JP2021167939A - Photosensitive resin composition, dry film, cured product, and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition with large dissolution contrast and excellent resolution.SOLUTION: The photosensitive resin composition comprises (A) a polyimide precursor with at least one of structures represented by general formulas (1) and (2), (B) a photoacid generator, and (C) a compound having two or more vinyl ether groups.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition containing a polyimide precursor having a specific structure, a dry film having a resin layer formed of the photosensitive resin composition, a cured product formed of the photosensitive resin composition, and the like. The present invention relates to electronic parts such as printed wiring boards and semiconductor elements having the cured product as a forming material.

Photosensitive resin compositions containing a polyimide precursor are widely used in various fields because they exhibit excellent properties such as insulation, heat resistance, and mechanical strength. For example, application to flexible printed wiring boards, buffer coated films for semiconductor elements, and insulating films for rewiring layers of wafer level packages (WLP) is being promoted.

Specifically, an alkali-developable photosensitive resin composition is applied onto a substrate, dried to form a coating film, exposed through a pattern mask, and then applied to an alkaline developer in exposed and unexposed areas. By performing alkaline development utilizing the difference in solubility of, a film having a desired pattern is formed, and by heating this pattern film, the polyimide precursor contained in the photosensitive resin composition is subjected to a ring-closing reaction. An imidized cured film can be obtained.

In recent semiconductor devices, with the demand for higher functionality and smaller size, it is required to form a cured film having a finer pattern on a buffer coat film or an insulating film for a rewiring layer of a wafer level package. The photosensitive resin composition is required to have excellent resolution. In response to such demands, the resolution is improved by increasing the difference in dissolution rate between the exposed portion and the unexposed portion in the alkaline developer, that is, the so-called dissolution contrast, in the coating film made of the photosensitive resin composition. Attempts have been made to make it. For example, in Patent Document 1, a highly sensitive and high-contrast pattern is produced by a photosensitive polyimide resin composition containing a polyimide precursor formed of a carboxylic acid dianhydride and a diamine having a siloxane structure and a diazonaphthoquinone-based compound. The technique to obtain is proposed.

JP-A-2006-267800

However, the composition of Patent Document 1 cannot sufficiently satisfy the dissolution contrast for realizing the resolution required for a recent semiconductor device, and cannot be said to be sufficient in the resolution.

The present invention has been made in view of the above problems, and a main object thereof is to provide a photosensitive resin composition having a large dissolution contrast and excellent resolution.

Another object of the present invention is to provide an electronic component such as a dry film, a printed wiring board, and a semiconductor element using the photosensitive resin composition.

The present inventors have found that by combining a polyimide precursor having a specific structure and a compound having two or more vinyl ether groups, the dissolution contrast can be increased and excellent resolution can be obtained. The present invention has been completed.

That is, the photosensitive resin composition of the present invention comprises (A) a polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2), (B) a photoacid generator, and (C). ) It is characterized by containing a compound having two or more vinyl ether groups. The coating film obtained by applying and drying the photosensitive resin composition of the present invention has a vinyl group of a compound having two or more carboxyl groups of the polyimide precursor of (A) and vinyl ether groups of (C) in the drying step. Reacts to form an ester bond, which improves the solubility resistance in the alkaline developing solution. Then, by exposing the coating film, acid is generated from the (B) photoacid generator, and the decomposition of the ester bond is promoted. As a result, it is presumed that there is a large difference in the dissolution rate in the alkaline developer between the unexposed part and the exposed part.

According to the present invention, there is provided a photosensitive resin composition having a large dissolution contrast and excellent resolution.

（式中、
Ｘは、４価の有機基であり、
Ａは、単結合、Ｏまたは２価の有機基であり、
Ｂは、フルオロアルコール基であり、
Ｒは、水素原子であるか、置換または無置換の、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルアミノ基またはアリール基であり、
ｎ１は、１以上の整数であり、
ｎ２は、０〜４の整数であり、ｎ３は、０〜４の整数であるが、ｎ２＋ｎ３は１以上であり、
ｎ４は、１〜４の整数である。） The gist of the present invention is as follows.
[1] (A) A polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2), and
(B) Photoacid generator and
(C) A compound having two or more vinyl ether groups and
A photosensitive resin composition comprising.

(During the ceremony,
X is a tetravalent organic group,
A is a single bond, O or divalent organic group,
B is a fluoroalcohol group
R is a hydrogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylamino group or aryl group.
n1 is an integer greater than or equal to 1 and
n2 is an integer from 0 to 4, n3 is an integer from 0 to 4, but n2 + n3 is 1 or more.
n4 is an integer of 1 to 4. )

（式中、
ａは、０〜２の整数であり、
ｂは、０〜２の整数である。） [2] The photosensitive resin composition of [1], wherein X is selected from the groups shown below.

(During the ceremony,
a is an integer from 0 to 2 and
b is an integer of 0 to 2. )

[3] The photosensitive resin composition according to the above [1] or [2], wherein the carbon atom number of the B is 1 to 10 and the fluorine atom number is 1 to 10.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the carboxyl group concentration in the polyimide precursor is 300 to 800 mol / g.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the fluorine concentration in the polyimide precursor is 20 to 200 mol / g.

[6] The photosensitive resin composition according to any one of [1] to [5], further comprising an adhesive.

[7] The photosensitive resin composition according to any one of [1] to [6], further comprising a base compound.

[8] The photosensitive resin composition according to any one of [1] to [7], further comprising a surfactant.

[9] The photosensitive resin composition according to any one of [1] to [8], wherein the photoacid generator contains an N-sulfonyloxyimide type photoacid generator.

[10] The photosensitive resin composition of [9], wherein the photoacid generator further contains a naphthoquinone diazide compound.

[11] The photosensitive resin composition according to any one of [1] to [10], wherein the compound having two or more vinyl ether groups is at least one selected from diethylene glycol divinyl ether and cyclohexanedimethanol divinyl ether.

[12] A dry film comprising a resin layer formed of the photosensitive resin composition according to any one of [1] to [10] on the film.

[13] A cured product, which is formed of the photosensitive resin composition according to any one of [1] to [11] or the resin layer of the dry film of [12].

[14] An electronic component comprising the cured product of [13] as a forming material.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2), (B) a photoacid generator, and (C) vinyl ether. Includes compounds having two or more groups. The photosensitive resin composition of the present invention is useful as a positive photosensitive resin composition.

