JP2021092758A - Negative type photosensitive resin composition and method for producing cured film - Google Patents

Abstract

To provide a negative type photosensitive resin composition capable of forming a cured film having high solvent resistance, a cured film formed of a cured product of the negative type photosensitive resin composition, and a method for producing a cured film using the negative type photosensitive resin composition.SOLUTION: A negative type photosensitive resin composition contains a resin (A) having a structure represented by the following formula (a1), and an oxime ester photopolymerization initiator (B) having a specific structure.SELECTED DRAWING: None

Description

The present invention relates to a negative photosensitive resin composition and a method for producing a cured film using the negative photosensitive resin composition.

Photosensitive resin compositions for displays applied to thin film transistor type liquid crystal display devices (TFT-LCD), organic light emitting elements (OLED), touch screen panels (TSP), etc. are cured and photodecomposed by irradiation with UV (ultraviolet rays). It is divided into a positive type photosensitive material and a negative type photosensitive material according to a method of causing a reaction to form a pattern. In the positive photosensitive material, a photodecomposition reaction occurs in the UV-irradiated region and dissolves in the developing solution to form a pattern. In the negative photosensitive material, the UV-irradiated region undergoes a photocuring reaction and is insoluble in the developing solution, and the non-UV-irradiated region is dissolved in the developing solution to form a pattern.

It is very important for the photosensitive resin composition to ensure resistance to heat treatment applied to the process and resistance to chemical etching and gas etching processes, and particularly recently, in order to increase the light efficiency of the display. , High transmittance and high refraction characteristics are emphasized. In order to secure the characteristics of high heat resistance, chemical resistance (etching resistance), high transparency and high refraction of the photosensitive resin composition, above all, the structure and characteristics of the binder in the composition constituting the photosensitive material. Is very important. For this reason, research has been conducted on imparting photosensitivity to binder resins such as novolak resin and polyimide, including acrylic photosensitive resins used as typical binder resins for photosensitive resin compositions. It has been actively done. However, the conventionally used photosensitive resin composition using an acrylic photosensitive resin, a novolak resin, or the like has poor heat resistance in a high-temperature heat treatment step of 300 ° C. or higher, so that impurities due to outgassing are generated. Then, the display is seriously contaminated. It should be noted that there is a problem that the transmittance is lowered by the high temperature heat treatment and the light efficiency characteristics of the display are deteriorated.

For example, Patent Document 1 discloses a photosensitive resin composition produced by using a copolymer of an acrylic compound and an acrylate compound as a binder resin and using an acrylate compound as a polyfunctional monomer. .. However, the difference in solubility between the exposed and non-exposed areas is insufficient, so the development characteristics are not excellent, and the binder resin that should have been left during the development process is partially dissolved in the developing solution to create a fine pattern of 10 μm or less. There is a problem that it is difficult to obtain.

Further, Patent Documents 2 and 3 disclose a photosensitive photoresist composition in which a polyamic acid as a polyimide precursor and a naphthoquinone diazide compound as a dissolution inhibitor are contained to enhance thermal stability. However, in forming a high-resolution pattern, there is a problem that the difference in dissolution rate between the exposed portion and the non-exposed portion is insufficient.

Further, the photosensitive resin composition needs to have good adhesion to the lower layer and the upper layer, and to have a wide process margin capable of forming a high-resolution fine pattern under various process conditions according to the purpose of use. Since high-sensitivity characteristics are required as a photosensitive material, studies for improving such characteristics are being actively conducted.

As a technique for solving the above-mentioned problems, Patent Document 4 describes a negative photosensitive resin composition using a polymer having a specific structure having excellent heat resistance, high transmission, and high refraction as a binder resin. And positive photosensitive resin compositions are disclosed.

U.S. Pat. No. 4,139,391 Japanese Unexamined Patent Publication No. 52-13315 Japanese Unexamined Patent Publication No. 62-135824 JP-A-2018-5313111

By the way, in manufacturing a display, after forming a photosensitive resin layer using a photosensitive resin composition, different layers may be laminated. For example, a light extraction film that improves light extraction efficiency may be produced by laminating a low refractive index layer on a high refractive index layer formed by using a photosensitive resin composition. Such a laminating process is carried out using a composition in which a component such as a resin is dissolved in a solvent, but when the high refractive index layer on which the low refractive index layer is laminated does not have resistance to the solvent, There is a concern that the film thickness of the high-refractive index layer cannot be guaranteed by the laminating process, and that the characteristics such as the refractive index of the high-refractive index layer are deteriorated.

