JP7556263B2 - Negative-type photosensitive resin composition, negative-type photosensitive polymer, and uses thereof - Google Patents

Description

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

Polyimide resins have high mechanical strength, heat resistance, insulating properties, and solvent resistance, and are therefore widely used as protective materials in liquid crystal display elements and semiconductors, insulating materials, and thin films for electronic materials such as color filters.
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 polyimide precursors having a specific structure.

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

Patent Document 6 discloses a resin composition containing a polyimide resin having a specific 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 specific repeating unit, a photoinitiator, and an organic solvent.
The examples of Patent Documents 6 to 8 describe synthesis methods using an amine, 3,3',4,4'-diphenylethertetracarboxylic dianhydride as an acid anhydride, and a compound having a (meth)acrylate group as a modifier.

JP 2013-241607 A JP 2013-95894 A JP 2014-172994 A International Publication No. 2010/110335 JP 2004-133435 A JP 2018-070829 A JP 2000-147761 A Japanese Patent Application Publication No. 05-232701

However, in the conventional techniques described in Patent Documents 1 to 8, there was room for improvement in the mechanical strength of films containing polyimide obtained from photosensitive resin compositions.

Furthermore, 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 resulting coating film is exposed to light and then cured, the dimensional stability of the film is affected by the cure shrinkage that occurs when the polyimide precursor changes to polyimide. If a photosensitive resin composition is used in which polyimide is dissolved in an organic solvent, the cure shrinkage of the resulting resin is suppressed, but conventional polyimides have room for improvement in terms of their solubility in organic solvents.

The present inventors have found that the above problems can be solved by using a polyimide having a specific structure, and have completed the present invention.
That is, the present invention can be shown as follows.

（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) a polyimide;
(B) a crosslinking agent containing a polyfunctional (meth)acrylate;
(C) a photopolymerization initiator;
Including,
A negative photosensitive resin composition is provided, in which 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):

In the general formula (1-1), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and a plurality of Q's may be the same or different.
R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's 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(.dbd.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, and multiple X's may be the same or different.
In the general formula (1-2), Y is selected from groups represented by the following general formulas (1a), (1b), and (1c), and a plurality of Y's may be the same or different.

(In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^1s and a plurality of R ^2s may be the same or different. R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^3s may be the same or different. * represents a bond.
In general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^4s and a plurality of R ^5s may be the same or different. * represents a bond.
In formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond.)

According to the present invention,
There is provided a negative photosensitive polymer comprising 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).

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

According to the present invention, a semiconductor device is provided that includes a resin film containing a cured product of the negative-type photosensitive resin composition.

The negative photosensitive resin composition of the present invention has excellent mechanical strength, and can produce cured products such as films with suppressed cure shrinkage and excellent dimensional stability.

1 is a schematic cross-sectional view of a semiconductor device according to an embodiment of the present invention; 1 is a ¹ H-NMR chart of the polyimide containing a crosslinking group obtained in Example 1. 1 is a ¹ H-NMR chart of the polyimide containing a crosslinking group obtained in Example 7.

The following describes an embodiment of the present invention with reference to the drawings. In all drawings, similar components are given similar reference symbols and descriptions are omitted where appropriate. In addition, "~" indicates "above" to "below" unless otherwise specified.

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

[Polyimide (A)]
The polyimide (A) of the present embodiment contains a compound (negative type photosensitive polymer) 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 general formula (1-1), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.

Examples of divalent to tetravalent organic groups having 1 to 10 carbon atoms include ester groups, divalent to tetravalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms, and divalent to tetravalent alicyclic hydrocarbon groups having 3 to 10 carbon atoms. These hydrocarbon groups may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and may have ester bonds, thioester bonds, urethane bonds, thiourethane bonds, etc. in their structures.

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

X represents a single bond, --SO ₂ --, --C(.dbd.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, and multiple X's may be the same or different.
From the viewpoint of the effects 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 general formula (1-2), Y is selected from groups represented by the following general formulas (1a), (1b), and (1c), and multiple Ys may be the same or different.

In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^1s and a plurality of R ^2s may be the same or different.
From the viewpoint of the effects 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.

^R3 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of ^R3 's may be the same or different.
From the viewpoint of the effects of the present invention, ^R3 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 general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^4s and a plurality of R ^5s may be the same or different.
From the viewpoint of the effects of the present invention, R ⁴ and R ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably at least one of R ⁴ and at least one of R ⁵ are an alkyl group having 1 to 3 carbon atoms, even more preferably three R ⁴ are alkyl groups having 1 to 3 carbon atoms, one R ⁴ is a hydrogen atom, and three R ⁵ are alkyl groups having 1 to 3 carbon atoms, and one R ⁵ is a hydrogen atom, particularly preferably three R ⁴ are methyl groups, one R ⁴ is a hydrogen atom, and three R ⁵ are methyl groups, and one R ⁵ is a hydrogen atom.
* indicates a bond.

In formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond.

In 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), or the general formula (1c) in the main chain, and therefore the polymer main chain can withstand deformation, and furthermore, the slippage between polymer chains is improved, so that elongation is significantly improved and a cured product such as a film having excellent mechanical strength, suppressed cure shrinkage, and excellent dimensional stability can be obtained.
The reason why such an effect is obtained is unclear, but it is presumed that the strong packing between the polymer chains suppresses breakage due to the polymer chains slipping through each other, improving elongation and providing excellent flexibility.

