an organic group, and n ₁ and n ₂ are each an integer of 0 to _2. )

  (A) alkali-soluble resin of this embodiment is included as a structural unit derived from a cyclic olefin as a structural unit of a1). The cyclic olefin is a polymerizable cyclic olefin having an ethylenic double bond in the ring, and as a typical bicyclic olefin containing a bicyclic olefin, for example, norbornene which may have a substituent Examples thereof include (2-norbornene) and octaline (octahydronaphthalene) which may have a substituent. These substituents may be used alone or in combination of two or more.

  Specifically, as the bicyclic olefin, for example, 2-norbornene; 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene Norbornenes having an alkyl group (C1-C10 alkyl group) such as: norbornenes having an alkenyl group such as 5-ethylidene-2-norbornene; 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl- Norbornenes having an alkoxycarbonyl group such as 2-norbornene; norbornenes having a cyano group such as 5-cyano-2-norbornene; 5-phenyl-2-norbornene, 5-phenyl-5-methyl-2-norbornene, etc. Norbornenes having an aryl group; octalin; 6 Ethyl - such -octalin having an alkyl group such as octahydronaphthalene can be exemplified.

  These bicyclic olefins can be used alone or in combination of two or more. Of these bicyclic olefins, norbornenes such as norbornene and norbornene having an alkyl group (C1-C10 alkyl group such as methyl group or ethyl group) are preferable.

  The cyclic olefin may contain a bicyclic olefin, and may further contain a monocyclic olefin and / or a polycyclic olefin having three or more rings. Examples of monocyclic olefins include cyclic C4-C12 cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene. Examples of the polycyclic olefin include dicyclopentadiene; 2,3-dihydrodicyclopentadiene, methanooctahydrofluorene, dimethanooctahydronaphthalene, dimethanocyclopentadienonaphthalene, methanooctahydrocyclopentadienaphthalene, and the like. Derivatives having substituents such as 6-ethyl-octahydronaphthalene; adducts of cyclopentadiene and tetrahydroindene, 3-pentamers of cyclopentadiene, and the like.

  Moreover, (A) alkali-soluble resin of this embodiment is included as a structural unit derived from maleimide or a maleimide derivative as a structural unit of a2). Thereby, it can contribute to improvement of workability as a positive photosensitive resin composition, improvement of mechanical strength, and reduction of residual stress.

In this embodiment, examples of the organic group constituting R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, Examples include an organic group having a carboxyl group and an organic group having a heterocycle, and can be selected from these. As the alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, and a decyl group are mentioned. Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group, and can be selected from these. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the organic group having a heterocycle include an epoxy group and an organic group having an oxetanyl group.

In addition, the film forming property of the photosensitive resin composition can be improved by including an alkyl group as R ₁ , R ₂ , R ₃ and R ₄ . Moreover, by including an aryl group as R ₁ , R ₂ , R _3, and R ₄ , film loss during development using an alkaline developer in a lithography process can be suppressed for the photosensitive resin composition. Further, R _{1, R 2,} by including an organic group or an organic group having a hetero ring having a carboxyl group as R ₃ and R _4, it is possible to improve the heat resistance and strength of the cured film. From the viewpoint of particularly improving the heat resistance of the cured _film, a structural unit containing an organic group having a carboxyl group as R _1, R 2, _{R 3} and _{R 4,} heteroaryl as R _1, R 2, _{R 3} and _{R 4} It is more preferable to include both the structural unit containing an organic group having a ring in the structure represented by the above formula a1).

  In addition, the above-described alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, organic group having a carboxyl group, and organic group having a heterocyclic ring are one or more hydrogen atoms. May be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

In the present embodiment, R ₅ is a hydrogen atom or a C1-C30 organic group. Examples of the C1-C30 organic group constituting R ₅ include hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, or cycloalkyl groups. As the alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, and a decyl group are mentioned. Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. One or more hydrogen atoms contained in R ₅ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine.

  Said (A) alkali-soluble resin may contain the structural unit derived from the compound which has another ethylenic double bond other than the structural unit of a1) and a2). Examples of other compounds having an ethylenic double bond include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3- Α-olefins having 2 to 20 carbon atoms such as ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc .; 1,4-hexadiene Non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; acrylic acid, methacrylic acid, α-ethyl Acrylic acids such as polyacrylic acid and 2-hydroxyethyl (meth) acrylic acid; maleic acids such as maleic acid, maleic anhydride, dimethylmaleic acid, diethylmaleic acid and dibutylmaleic acid. These monomers can be used alone or in combination of two or more.

((B) Photoacid generator)
The positive photosensitive resin composition of this embodiment contains (B) a photoacid generator.
Examples of the photoacid generator (B) include photosensitive diazoquinone compounds, diaryliodonium salts, onium salts such as triarylsulfonium salts or sulfonium borate salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imidosulfonates. A compound, a 2,6-bis (trichloromethyl) -1,3,5-triazine compound, or a dihydropyridine compound can be used. Among these, it is particularly preferable to use a photosensitive diazoquinone compound having excellent sensitivity and solvent solubility.
As the photosensitive diazoquinone compound, for example, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid is more preferably used. preferable. The photosensitizer remaining in the relief pattern in the unexposed area is considered to decompose by heat at the time of curing to generate an acid, and the photoacid generator (B) plays an important role as a reaction accelerator. As the photosensitive diazoquinone compound having such a role, it is particularly preferable to use an ester of 1,2-naphthoquinone-2-diazido-4-sulfonic acid which is easily decomposed by heat.

