JP2012123378A - Photosensitive resin composition for surface protective film of semiconductor element or interlayer insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic resin composition, which shows high elongation even when the composition is applied to a semiconductor device and cured by heat at 250°C or lower, and can be used as an alternative material of a polyimide resin or a polybenzoxazole resin, and to provide a method for producing a cured relief pattern using the composition, and a semiconductor device having the cured relief pattern.SOLUTION: A photosensitive resin composition for a surface protective film of a semiconductor element or an interlayer insulating film contains the following ingredients in a solvent: 100 pts.mass of a phenolic resin (A) having a biphenyl diyl structure in the main chain; 1 to 30 pts.mass of a photoacid generator (B); and 1 to 60 pts.mass of a compound (C) capable of reacting with the ingredient (A) by an acid generated by the photoacid generator (B) or heat.

Description

  The present invention relates to a photosensitive resin composition for a semiconductor element surface protective film or an interlayer insulating film. More specifically, the present invention relates to a relief pattern forming material such as a surface protective film (buffer coat film) or an interlayer insulating film (passivation film) such as a semiconductor element, a method for producing a relief pattern using the relief pattern forming material, and The present invention relates to a semiconductor device having the relief pattern.

  Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been widely used for surface protective films and interlayer insulating films used in semiconductor devices. Since these resins have low solubility in various solvents, they are generally used as a composition dissolved in a solvent in the form of a precursor. Therefore, a step for cyclizing such a precursor is required in use. This ring closing step is usually performed by thermosetting which is heated to 300 ° C. or higher.

However, in recent years, semiconductor devices that are inferior in heat resistance compared to conventional products have been developed, and a material for forming a surface protective film or an interlayer insulating film is required to have a lower thermosetting temperature, particularly at 250 ° C. or lower. The thermosetting property is often required.
In response to this requirement, Patent Document 1 below is obtained by condensing phenols and aldehydes that do not require a ring-closing step, are excellent in cost and photosensitivity, and are widely used as a base resin in the resist field. In order to improve the thermal shock resistance of the phenolic resin and the phenolic resin, materials using crosslinkable fine particles have been proposed.

  Further, in Patent Document 2 below, in order to improve the thermal shock resistance of the phenol resin, when synthesizing the phenol resin, an α, α′-dihaloxylene compound, α, α′- A material obtained by using at least one substituted xylene compound selected from the group consisting of a dihydroxyxylene compound and an α, α′-dialkoxyxylene compound and condensing it with a phenol compound has also been proposed.

  Furthermore, Patent Document 3 below also describes a material in which a phenol resin having a skeleton of a condensate of a biphenyl compound and phenols and a photoacid generator are used in combination. However, Patent Document 3 discloses the material as a material for forming a liquid crystal alignment control protrusion and / or a spacer, or as a material for simultaneously forming a liquid crystal alignment control protrusion and a spacer.

JP 2003-215789 A JP 2007-057595 A JP 2008-292677 A

Although the materials disclosed in Patent Documents 1 and 2 have improved thermal shock resistance, the elongation, which is one of important film properties when applied to a semiconductor device as a surface protective film or an interlayer insulating film Has not been studied at all.
In view of the current situation, the problem to be solved by the present invention is that it has a high elongation even when applied to a semiconductor device and cured with heat of 250 ° C. or less, and is an alternative material for polyimide resin and polybenzoxazole resin. It is to provide a phenol resin composition to be obtained, a method for producing a cured relief pattern using the composition, and a semiconductor device having the cured relief pattern.

  As a result of intensive investigations and repeated experiments to solve the above problems, the present inventors have found that a semiconductor having excellent elongation even when applied to a semiconductor device even at a low thermosetting temperature of 250 ° C. or less. The present inventors have completed the present invention by unexpectedly finding a material that can form a protective film or an interlayer insulating film.

That is, the present invention is as follows.
[1] In the solvent, the following components:
Phenol resin (A) having a biphenyldiyl structure in the main chain: 100 parts by mass;
Photoacid generator (B): 1 to 30 parts by mass; and Compound (C) capable of reacting with component (A) by heat generated from the photoacid generator (B) or heat (C): 1 to 60 parts by mass Part;
The photosensitive resin composition for semiconductor element surface protection films or interlayer insulation films containing this.

｛式中、Ｒは、ハロゲン原子、カルボキシル基、水酸基、炭素数１〜１０の不飽和結合を有していてもよい脂肪族基、炭素数３〜１０の脂環式基、及び炭素数６〜２０の芳香族基から成る群から選ばれる基であり、各々の基の水素原子は、さらにハロゲン原子、カルボキシル基及び／又は水酸基で置換されていてもよく、ｐ及びｑはそれぞれ独立に０〜４の整数であり、ｒは０〜３の整数であり、そしてｐ、ｑ、又はｒが２以上の場合、各々のＲはそれぞれ同じであっても、異なってもよい。｝で表される繰り返しユニットを含む、前記［１］に記載の感光性樹脂組成物。 [2] The phenol resin (A) is represented by the following general formula (1):

{In the formula, R is a halogen atom, a carboxyl group, a hydroxyl group, an aliphatic group optionally having an unsaturated bond having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and 6 carbon atoms. -20 groups selected from the group consisting of aromatic groups, the hydrogen atom of each group may be further substituted with a halogen atom, a carboxyl group and / or a hydroxyl group, and p and q are each independently 0 Is an integer of -4, r is an integer of 0-3, and when p, q, or r is 2 or more, each R may be the same or different. } The photosensitive resin composition as described in said [1] containing the repeating unit represented by these.

  [3] The photosensitive resin composition according to [1] or [2], wherein the number of repeating units of the phenol resin (A) is 8 or more and 100 or less.

