JP2023004156A - negative photosensitive polymer - Google Patents

Abstract

To provide a negative photosensitive polymer that has excellent solubility in an organic solvent and is less prone to hydrolysis and can give a cured product, such as a film, having high mechanical strength.SOLUTION: A negative photosensitive polymer has an imide constitutional unit, an aromatic condensed constitutional unit and a biphenyl constitutional unit having a methacryloyl group.SELECTED DRAWING: None

Description

The present invention relates to negative-acting photosensitive polymers.

Polyimide resin has high mechanical strength, heat resistance, insulation, and solvent resistance, so it is widely used as a protective material for liquid crystal display elements and semiconductors, as an insulating material, and as a thin film for electronic materials such as color filters. there is

Patent Document 1 discloses a liquid crystal containing at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine and a polyimide obtained by dehydrating and ring-closing the polyamic acid. An alignment agent is disclosed. The literature mentions 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine (hereinafter also referred to as TMDA) as a diamine. ing.

U.S. Pat. No. 5,400,001 discloses a polyimide polymer comprising a reaction product of a diamine, a tetracarboxylic dianhydride, and a compound having a predetermined functional group. The document mentions TMDA as a diamine.

US Pat. No. 5,300,003 discloses a dry film construction comprising a carrier substrate and a photopolymer layer comprising a fully imidized polyimide polymer. The document mentions TMDA as a diamine that constitutes a fully imidized polyimide polymer.

US Pat. No. 5,331,001 discloses a photosensitive composition comprising a fully imidized polyimide polymer, a solubility switching compound, a photoinitiator, and a solvent, capable of forming a film exhibiting a predetermined dissolution rate. . The document mentions TMDA as a diamine that constitutes a fully imidized polyimide polymer.

Patent Document 5 discloses a photosensitive resin composition containing a polyimide resin having a predetermined structure and a weight average molecular weight of 70,000 or less. This document describes that at least one terminal of the polyimide resin is a group containing a (meth)acrylate group.

JP 2011-257736 A JP 2017-513959 A Japanese Patent Application Laid-Open No. 2018-517168 JP 2018-517169 A WO2020/246349

However, in the conventional techniques described in Patent Documents 1 to 5, there is room for improvement in the mechanical strength of films containing polyimide obtained from photosensitive resin compositions.

Conventionally, in order to improve the solubility of polyimide in organic solvents, fluorine atoms have been introduced into the skeleton of the polyimide. When synthesized, we have found that the strong electron-withdrawing properties of fluorine atoms affect the electrons of the imide ring, making the resulting polyimide susceptible to hydrolysis, thereby reducing its mechanical strength.
That is, conventional polyimides have room for improvement in terms of the balance between solubility in organic solvents and mechanical strength.

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

（一般式（ａ１）中、Ｙは２価の有機基である。
一般式（ａ２）中、Ｒ^１、Ｒ^２は、それぞれ独立して、水素原子、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基を示す。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。
一般式（ａ３）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^５およびＲ^６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す。
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。） According to the invention,
a structural unit (a1) represented by the following general formula (a1);
a structural unit (a2) represented by the following general formula (a2);
a structural unit (a3) represented by the following general formula (a3);
A negative-acting photopolymer is provided comprising:

(In general formula (a1), Y is a divalent organic group.
In general formula (a2), 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. A plurality of R ¹ 's and a plurality of R ² 's may be the same or different.
In general formula (a3), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.
R ⁵ and R ⁶ 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.
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; Multiple X's may be the same or different. )

According to the present invention, it is possible to provide a negative photosensitive polymer that is excellent in solubility in organic solvents, inhibits hydrolysis, and provides a cured product such as a film having excellent mechanical strength.

1 is a schematic cross-sectional view of a semiconductor device according to an embodiment; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the description thereof will be omitted as appropriate. In addition, "A to B" represents "above A" to "below B" unless otherwise specified.