  Although content of (B) photo-acid generator in the positive photosensitive resin composition of this embodiment is not specifically limited, (A) 5 mass parts or more with respect to 100 mass parts of alkali-soluble resin. Preferably, it is more preferably 8 parts by mass or more. In addition, the content of the (B) photoacid generator in the positive photosensitive resin composition is preferably 40 parts by mass or less, and 30 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. More preferably. (B) Good patterning performance can be exhibited because the content of the photoacid generator is within the above range.

((C) phenol compound)
The positive photosensitive resin composition of this embodiment contains (C) a phenol compound.
Thereby, sufficient crosslinking can be promoted, and a film excellent in the balance between mechanical strength and residual stress can be obtained.

  This (C) phenol compound can be selected from compounds having one or more phenolic hydroxyl groups in the molecule, and the type of the above-mentioned (A) alkali-soluble resin and the positive photosensitivity of this embodiment. What is necessary is just to select suitably according to the use etc. of a resin composition.

  The number of phenolic hydroxyl groups in the molecule is more preferably 2 or more, and further preferably 3 or more. Further, the upper limit of the number of phenolic hydroxyl groups in the molecule is not particularly limited, but is, for example, 15 or less.

  More specifically, in this embodiment, a compound represented by the following general formula (1) can be used as the (C) phenol compound.

〔式（１）中、ｎは、１〜４の整数である。Ｒ^ａは、それぞれ独立して、水素原子、水酸基、炭素原子数１〜６の直鎖状、分岐状もしくは環状のアルキル基もしくは下記式（２）

（式（２）中、Ｒ^ｂは、それぞれ独立して、水素原子、水酸基、または炭素原子数１〜６の直鎖状、分岐状もしくは環状のアルキル基である。）で表される置換フェニル基であり、Ｒ^ａの少なくとも一つは水酸基である。Ａは、炭素原子数２〜４０のｎ価の有機基もしくは炭素原子であり、ｎが２である場合は、Ａは単結合、ケトン基、エーテル基、エステル基、硫黄原子、スルホニル基もしくはアゾ基であってもよい。〕

[In Formula (1), n is an integer of 1-4. R ^a is independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or the following formula (2)

(In formula (2), each R ^b is independently a hydrogen atom, a hydroxyl group, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.) And at least one of R ^a is a hydroxyl group. A is an n-valent organic group or carbon atom having 2 to 40 carbon atoms, and when n is 2, A is a single bond, ketone group, ether group, ester group, sulfur atom, sulfonyl group or azo group. It may be a group. ]

  Specifically, examples of the phenol compound represented by the general formula (1) include, but are not limited to, compounds represented by the following formulas (3A) to (3D). Moreover, these phenol compounds can be used 1 type or in combination of 2 or more types.

  Among these, it is particularly preferable to use a compound group represented by the following formula (4) from the viewpoint of adjusting the patterning and further improving the residual stress of the cured film.

In the present embodiment, the content of the (C) phenol compound in the positive photosensitive resin composition is preferably 1 part by mass or more with respect to 100 parts by mass of the (A) alkali-soluble resin, and 2 parts by mass. More preferably, it is more preferably 3 parts by mass or more.
In addition, the content of the (C) phenol compound in the positive photosensitive resin composition is preferably 50 parts by mass or less, and 40 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. More preferably, it is more preferably 30 parts by mass or less.
(C) By setting content of a phenol compound in the said range, it can be made favorable about both the residual stress of a cured film, and pattern moldability.

((D) Adhesion aid)
The positive photosensitive resin composition of the present embodiment can contain (D) an adhesion assistant as required.
The (D) adhesion assistant used here is a component having a function of improving the bond strength between the coating film obtained by curing the photosensitive resin composition and the substrate on which the coating film is formed.
Examples of such adhesion assistants include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyl Trimethoxy Lan, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Examples thereof include, but are not limited to, propyltriethoxysilane, a silicon compound obtained by reacting an amino group-containing silicon compound with an acid dianhydride or an acid anhydride.
Among these compounds, a silicon compound obtained by reacting an amino group-containing silicon compound with an acid dianhydride or an acid anhydride has an intramolecular structure when the acid dianhydride or acid anhydride is ring-opened. To form a carboxyl group.
As described above, (D) as an adhesion aid, by containing at least one carboxyl group in the molecule, the cured product of the photosensitive resin composition exhibits an appropriate affinity with an organic solvent described later. Adhesion to the substrate can be improved.