  [4] The photoacid generator (B) is an ester compound of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. The photosensitive resin composition according to any one of [1] to [3].

｛式中、Ｑは、水素原子又は下記：

で表されるナフトキノンジアジドスルホン酸エステル基であり、全てのＱが同時に水素原子であることはない。｝で示される化合物である、前記［１］〜［４］のいずれかに記載の感光性樹脂組成物。 [5] The photoacid generator (B) has the following formula:

{Wherein Q is a hydrogen atom or the following:

And all Qs are not simultaneously hydrogen atoms. } The photosensitive resin composition in any one of said [1]-[4] which is a compound shown by these.

[6] The compound (C) is an epoxy group, an oxetane group, a —N— (CH ₂ —OR ′) group {wherein R ′ is hydrogen or an alkyl group having 1 to 4 carbon atoms. } And —C— (CH ₂ —OR ′) group {wherein R ′ is hydrogen or an alkyl group having 1 to 4 carbon atoms. } The photosensitive resin composition according to any one of [1] to [5], which has at least two groups selected from the group consisting of:

[7] The photosensitive resin composition according to any one of claims 1 to 6, further comprising a thermal base generator (D).
[8] The following steps:
Forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [7] on a semiconductor substrate;
Exposing the photosensitive resin layer with actinic rays;
The manufacturing method of a semiconductor device including the process of developing this exposed photosensitive resin layer, obtaining a relief pattern, and the process of heating the obtained relief pattern.
[9] A semiconductor device manufactured by the method according to [8].

  By using the photosensitive resin composition of the present invention that can be cured at low temperature and has excellent mechanical properties of a cured film such as elongation, a highly reliable semiconductor element and a highly reliable semiconductor using the semiconductor element The device can be manufactured.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention (hereinafter also simply referred to as “the present composition”) includes the following components (A) to (C) in a solvent: a phenol resin having a biphenyldiyl structure in the main chain (A ): 100 parts by mass; photoacid generator (B): 1 to 30 parts by mass; compound (C) capable of reacting with component (A) by acid generated from photoacid generator (B) or heat (C): 1 ~ 60 parts by mass;

Hereinafter, although each component of the photosensitive resin composition of this invention is demonstrated in detail, this description is an illustration and this invention is not limited to this.
[Phenol resin (A) having a biphenyldiyl structure in the main chain]
The phenol resin (A) having a biphenyldiyl structure in the main chain used in the present composition (hereinafter also simply referred to as “biphenyldiyl-phenolic resin”) is a polymer containing a repeating unit having a phenol structure and a biphenyldiyl structure. is there. The phenol structure and the biphenyldiyl structure may be bonded in any order. The phenol structure and the biphenyldiyl structure are preferably bonded via a methylene group from the viewpoint of further elongation.

  The biphenyldiyl-phenol resin may have an alkylene structure having 20 or less carbon atoms, for example, a structure such as methylene and ethylene, in addition to the phenol structure and the biphenyldiyl structure.

The biphenyldiyl-phenolic resin can be produced by any known method. Examples of the production method include a condensation reaction between a compound having a biphenyldiyl structure (hereinafter also simply referred to as “biphenyldiyl compound”) and a phenol compound.
Examples of the biphenyldiyl compound that can be condensed with a phenol compound include 4,4′-bischloromethylbiphenyl, 4,4′-bischloromethyl-biphenyl-2-carboxylic acid, and 4,4′-bischloromethyl. -Biphenyl-2,2'-dicarboxylic acid, 4,4'-bischloromethyl-2-methylbiphenyl, 4,4'-bischloromethyl-2,2'-dimethylbiphenyl, 4,4'-biphenyldimethanol 4,4′-bis (methoxymethyl) biphenyl and the like. In addition to these, those having various substituents or reactive groups may be employed. In the above, a 4,4′-structure is given as a specific example of a biphenyldiyl compound, but for example, a compound having other substitution structure such as 2,2′-, 2,3′-, 3,4′-, etc. There may be. Among these, 4,4′-substituted biphenyldiyl compounds are preferable from the viewpoint of further elongation. These biphenyldiyl compounds may be used alone or in combination of two or more.

  On the other hand, the phenol compound to be condensed with the biphenyldiyl compound refers to an aromatic compound having at least one phenolic hydroxyl group in one molecule, and specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, Various o-, m-, and p-isomers of alkylphenols such as isobutylphenol, t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol and the like, vinylphenol, allylphenol, propenylphenol, Cycloalkylphenols such as various o-, m-, and p-isomers of ethynylphenol, cyclopentylphenol, cyclohexylphenol, cyclohexylresole, etc., phenylphenol Substituted phenols, such as Le, and the like. Specific examples having two or more phenolic hydroxyl groups in one molecule include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, and the like. These phenols may be used alone or in combination of two or more.

The condensation reaction of these biphenyldiyl compounds and phenolic compounds can be carried out, for example, by the method described in JP-A-2001-329051.
The condensation reaction between these biphenyldiyl compounds and phenolic compounds will be briefly described below.
The biphenyldiyl compound and the phenol compound can be polymerized while dehydrating or dealcoholizing them, but a catalyst may be used during the polymerization. Acidic catalysts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1′-diphosphone Examples thereof include acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, and the like. On the other hand, alkaline catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, piperazine, 1 , 4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, ammonia, hexa And methylenetetramine.
When carrying out the synthesis reaction of the biphenyldiyl-phenol resin, an organic solvent can be used as necessary. Specific examples of organic solvents that can be used include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, Examples include toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, but are not limited thereto. The amount of the organic solvent used is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass with respect to 100 parts by mass of the total mass of the raw materials charged. Moreover, reaction temperature is 40-250 degreeC normally, and the range of 100-200 degreeC is more preferable. The reaction time is usually 1 to 10 hours.

