JP2015028608A - Negative photosensitive resin composition, cured film, electronic apparatus and polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition having an excellent balance of various properties required for an insulating film.SOLUTION: A negative photosensitive resin composition comprises a polymer comprising a copolymer represented by the following formula (1), photoacid generator, and a first crosslinking agent for cross-linking of the polymer with the acid generated from the photoacid generator as a catalyst.

Description

  The present invention relates to a negative photosensitive resin composition, a cured film, an electronic device, and a polymer.

In the process of manufacturing a semiconductor integrated circuit, a display surface of a flat panel display (FPD), and the like, a photolithography technique is used to form a fine element or perform fine processing.
In the photolithography technique, a photosensitive resin composition is used to form a resist pattern.

  For example, Patent Document 1 (Japanese Patent Laid-Open No. 2-146045) discloses a photosensitive resin composition containing a polymer and a photosensitive agent. It is disclosed that the polymer has a unit composed of a cyclic aliphatic hydrocarbon skeleton and a unit derived from maleic anhydride, and is obtained by hydrolyzing an acid anhydride ring of a unit derived from maleic anhydride. .

Japanese Patent Laid-Open No. 2-146045

However, since the photosensitive resin composition containing the polymer has a poor crosslinking reaction efficiency, it is necessary to add a large amount of a photoacid generator or a crosslinking agent.
When a large amount of a photoacid generator or a crosslinking agent is added to the photosensitive resin composition, various characteristics of the obtained negative photosensitive insulating film are deteriorated.

  By using a negative photosensitive resin composition containing a copolymer represented by the following formula (1), the present inventors have a negative having an excellent balance of various properties required for a negative photosensitive insulating film. The present inventors have found that a type photosensitive insulating film can be formed and have reached the present invention.

（式（１）中、ｌ、ｐおよびｍは、ポリマー中におけるモル含有率を示し、かつ、ｌ＋ｐ＋ｍ≦１、０≦ｌ＜１、０＜ｐ＜１、および０＜ｍ＜１の条件を満たし、
ｎおよびｑはそれぞれ独立して０、１または２であり、
Ｒ_１〜Ｒ_４およびＲ_８〜Ｒ_１１はそれぞれ独立して水素または炭素数１〜３０の有機基であり、
Ｒ_８、Ｒ_９、Ｒ_１０およびＲ_１１から選択される１または２以上がアルコール性水酸基を有する有機基であり、
Ａは下記式（２ａ）、（２ｂ）、（２ｃ）または（２ｄ）により示される構造単位である）

（式（２ａ）および式（２ｂ）中、Ｒ_５、Ｒ_６およびＲ_７は、それぞれ独立して炭素数１〜１８の有機基である） That is, according to the present invention,
A negative photosensitive resin composition comprising:
A polymer composed of a copolymer represented by the following formula (1);
A photoacid generator;
A first crosslinking agent that crosslinks the polymer using an acid generated from the photoacid generator as a catalyst;
A negative photosensitive resin composition is provided.

(In the formula (1), l, p and m represent the molar content in the polymer, and the conditions of l + p + m ≦ 1, 0 ≦ l <1, 0 <p <1, and 0 <m <1 are satisfied. Meet,
n and q are each independently 0, 1 or 2,
R _{1 to} R ₄ and R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms,
One or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having an alcoholic hydroxyl group;
A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d))

(In Formula (2a) and Formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms)

Furthermore, according to the present invention,
There is provided a cured film obtained by curing the negative photosensitive resin composition.

Furthermore, according to the present invention,
An electronic device comprising the cured film is provided.

（式（１）中、ｌ、ｐおよびｍは、ポリマー中におけるモル含有率を示し、かつ、ｌ＋ｐ＋ｍ≦１、０≦ｌ＜１、０＜ｐ＜１、および０＜ｍ＜１の条件を満たし、
ｎおよびｑはそれぞれ独立して０、１または２であり、
Ｒ_１〜Ｒ_４およびＲ_８〜Ｒ_１１はそれぞれ独立して水素または炭素数１〜３０の有機基であり、
Ｒ_８、Ｒ_９、Ｒ_１０およびＲ_１１から選択される１または２以上がアルコール性水酸基を有する有機基であり、
Ａは下記式（２ａ）、（２ｂ）、（２ｃ）または（２ｄ）により示される構造単位である）

（式（２ａ）および式（２ｂ）中、Ｒ_５、Ｒ_６およびＲ_７は、それぞれ独立して炭素数１〜１８の有機基である） Furthermore, according to the present invention,
A polymer composed of a copolymer represented by the following formula (1) is provided.

(In the formula (1), l, p and m represent the molar content in the polymer, and the conditions of l + p + m ≦ 1, 0 ≦ l <1, 0 <p <1, and 0 <m <1 are satisfied. Meet,
n and q are each independently 0, 1 or 2,
R _{1 to} R ₄ and R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms,
One or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having an alcoholic hydroxyl group;
A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d))

(In Formula (2a) and Formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms)

  ADVANTAGE OF THE INVENTION According to this invention, the negative photosensitive resin composition which can form the negative photosensitive insulating film excellent in the balance of the various characteristics requested | required of a negative photosensitive insulating film can be provided.

It is sectional drawing which shows an example of the electronic device which concerns on this embodiment. It is sectional drawing which shows an example of the electronic device which concerns on this embodiment.

  Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate. In addition, unless otherwise specified, “to” represents the following.

<Negative photosensitive resin composition>
The negative photosensitive resin composition P according to this embodiment was generated from the first polymer composed of a copolymer represented by the following formula (1), a photoacid generator, and the photoacid generator. And a first crosslinking agent that crosslinks the first polymer using an acid as a catalyst.

（式（１）中、ｌ、ｐおよびｍは、ポリマー中におけるモル含有率を示し、かつ、ｌ＋ｐ＋ｍ≦１、０≦ｌ＜１、０＜ｐ＜１、および０＜ｍ＜１の条件を満たし、ｎおよびｑはそれぞれ独立して０、１または２であり、Ｒ_１〜Ｒ_４およびＲ_８〜Ｒ_１１はそれぞれ独立して水素または炭素数１〜３０の有機基であり、Ｒ_８、Ｒ_９、Ｒ_１０およびＲ_１１から選択される１または２以上がアルコール性水酸基を有する有機基であり、Ａは下記式（２ａ）、（２ｂ）、（２ｃ）または（２ｄ）により示される構造単位である）

(In the formula (1), l, p and m represent the molar content in the polymer, and the conditions of l + p + m ≦ 1, 0 ≦ l <1, 0 <p <1, and 0 <m <1 are satisfied. And n and q are each independently 0, 1 or 2, R _{1 to} R ₄ and R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms, R ₈ , One or more selected from R ₉ , R ₁₀ and R ₁₁ is an organic group having an alcoholic hydroxyl group, and A is a structure represented by the following formula (2a), (2b), (2c) or (2d) Unit)

（式（２ａ）および式（２ｂ）中、Ｒ_５、Ｒ_６およびＲ_７は、それぞれ独立して炭素数１〜１８の有機基である）

(In Formula (2a) and Formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms)

According to such a negative photosensitive resin composition P, by using the first polymer described above, for example, developability, resolution, residual film properties, insulation properties, transparency, heat resistance, resistance to heat, etc. It is possible to provide a negative photosensitive insulating film excellent in balance of various properties required for a negative photosensitive insulating film such as a solvent.
Since the first polymer has an alcoholic hydroxyl group on the side chain, it has excellent reactivity with the first crosslinking agent. Thereby, since the addition amount of an expensive photo-acid generator can be reduced, it is excellent in economical efficiency. In addition, since the amount of crosslinking agent that deteriorates developability can be reduced, film loss during development can be greatly reduced.As a result, uneven thickness of the negative photosensitive insulating film can be reduced, and film flatness can be reduced. It can be improved. Furthermore, since a negative photosensitive insulating film having a higher degree of crosslinking can be obtained, the remaining film property, heat resistance, transparency, solvent resistance, and the like can be improved. Further, the resolution and insulation can be maintained at conventional levels.

  The negative photosensitive resin composition P may further contain other materials such as additives. Hereinafter, each component will be described.

<First polymer>
The first polymer according to this embodiment is a copolymer represented by the following formula (1).

In the formula (1), l, p and m represent the molar content (mol%) in the polymer, and l + p + m ≦ 1, 0 ≦ l <1, 0 <p <1, and 0 <m <1 And n and q are each independently 0, 1 or 2. Further, l, p and m are preferably 0 ≦ l ≦ 0.25, 0.25 ≦ p ≦ 0.50, and 0.50 ≦ m ≦ 0.75.
n and q are each independently 0, 1 or 2.
R _{1 to} R ₄ and R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. R _{1 to} R ₄ and R _{8 to} R ₁₁ may be the same as or different from each other.
One or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having an alcoholic hydroxyl group. Here, in this embodiment, the alcoholic hydroxyl group means a hydroxyl group bonded to a carbon atom of a chain or cyclic hydrocarbon group.
A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d). The copolymer represented by the above formula (1) includes one or more structural units A selected from the following formulas (2a), (2b), (2c) and (2d). In the present embodiment, one or more structural units A selected from the following formulas (2a) and (2c) are preferably included, and from the following formulas (2a), (2b) and (2c) More preferably, one or more selected structural units A are included. In addition, the 1st polymer may contain other structural units other than the structural unit shown to the said Formula (1).

式（２ａ）および式（２ｂ）中、Ｒ_５、Ｒ_６およびＲ_７は、それぞれ独立して炭素数１〜１８の有機基である。

In formula (2a) and formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms.

The organic group having 1 to 30 carbon atoms constituting the R ₁ to R ₄ and _R 8 _{to R 11} are, O in their structure, N, S, may contain one or more selected from P and Si. However, none of the organic groups constituting R _{1 to} R ₄ has an alcoholic hydroxyl group.

