JP2021060458A - Photosensitive resin composition, dry film, cured object, and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition which contains a copolymer having dissolubility in various solvents and has high dissolution contrast.SOLUTION: A photosensitive resin composition comprises (A) a copolymer, which is produced by the reaction of at least one of a bisphenylene diamine derivative and a phenylene diamine derivative, at least one of a bisphenylene diamine derivative having a hydroxyl group and a hydroxy phenylene diamine derivative, and at least one of a carboxylic acid anhydride and a carboxylic acid chloride and (B) a photosensitive agent.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition containing a copolymer containing a diamine compound having a specific structure as a polymerization component, a dry film having a resin layer formed of the photosensitive resin composition, and the photosensitive resin composition. The present invention relates to a cured product formed by, and an electronic component such as a printed wiring board or a semiconductor element 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, flexible printed wiring boards, buffer coated films for semiconductor elements, and wafer level packages (WLPs) are being applied to insulating films for rewiring layers.

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 the above, 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. A 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 a requirement, Patent Document 1 discloses a photosensitive polyimide resin composition containing a polyimide precursor, and Patent Document 2 has a high solution while having characteristics equivalent to those of a polyimide resin. A composition using a polybenzoxazole precursor as a photosensitive resin having image quality is disclosed.

In order to realize such excellent resolution, in the coating film made of the photosensitive resin composition, the dissolution rate of the exposed portion in the alkaline developer (hereinafter, simply referred to as the exposure portion dissolution rate) is high and It is important that the unexposed portion has excellent solubility resistance to an alkaline developer. That is, there is a demand for a photosensitive resin composition having a large difference in dissolution rate in an alkaline developer, that is, a so-called dissolution contrast between an exposed portion and an unexposed portion.

On the other hand, in the cured film formed of the photosensitive resin composition containing the polyimide precursor, an attempt has been made to lower the heating temperature of the pattern film in order to suppress the occurrence of warpage due to the ring closure reaction (Patent Document 3). reference).

JP-A-2006-267800 Japanese Patent Application Laid-Open No. 2003-241377 JP-A-2018-146964

However, it cannot be said that the compositions described in Patent Documents 1 and 2 can sufficiently satisfy the dissolution contrast for realizing the resolution required for recent semiconductor devices, and Patent Document 3 also states. In addition to the problem of resolution, the described composition requires the use of a high boiling point solvent such as N-methyl-2-pyrrolidone (NMP) or γ-butyrolactone (GBL), and thus at a low heating temperature. There is a problem that a high boiling point solvent remains in the cured product even if the curing is realized.

The present invention has been made in view of the above problems, and its main purpose is to have excellent insulating properties, heat resistance, mechanical strength, etc., and also have solubility in various solvents (hereinafter, simply referred to as solvent solubility). It is an object of the present invention to provide a photosensitive resin composition containing a resin component and having a large dissolution contrast (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 focused on obtaining an excellent dissolution contrast by increasing the dissolution rate of the exposed portion, and as a result of diligent studies, they have identified that the resolution of the photosensitive resin composition can be remarkably improved. A new copolymer having the above structure was found, and the present invention was completed. Further, the copolymer has high solubility in various solvents including low boiling point solvents such as -2-methoxy-1-methyl ethyl acetate (PGMEA) and 4-methyl-2-pentanone. I found it.

（式中、
Ａは、単結合、Ｏおよび２価の有機基から選択され、
Ｂは、フルオロアルコールであり、
Ｒは、置換または無置換のアルキル基またはアリール基であり、
ｎ１およびｎ２は、それぞれ独立して、０〜４の整数であり、かつｎ１＋ｎ２は１以上であり、
ｎ３およびｎ４は、それぞれ独立して、０〜３の整数であり、
ｎ５は、１〜４の整数であり、
ｎ６は、０〜３の整数であり、
ｎ７およびｎ８は、それぞれ独立して、０〜４の整数であり、かつｎ７＋ｎ８は１以上であり、
ｎ９およびｎ１０は、それぞれ独立して、０〜３の整数であり、
ｎ１１は、１〜４の整数であり、
ｎ１２は、０〜３の整数である。） That is, the photosensitive resin composition of the present invention comprises (A) at least one of the diamine compounds represented by the following general formulas (1) and (2) and the diamine compound represented by the following general formulas (3) and (4). It is characterized by containing a copolymer which is a reaction product of at least one of the above and at least one of a carboxylic acid anhydride and a carboxylic acid chloride, and (B) a photosensitizer.

(During the ceremony,
A is selected from single bond, O and divalent organic groups.
B is a fluoroalcohol,
R is a substituted or unsubstituted alkyl or aryl group.
n1 and n2 are independently integers from 0 to 4, and n1 + n2 is 1 or more.
n3 and n4 are independently integers from 0 to 3, respectively.
n5 is an integer of 1 to 4 and
n6 is an integer from 0 to 3 and
n7 and n8 are independently integers from 0 to 4, and n7 + n8 is 1 or more.
n9 and n10 are independently integers of 0 to 3, respectively.
n11 is an integer of 1 to 4,
n12 is an integer from 0 to 3. )

In the present invention, the fluorine concentration in the copolymer is preferably 20 to 200 mol / g.

In the present invention, the carboxyl group concentration in the copolymer is preferably 300 to 800 mol / g.

In the present invention, the hydroxyl group concentration in the copolymer is preferably 200 to 600 mol / g.

In the present invention, the composition ratio of the diamine compounds represented by the general formulas (1) and (2) in the copolymer is preferably 5 mol% or more and 40 mol% or less.

In the present invention, the composition ratio of the diamine compounds represented by the general formulas (3) and (4) in the copolymer is preferably 10 mol% or more and 45 mol% or less.

（上記式中、ａは、それぞれ独立して０〜２の整数であり、ｂは、それぞれ独立して１〜３の整数である。） In the present invention, it is preferable that A in the general formulas (1) and (2) is selected from divalent organic groups having the following structures.