｛式中、Ｒは、ハロゲン原子、カルボキシル基、水酸基、炭素数１〜１０の不飽和結合を有していてもよい脂肪族基、炭素数３〜１０の脂環式基、及び炭素数６〜２０の芳香族基から成る群から選ばれる基であり、各々の基の水素原子は、さらにハロゲン原子、カルボキシル基、水酸基で置換されていてもよい。ｐ及びｑはそれぞれ独立に０〜４の整数であり、ｒは０〜３の整数である。ｐ、ｑ、又はｒが２以上の場合、各々のＲはそれぞれ同じであっても、異なってもよい。｝で表される繰り返しユニットを含むフェノール樹脂である。 The biphenyldiyl-phenol resin used in the present composition is preferably the following formula (1):

{In the formula, R is a halogen atom, a carboxyl group, a hydroxyl group, an aliphatic group optionally having an unsaturated bond having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and 6 carbon atoms. -20 groups selected from the group consisting of aromatic groups, and the hydrogen atom of each group may be further substituted with a halogen atom, a carboxyl group, or a hydroxyl group. p and q are each independently an integer of 0 to 4, and r is an integer of 0 to 3. When p, q, or r is 2 or more, each R may be the same or different. } It is a phenol resin containing the repeating unit represented by this.

The number of repeating units of the repeating unit of the above formula (1) is 2 to 100, more preferably 8 to 80, and still more preferably 18 to 80 from the viewpoint of elongation.
In the above formula (1), it is more preferable from the viewpoint of elongation that R ₈ is independently hydrogen, fluorine, methyl group or trifluoromethyl group. In the above formula (1), the biphenyldiyl structure is preferably connected at the 4,4′-position from the viewpoint of elongation.

で表される繰り返しユニットを含むフェノール樹脂である。上記式（２）の繰り返しユニットの繰り返し単位数は、２〜１００、伸度の観点から、より好ましくは８〜８０、更に好ましくは１８〜８０である。 The biphenyldiyl-phenol resin used in the present composition is more preferably the following formula (2):

It is a phenol resin containing the repeating unit represented by these. The number of repeating units of the repeating unit of the above formula (2) is 2 to 100, more preferably 8 to 80, and still more preferably 18 to 80 from the viewpoint of elongation.

As a specific example of what is represented by the said Formula (2), MEH-7851 series phenol resin by Meiwa Kasei Co., Ltd. which is a commercial item is mentioned, for example.
In the present invention, the biphenyldiyl-phenol resin has a weight average molecular weight of 700 to 35,000, preferably 2,500 to 25,000, and more preferably 5,000 to 25,000. The weight average molecular weight is preferably 700 or more from the viewpoint of elongation, and is preferably 35,000 or less from the viewpoint of alkali solubility of the composition.

Moreover, as long as the effect of this invention is not affected, it can also be used for the photosensitive resin composition by mixing with other alkaline aqueous solution soluble resin other than the said phenol resin (A). Specific examples of other aqueous alkali-soluble resins include phenol resins that do not contain a biphenyldiyl structure, polymer resins of phenol and unsaturated bond-containing compounds, polyhydroxystyrene resins, polyamides, polyimides, and derivatives of these resins. , Precursors or copolymers.
The phenol resin not containing the biphenyldiyl structure can be obtained by polymerizing phenol or a derivative thereof and an aldehyde compound, a ketone compound, a methylol compound, or an alkoxymethyl compound.

  Examples of phenol or derivatives thereof include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, catechol, resorcinol, ethylresorcinol, hexylresorcinol, hydroquinone, pyrogallol, Phloroglucinol, 1,2,4-trihydroxybenzene, pararozolic acid, biphenol, bisphenol A, bisphenol AF, bisphenol B, bisphenol F, bisphenol S, dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,4-bis (3-hydroxyphenoxybenzene), 2,2-bis (4-hydro Cis-3-methylphenyl) propane, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2,2- Examples thereof include bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (2-hydroxy-5-biphenylyl) propane, and dihydroxybenzoic acid.

  Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2 -Carboxaldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde and the like.

  Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butyn-2-one, 2-norbornanone, adamantanone, Examples include 2,2-bis (4-oxocyclohexyl) propane.

  Examples of methylol compounds include 1,3-bis (hydroxymethyl) urea, ribitol, arabitol, allitol, 2,2-bis (hydroxymethyl) butyric acid, 2-benzyloxy-1,3-propanediol, cyclohexanedimethanol, 2 , 2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornene-2,2- Dimethanol, 5-norbornene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis (hydroxymethyl) durene, 2,6 -Bis (hydroxymethyl) -p-cresol, 2,3-bis (hydro Cymethyl) naphthalene, 2,2′-bis (hydroxymethyl) diphenyl ether, 1,8-bis (hydroxymethyl) anthracene, 2,6-bis (hydroxymethyl) -1,4-dimethoxybenzene, 1,4-benzenedi Examples include methanol, 2-nitro-p-xylylene glycol, and 1,3-benzenedimethanol.

  Examples of the alkoxymethyl compound include 1,4-bis (methoxymethyl) benzene, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 2,4,6-tris [bis (methoxymethyl) amino] -1 , 3,5-triazine and the like.