The photosensitive resin composition of the present invention has a large solubility contrast, and the dissolution rate of the coating film composed of the composition in a 2.38% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) at 25 ° C. in the unexposed portion. The ratio of the dissolution rate of the exposed part to 2.38% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) at 25 ° C. can be set to, for example, 500 or more, which brings about excellent resolution. ..
The dissolution rate of the exposed portion can be 50 to 3000 nm / s, preferably 100 to 2000 nm / s. On the other hand, the dissolution rate of the unexposed portion can be 0 to 20 nm / s, preferably 0 to 5 nm / s.
The dissolution rate in the present specification can be measured by the method described in Examples.

[(A) Polyimide precursor]
The polyimide precursor (A) is a polyamic acid having at least one of the structures represented by the following general formulas (1) and (2), and has only one structure of the general formula (1) or the general formula (2). It may have both structures.

In the general formulas (1) and (2), X is a tetravalent organic group.
Examples of the tetravalent organic group include, but are not limited to, groups having the following structures.
A and b in the structure are independently integers of 0 to 2, and are easily soluble in various solvents (that is, have good solvent solubility) and have good light transmittance of the dry coating film. It is preferably 0 to 1, and particularly preferably 0.

Among the above tetravalent organic groups, the following structure is preferable from the viewpoint of obtaining good solvent solubility.

Specific examples of the above-mentioned preferable tetravalent organic group include, but are not limited to, the following structures.

The following structure is particularly preferable from the viewpoint of improving the dissolution rate of the exposed portion and obtaining a large dissolution contrast.

In the general formulas (1) and (2), A is a single bond, O or divalent organic group.
The divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
Examples of the divalent organic group include an alkylene group, a cycloalkylene group, an arylene group, an alkyl ether group, a ketone group and an ester group.

In the general formulas (1) and (2), B is a fluoroalcohol group and can be a hydroxyalkyl group in which the hydrogen atom of the alkyl moiety is substituted with one or more fluorine atoms. When the general formula (1) or (2) has a plurality of B's, they may be the same or different.
The number of carbon atoms of the fluoroalcohol group is preferably 1 to 10, and more preferably 3 to 6.
The number of fluorine atoms of the fluoroalcohol group is preferably 1 to 10, and more preferably 4 to 8.
Thereby, the solvent solubility and the light transmittance of the cured product can be improved.

A fluoroalcohol group having one or more trifluoromethyl groups is preferable, and a fluoroalkyl group having one or two trifluoromethyl groups is more preferable.
Examples of the fluoroalcohol group include, but are not limited to, the following groups.

In the general formulas (1) and (2), R is a hydrogen atom or is an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylamino group or an aryl group, and these groups are unsubstituted. However, it may have a substituent. R is preferably a hydrogen atom or the like. If there are multiple Rs in the structure, they may be the same or different.

The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 6. The same applies to the preferred number of carbon atoms in the alkyl moiety of the alkoxy group and the alkylamino group.
The number of carbon atoms of the cycloalkyl group is preferably 4 to 12, more preferably 5 to 10. The same applies to the preferable number of carbon atoms of the cycloalkyl moiety of the cycloalkoxy group.
The number of carbon atoms of the aryl group is preferably 6 to 20, and more preferably 6 to 18.
Examples of the substituent include a halogen atom, an amino group, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, a sulfonic acid group and the like.

Examples of R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group and fluoromethyl group. Difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, chloroethyl group, dichloro Ethyl group, trichloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, hydroxymethyl group, hydroxyethyl group, hydroxylpropyl group, etc .; cyclohexyl group; methoxy group, ethoxy group, n-propoxy group, n- Butoxy group, n-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, trifluoromethoxy group, etc .; Hexyloxy group, etc .; Methylamino group, dimethylamino group, trimethylamino group, ethylamino group, propylamino group, etc .; Can be mentioned.

In the general formulas (1) and (2), n1 is an integer of 1 or more, preferably an integer of 1 to 20, respectively. When n1 is an integer of 2 or more, each structure may be the same or different, and is preferably the same.
In the general formula (1), n2 and n3 are independently integers of 0 to 4, but n2 + n3 is 1 or more. n2 + n3 is preferably an integer of 1 to 2, more preferably n2 is 1 and n3 is 1.
In the general formula (2), n4 is an integer of 1 to 4, preferably an integer of 1 to 2.

Examples of the structure satisfying the general formula (1) or (2) include, but are not limited to, the following structures.

The weight average molecular weight (Mw) of the (A) polyimide precursor is preferably 4,000 to 80,000, more preferably 6,000 to 60,000. Thereby, the occurrence of cracks in the cured product can be further reduced.
The number average molecular weight (Mn) of the (A) polyimide precursor is preferably 2,000 to 30,000, more preferably 2,500 to 20,000. As a result, the solubility of the exposed portion in the alkaline developer and the solubility resistance of the unexposed portion in the alkaline developer of the photosensitive resin composition can be obtained in a well-balanced manner.
Mw / Mn is preferably 2.0 to 4.0, more preferably 2.3 to 3.0. As a result, residues and swelling generated during development are reduced.
In the present specification, the weight average molecular weight and the number average molecular weight are numerical values measured by gel permeation chromatography (GPC) and converted with standard polystyrene.

The glass transition temperature (Tg) of the polyimide obtained by ring-closing the polyimide precursor (A) is preferably 180 ° C. or higher, more preferably 200 ° C. or higher. As a result, excellent heat resistance as a cured product can be obtained.

The carboxyl group concentration in the (A) polyimide precursor is preferably 300 to 800 mol / g, more preferably 300 to 600 mol / g. Thereby, the dissolution rate and the dissolution contrast of the exposed portion can be further improved.

The fluorine concentration in the (A) polyimide precursor is preferably 20 to 200 mol / g, more preferably 40 to 100 mol / g. Thereby, the solvent solubility and the light transmittance can be further improved.

As long as the effect of the present invention is not impaired, a part of the (A) polyimide precursor may have a ring-closed structure represented by the general formulas (1) and (2), for example, as follows. The structure can be mentioned.

