JP2021152634A - Negative photosensitive resin composition, negative photosensitive polymer and applications thereof - Google Patents

Abstract

To provide a negative photosensitive resin composition that can produce a cured product such as a film, which has excellent mechanical strength, resists shrinkage by curing, and has excellent dimensional stability.SOLUTION: A negative photosensitive resin composition has polyimide (A), crosslinker having polyfunctional (meth)acrylate (B), and photopolymerization initiator (C).SELECTED DRAWING: None

Description

The present invention relates to a negative photosensitive resin composition, a negative photosensitive polymer, and uses thereof.

Since polyimide resin has high mechanical strength, heat resistance, insulating property, and solvent resistance, it is widely used as a thin film for electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display elements and semiconductors. There is.
Patent Document 1 discloses a polyimide precursor containing an acid dianhydride, a diamine, and 1,3-bis (3-aminophenoxy) benzene.
Patent Documents 2 to 4 disclose photosensitive resin compositions containing a polyimide precursor having a predetermined structure.

Patent Document 5 discloses a negative photosensitive resin precursor composition containing a polymer, a phenolic low molecular weight compound, a low molecular weight compound having a polymerizable group, and a photopolymerization initiator. ing.

Patent Document 6 discloses a resin composition containing a polyimide resin having a predetermined structure.
Patent Document 7 discloses a photosensitive polyimide obtained by reacting a polyimide with an isocyanate compound having a carbon-carbon double bond.
Patent Document 8 discloses a photosensitive resin composition containing a polyimide having a predetermined repeating unit, a photoinitiator, and an organic solvent.
In the examples of Patent Documents 6 to 8, amine, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride as an acid anhydride, and a compound having a (meth) acrylate group as a modified product are used. The synthetic method used is described.

Japanese Unexamined Patent Publication No. 2013-241607 Japanese Unexamined Patent Publication No. 2013-95894 Japanese Unexamined Patent Publication No. 2014-172994 International Publication No. 2010/11335 Japanese Unexamined Patent Publication No. 2004-133435 Japanese Unexamined Patent Publication No. 2018-070829 Japanese Unexamined Patent Publication No. 2000-147761 Japanese Unexamined Patent Publication No. 05-232701

However, in the conventional techniques described in Patent Documents 1 to 8, there is room for improvement in the mechanical strength of a film or the like containing polyimide obtained from a photosensitive resin composition.

Further, in the conventional techniques described in Patent Documents 1 to 8, when a photosensitive resin composition containing a polyimide precursor and an organic solvent is applied and the obtained coating film is exposed and then cured, the polyimide precursor is used. Curing shrinkage when changing to polyimide affects the dimensional stability of the film. If the photosensitive resin composition is prepared by dissolving polyimide in an organic solvent, the curing shrinkage of the obtained resin is suppressed, but the conventional polyimide has room for improvement in solubility in an organic solvent.

The present inventors have found that a polyimide having a specific structure can solve the above-mentioned problems, and have completed the present invention.
That is, the present invention can be shown below.

（一般式（１−１）中、Ｑは、２価〜４価の炭素数１〜１０の有機基を示し、複数存在するＱは同一でも異なっていてもよい。
Ｒは、水素原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基を示し、複数存在するＲは同一でも異なっていてもよい。
ｍ１およびｍ２は、それぞれ独立して１〜３の整数を示す。
Ｘは単結合、−ＳＯ_２−、−Ｃ（＝Ｏ）−、炭素数１〜５の直鎖または分岐のアルキレン基、または炭素数１〜５の直鎖または分岐のフルオロアルキレン基を示し、複数存在するＸは同一でも異なっていてもよい。
一般式（１−２）中、Ｙは下記一般式（１ａ）、下記一般式（１ｂ）および下記一般式（１ｃ）で表される基から選択され、複数存在するＹは同一でも異なっていてもよい。）

（一般式（１ａ）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基を示し、複数存在するＲ^１同士、複数存在するＲ^２同士は同一でも異なっていてもよい。Ｒ^３は、水素原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基を示し、複数存在するＲ^３同士は同一でも異なっていてもよい。＊は結合手を示す。
一般式（１ｂ）中、Ｒ^４およびＲ^５は、それぞれ独立して、水素原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基を示し、複数存在するＲ^４同士、複数存在するＲ^５同士は同一でも異なっていてもよい。＊は結合手を示す。
一般式（１ｃ）中、Ｚは炭素数１〜５のアルキレン基、２価の芳香族基を示す。
＊は結合手を示す。） According to the present invention
(A) Polyimide and
(B) A cross-linking agent containing a polyfunctional (meth) acrylate and
(C) Photopolymerization initiator and
Including
The polyimide (A) contains a compound having a structural unit (a) represented by the following general formula (1-1) and a structural unit (b) represented by the following general formula (1-2), and is a negative type photosensitive member. A sex resin composition is provided.

(In the general formula (1-1), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and a plurality of Qs existing may be the same or different.
R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms, and a plurality of Rs existing may be the same or different.
m1 and m2 each independently represent an integer of 1 to 3.
X represents a single bond, -SO _2- , -C (= O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different.
In the general formula (1-2), Y is selected from the groups represented by the following general formula (1a), the following general formula (1b), and the following general formula (1c), and a plurality of Ys existing are the same but different. May be good. )

(In the general formula (1a), ^{R 1} and ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, each other ^{R 1} there are a plurality of, R ² to each other is good .R ³ be the same or different where there are a plurality of hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, each other multiple R ³ groups same However, they may be different. * Indicates a bond.
In the general formula (1b), ^{R 4} and ^{R 5} are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, ^{R 4} together there are a plurality of, more R ⁵ each other there may be the same or different. * Indicates a bond.
In the general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms and a divalent aromatic group.
* Indicates a bond. )

According to the present invention
Provided is a negative photosensitive polymer containing a compound having a structural unit (a) represented by the general formula (1-1) and a structural unit (b) represented by the general formula (1-2). NS.

According to the present invention, there is provided a cured film made of a cured product of the negative photosensitive resin composition.

According to the present invention, there is provided a semiconductor device including a resin film containing a cured product of the negative photosensitive resin composition.

The negative photosensitive resin composition of the present invention is excellent in mechanical strength and suppresses curing shrinkage, so that a cured product such as a film having excellent dimensional stability can be obtained.

It is a schematic cross-sectional view of the semiconductor device of this embodiment. ^{It is 1} H-NMR chart of the polyimide containing the cross-linking group obtained in Example 1. FIG. ^{6 is a 1} H-NMR chart of the polyimide containing a cross-linking group obtained in Example 7.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate. In addition, "~" represents "greater than or equal to" to "less than or equal to" unless otherwise specified.

The negative photosensitive resin composition of the present embodiment is a compound having a structural unit (a) represented by the general formula (1-1) and a structural unit (b) represented by the general formula (1-2). It contains a polyimide (A) containing the above, a cross-linking agent (B) containing a polyfunctional (meth) acrylate, and a photopolymerization initiator (C).
The cured product such as a film obtained from the negative photosensitive resin composition of the present embodiment has suppressed curing shrinkage and is excellent in dimensional stability.

[Polyimide (A)]
The polyimide (A) of the present embodiment is a compound having a structural unit (a) represented by the following general formula (1-1) and a structural unit (b) represented by the following general formula (1-2). Negative photosensitive polymer) is included.

In the general formula (1-1), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and a plurality of Qs existing may be the same or different.

Examples of the divalent to tetravalent organic group having 1 to 10 carbon atoms include an ester group, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a divalent to tetravalent carbon number of 3 to 10 carbon atoms. Examples thereof include an alicyclic hydrocarbon group, and these hydrocarbon groups may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and have an ester bond, a thioester bond, a urethane bond, a thiourethane bond, and the like. You may have it inside.