The polymerization resin of the phenol and the unsaturated bond-containing compound can be obtained by polymerizing phenol or a derivative thereof and the unsaturated bond-containing compound.
As the phenol or derivative thereof, the same compounds as described above can be used, and as the unsaturated bond-containing compound, butadiene, pentadiene, 1,3-butanediol-dimethacrylate, cyclohexadiene, cyclopentadiene, allyl ether. Allyl sulfide, diallyl adipate, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, 2,5-norbornadiene, tetrahydroindene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, Examples include triallyl cyanurate.

  The polyamide, polyimide and precursor thereof, or a copolymer of these resins can be synthesized by a known method. For example, polyamide is synthesized by a condensation reaction of a dicarboxylic acid or an acid chloride derivative thereof and a diamine. Can do. The polyimide and its precursor can be synthesized from a condensation reaction of tetracarboxylic dianhydride and diamine. From the viewpoint of ensuring the solubility in an aqueous alkali solution, it is preferable that the structural formula of diamine used when synthesizing the polyamide, polyimide and its precursor has at least one phenolic hydroxyl group. Specific examples of these diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4, 4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4- Hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4- Amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4′-diamy -3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4 ' -Dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like can be mentioned. These diamine compounds may be used alone or in combination.

In addition, when biphenyldiyl-phenol resin is used by mixing with other alkaline aqueous solution-soluble resin, the content of biphenyldiyl-phenol resin in the composition of the mixed resin is 50% by mass or more from the viewpoint of elongation. It is preferable that it is 60 mass% or more.
The elongation when the photosensitive resin composition is a cured product is preferably 8% or more, more preferably 10% or more from the viewpoint of reliability of a semiconductor element or a semiconductor component using the semiconductor element.

[Photoacid generator (B)]
The photosensitive resin composition of the present invention is not particularly limited as long as it is a composition that can form a resin pattern in response to radiation including ultraviolet rays, electron beams, and X-rays. Any of the photosensitive compositions may be used.

  When the photosensitive resin composition of the present invention is used as a negative photosensitive composition, the photoacid generator (B) generates an acid upon irradiation with radiation, and the generated acid is the phenol resin (A). ) And other components of the composition to be described later. Examples of such compounds include the following compounds:

(I) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) ) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4 , 6-Trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloro Methyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) ) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4 6-trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) ) -S-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis ( 4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio- - styryl) - bis (4,6-trichloromethyl) -s-triazine and the like;

(Ii) Diaryliodonium compounds diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxy Phenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4 − Methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, etc .;

(Iii) Triarylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluene Sulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium Trifluoroacetate 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyl Diphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, and the like.

  Among these compounds, trichloromethyl-S-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-chlorophenyl) -bis (4, 6-trichloromethyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxy-β-styryl) -bis (4,6 -Trichloromethyl) -S-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine, and the like as diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethane. Sulfonate, 4-methoxyphenylphenyliodonium trifluoromethane For example, sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyl. Diphenylsulfonium trifluoroacetate, 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate and the like can be mentioned as suitable ones.

In addition, the following compounds can also be used as the photoacid generator (B).
(1) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound, and the like, and specific examples include 1,2-naphthoquinone diazide of phenols. A 4-sulfonic acid ester compound can be mentioned.

(2) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphena. Examples include silsulfone and bis (phenacylsulfonyl) methane.

(3) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl-p-toluene sulfonate, and the like.

(4) Sulfonimide compound Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( (Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

(5) Oxime ester compound As an oxime ester compound, specifically, 2- [2- (4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methyl Phenyl) acetonitrile (trade name “Irgacure PAG121” manufactured by Ciba Specialty Chemicals), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty) Chemicals trade name “Irgacure PAG103”), [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name) "Irgacure PAG 108 ”), α- (n-octanesulfonyloxyimino) -4-methoxybenzyl cyanide (trade name“ CGI725 ”manufactured by Ciba Specialty Chemicals) and the like.

(6) Diazomethane compound Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.
From the viewpoint of sensitivity, the above (5) oxime ester compound is particularly preferable.

  In the photosensitive resin composition of the present invention, the amount of the compound that generates an acid by light irradiation as the component (B) is 100 parts by mass of the biphenyldiyl-phenol resin that is the component (A) of the composition. And 1 to 30 parts by mass. If this addition amount is 1 part by mass or more, the amount of acid generated by radiation irradiation will be sufficient and the sensitivity will be improved. If this addition amount is 30 parts by mass or less, the mechanical properties after curing will be good. .

  The photosensitive resin composition of the present invention can also be used as a positive photosensitive composition. In this case, the photoacid generator (B) preferably contains a naphthoquinonediazide derivative. Examples of the naphthoquinonediazide derivative include compounds having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure. Examples of these compounds include US Pat. No. 2,772,972, US Pat. No. 2,797,213, US Pat. No. 3,669,658 and the like. The naphthoquinonediazide derivative is obtained from 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound. And at least one compound selected from the group consisting of the following (hereinafter also referred to as “NQD compound”).

  The NQD compound is obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound. For example, a polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or a predetermined amount of 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone or tetrahydrofuran, a base such as triethylamine It can be obtained by reacting in the presence of a sex catalyst to carry out esterification, and washing the resulting product with water and drying.

｛式中、Ｑは、水素原子又は下記：

で表されるナフトキノンジアジドスルホン酸エステル基であり、全てのＱが同時に水素原子であることはない。｝。 Examples of preferable NQD compounds from the viewpoint of physical properties of the cured film such as sensitivity and elongation include the following.

{Wherein Q is a hydrogen atom or the following:

And all Qs are not simultaneously hydrogen atoms. }.

  Further, as the NQD compound, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be used, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide. It can also be used by mixing with a sulfonyl ester compound.