In the (A) polyimide precursor, the content (that is, the imidization ratio) of the structure represented by the general formulas (1) and (2) in which the structure is closed improves the solubility of the unexposed portion in the alkaline developer. From this point of view, it is preferably 50% or less, more preferably 40% or less, and further preferably 20% or less. The imidization ratio may be 0%.

（式中、Ｘ、Ａ、Ｂ、Ｒ、ｎ２、ｎ３、ｎ４は一般式（１）および（２）と同義である。） The polyimide precursor (A) is represented by the acid dianhydride represented by the general formula (i) and the general formula (ii) and / or the general formula (iii) in the structures of the general formulas (1) and (2). It can be obtained by reacting the diamine. The reaction can be carried out under known conditions, for example, the diamine is dissolved in a reaction solvent, the acid dianhydride is added as a solid to the solution, the acid dianhydride is dissolved in the solution, and then the terminal group is added. By introducing it, the target product can be obtained. The terminal group can be one known as the terminal group of the polyimide precursor.

(In the formula, X, A, B, R, n2, n3, n4 are synonymous with the general formulas (1) and (2).)

[(B) Photoacid generator]
The photosensitive resin composition of the present invention contains (B) a photoacid generator, whereby the solubility of the photosensitive resin composition in an alkaline developer can be adjusted. (B) The photoacid generator may be used alone or in any combination of two or more kinds.

The amount of the photoacid generator (B) to be blended can be appropriately selected, and can be, for example, 0.1 to 35 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, preferably 1. ~ 23 parts by mass.

The photoacid generator is a compound that generates an acid by irradiation with light such as ultraviolet rays or visible light. For example, a diazomethane compound, an onium salt compound, a sulfonimide compound, a disulfone compound, a sulfonic acid derivative compound, a nitrobenzyl compound, and a benzoin. Examples thereof include tosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds.

Of these, a photoacid generator that generates sulfonic acids is preferable. The blending amount of the photoacid generator for generating sulfonic acids can be 0.10 to 5 parts by mass, preferably 0.15 to 4 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. be.

Examples of sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, dodecylbenzenesulfonic acid, pentafluorobenzenesulfonic acid, and trifluoromethane. Sulfonic acid, 2,2,2-trifluoroethane sulfonic acid, nonafluorobutane sulfonic acid, heptadecafluorooctane sulfonic acid, camphor sulfonic acid, 4-trifluoromethylbenzene sulfonic acid, 4-fluorobenzene sulfonic acid and the like can be mentioned. Be done.

Examples of the photoacid generator that generates sulfonic acids include N-sulfonyloxyimide type photoacid generators.

Examples of the N-sulfonyloxyimide type photoacid generator include naphthalenedicarboxylic acid imide, succinimide, phthalimide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicyclo [2.2. 1] The hydrogen atom bonded to the nitrogen atom of an imide such as -5-heptene-2,3-dicarboxylic acid imide is a methanesulfonyloxy group, an ethanesulfonyloxy group, a propanesulfonyloxy group, a butanesulfonyloxy group, or an octanesulfonyloxy. Group, benzenesulfonyloxy group, toluenesulfonyloxy group, naphthalenesulfonyloxy group, dodecylbenzenesulfonyloxy group, pentafluorobenzenesulfonyloxy group, trifluoromethanesulfonyloxy group, 2,2,2-trifluoroethanesulfonyloxy group, nona Examples thereof include compounds substituted with a sulfonyloxy group such as a fluorobutane sulfonyloxy group, a heptadecafuolooctanesulfonyloxy group, a camphorsulfonyloxy group, a 4-trifluoromethylbenzenesulfonyloxy group, and a 4-fluorobenzenesulfonyloxy group. Of these, a compound in which the hydrogen atom bonded to the nitrogen atom of the naphthalenedicarboxylic acid imide is replaced with a sulfonyloxy group is preferable.

As the N-sulfonyloxyimide type photoacid generator, a photoacid generator having a naphthalenedicarboxylic acid imide structure is preferable, and the sulfonic acid derivative compound described in International Publication No. 2014/0842669 can be used.

（式中、
Ｒ^１は、水素原子、炭素原子数１〜１４の炭化水素基（例えば、アルキル基、アルケニル基、アルキニル基、アリール基等）、アミノ基、エーテル基、チオエーテル基であり、
Ｒ^２は、炭素原子数１〜１８のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基または１０−カンファーイル基であり、これらの基は無置換もしくはハロゲン原子（例えばフッ素原子、塩素原子。）で置換されていてもよい。）で表されるＮ−スルホニルオキシイミド型光酸発生剤であり、より具体的には、以下の光酸発生剤である。これらの光酸発生剤は、ナフタレン環上に置換基を有していてもよい。 For example, the formula:

(During the ceremony,
R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 14 carbon atoms (for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc.), an amino group, an ether group, and a thioether group.
R ² is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, or 10-camphorsulfonic yl group having 7 to 20 carbon atoms, these radicals are unsubstituted or It may be substituted with a halogen atom (for example, a fluorine atom or a chlorine atom). ), More specifically, the following photoacid generators. These photoacid generators may have a substituent on the naphthalene ring.

It is preferable to combine a photoacid generator that generates sulfonic acids with a naphthoquinone diazide compound from the viewpoint of obtaining a high residual film ratio. In this case, the blending amount of the naphthoquinone diazide compound can be 1 to 30 parts by mass, preferably 3 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

Specific examples of the naphthoquinone diazide compound include naphthoquinone diazide adducts of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, manufactured by Sanpo Chemical Laboratory Co., Ltd.). TS593), naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Laboratory Co., Ltd.), 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, naphthoquinone diazide adduct of α-dimethylbenzyl} phenol (for example, TKF-428, TKF-528 manufactured by Sanpo Chemical Laboratory Co., Ltd.), bis {3- (4-hydroxybenzyl) -4-hydroxy-2,5-dimethyl Examples thereof include a naphthoquinone diazide adduct of phenyl} methane (for example, CBN-250 of Toyo Synthetic Industry Co., Ltd.), tris (4-hydroxyphenyl) ethane (for example, HP-190DF of Toyo Synthetic Industry Co., Ltd.) and the like.