The negative photosensitive polymer of the present embodiment comprises a structural unit (a1) represented by the following general formula (a1), a structural unit (a2) represented by the following general formula (a2), and the following general formula (a3 ) and a structural unit (a3) represented by

In general formula (a1), Y is a divalent organic group.
As the divalent organic group, a known organic group can be used as long as the effects of the present invention are exhibited. 2) and a divalent organic group selected from general formula (a1-3) below.

In general formula (a1-1), R ⁷ and R ⁸ 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 multiple R ⁷ , multiple R ⁸ may be the same or different.
From the viewpoint of the effects of the present invention, R ⁷ and R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
R ⁹ 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 ⁹ may be the same or different.
From the viewpoint of the effects of the present invention, R ⁹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
* indicates a bond.

In general formula (a1-2), each of R ¹⁰ and R ¹¹ independently represents a hydrogen atom, an alkyl group having ¹ to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R ¹¹ may be the same or different.

From the viewpoint of the effect of the present invention, R ¹⁰ and R ¹¹ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably at least one of R ¹⁰ and at least one of R ¹¹ an alkyl group having 1 to 3 carbon atoms, more preferably three R ¹⁰ are alkyl groups having 1 to 3 carbon atoms, one R ¹⁰ is a hydrogen atom, and three R ¹¹ are alkyl groups having 1 to 3 carbon atoms one R ¹¹ is a hydrogen atom, particularly preferably three R ¹⁰ are methyl groups and one R ¹⁰ is a hydrogen atom, and three R ¹¹ are methyl groups and one R ¹¹ is It is a hydrogen atom.
* indicates a bond.

In general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond.

In general formula (a2), 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. A plurality of R ¹ 's and a plurality of R ² 's 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, more preferably a hydrogen atom.

By containing the structural unit represented by the general formula (a2), the polyimide (A) of the present embodiment suppresses the influence of the imide ring on electrons, suppresses hydrolysis of the polyimide, and has excellent mechanical strength. In addition, it has excellent solubility in organic solvents. In other words, the polyimide (A) of the present embodiment and the negative photosensitive resin composition containing the polyimide (A) have an excellent balance of these properties.

In general formula (a3), 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 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. Alicyclic hydrocarbon groups and the like may be mentioned, and these hydrocarbon groups may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and have structures such as ester bonds, thioester bonds, urethane bonds, and thiourethane bonds. You may have it inside.
R ⁵ and R ⁶ 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.
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; Multiple X's 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.
Specifically, the polyimide (A) of the present embodiment can contain a structural unit represented by the following general formula (1).

In general formula (1), R ¹ and R ² have the same meanings as in general formula (a2), and Y has the same meaning as in general formula (a1).
Specifically, the polyimide (A) of the present embodiment can contain a structural unit represented by the following general formula (2) together with the structural unit represented by the general formula (1).

In general formula (2), Q, R ⁵ , R ⁶ , m1, m2, and X are synonymous with general formula (a3), and Y is synonymous with general formula (a1).
Specifically, the polyimide (A) of the present embodiment can contain a structural unit represented by the general formula (3).

In general formula (3), Q, R ⁵ , R ⁶ , m1, m2, and X are synonymous with general formula (a3), Y is synonymous with general formula (a1), and R ¹ and R ² are It is synonymous with general formula (a2).
The polyimide (A) of the present embodiment contains the structural units described above, and may further partially contain the following structural units.

In this embodiment, at least one of both ends of the polyimide (A) is preferably a (meth)acrylate group. By containing the group, hydrolysis is suppressed and the mechanical strength is excellent.
The polyimide (A) of the present embodiment has a weight average molecular weight of 5,000 to 200,000, preferably 10,000 to 100,000.