The amount of the naphthoquinonediazide derivative used as the component (B) in the photosensitive resin composition of the present invention is 1 to 30 parts by mass with respect to 100 parts by mass of the biphenyldiyl-phenol resin (A) of the present composition. The amount is preferably 1 to 20 parts by mass. When this addition amount is 1 part by mass or more, the amount of acid generated by radiation irradiation is sufficient, the sensitivity is improved, and the patterning property is good. On the other hand, if this addition amount is 30 parts by mass or less, curing is achieved. The mechanical properties of the subsequent film are good and there is little development residue (scum) in the exposed area.
The naphthoquinonediazide derivatives may be used alone or in combination of two or more.

[(C) a compound capable of reacting with the component (A) by an acid generated from the photoacid generator (B) or by heat]
An acid generated from the photoacid generator (B) or a compound capable of reacting with the biphenyldiyl-phenolic resin as the component (A) by the action of heat (hereinafter also simply referred to as “crosslinking agent”) is used as the component (A). When added to the component (B), film properties such as mechanical properties, heat resistance, and chemical resistance can be enhanced when the coating film is heated and cured. In order to sufficiently enhance the membrane performance, the crosslinking agent is preferably an epoxy group, an oxetane group, a —N— (CH ₂ —OR ′) group {wherein R ′ is hydrogen or a carbon number of 1 to 4 It is an alkyl group. } And —C— (CH ₂ —OR ′) group {wherein R ′ is hydrogen or an alkyl group having 1 to 4 carbon atoms. } Is a compound having at least two groups selected from the group consisting of:

In the molecular structural formula of the crosslinking agent, an N— (CH ₂ —OR ′) group {wherein R ′ is hydrogen or an alkyl group having 1 to 4 carbon atoms. }, For example, a melamine resin or urea resin in which the N-position is substituted with a methylol group or an alkoxymethyl group is exemplified. Specifically, melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, alkoxymethylated urea Resins can be mentioned. Among these, alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins are known methylolated melamine resins, methylolated benzoguanamine resins, and methylol groups of methylolated urea resins. Obtained by conversion to an alkoxymethyl group.

  Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, and the like, but commercially available Cymel 300, 301, 303, 370, 325. 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280, -290, Nicarak MS-11, Nicarak MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used. These compounds can be used alone or in combination.

In the molecular structural formula of the crosslinking agent, a C— (CH ₂ —OR ′) group {wherein R ′ is hydrogen or an alkyl group. }, For example, 1,4-bis (methoxymethyl) benzene, 4,4′-biphenyldimethanol, 4,4′-bis (methoxymethyl) biphenyl, commercially available 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML- PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML Bis25X-PCHP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymer-p-cresol, TriML-P, TriML-35XL, TriML- TrisCR-HAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPHAP (made by Honshu Chemical Industry Co., Ltd.), etc. are mentioned. These compounds can be used alone or in combination.

  Examples of the cross-linking agent having two or more epoxy groups or oxetane groups in the molecular structural formula include 1,1,2,2-tetra (p-hydroxyphenyl) ethane tetraglycidyl ether, glycerol triglycidyl ether, and the like. , Ortho secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, triglycidyl isocyanurate, Denacol EX-201, EX-313, EX- 314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-731, EX-810, EX-911, EM-150 (trade name, Nagase Manufactured by Chemtex) Epoxy compounds, xylylene bisoxetane, 3-ethyl-3 {[(3-ethyloxetane - yl) methoxy] methyl} oxetane compound oxetane, and the like. These compounds can be used alone or in combination.

  The addition amount of these crosslinking agents is 1-60 mass parts with respect to 100 mass parts of biphenyldiyl-phenol resin (A), Preferably, it is 3-50 mass parts. When this addition amount is 1 part by mass or more, crosslinking proceeds sufficiently, and an effect of enhancing film properties can be obtained. If this addition amount is 60 parts by mass or less, the elongation is maintained.

  As the crosslinking agent used in the present composition, in addition to those described above, for example, 2,2′-bis (2-oxazoline), 2,2′-isopropylidenebis (4-phenyl-2-oxazoline), 1,3 -Bis (4,5-dihydro-2-oxazolyl) benzene, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, Epocross K-2010E, K-2020E, K-2030E, WS-500, Oxazoline compounds such as WS-700, RPS-1005 (trade name, manufactured by Nippon Shokubai Co., Ltd.), carbodilite SV-02, V-01, V-02, V-03, V-04, V-05, V-07, Carbodiimide compounds such as V-09, E-01, E-02, LA-1 (trade name, manufactured by Nisshinbo Chemical Co., Ltd.), formaldehyde, glutaraldehyde, hexamethylene tet Aldehyde and aldehyde-modified products such as min, trioxane, glyoxal, malondialdehyde, succindialdehyde, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4 ′ -Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate 500, 600, Cosmonate NBDI, ND (trade name, manufactured by Mitsui Chemicals) Duranate 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T ( Isocyanate-based crosslinking agents such as trade name, manufactured by Asahi Kasei Chemical Co., Ltd., acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chloride (III) salt, acetylacetone magnesium (II) salt, acetylacetone nickel (II) salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, trifluoroacetylacetone magnesium (II) salts, metal chelating agents such as trifluoroacetylacetone nickel (II) salt, vinyl acetate, trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitic acid, pyromellitic acid tetraallyl ester , Pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraa Unsaturated bond-containing compounds such as chlorate, BANI-M, and BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) can be used.