In the present embodiment, examples of the organic group constituting R _{1 to} R ₄ and R _{8 to} R ₁₁ include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, And heterocyclic groups.
As the alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, and a decyl group are mentioned. Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
Note that by including an alkyl group as R ₁ to R ₄ and R ₈ to R _11, it is possible to improve the film formability of the film made of the negative photosensitive resin composition P comprising a first polymer. Further, development using an alkaline developer in a lithography process for a film made of the negative photosensitive resin composition P containing the first polymer by including an aryl group as R _{1 to} R ₄ and R _{8 to} R ₁₁ It is possible to suppress film loss during the process.

Furthermore, in the alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, and heterocyclic group described above, one or more hydrogen atoms may be substituted with halogen atoms. Good. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable. When at least one of R _{1 to} R ₄ and R _{8 to} R ₁₁ is a haloalkyl group to form the negative photosensitive resin composition P using the first polymer, this negative photosensitive resin The dielectric constant of the conductive resin composition P can be reduced.

Examples of the organic group having an alcoholic hydroxyl group constituting one or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ include, for example, carbonization in which one or more alcoholic hydroxyl groups are bonded to the alcoholic hydroxyl group. And a group having a hydrogen group.
The alcoholic hydroxyl group is a primary or secondary alcoholic hydroxyl group or a chain-like tertiary alcoholic hydroxyl group. Among these, from the viewpoint of excellent crosslinking reactivity, a linear primary or secondary alcoholic hydroxyl group is preferable, and a linear primary alcoholic hydroxyl group is particularly preferable.
Here, the “primary alcoholic hydroxyl group” refers to a hydroxyl group bonded to a primary carbon atom constituting a chain or cyclic hydrocarbon group. “Secondary alcoholic hydroxyl group” refers to a hydroxyl group bonded to a secondary carbon atom constituting a chain or cyclic hydrocarbon group. The “tertiary alcoholic hydroxyl group” refers to a hydroxyl group bonded to a tertiary carbon atom constituting a chain hydrocarbon group.

Examples of the chain hydrocarbon group include a linear or branched hydrocarbon group.
In addition, examples of the cyclic hydrocarbon group include an aliphatic cyclic group.
The hydrocarbon group may be either saturated or unsaturated, but is usually preferably saturated. Moreover, a part of hydrogen atoms constituting the hydrocarbon group may be substituted. Examples of the substituent that substitutes a part of the hydrogen atom include a fluorine atom, an oxygen atom (═O), a cyano group, and the like.

When the hydrocarbon group is linear, the number of carbon atoms is preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.
When the hydrocarbon group is an aliphatic cyclic group, examples include groups in which two or more hydrogen atoms have been removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane.
Among these, a linear hydrocarbon group having 1 to 10 carbon atoms is preferable, and a linear hydrocarbon group having 1 to 5 carbon atoms is more preferable.

The organic group having an alcoholic hydroxyl group constituting one or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ may contain a divalent linking group containing a hetero atom. Examples of such an organic group include a group in which an alcoholic hydroxyl group is bonded to the end of a divalent linking group containing a hetero atom.
Examples of the divalent linking group containing a hetero atom include -O-, -C (= O) -O-, -C (= O)-, -O-C (= O) -O-, -C. (= O) -NH -, - NH -, - S -, - S (= O) 2 -, - S (= O) 2 -O-, and the like.

In addition, from the viewpoint of increasing the light transmittance of the film including the first polymer, any of R ₁ , R ₂ , R ₃ and R ₄ is preferably hydrogen, and R ₁ , R ₂ , It is particularly preferred that all of R ₃ and R ₄ are hydrogen.
_It is preferable that one of R _8, R _{9, R 10} and _{R 11} is _hydrogen, it is particularly preferred 3 selected from R _8, R _{9, R 10} and _{R 11} is hydrogen.

The organic group having 1 to 18 carbon atoms constituting R ₅ , R ₆ and R ₇ may contain any one or more of O, N, S, P and Si in the structure. The organic group constituting R _5, R ₆ and R _7, can be made free of acid functionality. Thereby, control of the acid value in the first polymer can be facilitated.

In this embodiment, examples of the organic group constituting R ₅ , R ₆ and R ₇ include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and a heterocyclic ring. Groups. Here, as the alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl Groups, octyl groups, nonyl groups, and decyl groups. Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

  Furthermore, in the alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, and heterocyclic group described above, one or more hydrogen atoms may be substituted with halogen atoms. Good. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable.

The copolymer represented by the above formula (1) is derived from, for example, a repeating unit derived from a norbornene type monomer represented by the following formula (3) or (4) and a maleic anhydride represented by the following formula (5). An alternating copolymer in which repeating units are alternately arranged is preferable. The copolymer represented by the above formula (1) may be a random copolymer or a block copolymer.
The repeating unit derived from maleic anhydride shown in the following formula (5) is a structural unit represented by A in the above formula (1). In addition, the 1st polymer may contain the monomer shown by following formula (3), (4), and (5) as a low molecular weight component.

式（３）および（４）中、ｎおよびｑはそれぞれ独立して０、１または２である。Ｒ_１〜Ｒ_４およびＲ_８〜Ｒ_１１はそれぞれ独立して水素または炭素数１〜３０の有機基である。Ｒ_１〜Ｒ_４およびＲ_８〜Ｒ_１１は、互いに同一であってもよく、また互いに異なっていてもよい。
Ｒ_８、Ｒ_９、Ｒ_１０およびＲ_１１から選択される１または２以上は、アルコール性水酸基および加水分解してアルコール性水酸基を生成する基から選択される少なくとも一つを有する有機基である。加水分解してアルコール性水酸基を生成する基としては、アルコール性水酸基をアルキル基やアセチル基などの保護基で保護したものが挙げられる。

In formulas (3) and (4), n and q are each independently 0, 1 or 2. R _{1 to} R ₄ and R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. R _{1 to} R ₄ and R _{8 to} R ₁₁ may be the same as or different from each other.
One or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having at least one selected from an alcoholic hydroxyl group and a group that hydrolyzes to form an alcoholic hydroxyl group. Examples of the group that generates an alcoholic hydroxyl group by hydrolysis include those obtained by protecting the alcoholic hydroxyl group with a protecting group such as an alkyl group or an acetyl group.

The first polymer in the present embodiment has, for example, Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.5 or more and 2.5 or less. Mw / Mn is a degree of dispersion indicating the width of the molecular weight distribution.
The present inventor has found that, by controlling the molecular weight distribution in the first polymer within a certain range, the deformation of the pattern at the time of curing can be suppressed for the film formed by the first polymer. For this reason, the pattern shape of the film | membrane which consists of negative photosensitive resin composition P containing a 1st polymer can be made favorable by making Mw / Mn of a 1st polymer into the said range.
The Mw (weight average molecular weight) of the first polymer is, for example, 3,000 or more and 30,000 or less.

For the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn), for example, a polystyrene conversion value obtained from a standard polystyrene (PS) calibration curve obtained by GPC measurement is used. The measurement conditions are, for example, as follows.
Tosoh gel permeation chromatography device HLC-8320GPC
Column: Tosoh TSK-GEL Supermultipore HZ-M
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / ml

  The first polymer according to this embodiment is manufactured as follows, for example.

(Polymerization step (Process S1))
First, a norbornene-type monomer represented by the formula (4), maleic anhydride as a monomer, and a norbornene-type monomer represented by the formula (3) as necessary are prepared.
In the norbornene-type monomer represented by the formula (3), n may be 0, 1 or 2, but is preferably 0 or 1. Thereby, the softness | flexibility of the film | membrane formed with the resin composition containing the polymer of this embodiment can be improved.
Similarly, in the norbornene-type monomer represented by the formula (4), q may be 0, 1 or 2, but is preferably 0 or 1. Thereby, the softness | flexibility of the film | membrane formed with the resin composition containing the polymer of this embodiment can be improved.

Specific examples of the norbornene-type monomer represented by the formula (3) include bicyclo [2.2.1] -hept-2-ene (common name: norbornene), and further have an alkyl group. As those having an alkenyl group, such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, As those having an alkynyl group, such as 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, and 5- (1-methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2 Examples of those having an aralkyl group such as norbornene include 5-benzyl-2-norbornene and 5-phenethyl-2-norbornene. And the like.
Any one or more of these can be used as the norbornene-type monomer. Especially, it is preferable to use bicyclo [2.2.1] -hept-2-ene (common name: norbornene) from a viewpoint of the light transmittance of a polymer.

  Specifically, as the norbornene-type monomer represented by the formula (4), a part of hydrogen of the norbornene-type monomer represented by the formula (3) is hydrolyzed and hydrolyzed to generate an alcoholic hydroxyl group. And those substituted with an organic group having at least one selected from the group.

Next, the norbornene type monomer represented by the formula (3), the norbornene type monomer represented by the formula (4), and maleic anhydride are subjected to addition polymerization. Here, a copolymer (copolymer 1) of a norbornene monomer represented by the formula (3), a norbornene monomer represented by the formula (4), and maleic anhydride is formed by radical polymerization.
From the viewpoint of further improving the efficiency of the crosslinking reaction, the number of moles of the norbornene-type monomer represented by the formula (3) is preferably 0 mol% or more and 25 mol% or less, and the number of moles of the norbornene-type monomer represented by the formula (4) Is preferably 25 mol% or more and 50 mol% or less, and the number of moles of maleic anhydride is preferably 50 mol% or more and 75 mol% or less.
The norbornene type monomer represented by the formula (3), the norbornene type monomer represented by the formula (4), maleic anhydride, and a polymerization initiator are dissolved in a solvent, and then heated for a predetermined time. The norbornene type monomer represented by 3), the norbornene type monomer represented by the formula (4), maleic anhydride and maleic anhydride are solution polymerized. The heating temperature is, for example, 50 to 80 ° C., and the heating time is 10 to 20 hours.

As the solvent, for example, one or more of tetrahydrofuran, toluene, methyl ethyl ketone and the like can be used.
As the polymerization initiator, any one or more of an azo compound and an organic peroxide can be used.
Examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis (2-methylpropionate), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), Any one or more of these can be used.
Examples of organic peroxides include hydrogen peroxide, ditertiary butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Any one or more of them can be used.