(In the above formula, a is an integer of 0 to 2 independently, and b is an integer of 1 to 3 independently.)

In the present invention, the number of carbon atoms of the fluoroalcohol represented by B in the general formulas (1) and (2) is 1 to 10 independently, and the number of fluorines is 1 to 10 independently. Is preferable.

（式中、Ｘは以下の構造を有する４価の有機基である。） In the present invention, the carboxylic acid anhydride is preferably represented by the following general formula (5).

(In the formula, X is a tetravalent organic group having the following structure.)

（式中、
Ｙは、単結合、Ｏおよび２価の有機基から選択され、
Ｚは、ハロゲン元素である。） In the present invention, it is preferable that the carboxylated product is represented by the following general formula (6).

(During the ceremony,
Y is selected from single bond, O and divalent organic groups,
Z is a halogen element. )

In the present invention, the photosensitive resin composition preferably further contains an adhesive.

In the present invention, the photosensitizer is preferably a naphthoquinone diazide compound.

The dry film of the present invention is characterized in that a resin layer formed of the above-mentioned photosensitive resin composition is provided on the film.

The cured product of the present invention is characterized by being formed by the photosensitive resin composition or the resin layer of the dry film.

The electronic component of the present invention, such as a printed wiring board or a semiconductor element, is characterized by having the cured product as a forming material.

According to the present invention, it is possible to provide a photosensitive resin composition having a high dissolution rate in an exposed portion and capable of realizing excellent dissolution contrast (resolution). Further, since the copolymer contained in the photosensitive resin composition is excellent in solubility in various solvents including low boiling point solvents, the above-mentioned problem of residual solvent can be solved.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) at least one of the diamine compounds represented by the following general formulas (1) and (2) and at least one of the diamine compounds represented by the following general formulas (3) and (4). It is characterized by containing a copolymer, which is a reaction product of one with at least one of a carboxylic acid anhydride and a carboxylic acid chloride, and (B) a photosensitizer.

The dissolution rate of the exposed portion formed by the photosensitive resin composition of the present invention in a 2.38% TMAH aqueous solution at 25 ° C. is preferably 200 to 1000 nm / min, and preferably 500 to 900 nm / min. More preferred.
As a result, the development process conditions can be easily controlled, and the formation of fine patterns becomes extremely easy.
The dissolution rate is measured as follows.
The photosensitive resin composition is applied and dried on a silicon substrate to form a dry coating film having a thickness of 2 μm, and the dry coating film is irradiated with broad light through a photomask having a pattern. The exposure amount is 200 mJ / cm ² .
The dry coating film after exposure is developed with a 2.38% TMAH aqueous solution at 25 ° C., and a dry coating is applied in the exposed area using a development speed measuring device (RDA-790 manufactured by Lithotech Japan Co., Ltd.). Measure the dissolution rate of the membrane.

Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.

[(A) Copolymer]
The copolymer contained in the photosensitive resin composition of the present invention includes at least one of the diamine compounds represented by the following general formulas (1) and (2) and the diamine represented by the following general formulas (3) and (4). It is characterized by being a reaction product of at least one of the compounds and at least one of a carboxylic acid anhydride and a carboxylic acid chloride.

In the general formulas (1) and (3), A is selected from single bond, O and divalent organic groups.
The divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further 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, an ester group and the like.
More specifically, examples of the divalent organic group include, but are not limited to, the following. In addition, a in the structure is independently an integer of 0 to 2, and from the viewpoint of solvent solubility, it is preferably 0 to 1, and particularly preferably 0. Further, b in the structure is an integer of 1 to 3, and is preferably 2 to 3 and particularly preferably 3 from the viewpoint of solvent solubility and transparency of the cured product.

In the above general formulas (1) and (2), B is a fluoroalcohol group.
The number of carbon atoms of the fluoroalcohol group is preferably 1 to 10 and more preferably 3 to 6 independently of each other.
The number of fluorines in the fluoroalcohol group is preferably 1 to 10 and more preferably 4 to 8 independently of each other. Thereby, the solvent solubility and the transparency of the cured product can be improved.
Specific examples of the fluoroalcohol group include, but are not limited to, a group having the following structure.

In the above general formulas (1) to (4), R is a substituted or unsubstituted alkyl group or aryl group.
The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 6.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a sec-pentyl group, an n-hexyl group and a cyclohexyl. Group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group Group, chloroethyl group, dichloroethyl group, trichloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, hydroxymethyl group, hydroxyethyl group, hydroxylpropyl group, methoxy group, ethoxy group, n-propoxy group, n- Butoxy group, n-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, trifluoro Examples thereof include a methoxy group, a methylamino group, a dimethylamino group, a trimethylamino group, an ethylamino group, a propylamino group and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, a biphenyl group and the like.
Examples of the substituent include an alkyl group, an alkyl group having a halogen such as a fluoro group and a chloro group, a halogen group, an amino group, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, a sulfonic acid group and the like.

In the above general formula (1), n1 and n2 are each independently an integer of 0 to 4, preferably an integer of 1 to 2. In addition, n1 + n2 is 1 or more.
In the above general formula (1), n3 and n4 are independently integers of 0 to 3, preferably an integer of 0 to 1.
In the above general formula (2), n5 is an integer of 1 to 4, preferably an integer of 1 to 2.
In the above general formula (2), n6 is an integer of 0 to 3, preferably an integer of 0 to 1.
In the above general formula (3), n7 and n8 are each independently an integer of 0 to 4, preferably an integer of 1 to 2. In addition, n7 + n8 is 1 or more.
In the above general formula (3), n9 and n10 are independently integers of 0 to 3, preferably an integer of 0 to 1.
In the above general formula (4), n11 is an integer of 1 to 4, preferably an integer of 1 to 2.
In the above general formula (4), n12 is an integer of 0 to 3, preferably an integer of 0 to 1.

Examples of the diamine compound satisfying the above general formula (1) include, but are not limited to, the following.

Examples of the diamine compound satisfying the above general formula (2) include, but are not limited to, the following.