The polyimide (A) of this embodiment has (meth)acrylate groups in the side chains, and in the exposure step, these groups polymerize with the crosslinking agent (B) to become insoluble in a solvent, and the ring does not close during subsequent curing, so that curing shrinkage is suppressed and a cured product such as a film with excellent dimensional stability can be obtained.

The polyimide (A) of this embodiment preferably contains a compound having a structural unit (a) represented by general formula (1-1), a structural unit (b) represented by the following general formula (1-2), and further a structural unit (c) represented by the following general formula (1-3).

In general formula (1-3), ^Z1 and ^Z2 each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, or 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 this embodiment further contains the structural unit (c) represented by the general formula (1-3), which reduces the linear expansion coefficient and further suppresses warping of wafers and the like, and improves the tensile strength and elongation, resulting in a resin film with even greater mechanical strength.

The polyimide (A) of this embodiment includes a compound having a structural unit in which structural unit (a) and structural unit (b) are bonded together. The compound may further have a structural unit in which structural unit (b) and structural unit (c) are bonded together, and may also have a structural unit in which structural unit (a) is bonded to structural unit (a) and structural unit (c).

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

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

Specifically, the polyimide (A) of this embodiment can contain a compound (negative photosensitive polymer) having a structural unit represented by the following general formula (2) in addition to the structural unit represented by the above general formula (1).

In formula (2), Y has the same meaning as in formula (1-2), and ^Z1 and ^Z2 have the same meaning as in formula (1-3).

In addition, the polyimide (A) of this embodiment can specifically contain a compound (negative-type photosensitive polymer) having a structural unit represented by the following general formula (3):

In formula (3), Q, X, R, m1, and m2 are the same as those in formula (1-1), Y is the same as those in formula (1-2), and ^Z1 and ^Z2 are the same as those in formula (1-3).

The polyimide (A) of this embodiment includes a compound having the above structural unit, and the compound may further include a compound having the following structural unit in part:

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

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

<Method for producing polyimide (A)>
The method for producing the polyimide (A) will be described with reference to a first or second embodiment.
First Embodiment
The method for producing a polyimide (A) (negative type photosensitive polymer) having a structural unit represented by general formula (1) of the present embodiment includes the following steps:
A step a of imidizing a bisaminophenol (a) represented by the following general formula (a) and an acid anhydride (b) represented by the following general formula (b) at a temperature of 100° C. or higher and 250° C. or lower;
a step b of reacting a compound having a (meth)acrylate group with the hydroxyl group of the polyhydroxyimide obtained in the step a to introduce a group containing a (meth)acrylate group;
Includes.
According to this embodiment, a polyimide (A) having excellent solubility in organic solvents can be synthesized by a simple method.

In general formula (a), X has the same meaning as in general formula (1).

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

In general formula (1a), ^R1 , ^R2 and ^R3 have the same meanings as ^R1 , ^R2 and ^R3 in general formula (1a) for Y in general formula (1), in general formula (1b), ^R4 and ^R5 have the same meanings as ^R4 and ^R5 in general formula (1b) for Y in general formula (1), and in general formula (1c), Z has the same meaning as Z in general formula (1c) for Y in general formula (1). * indicates a bond.
In order to control the molecular weight of the resulting polyhydroxyimide, it is also possible to carry out the reaction by adding a small amount of an acid anhydride (b) or an aromatic amine as an end-capping agent.

Examples of the acid anhydride (b) used as the end-capping agent include phthalic anhydride, maleic anhydride, and nadic anhydride, and examples of the aromatic amine include p-methylaniline, p-methoxyaniline, and p-phenoxyaniline. The amount of the acid anhydride (b) or aromatic amine used as the end-capping agent is preferably 5 mol% or less. If the amount exceeds 5 mol%, the molecular weight of the resulting polyhydroxyimide will decrease significantly, causing problems with heat resistance and mechanical properties.

The equivalent ratio of the acid anhydride (b) and the bisaminophenol (a) in the imidization reaction in step a is an important factor that determines the molecular weight of the polyhydroxyimide obtained. It is generally 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 with practically excellent strength, it is necessary to have a relatively high molecular weight. In the present invention, there is no particular restriction on the equivalent ratio of the acid anhydride (b) and the bisaminophenol (a) used, but it is preferable that the equivalent ratio of the acid anhydride (b) to the bisaminophenol (a) is in the range of 0.90 to 1.06. If it is less than 0.90, the molecular weight is low and the polymer becomes brittle, resulting in weak mechanical strength. Also, if it exceeds 1.06, unreacted carboxylic acid may decarbonate during heating, causing gas generation and foaming, which is undesirable. In other words, if the equivalent ratio is in the above range, the polymer has excellent mechanical strength and excellent manufacturing stability.

From the viewpoint of improving mechanical properties, even if the equivalent ratio of the acid anhydride (b) to the bisaminophenol (a) is outside the above range, the apparent molecular weight can be increased by crosslinking the resin at its side chains.
The 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-butyrolactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane, and one or more of these may be used in combination. In this case, a nonpolar solvent that is compatible with the aprotic polar solvent may be mixed and used. Examples of the nonpolar 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 nonpolar solvent in the mixed solvent can be 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 is reduced and the polyamic acid resin obtained by the reaction is not precipitated.
The reaction temperature is from 0° C. to 100° C., preferably from 20° C. to 80° C., for about 30 minutes to 2 hours, and then from 100° C. to 250° C., preferably from 120° C. to 200° C., for about 1 to 5 hours.