The polyimide (A) (negative photosensitive polymer) of the present embodiment is excellent in hydrolysis resistance, and has a weight average molecular weight reduction rate of 15% or less, preferably 12% or less, measured under the following conditions. More preferably 10% or less, particularly preferably 5% or less.
(conditions)
400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water are added to 100 parts by mass of the negative photosensitive polymer, and the mixture is stirred at 100°C for 6 hours. .
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100

With the negative photosensitive polymer of the present embodiment, a cured product such as a film having excellent mechanical strength such as elongation can be obtained by setting the reduction rate of the weight average molecular weight within the above range.

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

<Method for producing polyimide (A)>
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) A method for producing a polyimide (A) (negative photosensitive polymer) having a structural unit

An acid anhydride (a1′) represented by the following general formula (a1′), a diamine (a2′) represented by the following general formula (a2′), and a bis represented by the following general formula (a3′) A step 1 of imidizing the aminophenol (a3′) at a temperature of 100° C. or higher and 250° C. or lower;

A compound having a (meth)acrylate group is reacted with the hydroxyl group of the structural unit derived from the bisaminophenol (a3′) of the general formula (a3′) of the polymer obtained in step 1 to convert the (meth)acrylate group. Step 2 of introducing a group containing
including.
According to this embodiment, a polyimide (A) having excellent solubility in organic solvents can be synthesized by a simple method.

In general formula (a1′), Y is selected from the groups represented by general formulas (a1-1), (a1-2) and (a1-3).

In general formula (a2'), R ¹ and R ² have the same meanings as in general formula (a2).

In general formula (a3'), X has the same meaning as in general formula (a3).
In order to control the molecular weight of the resulting polyhydroxyimide, it is also possible to add a small amount of acid anhydride or aromatic amine as an endcapping agent to carry out the reaction.

Acid anhydrides as end capping agents include phthalic anhydride, maleic anhydride, nadic anhydride and the like, and aromatic amines include p-methylaniline, p-methoxyaniline, p-phenoxyaniline and the like. The amount of acid anhydride or aromatic amine added as the end capping agent is preferably 5 mol % or less. If it exceeds 5 mol %, the molecular weight of the resulting polyhydroxyimide is significantly lowered, causing problems in heat resistance and mechanical properties.

The equivalent ratio of acid anhydride (a1′), diamine (a2′) and bisaminophenol (a3′) in the imidization reaction of step 1 is an important factor that determines the molecular weight of the resulting polymer. In general, it is well known that there is a correlation between the molecular weight and mechanical properties of polymers, 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 acid anhydride (a1′), the diamine (a2′) and the bisaminophenol (a3′) to be used is not particularly limited. ) and bisaminophenol (a3′) is preferably in the range of 0.70 to 1.3. If the corresponding amount ratio is within the above range, the mechanical strength is excellent and the manufacturing stability is excellent.

From the viewpoint of improving mechanical properties, even if the equivalent ratio of diamine (a2') and bisaminophenol (a3') to acid anhydride (a1') is outside the above range, The apparent molecular weight can also be increased by chain cross-linking.
Step 1 (imidization reaction step) can be performed in an organic solvent by a known method.

Examples of organic solvents 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. , and one type or two or more types may be used in combination. At this time, a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used. Examples of nonpolar solvents 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 set arbitrarily according to the resin properties such as the stirring device capacity and 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. React for some time.

In step 1, a polyhydroxyimide having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2′), or a structural unit represented by the following general formula (3′) It is possible to obtain a polyhydroxyimide containing structural units having In step 1, the polyhydroxyimide can be purified by a known method. can be done.

In step 2, the hydroxyl groups of the polyhydroxyimide obtained in step 1 are reacted with a compound having (meth)acrylate groups to introduce cross-linking groups containing (meth)acrylate groups.
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 area becomes insoluble in the organic solvent.

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

In order to introduce a cross-linking group containing a (meth)acrylate group into polyhydroxyimide, polyhydroxyimide and a compound having a (meth)acrylate group are mixed in an organic solvent at 60° C. to 150° C. for 2 hours. React for about 10 hours. Although the reaction is not particularly limited, it can be carried out at normal pressure.