Examples of the diamine compound satisfying the above general formula (3) include, but are not limited to, the following.

Examples of the diamine compound satisfying the above general formula (4) include, but are not limited to, the following.

The composition ratio of the diamine compounds represented by the general formulas (1) and (2) in the copolymer is preferably 5 mol% or more and 40 mol% or less, and more preferably 15 mol% or more and 35 mol% or less. This can be expected to adjust the dissolution rate during development and improve the ring closure rate during low-temperature curing.

The composition ratio of the diamine compounds represented by the general formulas (3) and (4) in the copolymer is preferably 10 mol% or more and 45 mol% or less, and more preferably 15 mol% or more and 35 mol% or less. This can be expected to adjust the dissolution rate during development and improve the ring closure rate during low-temperature curing.

The carboxylic acid anhydride constituting the copolymer is preferably represented by the following general formula (5).

In the above general formula (5), X is a tetravalent organic group.
Examples of the tetravalent organic group include, but are not limited to, a group having the following structure.
Note that a in the structure is an integer of 0 to 2 that is independently selected from each other, and is preferably 0 to 1 and particularly preferably 0 from the viewpoint of solvent solubility. Further, b in the structure is an integer of 1 to 3, and is preferably 2 to 3 and particularly preferably 3 from the viewpoint of solvent solubility and transparency of the cured product.

Among the tetravalent organic groups described above, a group having the following structure is preferable from the viewpoint of solvent solubility.

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

Among the tetravalent organic groups described above, a group having the following structure is particularly preferable from the viewpoint of the dissolution rate and dissolution contrast of the exposed portion.

The composition ratio of the carboxylic acid anhydride in the copolymer is preferably 0 mol% or more and 40 mol% or less, and more preferably 0 mol% or more and 35 mol% or less. As a result, the dissolution rate of the exposed portion can be accelerated and the resolution can be improved.

The carboxyl chloride product constituting the copolymer is preferably represented by the following general formula (6).

In the above general formula (6), Y is selected from single bond, O and divalent organic groups. As the divalent organic group, those described above can be used.

In the above general formula (6), Z is a halogen element, preferably Cl.

The composition ratio of the carboxyl chloride in the copolymer is preferably 10 mol% or more and 50 mol% or less, and more preferably 15 mol% or more and 50 mol% or less. As a result, the dissolution rate of the unexposed portion can be suppressed.

The photosensitive resin composition may contain other reaction components as long as the characteristics of the present invention are not impaired.

The number average molecular weight (Mn) of the copolymer is preferably 2,000 to 30,000, more preferably 5,000 to 10,000. 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.
The weight average molecular weight (Mw) of the copolymer is preferably 4,000 to 80,000, and more preferably 10,000 to 30,000. Thereby, the occurrence of cracks in the cured product can be further reduced.
Further, Mw / Mn is preferably 2.0 to 4.0, and more preferably 2.3 to 3.0. As a result, residues and swelling generated during development are reduced.
In the present invention, 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.

The glass transition temperature (Tg) of the copolymer after the ring closure reaction 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.
In the present invention, Tg is a value obtained by differential scanning calorimetry (DSC) in accordance with JIS K 7121.

The carboxyl group concentration in the copolymer before the ring closure reaction is preferably 300 to 800 mol / g, more preferably 300 to 650 mol / g. Thereby, the dissolution rate and the dissolution contrast of the exposed portion can be further improved.

The hydroxyl group concentration in the copolymer before the ring closure reaction is preferably 200 to 600 mol / g, more preferably 300 to 500 mol / g. Thereby, the dissolution rate and the dissolution contrast of the exposed portion can be further improved.

The fluorine concentration in the copolymer is preferably 20 to 200 mol / g, more preferably 50 to 100 mol / g. Thereby, the solvent solubility and the transparency of the cured product can be further improved.

As long as the characteristics of the present invention are not impaired, the copolymer contained in the photosensitive resin composition of the present invention may have a partially ring-closed structure.

[(B) Photosensitizer]
The photosensitive resin composition of the present invention contains a photosensitive agent, whereby the solubility of the photosensitive resin composition in an alkaline developer can be adjusted. Examples of the photosensitizer include a photoacid generator and a photobase generator. Among these, a photoacid generator is preferable from the viewpoint of dissolution contrast.
This photosensitizer can be blended in a known and commonly used ratio. For example, for a photoacid generator, 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer. It is preferable to mix in the ratio of.
The photosensitive resin composition may contain two or more kinds of photosensitive agents.

The photoacid generator is a compound that generates an acid by irradiation with light such as ultraviolet rays or visible light. For example, a naphthoquinone diazide compound, a diarylsulfonium salt, a triarylsulfonium salt, a dialkylphenacylsulfonium salt, a diaryliodonium salt, and an aryldiazonium Examples thereof include salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyimide sulfonates, aromatic sulfamides and benzoquinone diazosulfonic acid esters.
Among the above, the naphthoquinone diazide compound is preferable from the viewpoint of dissolution contrast.
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 adducts of tetrahydroxybenzophenone (eg, BS550, BS570, BS599 manufactured by Sanpo Chemical Laboratory Co., Ltd.), and 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α. , Β-Dimethylbenzyl} phenol naphthoquinone diazide adduct (for example, TKF-428, TKF-528 manufactured by Sanpo Chemical Laboratory Co., Ltd.) and the like.