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 by improving the dehydration efficiency in the polymerization, steps a and b can be carried out continuously without purifying the obtained polyhydroxyimide.

In the step b, a compound having a (meth)acrylate group is reacted with the hydroxyl group of the polyhydroxyimide obtained in the step a to introduce a crosslinking group containing a (meth)acrylate group.
The crosslinking groups introduced into the polyimide (A) react with the crosslinking agent (B) described below in the exposure step, making the exposed areas insoluble in organic solvents.
In addition, in step b, the polyhydroxyimide obtained in step a is purified.

Examples of compounds containing a (meth)acrylate group include 2-isocyanatoethyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

To introduce a crosslinking group containing a (meth)acrylate group into a polyhydroxyimide, the polyhydroxyimide and a compound containing a (meth)acrylate group are mixed in an organic solvent and reacted at 60° C. to 150° C. for about 2 to 10 hours. The reaction can be carried out at normal pressure, although there is no particular limitation.
The compound having a (meth)acrylate group can be appropriately selected according to the amount of crosslinking group to be introduced into the polyhydroxyimide, and can be added, for example, in an amount of 0.8 to 3.0 times the molar amount of the hydroxyl group of the polyhydroxyimide, preferably equimolar. If the polyhydroxyimide has a group capable of introducing a crosslinking group, the group can be added to the molar amount.

Examples of the organic solvent include aprotic polar solvents such as γ-butyrolactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane, and these may be used alone or in combination of two or more. In this case, a nonpolar solvent that is compatible with the above aprotic polar solvent may be mixed and used. Examples of the nonpolar solvent include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene, and solvent naphtha, and ether solvents such as cyclopentyl methyl ether.
In the reaction, a base such as triethylamine or 1,1,3,3-tetramethylguanidine can be added.

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

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

In formula (c), ^Z1 and ^Z2 have the same meanings as in formula (1-3).

The equivalent ratio of bisaminophenol (a), acid anhydride (b), and diaminobiphenyl (c) in the imidization reaction in step 1 is an important factor that determines the molecular weight of the resulting polymer. It is generally 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 with practically excellent strength, a certain degree of high molecular weight is necessary. In the present invention, the equivalent ratio of bisaminophenol (a), acid anhydride (b), and diaminobiphenyl (c) used is not particularly limited, but it is preferable that the equivalent ratio of acid anhydride (b) to bisaminophenol (a) is in the range of 1.00 to 10.00, and the equivalent ratio of diaminobiphenyl (c) is in the range of 0.10 to 10.00. If the equivalent ratio is within the above range, the mechanical strength and production stability are excellent.

From the viewpoint of improving mechanical properties, even if the equivalent ratio of the acid anhydride (b) or diaminobiphenyl (c) to the bisaminophenol (a) is outside the above range, the apparent molecular weight can be increased by crosslinking the resin at the side chains.

The reaction conditions in steps 1 and 2 of this embodiment are similar to those in steps a and b of the first embodiment, and therefore will not be described here.
According to this embodiment, a polyimide (A) having excellent solubility in organic solvents can be synthesized by a simple method.

By using the manufacturing method of the first or second embodiment described above, a reaction solution containing the polyimide (A) (negative photosensitive polymer) of this embodiment can be obtained, which can be further diluted with an organic solvent or the like as necessary and used as a polymer solution (varnish for application). As the organic solvent, those exemplified in the reaction process can be used, and may be the same organic solvent as in the reaction process or a different organic solvent.

Also, this reaction solution can be poured into a poor solvent to reprecipitate the polyimide (A) resin, remove unreacted monomers, and then dry and solidify it, which can then be dissolved in an organic solvent again and used as a refined product. In particular, for applications where impurities and foreign matter are a problem, it is preferable to dissolve it in an organic solvent again and filter it to make a refined varnish.

[Crosslinking agent (B)]
In this embodiment, as the crosslinking agent (B), a known crosslinking agent can be used.
The crosslinking agent (B) reacts with the crosslinking groups introduced into the polyimide (A) in the exposure step to crosslink them, thereby making the exposed areas insoluble in organic solvents.

As the crosslinking agent (B), for example, it is preferable to use a (meth)acrylate containing a (meth)acrylic group, and it is more preferable to use a polyfunctional (meth)acrylate. 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 polyfunctional acrylic compounds include difunctional (meth)acrylates such as diethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, and polyethylene glycol #400 di(meth)acrylate, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ethoxylated isocyanuric acid triacrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate, octafunctional (meth)acrylates such as tripentaerythritol octa(meth)acrylate, and decafunctional (meth)acrylates such as tetrapentaerythritol deca(meth)acrylate. Of these, one or more may be used.
In this embodiment, the (meth)acrylate group refers to an acrylate group or a methacrylate group.

In this embodiment, the lower limit of the content of the crosslinking agent (B) may be 20 parts by mass or more, preferably 25 parts by mass or more, and more preferably 30 parts by mass or more, per 100 parts by mass of the polyimide (A). This makes it possible to achieve improved heat resistance, improved solvent resistance, and improved film remaining rate after development.

The upper limit of the content of the crosslinking agent (B) may be 80 parts by mass or less, preferably 75 parts by mass or less, and more preferably 70 parts by mass or less, per 100 parts by mass of the polyimide (A). This prevents the crosslinking agent (B) from contributing excessively to the crosslinked structure, and improves the heat resistance, solvent resistance, and film remaining rate 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 when irradiated with active light such as ultraviolet light and functions as a photopolymerization initiator for the polyimide (A) described above.