The compound having a (meth)acrylate group can be appropriately selected according to the amount of cross-linking groups to be introduced into the polyhydroxyimide. It can be added so as to double, preferably 2.0 to 3.0 mol times. In addition, when the polyhydroxyimide has a group capable of introducing a cross-linking group, the group can be added in a molar amount.

Examples of organic solvents 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. , and one type or two or more types may be used in combination. At this time, a nonpolar solvent compatible with the aprotic polar solvent may be mixed and used. Examples of non-polar solvents include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene and solvent naphtha, and ether solvents such as cyclopentyl methyl ether.
A base such as triethylamine or 1,1,3,3-tetramethylguanidine may be added during the reaction.

Through step 2, a polyimide (A) having a structural unit represented by general formula (1) and a structural unit represented by general formula (2), or a polyimide having a structural unit represented by general formula (3) ( A) can be obtained.

In step 2, the polyhydroxyimide obtained by purifying the reaction solution containing polyhydroxyimide obtained in step 1 by reprecipitation or the like can be used. can be used.

By the production method of the present embodiment described above, 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, and the polymer solution ( It can be used as a 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.

Alternatively, the reaction solution may be put into a poor solvent to reprecipitate the polyimide (A) resin to remove unreacted monomers, dry and solidify, and dissolve again in an organic solvent for use as a purified product. Particularly in applications where impurities and foreign matters are a problem, it is preferable to redissolve the varnish in an organic solvent to obtain a filtration-purified varnish.

<Negative photosensitive resin composition>
In this embodiment, the negative photosensitive resin composition can contain the negative photosensitive polymer described above. The negative photosensitive resin composition of the present embodiment contains a negative photosensitive polymer and is not particularly limited as long as it is negative photosensitive. For example, a negative photosensitive polymer (polyimide (A)) and a polyfunctional It is preferable that a cross-linking agent (B) containing (meth)acrylate and a photopolymerization initiator (C) are included.

[Crosslinking agent (B)]
A cross-linking agent (B) contains a polyfunctional (meth)acrylate.
The polyfunctional (meth)acrylate is a compound having two or more (meth)acryloyl groups, and conventionally known compounds can be used as long as the effects of the present invention can be exhibited. In addition, in this embodiment, a (meth)acryl group indicates an acryl group or a methacryl group.

Specific polyfunctional (meth)acrylates include bifunctional (meth)acrylates such as diethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, polyethylene glycol #400 di(meth)acrylate, and trimethylolpropane. tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trifunctional (meth)acrylate such as ethoxylated isocyanuric acid triacrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate and other tetrafunctional ( Hexafunctional (meth)acrylates such as meth)acrylates, dipentaerythritol hexa(meth)acrylate, octafunctional (meth)acrylates such as tripentaerythritol octa(meth)acrylate, and deca(meth)acrylates such as tetrapentaerythritol deca(meth)acrylate. (Meth)acrylates are mentioned. You may use 1 type(s) or 2 or more types among these.

The amount of the cross-linking agent (B) with respect to 100 parts by mass of the polyimide (A) is 1 part by mass or more and 30 parts by mass or less, preferably 2 parts by mass or more and 20 parts by mass or less, preferably 3 parts by mass, from the viewpoint of the effect of the present invention. parts or more and 15 parts by mass or less. Within this range, elongation is further improved.

[Photoinitiator (C)]
As the photopolymerization initiator (C), for example, a photoradical generator can be used. The photo-radical generator includes a photo-radical generator that generates radicals upon irradiation with actinic rays such as ultraviolet rays and functions as a photopolymerization initiator for the polyimide (A) described above.

Examples of the photoradical generator include alkylphenone type initiators, oxime ester type initiators, acylphosphine oxide type initiators, and the like. For example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-morifolinopropan-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-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)), ethanone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)- 2-(phenylmethyl)-1-butanone, Irgacure 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), and the like. Any one or more of these can be used.
Among these, the oxime ester type initiator is preferable from the viewpoint of the effect of the present invention and from the viewpoint of producing a resin film composed of a photosensitive resin composition having excellent exposure sensitivity.