The photobase generator produces one or more basic substances (secondary amine, tertiary amine, etc.) by changing the molecular structure by irradiation with light such as ultraviolet rays or visible light, or by cleaving the molecule. It is a compound that
The photobase generator may be an ionic photobase generator or a nonionic photobase generator, but an ionic photobase generator is preferable from the viewpoint of the sensitivity of the photosensitive resin composition.
Examples of the ionic photobase generator include a salt of an aromatic component-containing carboxylic acid and a tertiary amine, and examples of this commercially available product include WPBG-082 and WPBG- of ionic PBG manufactured by Wako Pure Chemical Industries, Ltd. 167, WPBG-168, WPBG-266, WPBG-300 and the like can be mentioned.
Examples of the nonionic photobase generator include α-aminoacetophenone compound, oxime ester compound, N-formylated aromatic amino group, N-acylated aromatic amino group, nitrobenzyl carbamate group and alcooxybenzyl. Examples thereof include compounds having a substituent such as a carbamate group.
Other photobase generators include WPBG-018 (trade name: 9-anthrylmethyl N, N'-diesylcarbamate) and WPBG-027 (trade name: (E) -1- [3- (2), manufactured by Wako Junyaku Co., Ltd. -Hydroxyphenyl) -2-propenoyl] piperidine), WPBG-140 (trade name: 1- (anthraquinone-2-yl) ethyl imidazolecarboxylate), WPBG-165 and the like.

[Crosslinking agent]
The photosensitive resin composition of the present invention can contain a cross-linking agent. By adding a cross-linking agent, the curing temperature of the photosensitive resin composition can be lowered. The cross-linking agent is not particularly limited, and examples thereof include known and commonly used cross-linking agents.
In the present specification, the cross-linking agent is preferably a compound capable of reacting with a carboxyl group or a hydroxyl group in the copolymer to form a cross-linked structure.
Examples of the polyimide precursor or the compound that reacts with the hydroxyl group in the polyimide include a cyclic ether group such as an epoxy group, a cross-linking agent having a cyclic thioether group such as an episulfide group, and a hydroxyl group on an alkylene group having 1 to 12 carbon atoms such as a methylol group. Examples thereof include a cross-linking agent having an alcoholic hydroxyl group bonded with, a compound having an ether bond such as an alkoxymethyl group, a cross-linking agent having a triazine ring structure, and a urea-based cross-linking agent.
Among these, a cyclic ether group, particularly a cross-linking agent having an epoxy group and an alcoholic hydroxyl group, particularly a cross-linking agent having a methylol group to which a hydroxyl group is bonded are preferable.
As the cross-linking agent, one type may be used alone, or two or more types may be used in combination.
The blending amount of the cross-linking agent in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the non-volatile component of the copolymer. Further, 0.1 to 20 parts by mass is more preferable.

(Crosslinking agent with epoxy group)
The photosensitive resin composition of the present invention preferably contains a cross-linking agent having an epoxy group as a cross-linking agent. The cross-linking agent having an epoxy group thermally reacts with the polyimide precursor or the hydroxyl group of the polyimide to form a cross-linked structure. The number of functional groups of the cross-linking agent having an epoxy group is preferably 2 to 4. When the photosensitive resin composition contains a cross-linking agent having an epoxy group, low-temperature curability can be obtained, and the dissolution contrast of the formed dry coating film can be further improved.
Among the cross-linking agents having an epoxy group, a bifunctional or higher functional epoxy compound having a naphthalene skeleton is preferable. Not only can an excellent insulating film be obtained due to its flexibility and chemical resistance, but it is also possible to reduce the CTE, which has an antinomy relationship with flexibility, and it is possible to suppress the occurrence of warpage and cracks in the insulating film. Further, a bisphenol A type epoxy compound can also be preferably used from the viewpoint of flexibility.

（一般式（７）中、Ｒ^Ａ１は２〜１０価の有機基を示す。Ｒ^Ａ２は、それぞれ独立に、水素原子または炭素数１〜４のアルキル基を示す。ｒは２〜１０の整数を示す。） (Crosslinking agent having a methylol group)
The photosensitive resin composition of the present invention preferably contains a cross-linking agent having a methylol group as a cross-linking agent. The cross-linking agent having a methylol group preferably has two or more methylol groups, and more preferably a compound represented by the following general formula (7).

(In the general formula ^{(7), .R A2 R A1} is shown a 2-10 monovalent organic group, each independently, .r represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms 2-10 integer Shows.)

In the general formula (7), ^RA1 is preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent.

In the general formula (7), ^RA2 is preferably a hydrogen atom.

In the general formula (7), r is preferably an integer of 2 to 4, and more preferably 2.

Further, the cross-linking agent having a methylol group preferably has a fluorine atom, and more preferably has a trifluoromethyl group. The fluorine atom or the trifluoromethyl group is preferably to 2-10 monovalent organic group represented by R ^A1 in the general formula (5) has, it R ^A1 is di (trifluoromethyl) methylene group Is preferable. Further, the cross-linking agent having a methylol group preferably has a bisphenol structure, and more preferably has a bisphenol AF structure.

[Plasticizer]
The photosensitive resin composition of the present invention preferably contains a plasticizer. In the present invention, the plasticizing action of the plasticizer, that is, the aggregating action between the polymer molecular chains is reduced, and the mobility and flexibility between the molecular chains are improved, so that the thermal molecular motion of the polyimide precursor is improved. It is considered that low temperature curability is imparted by promoting the cyclization reaction. The plasticizing agent is not particularly limited as long as it is a compound that improves plasticity, and is a bifunctional (meth) acrylic compound, a sulfonamide compound, a phthalic acid ester compound, a maleic acid ester compound, an aliphatic dibasic acid ester, and a phosphoric acid ester. , Ether compounds such as crown ether and the like. Above all, a bifunctional (meth) acrylic compound is preferable. The bifunctional (meth) acrylic compound is preferably a compound that does not form a crosslinked structure with other components in the composition. Further, the bifunctional (meth) acrylic compound is preferably a compound that forms a linear structure by self-polymerization from the viewpoint of further relaxing the internal stress of the cured product. The blending amount of the plasticizer in the photosensitive resin composition of the present invention is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the non-volatile component of the copolymer.

Among the bifunctional (meth) acrylic compounds, the di (meth) acrylate of the alkylene oxide adduct (such as ethylene oxide and propylene oxide) of the diol and the bifunctional polyester (meth) acrylate are preferable, and the bifunctional polyester (meth) acrylate is preferable. ) Acrylate is more preferable.