However, when the negative photosensitive resin composition described in Patent Document 4 is used, the solvent resistance of the formed photosensitive resin layer (cured film) is poor, and therefore, it is desirable to apply the above lamination process. There is a problem that the photosensitive resin layer cannot be realized.

The present invention has been made in view of the above problems, and comprises a negative photosensitive resin composition capable of forming a cured film having high solvent resistance, and a cured product of the negative photosensitive resin composition. An object of the present invention is to provide a cured film and a method for producing a cured film using the above-mentioned negative photosensitive resin composition.

As a result of intensive studies to achieve the above object, the present inventors have obtained a negative photosensitive resin composition containing a resin (A) having a specific structure and a photopolymerization initiator (B) having a specific structure. We have found that the above problems can be solved, and have completed the present invention. Specifically, the present invention provides the following.

（式（ａ１）中、Ｒ^１ａ及びＲ^２ａは、それぞれ独立に、炭素原子数１以上２０以下でありヘテロ原子を含んでいてもよいアルキル基、炭素原子数６以上２０以下でありヘテロ原子を含んでいてもよいアリール基、−Ｒ^４ａＳＲ^５ａ又は−Ｒ^６ａＣ（＝Ｏ）Ｒ^７ａを表し、
Ｒ^３ａは、炭素原子数１以上２０以下でありヘテロ原子を含んでいてもよい４価の芳香族炭化水素基又は脂環族炭化水素基を表し、
Ａは、下記式（ａ２）で表される２価の基を表し、
ｊ１及びｊ２は、それぞれ独立に、１以上６以下の整数を表し、
Ｒ^４ａは、単結合、炭素原子数１以上１０以下のアルキレン基、又は炭素原子数６以上１５以下のアリーレン基を表し、
Ｓは硫黄原子を表し、
Ｒ^５ａは、炭素原子数１以上１０以下のアルキル基、又は炭素原子数６以上１５以下のアリール基を表し、
Ｒ^６ａは、単結合、炭素原子数１以上１０以下のアルキレン基、又は炭素原子数６以上１０以下のアリーレン基を表し、
Ｒ^７ａは、炭素原子数１以上１０以下のアルキル基、炭素原子数１以上１０以下のアルケニル基、又は炭素原子数６以上１５以下のアリール基を表す。）

（式（ａ２）中、
Ｒ^８ａ及びＲ^９ａは、それぞれ独立に、水素原子、ヒドロキシ基、メルカプト基、アミノ基、ニトロ基、ハロゲン原子、シアノ基又はアルキル基を表し、
Ｒ^１０ａ及びＲ^１１ａは、それぞれ独立に、水素原子、アルキル基又はアリール基を表し、
ｋ１及びｋ２は、それぞれ独立に、０以上４以下の整数を表し、
ｍ１及びｍ２は、それぞれ独立に、０以上３以下の整数を表す。）

（式（ｂ１）中、
Ｒ^１ｂは、水素原子、ニトロ基又は１価の有機基を表し、
Ｒ^２ｂ及びＲ^３ｂは、それぞれ独立に、置換基を有していてもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子を表し、Ｒ^２ｂとＲ^３ｂとは相互に結合して環を形成してもよく、
Ｒ^４ｂは１価の有機基を表し、
Ｒ^５ｂは、水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基を表し、
ｐは、０以上４以下の整数であり、
ｑは、０又は１である。） The first aspect of the present invention is a negative type containing a resin (A) having a structural unit represented by the following formula (a1) and a photopolymerization initiator (B) represented by the following formula (b1). Photosensitive resin composition.