  The amount (number of moles) of the polymerization initiator is 1% to 10% of the total number of moles of the norbornene type monomer represented by the formula (3), the norbornene type monomer represented by the formula (4), and maleic anhydride. It is preferable to do. The weight average molecular weight (Mw) of the obtained polymer is adjusted to 3,000 or more and 30,000 or less by appropriately setting the amount of the polymerization initiator within the above range and appropriately setting the reaction temperature and reaction time. be able to.

By this polymerization step (treatment S1), a copolymer having a repeating unit represented by the following formula (6), a repeating unit represented by the following formula (7), and a repeating unit represented by the following formula (8): The polymer 1 can be polymerized.
However, in the copolymer 1, R _{1 in} the structure of the formula (7) is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{2 to} R ₄ and R _{8 to} R ₁₁ .

（式（７）において、ｎ、Ｒ_１〜Ｒ_４は、上記式（１）と同じである。すなわち、ｎは０、１、２のいずれかである。Ｒ_１〜Ｒ_４は、それぞれ独立した水素または炭素数１〜３０の有機基である。式（７）において、Ｒ_１〜Ｒ_４は、同一のものであっても異なっていてもよい）
（式（８）において、ｑ、Ｒ_８〜Ｒ_１１は、上記式（１）と同じである。すなわち、ｑは０、１、２のいずれかである。また、Ｒ_８〜Ｒ_１１は、それぞれ独立した水素または炭素数１〜３０の有機基である。Ｒ_８、Ｒ_９、Ｒ_１０およびＲ_１１から選択される１または２以上はアルコール性水酸基を有する有機基である。式（８）において、Ｒ_８〜Ｒ_１１は、同一のものであっても異なっていてもよい）

(In the formula (7), n and R _{1 to} R ₄ are the same as in the above formula (1). That is, n is 0, 1, or 2. R _{1 to} R ₄ are independent of each other. Hydrogen or an organic group having 1 to 30 carbon atoms.In formula (7), R _{1 to} R ₄ may be the same or different.
In (Equation _{(8), q,} R 8 _{to R 11} are the same as in the formula (1). That is, q is 0, 1 or 2.. _Also, R 8 _{to R 11} are, Each independently hydrogen or an organic group having 1 to 30 carbon atoms, one or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having an alcoholic hydroxyl group Formula (8) R _{8 to} R ₁₁ may be the same or different)

  The copolymer 1 may be one in which the repeating unit represented by the formula (6), the repeating unit represented by the formula (7), and the repeating unit represented by the formula (8) are randomly arranged. Alternatively, they may be arranged alternately. Moreover, the norbornene-type monomer shown by Formula (3), the norbornene-type monomer shown by Formula (4), and maleic anhydride may be block copolymerized. However, from the viewpoint of ensuring the uniformity of solubility of the negative photosensitive resin composition P using the polymer produced in this embodiment, the repeating unit represented by the formula (6) and the formula (8) A structure in which the repeating units shown are alternately arranged is preferable. That is, it is preferable that the copolymer 1 has a repeating unit represented by the following formula (9).

（式（９）において、ｑ、Ｒ_８〜Ｒ_１１は、上記式（１）と同じである。すなわち、ｑは０、１、２のいずれかである。Ｒ_８〜Ｒ_１１は、水素または炭素数１〜３０の有機基である。また、Ｒ_８、Ｒ_９、Ｒ_１０およびＲ_１１から選択される１または２以上はアルコール性水酸基を有する有機基である。Ｒ_８〜Ｒ_１１は、同一のものであっても異なっていてもよい。また、ａは１０以上、２００以下の整数である）

(In the formula (9), q and R _{8 to} R ₁₁ are the same as those in the above formula (1). That is, q is 0, 1, or 2. R _{8 to} R ₁₁ are hydrogen or It is an organic group having 1 to 30 carbon atoms, and one or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having an alcoholic hydroxyl group, and R _{8 to} R ₁₁ are They may be the same or different, and a is an integer of 10 or more and 200 or less)

Here, R _{8 in} the structure of the formula (9) is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{9 to} R ₁₁ .

(Ring opening process (Process S2))
Next, among the repeating units of the cyclic structure derived from maleic anhydride of the obtained copolymer 1, the remaining repeating units are opened while some of the repeating units are closed. Thereby, the quantity of the carboxyl group in the copolymer 1 can be adjusted. That is, it becomes possible to control the acid value in the first polymer to be produced.
In this embodiment, among the repeating units derived from maleic anhydride of Copolymer 1, for example, 50% or more of the repeating units are not opened, and the cyclic structure (anhydrous ring) of the remaining repeating units is opened. To do. That is, the ring opening rate of the copolymer 1 is, for example, less than 50%. Among these, it is preferable that 60% or more and 90% or less of the repeating units of the cyclic structure derived from maleic anhydride of the copolymer 1 are not ring-opened.

Here, the ring-opening rate of the repeating unit derived from maleic anhydride can be measured as follows.
The IR absorption intensity (A1) of (C═O) in the acid anhydride structure of copolymer 1 before ring opening was measured, and the IR absorption intensity (A2) of (C═O) in the acid anhydride structure after ring opening (A2) ) To calculate the ring opening rate according to the following formula.
Ring-opening rate (%) = ((A1-A2) / A1) × 100
Acetonitrile is used as an internal standard substance.

In particular,
(A) One of the metal alkoxide (B) alcohol as the base and the alkali metal hydroxide as the base is added to the reaction solution obtained by polymerizing the copolymer 1 in the polymerization step, and methyl ethyl ketone. An organic solvent such as (MEK) is further added and stirred at 40 to 50 ° C. for 1 to 5 hours to obtain a reaction liquid L1. In the reaction liquid L1, a part of the anhydride ring of the repeating unit derived from the maleic anhydride of the copolymer 1 is opened, and a part of the terminal formed by the ring opening is esterified. The remaining terminals are not esterified and have a metal salt structure.

In the present embodiment, the number of moles of metal alkoxide or alkali metal hydroxide is preferably 50% or less of the number of moles of maleic anhydride used in the polymerization step. Among these, the number of moles of metal alkoxide or alkali metal hydroxide is preferably 40% or less, 10% or more, and more preferably 30% or less of the number of moles of maleic anhydride used in the polymerization step. It is preferable. By doing so, the amount of metal alkoxide or alkali metal hydroxide can be reduced, and the alkali metal concentration in the finally obtained polymer can be reduced.
By reducing the alkali metal concentration in the polymer, migration of metal ions can be suppressed when a device using this polymer is formed.

As the metal alkoxide described above, one represented by M (OR ₅ ) (M is a monovalent metal and R ₅ is an organic group having 1 to 18 carbon atoms) is preferable. Examples of the metal M include alkali metals, and sodium is preferable from the viewpoint of handleability. The R _5, are the same as those for _{R 5} in example above formula (2a).
Two or more different metal alkoxides may be used. However, from the viewpoint of production stability, it is preferable to use one kind of metal alkoxide.

On the other hand, as described above, the maleic anhydride-derived structure of the copolymer 1 may be ring-opened in the presence of (B) an alcohol and an alkali metal hydroxide as a base.
As the alkali metal hydroxide, sodium hydroxide is preferable from the viewpoint of handleability.
As the alcohol, monovalent alcohol (R ₅ OH) is preferable. As R ₅ which is an organic group, those described above can be used. R ₅ preferably has 10 or less carbon atoms.

  The repeating unit derived from maleic anhydride opened in this ring-opening step (treatment S2) has a structure represented by the following formula (10), and has a structure having a carboxyl group salt moiety. What has this structure of Formula (10) is called Copolymer 2.

（式（１０）において、Ｒ_５は、前述したＲ_５と同様であり、前述したアルコールあるいは金属アルコキシド由来のものである）

(In Formula (10), R ₅ is the same as R ₅ described above, and is derived from the alcohol or metal alkoxide described above)

  In the copolymer 2, a structure represented by the following formula (11) may be formed, although it is slight.

  Moreover, in the copolymer 2, although it is slight, the structure shown by the following formula | equation (12) may be formed.

  Next, an aqueous solution such as hydrochloric acid or formic acid is added to the reaction solution L1, and the copolymer 2 is acid-treated to replace the metal ions (Na +) with protons (H +). Thereby, in the copolymer 3 obtained by acid-treating the copolymer 2, the ring-opened maleic anhydride-derived repeating unit represented by the formula (10) is represented by the following formula (13). It becomes a structure, and one terminal becomes a carboxyl group.

（式（１３）において、Ｒ_５は、前述したＲ_５と同様である）

(In Formula (13), R ₅ is the same as R ₅ described above)

  When the copolymer 2 has a structure represented by the formula (12), the structure has a structure represented by the following formula (14).

  The copolymer 3 obtained by acid-treating the copolymer 2 is represented by the above-described repeating unit represented by the formula (8), the repeating unit represented by the formula (6), and the formula (13). It has a repeating unit, a repeating unit represented by formula (7) in some cases, a structure of formula (11), and a structure of formula (14). Of the total number of structural units derived from maleic anhydride, 50% or more are the repeating units represented by the formula (6). When the repeating unit represented by the formula (6) and the repeating unit represented by the formula (13) (the structure of the formula (11) and the structure of the formula (14) are included, the structure is represented by the formula (13). Ratio (molar ratio (formula (6): formula (13) (formula (11) structure, formula (11)) of the repeating unit, the structure of formula (11), and the structure of formula (14)) In the case where the structure of 14) is included, the formula (13) + the formula (11) + the formula (14)))) is, for example, 1: 1 to 3: 1.

  Among these, it is preferable that the structure has the following formulas (15) and (16) as repeating units, and a structure derived from a norbornene-type monomer and a structure derived from a maleic anhydride monomer are alternately arranged. . Part of the following formulas (17) and (18) may be included as a repeating unit.