As the di (meth) acrylate of the alkylene oxide adduct of the diol, specifically, the diol is preferably alkylene oxide-modified and then the (meth) acrylate is added to the terminal, and the diol having an aromatic ring is more preferable. .. For example, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A PO (propylene oxide) adduct diacrylate and the like can be mentioned. The specific structure of the di (meth) acrylate of the alkylene oxide adduct of the diol is shown in the following general formula (8), but the present invention is not limited thereto.

In the general formula (8), p + q is 2 or more, preferably 2 to 40, and more preferably 3.5 to 25.

[Adhesive]
The photosensitive resin composition of the present invention preferably contains an adhesive, which can improve the adhesiveness to a base material or the like. As the adhesive, a silane coupling agent, a titanate coupling agent and an aluminum coupling agent can be used.
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 diisopropyrate and the like. Among the above, N-phenyl-3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane. Is preferable because it improves the adhesion to the substrate and does not adversely affect the development speed.

The blending amount of the adhesive in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the non-volatile component of the copolymer.

[Thermal acid generator, sensitizer, and other ingredients]
The photosensitive resin composition of the present invention includes a heat acid generator known for further promoting the cyclization reaction of the copolymer and known for improving the photosensitivity within a range not impairing the effect of the present invention. It is also possible to add a sensitizer or the like. Further, in order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various other organic or inorganic low molecular weight or high molecular weight compounds may be blended. For example, a surfactant, a leveling agent, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon and layered silicate. Further, various colorants, fibers and the like may be blended with the photosensitive resin composition of the present invention.

[solvent]
The photosensitive resin composition of the present invention may contain a solvent. In the present invention, the solvent is not particularly limited, but a solvent having a boiling point of 200 ° C. or lower is preferable in consideration of the persistence when the heating temperature of the pattern film is lowered.
Examples of the solvent having such a melting point include -2-methoxy-1-methyl ethyl acetate (PGMEA), 4-methyl-2-pentanone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone and hexa. Methyl sulfoxide, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-ethoxy Ethyl propionate, 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 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 can be mentioned.

The content of the solvent in the photosensitive resin composition is not particularly limited and is preferably changed as appropriate according to the intended use. For example, with respect to 100 parts by mass of the polyimide precursor contained in the photosensitive resin composition. , 200 to 2000 parts by mass or less.
The photosensitive resin composition may contain two or more kinds of solvents.

[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 by using the photosensitive resin composition. Further, the dry film may be provided with a film (so-called protective film) that further protects (covers) the resin layer formed on the film.

(the film)
The film is not particularly limited, and for example, a film made of a polyester film such as polyethylene terephthalate and polyethylene naphthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a thermoplastic resin such as a polystyrene film can be used. it can.
Among these, polyethylene terephthalate is preferable from the viewpoint of heat resistance, mechanical strength, handleability and the like. Further, a laminate of these films can also be used as a film.

Further, the thermoplastic resin film as described above is preferably a film stretched in the uniaxial direction or the biaxial direction from the viewpoint of improving the mechanical strength.

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

(Resin layer)
The resin layer is formed by using the above-mentioned photosensitive resin composition, and its thickness is not particularly limited and is preferably changed as appropriate depending on the intended use. For example, 1 μm or more and 150 μm. It can be as follows.

The resin layer has a uniform thickness of the photosensitive resin composition on the film with 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. It can be formed by applying and drying.
Further, in another embodiment, the resin layer can be formed by applying a photosensitive resin composition on a protective film and drying it.

(Protective film)
In the present invention, it is preferable to laminate a peelable protective film on the surface of the resin layer for the purpose of preventing dust from adhering to 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 film when the protective film is peeled off. For example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper and the like can be used.

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

[Cured product]
The cured product of the present invention is characterized by being formed by using the above-mentioned photosensitive resin composition. Further, the cured product may have a pattern formed.
Hereinafter, a method for producing a cured product of the present invention will be described.

[First step]
In the method for producing a cured product of the present invention, a photosensitive resin composition is applied onto a substrate to form a coating film, which is dried, or the resin layer is transferred from the dry film onto the substrate. This includes a step of forming a dry coating film.

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 with a spray coater. And the inkjet method and the like.

As a method for drying the coating film, a method such as air drying, heat drying using an oven or a hot plate, and vacuum drying is used.
Further, it is desirable that the coating film is dried under conditions that do not cause ring closure of the polyimide precursor in the photosensitive resin composition.
Specifically, it is preferable to carry out natural drying, blast drying, or heat drying at 70 to 140 ° C. for 1 to 30 minutes. Moreover, since the operation method is simple, it is preferable to dry for 1 to 20 minutes using a hot plate.
Vacuum drying is also possible, and in this case, it can be performed at room temperature for 20 minutes to 1 hour.

The transfer of the dry film onto the substrate is preferably carried out under pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, when a circuit-formed substrate is used, even if the surface of the circuit board is uneven, the resin layer of the dry film fills the unevenness of the circuit board under vacuum conditions. , No air bubbles are mixed in, and the hole filling property of the concave portion on the substrate surface is improved.

As the base material, in addition to printed wiring boards and flexible printed wiring boards whose circuits are formed in advance with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, etc. It is made of materials such as copper-clad laminates for high-frequency circuits using synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc., and all grades (FR-4, etc.) of copper-clad laminates. In addition, metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

[Second step]
Next, the coating film is irradiated with active energy rays and exposed selectively through a photomask having a pattern or non-selectively through a photomask.

As the active energy ray, for example, one having a wavelength capable of activating the photoacid generator as the (B) photosensitizer is used. Specifically, the active energy ray preferably has a maximum wavelength in the range of 350 to 410 nm.
The amount of exposure varies depending on the film thickness and the like, but is generally 10 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .
The exposure machine used for the above-mentioned active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. Further, 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) can also be used.

[Third step]
The step is performed as needed, and a part of the copolymer in the unexposed portion may be closed by heating the coating film for a short time. Here, the ring closure rate is about 30%. The heating time and heating temperature are appropriately changed depending on the type of polyimide precursor, coating film thickness, and (B) type of photosensitizer.