｛式中、ｎは、１〜２０の整数である。｝

｛式中、ｍ、及びｎは、それぞれ独立に、１〜２０の整数である。｝。 (D) Thermal base generator The photosensitive resin composition of this invention can further contain (D) a thermal base generator from a viewpoint of the physical property improvement of a cured film. In particular, when the crosslinking agent as component (C) contains an epoxy group or oxetane group, the crosslinking reaction between the crosslinking agent as component (C) and the resin as component (A) is accelerated during thermosetting. In addition, since the film physical properties of the present composition can be further enhanced, it is preferable to further contain (D) a thermal base generator. The thermal base generator used in the present composition has a thermal decomposition temperature of 50 ° C. or higher, preferably 70 ° C. or higher, more preferably 90 ° C. or higher. (D) Specific examples of the thermal base generator include compounds represented by the following formulae.

{Wherein n is an integer of 1-20. }

{In formula, m and n are the integers of 1-20 each independently. }.

で表される。 Particularly preferably, the (D) thermal base generator used in the present composition has the following formula:

It is represented by

  When added to the present composition, the amount of (D) thermal base generator added is preferably 0.1 to 40 parts by weight, more preferably 100 parts by weight of biphenyldiyl-phenol resin (A). 0.5 to 30 parts by mass. From the viewpoint of sufficiently promoting the cross-linking and obtaining the effect of enhancing the film properties, 0.1 part by mass or more is preferable, and from the viewpoint of elongation, 40 parts by mass or less is preferable.

(E) Solvent Examples of the solvent used in the present composition include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and the like. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, Ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydroflur Ril alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene Etc. can be used.
The addition amount of the solvent in this composition is 100-1000 mass parts with respect to 100 mass parts of biphenyldiyl-phenol resin (A), Preferably it is 120-700 mass parts, More preferably, it is 150-500 mass. Part range.

(F) Other components In the photosensitive resin composition of the present invention, if necessary, a dye, a surfactant, an adhesion aid for improving adhesion to the substrate, a dissolution accelerator, a crosslinking accelerator, and the like. It can be included.
Examples of the dye include methyl violet, crystal violet, and malachite green. As a compounding quantity of dye, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of biphenyldiyl-phenol resin (A).

As the surfactant, for example, non-ionic surfactants composed of polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether or derivatives thereof, for example, Fluorard (registered trademark, trade name, manufactured by Sumitomo 3M) Fluorosurfactants such as Megafac (registered trademark, trade name, manufactured by Dainippon Ink & Chemicals), Lumiflon (registered trademark, trade name, manufactured by Asahi Glass Co., Ltd.), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) ), DBE (trade name, manufactured by Chisso Corporation), granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and other organosiloxane surfactants.
As a compounding quantity in the case of using surfactant, 0.01-10 mass parts is preferable with respect to 100 mass parts of biphenyldiyl-phenol resin (A).

  Examples of the adhesion aid include various alkoxysilanes such as alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, and epoxy polymer.

Preferred examples of alkoxysilane include tetraalkoxysilane, bis (trialkoxysilyl) methane, bis (trialkoxysilyl) ethane, bis (trialkoxysilyl) ethylene, bis (trialkoxysilyl) hexane, and bis (trialkoxysilyl). Octane, bis (trialkoxysilyl) octadiene, bis [3- (trialkoxysilyl) propyl] disulfide, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) ) Pyridine, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, vinyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, 3- Socyanate propyltrialkoxysilane, 3- (trialkoxysilyl) propyl succinic anhydride, N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole, 2- (3,4-epoxycyclohexyl) ethyltri Alkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxyalkylsilane and 3-aminopropyl dialkoxyalkylsilane and acid anhydrides or acid dianhydrides. Examples include reactants, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane in which the amino group is converted to a urethane group or a urea group. In addition, examples of the alkyl group in the above compound include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the acid anhydride include maleic acid anhydride, phthalic acid anhydride, 5-norbornene-2,3- Examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 4,4′-oxydiphthalic dianhydride. Examples of the urethane group include a t-butoxycarbonylamino group, and examples of the urea group include a phenylaminocarbonylamino group.
As a compounding quantity in the case of using an adhesion aid, 0.1-30 mass parts is preferable with respect to 100 mass parts of biphenyldiyl-phenol resin (A).

  As the dissolution accelerator, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of the compound having a hydroxyl group include a ballast agent, paracumylphenol, bisphenols, resorcinols, and linear phenolic compounds such as MtrisPC and MtetraPC, which are used in the above-mentioned naphthoquinonediazide compounds, TrisP-HAP, TrisP- Non-linear phenolic compounds such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2-5 phenol substitutes of diphenylmethane, 1-5 phenol substitutes of 3,3-diphenylpropane, 2 , 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane and 5-norbornene-2,3-dicarboxylic anhydride, a one-to-two reaction product, bis- (3-amino-4-hydroxyphenyl) ) 1 of sulfone and 1,2-cyclohexyldicarboxylic anhydride 2 reactants, N- hydroxysuccinimide, N- hydroxy phthalimide, and the like N- hydroxy 5-norbornene-2,3-dicarboxylic acid imide.

Examples of the compound having a carboxyl group include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2. -(1-Naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxy Examples include mandelic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid and the like.
As a compounding quantity in the case of using a solubility promoter, it is preferable that it is 0.1-50 mass parts with respect to 100 mass parts of biphenyldiyl-phenol resin (A).

  As the crosslinking accelerator, those that generate radicals by heat or light are preferable. Examples of radicals generated by heat or light include alkylphenones such as Irgacure 651, 184, 2959, 127, 907, 369, 379 (trade name, manufactured by BASF Japan), Irgacure 819 (trade name, manufactured by BASF Japan). ), Etc., titanocene such as Irgacure 784 (trade name, manufactured by BASF Japan), and oxime ester such as Irgacure OXE01, 02 (trade name, manufactured by BASF Japan).