In Formula (15) and Formula (16), q and R _{8 to} R ₁₁ are the same as in Formula (1) above. That is, q is 0, 1, or 2. R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. One or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having at least one selected from an alcoholic hydroxyl group and a group that hydrolyzes to form an alcoholic hydroxyl group. R _{8 to} R ₁₁ may be the same or different. In the structure of the formula (16), Z represents either one of —O—H and —O—R ₅ , and W is slightly different from the structure representing either one of Z and Any structure in which W is —O—R ₅ is included. R ₅ is the same as R ₅ described above.
Moreover, although it is slight, the repeating unit represented by the formula (16) may include a structure in which both Z and W are —O—H.

In addition, when Formula (15) is a repeating unit, R ₈ is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{9 to} R ₁₁ .
Similarly, when Formula (16) is a repeating unit, R ₈ is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{9 to} R ₁₁ , W, and Z.

In Formula (17) and Formula (18), n and R _{1 to} R ₄ are the same as in Formula (1) above. That is, n is 0, 1, or 2. R _{1 to} R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. R _{1 to} R ₄ may be the same or different. Further, in the structure of formula (18), Z represents either one of —O—H and —O—R ₅ , and W represents a structure that represents one of the other, although slightly, Z and Any structure in which W is —O—R ₅ is included. R ₅ is the same as R ₅ described above.
In addition, although it is slight, the repeating unit represented by the formula (18) may include a structure in which both Z and W are —O—H.

In addition, when Formula (17) is a repeating unit, R ₁ is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{2 to} R ₄ .
Similarly, when Formula (18) is a repeating unit, R ₁ is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{2 to} R ₄ , W, and Z.

  In this ring-opening step (treatment S2), 50% or more of the repeating units derived from maleic anhydride of copolymer 1 are not opened, and the cyclic structure (anhydrous ring) of the remaining repeating units is formed. Ring-opening yields copolymer 2. In the copolymer 2, as described above, a metal (for example, Na) is bonded to one end formed by opening an anhydrous maleic ring, but 50% or more of repeating units must not be opened. Thus, the amount of metal contained in the product polymer can be reduced. Thereby, the quantity of the alkali metal in the polymer finally obtained by this embodiment can be reduced, and the desired characteristic can be exhibited in the negative photosensitive resin composition P using this polymer.

(Washing process (Processing S3))
Next, the solution containing the copolymer 3 obtained by the above steps is washed with a mixture of water and an organic solvent (for example, MEK) to remove residual metal components. Copolymer 3, residual monomers and oligomers move to the organic layer. Thereafter, the aqueous layer is removed (first cleaning).
Thereafter, again, a mixture of water and an organic solvent (for example, MEK) is added to the organic layer for washing (second washing).

(Low molecular weight component removal step (processing S4))
Next, the organic layer containing the copolymer 3 and low molecular weight components such as residual monomers and oligomers is concentrated and then dissolved again in an organic solvent such as THF. And hexane and methanol are added to this solution, and the polymer containing the copolymer 3 is coagulated and precipitated. Here, as a low molecular weight component, a residual monomer, an oligomer, a polymerization initiator, and the like are included. Next, filtration is performed, and the obtained coagulum is dried. Thereby, the polymer which has the copolymer 3 from which the low molecular weight component was removed as a main component (main product) can be obtained.

  In addition, when implementing the heating process mentioned later, in this low molecular weight component removal process (process S4), the said organic layer containing the copolymer 3, the residual monomer, and the oligomer is made into methanol, water, hexane, for example. Wash with mixture to remove organic layer.

(Heating step (Process S5))
In this embodiment, by adjusting the ring-opening rate of the repeating unit derived from maleic anhydride in the above-described ring-opening step (Process S2), an alkali developer (for example, TMAH (tetrahydroxide hydroxide) of the first polymer is adjusted. Although the dissolution rate with respect to the aqueous methylammonium solution)) is adjusted, it is preferable to carry out this heating step (treatment S5) when it is necessary to strictly adjust the dissolution rate. In this heating step (Process S5), the dissolution rate of the first polymer in the alkaline developer is further adjusted by heating the copolymer 3.

A heating process (process S5) is performed as follows.
Alcohol is added to the liquid from which the organic layer has been removed in the low molecular weight component removing step (processing S4), and methanol is evaporated, followed by heating at 120 to 140 ° C. for 0.5 to 10 hours. As the alcohol used here, any of those exemplified as the alcohol (R ₅ OH) described above can be used.

In this heating step (processing S5), a part of the carboxyl groups of the copolymer 3, that is, the carboxyl groups formed at the ends of the ring-opening structure of the structure derived from maleic anhydride are esterified. In addition to this, in this heating step (processing S5), the ring-opening structure of the structure derived from maleic anhydride of the copolymer 3 is dehydrated and closed again.
Therefore, the copolymer 4 obtained through this step has a repeating unit represented by the above formula (8), a repeating unit represented by the formula (6), a repeating unit represented by the formula (13), and the following: And a repeating unit represented by the formula (19).

In the formula (19), _{R 6} and _{R 7} are the same as _{R 6} and _{R 7} in the formula (2b), comprising a structure which is independent organic group having 1 to 18 carbon atoms.
In the structure represented by the formula (19), R ₇ is R ₅ described above, and the organic group having 1 to 18 carbon atoms of R ₆ is derived from the alcohol used in this heating step (processing S5). Including cases. In this case, R ₆ can be any of the organic groups exemplified for R ₅ described above.
Further, the structure represented by the formula (19) may include the structure represented by the formula (11). In this case, R ₆ and R ₇ in the formula (19) are the same group as R ₅ shown in the formula (11).
Furthermore, the structure represented by Formula (19) may include a structure in which two carboxyl groups are esterified in Formula (14). In this case, R ₆ and R ₇ are all derived from the alcohol used in the main heating step (processing S5), and can be any of the organic groups exemplified for R ₅ described above.

Thereby, the product (polymer) which uses the copolymer 4 as a main product can be obtained.
Similarly to the copolymer 3, the copolymer 4 preferably has a structure in which a structure derived from a norbornene monomer and a structure derived from a maleic anhydride monomer are alternately arranged. And it is preferable that the copolymer 4 has a structure shown by the following formula | equation (20) in addition to Formula (15), (16) mentioned above.

In the formula (20), q and R _{8 to} R ₁₁ are the same as the above formula (1). That is, q is 0, 1, or 2. R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms. One or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having at least one selected from an alcoholic hydroxyl group and a group that hydrolyzes to form an alcoholic hydroxyl group. is there. R _{8 to} R ₁₁ may be the same or different. X represents one of —O—R ₆ and —O—R ₇ , and Y represents the other. R ₆ and R ₇ are the same as in the above formula (19).

  By passing through the above process, the 1st polymer which concerns on this embodiment shown in the said Formula (1) will be obtained.

  The proportion of the first polymer in the negative photosensitive resin composition P is preferably 40% by mass when the total solid content of the negative photosensitive resin composition P (that is, the component excluding the solvent) is 100% by mass. It is -90 mass%, More preferably, it is 60 mass%-80 mass%.

<Photo acid generator>
The negative photosensitive resin composition P contains a photoacid generator that generates an acid upon irradiation with actinic rays such as ultraviolet rays. Examples of the photoacid generator include onium salt compounds, and examples include sulfonium salts and iodonium salts.

Examples of the sulfonium salts include triarylsulfonium salts, trialkylsulfonium salts, dialkylphenacylsulfonium salts, dialkyl-4-hydroxyphenylsulfonium salts, and the like. Of these, triarylsulfonium salts are preferred.
As the iodonium salt, a diaryl iodonium salt is preferable.
A photo-acid generator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of commercially available photoacid generators include CPI-100P, CPI-101A, CPI-200K, and CPI-210S (manufactured by San Apro).

  The ratio of the photoacid generator in the negative photosensitive resin composition P is preferably 0.1 to 5% by mass when the total solid content of the negative photosensitive resin composition P is 100% by mass.

<First cross-linking agent>
The first cross-linking agent is not particularly limited as long as it can cross-link the first polymer by the action of an acid, and examples thereof include melamine-based cross-linking agents, urea-based cross-linking agents, and glycoluril-based cross-linking agents.
Examples of the melamine-based cross-linking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like, among which hexamethoxymethyl melamine is preferable.
Examples of commercially available hexamethoxymethylmelamine include Mw-390 (manufactured by Sanwa Chemical Co., Ltd.).
Examples of the urea-based crosslinking agent include methylated urea resin, bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and the like, and methylated urea resin is particularly preferable.
Examples of commercially available methylated urea resins include MX-280 and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
Examples of the glycoluril-based crosslinking agent include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N, N, N, N- Examples include alkoxymethylated glycolurils such as tetra (propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, and N, N, N, N-tetra (butoxymethyl) glycoluril. .
Examples of commercially available glycoluril-based crosslinking agents include PL-1170, 1171, 1172, and 1174 (manufactured by Mitsui Cytec Co., Ltd.), MX-270 (manufactured by Sanwa Chemical Co., Ltd.), and the like.

Among the first crosslinking agents, glycoluril-based crosslinking agents are preferable, alkoxymethylated glycoluril is more preferable, and N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.
Since the alcoholic hydroxyl group in the first polymer and the glycoluril in the glycoluril-based cross-linking agent are much more reactive, a negative photosensitivity is obtained when a glycoluril-based cross-linking agent is used as the first cross-linking agent. The heat resistance and residual film property of the conductive insulating film can be further improved.

  The ratio of the first crosslinking agent in the negative photosensitive resin composition P is preferably 5 to 40% by mass when the total solid content of the negative photosensitive resin composition P is 100% by mass. From a viewpoint of property, More preferably, it is 5-30 mass%, More preferably, it is 10-25 mass%.