(In the formula (a1), R ^1a and R ^2a are each independently an alkyl group having 1 or more and 20 or less carbon atoms and may contain a hetero atom, and 6 or more and 20 or less carbon atoms and heteroatoms. Represents an aryl group that may be included, -R ^4a SR ^5a or -R ^6a C (= O) R ^7a .
R ^3a represents a tetravalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 1 or more and 20 or less carbon atoms and may contain a heteroatom.
A represents a divalent group represented by the following formula (a2).
j1 and j2 each independently represent an integer of 1 or more and 6 or less.
R ^4a represents a single bond, an alkylene group having 1 or more and 10 or less carbon atoms, or an arylene group having 6 or more and 15 or less carbon atoms.
S represents a sulfur atom
R ^5a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
R ^6a represents a single bond, an alkylene group having 1 or more and 10 or less carbon atoms, or an arylene group having 6 or more and 10 or less carbon atoms.
R ^7a represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. )

(In equation (a2),
R ^8a and R ^9a independently represent a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group or an alkyl group.
R ^10a and R ^11a independently represent a hydrogen atom, an alkyl group or an aryl group, respectively.
k1 and k2 independently represent integers of 0 or more and 4 or less, respectively.
m1 and m2 independently represent integers of 0 or more and 3 or less. )

(In equation (b1),
R ^1b represents a hydrogen atom, a nitro group or a monovalent organic group.
R ^2b and R ^3b independently represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R ^2b and R ^3b are They may combine with each other to form a ring.
R ^4b represents a monovalent organic group
R ^5b represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
p is an integer of 0 or more and 4 or less,
q is 0 or 1. )

A second aspect of the present invention is a cured film made of a cured product of the negative photosensitive resin composition according to the first aspect.

A third aspect of the present invention includes a step of applying the negative photosensitive resin composition according to the first aspect onto a substrate to form a coating film.
A method for producing a cured film, which comprises a step of exposing the coating film.

According to the present invention, a negative photosensitive resin composition capable of forming a cured film having high solvent resistance, a cured film made of a cured product of the negative photosensitive resin composition, and the above-mentioned negative photosensitive resin composition. It is possible to provide a method for producing a cured film using a sex resin composition.

Hereinafter, the present invention will be described in detail.
≪Negative type photosensitive resin composition≫
The negative photosensitive resin composition contains a resin (A) having a structural unit represented by the following formula (a1) and a photopolymerization initiator (B) represented by the following formula (b1).
The negative photosensitive resin composition may contain an adhesion enhancer (C), a photopolymerizable compound (D), a solvent (S), and other components, if necessary.

Hereinafter, essential or arbitrary components contained in the negative photosensitive resin composition and a method for producing the negative photosensitive resin composition will be described.

（式（ａ１）中、Ｒ^１ａ及びＲ^２ａは、それぞれ独立に、炭素原子数１以上２０以下でありヘテロ原子を含んでいてもよいアルキル基、炭素原子数６以上２０以下でありヘテロ原子を含んでいてもよいアリール基、−Ｒ^４ａＳＲ^５ａ又は−Ｒ^６ａＣ（＝Ｏ）Ｒ^７ａを表し、
Ｒ^３ａは、炭素原子数１以上２０以下でありヘテロ原子を含んでいてもよい４価の芳香族炭化水素基又は脂環族炭化水素基を表し、
Ａは、下記式（ａ２）で表される２価の基を表し、
ｊ１及びｊ２は、それぞれ独立に、１以上６以下の整数を表し、
Ｒ^４ａは、単結合、炭素原子数１以上１０以下のアルキレン基、又は炭素原子数６以上１５以下のアリーレン基を表し、
Ｓは硫黄原子を表し、
Ｒ^５ａは、炭素原子数１以上１０以下のアルキル基、又は炭素原子数６以上１５以下のアリール基を表し、
Ｒ^６ａは、単結合、炭素原子数１以上１０以下のアルキレン基、又は炭素原子数６以上１０以下のアリーレン基を表し、
Ｒ^７ａは、炭素原子数１以上１０以下のアルキル基、炭素原子数１以上１０以下のアルケニル基、又は炭素原子数６以上１５以下のアリール基を表す。）

（式（ａ２）中、
Ｒ^８ａ及びＲ^９ａは、それぞれ独立に、水素原子、ヒドロキシ基、メルカプト基、アミノ基、ニトロ基、ハロゲン原子、シアノ基又はアルキル基を表し、
Ｒ^１０ａ及びＲ^１１ａは、それぞれ独立に、水素原子、アルキル基又はアリール基を表し、
ｋ１及びｋ２は、それぞれ独立に、０以上４以下の整数を表し、
ｍ１及びｍ２は、それぞれ独立に、０以上３以下の整数を表す。） <Resin (A) (Binder resin)>
The resin (A) has a structural unit represented by the following formula (a1).