Examples of the photoradical generator include an alkylphenone type initiator, an oxime ester type initiator, and an acylphosphine oxide type initiator. For example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylphenyl)propan-1-one, and bis(2,4,6-trimethylphenyl)propan-1-one are listed below. 1-[4-(phenylthio)-, 2-(O-benzoyloxime)), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)-2-(phenylmethyl)-1-butanone, Irgacure Examples of the compound include Oxe01 (BASF Japan Ltd.), Irgacure Oxe02 (BASF Japan Ltd.), Irgacure Oxe03 (BASF Japan Ltd.), Irgacure Oxe04 (BASF Japan Ltd.), N-1919T (ADEKA Corporation), NCI-730 (ADEKA Corporation), NCI-831E (ADEKA Corporation), NCI-930 (ADEKA Corporation), etc. Any one or more of these may be used.
Among these, NCI-930 is preferred from the viewpoint of producing a resin film made of a photosensitive resin composition having superior exposure sensitivity.

The amount of photopolymerization initiator (C) added is not particularly limited, but is preferably about 0.3 to 10 mass % of the total solid content of the negative photosensitive resin composition, more preferably about 0.5 to 7.5 mass %, and even more preferably about 1 to 5 mass %. By setting the amount of photopolymerization initiator (C) added within the above range, it is possible to improve the patterning properties of the photosensitive resin layer containing the negative photosensitive resin composition and to improve the long-term storage properties of the negative photosensitive resin composition.

(solvent)
The negative photosensitive resin composition according to the present embodiment may contain a urea compound or an amide compound having a non-cyclic structure as a solvent. For example, the solvent may preferably contain a urea compound. This can further improve the adhesion between the cured product of the negative photosensitive resin composition and metals such as Al and Cu.

In this specification, a urea compound refers to a compound having a urea bond, i.e., a urea bond. An amide compound refers to a compound having an amide bond, i.e., an amide. Specific examples of amides include primary amides, secondary amides, and tertiary amides.

In this embodiment, a non-cyclic structure means that the compound does not have a cyclic structure such as a carbon ring, an inorganic ring, or a heterocyclic ring. Examples of compound structures that do not have a cyclic structure include a linear structure and a branched structure.

As for urea compounds and non-cyclic amide compounds, those with a large number of nitrogen atoms in the molecular structure are preferred. Specifically, it is preferred that the number of nitrogen atoms in the molecular structure is two or more. This allows the number of lone electron pairs to be increased, and 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. Of the above specific examples, the structure of the urea compound is preferably a non-cyclic structure. This improves the adhesion between the cured product of the negative photosensitive resin composition and metals such as Al and Cu. The reason for this is presumed to be as follows. It is presumed that a urea compound with a non-cyclic structure is more likely to form a coordinate bond than a urea compound with a cyclic structure. This is because a urea compound with a non-cyclic structure has less constraints on molecular movement and a greater degree of freedom in deformation of the molecular structure than a urea compound with a cyclic structure. Therefore, when a urea compound with a non-cyclic structure is used, a strong coordinate bond can be formed and adhesion can be improved.

Specific examples of urea compounds 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, O-ethyl-N,N'-diisopropylisourea, and O-benzyl-N,N'-diisopropylisourea. The urea compounds may be used alone or in combination of two or more of the above specific examples. As the urea compound, it is preferable to use one or more selected from the group consisting of tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, and O-benzyl-N,N'-diisopropylisourea, among the above specific examples, and it is more preferable to use tetramethylurea (TMU). This allows for the formation of strong coordinate bonds and improved adhesion.

Specific examples of the amide compound having a non-cyclic structure include 3-methoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N,N-dimethylpropionamide, N,N-diethylacetamide, 3-butoxy-N,N-dimethylpropanamide, and N,N-dibutylformamide.
The negative photosensitive resin composition according to this embodiment may contain, as a solvent, a solvent not having a nitrogen atom, in addition to the urea compound and the amide compound having a non-cyclic structure.

Specific examples of solvents that do not have nitrogen atoms include ether solvents, acetate solvents, alcohol solvents, ketone solvents, lactone solvents, carbonate solvents, sulfone solvents, ester solvents, and aromatic hydrocarbon solvents. As solvents that do not have nitrogen atoms, one or a combination of two or more of the above specific examples can be used.

Specific examples of the ether solvents 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, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, and 1,3-butylene glycol-3-monomethyl ether.

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

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 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, and xylene.

The lower limit of the content of the urea compound and the amide compound having a non-cyclic structure in the solvent is, for example, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, and especially preferably 70 parts by mass or more, when the solvent is taken as 100 parts by mass. This can further improve the adhesion between the cured product of the negative photosensitive resin composition and metals such as Al and Cu.

The lower limit of the content of the urea compound and the amide compound having a non-cyclic structure in the solvent can be, for example, 100 parts by mass or less when the solvent is taken as 100 parts by mass. From the viewpoint of improving adhesion, it is preferable that the content of the urea compound and the amide compound having a non-cyclic structure in the solvent is high.