<Second cross-linking agent>
The negative photosensitive resin composition P may include a thermosetting second crosslinking agent that can crosslink the first polymer by applying heat and is different from the first crosslinking agent. The second cross-linking agent is preferably a compound having a cyclic ether group as a reactive group, and particularly a compound having a glycidyl group or an oxetanyl group. By using such a second crosslinking agent, the chemical resistance of the film composed of the negative photosensitive resin composition P can be improved.
Examples of the compound having a glycidyl group include an epoxy resin, and any of the following epoxy resins can be used.
For example, bisphenol A epoxy resin (for example, LX-1, Daiso Chemical Co., Ltd.), 2,2 '-((((1- (4- (2- (4- (oxiran-2-ylmethoxy) phenyl) propane- 2-yl) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane) (for example, Techmore, VG3101L, Printec Co., Ltd.), Trimethylolpropane triglycidyl ether (eg, TMPTGE, CVC Specialty Chemicals), and 1,1,3,3,5,5-hexamethyl-1,5-bis (3- (oxiran-2-ylmethoxy) Propyl) trisiloxane (for example, DMS-E09, Gerest). These structures are shown below. Other examples include Araldite MT0163 and Araldite CY179 (Ciba Geigy), EHPE-3150, and Epolite GT300 (Daicel Chemical Industries, Ltd.). Any one or more of the above can be used. In addition, it is not limited to the illustration here.

ここで、ｎの平均値は、０以上３以下の整数である。

Here, the average value of n is an integer of 0 or more and 3 or less.

Moreover, as an epoxy resin, it is preferable to use a polyfunctional alicyclic epoxy resin from the viewpoint of transparency of the negative photosensitive resin composition P and a dielectric constant.
As a polyfunctional alicyclic epoxy resin, what is shown by the following chemical formula can be used, for example. This epoxy resin is, for example, Poly [(2-oxylanyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propandiol ether (3: 1). The polyfunctional alicyclic epoxy resin is preferably 20% by mass or more and 100% by mass or less of the entire second crosslinking agent (excluding the first crosslinking agent). Especially, it is more preferable to make this polyfunctional alicyclic epoxy resin into 50 mass% or more of the whole 2nd crosslinking agent.

式中、Ｒ^３６は炭素数１〜１０の炭化水素基、ｓは１〜３０の整数、ｔは１〜６の整数である。

In the formula, R ³⁶ is a hydrocarbon group having 1 to 10 carbon atoms, s is an integer of 1 to 30, and t is an integer of 1 to 6.

Moreover, as a compound which has an oxetanyl group, any of the following can be used, for example.
For example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′-bis [(3-ethyl-3- Oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanyl) Methyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, poly [ [3-[(3-Ethyl-3-oxy Taniru) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolak type oxetane, 1,3-bis [(3-ethyl oxetane over 3-yl) methoxy] Although benzene, and the like, without limitation. These may be used alone or in combination.

  The ratio of the second crosslinking agent in the negative photosensitive resin composition P is preferably 5 masses when the total solid content of the negative photosensitive resin composition P (that is, the component excluding the solvent) is 100 mass%. % To 40% by mass.

<Other additives>
Moreover, you may add additives, such as antioxidant, a filler, surfactant, and a sensitizer, to the negative photosensitive resin composition P as needed.
As the antioxidant, one or more selected from a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant can be used. Antioxidants can suppress oxidation during curing and oxidation of the film in subsequent processes.
Examples of 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-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-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-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) Lopionate], 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-tert-butyl-6-butylphenol), 2, -2′-methylenebis (4-ethyl-6-tert-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-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl- 3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-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-methylbenzyl) phenol, 3,9-bis (1,1- Dimethyl-2-hydroxyethyl) -2,4-8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tri Ethylene glycol bis [β- (3-tert-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-tert-butylphenol), 3,9-bis (2- (3-tert-butyl-4-hydroxy-5-methylphenol) Nylpropionyloxy) 1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 4,4′-thiobis (3-methyl-6-tert-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-methylphenyl acrylate, 2,4-dimethyl-6- (1-methylcyclohexyl, styrene Examples thereof include natural phenol and 2,4-bis ((octylthio) methyl) -5-methylphenol. In these, a hindered phenolic antioxidant is preferable.
Phosphorus antioxidants include bis- (2,6-di-t-butyl-4-methylphenyl) pentapentaerythritol diphosphite, tris (2,4-di-t-butylphenyl phosphite), 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) octyl phosphite, tris (mixed mono and di-nonylphenyl phosphite), bis (2, 4-di-t-butylphenyl) pentapentaerythritol-di-phosphite, bis (2,6-di-t-butyl) 4-methoxycarbonyl-ethyl - butylphenyl) pentaerythritol diphosphite, bis (2,6-di -t- butyl-4-octadecyloxycarbonyl ethyl - phenyl) pentaerythritol-di-phosphite. Of these, phosphites and phosphates are preferred.
Examples of the thioether-based antioxidant 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 can be mentioned.
The antioxidant can be 0.1 to 5% by weight of the entire negative photosensitive resin composition P.

Moreover, the negative photosensitive resin composition P mentioned above may contain polyphenols.
Examples of polyphenols include phenol novolak, o-cresol novolak, p-cresol novolak, pt-butylphenol novolak, hydroxynaphthalene novolak, bisphenol A novolak, bisphenol F novolak, terpene modified novolak, dicyclopentadiene modified novolak, para Examples include xylene-modified novolak and polybutadiene-modified phenol, and any one or more of them can be used.

The following phenolic compounds can also be used.
o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, C, E, F and G, 4,4 ′, 4 ′ '-Methylidinetrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4'-[1- [4- [1- (4-hydroxyphenyl) ) -1-Methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4 ′, 4 '' -Ethyridinetrisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4,4 '-[(2-hydroxyphenyl) methylene] bis [2, -Dimethylphenol], 4,4 '-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4'-[(4-hydroxyphenyl) methylene] bis [2,6-dimethyl Phenol], 2,2 ′-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol] 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl]- 1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4,4 ′-[ 2-hydroxyphenyl) methylene] bis [3-methylphenol], 4,4 ′, 4 ″-(3-methyl-1-propanyl-3-ylidine) trisphenol, 4,4 ′, 4 ″, 4 '''-(1,4-phenylenedimethylidene) tetrakisphenol, 2,4,6-tris "(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,3-benzenediol, 2,4 6-tris [(3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 ′-[1- [4- [1- [4-hydroxy-3,5-bis] [(Hydroxy-3-methylphenyl) methyl] phenyl] -1-methylethyl] phenyl] ethylidene] bis [2,6-bis (hydroxy-3-methylphenyl) methyl] phenol and the like.
Of these compounds, 4,4 ′, 4 ″ -methylidynetrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 ′-[ 1- [4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] ] Phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidinetrisphenol and the like are preferable. Any one or more of these can be used.
Particularly preferably, it is at least one of the following compounds.

  In the negative photosensitive resin composition P, the content of the polyphenols is preferably 0% by mass to 30% by mass, for example, 3% by mass when the solid content excluding the solvent is 100% by mass. The above is preferable.

<Solvent>
The negative photosensitive resin composition P may contain a solvent. Examples of the solvent 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 n -Amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, or mixtures thereof can be employed. In addition, it is not limited to what was illustrated here.

<Preparation method of negative photosensitive resin composition P>
The preparation method of the negative photosensitive resin composition P is not specifically limited, Generally, it can manufacture by a well-known method. For example, the following method is mentioned. Negative photosensitive resin composition by blending first polymer, photoacid generator, first cross-linking agent, second cross-linking agent and other additives as described above, and solvent, if necessary, and mixing uniformly. P is obtained.

<Method for forming resist pattern>
Examples of the method for forming a resist pattern using the negative photosensitive resin composition P include the following methods.

  First, the negative photosensitive resin composition P is applied to a support such as a silicon wafer. As a method for applying the negative photosensitive resin composition P to the support, application methods such as spin coating, roll coating, flow coating, dip coating, spray coating, and doctor coating can be used. Among these, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

  Next, the support is heated at an appropriate temperature and time to remove almost all of the solvent in the negative photosensitive resin composition P, thereby forming a coating film. The heating temperature and time are, for example, 60 to 130 ° C for 1 to 5 minutes, preferably 80 to 120 ° C for 1 to 3 minutes. Moreover, as for the thickness of the coating film of the negative photosensitive resin composition P, 1.0-5.0 micrometers is preferable.

Then, it exposes and heats through the mask for forming the target pattern.
Pattern formation on the coating film is performed by irradiating actinic rays or the like using a mask for forming a target pattern. And it heats at 80-140 degreeC for 1 to 5 minutes, Preferably it is 1 to 3 minutes at 90-130 degreeC, and accelerates | stimulates hardening. The curing conditions are not limited to the above.

Then, it develops with an alkaline developing solution, melt | dissolves and removes an unexposed part, Furthermore, the target resist pattern can be obtained by heating.
Examples of the development method include a shower development method, a spray development method, and an immersion development method. The development conditions are usually about 1 to 10 minutes at 23 ° C.

  Examples of the developer include an alkaline aqueous solution having a concentration of about 0.1 to 10% by mass such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide and the like. After the development, it is further baked at 150 to 300 ° C. for 30 to 120 minutes and sufficiently cured to obtain a target pattern. The curing conditions are not limited to the above.

<Characteristic>
According to the negative photosensitive resin composition P described above, a negative photosensitive insulating film having at least one of the following characteristics can be realized. In addition, even if the negative photosensitive resin composition P contains other additives as shown in the following examples, these characteristics are realized.

<Characteristic 1: High residual film ratio>
The negative photosensitive resin composition P is formed on a silicon wafer by spin coating, and then baked on a hot plate at 110 ° C. for 100 seconds. The film thickness of 1 is 2.0 μm or more and 4.0 μm or less. Next, exposure is performed using an exposure apparatus with an optimum exposure amount at which the width of the line and the space having a pattern dimension of 10 μm is 1: 1. Then, the first layer is further baked on a hot plate at 120 ° C. for 120 seconds and developed with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 20 seconds. The film thickness of this layer is the second film thickness. At this time, {(second film thickness) / (first film thickness)} × 100 ≧ 80 (%) is satisfied, and preferably {(second film thickness) / (first film thickness)} ×. 100 ≧ 90 (%) is satisfied.