[Fourth step]
Next, the exposed coating film is treated with a developing solution to remove the exposed portion in the coating film, whereby a pattern film can be obtained.
In this step, any method can be selected from conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment.

The developing solution includes 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 tetrabutylammonium hydroxide. Examples thereof include aqueous solutions of quaternary ammonium salts and the like.
Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol or a surfactant may be added in an appropriate amount.

Then, if necessary, the coating film is washed with a rinsing liquid to obtain a patterned film.
Distilled water, methanol, ethanol, isopropyl alcohol and the like can be used alone or in combination as the rinsing solution. Moreover, you may use the said solvent as a developer.

[Fifth step]
Next, the pattern film is heated to obtain a cured coating film (cured product).
By the heating step, a cyclization reaction occurs in the copolymer contained in the photosensitive resin composition, and a polyimide structure and / or a polybenzoxazole structure is formed.

The heating temperature is preferably 120 to 250 ° C., more preferably 150 to 200 ° C. from the viewpoint of preventing warpage 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.
It may be under a heating atmosphere (gas) or air, or under an inert gas such as nitrogen or argon.

[Use]
The use of the photosensitive resin composition of the present invention is not particularly limited, and for example, it is suitably used as a forming material for paints, printing inks, adhesives, display devices, semiconductor elements, electronic parts, optical parts, building materials and the like.

Specifically, examples of the material for forming 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 resist material, a buffer coat film, an insulating film for a rewiring layer of a wafer level package (WLP), and the like.
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.
Further, 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 mainly 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. Suitable as a protective film for a device, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, an insulating material for a passive component, a protective film for a printed wiring board such as a solder resist or a coverlay film, and a liquid crystal alignment film. Available.

Hereinafter, 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, "part" and "%" are all based on mass unless otherwise specified.

(Reference Example 1: Synthesis of copolymer A-1)
64 g of N-methylpyrrolidone was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl). Stir 4.23 g (7.98 mmol) of -4,4'-methylenedianiline (HFA-MDA) and 2.92 g (7.98 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP). Dissolved.

After confirming that the monomer was completely dissolved, 3.12 g (7.02 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added as a solid over 5 minutes, and at room temperature. Stirring was continued for 1 hour.

Then, the flask is immersed in a surface bath, and 2.07 g (7.02 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) is added as a solid while keeping the inside of the flask at 0 to 5 ° C. in an ice bath. The mixture was stirred for 30 minutes. Then, stirring was continued for 4 hours at room temperature.

0.63 g (3.83 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. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered.
After recovery, the copolymer was dried under reduced pressure to obtain A-1 having a carboxyl group terminal and having the following repeating structure. The number average molecular weight (Mn) of the copolymer A-1 was 6,070, the weight average molecular weight (Mw) was 15,780, and Mw / Mn was 2.60. The obtained copolymer A-1 had a carboxyl group concentration of 586 g / mol, a hydroxyl group concentration of 391 g / mol, and a fluorine concentration of 81 g / mol.

(Reference Example 2: Synthesis of copolymer A-2)
69 g of N-methylpyrrolidone was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 2.59 g (4.88 mmol) of HFA-MDA and 4.17 g (11.38 mmol) of 6FAP were dissolved by stirring.

After confirming that the monomer was completely dissolved, 5,5'-[1-methyl-1,1-ethanediylbis (1,4-phenylene) bisoxy] bis (isobenzofuran-1,3-dione) (BPADA) 5.10 g (9.62 mmol) was added as a solid over 5 minutes and stirring was continued for 1 hour at room temperature.

Then, the flask was immersed in a front bath, 1.22 g (4.12 mmol) of DEDC was added as a solid while keeping the inside of the flask at 0 to 5 ° C., and the mixture was stirred in an ice bath for 30 minutes. Then, stirring was continued for 4 hours at room temperature. 0.82 g (5.01 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. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered.

After recovery, the copolymer was dried under reduced pressure to obtain a copolymer A-2 having a carboxyl group terminal and having the following repeating structure. The number average molecular weight (Mn) of the copolymer A-2 was 5,000, the weight average molecular weight (Mw) was 13,150, and Mw / Mn was 2.63. The obtained copolymer A-2 had a carboxyl group concentration of 550 g / mol, a hydroxyl group concentration of 423 g / mol, and a fluorine concentration of 54 g / mol.

(Reference Example 3: Synthesis of Copolymer A-3)
62 g of N-methylpyrrolidone was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 5.85 g (11.04 mmol) of HFA-MDA and 1.73 g (4.73 mmol) of 6FAP were dissolved by stirring.

After confirming that the monomer was completely dissolved, 1.32 g (4.27 mmol) of oxydiphthalic anhydride (ODPA) was added as a solid over 5 minutes, and stirring was continued at room temperature for 1 hour. Then, the flask was immersed in a front bath, and 2.94 g (9,96 mmol) of DEDC was added as a solid while keeping the inside of the flask at 0 to 5 ° C., and the mixture was stirred in an ice bath for 30 minutes. Then, stirring was continued for 4 hours at room temperature. 0.51 g (3.09 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. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered.

After recovery, the copolymer was dried under reduced pressure to obtain a copolymer A-3 having a carboxyl group terminal and having the following repeating structure. The number average molecular weight (Mn) of the copolymer A-3 was 7,080, the weight average molecular weight (Mw) was 18,120, and Mw / Mn was 2.56. The obtained copolymer A-3 had a carboxyl group concentration of 621 g / mol, a hydroxyl group concentration of 365 g / mol, and a fluorine concentration of 74 g / mol.

(Reference Example 4: Synthesis of copolymer A-4)
60 g of N-methylpyrrolidone was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 4.26 g (8.04 mmol) of HFA-MDA and 2.94 g (8.04 mmol) of 6FAP were stirred and dissolved.

After confirming that the monomer was completely dissolved, the flask was immersed in a front bath, and while keeping the temperature inside the flask at 0 to 5 ° C., 4.11 g (13.92 mmol) of DEDC was added as a solid, and the mixture was placed in an ice bath for 30 minutes. Stirred. Then, stirring was continued for 4 hours at room temperature. 0.71 g (4.31 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. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered.