[(C) Compound having two or more vinyl ether groups]
The photosensitive resin composition of the present invention _{contains a compound having two or more (C) vinyl ether groups (CH 2} = CH—O−), and is large due to the interaction between this compound and the (A) polyimide precursor. A dissolution contrast is obtained. From the viewpoint of the effect of suppressing dissolution of the unexposed portion, 2 to 6 vinyl ether groups are preferable, and 2 to 4 vinyl ether groups are more preferable. (C) The compound having two or more vinyl ether groups may be used alone or in any combination of two or more kinds. It is preferable to combine compounds having two or more two types of (C) vinyl ether groups at a mass ratio of 3: 7 to 7: 3 from the viewpoint of dissolution contrast and resolution. The ratio is more preferably 4: 6 to 6: 4.

The compound having two or more vinyl ether groups is not particularly limited, and is bis (4- (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipate divinyl ester, diethylene glycol divinyl ether, tris (4-). Vinyloxy) butyl trimerate, bis (4- (vinyloxy) butyl) terephthalate, bis (4- (vinyloxy) butyl) isophthalate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, Tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylol ethanetrivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, penta Ellisritol trivinyl ether, cyclohexanedimethanol divinyl ether, 2,2-bis {4- [2- (vinyloxy) ethoxy] phenyl} propane, 1,1,1-tris {4- [2- (vinyloxy) ethoxy] phenyl} Etan, 1,3,5-tris [2- (vinyloxy) ethoxy] benzene, 1,2,3-tris [2- (vinyloxy) ethoxy] benzene, 2,2-bis {4- [2- (vinyloxy)) Examples thereof include ethoxy] cyclohexyl} propane and 1,4-bis {4- [2- (vinyloxy) ethoxy] phenyl} cyclohexane.

From the viewpoint of dissolution contrast, it is preferable to contain diethylene glycol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether, and it is more preferable to combine these in a mass ratio of 3: 7 to 7: 3, and the ratio is even more preferable. Is 4: 6 to 6: 4.

The blending amount of the compound having two or more vinyl ether groups (C) can be 5 to 100 parts by mass, preferably 10 to 80 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. More preferably, it is 15 to 40 parts by mass.

[Adhesive]
The photosensitive resin composition of the present invention preferably contains an adhesive from the viewpoint of obtaining good adhesiveness to a substrate or the like.
The adhesive is not particularly limited, and examples thereof include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent. The adhesive may be used alone or in any combination of two or more.
Examples of the silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-. Examples thereof include acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, and phenyltrimethoxysilane.
Examples of the titanate coupling agent include isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphate) titanate, and tetraoctylbis (ditridecylphosphite). Examples thereof include titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.
Examples of the aluminum coupling agent include acetalkoxyaluminum diisopropirate and the like.

Among them, N-phenyl-3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane improve the adhesion to the substrate and do not adversely affect the development speed. Preferred for reasons.

The blending amount of the adhesive may be 10 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, preferably 0.1 to 10 parts by mass.

[Base compound]
The photosensitive resin composition of the present invention is obtained from the viewpoints of improving the dissolution contrast and resolution, and improving the stability of the coating film during the leaving time from application of the photosensitive resin composition to exposure. It preferably contains a basic compound.
The base compound may be used alone or in any combination of two or more. Examples of the basic compound include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine and n. -Heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- Amine compounds such as diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine; formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide , Propionamide, benzamide and other amide compounds; pyrrolidone, N-methylpyrrolidone and other lactams; methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1 , 3-Diphenylurea and other urea compounds; imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinolin, acrydin, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, Nitrogen-containing heterocyclic compounds such as piperazine, 1,4-dimethylpiperazin, 1,4-diazabicyclo [2.2.2] octane and pyridine; morpholin compounds such as morpholin and 4-methylmorpholin can be mentioned. Of these, amine compounds are preferable, and alkanolamines such as triethanolamine are more preferable.

The blending amount of the base compound can be 5 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, preferably 0.01 parts by mass or more and 3 parts by mass or less.

[Surfactant]
The photosensitive resin composition of the present invention preferably contains a surfactant in order to improve adhesion to the substrate and resolution. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant and a silicon-based surfactant.

Fluorine-based surfactants include the "Mega Fvck" series manufactured by DIC (for example, Mega Fvck F-281, F-477, F-553, F-554, F-555, F-556, F-557, etc. F-558, F-559, F-560, F-561, F-563, F-569, etc.) and the like.
Silicon-based surfactants include Big Chemie's surface conditioner series (for example, BYK-302, BYK-307, BYK-322, BYK-323, BYK-326, BYK-331, BYK-332, BYK-333, BYK. -348, BYK-349, BYK-377, BYK-378, BY-3455, BYK-3760, etc.), etc., and these may be used alone or in combination of two or more.

The blending amount of the surfactant can be 1 part by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, and is preferably 0.01 part by mass or more and 0.5 part by mass or less.

[Crosslinking agent]
The photosensitive resin composition of the present invention may contain a cross-linking agent as long as the effects of the present invention are not impaired. By containing a cross-linking agent, it can be expected that the curing temperature of the photosensitive resin composition will be lowered.
The cross-linking agent is not particularly limited, and is an alcoholic cross-linking agent having a cyclic ether group such as an epoxy group or a cyclic thioether group such as an episulfide group, or an alcoholic group in which a hydroxyl group is bonded to an alkylene group having 1 to 12 carbon atoms such as a methylol group. Examples thereof include a cross-linking agent having a hydroxyl group, a compound having an ether bond such as an alkoxymethyl group, a cross-linking agent having a triazine ring structure, a urea-based cross-linking agent, and the like, among which a cross-linking agent having an epoxy group and a cross-linking agent having a methylol group are preferable. ..
The cross-linking agent may be used alone or in any combination of two or more kinds, and when the cross-linking agent is contained, it is 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. It is possible to use 0.1 to 20 parts by mass, preferably 0.1 to 20 parts by mass.

[Plasticizer]
The photosensitive resin composition of the present invention may contain a plasticizer as long as the effects of the present invention are not impaired. By containing a plasticizer, it can be expected to promote low temperature curability.
The plasticizer is not particularly limited, and examples thereof include bifunctional (meth) acrylic compounds, sulfonamide compounds, phthalic acid ester compounds, maleic acid ester compounds, aliphatic dibasic acid esters, phosphoric acid esters, and ether compounds such as crown ether. Among them, a bifunctional (meth) acrylic compound is preferable.
The plasticizer may be used alone or in any combination of two or more kinds, and when the plasticizer is contained, the amount should be 3 to 40 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. Can be done.