R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms, and a plurality of Rs existing may be the same or different. As R, a hydrogen atom and an alkyl group having 1 to 3 carbon atoms are preferable.
m1 and m2 each independently represent an integer of 1 to 3.

X represents a single bond, -SO _2- , -C (= O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different.
From the viewpoint of the effect of the present invention, X is preferably a linear or branched alkylene group having 1 to 5 carbon atoms or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms.

In the general formula (1-2), Y is selected from the groups represented by the following general formula (1a), the following general formula (1b), and the following general formula (1c), and a plurality of Ys existing are the same but different. May be good.

In the general formula (1a), ^{R 1} and ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, each other ^{R 1} there are a plurality of, more R ² together present may be the same or different.
From the viewpoint of the effect of the present invention, R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, among multiple R ³ groups may be the same or different.
From the viewpoint of the effect of the present invention, R ³ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
* Indicates a bond.

In the general formula (1b), ^{R 4} and ^{R 5} are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, ^{R 4} together there are a plurality of, more R ⁵ each other there may be the same or different.
From the viewpoint of the effect of the present invention, R ⁴ and R ⁵ are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and more preferably ^{at least one of R 4} and at least one of R ⁵ have carbon atoms. is 1-3 alkyl group, more preferably three ^{R 4} is one ^{R 4} is a hydrogen atom an alkyl group having 1 to 3 carbon atoms, and the three alkyl ^{R 5} is 1 to 3 carbon atoms A group and one R ⁵ is a hydrogen atom, particularly preferably three R ^4s are methyl groups, one R ⁴ is a hydrogen atom, and three R ^5s are methyl groups and one R ⁵ is. It is a hydrogen atom.
* Indicates a bond.

In the general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms and a divalent aromatic group.
* Indicates a bond.

By the polyimide (A) of the present embodiment, Y contains a compound (polymer) having a group represented by the general formula (1a), the general formula (1b) and the general formula (1c) in the main chain. Since the polymer main chain can withstand deformation and the slip between the polymer chains is improved, the elongation is remarkably improved, the mechanical strength is excellent, and the curing shrinkage is suppressed, resulting in dimensional stability. A cured product such as an excellent film can be obtained.
The reason why such an effect is obtained is not clear, but it is presumed that the strong packing between the polymer chains suppresses the breakage of the polymer chains due to slippage, improves the elongation, and has excellent flexibility.

Since the polyimide (A) of the present embodiment has a (meth) acrylate group in the side chain, these groups and the cross-linking agent (B) are polymerized in the exposure step to become insoluble in the solvent, and during the subsequent curing. Since the ring is not closed, a cured product such as a film having excellent dimensional stability can be obtained because the curing shrinkage is suppressed.

The polyimide (A) of the present embodiment has a structural unit (a) represented by the general formula (1-1), a structural unit (b) represented by the following general formula (1-2), and the following general. It is preferable to contain a compound having the structural unit (c) represented by the formula (1-3).

In the general formula (1-3), Z ¹ and Z ² independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a fluoroalkyl group having 1 to 3 carbon atoms. It is preferably an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, and more preferably a fluoroalkyl group having 1 to 3 carbon atoms.

The polyimide (A) of the present embodiment further contains the structural unit (c) represented by the general formula (1-3), so that the linear expansion coefficient is low and the warpage of the wafer or the like is further suppressed, and the tensile strength and elongation are further suppressed. Since the coefficient is improved, a resin film having further excellent mechanical strength can be obtained.

The polyimide (A) of the present embodiment contains a compound having a structural unit in which the structural unit (a) and the structural unit (b) are bonded. The compound can further have a structural unit in which the structural unit (b) and the structural unit (c) are bonded, and the structure in which the structural unit (a) and the structural unit (c) are bonded to the structural unit (a). It can also have a unit.

Specifically, the polyimide (A) of the present embodiment can contain a compound (negative photosensitive polymer) having a structural unit represented by the following general formula (1).

In the general formula (1), Q, X, R, m1 and m2 are synonymous with the general formula (1-1), and Y is synonymous with the general formula (1-2).

Specifically, the polyimide (A) of the present embodiment is a compound (negative photosensitive polymer) having a structural unit represented by the general formula (1) and a structural unit represented by the following general formula (2). ) Can be included.

In the general formula (2), Y is synonymous with the general formula (1-2), and Z ¹ and Z ² are synonymous with the general formula (1-3).

Further, the polyimide (A) of the present embodiment can specifically contain a compound (negative photosensitive polymer) having a structural unit represented by the following general formula (3).

In the general formula (3), Q, X, R, m1 and m2 are synonymous with the general formula (1-1), Y is synonymous with the general formula (1-2), and Z ¹ and Z ² are synonymous with the general formula (1-2). It is synonymous with the general formula (1-3).

The polyimide (A) of the present embodiment contains the compound having the structural unit, and the compound may further contain a compound having the following structural unit.

The weight average molecular weight of the polyimide (A) of the present embodiment is 10,000 to 300,000, preferably 15,000 to 200,000.

Further, since the polyimide (A) of the present embodiment has excellent solubility in a solvent and does not need to be made into a varnish in the state of a precursor, a varnish containing the polyimide (A) can be prepared. A cured product such as a film having excellent dimensional stability can be obtained from the varnish.

<Manufacturing method of polyimide (A)>
The method for producing polyimide (A) will be described with reference to the first or second embodiment.
(First Embodiment)
The method for producing the polyimide (A) (negative photosensitive polymer) having the structural unit represented by the general formula (1) of the present embodiment is
The bisaminophenol (a) represented by the following general formula (a) and the acid anhydride (b) represented by the following general formula (b) are imidized at a temperature of 100 ° C. or higher and 250 ° C. or lower. Step a and
In step b, a compound having a (meth) acrylate group is reacted with the hydroxyl group of the polyhydroxyimide obtained in step a to introduce a group containing a (meth) acrylate group.
including.
According to this embodiment, the polyimide (A) having excellent solubility in an organic solvent can be synthesized by a simple method.

In the general formula (a), X is synonymous with the general formula (1).

In the general formula (b), Y is selected from the groups represented by the following general formulas (1a), (1b) or (1c).

In the general formula (1a), R ¹ , R ² and R ^{3 are synonymous with R 1} , R ² and R ³ in the general formula (1a) in Y of the general formula (1), and in the general formula (1b). , R ⁴ and R ^{5 are synonymous with R 4} and R ⁵ of the general formula (1b) in Y of the general formula (1), and in the general formula (1c), Z is the Y of the general formula (1). It is synonymous with Z in the general formula (1c). * Indicates a bond.
In order to control the molecular weight of the obtained polyhydroxyimide, it is also possible to add a small amount of acid anhydride (b) or aromatic amine as an end cap agent to carry out the reaction.

Phthalic anhydride, maleic anhydride, nadicic anhydride and the like are examples of the acid anhydride (b) as the end cap agent, and p-methylaniline, p-methoxyaniline, p-phenoxyaniline and the like are examples of the aromatic amine. Can be mentioned. The amount of the acid anhydride (b) or aromatic amine added as these end cap agents is preferably 5 mol% or less. If it exceeds 5 mol%, the molecular weight of the obtained polyhydroxyimide is significantly reduced, which causes problems in heat resistance and mechanical properties.