  The thickness of the third layer after the second layer is heat-treated at 230 ° C. for 60 minutes in the oven is defined as the third thickness. At this time, {(third film thickness) / (second film thickness)} × 100 ≧ 70 (%) is satisfied, and preferably {(third film thickness) / (second film thickness)} ×. 100 ≧ 75 (%) is satisfied.

  According to the negative photosensitive resin composition P having such a characteristic 1, since the change in the film thickness due to the development process and the baking process is small, it is possible to accurately control the film thickness after these processes. It becomes.

  By the way, the negative photosensitive resin composition P is not only used for forming a film that exists only for a predetermined period of time and is removed when it is no longer needed like a photoresist. It can also be used to form a permanent film that remains in the product without being lost. Such a permanent film needs to be controlled to a film thickness according to the design, but the negative photosensitive resin composition P is preferable because the film thickness can be accurately controlled as described above.

<Characteristic 2: Low relative dielectric constant>
After forming a film having a thickness of 3 μm using the negative photosensitive resin composition P, the relative dielectric constant measured at a frequency of 10 kHz is 4.0 or less, preferably 3.5 or less. The lower limit value of the relative dielectric constant is not particularly limited, but is, for example, 2.5.

The relative dielectric constant can be measured as follows.
The negative photosensitive resin composition P is spin-coated on an aluminum substrate (rotation speed: 1000 to 3000 rpm) and baked on a hot plate at 110 ° C. for 100 seconds. Subsequently, it exposes by 500 mJ / cm < ² > using an exposure apparatus. Further, baking is performed on a hot plate at 120 ° C. for 120 seconds. Thereafter, it is heated in an oven at 230 ° C. for 60 minutes to form a film having a thickness of 3 μm.
Thereafter, a gold electrode is formed on the film and measured under conditions at room temperature (25 ° C.) and 10 kHz.
By the way, the negative photosensitive resin composition P is not only used for the formation of a temporary film which exists only for a predetermined period and is removed when it is no longer needed, as in the case of a photoresist. It can also be used to form a permanent film that continues to remain in the product. When such a permanent film is applied to an electronic device, the dielectric constant is preferably low. Therefore, the negative photosensitive resin composition P of the present embodiment is also suitable for a permanent film mounted on an electronic device.

<Characteristic 3: High transmittance>
Further, the light transmittance at a wavelength of 400 nm in the layer thickness direction of a 3 μm thick cured film obtained by curing the negative photosensitive resin composition P is 85% or more. Especially, it is preferable that the said transmittance | permeability is 90% or more. The upper limit of the transmittance is not particularly limited, but is 99%, for example.

The transmittance can be measured as follows.
The negative photosensitive resin composition P is spin-coated on a glass substrate (rotation speed 1000 to 3000 rpm) and baked on a hot plate at 110 ° C. for 100 seconds. Subsequently, it exposes by 500 mJ / cm < ² > using an exposure apparatus. Further, baking is performed on a hot plate at 120 ° C. for 120 seconds. Thereafter, it is heated in an oven at 230 ° C. for 60 minutes to form a film having a thickness of 3 μm.
The transmittance of the film at a wavelength of 400 nm is measured using an ultraviolet-visible light spectrophotometer.

<Characteristic 4: High solvent resistance>
The negative photosensitive resin composition P is spin-coated on a glass substrate (rotation speed 1000 to 3000 rpm) and baked on a hot plate at 110 ° C. for 100 seconds. Subsequently, it exposes by 500 mJ / cm < ² > using an exposure apparatus. Further, baking is performed on a hot plate at 120 ° C. for 120 seconds. Thereafter, the film is heated in an oven at 230 ° C. for 60 minutes to obtain a first film having a thickness of 3 μm. When the film thickness of the first film is the first film thickness and the film thickness after immersing the first film in N-methylpyrrolidone for 10 minutes at room temperature is the second film thickness, [{(second Film thickness) − (first film thickness)} / (first film thickness)] × 100 ≦ 5 (%).

  According to the negative photosensitive resin composition P having such a characteristic 4, even when immersed in N-methylpyrrolidone in the manufacturing process after film formation, the film thickness hardly changes. For this reason, it becomes possible to manufacture a film having a predetermined design thickness with high accuracy.

<Application>
Next, the use of the negative photosensitive resin composition P will be described.
The negative photosensitive resin composition P exists not only for a predetermined period of time like a photoresist, but is used not only for forming a film that is removed when it is no longer needed, but without being removed after the film formation. It can also be used to form a permanent film (cured film) that remains in the product.

For example, as shown in FIG. 1, it can be used as a planarizing film covering a transistor.
Further, as shown in FIG. 2, it can also be used as an interlayer insulating film covering the rewiring layer of the semiconductor device. It can also be applied to a pigment-dispersed color resist.

Further, the negative photosensitive resin composition P may be a microlens array. For example, the negative photosensitive resin composition P can be filled in a mold for a microlens array, and then photocured and heat-cured as necessary to form a microlens array.
The microlens array thus manufactured can be used for a liquid crystal display device, a plasma display, a field emission display, an electroluminescence display, and the like.
Hereinafter, an example of an electronic device having a film formed using the negative photosensitive resin composition P will be described.

<Electronic device>
1 and 2 are cross-sectional views showing examples of the electronic device 100 according to the present embodiment. In any case, a part of the electronic device 100 including the insulating film 20 is shown.
The electronic device 100 according to the present embodiment includes an insulating film 20 that is a permanent film formed of, for example, a negative photosensitive resin composition P.

  As an example of the electronic apparatus 100 according to the present embodiment, a liquid crystal display device is shown in FIG. However, the electronic device 100 according to the present embodiment is not limited to the liquid crystal display device, and includes other electronic devices including a permanent film made of the negative photosensitive resin composition P.

  As shown in FIG. 1, an electronic device 100 that is a liquid crystal display device includes, for example, a substrate 10, a transistor 30 provided on the substrate 10, and an insulating film 20 provided on the substrate 10 so as to cover the transistor 30. And a wiring 40 provided on the insulating film 20.

The substrate 10 is, for example, a glass substrate.
The transistor 30 is a thin film transistor that constitutes a switching element of a liquid crystal display device, for example. On the substrate 10, for example, a plurality of transistors 30 are arranged in an array. The transistor 30 according to the present embodiment includes, for example, a gate electrode 31, a source electrode 32, a drain electrode 33, a gate insulating film 34, and a semiconductor layer 35. The gate electrode 31 is provided on the substrate 10, for example. The gate insulating film 34 is provided on the substrate 10 so as to cover the gate electrode 31. The semiconductor layer 35 is provided on the gate insulating film 34. The semiconductor layer 35 is, for example, a silicon layer. The source electrode 32 is provided on the substrate 10 so that a part thereof is in contact with the semiconductor layer 35. The drain electrode 33 is provided on the substrate 10 so as to be separated from the source electrode 32 and partially in contact with the semiconductor layer 35.

The insulating film 20 functions as a planarization film for eliminating a step due to the transistor 30 and the like and forming a flat surface on the substrate 10. The insulating film 20 is made of a cured product of the negative photosensitive resin composition P. The insulating film 20 is provided with an opening 22 that penetrates the insulating film 20 so as to be connected to the drain electrode 33.
A wiring 40 connected to the drain electrode 33 is formed on the insulating film 20 and in the opening 22. The wiring 40 functions as a pixel electrode that constitutes a pixel together with the liquid crystal.
An alignment film 90 is provided on the insulating film 20 so as to cover the wiring 40.

A counter substrate 12 is disposed above one surface of the substrate 10 where the transistor 30 is provided so as to face the substrate 10. A wiring 42 is provided on one surface of the counter substrate 12 facing the substrate 10. The wiring 42 is provided at a position facing the wiring 40. An alignment film 92 is provided on the one surface of the counter substrate 12 so as to cover the wiring 42.
The liquid crystal constituting the liquid crystal layer 14 is filled between the substrate 10 and the counter substrate 12.

The electronic device 100 shown in FIG. 1 is formed as follows, for example.
First, the transistor 30 is formed over the substrate 10. Next, the negative photosensitive resin composition P is applied to one surface of the substrate 10 on which the transistor 30 is provided by a printing method or a spin coating method to form the insulating film 20 that covers the transistor 30. Thus, a planarization film that covers the transistor 30 provided over the substrate 10 is formed.
Next, the insulating film 20 is exposed and developed to form an opening 22 in a part of the insulating film 20. At this time, the unexposed portion is dissolved in the developer, and the exposed portion remains. This also applies to each example of the electronic device 100 described later.
Next, the insulating film 20 is heated and cured. Then, a wiring 40 connected to the drain electrode 33 is formed in the opening 22 of the insulating film 20. Thereafter, the counter substrate 12 is disposed on the insulating film 20, and liquid crystal is filled between the counter substrate 12 and the insulating film 20 to form the liquid crystal layer 14.
As a result, the electronic device 100 shown in FIG. 1 is formed.

Further, as an example of the electronic device 100 according to the present embodiment, FIG. 2 shows a semiconductor device in which the rewiring layer 80 is configured by a permanent film made of the negative photosensitive resin composition P.
An electronic device 100 shown in FIG. 2 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer provided on the semiconductor substrate (not shown). An insulating film 50 that is an interlayer insulating film and an uppermost layer wiring 72 provided on the insulating film 50 are provided in the uppermost layer of the multilayer wiring layer. The uppermost layer wiring 72 is made of, for example, Al.

A rewiring layer 80 is provided on the insulating film 50. The rewiring layer 80 includes an insulating film 52 provided on the insulating film 50 so as to cover the uppermost wiring 72, a rewiring 70 provided on the insulating film 52, and on the insulating film 52 and the rewiring 70. And an insulating film 54 provided.
An opening 24 connected to the uppermost layer wiring 72 is formed in the insulating film 52. The rewiring 70 is formed on the insulating film 52 and in the opening 24, and is connected to the uppermost layer wiring 72. The insulating film 54 is provided with an opening 26 connected to the rewiring 70.
The insulating film 52 and the insulating film 54 are constituted by permanent films made of the negative photosensitive resin composition P. The insulating film 52 is obtained, for example, by forming the opening 24 by performing exposure / development on the negative photosensitive resin composition P applied on the insulating film 50, and then heat-curing the opening 24. The insulating film 54 is obtained, for example, by forming the opening 26 by performing exposure / development on the negative photosensitive resin composition P applied on the insulating film 52, and then heat-curing the opening 26.