The type of silicon compound having an amino group is not particularly limited as long as adhesion can be improved. For example, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane and the like.
The acid dianhydride or acid anhydride is not particularly limited as long as adhesion can be improved. For example, 3,3′4,4′-benzophenonetetracarboxylic acid anhydride And cyclohexene dicarboxylic acid anhydride, maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, phthalic anhydride, and the like. Moreover, in using, it can be used individually or in combination of 2 or more types.

The content of the (D) adhesion assistant in the positive photosensitive resin composition of the present embodiment is not particularly limited, but is 0.01 parts by mass with respect to (A) 100 parts by mass of the alkali-soluble resin. It is preferable that it is above, and it is more preferable that it is 0.1 parts by mass or more.
Further, the content of the (D) adhesion assistant in the positive photosensitive resin composition is preferably 20 parts by mass or less, and 15 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. It is more preferable. Moreover, in one Embodiment, it can also be 10 mass parts or less.
(D) If the content of the adhesion assistant is within the above range, the adhesion to the substrate and the storage stability of the photosensitive resin composition can be improved in a balanced manner.

((E) Thermal crosslinking agent)
The positive photosensitive resin composition of this embodiment may contain (E) a thermal crosslinking agent. (E) The thermal crosslinking agent is preferably a compound having a hetero ring as a reactive group, and among them, a compound having a glycidyl group or an oxetanyl group is preferable. Among these, a compound having a glycidyl group is more preferable from the viewpoint of reactivity with a functional group having an active hydrogen such as a carboxyl group or a hydroxyl group. An example of the compound having a glycidyl group is an epoxy compound.

  Examples of the epoxy compound include n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether. Glycidyl ethers such as sorbitol polyglycidyl ether, glycidyl ether of bisphenol A (or F), glycidyl esters such as adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4- Epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy) -6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2,3-epoxycyclopentyl) ether, and Celoxide manufactured by Daicel Corporation 2021, celoxide 2081, celoxide 2083, celoxide 2085, celoxide 8000, epoxide GT401, and the like, 2,2 ′-(((((1- (4- (2- (4- (oxiran-2-ylmethoxy) ) Phenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane) (eg Techmore VG3101L ) Made by Printec)), Eporai Aliphatic polyglycidyl ethers such as 100MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and Epiol TMP (manufactured by NOF Corporation), 1,1,3,3,5,5-hexamethyl-1,5-bis (3 -(Oxiran-2-ylmethoxy) propyl) tri-siloxane (for example, DMS-E09 (manufactured by Gerest)) and the like can be used.

In addition, bisphenols such as LX-01 (manufactured by Daiso Corporation), jER1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (trade names; manufactured by Mitsubishi Chemical Corporation) A type epoxy resin, bisphenol F type epoxy resin such as jER807 (trade name; manufactured by Mitsubishi Chemical Corporation), jER152, 154 (trade name; manufactured by Mitsubishi Chemical Corporation), EPPN201, 202 (trade name; Japan) Phenolic novolak type epoxy resins such as EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), jER157S70 (trade name; Mitsubishi Chemical Corporation) Cresol novolac type epoxy resin, Araldite CY179, 184 (trade name; Hunts) Advanced Materials), ERL-4206, 4221, 4234, 4299 (trade name; manufactured by Dow Chemical Company), Epicron 200, 400 (trade name; manufactured by DIC Corporation), jER871, 872 (trade name; Mitsubishi) (Chemical Co., Ltd.) and other cyclic aliphatic epoxy resins such as Poly [(2-oxylanyl) -1,2-cyclohexanediol] -2-ethyl-2- (hydroxymethyl) -1,3-propanediol (3: 1), etc. The polyfunctional alicyclic epoxy resin of EHPE-3150 (made by Daicel Corporation) can also be used.
In addition, the positive photosensitive resin composition in this embodiment can contain 1 type, or 2 or more types of the epoxy compound illustrated above.

  (E) As a compound having an oxetanyl group used as a thermal crosslinking agent, for example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] Methyl ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl- 3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, Pentaerythritol tetrakis (3-ethyl- -Oxetanylmethyl) ether, poly [[3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane -3-yl) methoxy] benzene and the like, but is not limited thereto. These may be used alone or in combination.

Although content of (E) thermal crosslinking agent in the positive photosensitive resin composition of this embodiment is not specifically limited, (A) It is 1 mass part or more with respect to 100 mass parts of alkali-soluble resin. It is preferable that it is 5 parts by mass or more.
Moreover, it is preferable that content of (E) thermal crosslinking agent in a positive type photosensitive resin composition is 200 mass parts or less with respect to 100 mass parts of (A) alkali-soluble resin, and is 100 mass parts or less. It is more preferable.
(E) By making content of a thermal crosslinking agent in the said range, the cured film excellent in the residual film rate at the time of hardening and heat resistance can be formed.