<Method for forming cured relief pattern>
Hereinafter, an example of a method for forming a cured relief pattern on a substrate when a photosensitive agent is added to the composition will be described.
First, the composition is applied to a suitable support such as a silicon wafer, ceramic, aluminum substrate, copper substrate and the like. At this time, in order to ensure the water-resistant adhesion between the pattern to be formed and the support, an adhesion assistant such as a silane coupling agent may be applied to the support in advance. The composition can be applied by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Next, after pre-baking at 80 to 140 ° C. to dry the coating film, irradiation with actinic radiation is performed using an exposure apparatus such as a contact aligner, mirror projection, or stepper. 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. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably g-line, h-line or i-line of a mercury lamp, which may be used alone or in combination. As the exposure apparatus, a contact aligner, a mirror projection, and a stepper are particularly preferable.

  Next, development is performed, and the development method can be selected from methods such as an immersion method, a paddle method, and a rotary spray method. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution such as quaternary ammonium salts such as quaternary ammonium salts, and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added as required can be used. In particular, an aqueous tetramethylammonium hydroxide solution is preferable, and the concentration thereof is 0.5 to 10% by weight, preferably 1.0 to 5% by weight.

After development, the pattern film can be obtained by washing with a rinse solution and removing the developer. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol or the like can be used alone or in combination.
Finally, a cured relief pattern can be obtained by heating the relief pattern thus obtained. The heating temperature is preferably 150 ° C. or higher.

In a general method for forming a cured relief pattern using a polyimide or polybenzoxazole precursor composition, it is necessary to convert it to polyimide or polybenzoxazole by heating to 300 ° C. or more to advance a dehydration cyclization reaction. However, since this method is not necessary, it can be suitably used for heat-sensitive semiconductor devices. For example, it is suitably used for a semiconductor device having an insulating layer made of an oxide of a high-melting-point metal such as titanium, tantalum, or hafnium, which is a high-dielectric material or a ferroelectric material having a process temperature restriction .
Of course, if the semiconductor device does not have such heat resistance restrictions, heat treatment may be performed at 300 to 400 ° C. also in this method. As such a heat treatment apparatus, a hot plate, an oven, and a temperature rising oven capable of setting a temperature program can be used. Air may be used as the atmospheric gas when performing the heat treatment, and an inert gas such as nitrogen or argon may be used. Further, when it is necessary to perform heat treatment at a lower temperature, heating may be performed under reduced pressure using a vacuum pump or the like.

<Semiconductor device>
The above-described cured relief pattern is used as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a device having a bump structure, and a process in a known method for manufacturing a semiconductor device In combination, the semiconductor device of the present invention can be manufactured.

で表される熱塩基発生剤（Ｄ−１）を、下記方法に従い合成した。
５００ｍＬのセパラブルフラスコに二炭酸ジ−ｔ−ブチル４３．７ｇ（０．２ｍｏｌ）、４−Ｎ，Ｎ−ジメチルアミノピリジン０．２５ｇ（０．００２ｍｏｌ）を入れ、３５℃まで加熱、撹拌しながら１，３−ジ−４−ピペリジルプロパン２１．０４ｇ（０．１ｍｏｌ）を、反応液の温度が４０℃を超えないように、３０分間かけて添加した。添加終了後、５５℃に昇温して８時間撹拌した。反応終了後、不溶物をろ別し、ろ液に水２００ｇを加えた後、有機層を酢酸エチルで抽出し、炭酸水素ナトリウム水溶液で洗浄し、硫酸マグネシウムで乾燥してから溶媒を減圧留去して、熱塩基発生剤（Ｄ−１）３２．５ｇを得た。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
<Synthesis example>
Following formula:

Was synthesized according to the following method.
A 500 mL separable flask is charged with 43.7 g (0.2 mol) of di-t-butyl dicarbonate and 0.25 g (0.002 mol) of 4-N, N-dimethylaminopyridine, and heated to 35 ° C. with stirring. 21.04 g (0.1 mol) of 1,3-di-4-piperidylpropane was added over 30 minutes so that the temperature of the reaction solution did not exceed 40 ° C. After completion of the addition, the temperature was raised to 55 ° C. and stirred for 8 hours. After completion of the reaction, insoluble matters were filtered off, 200 g of water was added to the filtrate, the organic layer was extracted with ethyl acetate, washed with aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. As a result, 32.5 g of a thermal base generator (D-1) was obtained.

Ａ−３：旭有機材工業株式会社ＥＰ４０２０Ｇ （重量平均分子量＝１１７１９）

上記（Ａ）成分の重量平均分子量は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）により、標準ポリスチレン（昭和電工社製 有機溶媒系標準試料 ＳＴＡＮＤＡＲＤ ＳＭ−１０５）換算で算出した。
使用したＧＰＣ装置及び測定条件は以下の通りであった。
ポンプ：ＪＡＳＣＯ ＰＵ−９８０
検出器：ＪＡＳＣＯ ＲＩ−９３０
カラムオーブン：ＪＡＳＣＯ ＣＯ−９６５ ４０℃
カラム：Ｓｈｏｄｅｘ ＫＤ−８０６Ｍ 直列に２本
移動相：０．１ｍｏｌ／ｌ ＥｔＢｒ／ＮＭＰ
流速：１ｍｌ／ｍｉｎ． <Preparation of photosensitive resin composition>
[Examples 1-7, Comparative Examples 1-4]
Each component used in the examples and comparative examples of the present invention was as follows.
(A) Component A-1: MEH-7851 4H manufactured by Meiwa Kasei Co., Ltd. (weight average molecular weight = 9986)
A-2: MEH-7851 H manufactured by Meiwa Kasei Co., Ltd. (weight average molecular weight = 2769)

A-3: Asahi Organic Materials Co., Ltd. EP4020G (weight average molecular weight = 11719)

The weight average molecular weight of the component (A) was calculated by gel permeation chromatography (GPC) in terms of standard polystyrene (an organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko KK).
The GPC apparatus used and the measurement conditions were as follows.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l EtBr / NMP
Flow rate: 1 ml / min.