The amount of the polymerization initiator (C) added is not particularly limited, but it is preferably about 0.3 to 20% by mass of 100% by mass of the non-volatile components of the negative photosensitive resin composition excluding the solvent, and 0.5% by mass. About 15% by mass is more preferable, and about 1 to 10% by mass is even more preferable. By setting the addition amount of the polymerization initiator (C) within the above range, the patterning property of the photosensitive resin layer containing the negative photosensitive resin composition is enhanced, and the long-term storage stability of the negative photosensitive resin composition is improved. can be improved.

(solvent)
The negative photosensitive resin composition according to this embodiment can contain a solvent. Thereby, a uniform photosensitive resin film can be formed on various substrate surfaces.

An organic solvent is preferably used as the solvent. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.

Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma-butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl- Mention may be made of n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof.
The amount of solvent used is not particularly limited. For example, it is used in such an amount that the concentration of non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

(Surfactant)
The negative photosensitive resin composition according to this embodiment may further contain a surfactant.
The surfactant is not limited, and specifically polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Ftop EF301, Ftop EF303, Ftop EF352 (manufactured by Shin-Akita Kasei), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (DIC Corporation) manufactured), Florado FC-430, Florard FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan), 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, commercially available fluorine-based surfactants (manufactured by AGC Seimi Chemical Co., Ltd.); Combined KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid-based copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. Among the specific examples of the perfluoroalkyl group-containing fluorosurfactant, Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, and Megafac One or more selected from F477 (manufactured by DIC), 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) is preferably used.

As the surfactant, a silicone-based surfactant (for example, polyether-modified dimethylsiloxane) can also be preferably used. Specific examples of silicone surfactants include SH series, SD series and ST series from Dow Corning Toray Co., Ltd., BYK series from BYK Chemie Japan, KP series from Shin-Etsu Chemical Co., Ltd., Disfoam from NOF CORPORATION ( (registered trademark) series, TSF series of Toshiba Silicone Co., Ltd., and the like.

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

In addition, although there is no particular lower limit for the content of the surfactant in the negative photosensitive resin composition, 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).
Applicability and uniformity of the coating film can be improved while maintaining other properties by appropriately adjusting the amount of the surfactant.

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

Phenolic 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 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]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-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], 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'-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, styreneated 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), 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 mono and 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 antioxidants include dilauryl-3,3′-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl)sulfide , distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis(3-lauryl)thiopropionate, and the like.

(adherence aid)
The negative photosensitive resin composition according to this embodiment may further contain an adhesion aid.
Examples of adhesion aids that can be used include silane coupling agents such as aminosilane, epoxysilane, (meth)acrylsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride-functional silane, and sulfidesilane. Silane coupling agents may be used alone or in combination of two or more. Among these, epoxysilanes (i.e., compounds containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule) or anhydride-functional silanes (i.e., in one molecule, an anhydride and a group that generates a silanol group by hydrolysis) are preferred.

Examples of aminosilanes include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-amino propylmethyldimethoxysilane, N-β (aminoethyl)γ-aminopropyltrimethoxysilane, N-β (aminoethyl)γ-aminopropyltriethoxysilane, N-β (aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, and the like.

Examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidylpropyltrimethoxysilane. Silane etc. are mentioned.

Examples of acrylic silanes include γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-(methacryloxypropyl)methyldiethoxysilane, and the like.
Mercaptosilanes include, for example, 3-mercaptopropyltrimethoxysilane.

Vinylsilanes include, for example, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like.
Ureidosilanes include, for example, 3-ureidopropyltriethoxysilane.

Examples of the acid anhydride-functional silane include X-12-967C (product name: 3-trimethoxysilylpropylsuccinic anhydride) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

Examples of sulfide silanes include bis(3-(triethoxysilyl)propyl)disulfide and bis(3-(triethoxysilyl)propyl)tetrasulfide.
The amount of the adhesion aid added is not particularly limited, but is 0.1 to 5% by mass, preferably 0.5 to 3% by mass, based on the total solid content of the negative photosensitive resin composition.