(In the formula (a1), R ^1a and R ^2a are each independently an alkyl group having 1 or more and 20 or less carbon atoms and may contain a hetero atom, and 6 or more and 20 or less carbon atoms and heteroatoms. Represents an aryl group that may be included, -R ^4a SR ^5a or -R ^6a C (= O) R ^7a .
R ^3a represents a tetravalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 1 or more and 20 or less carbon atoms and may contain a heteroatom.
A represents a divalent group represented by the following formula (a2).
j1 and j2 each independently represent an integer of 1 or more and 6 or less.
R ^4a represents a single bond, an alkylene group having 1 or more and 10 or less carbon atoms, or an arylene group having 6 or more and 15 or less carbon atoms.
S represents a sulfur atom
R ^5a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
R ^6a represents a single bond, an alkylene group having 1 or more and 10 or less carbon atoms, or an arylene group having 6 or more and 10 or less carbon atoms.
R ^7a represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. )

(In equation (a2),
R ^8a and R ^9a independently represent a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group or an alkyl group.
R ^10a and R ^11a independently represent a hydrogen atom, an alkyl group or an aryl group, respectively.
k1 and k2 independently represent integers of 0 or more and 4 or less, respectively.
m1 and m2 independently represent integers of 0 or more and 3 or less. )

As can be confirmed from the structure of the above formula (a2), the resin (A) has a bisphenylfluorene structure as a basic structure in its structural unit.

In the formula (a1), the hetero atom means an element excluding a carbon atom and a hydrogen atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, and a silicon atom. A plurality of these heteroatoms may be contained. Heteroatoms are preferably sulfur atoms, which have particularly good effects on heat resistance, chemical resistance, high permeability, high refraction and optical properties.

In the formula (a1), the ^{number of carbon atoms of the alkyl group which may contain heteroatoms as R 1a} and R ^2a is 1 or more and 20 or less, preferably 2 or more and 15 or less, and more preferably 2 or more. It is 10 or less. Specific examples of the alkyl group which may contain a hetero atom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-. Examples thereof include a pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group and an n-decyl group.
The ^{number of carbon atoms of the aryl group which may contain heteroatoms as R 1a} and R ^2a is 6 or more and 20 or less, preferably 6 or more and 15 or less, and more preferably 6 or more and 10 or less. Specific examples of the aryl group which may contain a hetero atom include a phenyl group, a naphthyl group, a frill group, a thienyl group and the like.

Specific examples of the alkylene group having 1 or more and 10 or less carbon atoms as R ^4a include a methylene group, an ethylene group, an n-propylene group, an isopropylene group and the like.
Specific examples of the arylene group having 6 or more and 15 or less carbon atoms as R ^{4a include a phenylene group and a naphthylene group.}
Specific examples of the alkyl group having 1 or more and 10 or less carbon atoms as R ^5a include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl. Examples thereof include a group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group and the like.
Specific examples of the aryl group having 6 or more and 15 or less carbon atoms as R ^{5a include a phenyl group and a naphthyl group.}
When R ^1a and R ^2a are −R ^4a SR ^5a , there are particularly excellent effects in heat resistance, high transmission and high refraction characteristics.

Specific examples of the alkylene group having 1 or more and 10 or less carbon atoms as R ^6a include the same groups as the alkylene group exemplified for ^{R 4a.}
Specific examples of the arylene group having 6 or more carbon atoms and 10 or less carbon atoms as R ^6a include the same group as the arylene group exemplified for ^{R 4a.}
Specific examples of the alkyl group having 1 or more and 10 or less carbon atoms as R ^7a include the same group as the alkyl group exemplified for ^{R 5a.}
Specific examples of the aryl group having 6 or more carbon atoms and 15 or less carbon atoms as R ^7a include the same group as the aryl group exemplified for ^{R 5a.}
Specific examples of the alkenyl group having 1 or more and 10 or less carbon atoms as R ^{7a include a vinyl group and an allyl group.}