  For example, bumps 74 are formed in the openings 26. The electronic device 100 is connected to a wiring board or the like via bumps 74, for example.

  Furthermore, the electronic device 100 according to the present embodiment may be an optical device in which a microlens is configured by a permanent film made of the negative photosensitive resin composition P. Examples of the optical device include a liquid crystal display device, a plasma display, a field emission display, and an electroluminescence display.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.

[Example 1]
<Synthesis example 1 of first polymer>
In a suitably sized reaction vessel equipped with a stirrer, maleic anhydride (MA, 5.88 g, 60 mmol), 5- (acetoxymethyl) norborna-2-ene (MeOAcNB, 9.96 g, 60 mmol) and dimethyl 2, 2′-azobis (2-methylpropionate) (1.38 g, 6 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 2.7 g) and toluene (2.7 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated at 70 ° C. for 16 hours with stirring. The reaction mixture was then diluted with MEK (56.6 g) and poured into a large amount of methanol to precipitate the polymer. The solid was collected by filtration and vacuum dried at 40 ° C. to obtain 13.3 g of a polymer. The weight average molecular weight was 6,900, and the molecular weight distribution (Mw / Mn) was 1.7.

  Sodium hydroxide (6.1 g, 0.15 mol), butanol (14.0 g) and toluene (20 g) were weighed into a suitably sized reaction vessel equipped with a stirrer and mixed at 45 ° C. for 1 hour. The polymer (10 g) obtained above was redissolved in MEK to make a 25 wt% solution, added to the above suspension, and further heated and stirred at 45 ° C. for 3 hours. The mixture was cooled to 40 ° C., treated with formic acid (88 wt% aqueous solution, 23.8 g, 0.46 mol) and protonated, then MEK and water were added, and the aqueous layer was separated. Residue was removed. The reaction mixture was then poured into a large amount of hexane to precipitate the polymer. The solid was collected by filtration and vacuum dried at 40 ° C. to obtain 10.6 g of a polymer. The weight average molecular weight was 7,800, and the molecular weight distribution (Mw / Mn) was 2.0.

<Preparation of negative photosensitive resin composition>
25 g of a 20% propylene glycol monomethyl ether (PGME) solution of the first polymer synthesized in Synthesis Example 1, CPI-210S as a photoacid generator, 0.1 g manufactured by San Apro, and glycoluril as a first crosslinking agent 1.5 g of cross-linking agent (Mx-270, manufactured by Sanwa Chemical Co., Ltd.), 0.05 g of silane coupling agent (KBM-303, manufactured by Shin-Etsu Silicone Co., Ltd.) for improving adhesion to the substrate, and spin coating In order to prevent radial striations formed on the negative photosensitive insulating film, 200 ppm of F-557 (manufactured by DIC) was dissolved in an appropriate amount of PGMEA and stirred, and then a 0.2 μm filter. The resin composition was prepared by filtration.

[Example 2]
A negative photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the first polymer was changed to the following.

<Synthesis example 2 of first polymer>
In a suitably sized reaction vessel equipped with a stirrer, maleic anhydride (MA, 6.13 g, 62.5 mmol), 5-norbornene-2-butyl acetate (BuOAcNB, 13.00 g, 62.5 mmol) and dimethyl 2 , 2′-Azobis (2-methylpropionate) (1.44 g, 6.3 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 3.4 g) and toluene (3.4 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated at 70 ° C. for 16 hours with stirring. The reaction mixture was then diluted with MEK (68.3 g) and poured into a large amount of methanol to precipitate the polymer. The solid was collected by filtration and vacuum dried at 40 ° C. to obtain 15.0 g of a polymer. The weight average molecular weight was 10,800, and the molecular weight distribution (Mw / Mn) was 1.7.

  Sodium hydroxide (5.2 g, 0.13 mol), butanol (12.1 g), and toluene (20 g) were weighed into an appropriately sized reaction vessel equipped with a stirrer and mixed at 45 ° C. for 1 hour. The polymer (10 g) obtained above was redissolved in MEK to make a 25 wt% solution, added to the above suspension, and further heated and stirred at 45 ° C. for 3 hours. The mixture was cooled to 40 ° C., treated with formic acid (88 wt% aqueous solution, 20.5 g, 0.39 mol), protonated, then added with MEK and water, and the aqueous layer was separated to give an inorganic layer. Residue was removed. The reaction mixture was then poured into a large amount of hexane to precipitate the polymer. The solid was collected by filtration and vacuum dried at 40 ° C. to obtain 10.8 g of a polymer. The weight average molecular weight was 15,300, and the molecular weight distribution (Mw / Mn) was 2.3.

[Example 3]
A negative photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the first polymer was changed to the following.

<Synthesis example 3 of first polymer>
To a suitably sized reaction vessel equipped with a stirrer, maleic anhydride (MA, 6.13 g, 62.5 mmol), 5-norbornene-2-butyl acetate (BuOAcNB, 11.70 g, 56.25 mmol), 2- Norbornene (NB, 0.59 g, 6.25 mmol) and dimethyl 2,2′-azobis (2-methylpropionate) (1.44 g, 6.3 mmol) are weighed and methyl ethyl ketone (MEK, 4.0 g) and Dissolved in toluene (3.5 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated at 60 ° C. for 12 hours with stirring. The reaction mixture was then diluted with MEK (70 g) and poured into a large amount of methanol to precipitate the polymer. The solid was collected by filtration and vacuum dried at 40 ° C. to obtain 15.5 g of a polymer. The weight average molecular weight was 12,500, and the molecular weight distribution (Mw / Mn) was 1.9.

  Sodium hydroxide (5.6 g, 0.14 mol), butanol (14 g), and toluene (20 g) were weighed into an appropriately sized reaction vessel equipped with a stirrer and mixed at 45 ° C. for 1 hour. The polymer (10 g) obtained above was redissolved in MEK to make a 25 wt% solution, added to the above suspension, and further heated and stirred at 45 ° C. for 3 hours. The mixture was cooled to 40 ° C., treated with formic acid (88 wt% aqueous solution, 19.3 g, 0.42 mol) and protonated, and then MEK and water were added, and the aqueous layer was separated. Residue was removed. The reaction mixture was then poured into a large amount of hexane to precipitate the polymer. The solid was collected by filtration and vacuum dried at 40 ° C. to obtain 10.5 g of a polymer. The weight average molecular weight was 15,800, and the molecular weight distribution (Mw / Mn) was 2.4.

[Example 4]
25 g of a 20% propylene glycol monomethyl ether (PGME) solution of the first polymer synthesized in Synthesis Example 2, CPI-210S as a photoacid generator, 0.1 g manufactured by San Apro, and glycoluril as a first crosslinking agent In order to improve the adhesion to the substrate, 1.5 g of the crosslinking agent (Mx-270, manufactured by Sanwa Chemical Co., Ltd.) and 1.0 g of the epoxy resin (VG-3101L, manufactured by Printec Co., Ltd.) as the second crosslinking agent. 0.05 g of silane coupling agent (KBM-303, manufactured by Shin-Etsu Silicone), F-557 (manufactured by DIC) in order to prevent radial striations formed on the negative photosensitive insulating film during spin coating ) Was dissolved in an appropriate amount of PGME and stirred, and then filtered through a 0.2 μm filter to prepare a resin composition.

[Example 5]
25 g of a 20% propylene glycol monomethyl ether (PGME) solution of the first polymer synthesized in Synthesis Example 2, CPI-210S as a photoacid generator, 0.1 g manufactured by San Apro, and glycoluril as a first crosslinking agent 1.5 g of cross-linking agent (Mx-270, manufactured by Sanwa Chemical Co., Ltd.), 1.0 g of epoxy resin (Epolite 100MF, manufactured by Kyoeisha Chemical Co., Ltd.) as the second cross-linking agent, and silane coupling to improve adhesion to the substrate 0.05 g of the agent (KBM-303, manufactured by Shin-Etsu Silicone), 200 ppm of F-557 (manufactured by DIC) in order to prevent radial striations formed on the negative photosensitive insulating film during spin coating. Were dissolved in an appropriate amount of PGME and stirred, and then filtered through a 0.2 μm filter to prepare a resin composition.

[Comparative Example 1]
<Polymer synthesis>
In a suitably sized reaction vessel equipped with stirrer and condenser, maleic anhydride (MA, 122.4 g, 1.25 mol), 2-norbornene (NB, 117.6 g, 1.25 mol) and dimethyl 2,2 '-Azobis (2-methylpropionate) (11.5 g, 50.0 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 150.8 g) and toluene (77.7 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, then heated to 60 ° C. with stirring and heated for 16 hours. Thereafter, MEK (320 g) was added to the solution, and this was added with sodium hydroxide (12.5 g, 0.31 mol), butanol (463.1 g, 6.25 mol), toluene (480 g). Added to the suspension and mixed at 45 ° C. for 3 hours. The mixture is cooled to 40 ° C., treated with formic acid (88 wt% aqueous solution, 49.0 g, 0.94 mol) and protonated, and then MEK and water are added to separate the aqueous layer. Inorganic residues were removed. Subsequently, methanol and hexane were added and the organic layer was separated to remove unreacted monomers. Further, PGMEA was added, and methanol and butanol in the system were distilled off under reduced pressure until the residual amount was less than 1%. As a result, 1107.7 g of a 20 wt% polymer solution was obtained (GPC Mw = 13,700, Mn = 7,400).