(Surfactant)
The negative photosensitive resin composition according to this embodiment may further contain a surfactant.
The surfactant is not limited, and specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; EFTOP EF301, EFTOP EF303, EFTOP EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafack F171, Megafack F172, Megafack F173, Megafack F177, and Megafack F444. , Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Fluorad FC-430, Fluorad FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan Ltd.), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, (manufactured by AGC Seimi Chemical Co., Ltd.), and other commercially available fluorosurfactants under the names; organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

Among these, it is preferable to use a fluorosurfactant having a perfluoroalkyl group. As the fluorosurfactant having a perfluoroalkyl group, it is preferable to use one or more selected from the above specific examples: Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Surflon S-381, Surflon S-383, Surflon S-393 (manufactured by AGC Seimi Chemical Co., Ltd.), Novec FC4430, and Novec FC4432 (manufactured by 3M Japan Ltd.).

As the surfactant, silicone surfactants (such as polyether-modified dimethylsiloxane) can also be preferably used. Specific examples of silicone surfactants include the SH series, SD series, and ST series from Dow Corning Toray Co., Ltd., the BYK series from BYK Japan Co., Ltd., the KP series from Shin-Etsu Chemical Co., Ltd., the Disform (registered trademark) series from NOF Corporation, and the TSF series from Toshiba Silicones Co., Ltd.

The upper limit of the surfactant content in the negative photosensitive resin composition is preferably 1% by mass (10,000 ppm) or less, more preferably 0.5% by mass (5,000 ppm) or less, and even more preferably 0.1% by mass (1,000 ppm) or less, based on the total amount of the negative photosensitive resin composition (including the solvent).

There is no particular lower limit for the content of the surfactant in the negative photosensitive resin composition. From the viewpoint of obtaining a sufficient effect of the surfactant, the content is, for example, 0.001 mass % (10 ppm) or more with respect to the entire negative photosensitive resin composition (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 performance properties.

(Antioxidants)
The negative photosensitive resin composition according to this 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 oxidation of the resin film formed from 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-(3,5-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-octadecyloxyphenol, stearyl(3,5-di-t-butyl-4-hydroxyphenyl)propionate, distearyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, thiodiethylene ethylene glycol bis[(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)butyric acid cid] glycol ester, 4,4'-butylidenebis(6-t-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(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-tris[(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-methyl 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], triethylene glycol bis[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'-methyl 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-methylphenylpropionyloxy)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, etc.

Examples of phosphorus-based antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl phosphite), tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-biphenylene diphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis-(2,6-dicumylphenyl)pentaerythritol diphosphite, 2,2-methylene biphosphonate, and the like. bis(4,6-di-t-butylphenyl)octyl phosphite, tris(mixed mono- and di-nonylphenyl phosphite), 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.

Examples of thioether antioxidants include dilauryl-3,3'-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl)sulfide, distearyl-3,3'-thiodipropionate, and pentaerythritol-tetrakis(3-lauryl)thiopropionate.

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

Specific examples of the inorganic filler include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely powdered silica; metal compounds such as alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, and titanium white; talc; clay; mica; and glass fiber. The inorganic filler may be one or a combination of two or more of the above specific examples.

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 specific examples above can be used.

(Preparation of negative photosensitive resin composition)
The method for preparing the negative photosensitive resin composition in this embodiment is not limited, and any known method can be used depending on the components contained in the negative photosensitive resin composition.
For example, the above components can be mixed and dissolved in a solvent to prepare the composition.

(Negative Photosensitive Resin Composition)
The negative type photosensitive resin composition according to this embodiment is used by applying the negative type photosensitive resin composition to a surface comprising a metal such as Al or Cu, then pre-baking to dry and form a resin film, then exposing and developing to pattern the resin film into a desired shape, and then post-baking the resin film to harden it and form a hardened film.

When producing the permanent film, the pre-baking conditions can be, for example, a heat treatment at a temperature of 90°C to 130°C for 30 seconds to 1 hour. The post-baking conditions can be, for example, a heat treatment at a temperature of 150°C to 350°C for 30 minutes to 10 hours.

The viscosity of the negative photosensitive resin composition according to this 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. During the adjustment, it is necessary to keep the content of the urea compound and the non-cyclic amide compound in the solvent constant.

The upper limit of the viscosity of the negative photosensitive resin composition according to this embodiment may be, for example, 2000 mPa·s or less, 1800 mPa·s or less, or 1500 mPa·s or less. The lower limit of the viscosity of the negative photosensitive resin composition according to this 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 type photosensitive resin composition of the present embodiment has a maximum elongation of 2 to 200%, preferably 5 to 150%, and an average elongation of 1 to 150%, preferably 2 to 120%, as measured by a tensile test using a Tensilon tester.
The film obtained from the negative photosensitive resin composition of this embodiment can have a tensile strength of 30 to 300 MPa, preferably 50 to 200 MPa.

In this way, the negative photosensitive resin composition of this embodiment can provide a cured product such as a film that has excellent mechanical strength. The reason for this is unclear, but it is presumed that the strong packing between the polymer chains suppresses breakage due to the polymer chains slipping through, improving elongation and providing excellent flexibility.