[Other ingredients]
To the extent that the effects of the present invention are not impaired, the photosensitive resin composition of the present invention is a known thermal acid generator for promoting the cyclization reaction of the polyimide precursor, and a known sensitizer for improving photosensitivity. It can also contain various organic or inorganic low molecular weight or high molecular weight compounds in order to impart processing properties and various functionalities such as agents. Examples thereof include surfactants, leveling agents, colorants, fibers, fine particles, etc., and the fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon, and layered silicate. ..

[solvent]
The photosensitive resin composition of the present invention can contain a solvent. The solvent is not particularly limited, but a solvent having a boiling point of 200 ° C. or lower is preferable because the residual solvent can be easily reduced even when the heating temperature of the pattern film is lowered. For example, -2-acetate-2. Methoxy-1-methylethyl (PGMEA), 4-methyl-2-pentanone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ethyl acetate, butyl acetate, ethyl lactate, 3 -Methyl methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol Examples thereof include monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone. The solvent may be used alone or in any combination of two or more kinds.

The blending amount of the solvent is not particularly limited, and may be 200 to 2000 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[Preparation of photosensitive resin composition]
The photosensitive resin composition of the present invention is a mixture of (A) a polyimide precursor, (B) a photoacid generator, (C) a compound having two or more vinyl ether groups, and an arbitrary component such as a solvent. Can be obtained by Mixing may be carried out under heating.

<Dry film>
The dry film of the present invention includes a film (for example, a support (carrier) film) and a resin layer formed on the film using the photosensitive resin composition of the present invention. The dry film may be provided with a film (protective film) that further protects (covers) the resin layer formed on the film.

[Support (carrier) film]
The support (carrier) film is not particularly limited, and examples thereof include a polyester film such as polyethylene terephthalate and polyethylene naphthalate, and a film made of a thermoplastic resin such as a polyimide film, a polyamide-imide film, a polypropylene film, and a polystyrene film. Among them, a film made of polyethylene terephthalate is preferable from the viewpoint of heat resistance, mechanical strength, handleability and the like. A laminate of these films can also be used as a support (carrier) film.

The support (carrier) film is preferably a film stretched in the uniaxial direction or the biaxial direction from the viewpoint of improving mechanical strength.

The thickness of the support (carrier) film is not particularly limited, and can be, for example, 10 to 150 μm.

[Protective film]
For the purpose of preventing dust from adhering to the surface of the resin layer, it is preferable to laminate a peelable protective film on the surface of the resin layer.

The peelable protective film is not particularly limited as long as the adhesive force between the resin layer and the protective film is smaller than the adhesive force between the resin layer and the supporting (carrier) film at the time of peeling. Examples thereof include polyethylene film, polytetrafluoroethylene film, polypropylene film, and surface-treated paper.

The thickness of the protective film is not particularly limited, and can be, for example, 10 to 150 μm.

[Resin layer]
The resin layer is formed by using the photosensitive resin composition of the present invention.
The thickness of the resin layer is not particularly limited and can be appropriately selected depending on the intended use and the like, and can be, for example, 1 to 150 μm.

The method for forming the resin layer is not particularly limited, and for example, it can be formed by applying a photosensitive resin composition on a support (carrier) film and drying it. The coating method is not particularly limited, and a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer coater, a gravure coater, a spray coater and the like can be used. The resin layer is preferably applied so as to have a uniform thickness and dried.
The resin layer may be formed by applying a photosensitive resin composition on a protective film and drying it.

<Cured product>
The cured product of the present invention is formed by using the photosensitive resin composition of the present invention. A pattern may be formed on the cured product. Examples of the method for producing the cured product include the following.

[First step]
The first step is a step of forming a dry coating film of the photosensitive resin composition of the present invention. For example, the photosensitive composition of the present invention is applied onto a substrate to form a coating film, which is then dried, or a resin layer is transferred from the dry film of the present invention onto a substrate for dry coating. A film can be formed.

The method of applying the photosensitive resin composition onto the substrate is not particularly limited, and for example, a method of applying the photosensitive resin composition using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or spray coating using a spray coater. The method of printing, the inkjet method, and the like can be mentioned.

The method for drying the coating film is not particularly limited, and examples thereof include air drying, heat drying using an oven or a hot plate, and vacuum drying. It is desirable that the coating film is dried under conditions such that ring closure of the polyimide precursor in the photosensitive resin composition does not occur. For example, natural drying, blast drying, and conditions of 70 to 140 ° C. for 1 to 30 minutes. Heat drying can be mentioned. From the viewpoint of simple operation method, it is preferable to dry for 1 to 20 minutes using a hot plate. Vacuum drying is also possible, in which case it can be carried out at room temperature for 20 minutes to 1 hour.

The transfer of the resin layer of the dry film onto the substrate is preferably performed under pressure and heating using a vacuum laminator or the like. By using a vacuum laminator, in the case of a substrate on which a circuit is formed, even if the surface of the circuit board is uneven, the resin layer of the dry film is filled with the unevenness under vacuum conditions, so that air bubbles are mixed. In addition, it is possible to improve the hole filling property of the concave portion on the surface of the circuit board.

The base material is not particularly limited, and examples thereof include a printed wiring board in which a circuit is formed in advance with copper or the like, and a flexible printed wiring board. Copper for high frequency circuits using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. It uses materials such as stretched laminates, and is made of copper-clad laminates of all grades (FR-4, etc.), other metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, etc. Ceramic substrates, wafer plates and the like can also be used.

[Second step]
The second step is a step of irradiating and exposing the dry coating film formed in the first step with active energy rays. The exposure may be selectively performed through a photomask having a pattern, or may be performed non-selectively through a photomask having a pattern.

As the active energy ray, one having a wavelength capable of activating a photoacid generator such as a photoacid generator is used, and one having a maximum wavelength in the range of 350 to 410 nm is preferable. The exposure amount can be appropriately adjusted depending on the film thickness and the like, and is generally 10 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .
As the exposure machine, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like is mounted, and a device that irradiates ultraviolet rays in the range of 350 to 450 nm can be used. A direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser based on CAD data from a computer) may be used.