The equivalent ratio of acid anhydride (b) to bisaminophenol (a) in the imidization reaction of step a is an important factor in determining the molecular weight of the obtained polyhydroxyimide. In general, it is well known that there is a correlation between the molecular weight and mechanical properties of a polymer, and the higher the molecular weight, the better the mechanical properties. Therefore, in order to obtain a polyhydroxyimide having a practically excellent strength, it is necessary to have a high molecular weight to some extent. In the present invention, the equivalent ratio of the acid anhydride (b) and the bisaminophenol (a) to be used is not particularly limited, but the equivalent ratio of the acid anhydride (b) to the bisaminophenol (a) is 0.90 to 0. It is preferably in the range of 1.06. If it is less than 0.90, the molecular weight is low and the material becomes brittle, so that the mechanical strength becomes weak. If it exceeds 1.06, the unreacted carboxylic acid may be decarboxylated during heating, causing gas generation and foaming, which is not preferable. That is, when the equivalent ratio is within the above range, the mechanical strength is excellent and the production stability is excellent.

From the viewpoint of improving the mechanical properties, even when the equivalent ratio of the acid anhydride (b) to the bisaminophenol (a) is out of the above range, the apparent molecular weight can be increased by side chain cross-linking of the resin. You can also raise it.
Step a (imidization reaction step) can be carried out in an organic solvent by a known method.

Examples of the organic solvent include aprotic polar solvents such as γ-butyl lactone (GBL), N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane. Types may be mentioned, and one type or a combination of two or more types may be used. At this time, a non-polar solvent compatible with the aprotic polar solvent may be mixed and used. Examples of the non-polar solvent include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene and solvent naphtha, and ether solvents such as cyclopentyl methyl ether. The ratio of the non-polar solvent in the mixed solvent is arbitrarily set according to the resin properties such as the stirring device capacity and the solution viscosity as long as the solubility of the solvent decreases and the polyamic acid resin obtained by the reaction does not precipitate. can do.
The reaction temperature is 0 ° C. or higher and 100 ° C. or lower, preferably 20 ° C. or higher and 80 ° C. or lower for about 30 minutes to 2 hours, and then 100 ° C. or higher and 250 ° C. or lower, preferably 120 ° C. or higher and 200 ° C. or lower, 1 to 5 React for about an hour.

By step a, a polyhydroxyimide containing the following structural units can be obtained. In step a, the polyhydroxyimide can be purified by a known method, but the dehydration efficiency in polymerization is improved, and the steps a and b can be continuously carried out without purifying the obtained polyhydroxyimide. Can be done.

In step b, a compound having a (meth) acrylate group is reacted with the hydroxyl group of the polyhydroxyimide obtained in step a to introduce a cross-linking group containing a (meth) acrylate group.
The cross-linking group introduced into the polyimide (A) reacts with the cross-linking agent (B) described later in the exposure step, and the exposed portion becomes insoluble in the organic solvent.
In step b, the polyhydroxyimide obtained in step a is purified.

Examples of the compound having a (meth) acrylate group include 2-isocyanatoethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, and 1,1- (bisacryloyloxymethyl) ethyl isocyanate. , Glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether and the like.

To introduce a cross-linking group containing a (meth) acrylate group into the polyhydroxyimide, the polyhydroxyimide and the compound having the (meth) acrylate group are mixed in an organic solvent at 60 ° C. to 150 ° C. for 2 React for about 10 hours. The reaction is not particularly limited, but can be carried out under normal pressure.
The compound having a (meth) acrylate group can be appropriately selected according to the amount of the cross-linking group introduced into the polyhydroxyimide. For example, 0.8 to 3.0 mol with respect to the molar amount of the hydroxyl group of the polyhydroxyimide. It can be added in a doubling manner and is preferably equimolar. If the polyhydroxyimide has a group into which a cross-linking group can be introduced, the group can be added to the molar amount.

Examples of the organic solvent include aprotic polar solvents such as γ-butyl lactone (GBL), N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane. Types may be mentioned, and one type or a combination of two or more types may be used. At this time, a non-polar solvent compatible with the aprotic polar solvent may be mixed and used. Examples of the non-polar solvent include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene and solvent naphtha, and ether solvents such as cyclopentyl methyl ether.
In the reaction, bases such as triethylamine and 1,1,3,3-tetramethylguanidine can also be added.

In step b, the reaction solution containing the polyhydroxyimide obtained in step a can be purified by reprecipitation or the like, and the obtained polyhydroxyimide can be used, but the reaction solution of step a can be used as it is in step b. Can be used.

(Second Embodiment)
Polyimide (A) (negative photosensitive polymer) having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) of the present embodiment, or represented by the general formula (3). The method for producing the polyimide (A) (negative photosensitive polymer) having the structural unit is as follows.
The bisaminophenol (a) represented by the general formula (a), the acid anhydride (b) represented by the general formula (b), and the diaminobiphenyl represented by the following general formula (c) ( In step 1 of imidizing c) at a temperature of 100 ° C. or higher and 250 ° C. or lower,
A group containing a (meth) acrylate group by reacting a hydroxyl group of a structural unit derived from the bisaminophenol (a) of the general formula (a) of the polymer obtained in step 1 with a compound having a (meth) acrylate group. Step 2 to introduce
including.

In the general formula (c), Z ¹ and Z ² are synonymous with the general formula (1-3).

The equivalent ratio of bisaminophenol (a), acid anhydride (b) and diaminobiphenyl (c) in the imidization reaction of Step 1 is an important factor for determining the molecular weight of the obtained polymer. In general, it is well known that there is a correlation between the molecular weight and mechanical properties of a polymer, and the higher the molecular weight, the better the mechanical properties. Therefore, in order to obtain a polymer having practically excellent strength, it is necessary to have a high molecular weight to some extent. In the present invention, the equivalent ratio of the bisaminophenol (a) to the acid anhydride (b) and the diaminobiphenyl (c) to be used is not particularly limited, but the acid anhydride (b) is relative to the bisaminophenol (a). ) Is in the range of 1.00 to 10.00, and the equivalent ratio of diaminobiphenyl (c) is preferably in the range of 0.10 to 10.00. When the corresponding amount ratio is within the above range, the mechanical strength is excellent and the production stability is excellent.

From the viewpoint of improving mechanical properties, the resin is side-chain crosslinked even when the equivalent ratio of the acid anhydride (b) or diaminobiphenyl (c) to the bisaminophenol (a) is out of the above range. It is also possible to increase the apparent molecular weight.

Since the reaction conditions and the like of the steps 1 and 2 of the present embodiment are the same as those of the steps a and b of the first embodiment, the description thereof will be omitted.
According to this embodiment, the polyimide (A) having excellent solubility in an organic solvent can be synthesized by a simple method.

By the above-mentioned production method of the first or second embodiment, a reaction solution containing the polyimide (A) (negative photosensitive polymer) of the present embodiment can be obtained, and further diluted with an organic solvent or the like as necessary. , Can be used as a polymer solution (varnish for coating). As the organic solvent, those exemplified in the reaction step can be used, and the same organic solvent as in the reaction step may be used, or a different organic solvent may be used.

Further, this reaction solution can be put into a poor solvent to reprecipitate the polyimide (A) resin to remove unreacted monomers, dried and solidified, and then dissolved in an organic solvent again to be used as a refined product. In particular, in applications where impurities and foreign substances are a problem, it is preferable to dissolve the varnish in an organic solvent again to obtain a filtered and purified varnish.

[Crosslinking agent (B)]
In the present embodiment, a known cross-linking agent can be used as the cross-linking agent (B).
The cross-linking agent (B) reacts with the cross-linking groups introduced into the polyimide (A) in the exposure step to crosslink them, so that the exposed portion becomes insoluble in the organic solvent.