((F) curing accelerator)
The positive photosensitive resin composition of the present embodiment can contain (F) a curing accelerator from the viewpoint of improving thermal crosslinking.
(F) As a hardening accelerator, the compound which generate | occur | produces an acid by a hetero five-membered ring compound containing nitrogen, for example can be used. These may be used alone or in combination. (F) Examples of the nitrogen-containing heterocyclic five-membered ring compound used as a curing accelerator include pyrrole, pyrazole, imidazole, 1,2,3-triazole, and 1,2,4-triazole. Examples of compounds that generate an acid by heat used as a curing accelerator include sulfonium salts, iodonium salts, sulfonates, phosphates, borates, and salicylates, 1,8-diazabicyclo [5.4. .0] -7-undecene and its phenol salt, octylate, oleate, p-toluenesulfonate, formate, orthophthalate, tetraphenylborate and the like. From the viewpoint of more effectively improving curability at low temperatures, among the compounds that generate acid by heat, 1,8-diazabicyclo [5.4.0] -7-undecene sulfonate and 1,8- More preferably, one or both of the tetraphenylborate salts of diazabicyclo [5.4.0] -7-undecene are included.

(F) Although the addition amount of a hardening accelerator is not specifically limited, It is preferable that it is 0.01 mass part or more with respect to 100 mass parts of (A) alkali-soluble resin, 0.1 mass part More preferably.
Moreover, the addition amount of (F) hardening accelerator is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of (A) alkali-soluble resin.
(F) By making content of a hardening accelerator into the said range, thermal crosslinkability and the preservability of the photosensitive resin composition can be made to make compatible both suitably.

((G) Surfactant)
The positive photosensitive resin composition of this embodiment may contain (G) a surfactant. The (G) surfactant includes, for example, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton.
In the present embodiment, it is more preferable to use a fluorine-containing surfactant or a silicone-containing surfactant as the surfactant (G), and it is particularly preferable to use a fluorine-based surfactant. Examples of the fluorosurfactant include Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F manufactured by DIC Corporation. -554, F-556, and F-557, Sumitomo 3M Co., Ltd. Novec FC4430, FC4432 etc. are mentioned, However, It is not limited to these.

  In addition, additives such as an antioxidant, a filler, a photopolymerization initiator, a terminal blocking agent, and a sensitizer may be added to the positive photosensitive resin composition of the present embodiment as necessary. .

((S) solvent)
The positive photosensitive resin composition of the present embodiment is usually used by dissolving the above components in the (S) solvent and varnishing. As such (S) solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene Glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl -3-Methoxypropionate and the like may be mentioned, and these may be used alone or in combination.

  The content of the (S) solvent in the positive photosensitive resin composition of the present embodiment is not particularly limited, but (A) 50 parts by mass or more and 1000 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. It is preferable that the amount is 100 parts by mass or more and 500 parts by mass or less. (S) When content of a solvent exists in the said range, resin can fully melt | dissolve and a varnish with high handleability can be produced.

<Curing film>
In the method of using the positive photosensitive resin composition of the present embodiment, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. When applying on a semiconductor element, the application amount is generally applied so that the final film thickness after curing is 0.1 to 30 μm. By setting it as such a numerical value range, the function as a protective film of a semiconductor element and an insulating film is fully exhibited, and a fine relief pattern can be obtained.
Application methods include spin coating using a spin coater, spray coating using a spray coater, dipping, printing, roll coating, and the like.
Next, when a relief pattern is formed after pre-baking at 60 to 130 ° C. and drying the coating film, the desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

  Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di- Secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; secondary amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a quaternary ammonium salt; and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol, or a surfactant to these can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment (curing) is performed to obtain a cured film as a cured product having excellent heat resistance.
The heat treatment can be performed at a high temperature or a low temperature, and the heat treatment temperature at a high temperature is preferably 280 ° C to 380 ° C, more preferably 290 ° C to 350 ° C. The heat treatment temperature at low temperature is preferably 150 ° C. to 280 ° C., more preferably 180 ° C. to 260 ° C. An oven, a hot plate, an electric furnace (furnace), infrared rays, microwaves, etc. are used for the heat treatment.

<Application>
Next, the use of the positive photosensitive resin composition of the present embodiment will be described.

  The cured film formed using the positive photosensitive resin composition of the present embodiment is used not only for semiconductor devices such as semiconductor elements, but also for display device devices such as TFT liquid crystal and organic EL, and interlayer insulation for multilayer circuits. It is also useful as a film, a cover coat of a flexible copper-clad plate, a solder resist film or a liquid crystal alignment film.

  Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described photosensitive resin composition on a semiconductor element, and a buffer formed by forming a cured film of the above-described photosensitive resin composition on the passivation film. Protective film such as a coating film, insulating film such as an interlayer insulating film formed by forming a cured film of the above-mentioned photosensitive resin composition on a circuit formed on a semiconductor element, α-ray blocking film, planarizing film, protrusion (Resin post), partition walls and the like.

Examples of display device applications include a protective film formed by forming a cured film of the photosensitive resin composition of the present embodiment on a display element, an insulating film or a planarizing film for TFT elements, color filters, and the like, MVA Protrusions for a liquid crystal display device, partition walls for an organic EL element cathode, and the like.
The use method is based on forming the photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed according to the semiconductor device application by the above method. High transparency is required for display device applications, particularly for insulating films and planarization films, but by introducing a post-exposure step before curing the coating film of the photosensitive resin composition of the present embodiment, A resin layer excellent in transparency can also be obtained, which is more preferable in practical use.