(Preparation of negative photosensitive resin composition)
A 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, it can be prepared by mixing and dissolving the above components in a solvent.

(Negative photosensitive resin composition)
The negative photosensitive resin composition according to the present embodiment is formed by applying the negative photosensitive resin composition to a surface comprising a metal such as Al or Cu, and then pre-baking to dry it to form a resin film. Then, the resin film is patterned into a desired shape by exposure and development, and then the resin film is cured by heat treatment to form a cured film.

In addition, when producing the said permanent film, as conditions of a pre-baking, it can be set as the heat processing for 30 seconds or more and 1 hour or less at the temperature of 90 degreeC or more and 130 degrees C or less, for example. The heat treatment conditions are, for example, heat treatment at a temperature of 150° C. to 250° C. for 30 minutes to 10 hours, preferably about 170° C. for 1 to 6 hours.

The film obtained from the negative photosensitive resin composition of the present embodiment has a maximum elongation of 15 to 200%, preferably 20 to 150%, and an average elongation of 10 as measured by a tensile test using a Tensilon tester. ~150%, preferably 15-120%.
In addition, since the negative photosensitive resin composition of the present embodiment contains polyimide (A) (negative photosensitive polymer) having excellent hydrolysis resistance, it can be , Even after performing a HAST test (unsaturated pressurized steam test) for 96 hours, the rate of decrease in the elongation rate (maximum value, average value) represented by the following formula is 20% or less, preferably 15% or less, More preferably, it is 12% or less.
[(Elongation before test - Elongation after test) / Elongation before test)] × 100

The negative photosensitive resin composition of this embodiment is excellent in low-temperature curability.
For example, the cured product obtained by curing the negative photosensitive resin composition of the present embodiment at 170°C for 4 hours has a glass transition temperature (Tg) of 200°C or higher, preferably 210°C or higher, more preferably 220°C. °C or higher.

Furthermore, the cured product obtained by curing the negative photosensitive resin composition of the present embodiment at 170° C. for 4 hours has a storage elastic modulus E′ at 30° C. of 2.0 GPa or more, preferably 2.5 GPa or more, More preferably, it can be 3.0 GPa or more. Furthermore, the storage elastic modulus E' at 200°C can be 0.5 GPa or more, preferably 0.7 GPa or more, and more preferably 0.8 GPa or more.

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.

A cured product such as a film obtained from the negative photosensitive resin composition of the present embodiment has excellent chemical resistance.
Specifically, the film is immersed in a solution of less than 99% by mass of dimethyl sulfoxide and less than 2% by mass of tetramethylammonium hydroxide at 40° C. for 10 minutes, then thoroughly washed with isopropyl alcohol and air-dried. to measure. The film thickness change rate between the film thickness after treatment and the film thickness before treatment is calculated from the following formula and evaluated as the reduction rate of the film.
Formula: Film reduction rate (%) {(film thickness after immersion - film thickness before immersion) / film thickness before immersion x 100 (%)}

The film thickness change rate is preferably 40% or less, more preferably 30% or less. As a result, even when the cured film is subjected to a step of being immersed in dimethylsulfoxide, the film thickness hardly decreases. Therefore, a cured film that can maintain its functions even after being subjected to such steps can be obtained.

The negative photosensitive resin composition of the present embodiment has suppressed curing shrinkage, and is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm, pre-baked at 120° C. for 3 minutes, and placed under a high-pressure mercury lamp. In the case where a film is prepared by exposing to 600 mJ / cm ² and then performing heat treatment at 170 ° C. for 120 minutes in a nitrogen atmosphere, the film thickness after the pre-bake is the film thickness A, and the film thickness after the heat treatment. is the film thickness B, and the cure shrinkage calculated from the following formula is 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 the present embodiment has high heat resistance, and the resulting film has a weight loss temperature (Td5) measured by simultaneous thermogravimetric differential thermal measurement of 200° C. or higher, preferably 300° C. or higher. be able to.