As the cross-linking agent (B), for example, a (meth) acrylate containing a (meth) acrylic group is preferably used, and a polyfunctional (meth) acrylate is more preferable. Here, the polyfunctional (meth) acrylate is a compound having two or more (meth) acrylic groups.
In this embodiment, the (meth) acrylic group refers to an acrylic group or a methacrylic group.

Specific examples of the polyfunctional acrylic compound include bifunctional (meth) acrylates such as diethylene glycol di (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate, and polyethylene glycol # 400 di (meth) acrylate, and trimethyl propantri (trimethylol propantri). Trifunctional (meth) acrylates such as meta) acrylates, pentaerythritol tri (meth) acrylates and ethoxylated isocyanuric acid triacrylates, tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylates and ditrimethylol propanetetra (meth) acrylates. Hexafunctional (meth) acrylates such as acrylates and dipentaerythritol hexa (meth) acrylates, octafunctional (meth) acrylates such as tripentaerythritol octa (meth) acrylates, and ten-functional (meth) acrylates such as tetrapentaerythritol deca (meth) acrylates. ) Acrylate can be mentioned. Of these, one or more may be used.
In this embodiment, the (meth) acrylate group refers to an acrylate group or a methacrylate group.

The lower limit of the content of the cross-linking agent (B) in the present embodiment may be 20 parts by mass or more, preferably 25 parts by mass or more, preferably 30 parts by mass or more with respect to 100 parts by mass of the polyimide (A). It is more preferable to make it by weight or more. As a result, it is possible to improve the heat resistance, the solvent resistance, and the residual film ratio after development.

The upper limit of the content of the cross-linking agent (B) may be 80 parts by mass or less, preferably 75 parts by mass or less, and 70 parts by mass or less with respect to 100 parts by mass of the polyimide (A). Is more preferable. As a result, it is possible to prevent the cross-linking agent (B) from excessively contributing to the cross-linked structure, and it is possible to improve the heat resistance, the solvent resistance, and the residual film ratio after development. ..

[Photopolymerization Initiator (C)]
As the photopolymerization initiator (C), for example, a photoradical generator can be used. The photoradical generator contains a photoradical generator that generates radicals by irradiation with active rays such as ultraviolet rays and functions as a photopolymerization initiator of the above-mentioned polyimide (A).

Examples of the photoradical generator include an alkylphenone-type initiator, an oxime ester-type initiator, and an acylphosphine oxide-type initiator. For example, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-moriphorinopropane-1-one. , 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)), etanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), 2- (dimethylamino) -1- (4- (4-morpholino) phenyl)- 2- (Phenylmethyl) -1-butanone, Irgacure Oxe01 (BASF Japan Co., Ltd.), Irgacure Oxe02 (BASF Japan Co., Ltd.), Irgacure Oxe03 (BASF Japan Co., Ltd.), Irgacure Oxe04 (BASF Japan Co., Ltd.), N-1919T (ADEKA Co., Ltd.), NCI-730 (ADEKA Co., Ltd.), NCI-831E (ADEKA Co., Ltd.), NCI-930 (ADEKA Co., Ltd.) and the like can be mentioned. Any one or more of these can be used.
Among these, NCI-930 is preferable from the viewpoint of producing a resin film composed of a photosensitive resin composition having more excellent exposure sensitivity.

The amount of the photopolymerization initiator (C) added is not particularly limited, but is preferably about 0.3 to 10% by mass, preferably 0.5 to 7.5% by mass, based on the total solid content of the negative photosensitive resin composition. It is more preferably about 1 to 5% by mass, more preferably about 1 to 5% by mass. By setting the addition amount of the photopolymerization initiator (C) within the above range, the patternability of the photosensitive resin layer containing the negative photosensitive resin composition is enhanced, and the negative photosensitive resin composition is stored for a long period of time. The sex can be improved.

(solvent)
The negative photosensitive resin composition according to the present embodiment may contain a urea compound or an amide compound having an acyclic structure as a solvent. The solvent preferably contains, for example, a urea compound. Thereby, the adhesion between the cured product of the negative photosensitive resin composition and the metal such as Al and Cu can be further improved.

In the present specification, the urea compound refers to a compound having a urea bond, that is, a urea bond. Further, the amide compound means a compound having an amide bond, that is, an amide. Specific examples of the amide include primary amides, secondary amides, and tertiary amides.

Further, in the present embodiment, the non-cyclic structure means that the structure of the compound does not include a cyclic structure such as a carbon ring, an inorganic ring, or a heterocycle. Examples of the structure of the compound having no cyclic structure include a linear structure and a branched chain structure.

As the urea compound and the amide compound having an acyclic structure, those having a large number of nitrogen atoms in the molecular structure are preferable. Specifically, it is preferable that the number of nitrogen atoms in the molecular structure is two or more. This makes it possible to increase the number of lone electron pairs. Therefore, the adhesion to metals such as Al and Cu can be improved.

Specific examples of the structure of the urea compound include a cyclic structure and a non-cyclic structure. The structure of the urea compound is preferably a non-cyclic structure among the above specific examples. This makes it possible to improve the adhesion between the cured product of the negative photosensitive resin composition and a metal such as Al or Cu. The reason for this is presumed as follows. It is presumed that the urea compound having a non-cyclic structure is more likely to form a coordination bond than the urea compound having a cyclic structure. It is considered that this is because the urea compound having a non-cyclic structure has less binding of molecular motion than the urea compound having a cyclic structure, and further, the degree of freedom of deformation of the molecular structure is large. Therefore, when a urea compound having a non-cyclic structure is used, a strong coordination bond can be formed and the adhesion can be improved.

Specific examples of the urea compound include tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, tetrabutylurea, N, N'-dimethylpropyleneurea, 1, 3-Dimethoxy-1,3-dimethylurea, N, N'-diisopropyl-O-methylisourea, O, N, N'-triisopropylisourea, O-tert-butyl-N, N'-diisopropylisourea, Examples thereof include O-ethyl-N, N'-diisopropylisourea, O-benzyl-N, N'-diisopropylisourea and the like. As the urea compound, one or a combination of two or more of the above specific examples can be used. Examples of the urea compound include tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N, N'-diisopropyl-O-methylisourea, O, N among the above specific examples. , N'-triisopropylisourea, O-tert-butyl-N, N'-diisopropylisourea, O-ethyl-N, N'-diisopropylisourea and O-benzyl-N, N'-diisopropylisourea It is preferable to use one or more selected from the group, and it is more preferable to use tetramethylurea (TMU). As a result, a strong coordination bond can be formed and the adhesion can be improved.

Specific examples of the acyclic amide compound include 3-methoxy-N, N-dimethylpropanamide, N, N-dimethylformamide, N, N-dimethylpropionamide, N, N-diethylacetamide, and 3-. Butoxy-N, N-dimethylpropanamide, N, N-dibutylformamide and the like can be mentioned.
The negative photosensitive resin composition according to the present embodiment may contain, as a solvent, a urea compound, an amide compound having an acyclic structure, or a solvent not containing a nitrogen atom.

Specific examples of the solvent without a nitrogen atom include an ether solvent, an acetate solvent, an alcohol solvent, a ketone solvent, a lactone solvent, a carbonate solvent, a sulfone solvent, an ester solvent, and an aromatic hydrocarbon. Examples include system solvents. As the solvent not provided with a nitrogen atom, one or a combination of two or more of the above specific examples can be used.

Specific examples of the ether-based solvent include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, and diethylene glycol diethyl ether. , Diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol-3-monomethyl ether and the like.

Specific examples of the acetate solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate and the like.