[Third step]
The third step is a step of closing a part of the polyimide precursor of the unexposed portion by heating the coating film after exposure for a short time, and is an arbitrary step performed as necessary. When this step is performed, the ring closure rate is preferably about 30%. The heating time and heating temperature can be appropriately changed depending on the type of the polyimide precursor, the coating film thickness, and the type of the photoacid generator.

[Fourth step]
The fourth step is a step of treating a coating film after exposure, and in some cases, a coating film that has been heated for a short time, with a developing solution to remove an exposed portion in the coating film to obtain a pattern film. The developing method is not particularly limited, and examples thereof include a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment.

The developing solution is not particularly limited, and inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, tetramethylammonium hydroxide and tetra. Examples thereof include aqueous solutions of quaternary ammonium salts such as butylammonium hydroxide. If necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol or a surfactant may be added in an appropriate amount.

After the treatment with a developing solution, the coating film can be washed with a rinsing solution, if necessary, to obtain a patterned film. The rinsing liquid is not particularly limited, and examples thereof include distilled water, methanol, ethanol, isopropyl alcohol and the like. The rinsing solution may be used alone or in any combination of two or more.

[Fifth step]
The fifth step is a step of heating the pattern film to obtain a cured coating film (cured product). Upon heating, the polyimide precursor contained in the photosensitive resin composition undergoes a cyclization reaction to become polyimide.

The heating temperature is preferably 150 to 250 ° C., more preferably 170 to 220 ° C. from the viewpoint of preventing warping of the cured product.
For heating, for example, a hot plate, an oven, and a heating oven in which a temperature program can be set can be used. The heating may be performed in the atmosphere or in an atmosphere of an inert gas such as nitrogen or argon.

<Use>
The application of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include paints, printing inks, and adhesives. The photosensitive resin composition of the present invention can be suitably used as a forming material for display devices, semiconductor elements, electronic parts, optical parts, building materials and the like.

Examples of the forming material of the display device include a layer forming material and an image forming material in a color filter, a film for a flexible display, a resist material, an alignment film and the like.
Examples of the material for forming the semiconductor element include a layer forming material such as a resist material, a buffer coat film, and an insulating film for a rewiring layer of a wafer level package (WLP).
Examples of the material for forming the electronic component include a sealing material and a layer forming material in a printed wiring board, an interlayer insulating film, a wiring coating film, and the like.
Examples of the material for forming the optical component include an optical material and a layer forming material in a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, and the like.
As a building material, it can be used as a paint, a coating agent, or the like.

The photosensitive resin composition of the present invention is preferably used as a pattern forming material, and in particular, a surface protective film, a buffer coat film, an interlayer insulating film, an insulating film for rewiring, and a flip chip of a semiconductor device, a display device, and a light emitting device. Suitablely used as a protective film for devices, a protective film for devices having a bump structure, an interlayer insulating film for multilayer circuits, an insulating material for passive components, a protective film for printed wiring boards such as solder resist and coverlay films, and a liquid crystal alignment film. be able to.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.

The measurements and evaluations in the examples were performed as follows.
<Number average molecular weight, weight average molecular weight>
The number average molecular weight and the weight average molecular weight are numerical values measured by gel permeation chromatography (GPC) and converted with standard polystyrene.
[Measurement condition]
GPC measurement GL7700 (GL Science)
Column used: Tosoh TSKgel (R) α-2500 (φ7.8mm × 30cm) α-4000 (φ7.8mm × 30cm)
Column temperature: 40 ° C
Eluent conditions: 100 mmol / LH ₃ PO ₄ , 10 mmol / L LiBr, in NMP
Eluent flow rate: 0.5 mL / min
Calibration standard reagent: Polystyrene standard (Showdex)
Sample concentration: 0.1% Eluent detector: UV (wavelength 260 nm and 300 nm), room temperature

<Dissolution rate, dissolution contrast>
The varnish produced in Examples and Comparative Examples was applied onto a silicon wafer using a spin coater and dried at 110 ° C. for 3 minutes to obtain a dried film having a film thickness of about 1 μm. The obtained silicon wafer with a dry film was cut into strip-shaped test pieces and irradiated with a light beam having a wavelength of 365 nm using a high-pressure mercury lamp at the exposure amount shown in Table 1, and a test piece not irradiated with light. Two types were prepared. Each test piece was heated after exposure (PEB) under the conditions shown in Table 1, then developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, and the test piece was irradiated with light to dissolve the test piece. The rate was defined as the dissolution rate of the exposed portion, and the dissolution rate of the test piece not subjected to light irradiation was defined as the dissolution rate of the unexposed portion.
The dissolution rate of the exposed portion was calculated by the following formula, with the time from the immersion of the test piece in the developing solution to the complete dissolution of the dry film on the test piece in the developing solution as the developing time. Dissolution of the dry film in the developer is visual.
The dissolution rate of the unexposed portion was determined by the following formula, with the thickness of the dry film on the test piece at the stage one hour after immersion in the developing solution as the post-development film thickness. The development time is 1 hour (3600s).
The dissolution contrast is (exposure portion dissolution rate / unexposed portion dissolution rate).

<Resolution>
The silicon wafer with a dry film prepared in the above dissolution rate test was irradiated with light having a wavelength of 365 nm using a high-pressure mercury lamp through a mask engraved with a pattern at the exposure amount shown in Table 1. After the exposure, the mixture was heated after the exposure (PEB) under the conditions shown in Table 1, developed in a 2.38% TMAH aqueous solution for 60 seconds, and then rinsed with water to obtain a pattern of a positive cured film.
The L / S (line / space) of the pattern engraved on the mask was changed from 1 μm / 1 μm to 30 μm / 30 μm in 1 μm increments for both the line space, and the obtained positive cured film pattern was changed. Observation was performed using an electron microscope (SEM, JSM-6010 manufactured by JEOL Ltd.). The minimum L / S capable of patterning the exposed portion without scum (development residue) was set as the resolution.

<Residual film ratio>
With respect to the developed positive cured film pattern of the above resolution test, the film thickness of the unexposed portion was measured, and the residual film ratio was calculated by the following formula.

The components used in the examples and comparative examples are as follows.