Curing shrinkage of the film made of the negative photosensitive resin composition of the present embodiment is suppressed, and the coefficient of linear thermal expansion (CTE) can be 200 ppm/°C or less, preferably 100 ppm/°C or less.

The film made of the negative photosensitive resin composition of the present embodiment has excellent mechanical strength, and has an elastic modulus at 25° C. of 1.0 to 5.0 GPa, preferably 1.5 to 3.0 GPa. can do.

(Application)
The negative photosensitive resin composition of the present embodiment is used for forming resin films for semiconductor devices such as permanent films and resists. Among these, from the viewpoint of expressing in a well-balanced manner the improvement in adhesion between the negative photosensitive resin composition and the Al pad after prebaking and the suppression of the generation of residues of the negative photosensitive resin composition during development, Use of a permanent film from the viewpoint of improving the adhesion between the cured film of the negative photosensitive resin composition and the metal, and also from the viewpoint of improving the chemical resistance of the negative photosensitive resin composition after heat treatment. It is preferably used for

In addition, 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 obtained 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 curing it by heat treatment. Permanent films can be used as protective films, interlayer films, dam materials, and the like for semiconductor devices.

The above-mentioned resist can be obtained, for example, 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, and negative photosensitive resin composition. It is composed of a resin film obtained by removing the solvent from a flexible 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 resin film. Specifically, one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 in the semiconductor device 100 can be a resin film containing the cured product of the present embodiment. Here, the resin film is preferably the permanent film described above.

Semiconductor device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package is obtained by mounting the semiconductor device 100 on the wiring substrate via the bumps 52 .

The semiconductor device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and a top layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layers. The uppermost layer wiring 34 is made of aluminum Al, for example. A passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34 . A portion of the passivation film 32 is provided with an opening through 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, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, have An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42 . The rewiring 46 is formed on the insulating layer 42 and in openings provided in the insulating layer 42 and connected to the uppermost layer wiring 34 . The insulating layer 44 is provided with an opening connected to the rewiring 46 .

A bump 52 is formed in the opening provided in the insulating layer 44 via a UBM (Under Bump Metallurgy) layer 50, for example. Semiconductor device 100 is connected to a wiring substrate or the like via 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 employed within the scope that does not impair the effects of the present invention.

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

1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine (hereinafter also referred to as TMDA) represented by the following formula

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

4,4′-(hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene] (hereinafter also referred to as HFBAPP) represented by the following formula

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

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)-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)

[Example 1]
First, 3.54 g (13.7 mmol) of TMDA, 3.65 g (13.7 mmol) of BAPA, and 20.17 g (32.6 mmol) of TMPBP-TME were added to an appropriately sized reaction vessel equipped with a stirrer and condenser. ) and An additional 73.87 g of GBL was then added to the reaction vessel.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 1.5 hours. Thereafter, the reaction was further carried out at 180° C. for 3 hours to polymerize the bisaminophenol and the acid anhydride to prepare a polymerization solution.
GPC measurement of the polymer revealed a weight average molecular weight Mw of 15,800 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 1.73.
Next, 7.73 g (54.8 mmol) of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko Co., Ltd.) and γ-butyl lactone (GBL ) 23.49 g. After that, the temperature was raised to 120° C. while stirring, and the reaction was carried out for 6 hours.
The resulting reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was collected and vacuum-dried at a temperature of 40° C. to obtain 23.29 g of a polymer.
GPC measurement of the polymer revealed a weight average molecular weight Mw of 17,200 and a polydispersity (weight average molecular weight Mw/number average molecular weight Mn) of 1.78.
Further, ¹ H-NMR measurement confirmed a peak in the aromatic region (6.8 ppm to 8.9 ppm) with an area ratio corresponding to the number of protons.
Also, from the area ratio of the aromatic region (6.8 ppm to 8.9 ppm) and the alkene region (5.8 ppm to 6.5 ppm), the introduction rate of the cross-linking group was 100%.
The resulting polymer partially contained repeating units represented by the following formula.