Specific examples of the alcohol solvent include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol.
Specific examples of the ketone solvent include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone.
Specific examples of the lactone-based solvent include γ-butyrolactone (GBL) and γ-valerolactone.
Specific examples of the carbonate solvent include ethylene carbonate and propylene carbonate.
Specific examples of the sulfone-based solvent include dimethyl sulfoxide (DMSO) and sulfolane.
Specific examples of the ester solvent include methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate.
Specific examples of the aromatic hydrocarbon solvent include mesitylene, toluene, xylene and the like.

The lower limit of the content of the urea compound and the acyclic amide compound in the solvent is, for example, preferably 10 parts by mass or more, preferably 20 parts by mass or more, when the solvent is 100 parts by mass. More preferably, it is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 70 parts by mass or more. Thereby, the adhesion between the cured product of the negative photosensitive resin composition and the metal such as Al and Cu can be further improved.

The lower limit of the content of the urea compound and the acyclic amide compound in the solvent can be, for example, 100 parts by mass or less when the solvent is 100 parts by mass. It is preferable that the solvent contains a large amount of the urea compound and the amide compound having an acyclic structure from the viewpoint of improving the adhesion.

(Surfactant)
The negative photosensitive resin composition according to the present embodiment may further contain a surfactant.
Surfactants are not limited, and specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, and polyoxyethylene. Polyoxyethylene aryl ethers such as nonylphenyl ethers; nonionic surfactants such as polyoxyethylene dilaurates, polyoxyethylene distearates and the like; Ftope EF301, Ftope EF303, Ftope EF352 (Made by Shin-Akita Kasei Co., Ltd.), Mega Fuck F171, Mega Fuck F172, Mega Fuck F173, Mega Fuck F177, Mega Fuck F444, Mega Fuck F470, Mega Fuck F471, Mega Fuck F475, Mega Fuck F482, Mega Fuck F477 (DIC) ), Florard FC-430, Florard FC-431, Novec FC4430, Novell FC4432 (manufactured by 3M Japan), Surfron S-381, Surfron S-382, Surfron S-383, Surfron S-393, Surfron SC-101, Fluorosurfactants commercially available under the names of Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, (manufactured by AGC Seimi Chemical Co., Ltd.); Organosiloxane co-weight Combined KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); (meth) acrylic acid-based copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. Examples of the fluorine-based surfactant having a perfluoroalkyl group include Megafuck F171, Megafuck F173, Megafuck F444, Megafuck F470, Megafuck F471, Megafuck F475, Megafvck F482, and Megafvck. One or more selected from F477 (manufactured by DIC), Surflon S-381, Surfron S-383, Surfron S-393 (manufactured by AGC Seimi Chemical), Noveck FC4430 and Noveck FC4432 (manufactured by 3M Japan). Is preferably used.

Further, as the surfactant, a silicone-based surfactant (for example, polyether-modified dimethylsiloxane) can also be preferably used. Specifically, as silicone-based surfactants, SH series, SD series and ST series of Toray Dow Corning, BYK series of Big Chemie Japan, KP series of Shin-Etsu Chemical Co., Ltd., Disform of NOF Corporation ( Examples include the (registered trademark) series and the TSF series of Toshiba Silicone Co., Ltd.

The upper limit of the content of the surfactant in the negative photosensitive resin composition is preferably 1% by mass (10000 ppm) or less based on the entire negative photosensitive resin composition (including the solvent). It is more preferably 0.5% by mass (5000 ppm) or less, and further preferably 0.1% by mass (1000 ppm) or less.

Further, the lower limit of the content of the surfactant in the negative photosensitive resin composition is not particularly limited, but from the viewpoint of sufficiently obtaining the effect of the surfactant, for example, the negative photosensitive resin composition. It is 0.001% by mass (10 ppm) or more with respect to the whole (including the solvent).
By appropriately adjusting the amount of the surfactant, it is possible to improve the coatability and the uniformity of the coating film while maintaining other performances.

(Antioxidant)
The negative photosensitive resin composition according to the present embodiment may further contain an antioxidant. As the antioxidant, one or more selected from a phenol-based antioxidant, a phosphorus-based antioxidant and a thioether-based antioxidant can be used. The antioxidant can suppress the oxidation of the resin film formed by the negative photosensitive resin composition.

Phenol-based antioxidants include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3). -T-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5,5] undecane, octadecyl-3- (3,3) 5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t -Butyl-4-ethylphenol, 2,6-diphenyl-4-octadesiloxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t) -Butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycolbis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-m-cresol) , 2-octylthio-4,6-di (3,5-di-t-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-t-butyl-6- Butylphenol), 2,-2'-methylenebis (4-ethyl-6-t-butylphenol), bis [3,3-bis (4-hydroxy-3-t-butylphenyl) butyl acid] glycol ester, 4, 4'-Butylidenebis (6-t-butyl-m-cresol), 2,2'-etylidenebis (4,6-di-t-butylphenol), 2,2'-etylidenebis (4-s-butyl-6) -T-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-) 3-t-Butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tri Su [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane , 2-t-Butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl)- 2,4-8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], triethyleneglycolbis [β-( 3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-Methylenebis (4-ethyl-6-t-butylphenol), 2,2'-Methylenebis (6- (1-methylcyclohexyl) -4-methylphenol), 4,4'-butylidenebis (3-methyl) -6-t-butylphenol), 3,9-bis (2- (3-t-butyl-4-hydroxy-5-methylphenylpropioniloxy) 1,1-dimethylethyl) -2,4,8,10- Tetraoxaspiro (5,5) undecane, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-bis (3,5-di-t-butyl-4-hydroxybenzyl) Sulfide, 4,4'-thiobis (6-t-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butyl-6 -(3-t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-dimethyl-6- (1-methylcyclohexyl, styrenated phenol, 2,4-bis ((( Octylthio) methyl) -5-methylphenol, and the like.

Phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), and tetrakis (2). , 4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2,6) -Dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, tris (mixed monoand di-nonylphenylphosphite), bis (2, 4-di-t-Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-t) −Butyl-4-octadecyloxycarbonylethylphenyl) pentaerythritol diphosphite and the like.

Thioether-based antioxidants include dilauryl-3,3'-thiodipropionate and bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-t-butylphenyl) sulfide. , Distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis (3-lauryl) thiopropionate and the like.

(Filler)
The negative photosensitive resin composition according to the present embodiment may further contain a filler. As the filler, an appropriate filler can be selected according to the mechanical properties and thermal properties required for the resin film made of the negative photosensitive resin composition.
Specific examples of the filler include an inorganic filler and an organic filler.

Specific examples of the inorganic filler include fused crushed silica, molten spherical silica, crystalline silica, secondary aggregated silica, and fine powder silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, and silicon carbide. , Metal compounds such as aluminum hydroxide, magnesium hydroxide, titanium white; talc; clay; mica; glass fiber and the like. As the inorganic filler, one or a combination of two or more of the above specific examples can be used.

Specific examples of the organic filler include organosilicone powder and polyethylene powder. As the organic filler, one or a combination of two or more of the above specific examples can be used.

(Preparation of Negative Photosensitive Resin Composition)
The method for preparing the negative photosensitive resin composition in the present embodiment is not limited, and a known method can be used depending on the components contained in the negative photosensitive resin composition.
For example, each of the above components can be prepared by mixing and dissolving in a solvent.

(Negative photosensitive resin composition)
In the negative photosensitive resin composition according to the present embodiment, the negative photosensitive resin composition is applied to a surface containing a metal such as Al or Cu, and then prebaked to dry the resin film. Then, the resin film is patterned into a desired shape by exposure and development, and then the resin film is cured by post-baking to form a cured film.