After recovery, the copolymer was dried under reduced pressure to obtain a copolymer A-4 having a carboxyl group terminal and having the following repeating structure. The number average molecular weight (Mn) of the copolymer A-4 was 3,990, the weight average molecular weight (Mw) was 10,090, and Mw / Mn was 2.53. The obtained copolymer A-4 had a carboxyl group concentration of 0 g / mol, a hydroxyl group concentration of 336 g / mol, and a fluorine concentration of 82 g / mol.

(Reference Example 5: Synthesis of copolymer A-5)
100 g of N-methylpyrrolidone was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 5.16 g (25.75 mmol) of diaminodiphenyl ether was stirred and dissolved.

After confirming that the monomer was completely dissolved, 5.29 g (24.25 mmol) of pyromellitic anhydride (PMDA) was added as a solid over 5 minutes, and stirring was continued at room temperature for 1 hour. Then, 0.49 g (2.98 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. The stirred solution was poured into 600 mL of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered.

After recovery, the copolymer was dried under reduced pressure to obtain a copolymer A-5 having a carboxyl group terminal and having the following repeating structure. The number average molecular weight (Mn) of the copolymer A-5 was 6,800, the weight average molecular weight (Mw) was 17,000, and Mw / Mn was 2.51. The obtained copolymer A-5 had a carboxyl group concentration of 210 g / mol, a hydroxyl group concentration of 0 g / mol, and a fluorine concentration of 0 g / mol.

(Reference Example 6: Synthesis of Polybenzoxazole Precursor)
10.0 g (27.3 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 1500 g of N-methylpyrrolidone in a 0.5 liter flask equipped with a stirrer and a thermometer. ..

Then, the flask is immersed in an ice bath, and 8.78 g (29.8 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride is added as a solid over 10 minutes while keeping the temperature inside the flask at 0 to 5 ° C. Was stirred for 30 minutes.

Then, stirring was continued for 18 hours at room temperature. The stirred solution was poured into 700 mL of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered.

Then, the obtained solid was dissolved in 420 mL of acetone and put into 1 L of ion-exchanged water.
The precipitated individual was recovered and dried under reduced pressure to obtain a carboxyl group-terminated polybenzoxazole precursor. Mw was 29,500, Mn was 11,600, and Mw / Mn was 2.54. The obtained polybenzoxazole precursor had a carboxyl group concentration of 0 g / mol, a hydroxyl group concentration of 295 g / mol, and a fluorine concentration of 98 g / mol.

<Example 1>
100 parts by mass of the copolymer A-1 obtained in Reference Example 1, 20 parts by mass of the naphthoquinone diazide compound (TKF-528 manufactured by Sanpo Chemical Laboratory Co., Ltd.), and an adhesive (KBM-manufactured by Shinetsu Chemical Industry Co., Ltd.). 573) was put into a light-shielding container so as to have 5 parts by mass and PGMEA to 400 parts by mass, and the mixture was stirred to obtain a varnish containing a photosensitive resin composition.

<Examples 2 to 4 and Comparative Examples 1 to 2>
A varnish was obtained in the same manner as in Example 1 except that the copolymer A-1 was changed to the copolymers A-2 to A-6 as shown in Table 2.

<< Solubility evaluation >>
The varnishes obtained in the above Examples and Comparative Examples were visually observed, and the solubility was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 2.
Moreover, the solvent was changed to 4-methyl-2-pentanone, the solubility was evaluated in the same manner as above, and the results are summarized in Table 1.
(Evaluation criteria)
〇: There was no undissolved residue (precipitate), and no varnish turbidity was observed.
Δ: There was no undissolved residue, but varnish was turbid.
X: There was undissolved residue.

<< Evaluation of dissolution rate >>
The varnishes obtained in the above examples and the varnishes obtained in Comparative Examples 1 and 2 in which PGMEA was changed to γ-butyrolactone were prepared.
This varnish was applied to a silicon substrate using a spin coater to a film thickness of about 2 μm.
Then, it was dried at 110 ° C. for 3 minutes using a hot plate to obtain a dry coating film. A high-pressure mercury lamp was used for the coating film, and half of the dry coating film was irradiated with i-ray ^{of 200 mJ / cm 2.} After exposure, soak in 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, measure the dissolution time, calculate the dissolution rate by the following formula, and use the dissolution rate of the exposed and unexposed areas as the following evaluation criteria. Evaluated based on. The evaluation results are summarized in Table 2.
Further, the dissolution contrast (dissolution rate of the exposed part / dissolution rate of the unexposed part) was obtained from the obtained dissolution rate of the exposed part and the dissolution rate of the unexposed part, and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 2.
Dissolution rate = initial film thickness (nm) / dissolution time (s)
(Exposure part dissolution rate evaluation standard)
⊚: dissolution rate 500 nm / s or more, 1000 nm / s or less ◯: dissolution rate 200 nm / s or more, less than 500 nm / s ×: dissolution rate less than 200 nm / s, or more than 1000 nm / s
(Evaluation criteria for dissolution rate in unexposed areas)
⊚: Dissolution rate less than 5 nm / s,
◯: Dissolution rate 5 nm / s or more, less than 20 nm / s ×: Dissolution rate 20 nm / s or more (dissolution contrast evaluation standard)
⊚: Melt contrast is 200 or more ○: Melt contrast is 100 or more and less than 200 ×: Melt contrast is less than 100