<Synthesis Example 1: Polyimide precursor (A-1)>
53 g of propylene glycol monomethyl ether acetate (PGMEA) in a flask, 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-methylene dianiline ( 6.91 g (13.02 mmol) of HFA-MDA) was charged and dissolved by stirring. After confirming that the monomer was completely dissolved, 5,5'-[1-methyl 1,1-ethanediyl bis (1,4-phenylene) bisoxy] bis (isobenzofuran-1,3-dione) (BPADA) 5 .20 g (10.00 mmol) was added as a solid over 5 minutes and stirring was continued for 1 hour at room temperature. Then, 0.26 g (1.59 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added to the stirring solution as a solid, and the mixture was stirred at room temperature for 16 hours to obtain a polyimide precursor (A-1) (HFA-containing polyamic). Acid) Obtained varnish. The polyimide precursor (A-1) had a number average molecular weight (Mn) of 3,200, a weight average molecular weight (Mw) of 7,950, a carboxyl group equivalent of 525 g / mol, and a fluorine group equivalent of 87 g / mol.

Polyimide precursor A-1

<Synthesis Example 2: Polyimide precursor (A-2)>
15 g of PGMEA and 1.33 g (3.00 mmol) of HFA-MDA were placed in a flask and dissolved by stirring. After confirming that the monomer was completely dissolved, 1.59 g (3.00 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 5-norbornene-2,3-dicarboxylic acid anhydride were used. 0.023 g (0.14 mmol) of the product was added as a solid and stirred at room temperature for 16 hours to obtain a polyimide precursor (A-2) (HFA-containing polyamic acid) varnish. The polyimide precursor (A-2) had a number average molecular weight (Mn) of 16,900, a weight average molecular weight (Mw) of 41,700, a carboxyl group equivalent of 487 g / mol, and a fluorine group equivalent of 54 g / mol.

Polyimide precursor (A-2)

<Synthesis Example 3: Polyimide precursor (A-3)>
27 g of PGMEA and 1.59 g (3.00 mmol) of HFA-MDA were placed in a flask and dissolved by stirring. After confirming that the monomer was completely dissolved, 0.97 g (3.00 mmol) of 3,3', 4,4'-benzophenone tetracarboxylic acid anhydride and 5-norbornene-2,3-dicarboxylic acid anhydride 0. .14 g (0.023 mmol) was added as a solid and stirred at room temperature for 16 hours to obtain a polyimide precursor (A-3) (HFA-containing polyamic acid) varnish. The polyimide precursor (A-3) had a number average molecular weight (Mn) of 15,400, a weight average molecular weight (Mw) of 36,500, a carboxyl group equivalent of 426 g / mol, and a fluorine group equivalent of 71 g / mol.

Polyimide precursor (A-3)

<Synthesis Example 4: Polyimide Precursor (A'-1)>
81 g of PGMEA and 6.96 g (21.74 mmol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) were charged in a flask and dissolved by stirring. After confirming that the monomer was completely dissolved, 8.11 g (18.26 mmol) of 6FDA was added as a solid over 5 minutes, and stirring was continued for 1 hour at room temperature. Then, 1.15 g (6.98 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added to the stirring solution as a solid, and the mixture was stirred at room temperature for 16 hours to prepare a polyimide precursor (A'-1) (polyamic acid). ) I got a crocodile. The polyimide precursor (A'-1) had a number average molecular weight of 5,200, a weight average molecular weight (Mw) of 13,000, a carboxyl group equivalent of 382 g / mol, and a fluorine group equivalent of 63 g / mol.

Polyimide precursor (A'-1)

（ＡＤＥＫＡ製、ＳＰ−６１２） <Photoacid generator (B-1)>

(Made by ADEKA, SP-612)

（東洋合成社製、ＣＮＢ-２５０） <Photoacid generator (B-2)>

(Manufactured by Toyo Synthetic Co., Ltd., CNB-250)

（ＡＤＥＫＡ製、ＳＰ−６０６） <Photoacid generator (B-3)>

(Made by ADEKA, SP-606)

（日本カーバイド工業社製、ＤＥＧＤＶＥ） <Vinyl ether compound (C-1)>

(Manufactured by Nippon Carbide Industry Co., Ltd., DEGDVE)

（日本カーバイド工業社製、ＣＨＤＶＥ） <Vinyl ether compound (C-2)>

(CHDVE manufactured by Nippon Carbide Industry Co., Ltd.)

<Vinyl ether compound (trifunctional vinyl ether compound) (C-3)>
1.23 g (9.79 mmol) of fluoroglycinol, 1.67 g (41.9 mmol) of NaOH, and 15 mL of dimethylformamide (DMF) were added to a flask equipped with a cooling tube and a thermometer, and the mixture was stirred at 60 ° C. for 1 hour. Then, 4.46 g (41.9 mmol) of 2-chloroethyl vinyl ether was added, and the mixture was stirred at 70 ° C. for 15 hours. The reaction mixture was quenched with water, extracted with toluene, and the organic layer was washed with aqueous NaCl solution. The organic layer was dried over magnesium sulfate, and then the solvent was removed with an evaporator to obtain a trifunctional vinyl ether compound (C-3) having the following structure.

Vinyl ether compound (C-3)

（信越化学工業社製、ＫＢＭ−５７３） <Adhesive agent D-1>

(KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Basic compound E-1>
Triethanolamine

<Surfactant F-1>
Megafuck F-477 manufactured by DIC (fluorine-containing group, hydrophilic tree, lipophilic group-containing oligomer)
<Surfactant F-2>
Megafuck F-554 manufactured by DIC (fluorine-containing group / lipophilic group-containing oligomer)
<Surfactant F-3>
Megafuck F-563 manufactured by DIC (fluorine-containing group / lipophilic group-containing oligomer)
<Surfactant F-4>
BYK-322 manufactured by Big Chemie (silicon-based surface conditioner for solvent-based paints)
<Surfactant F-5>
BYK-331 manufactured by Big Chemie (solvent-free and solvent-based general industrial and automobile paints, and silicon-based surface conditioners for printing inks)
<Surfactant F-6>
BYK-333 manufactured by Big Chemie (solvent-free type, solvent type, silicon-based surface conditioner for water-based paints and printing inks)
<Surfactant F-7>
BYK-3760 manufactured by Big Chemie (solvent type, water-based and UV curable paint, silicon-based surface conditioner for printing ink)

<Example 1>
100 parts by mass (equivalent to solid content) of the polyimide precursor (A-1), the varnish of Synthesis Example 1, 0.3 parts by mass of the photoacid generator (B-1) and 56 parts by mass of the vinyl ether compound (C-1) are blended. Then, the photosensitive resin composition of Example 1 was obtained.