The negative type photosensitive resin composition of the present embodiment is suppressed in curing shrinkage, and in the case where a film is prepared by spin-coating the composition on a silicon wafer surface so as to have a film thickness after drying of 10 μm, pre-baking at 120° C. for 3 minutes, exposing the film to light at 600 mJ/ ^cm2 using a high-pressure mercury lamp, and then post-baking at 170° C. for 120 minutes in a nitrogen atmosphere, the film thickness after the pre-baking is defined as film thickness A, and the film thickness after the post-baking is defined as film thickness B, the curing shrinkage calculated from the following formula can be preferably 12% or less, more preferably 10% or less.
Formula: Cure shrinkage rate [%] = {(film thickness A - film thickness B) / film thickness A} x 100

The negative photosensitive resin composition of this embodiment has suppressed cure shrinkage, and the resulting film can have a weight loss temperature (Td5) measured by simultaneous thermogravimetry and differential thermal analysis of 200°C or higher, preferably 300°C or higher.

The polyhydroxyimide film of this embodiment has reduced cure shrinkage and a linear thermal expansion coefficient (CTE) of 200 ppm or less, preferably 100 ppm or less.

(Application)
The negative photosensitive resin composition of the present embodiment is used to form a resin film for semiconductor devices such as a permanent film, a resist, etc. Among these, from the viewpoint of achieving a good balance between improving the adhesion between the negative photosensitive resin composition and an Al pad after pre-baking and suppressing the generation of residues of the negative photosensitive resin composition during development, improving the adhesion between the cured film of the negative photosensitive resin composition after post-baking and a metal, and further improving the chemical resistance of the negative photosensitive resin composition after post-baking, it is preferable to use the composition in applications using a permanent film.

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

The permanent film is composed of a resin film obtained by pre-baking, exposing, and developing a negative photosensitive resin composition, patterning it into a desired shape, and then hardening it by post-baking. The permanent film can be used as a protective film, interlayer film, dam material, etc. for semiconductor devices.

The resist is composed of a resin film obtained by applying a negative photosensitive resin composition to an object to be masked by the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., and then removing the solvent from the negative photosensitive resin composition.

An example of a semiconductor device according to this embodiment is shown in FIG.
The semiconductor device 100 according to this embodiment can be a semiconductor device including the above-mentioned 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 the resin film including the cured product of this 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, the semiconductor device 100 is mounted on a wiring board via bumps 52 to obtain a semiconductor package.

The semiconductor device 100 includes a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multi-layer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multi-layer wiring layer includes an interlayer insulating film 30 and a top-layer wiring 34 provided on the interlayer insulating film 30. The top-layer wiring 34 is made of, for example, aluminum Al. A passivation film 32 is provided on the interlayer insulating film 30 and the top-layer wiring 34. An opening is provided in a part of the passivation film 32 through which the top-layer wiring 34 is exposed.

A redistribution layer 40 is provided on the passivation film 32. The redistribution layer 40 has an insulating layer 42 provided on the passivation film 32, a redistribution 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the redistribution 46. An opening that connects to the top layer wiring 34 is formed in the insulating layer 42. The redistribution 46 is formed on the insulating layer 42 and in an opening provided in the insulating layer 42, and is connected to the top layer wiring 34. An opening that connects to the redistribution 46 is provided in the insulating layer 44.

In the openings provided in the insulating layer 44, bumps 52 are formed via, for example, an under bump metallurgy (UBM) layer 50. The semiconductor device 100 is connected to a wiring board or the like via the bumps 52, for example.
Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted as long as they do not impair the effects of the present invention.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
The following compounds were used in the examples.

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

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

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

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

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

3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter also referred to as BTDA) represented by the following formula:

3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter also referred to as ODPA) represented by the following formula:

4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (hereinafter 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 a suitable sized reaction vessel equipped with a stirrer and a condenser, and then 30.62 g of GBL was added to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a dilution solution, and then the dilution solution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 8.17 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 45,400 and the 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 a suitable sized reaction vessel equipped with a stirrer and a condenser, followed by the addition of 30.69 g of GBL to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a dilution solution, and then the dilution solution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 10.15 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 142,000 and the 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 a suitable sized reaction vessel equipped with a stirrer and a condenser, followed by the addition of 295.46 g of GBL to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the 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 dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 66.62 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 87,200 and the 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 added to a suitable sized reaction vessel equipped with a stirrer and a condenser, and then 50.72 g of GBL was added to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a dilution, and then the dilution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 15.44 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 63,900 and the 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 added to a suitable sized reaction vessel equipped with a stirrer and a condenser, and then 107.91 g of GBL was added to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the 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 dropped into a mixed solution of water/methanol = 1/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 37.58 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 36,900 and the 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 added to a suitable sized reaction vessel equipped with a stirrer and a condenser, and then 64.27 g of GBL was added to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the 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 dropped into a mixed solution of water/methanol = 1/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 24.13 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 70,700 and the 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 added to a suitable sized reaction vessel equipped with a stirrer and a condenser, and then 54.18 g of GBL was added to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a dilution solution, and then the dilution solution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 21.74 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 62,100 and the 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 added to a suitable sized reaction vessel equipped with a stirrer and a condenser, and then 63.14 g of GBL was added to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a dilution, and then the dilution was dropped into a mixed solution of water/methanol = 1/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 24.19 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 58,500 and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 1.72.

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

<Measurement method>
(5% weight loss temperature (Td5))
The films obtained from the polymers of Reference Synthesis Examples 1 to 7 were measured by thermogravimetry, differential scanning calorimetry, and simultaneous thermogravimetry. The measurement conditions were a nitrogen gas flow of 30 ml/min and a heating rate of 10°C/min. The temperature at which the weight had decreased by 5% from the initial value was measured and was taken as the 5% weight loss temperature (Td5). The results are shown in Table 1.