As a semiconductor device, a semiconductor chip (element) is formed on a semiconductor substrate and sealed with an airtight seal or a molding material. Specific examples include transistors, solar cells, diodes, solid-state imaging devices, various semiconductor packages in which semiconductor chips are stacked and sealed, and wafer level chip size packages (WLP).
Examples of the display device include a TFT liquid crystal, an organic EL, and a color filter.

  Hereinafter, an example of an electronic device having a film formed using the photosensitive resin composition of the present embodiment will be described.

<Electronic device>
1 and 2 are cross-sectional views showing examples of the electronic device 100 according to the present embodiment. In any case, a part of the electronic device 100 including an insulating film is shown.

  As an example of the electronic apparatus 100 according to the present embodiment, a liquid crystal display device is shown in FIG. However, the electronic device 100 according to the present embodiment is not limited to the liquid crystal display device, and includes other electronic devices including a permanent film made of the photosensitive resin composition of the present embodiment.

  As shown in FIG. 1, an electronic device 100 that is a liquid crystal display device includes, for example, a substrate 10, a transistor 30 provided on the substrate 10, and an insulating film 20 provided on the substrate 10 so as to cover the transistor 30. And a wiring 40 provided on the insulating film 20.

The substrate 10 is, for example, a glass substrate.
The transistor 30 is a thin film transistor that constitutes a switching element of a liquid crystal display device, for example. On the substrate 10, for example, a plurality of transistors 30 are arranged in an array. The transistor 30 according to the present embodiment includes, for example, a gate electrode 31, a source electrode 32, a drain electrode 33, a gate insulating film 34, and a semiconductor layer 35. The gate electrode 31 is provided on the substrate 10, for example. The gate insulating film 34 is provided on the substrate 10 so as to cover the gate electrode 31. The semiconductor layer 35 is provided on the gate insulating film 34. The semiconductor layer 35 is, for example, a silicon layer. The source electrode 32 is provided on the substrate 10 so that a part thereof is in contact with the semiconductor layer 35. The drain electrode 33 is provided on the substrate 10 so as to be separated from the source electrode 32 and partially in contact with the semiconductor layer 35.

The insulating film 20 functions as a planarization film for eliminating a step due to the transistor 30 and the like and forming a flat surface on the substrate 10. Moreover, the insulating film 20 is comprised with the hardened | cured material of the positive photosensitive resin composition of this embodiment. The insulating film 20 is provided with an opening 22 that penetrates the insulating film 20 so as to be connected to the drain electrode 33.
A wiring 40 connected to the drain electrode 33 is formed on the insulating film 20 and in the opening 22. The wiring 40 functions as a pixel electrode that constitutes a pixel together with the liquid crystal.
An alignment film 90 is provided on the insulating film 20 so as to cover the wiring 40.

A counter substrate 12 is disposed above one surface of the substrate 10 where the transistor 30 is provided so as to face the substrate 10. A wiring 42 is provided on one surface of the counter substrate 12 facing the substrate 10. The wiring 42 is provided at a position facing the wiring 40. An alignment film 92 is provided on the one surface of the counter substrate 12 so as to cover the wiring 42.
The liquid crystal constituting the liquid crystal layer 14 is filled between the substrate 10 and the counter substrate 12.

The electronic device 100 shown in FIG. 1 is formed as follows, for example.
First, the transistor 30 is formed over the substrate 10. Next, a photosensitive resin composition is applied to one surface of the substrate 10 on which the transistor 30 is provided by a printing method or a spin coating method to form the insulating film 20 that covers the transistor 30. Thus, a planarization film that covers the transistor 30 provided over the substrate 10 is formed.
Next, the insulating film 20 is exposed and developed to form an opening 22 in a part of the insulating film 20. At this time, the unexposed portion is dissolved in the developer, and the exposed portion remains. This also applies to each example of the electronic device 100 described later.
Next, the insulating film 20 is heated and cured. Then, a wiring 40 connected to the drain electrode 33 is formed in the opening 22 of the insulating film 20. Thereafter, the counter substrate 12 is disposed on the insulating film 20, and liquid crystal is filled between the counter substrate 12 and the insulating film 20 to form the liquid crystal layer 14.
As a result, the electronic device 100 shown in FIG. 1 is formed.

As an example of the electronic device 100 according to the present embodiment, FIG. 2 shows a semiconductor device in which the rewiring layer 80 is formed of a permanent film made of a photosensitive resin composition.
An electronic device 100 shown in FIG. 2 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer provided on the semiconductor substrate (not shown). An insulating film 50 that is an interlayer insulating film and an uppermost layer wiring 72 provided on the insulating film 50 are provided in the uppermost layer of the multilayer wiring layer. The uppermost layer wiring 72 is made of, for example, Al.