<Example 2>
100 parts by mass (equivalent to solid content) of the polyimide precursor (A-1) is blended with the varnish of Synthesis Example 1, 0.3 parts by mass of the photoacid generator (B-1) and 72 parts by mass of the vinyl ether compound (C-2). Then, the photosensitive resin composition of Example 2 was obtained.

<Example 3>
100 parts by mass (equivalent to solid content) of the polyimide precursor (A-1) is blended with the varnish of Synthesis Example 1, 0.3 parts by mass of the photoacid generator (B-1) and 62 parts by mass of the vinyl ether compound (C-3). Then, the photosensitive resin composition of Example 3 was obtained.

<Example 4>
100 parts by mass (equivalent to solid content) of the polyimide precursor (A-1), the varnish of Synthesis Example 1, 0.3 parts by mass of the photoacid generator (B-1), 44 parts by mass of the vinyl ether compound (C-1), and adhesion. 0.5 parts by mass of the agent (D-1) was blended to obtain the photosensitive resin composition of Example 4.

<Example 5>
Synthesis Example 1 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1) 0.5 parts by mass of photoacid generator (B-1), 20 parts by mass of photoacid generator (B-2) And 29 parts by mass of the vinyl ether compound (C-1) were blended to obtain the photosensitive resin composition of Example 5.

<Example 6>
Synthesis Example 1 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1) 1 part by mass of photoacid generator (B-1), 10 parts by mass of photoacid generator (B-2) and vinyl ether 29 parts by mass of compound (C-1) was blended to obtain the photosensitive resin composition of Example 6.

<Example 7>
Synthesis Example 1 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1) 1 part by mass of photoacid generator (B-1), 20 parts by mass of photoacid generator (B-2), vinyl ether 29 parts by mass of compound (C-1) and 0.5 parts by mass of adhesive (D-1) were blended to obtain a photosensitive resin composition of Example 7.

<Example 8>
Synthesis Example 2 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-2) 1 part by mass of photoacid generator (B-11), 10 parts by mass of photoacid generator (B-2) and vinyl ether 32 parts by mass of compound (C-1) was blended to obtain a photosensitive resin composition of Example 8.

<Example 9>
100 parts by mass (equivalent to solid content) of the polyimide precursor (A-3), the varnish of Synthesis Example 3, 1 part by mass of the photoacid generator (B-1), 10 parts by mass of the photoacid generator (B-2), and vinyl ether. 32 parts by mass of compound (C-1) was blended to obtain a photosensitive resin composition of Example 9.

<Comparative example 1>
100 parts by mass (equivalent to solid content) of the polyimide precursor (A'-1), 0.3 parts by mass of the photoacid generator (B-1) and 76 parts by mass of the vinyl ether compound (C-1) of Synthesis Example 4. It was blended to obtain a photosensitive resin composition of Comparative Example 1.

The photosensitive compositions of Examples 10 to 28 were prepared by blending the amounts of each component in the amounts shown in Table 1. In the table, the amounts of the resin, the photoacid generator, the vinyl ether compound, the adhesive, and the base compound are indicated by parts by mass. As for the polyimide precursor (A-1), the varnish of Synthesis Example 1 was used in an amount corresponding to the solid content in the table.

The photosensitive resin compositions of Examples and Comparative Examples were measured and evaluated under the conditions shown in Table 1. The results are shown in Table 1.

The photosensitive resin compositions of Examples 1 to 28 had a large dissolution contrast and exhibited excellent resolution.
Among them, Examples 5 to 8 in which the photoacid generator and the naphthoquinone diazide compound were used in combination as the photoacid generator showed a high residual film ratio.
In addition, Example 11 in which two kinds of vinyl ether compounds were combined and Example 12 in which a base compound was blended showed excellent resolution in dissolution contrast.
Further, Examples 13 to 28 were examples in which a surfactant was blended, and all of them showed a high residual film ratio. In Examples 20 to 28 in which two kinds of vinyl ether compounds were combined and a basic compound was further blended, the dissolution contrast was large and the resolution was extremely excellent.

Claims (14)

(A) A polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2), and
(B) Photoacid generator and
(C) A compound having two or more vinyl ether groups and
A photosensitive resin composition comprising.

(During the ceremony,
X is a tetravalent organic group,
A is a single bond, O or divalent organic group,
B is a fluoroalcohol group
R is a hydrogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylamino group or aryl group.
n1 is an integer greater than or equal to 1 and
n2 is an integer from 0 to 4, n3 is an integer from 0 to 4, but n2 + n3 is 1 or more.
n4 is an integer of 1 to 4. ) The photosensitive resin composition according to claim 1, wherein X is selected from the groups shown below.

(During the ceremony,
a is an integer from 0 to 2 and
b is an integer of 0 to 2. ) The photosensitive resin composition according to claim 1 or 2, wherein B has 1 to 10 carbon atoms and 1 to 10 fluorine atoms. The photosensitive resin composition according to any one of claims 1 to 3, wherein the carboxyl group concentration in the polyimide precursor is 300 to 800 mol / g. The photosensitive resin composition according to any one of claims 1 to 4, wherein the fluorine concentration in the polyimide precursor is 20 to 200 mol / g. The photosensitive resin composition according to any one of claims 1 to 5, further comprising an adhesive. The photosensitive resin composition according to any one of claims 1 to 6, further comprising a base compound. The photosensitive resin composition according to any one of claims 1 to 7, further comprising a surfactant. The photosensitive resin composition according to any one of claims 1 to 8, wherein the photoacid generator contains an N-sulfonyloxyimide type photoacid generator. The photosensitive resin composition according to claim 9, wherein the photoacid generator further contains a naphthoquinone diazide compound. The photosensitive resin composition according to any one of claims 1 to 10, wherein the compound having two or more vinyl ether groups is at least one selected from diethylene glycol divinyl ether and cyclohexanedimethanol divinyl ether. A dry film comprising a resin layer formed of the photosensitive resin composition according to any one of claims 1 to 11 on the film. A cured product, which is formed of the photosensitive resin composition according to any one of claims 1 to 11 or the resin layer of the dry film according to claim 12. An electronic component comprising the cured product according to claim 13 as a forming material.