When the permanent film is produced, the prebaking condition can be, for example, a heat treatment at a temperature of 90 ° C. or higher and 130 ° C. or lower for 30 seconds or longer and 1 hour or shorter. Further, as the post-baking condition, for example, the heat treatment can be performed at a temperature of 150 ° C. or higher and 350 ° C. or lower for 30 minutes or longer and 10 hours or shorter.

The viscosity of the negative photosensitive resin composition according to the present embodiment can be appropriately set according to the desired thickness of the resin film. The viscosity of the negative photosensitive resin composition can be adjusted by adding a solvent. At the time of adjustment, it is necessary to keep the content of the urea compound and the acyclic amide compound in the solvent constant.

The upper limit of the viscosity of the negative photosensitive resin composition according to the present embodiment may be, for example, 2000 mPa · s or less, 1800 mPa · s or less, or 1500 mPa · s or less. Further, the lower limit of the viscosity of the negative photosensitive resin composition according to the present embodiment may be, for example, 10 mPa · s or more, or 50 mPa · s or more, depending on the desired thickness of the resin film.

The film obtained from the negative photosensitive resin composition of the present embodiment has a maximum elongation rate of 2 to 200%, preferably 5 to 150%, as measured by a tensile test with a Tensilon tester, and has an average value of 1. ~ 150%, preferably 2-120%.
The film obtained from the negative photosensitive resin composition of the present embodiment can have a tensile strength of 30 to 300 MPa, preferably 50 to 200 MPa.

As described above, the negative photosensitive resin composition of the present embodiment can provide a cured product such as a film having excellent mechanical strength. The reason for this is not clear, but it is presumed that the strong packing between the polymer chains suppresses the breakage of the polymer chains due to slippage, improves the elongation, and has excellent flexibility.

The negative photosensitive resin composition of the present embodiment has suppressed curing shrinkage, is spin-coated on the surface of a silicon wafer so that the film thickness after drying is 10 μm, prebaked at 120 ° C. for 3 minutes, and then used as a high-pressure mercury lamp. When a film was prepared by exposing to 600 mJ / cm ² and then post-baking at 170 ° C. for 120 minutes in a nitrogen atmosphere, the film film thickness after pre-baking was set to film thickness A, and the film after post-baking was set. The film thickness is defined as the film thickness B, and the curing shrinkage rate calculated from the following formula can be preferably 12% or less, more preferably 10% or less.
Formula: Curing shrinkage rate [%] = {(film thickness A-film thickness B) / film thickness A} x100

The negative photosensitive resin composition of the present embodiment has suppressed curing shrinkage, and the obtained film has a weight loss temperature (Td5) measured by simultaneous measurement of thermogravimetric differential heat of 200 ° C. or higher, preferably 300 ° C. or higher. It can be the above.

The film made of polyhydroxyimide of the present embodiment has suppressed curing shrinkage, and the coefficient of linear thermal expansion (CTE) can be 200 ppm or less, preferably 100 ppm or less.

(Use)
The negative photosensitive resin composition of the present embodiment is used for forming a resin film for a semiconductor device such as a permanent film or a resist. Among these, from the viewpoint of achieving a good balance between improving the adhesion of the negative photosensitive resin composition and Al pad after prebaking and suppressing the generation of residues of the negative photosensitive resin composition during development, after post-baking. From the viewpoint of improving the adhesion between the cured film of the negative photosensitive resin composition and the metal, and from the viewpoint of improving the chemical resistance of the negative photosensitive resin composition after post-baking, the permanent film is used. It is preferably used for the intended purpose.

In the present embodiment, the resin film includes a cured film of a negative photosensitive resin composition. That is, the resin film according to the present embodiment is formed by curing a negative photosensitive resin composition.

The permanent film is composed of a resin film obtained by prebaking, exposing and developing a negative photosensitive resin composition, patterning it into a desired shape, and then curing it by post-baking. The permanent film can be used as a protective film, an interlayer film, a dam material, or the like of a semiconductor device.

In the resist, for example, a negative photosensitive resin composition is applied to an object to be masked by the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, and the negative photosensitive resin composition is applied. It is composed of a resin film obtained by removing a solvent from the sex resin composition.

An example of the semiconductor device according to this embodiment is shown in FIG.
The semiconductor device 100 according to the present embodiment can be a semiconductor device provided with the resin film. Specifically, in the semiconductor device 100, one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be a resin film containing the cured product of the present embodiment. Here, the resin film is preferably the above-mentioned permanent film.

The semiconductor device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package can be obtained by mounting the semiconductor device 100 on the wiring board via the bump 52.

The semiconductor device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multilayer wiring layer is provided with an interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30. The top layer wiring 34 is made of, for example, aluminum Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and on the uppermost layer wiring 34. A part of the passivation film 32 is provided with an opening in which the uppermost layer wiring 34 is exposed.

A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46. Has. The insulating layer 42 is formed with an opening for connecting to the uppermost layer wiring 34. The rewiring 46 is formed on the insulating layer 42 and in the openings provided in the insulating layer 42, and is connected to the uppermost layer wiring 34. The insulating layer 44 is provided with an opening for connecting to the rewiring 46.

Bumps 52 are formed in the openings provided in the insulating layer 44, for example, via the UBM (Under Bump Metallurgy) layer 50. The semiconductor device 100 is connected to a wiring board or the like via, for example, a bump 52.
Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted as long as the effects of the present invention are not impaired.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
In the examples, the following compounds were used.

2,2-Bis (3-amino-4-hydroxyphenyl) propane represented by the following formula (hereinafter, also referred to as BAP)

2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter, also referred to as BAFA) represented by the following formula.

4-{[4- (1,3-Dioxoisobenzofuran-5-ylcarbonyloxy) phenyl] cyclohexyl} phenyl 1,3-dioxoisobenzofuran-5-carboxylate represented by the following formula (hereinafter, Also referred to as BPZ-TME)

4- [4- (1,3-Dioxoisobenzofuran-5-ylcarbonyloxy) -2,3,5-trimethylphenyl] -2,3,6-trimethylphenyl 1,3 represented by the following formula -Dioxoisobenzofuran-5-carboxylate (hereinafter, also referred to as TMPBP-TME)

3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride represented by the following formula (hereinafter, also referred to as DSDA)

3,3', 4,4'-benzophenone tetracarboxylic dianhydride represented by the following formula (hereinafter, also referred to as BTDA).

3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride represented by the following formula (hereinafter, also referred to as ODPA).

4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (hereinafter, also referred to as TFMB) represented by the following formula.

[Reference Synthesis Example 1]
First, 3.87 g (15.0 mmol) of BAP and 9.25 g (15.0 mmol) of BPZ-TME were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 30.62 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 8.17 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 45400, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 2.04.

[Reference synthesis example 2]
First, 3.87 g (15.0 mmol) of BAP and 9.28 g (15.0 mmol) of TMPBP-TME were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 30.69 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 10.15 g of the polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 142000, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 2.21.

[Reference Synthesis Example 3]
First, 27.47 g (75.0 mmol) of BAFA and 46.39 g (75.0 mmol) of TMPBP-TME were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 295.46 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 66.62 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 87200, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.92.

[Reference Synthesis Example 4]
First, 10.99 g (30.0 mmol) of BAFA and 10.75 g (30.0 mmol) of DSDA were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 50.72 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 15.44 g of the polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 63900, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 4.75.

[Reference Synthesis Example 5]
First, 19.37 g (75.0 mmol) of BAP and 26.87 g (75.0 mmol) of DSDA were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 107.91 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 1/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 37.58 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 36900, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 2.69.