<< Evaluation of resolution >>
Similar to the above dissolution rate evaluation, the varnishes obtained in the above Examples and the varnishes obtained in Comparative Examples 1 and 2 in which PGMEA was changed to γ-butyrolactone were prepared.
This varnish was applied to a silicon substrate using a spin coater to a film thickness of about 2 μm.
Then, it was dried at 110 ° C. for 3 minutes using a hot plate to obtain a dry coating film. A high-pressure mercury lamp was used for the coating film, and broad light of ^{200 mJ / cm 2 was irradiated through a mask on which a pattern was engraved.} After exposure, it was developed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds and rinsed with water to obtain a positive pattern film.
The L / S (line / space) of the pattern engraved on the mask is changed from 1 μm / 1 μm to 30 μm / 30 μm (where L = S, where L and S are integers), and the electron microscope (SEM “SEM” The minimum L / S capable of forming a poly-type pattern film capable of patterning the exposed portion observed by JSM-6010 ”) without scum (development residue) was obtained and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 2.
(Evaluation criteria)
⊚: Even when the L / S of the pattern was 2 μm / 2 μm, it was possible to form a poly-type pattern film capable of patterning the exposed portion without scum (development residue).
◯: When the L / S of the pattern was 2 μm / 2 μm, it was not possible to form a poly-type pattern film capable of patterning the exposed portion without scum (development residue), but the L / S of the pattern was 3 μm / 3 μm. In the case of, it was possible.
Δ: When the L / S of the pattern was 3 μm / 3 μm, it was not possible to form a poly-type pattern film capable of patterning the exposed portion without scum (development residue), but the L / S of the pattern was 5 μm / 5 μm. In the case of, it was possible.
X: When the L / S of the pattern was 5 μm / 5 μm, it was not possible to form a poly-type pattern film capable of patterning the exposed portion without scum (development residue).

<< Evaluation of storage stability >>
The varnishes obtained in the above examples and the varnishes obtained in Comparative Examples 1 and 2 in which PGMEA was changed to γ-butyrolactone were prepared.
The viscosities of these varnishes were measured using a cone plate type viscometer (manufactured by Toki Sangyo Co., Ltd., TPE-100, rotation speed 50 rpm, 25 ° C.).
The varnish was then kept in a homeothermic at 4 ° C. for 7 days. The viscosity after 7 days was measured in the same manner, the viscosity change rate was calculated, and the evaluation was made based on the following evaluation criteria. The evaluation results are shown in Table 2.
⊚: Viscosity change rate is less than 5% ◯: Viscosity change rate is 5% or more and less than 10% ×: Viscosity change rate is 10% or more and less than 15%

As is clear from the evaluation results shown in Table 1 above, at least one of the diamine compounds represented by the general formulas (1) and (2) and at least one of the diamine compounds represented by the general formulas (3) and (4). The photosensitive resin composition containing a copolymer, which is a reaction product of at least one of a carboxylic acid anhydride and a carboxylic acid chloride, has excellent dissolution rate and dissolution contrast in an exposed portion, and achieves high resolution. You can see that you can. Further, it can be seen that the copolymer has high solubility in a low boiling point solvent such as PGMEA and 4-methyl-2-pentanone. Furthermore, it can be seen that the photosensitive resin composition has high storage stability.

Claims (15)

(A) At least one of the diamine compounds represented by the following general formulas (1) and (2), at least one of the diamine compounds represented by the following general formulas (3) and (4), and a carboxylic acid anhydride and a carboxylic acid. A copolymer, which is a reaction product with at least one of the chlorides,
(B) Photosensitizer and
A photosensitive resin composition comprising.

(During the ceremony,
A is selected from single bond, O and divalent organic groups.
B is a fluoroalcohol,
R is a substituted or unsubstituted alkyl or aryl group.
n1 and n2 are independently integers from 0 to 4, and n1 + n2 is 1 or more.
n3 and n4 are independently integers from 0 to 3, respectively.
n5 is an integer of 1 to 4 and
n6 is an integer from 0 to 3 and
n7 and n8 are independently integers from 0 to 4, and n7 + n8 is 1 or more.
n9 and n10 are independently integers of 0 to 3, respectively.
n11 is an integer of 1 to 4,
n12 is an integer from 0 to 3. ) The photosensitive resin composition according to claim 1, wherein the fluorine concentration in the copolymer is 20 to 200 mol / g. The photosensitive resin composition according to claim 1 or 2, wherein the carboxyl group concentration in the copolymer is 300 to 800 mol / g. The photosensitive resin composition according to any one of claims 1 to 3, wherein the hydroxyl group concentration in the copolymer is 200 to 600 mol / g. The photosensitive resin composition according to any one of claims 1 to 4, wherein the composition ratio of the diamine compound represented by the general formulas (1) and (2) in the copolymer is 5 mol% or more and 40 mol% or less. Stuff. The photosensitive resin composition according to any one of claims 1 to 5, wherein the composition ratio of the diamine compound represented by the general formulas (3) and (4) in the copolymer is 10 mol% or more and 45 mol% or less. Stuff. The photosensitive resin composition according to any one of claims 1 to 6, wherein A in the general formulas (1) and (3) is selected from a divalent organic group having the following structure.

(In the above formula, a is an integer of 0 to 2 independently, and b is an integer of 1 to 3 independently.) Claims 1 to 10, wherein the fluoroalcohol represented by B in the general formulas (1) and (2) has 1 to 10 carbon atoms independently, and the fluorine number has 1 to 10 independently. 7. The photosensitive resin composition according to any one of 7. The photosensitive resin composition according to any one of claims 1 to 8, wherein the carboxylic acid anhydride is represented by the following general formula (5).

(In the formula, X is a tetravalent organic group having the following structure.) The photosensitive resin composition according to any one of claims 1 to 9, wherein the carboxyl chloride is represented by the following general formula (6).

(During the ceremony,
Y is selected from single bond, O and divalent organic groups,
Z is a halogen element. ) The photosensitive resin composition according to any one of claims 1 to 10, further comprising an adhesive. The photosensitive resin composition according to any one of claims 1 to 11, wherein the photosensitive agent is a naphthoquinone diazide compound. A dry film comprising a resin layer formed of the photosensitive resin composition according to any one of claims 1 to 12 on the film. A cured product, which is formed of the photosensitive resin composition according to any one of claims 1 to 12 or the resin layer of the dry film according to claim 13. An electronic component comprising the cured product according to claim 14 as a forming material.