A rewiring layer 80 is provided on the insulating film 50. The rewiring layer 80 includes an insulating film 52 provided on the insulating film 50 so as to cover the uppermost wiring 72, a rewiring 70 provided on the insulating film 52, and on the insulating film 52 and the rewiring 70. And an insulating film 54 provided.
An opening 24 connected to the uppermost layer wiring 72 is formed in the insulating film 52. The rewiring 70 is formed on the insulating film 52 and in the opening 24, and is connected to the uppermost layer wiring 72. The insulating film 54 is provided with an opening 26 connected to the rewiring 70.
The insulating film 52 and the insulating film 54 are composed of permanent films made of the positive photosensitive resin composition of the present embodiment. The insulating film 52 is obtained, for example, by forming the opening 24 by exposing and developing the positive photosensitive resin composition applied on the insulating film 50, and then heat-curing the opening 24. The insulating film 54 is obtained, for example, by forming the opening 26 by exposing and developing the positive photosensitive resin composition applied on the insulating film 52, and then heat-curing the opening 26.

  For example, bumps 74 are formed in the openings 26. The electronic device 100 is connected to a wiring board or the like via bumps 74, for example.

  Furthermore, the electronic device 100 according to the present embodiment may be an optical device that forms a microlens with a permanent film made of a photosensitive resin composition. Examples of the optical device include a liquid crystal display device, a plasma display, a field emission display, and an electroluminescence display.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this.

(Synthesis Example 1)
<Synthesis of alkali-soluble resin (A-1)>
In a sealable reaction vessel, norbornene carboxylic acid (30.4 g, 220 mmol), methyl glycidyl ether norbornene (57.7 g, 320 mmol), maleimide (24.3 g, 250 mmol), and cyclohexylmaleimide (44.8 g, 250 mmol) Weighed. Furthermore, 113 g of propylene glycol monomethyl ether (PGME) in which dimethyl 2,2′-azobis (2-methylpropionate) (12.0 g, 52 mmol) was dissolved was added to the reaction vessel and stirred and dissolved. Next, after the dissolved oxygen in the system was removed by nitrogen bubbling, the container was sealed and reacted at 70 ° C. for 16 hours. The reaction mixture was then cooled to room temperature and diluted by adding 200 g of acetone. The diluted solution was poured into a large amount of hexane to precipitate a polymer. Next, the polymer was collected by filtration, further washed with hexane, and then vacuum dried at 30 ° C. for 16 hours to obtain an alkali-soluble resin (A-1). The polymer yield was 126 g and the yield was 80%. By the said operation, the alkali-soluble resin which has a repeating unit shown by following formula (8) whose weight average molecular weight Mw is 8500 was obtained.

(Synthesis Example 2)
<Synthesis of alkali-soluble resin (A-2)>
In a sealable reaction vessel, norbornene carboxylic acid (31.8 g, 230 mmol), ethyl oxetane vinyl ether (42.7 g, 300 mmol), maleimide (24.3 g, 250 mmol), and cyclohexylmaleimide (44.8 g, 250 mmol). Weighed. Furthermore, 104 g of propylene glycol monomethyl ether (PGME) in which dimethyl 2,2′-azobis (2-methylpropionate) (11.9 g, 52 mmol) was dissolved was added to the reaction vessel, and stirred and dissolved. Next, after the dissolved oxygen in the system was removed by nitrogen bubbling, the container was sealed and reacted at 70 ° C. for 16 hours. The reaction mixture was then cooled to room temperature and diluted by adding 187 g of acetone. The diluted solution was poured into a large amount of hexane to precipitate a polymer. Next, the polymer was collected by filtration, further washed with hexane, and then vacuum-dried at 30 ° C. for 16 hours. The yield of the polymer was 111 g, and the yield was 77%. By the said operation, the alkali-soluble resin (A-2) which has a repeating unit shown by following formula (9) whose weight average molecular weight Mw is 11500 was obtained.

(Synthesis Example 3)
<Synthesis of alkali-soluble resin (A-3)>
In a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet tube, 21.4 g (83 mmol) of diphenyl ether-4,4′-dicarboxylic acid and 1-hydroxy-1,2, 40.9 g (83 mmol) of a mixture of dicarboxylic acid derivatives obtained by reacting 22.4 g (166 mmol) of 3-benzotriazole with hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 36.6 g (100 mmol) was added, and 330 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath.
Next, 5.6 g (34 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride dissolved in 27.9 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 3 hours to complete the reaction.
After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( An alkali-soluble resin (A-3)) was obtained. The yield of polyamide resin was 53 g, and the yield was 63%. Moreover, the weight average molecular weight Mw of this polyamide resin was 14,500.

(Synthesis Example 4)
<Synthesis of Photoacid Generator (B-1)>
In a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 11.0 g (26 mmol) of the phenol compound represented by the formula (B-0) and 1,2- 18.8 g (70 mmol) of naphthoquinone-2-diazide-4-sulfonyl chloride and 170 g of acetone were added and stirred and dissolved.
Next, a mixed solution of 7.78 g (77 mmol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. The reaction was allowed to proceed at room temperature for 3 hours, and then 1.05 g (17 mmol) of acetic acid was added and the reaction was allowed to proceed for another 30 minutes. Next, after filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), and then the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum. A photoacid generator represented by the structure of the formula (B-1) was obtained.