The ^{number of carbon atoms of the tetravalent alicyclic hydrocarbon group which may contain a hetero atom as R 3a} is 1 or more and 20 or less, preferably 4 or more and 10 or less, and more preferably 4 or more and 6 or less. Is.
The ^{number of carbon atoms of the tetravalent aromatic hydrocarbon group which may contain a hetero atom as R 3a} is 1 or more and 20 or less, preferably 6 or more and 15 or less, and more preferably 6 or more and 12 or less. is there.
Such a ^{structure having R 3a} has excellent effects of heat resistance, high transmission, and high refraction.
Specific examples of R ^3a include a tetravalent group derived from tetracarboxylic dianhydride, which will be described later.

j1 and j2 are independently integers of 1 or more and 6 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.

In formula (a2), R ^8a and R ^9a independently represent a hydrogen atom, a hydroxy group (-OH), a mercapto group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ), respectively. It is a halogen atom, a cyano group or an alkyl group.
Specific examples of the halogen atom as R ^8a and R ^9a include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
The alkyl groups as R ^8a and R ^9a are, for example, alkyl groups having 1 or more and 10 or less carbon atoms. Specific examples thereof include groups similar to the alkyl groups exemplified for ^R5a.
R ^8a and R ^9a are preferably hydrogen atoms.

The alkyl groups as R ^10a and R ^11a are, for example, alkyl groups having 1 or more carbon atoms and 10 or less carbon atoms. Specific examples thereof include groups similar to the alkyl groups exemplified for ^R5a.
The aryl groups as R ^10a and R ^11a are, for example, aryl groups having 6 to 15 carbon atoms. Specific examples thereof include the same groups as the aryl group exemplified for R ^5a.

k1 and k2 are independently integers of 0 or more and 4 or less, and preferably 0 or more and 2 or less.
m1 and m2 are independently integers of 0 or more and 3 or less, and preferably 1 or more and 2 or less.

The number of structural units represented by the formula (a1) contained in the resin (A) is not particularly limited. The number of structural units represented by the formula (a1) of the resin (A) is, for example, an integer of 1 or more and 30 or less, preferably an integer of 1 or more and 10 or less. Within this range, there are particularly excellent effects on heat resistance, high transmission and high refraction characteristics.

The mass average molecular weight of the resin (A) can be, for example, 1,000 to 100,000 g / mol, preferably 2,000 to 50,000 g / mol, and more preferably 3,000 to 10,000 g / mol. Within this range, the heat resistance is excellent, the developing speed of the photosensitive material and the development with a developing solution are easy, which facilitates pattern formation and has the effect of exhibiting a high residual film ratio.

The dispersity of the resin (A) (mass average molecular weight Mw / number average molecular weight Mn) can be, for example, in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0. Within this range, the heat resistance is excellent, the developing speed of the photosensitive material and the development with a developing solution are easy, which facilitates pattern formation and has the effect of exhibiting a high residual film ratio.

The mass average molecular weight, the number average molecular weight, and the degree of dispersion in the present specification can be measured by a gel permeation chromatography (GPC) method.

By preparing a negative photosensitive resin composition containing such a specific resin (A) together with a specific photopolymerization initiator (B) described later, as shown in Examples described later, high solvent resistance It is possible to form a cured film having. In addition, a negative photosensitive resin composition having excellent resolution can be obtained. Further, as the resin (A), a resin having a high refractive index or a resin having high functionality such as heat resistance, chemical resistance, and high permeability can be selected, so that the negative type photosensitive including the resin (A) is photosensitive. The resin composition can form a cured film having a high refractive index or a cured film having high functionality such as heat resistance, chemical resistance, and high permeability.

（式（１）中、Ｒ^８ａ〜Ｒ^１１ａ、ｋ１、ｋ２、ｍ１及びｍ２は、それぞれ式（ａ２）におけるＲ^８ａ〜Ｒ^１１ａ、ｋ１、ｋ２、ｍ１及びｍ２と同様であり、Ｒ^１２ａ及びＲ^１３ａは、それぞれ独立に、ヒドロキシ基、チオール基、アミノ基、ニトロ基、シアノ基、ヘテロ原子を含む炭素原子数１以上２０以下の脂肪族アルキル基または脂環族アルキル基、またはヘテロ原子を含む炭素原子数６以上２０以下のアリール基を表す。）