[Reference Synthesis Example 6]
First, 14.65 g (40.0 mmol) of BAFA and 12.89 g (40.0 mmol) of BTDA were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 64.27 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 1/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 24.13 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 70700, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 3.63.

[Reference Synthesis Example 7]
First, 10.33 g (40.0 mmol) of BAP and 12.89 g (40.0 mmol) of BTDA were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 54.18 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 21.74 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 62100, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 3.24.

[Reference Synthesis Example 8]
First, 14.65 g (40.0 mmol) of BAFA and 12.41 g (40.0 mmol) of ODPA were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 63.14 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 1/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 24.19 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 58500, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.72.

(Preparation of film)
Reference Synthesis Examples 1 to 8 are spin-coated on the surface of a silicon wafer with a 12% by mass GBL solution (polymer solution) of the polymer, prebaked at 120 ° C. for 3 minutes, and then post-baked at 170 ° C. for 120 minutes under nitrogen to form a film. Prepared.

<Measurement method>
(5% weight loss temperature (Td5))
Reference The films obtained from the polymers of Synthesis Examples 1 to 7 were measured by thermogravimetric differential thermal simultaneous measurement. The measurement conditions were a heating rate of 10 ° C./min under a nitrogen stream of 30 ml / min. The temperature at which the weight was reduced by 5% from the initial stage was measured and used as the 5% weight loss temperature (Td5). The results are shown in Table 1.

(Coefficient of linear thermal expansion (CTE))
Reference A strip-shaped test piece having a length of 13 mm and a width of 5 mm was cut out from the film obtained from the polymers of Synthesis Examples 1 to 7. Thermal mechanical measurement in tension mode was performed at a distance between chucks of 10 mm, and the average coefficient of linear thermal expansion (CTE, 50 ° C. to 100 ° C.) was obtained from the thermal expansion curve. The results are shown in Table 1.

(Glass transition temperature: Tg)
Reference A strip-shaped test piece having a length of 50 mm and a width of 5 mm was cut out from the film obtained from the polymers of Synthesis Examples 1 to 7. Dynamic viscoelasticity was measured at a distance between chucks of 20 mm, and the peak temperature of the obtained loss tangent (tan δ) was defined as the glass transition temperature (Tg). The measurement conditions were a nitrogen stream of 30 ml / min, an applied frequency of 1 Hz, and a heating rate of 5 ° C./min. The results are shown in Table 1.

(Tensile strength, elongation and elastic modulus)
Reference A tensile test (stretching speed: 5 mm / min) was carried out on a test piece (6.5 mm × 60 mm × 10 μm thickness) cut out from a film obtained from the polymers of Synthesis Examples 1 to 8 in an atmosphere of 23 ° C. The tensile test was carried out using a tensile tester manufactured by Orientec (Tensilon RTC-1210A). Five test pieces were measured, and the average stress at the breaking point was taken as the strength. The tensile elongation was calculated from the fractured distance and the initial distance, and the maximum and average values of the elongation were obtained. The tensile elastic modulus was calculated from each of the initial gradients of the obtained stress-strain curve, and the averaged modulus was taken as the elastic modulus. The results are shown in Table 1.

From the results in Table 1, the polymers having Y of the general formula (1-2) contained in the polyimide used in the present invention (Reference Synthesis Examples 1 to 3) are the polymers not having the Y (Reference Synthesis Examples 4 to 8). ), The tensile strength was excellent, and the tensile elongation and its average value were remarkably excellent. Since these properties are considered to be due to the main chain of the polymer, it was inferred that similar physical property differences would occur even when a cross-linking group was introduced into the polymer chains of Reference Synthesis Examples 1 to 8. ..

[Synthesis Example 1]
First, 45.78 g (125.0 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter also referred to as BAFA) in an appropriately sized reaction vessel equipped with a stirrer and a cooling tube. And 4- [4- (1,3-dioxoisobenzofuran-5-ylcarbonyloxy) -2,3,5-trimethylphenyl] -2,3,6-trimethylphenyl 1,3-dioxoiso 77.32 g (125.0 mmol) of benzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME) was added. Then, GBL492.43 g was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 116.95 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 94800, the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 2.18, and n of the polymer (polyhydroxyimide) represented by the following formula was The average value was 44.
When IR measurement was performed on the polymer, it was confirmed that the peaks derived from the amide group near ^{1480, 1550 and 1670 cm-1 disappeared, and the imidization was completed.}
Further, when ¹ H-NMR measurement was carried out, a peak was confirmed in the aromatic region (6.9 ppm to 8.8 ppm) with an area ratio corresponding to the number of protons.

[Synthesis Example 2]
First, 3.66 g (10.0 mmol) of BAFA, 3.20 g (10.0 mmol) of TFMB, and 12.37 g (20.0 mmol) of TMPBP-TME were placed in an appropriately sized reaction vessel equipped with a stirrer and a cooling tube. I put it in. Then, 76.95 g of GBL was further added to the reaction vessel.
After aeration of nitrogen for 10 minutes, the temperature was raised to 60 ° C. with stirring, and the mixture was reacted for 1.5 hours. Then, by further reacting at 180 ° C. for 3 hours, bisaminophenol and acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 3/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120 ° C. to obtain 17.31 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 62300, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.98.
When IR measurement was performed on the polymer, it was confirmed that the peaks derived from the amide group near ^{1480, 1550 and 1670 cm-1 disappeared, and the imidization was completed.}
Further, when ¹ H-NMR measurement was carried out, a peak was confirmed in the aromatic region (6.9 ppm to 8.9 ppm) with an area ratio corresponding to the number of protons.

[Example 1]
(Introduction of cross-linking group)
First, 73.86 g (150.0 mmol in terms of hydroxyl group) of the polyhydroxyimide obtained in Synthesis Example 1 and 2-isocyanatoethyl acrylate (hereinafter referred to as AOI) were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. As shown, 21.17 g (150.0 mmol) of Showa Denko Corporation and 828.26 g of γ-butyl lactone (GBL) were added. Then, the temperature was raised to 120 ° C. with stirring, and the reaction was carried out for 6 hours.
The obtained reaction solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 2/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 40 ° C. to obtain 70.98 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 102,900, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 2.29.
^{1 1} H-NMR chart is shown in FIG. From this result, it was confirmed that a cross-linking group was introduced into the polymer. The polymer into which the cross-linking group was introduced contained the following repeating units as a part thereof.
Moreover, from the measurement result of gas chromatography, the introduction rate of the cross-linking group was 25%.

(Preparation of Negative Photosensitive Resin Composition)
Polyhydroxyimide (100 parts by mass) into which a cross-linking group was introduced, ethoxylated isocyanuric acid triacrylate (A9300, manufactured by Shin-Nakamura Chemical Co., Ltd., 50 parts by mass) as a cross-linking agent, and ADEKA ARCLUS NCI-930 as a radical generator. (Manufactured by ADEKA Corporation, trade name, 3 parts by mass) was mixed with FC4432 (0.05 parts by mass) as a surfactant in γ-butyrolactone (867 parts by mass) to prepare a photosensitive resin composition. ..