  Q in the formula (B-1) is represented by a hydrogen atom or the above formula (B-2), and 90% of the whole Q is the above formula (B-2).

(Synthesis Example 5)
<Synthesis of adhesion aid (D-1)>
Cyclohexene-1,2-dicarboxylic anhydride (45.6 g, 300 mmol) was dissolved in γ-butyrolactone (970 g) in a suitably sized reaction vessel equipped with a stirrer and a condenser, and the temperature was kept at 30 ° C. in a thermostatic bath. Adjusted. Subsequently, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was charged into the dropping funnel and dropped into the solution over 60 minutes. After completion of dropping, the mixture was stirred under conditions of 30 ° C. for 18 hours to obtain an adhesion assistant (D-1) represented by the following formula (10).

(Synthesis Example 6)
<Synthesis of adhesion aid (D-2)>
In a suitably sized reaction vessel equipped with a stirrer and a condenser, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (32.2 g, 100 mmol) was dissolved in γ-butyrolactone (669 g). The temperature was adjusted to 30 ° C. in a thermostatic bath. Subsequently, 3-aminopropyltriethoxysilane (42.1 g, 190 mmol) was charged into the dropping funnel and dropped into the solution over 60 minutes. After completion of dropping, the mixture was stirred under conditions of 30 ° C. for 18 hours to obtain an adhesion assistant (D-2) represented by the following formula (11).

(Preparation of photosensitive resin composition)
About each of Examples 1-8 and Comparative Examples 1-4, the photosensitive resin composition was prepared as follows. First, each component blended according to Table 1 is dissolved in γ-butyrolactone (GBL) so that the viscosity after blending is about 500 mPa · s and stirred in a nitrogen atmosphere, and then polyethylene having a pore size of 0.2 μm is prepared. The varnish-like photosensitive resin composition was obtained by filtering with the filter made from. Details of each component in Table 1 are as follows. Moreover, the unit in Table 1 is a mass part.

<(A) Alkali-soluble resin>
(A-1) Alkali-soluble resin obtained in Synthesis Example 1 (A-2) Alkali-soluble resin obtained in Synthesis Example 2 (A-3) Polyamide resin obtained in Synthesis Example 3

<(B) Photoacid generator>
(B-1) Photoacid generator obtained in Synthesis Example 4

<(C) Phenol compound>
(C-1) Methylenebisresorcin (Honshu Chemical Co., Ltd.)
(C-2) 2,4,6,3 ′, 5′-biphenylpentol (manufactured by Kanto Chemical Co., Inc.)
(C-3) OC4HBPA (manufactured by Honshu Chemical Co., Ltd.)
(C-4) OC4HBPM (manufactured by Honshu Chemical Co., Ltd.)
(C-5) TrisP-PA-MF (manufactured by Honshu Chemical Co., Ltd.)
(C-6) Bisphenol F (Honshu Chemical Co., Ltd.)

<(D) Adhesion aid>
(D-1) Silane coupling agent obtained in Synthesis Example 5 (D-2) Silane coupling agent obtained in Synthesis Example 6 (D-3) 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone) (Made by Co., Ltd.)

<(E) Thermal crosslinking agent>
(E-1) Celoxide 2021P (manufactured by Daicel Corporation)
(E-2) Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)

<(F) Curing accelerator>
(F-1) UCAT SA506 (manufactured by Sun Apro Co., Ltd.)
(F-2) UCAT 5002 (manufactured by Sun Apro Co., Ltd.)

<(G) Surfactant>
(G-1) FC4430 (manufactured by Sumitomo 3M)

<Processability evaluation>
Each of the photosensitive resin compositions obtained above was applied onto an 8-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120 ° C. for 3 minutes to form a coating film having a thickness of about 7.5 μm. Got. An i-line stepper (Nikon Corp., NSR-4425i) was used through this coating film through a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern having a width of 0.88 to 50 μm are drawn). Then, irradiation was carried out while changing the exposure amount.
Next, a 2.38% tetramethylammonium hydroxide aqueous solution is used as a developing solution, and the developing time is adjusted so that the difference between the film thickness after pre-baking and the film thickness after developing is 1.0 μm, and paddle twice. The exposed portion was dissolved and removed by developing, and then rinsed with pure water for 10 seconds. The value of the minimum exposure amount at which a 100 μm square via hole pattern was formed was evaluated as sensitivity (mJ / cm ² ).
The minimum exposure amount should be low in terms of process throughput.