<Preparation of negative photosensitive resin composition>
25 g of 20% propylene glycol monomethyl ether acetate (PGMEA) solution of the obtained polymer, CPI-210S as a photoacid generator, 0.1 g manufactured by San Apro, and glycoluril-based crosslinking agent (Mx- 270, manufactured by Sanwa Chemical Co., Ltd.), 1.5 g of a silane coupling agent (KBM-303, manufactured by Shin-Etsu Silicone Co., Ltd.) to improve the adhesion to the substrate, and negative-type photosensitive during spin coating. In order to prevent radial striations formed on the conductive insulating film, 200 ppm of F-557 (manufactured by DIC) was dissolved in an appropriate amount of PGMEA and stirred, and then filtered through a 0.2 μm filter. A resin composition was prepared.

[Comparative Example 2]
A negative photosensitive resin composition was prepared and evaluated in the same manner as Comparative Example 1, except that CPI-210S was changed to 0.5 g and Mx-270 was changed to 3.0 g.

<Evaluation of remaining film ratio after development and after baking>
About each Example and the comparative example, after developing and evaluating the post-baking residual film rate as follows using the obtained resin composition.
The obtained resin composition was spin-coated on a 4-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 110 ° C. for 100 seconds to obtain a thin film A having a thickness of 3 μm. For this thin film A, a mask with a 10 μm line and space width of 1: 1 is used with a g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc., and the width of the line and space with a pattern dimension of 10 μm is 1: 1. The exposure was performed with the optimal exposure amount. Furthermore, by baking at 120 ° C for 120 seconds on a hot plate and developing with 0.5% by weight tetramethylammonium hydroxide solution at 23 ° C for 20 seconds, a line and space pattern with a 1: 1 line and space width is provided. Thin film B was obtained. Then, the post-baking process was performed by heating for 60 minutes at 230 degreeC in oven, and the thin film C with a pattern was obtained.
From the film thicknesses of the thin film A, the thin film B, and the thin film C obtained by the above method, the remaining film ratio was calculated from the following formula.
Residual film ratio after development (%) = {(film thickness of thin film B (μm)) / (film thickness of thin film A (μm))} × 100
Residual film ratio after baking (%) = {(film thickness of thin film C (μm) / (film thickness of thin film A (μm))) × 100

<Development evaluation>
For each of the examples and comparative examples, a 10 μm pattern of the thin film B described in “Evaluation of remaining film ratio after development and after baking” was observed with a SEM (scanning electron microscope). The developability was evaluated as x when dissolved or when the resolution was low and could not be evaluated, and when no residue was observed.

<Evaluation of dielectric constant>
For each of the examples and comparative examples, the dielectric constant was evaluated as follows.
The obtained resin composition was spin-coated on an aluminum substrate treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 110 ° C. for 100 seconds. The obtained thin film was exposed at 500 mJ / cm ² using a Canon g + h + i line mask aligner (PLA-501F). Further, the film was baked on a hot plate at 120 ° C. for 120 seconds, and then heated in an oven at 230 ° C. for 60 minutes to obtain a 3 μm-thick film having no pattern on the aluminum substrate.
A gold electrode was formed on this thin film, and the dielectric constant was calculated from the capacitance obtained using a Hewlett Packard LCR meter (4282A) under conditions of room temperature (25 ° C.) and 10 kHz.

<Evaluation of transmittance>
The obtained resin composition was spin-coated on a 1737 glass substrate manufactured by Corning, which was 100 mm long and 100 mm wide, which had been treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 110 ° C. for 100 seconds. The obtained thin film was exposed at 500 mJ / cm ² using a Canon g + h + i line mask aligner (PLA-501F). Further, the film was baked on a hot plate at 120 ° C. for 120 seconds, and then heated in an oven at 230 ° C. for 60 minutes to obtain a 3 μm-thick film without a pattern on a glass substrate.
The transmittance of the thin film at a wavelength of 400 nm was measured using an ultraviolet-visible light spectrophotometer.

<Evaluation of solvent resistance>
A glass substrate with a thin film obtained by performing the same operation as in “Evaluation of transmittance” was immersed in N-methylpyrrolidone (Kanto Chemical) at room temperature (25 ° C.) for 10 minutes, and then rinsed with pure water. . In the case where the film thickness change rate defined by the following arithmetic expression is 5% or less, those exceeding 5% were evaluated as x.
Change rate of film thickness (%) = [{(film thickness after solvent immersion) − (film thickness before solvent immersion)} / (film thickness before solvent immersion)] × 100

(sensitivity)
The obtained resin composition was spin-coated on a 4-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 110 ° C. for 100 seconds to obtain a thin film A having a thickness of about 3 μm. The thin film A was exposed with a g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. using a mask having a 10 μm line and a space width of 1: 1. Next, after baking on a hot plate at 120 ° C. for 120 seconds and developing with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 20 seconds, the resist pattern formed is 10 μm line width: space width = The exposure amount (mJ / cm ² ) at 1: 1 was defined as sensitivity.

  The above evaluation results are summarized in Table 1.

From the above results, according to Examples 1 to 5 using a polymer having an alcoholic hydroxyl group, a film having a high residual film ratio and high resolution could be obtained. As a result, it was found that a desired pattern can be reliably formed.
Further, in Examples 1 to 5, the dielectric constant was low, the transparency was high, and the solvent resistance was also high.
On the other hand, in Comparative Example 1 using a polymer containing no alcoholic hydroxyl group, the film was dissolved in the development stage. This is presumably because a polymer containing no alcoholic hydroxyl group has poor crosslinkability. Further, even when the first crosslinking agent and the photoacid generator were added in a large amount, even 50 μm could not be resolved (Comparative Example 2).

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2013-137189 for which it applied on June 28, 2013, and takes in those the indications of all here.

10 substrate 12 counter substrate 14 liquid crystal layer 20, 50, 52, 54 insulating film 22, 24, 26 opening 30 transistor 31 gate electrode 32 source electrode 33 drain electrode 34 gate insulating film 35 semiconductor layer 40, 42 wiring 70 rewiring 72 top Upper wiring 74 Bump 80 Rewiring layer 90, 92 Alignment film 100 Electronic device

Claims (19)

A negative photosensitive resin composition comprising:
A polymer composed of a copolymer represented by the following formula (1);
A photoacid generator;
A first crosslinking agent that crosslinks the polymer using an acid generated from the photoacid generator as a catalyst;
A negative photosensitive resin composition.

(In the formula (1), l, p and m represent the molar content in the polymer, and the conditions of l + p + m ≦ 1, 0 ≦ l <1, 0 <p <1, and 0 <m <1 are satisfied. Meet,
n and q are each independently 0, 1 or 2,
R _{1 to} R ₄ and R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms,
One or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having an alcoholic hydroxyl group;
A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d))

(In Formula (2a) and Formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms) In the negative photosensitive resin composition according to claim 1,
The negative photosensitive resin composition in which the copolymer represented by the formula (1) includes at least a structural unit represented by the formula (2a) and a structural unit represented by the formula (2c). In the negative photosensitive resin composition according to claim 1 or 2,
A negative photosensitive resin composition, wherein the organic group having an alcoholic hydroxyl group is a group having an alcoholic hydroxyl group and a hydrocarbon group to which the alcoholic hydroxyl group is bonded. In the negative photosensitive resin composition according to claim 3,
The hydrocarbon group to which the alcoholic hydroxyl group is bonded is linear,
The negative photosensitive resin composition whose carbon number of the said linear hydrocarbon group is 1-5. In the negative photosensitive resin composition according to claim 4,
A negative photosensitive resin composition in which the alcoholic hydroxyl group is a primary alcoholic hydroxyl group. In the negative photosensitive resin composition according to any one of claims 1 to 5,
A negative photosensitive resin composition further comprising a thermosetting second crosslinking agent that is capable of crosslinking the polymer by applying heat and is different from the first crosslinking agent. In the negative photosensitive resin composition according to claim 6,
The negative photosensitive resin composition, wherein the second crosslinking agent is an epoxy resin. In the negative photosensitive resin composition according to claim 7,
The negative photosensitive resin composition, wherein the epoxy resin is a polyfunctional alicyclic epoxy resin. In the negative photosensitive resin composition as described in any one of Claims 1 thru | or 8,
The negative photosensitive resin composition, wherein the photoacid generator contains a sulfonium salt. In the negative photosensitive resin composition as described in any one of Claims 1 thru | or 9,
The negative photosensitive resin composition, wherein the first crosslinking agent is a glycoluril-based crosslinking agent.   The cured film obtained by hardening the negative photosensitive resin composition as described in any one of Claims 1 thru | or 10.   An electronic device comprising the cured film according to claim 11.   The electronic device according to claim 12, wherein the cured film is an interlayer insulating film or a planarizing film. A polymer composed of a copolymer represented by the following formula (1).

(In the formula (1), l, p and m represent the molar content in the polymer, and the conditions of l + p + m ≦ 1, 0 ≦ l <1, 0 <p <1, and 0 <m <1 are satisfied. Meet,
n and q are each independently 0, 1 or 2,
R _{1 to} R ₄ and R _{8 to} R ₁₁ are each independently hydrogen or an organic group having 1 to 30 carbon atoms,
One or more selected from R ₈ , R ₉ , R ₁₀ and R ₁₁ is an organic group having an alcoholic hydroxyl group;
A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d))

(In Formula (2a) and Formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms) The polymer of claim 14, wherein
The copolymer represented by the formula (1) is a polymer including at least a structural unit represented by the formula (2a) and a structural unit represented by the formula (2c). The polymer of claim 15,
The polymer in which the organic group having an alcoholic hydroxyl group is a group having an alcoholic hydroxyl group and a hydrocarbon group to which the alcoholic hydroxyl group is bonded. The polymer of claim 16, wherein
The hydrocarbon group to which the alcoholic hydroxyl group is bonded is linear,
The polymer whose carbon number of the said linear hydrocarbon group is 1-5. The polymer of claim 17,
A polymer, wherein the alcoholic hydroxyl group is a primary alcoholic hydroxyl group. A polymer according to any one of claims 14 to 18,
The polymer is a polymer for a negative photosensitive resin composition.

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