[Examples 2 to 6]
In Examples 2 to 6, a polymer having a cross-linking group introduced therein and a negative photosensitive resin composition were prepared in the same manner as in Example 1 except that the cross-linking agent was replaced with the following compounds shown in Table 1. ..
・ NK ester 2G: Diethylene glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ・ NK ester 4G: Polyethylene glycol # 200 dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ・ NK ester 9G: Polyethylene glycol # 400 dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. A-TMM-3LM-N: A mixture of the following two compounds, the amount of the compound on the left in the mixture based on gas chromatograph measurement is about 57%, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

-A-DPH: Dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[Example 7]
(Introduction of cross-linking group)
First, 14.43 g (15.0 mmol in terms of hydroxyl group) of the polymer obtained in Synthesis Example 2 and 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI) are placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. , Showa Denko KK) 2.12 g (15.0 mmol) and γ-butyl lactone (GBL) 163.80 g were added. Then, the temperature was raised to 120 ° C. with stirring, and the reaction was carried out for 6 hours.
The obtained reaction solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 2/1 to precipitate a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 40 ° C. to obtain 12.84 g of a polymer.
When the polymer was GPC-measured, the weight average molecular weight Mw was 84,400, and the degree of polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 2.07.
^{1 1} H-NMR chart is shown in FIG. From this result, it was confirmed that a cross-linking group was introduced into the polymer. The polymer into which the cross-linking group was introduced contained the following repeating units as a part thereof.
Moreover, from the measurement result of gas chromatography, the introduction rate of the cross-linking group was 51%.

(Preparation of Negative Photosensitive Resin Composition)
A polymer into which a cross-linking group was introduced (100 parts by mass), polyethylene glycol # 200 dimethacrylate (NK ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd., 50 parts by mass) as a cross-linking agent, and ADEKA ARCLUS NCI- as a radical generator. 930 (manufactured by ADEKA Corporation, trade name, 3 parts by mass) is mixed with FC4432 (0.05 parts by mass) as a surfactant in γ-butyrolactone (867 parts by mass) to prepare a photosensitive resin composition. bottom.

[Example 8]
In Example 8, a polymer having a cross-linking group introduced therein and a negative photosensitive resin composition were prepared in the same manner as in Example 7, except that the amount of the cross-linking agent was replaced with the amount shown in Table 1.

(Preparation of film)
The negative photosensitive resin compositions of Examples 1 to 8 were spin-coated on the surface of a silicon wafer so that the film thickness after drying was 10 μm, prebaked at 120 ° C. for 3 minutes, and then 600 mJ / cm ^{2 with a high-pressure mercury lamp.} After that, a film was prepared by post-baking at 170 ° C. for 120 minutes in a nitrogen atmosphere.
With respect to the obtained film, 5% weight loss temperature (Td5)) linear thermal expansion coefficient (CTE), glass transition temperature (Tg), tensile strength, elongation and elastic modulus were measured by the above-mentioned measuring method. The results are shown in Table 2.

(Curing shrinkage rate)
The film thickness after prebaking of the films obtained in Examples 1 to 8 is defined as the film thickness A, the film thickness after post-baking is defined as the film thickness B, and the film thickness A and the film thickness B are substituted into the following equations to cure shrinkage. The rate was calculated.
Curing shrinkage rate [%] = {(film thickness A-film thickness B) / film thickness A} x100

From the results in Table 2, it was clarified that the negative photosensitive resin composition of the present invention contains a polyimide having excellent solubility in a solvent, so that a resin film having excellent dimensional stability can be obtained. .. Furthermore, it has been clarified that according to the negative photosensitive resin composition of the present invention, a resin film having excellent mechanical strength can be obtained.

Claims (13)

(A) Polyimide and
(B) A cross-linking agent containing a polyfunctional (meth) acrylate and
(C) Photopolymerization initiator and
Including
The polyimide (A) contains a compound having a structural unit (a) represented by the following general formula (1-1) and a structural unit (b) represented by the following general formula (1-2), and is a negative type photosensitive member. Sex resin composition.

(In the general formula (1-1), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and a plurality of Qs existing may be the same or different.
R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms, and a plurality of Rs existing may be the same or different.
m1 and m2 each independently represent an integer of 1 to 3.
X represents a single bond, -SO _2- , -C (= O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different.
In the general formula (1-2), Y is selected from the groups represented by the following general formula (1a), the following general formula (1b), and the following general formula (1c), and a plurality of Ys existing are the same but different. May be good. )

(In the general formula (1a), ^{R 1} and ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, each other ^{R 1} there are a plurality of, R ² to each other is good .R ³ be the same or different where there are a plurality of hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, each other multiple R ³ groups same However, they may be different. * Indicates a bond.
In the general formula (1b), ^{R 4} and ^{R 5} are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, ^{R 4} together there are a plurality of, more R ⁵ each other there may be the same or different. * Indicates a bond.
In the general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms and a divalent aromatic group.
* Indicates a bond. ) The negative photosensitive resin composition according to claim 1, wherein the compound further has a structural unit (c) represented by the following general formula (1-3).

(In the general formula (1-3), Z ¹ and Z ² independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a fluoroalkyl group having 1 to 3 carbon atoms, respectively. .) The negative photosensitive resin composition according to claim 1 or 2, wherein the polyimide (A) contains a compound having a structural unit represented by the following general formula (1).

(In the general formula (1), Q, R, m1, m2, and X are synonymous with the general formula (1-1), and Y is synonymous with the general formula (1-2).) The negative photosensitive resin composition according to claim 3, wherein the compound further has a structural unit represented by the following general formula (2).

(In the general formula (2), Y is synonymous with the general formula (1-2), and Z ¹ and Z ² are synonymous with the general formula (1-3).) The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the cross-linking agent (B) is a polyfunctional (meth) acrylate. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the curing shrinkage rate is 12% or less. A negative photosensitive polymer comprising a compound having a structural unit (a) represented by the following general formula (1-1) and a structural unit (b) represented by the following general formula (1-2).

(In the general formula (1-1), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and a plurality of Qs existing may be the same or different.
R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms, and a plurality of Rs existing may be the same or different.
m1 and m2 each independently represent an integer of 1 to 3.
X represents a single bond, -SO _2- , -C (= O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different.
In the general formula (1-2), Y is selected from the groups represented by the following general formula (1a), the following general formula (1b), and the following general formula (1c), and a plurality of Ys existing are the same but different. May be good. )

(In the general formula (1a), ^{R 1} and ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, each other ^{R 1} there are a plurality of, R ² to each other is good .R ³ be the same or different where there are a plurality of hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, each other multiple R ³ groups same However, they may be different. * Indicates a bond.
In the general formula (1b), ^{R 4} and ^{R 5} are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, ^{R 4} together there are a plurality of, more R ⁵ each other there may be the same or different. * Indicates a bond.
In the general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms and a divalent aromatic group.
* Indicates a bond. ) The negative photosensitive polymer according to claim 7, wherein the compound further has a structural unit (c) represented by the following general formula (1-3).

(In the general formula (2), Z ¹ and Z ² independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a fluoroalkyl group having 1 to 3 carbon atoms.) The negative photosensitive polymer according to any one of claims 7 to 8, wherein the polyimide (A) contains a compound having a structural unit represented by the following general formula (1).

(In the general formula (1), Q, R, m1, m2, and X are synonymous with the general formula (1-1), and Y is synonymous with the general formula (1-2).) The negative photosensitive polymer according to claim 9, wherein the compound further has a structural unit represented by the following general formula (2).

(In the general formula (2), Y is synonymous with the general formula (1-2), and Z ¹ and Z ² are synonymous with the general formula (1-3).) A cured film made of a cured product of the negative photosensitive resin composition according to any one of claims 1 to 6. A semiconductor device including a resin film containing a cured product of the negative photosensitive resin composition according to any one of claims 1 to 6. Interlayer insulating film and
A resin film provided on the interlayer insulating film and containing a cured product of the negative photosensitive resin composition according to any one of claims 1 to 6.
With the rewiring embedded in the resin film,
12. The semiconductor device according to claim 12.

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