<Tensile elongation>
For each Example and each Comparative Example, a tensile test was performed on a test piece (10 mm × 60 mm × 10 μm thickness) obtained by curing the obtained photosensitive resin material under a nitrogen atmosphere at 300 ° C. for 30 minutes. (Stretching speed: 5 mm / min) was performed in a 23 ° C. atmosphere. The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. Five test pieces were measured, the tensile elongation was calculated from the fractured distance and the initial distance using the following formulas, and the averaged tensile elongation was determined. Table 1 shows the results.
Tensile elongation (%) = (breaking distance−initial distance) / initial distance × 100

<Residual stress>
First, the amount of warpage of an 8-inch silicon wafer (thickness: 725 μm) at 23 ° C. was measured with a thin film stress measuring device (FLX-2330S Toho Technology Co., Ltd.). Next, the photosensitive resin composition obtained in each example and each comparative example was coated on an 8-inch silicon wafer so that the film thickness would be 10 μm after curing, and after heat treatment at 120 ° C. for 4 minutes, nitrogen was further added. It hardened | cured on condition of 200 degreeC and 60 minutes in atmosphere. After cooling the cured film to 23 ° C., the amount of warpage after coating was measured again with a thin film stress measuring device, and the stress of the resin film was calculated from the amount of warpage before and after curing. The lower the stress of the resin film, the better for the purpose of preventing warpage of the chip.

<Fabrication of semiconductor device>
Each of the photosensitive resin compositions of Examples 1 to 8 was applied so as to have a final thickness of 5 μm using a simulated element wafer having an aluminum circuit on the surface, and then was subjected to patterning and cured. After that, each chip size is divided and mounted on a lead frame for 16-pin DIP (Dual Inline Package) using a conductive paste, and then sealed with an epoxy resin for semiconductor encapsulation (EME-6300H, manufactured by Sumitomo Bakelite Co., Ltd.) The semiconductor device was fabricated by molding. These semiconductor devices (semiconductor packages) were treated at 85 ° C./85% humidity for 168 hours, then immersed in a 260 ° C. solder bath for 10 seconds, and then subjected to a high-temperature, high-humidity pressure cooker treatment (125 ° C., 2. (3 atm, 100% relative humidity) was applied to check the open failure of the aluminum circuit. As a result, it is expected that the semiconductor device can be used without any problem without corrosion.

  Table 1 below shows examples and comparative examples.

  Examples 1 to 8 all contained an alkali-soluble resin having a specific structural unit and a phenol compound in the photosensitive resin composition. Thereby, the sensitivity by patterning can be improved, the tensile elongation rate after thermosetting is also high, and it was further confirmed that the evaluation results regarding the residual stress are also good.

100 electronic device 10 substrate 12 counter substrate 14 liquid crystal layer 20 insulating film 22 opening 24 opening 26 opening 30 transistor 31 gate electrode 32 source electrode 33 drain electrode 34 gate insulating film 35 semiconductor layer 40 wiring 42 wiring 50 insulating film 52 insulating film 54 insulating Film 70 Rewiring 72 Top layer wiring 74 Bump 80 Rewiring layer 90 Alignment film 92 Alignment film

Claims (11)

(A) an alkali-soluble resin containing the following structural units a1) and a2);
(B) a photoacid generator;
(C) a phenol compound;
A positive photosensitive resin composition comprising:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom, a hydroxyl group or an organic group having 1 to 30 carbon atoms, and R ₅ is a hydrogen atom or having 1 to 30 carbon atoms. Represents an organic group, and n ₁ and n ₂ are each an integer of 0 to _2. ) The positive photosensitive resin composition according to claim 1,
The positive photosensitive resin composition in which the (C) phenol compound is represented by the following general formula (1).

[In Formula (1), n is an integer of 1-4. R ^a is independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or the following formula (2)

(In formula (2), each R ^b is independently a hydrogen atom, a hydroxyl group, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.) And at least one of R ^a is a hydroxyl group. A is an n-valent organic group or carbon atom having 2 to 40 carbon atoms, and when n is 2, A is a single bond, ketone group, ether group, ester group, sulfur atom, sulfonyl group or azo group. It may be a group. ] The positive photosensitive resin composition according to claim 1, wherein
A positive photosensitive resin composition comprising 1 part by mass or more and 50 parts by mass or less of the (C) phenol compound with respect to 100 parts by mass of the (A) alkali-soluble resin. The positive photosensitive resin composition according to any one of claims 1 to 3,
Further, (D) a positive photosensitive resin composition containing an adhesion assistant. The positive photosensitive resin composition according to claim 4,
A positive photosensitive resin composition comprising 0.01 to 20 parts by mass of the adhesion assistant (D) with respect to 100 parts by mass of the (A) alkali-soluble resin. A positive photosensitive resin composition according to any one of claims 1 to 5,
Further, (E) a positive photosensitive resin composition containing a thermal crosslinking agent. The positive photosensitive resin composition according to claim 6,
A positive photosensitive resin composition comprising 1 part by mass or more and 200 parts by mass or less of the (E) thermal crosslinking agent with respect to 100 parts by mass of the (A) alkali-soluble resin.   The cured film comprised with the hardened | cured material of the positive photosensitive resin composition of any one of Claim 1 thru | or 7.   A protective film comprising the cured film according to claim 8.   The insulating film comprised with the cured film of Claim 8.   An electronic device comprising the cured film according to claim 8.

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