Coefficient of Linear Thermal Expansion (CTE)
A rectangular test piece having a length of 13 mm and a width of 5 mm was cut out from the film obtained from the polymer of Reference Synthesis Examples 1 to 7. Thermomechanical measurement was performed in a tensile mode with a chuck distance of 10 mm, and the average linear thermal expansion coefficient (CTE, 50°C to 100°C) was obtained from the thermal expansion curve. The results are shown in Table 1.

(Glass transition temperature: Tg)
A rectangular test piece of 50 mm length x 5 mm width was cut out from the film obtained from the polymer of Reference Synthesis Examples 1 to 7. Dynamic viscoelasticity measurement was performed with a chuck distance of 20 mm, and the peak temperature of the obtained loss tangent (tan δ) was taken as the glass transition temperature (Tg). The measurement conditions were a nitrogen flow 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)
A tensile test (stretching speed: 5 mm/min) was carried out in an atmosphere at 23° C. on test pieces (6.5 mm×60 mm×10 μm thick) cut out from the films obtained from the polymers of Reference Synthesis Examples 1 to 8. The tensile test was carried out using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec Co., Ltd. The strength was determined by measuring five test pieces and averaging the stresses at the break point. The tensile elongation was calculated from the break distance and the initial distance, and the maximum and average elongation values were obtained. The tensile modulus was calculated from the initial gradient of the obtained stress-strain curve, and the average was determined as the modulus of elasticity. The results are shown in Table 1.

From the results in Table 1, the polymers containing Y in general formula (1-2) contained in the polyimide used in the present invention (Reference Synthesis Examples 1 to 3) had superior tensile strength and significantly superior tensile elongation and average value compared to the polymers not containing Y (Reference Synthesis Examples 4 to 8). Since these characteristics are considered to be due to the main chain of the polymer, it was inferred that similar differences in physical properties would be expressed even if crosslinking groups were 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) and 77.32 g (125.0 mmol) of 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME) were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, an additional 492.43 g of GBL was added to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a dilution solution, and then the dilution solution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 116.95 g of a polymer.
When the polymer was subjected to GPC measurement, the weight average molecular weight Mw was 94,800, the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 2.18, and the average value of n of the polymer (polyhydroxyimide) represented by the following formula was 44.
When the polymer was subjected to IR measurement, it was confirmed that the peaks derived from the amide group at around 1480, 1550 and 1670 ^{cm −1} had disappeared, and thus the imidization was completed.
Furthermore, ¹ H-NMR measurement confirmed a peak 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 a suitable sized reaction vessel equipped with a stirrer and a condenser, followed by the addition of 76.95 g of GBL to the reaction vessel.
After nitrogen was passed through for 10 minutes, the temperature was raised to 60° C. with stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was allowed to proceed for an additional 3 hours at 180° C., whereby the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a dilution solution, and then the dilution solution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 120 ° C. to obtain 17.31 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 62,300 and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 1.98.
When the polymer was subjected to IR measurement, it was confirmed that the peaks derived from the amide group at around 1480, 1550 and 1670 ^{cm −1} had disappeared, and the imidization was completed.
Furthermore, ¹ H-NMR measurement confirmed a peak 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 Crosslinking Group)
First, 73.86 g (150.0 mmol calculated as hydroxyl groups) of the polyhydroxyimide obtained in Synthesis Example 1, 21.17 g (150.0 mmol) of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko K.K.), and 828.26 g of γ-butyrolactone (GBL) were placed in a reaction vessel of appropriate size equipped with a stirrer and a cooling tube. Thereafter, the temperature was raised to 120° C. with stirring, and the mixture was allowed to react for 6 hours.
The obtained reaction solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was dropped into a mixed solution of water/methanol = 2/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 40 ° C. to obtain 70.98 g of a polymer.
The polymer was subjected to GPC measurement, and the weight average molecular weight Mw was 102,900 and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 2.29.
The ¹ H-NMR chart is shown in Figure 2. From this result, it was confirmed that a crosslinking group had been introduced into the polymer. The polymer into which the crosslinking group had been introduced contained the following repeating unit in a part thereof.
Furthermore, the result of gas chromatography showed that the introduction rate of crosslinking groups was 25%.

(Preparation of negative photosensitive resin composition)
A photosensitive resin composition was prepared by mixing polyhydroxyimide having a crosslinking group (100 parts by mass), ethoxylated isocyanuric acid triacrylate (A9300, manufactured by Shin-Nakamura Chemical Co., Ltd., 50 parts by mass) as a crosslinking agent, ADEKA ARCLES NCI-930 (trade name, manufactured by ADEKA Corporation, 3 parts by mass) as a radical generator, and FC4432 (0.05 parts by mass) as a surfactant in γ-butyrolactone (867 parts by mass).

[Examples 2 to 6]
In Examples 2 to 6, polymers having crosslinking groups introduced therein and negative-type photosensitive resin compositions were prepared in the same manner as in Example 1, except that the crosslinking agent was replaced with the following compounds shown in Table 1.
NK Ester 2G: Diethylene glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. NK Ester 4G: Polyethylene glycol #200 dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. NK Ester 9G: Polyethylene glycol #400 dimethacrylate, manufactured by Shin-Nakamura Chemical 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 chromatography measurement is about 57%, manufactured by Shin-Nakamura Chemical Co., Ltd.