  A-1 to A-2 are commercially available MEH-7851 series phenol resins having a biphenyldiyl structure in the resin skeleton, and A-3 is a biphenyldiyl structure in the resin skeleton. It is a cresol type phenol resin manufactured by Asahi Organic Materials Co., Ltd., which does not contain.

｛式中、Ｑの内８３％が以下の：

で表される構造であり、残余が水素原子である。｝。
Ｂ−２：下記式で示す光酸発生剤

(B) Component B-1: Photoacid generator represented by the following formula

{In the formula, 83% of Q is the following:

The remainder is a hydrogen atom. }.
B-2: Photoacid generator represented by the following formula

(C) Component C-1: Nikalac MX-390 manufactured by Sanwa Chemical Co., Ltd.
C-2: Nikaluck MX-270 manufactured by Sanwa Chemical Co., Ltd.
C-3: Denasel EX-321L manufactured by Nagase ChemteX Corporation
C-4: ETERNACOLL OXBP manufactured by Ube Industries, Ltd.

(D) component:
D-1:

(E) Solvent γ-Butyrolactone (GBL)

The compositions of Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 1 below.
The numbers in the table indicate the parts by mass added for each composition. Each composition was mixed and dissolved, and then filtered through a 0.2 μm Teflon (registered trademark) filter to obtain a photosensitive varnish.

<Elongation evaluation>
A sample for measuring elongation according to the present invention was produced by the following method.
The photosensitive resin compositions obtained in Examples and Comparative Examples of the present invention were spin-coated on a 6-inch silicon wafer substrate provided with an aluminum vapor deposition layer on the outermost surface so that the film thickness after curing was about 10 μm. The resin cured film was obtained by heating at 250 ° C. for 2 hours in a nitrogen atmosphere. The obtained cured resin film was cut into a width of 3 mm with a dicing saw, and then peeled off from the wafer with a dilute hydrochloric acid aqueous solution. The elongation was measured with a tensile tester (for example, Tensilon). The measurement conditions of the tensile tester were as follows.
Temperature: 23 ° C
Humidity: 50%
Initial sample length: 50 mm
Test speed: 40 mm / min
Load cell rating: 2kgf

  In Examples 1 to 7 where biphenyldiyl-phenol resin was used as the component (A), the average elongation of the cured film (sample 20-point average value) showed a high value of 8% or more. On the other hand, in Comparative Examples 1 to 4 having no biphenyldiyl structure in the skeleton of the component (A), the average elongation of the cured film was low.

  The photosensitive resin composition for a semiconductor element surface protective film or interlayer insulating film according to the present invention has a surface protective film for a semiconductor device and a light emitting device, a protective film for a flip chip device, and a bump structure for the semiconductor element surface protective film. It can be suitably used for a protective film of a device having an insulating film, an insulating film for rewiring, an interlayer insulating film of a multilayer circuit, and the like for an interlayer insulating film.

Claims (9)

The following ingredients in the solvent:
Phenol resin (A) having a biphenyldiyl structure in the main chain: 100 parts by mass;
Photoacid generator (B): 1 to 30 parts by mass; and Compound (C) capable of reacting with component (A) by heat generated from the photoacid generator (B) or heat (C): 1 to 60 parts by mass Part;
The photosensitive resin composition for semiconductor element surface protection films or interlayer insulation films containing this. The phenol resin (A) is represented by the following general formula (1):

{In the formula, R is a halogen atom, a carboxyl group, a hydroxyl group, an aliphatic group optionally having an unsaturated bond having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and 6 carbon atoms. -20 groups selected from the group consisting of aromatic groups, the hydrogen atom of each group may be further substituted with a halogen atom, a carboxyl group and / or a hydroxyl group, and p and q are each independently 0 Is an integer of -4, r is an integer of 0-3, and when p, q, or r is 2 or more, each R may be the same or different. } The photosensitive resin composition of Claim 1 containing the repeating unit represented by these.   The photosensitive resin composition of Claim 1 or 2 whose repeating unit number of the repeating unit of the said phenol resin (A) is 8 or more and 100 or less.   The photoacid generator (B) is an ester compound of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Item 4. The photosensitive resin composition according to any one of Items 1 to 3. The photoacid generator (B) has the following formula:

{Wherein Q is a hydrogen atom or the following:

And all Qs are not simultaneously hydrogen atoms. } The photosensitive resin composition of any one of Claims 1-4 which is a compound shown by these. The compound (C), an epoxy group, an oxetane group, -N- _(CH 2 -OR ') group {wherein, R' is hydrogen or an alkyl group having 1 to 4 carbon atoms. } And —C— (CH ₂ —OR ′) group {wherein R ′ is hydrogen or an alkyl group having 1 to 4 carbon atoms. } The photosensitive resin composition of any one of Claims 1-5 which has at least 2 group chosen from the group which consists of.   The photosensitive resin composition of any one of Claims 1-6 which further contains a thermal base generator (D). The following steps:
Forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 7 on a semiconductor substrate;
Exposing the photosensitive resin layer with actinic rays;
The manufacturing method of a semiconductor device including the process of developing this exposed photosensitive resin layer, obtaining a relief pattern, and the process of heating the obtained relief pattern.   A semiconductor device manufactured by the method according to claim 8.