[Comparative Examples 1 and 2]
Comparative Examples 1 and 2 were synthesized in the same manner as in Example 1 except for the conditions described in Table 1. The obtained Mw, Mw/Mn and cross-linking group introduction rate are shown in the table.

[Solubility in organic solvents]
The solubility of the negative photosensitive polymers obtained in Example 1 and Comparative Examples 1 and 2 in γ-butyllactone (GBL) was evaluated according to the following criteria. Table 1 shows the results.
(Evaluation criteria for solubility)
○: 5% by mass or more of polymer dissolved △: 1 to 5% by mass of polymer dissolved ×: Less than 1% by mass of polymer dissolved

[Hydrolysis resistance]
The rate of decrease in the weight average molecular weight of the negative photosensitive polymers obtained in Examples and Comparative Examples was measured under the following conditions. Table 1 shows the results.
(Conditions (no addition of triethylamine))

400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of the negative photosensitive polymer, and the mixture was stirred at 100°C for 6 hours.
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100
(Conditions (addition of triethylamine))

10 parts by mass of triethylamine, 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of the negative photosensitive polymer, and the mixture was stirred at 100°C for 6 hours. Calculated by the formula.
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100

As shown in Table 1, the negative photosensitive polymers of the present invention obtained in Examples are excellent in solubility in organic solvents and inhibited in hydrolysis. It was inferred that the decrease was suppressed.

100 semiconductor device 30 interlayer insulating film 32 passivation film 34 top layer wiring 40 rewiring layer 42 insulating layer 44 insulating layer 46 rewiring 50 UBM layer 52 bump

Claims (5)

a structural unit (a1) represented by the following general formula (a1);
a structural unit (a2) represented by the following general formula (a2);
a structural unit (a3) represented by the following general formula (a3);
A negative photosensitive polymer comprising:

(In general formula (a1), Y is a divalent organic group.
In general formula (a2), 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. A plurality of R ¹ 's and a plurality of R ² 's may be the same or different.
In general formula (a3), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and multiple Qs may be the same or different.
R ⁵ and R ⁶ 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.
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; Multiple X's may be the same or different. ) Y in the general formula (a1) is a divalent organic group selected from the following general formula (a1-1), the following general formula (a1-2) and the following general formula (a1-3). Item 1. The negative photosensitive polymer according to item 1.

(In general formula (a1-1), R ⁷ and R ⁸ 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 ⁷ and a plurality of R ⁸ may be the same or different, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to ³ carbon atoms; may be the same or different, and * indicates a bond.
In general formula (a1-2), each of R ¹⁰ and R ¹¹ independently represents a hydrogen atom, an alkyl group having ¹ to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; , a plurality of R ¹¹ may be the same or different. * indicates a bond.
In general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group.
* indicates a bond. ) 3. The negative photosensitive polymer according to claim 2, wherein at least one of both ends is a (meth)acrylate group. 4. The negative photosensitive polymer according to claim 2, comprising structural units represented by the following general formulas (1) and (2).

(In general formula (1), R ¹ and R ² are synonymous with general formula (a2), and Y is synonymous with general formula (a1).)

(In general formula (2), Q, R ⁵ , R ⁶ , m1, m2, and X are synonymous with general formula (a3), and Y is synonymous with general formula (a1).) 5. The negative photosensitive polymer according to any one of claims 2 to 4, wherein the weight average molecular weight reduction rate measured under the following conditions is 15% or less.
(conditions)
400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water are added to 100 parts by mass of the negative photosensitive polymer, and the mixture is stirred at 100°C for 6 hours. .
Formula: [(weight average molecular weight before test - weight average molecular weight after test) / weight average molecular weight before test] × 100

Images