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

[Example 7]
(Introduction of Crosslinking Group)
First, 14.43 g (15.0 mmol calculated as hydroxyl groups) of the polymer obtained in Synthesis Example 2, 2.12 g (15.0 mmol) of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko K.K.), and 163.80 g of γ-butyrolactone (GBL) were placed in a reaction vessel of appropriate size equipped with a stirrer and a cooling tube. Thereafter, 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 dropped into a mixed solution of water/methanol = 2/1 to precipitate a white solid. The obtained white solid was collected and vacuum dried at a temperature of 40 ° C. to obtain 12.84 g of a polymer.
The polymer was measured by GPC to find that it had a weight average molecular weight Mw of 84,400 and a polydispersity index (weight average molecular weight Mw/number average molecular weight Mn) of 2.07.
The ¹ H-NMR chart is shown in Figure 3. From this result, it was confirmed that a crosslinking group had been introduced into the polymer. The polymer into which the crosslinking group had been introduced contained the following repeating unit in part.
Furthermore, the result of gas chromatography showed that the introduction rate of crosslinking groups was 51%.

(Preparation of negative photosensitive resin composition)
A photosensitive resin composition was prepared by mixing the polymer into which a crosslinking group had been 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 crosslinking agent, ADEKA ARCLES NCI-930 (trade name, manufactured by ADEKA Corporation, 3 parts by mass) as a radical generator, and FC4432 (0.05 parts by mass) as a surfactant in γ-butyrolactone (867 parts by mass).

[Example 8]
In Example 8, a polymer having a crosslinking 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 crosslinking agent was changed to the amount shown in Table 1.

(Film Preparation)
The negative photosensitive resin compositions of Examples 1 to 8 were spin-coated onto the surface of a silicon wafer so that the film thickness after drying would be 10 μm. After pre-baking at 120° C. for 3 minutes, the wafer was exposed to light at 600 mJ/ ^cm2 using a high-pressure mercury lamp, and then post-baked at 170° C. for 120 minutes in a nitrogen atmosphere to prepare a film.
The 5% weight loss temperature (Td5), coefficient of linear thermal expansion (CTE), glass transition temperature (Tg), tensile strength, elongation and elastic modulus of the obtained film were measured by the above-mentioned measuring methods. The results are shown in Table 2.

(Cure shrinkage rate)
The film thickness after pre-baking of the films obtained in Examples 1 to 8 was defined as film thickness A, and the film thickness after post-baking was defined as film thickness B. The film thicknesses A and B were substituted into the following formula to calculate the cure shrinkage rate.
Cure shrinkage rate [%] = {(film thickness A - film thickness B) / film thickness A} x 100

The results in Table 2 reveal that the negative-type photosensitive resin composition of the present invention contains polyimide that has excellent solubility in solvents, and therefore a resin film with excellent dimensional stability can be obtained. Furthermore, it is clear that the negative-type photosensitive resin composition of the present invention can produce a resin film with excellent mechanical strength.

Claims (13)

(A) a polyimide;
(B) a crosslinking agent containing a polyfunctional (meth)acrylate;
(C) a photopolymerization initiator;
Including,
The polyimide (A) is a negative photosensitive resin composition containing 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 Q's may be the same or different.
R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's 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(.dbd.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, and multiple X's may be the same or different.
In the general formula (1-2), Y is selected from groups represented by the following general formula (1a) and the following general formula (1b ) , and a plurality of Y's may be the same or different.

(In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^1s and a plurality of R ^2s may be the same or different. R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^3s may be the same or different. * represents a bond.
In general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^4s and a plurality of R ^5s may be the same or different. * represents a bond . The negative type 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 general formula (1-3), ^Z1 and ^Z2 each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms.) 3. The negative type photosensitive resin composition according to claim 1, wherein the polyimide (A) contains a compound having a structural unit represented by the following general formula (1):

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

(In formula (2), Y has the same meaning as in formula (1-2), and ^Z1 and ^Z2 have the same meaning as in formula (1-3).) The negative-type photosensitive resin composition according to any one of claims 1 to 4, wherein the crosslinking agent (B) is a multifunctional (meth)acrylate. The negative photosensitive resin composition according to any one of claims 1 to 5, having a cure shrinkage rate of 12% or less. A negative-type photosensitive polymer containing 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 used in a negative-type photosensitive 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 Q's may be the same or different.
R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's 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(.dbd.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, and multiple X's may be the same or different.
In the general formula (1-2), Y is selected from groups represented by the following general formula (1a) and the following general formula (1b ) , and a plurality of Y's may be the same or different.

(In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^1s and a plurality of R ^2s may be the same or different. R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^3s may be the same or different. * represents a bond.
In general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^4s and a plurality of R ^5s may be the same or different. * represents a bond . 8. 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 general formula (2), ^Z1 and ^Z2 each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms.) 9. The negative photosensitive polymer according to claim 7, wherein the polyimide (A) contains a compound having a structural unit represented by the following general formula (1):

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

(In formula (2), Y has the same meaning as in formula (1-2), and ^Z1 and ^Z2 have the same meaning as in formula (1-3).) A cured film comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 6. A semiconductor device having a resin film containing a cured product of the negative photosensitive resin composition according to any one of claims 1 to 6. An interlayer insulating film;
a resin film comprising a cured product of the negative type photosensitive resin composition according to any one of claims 1 to 6 provided on the interlayer insulating film;
a rewiring buried in the resin film;
The semiconductor device according to claim 12, comprising:

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