（式（２）中、Ｒ^８ａ〜Ｒ^１１ａ、ｋ１、ｋ２、ｍ１及びｍ２は、それぞれ式（ａ２）におけるＲ^８ａ〜Ｒ^１１ａ、ｋ１、ｋ２、ｍ１及びｍ２と同様であり、Ｒ^１ａ、Ｒ^２ａ、ｊ１及びｊ２は、それぞれ式（ａ１）におけるＲ^１ａ、Ｒ^２ａ、ｊ１及びｊ２と同様である。） The resin (A) can be produced, for example, by the method described in Patent Document 4.
Specifically, the resin (A) is a tetracarboxylic dianhydride after synthesizing a compound (monomer) containing a hydroxy group represented by the following formula (2) from a compound represented by the following formula (1). It can be synthesized by carrying out a polymerization reaction with.

(In the formula ^{(1), R 8a ~R 11a} , k1, k2, m1 and m2 are the same as ^{R 8a ~R 11a, k1, k2} , m1 and m2 in each formula ^{(a2), R 12a} and R ^{Each of 13a} independently contains an aliphatic alkyl group or an alicyclic alkyl group having 1 to 20 carbon atoms including a hydroxy group, a thiol group, an amino group, a nitro group, a cyano group, and a hetero atom, or a hetero atom. Represents an aryl group having 6 to 20 carbon atoms.)

(In the formula ^{(2), R 8a ~R 11a} , k1, k2, m1 and m2 are the same as ^{R 8a ~R 11a, k1, k2} , m1 and m2 in each formula ^{(a2), R} 1a, R ^2a , j1 and j2 are the same as R ^1a , R ^2a , j1 and j2 in the formula (a1), respectively.)

In the formula (1), the hetero atom means an element excluding a carbon atom and a hydrogen atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, and a silicon atom. A plurality of these heteroatoms may be contained. For example, R ^12a and R ^13a may contain a heteroatom in the form of a hydroxy group, a thiol group, an amino group, a nitro group, or a cyano group.

The ^{number of carbon atoms of the aliphatic alkyl group or the alicyclic alkyl group containing the heteroatom as R 12a} and R ^13a is 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 3 or more and 8 or less. It is particularly preferably 3 or more and 5 or less. Specific examples of the aliphatic alkyl group or the alicyclic alkyl group containing a hetero atom include a hydroxyalkyl group or a thioalkyl group having 1 to 5 carbon atoms.
The ^{number of carbon atoms of the aryl group containing the heteroatom as R 12a} and R ^13a is 6 or more and 20 or less, preferably 6 or more and 15 or less, more preferably 6 or more and 10 or less, and particularly preferably 7 or more. It is 10 or less.
R ^12a and R ^13a are preferably hydroxy groups.

Examples of the tetracarboxylic dianhydride include a tetracarboxylic dianhydride represented by the following formula (3).

（式（３）中、Ｒ^３ａは、式（ａ１）におけるＲ^３ａと同様である。）

(In the formula ^{(3), R 3a} is the same as ^{R 3a} in formula (a1).)

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic. Acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3' -Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfonate dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5 , 6-naphthalenetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluoric acid dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} Fluoleic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid An aromatic ring tetracarboxylic dianhydride such as dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, or 1,2,3,4-cyclobutanetetracarboxylic acid. Alicyclic tetracarboxylic dianhydride such as dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, Alternatively, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride and the like can be mentioned.

The polymerization reaction can be carried out, for example, between 2 hours and 24 hours, or 4 hours and 12 hours at 100 to 130 ° C., or 110 to 120 ° C.

The tetracarboxylic dianhydride is, for example, 5 to 40 parts by mass, 10 to 30 parts by mass, or 10 to 20 parts by mass based on 100 parts by mass of the compound containing a hydroxy group represented by the above formula (2). You may use it.

In the production of the resin (A), for example, after the above-mentioned polymerization reaction is started, an end-capping agent may be added to cause the reaction. The end sealant facilitates control of the mass average molecular weight of the resin (A).
The reaction of the end-capping agent (end-sealing reaction) can be carried out, for example, at 100 to 130 ° C. or 110 to 120 ° C. for 30 minutes to 4 hours, or 1 hour to 3 hours.

The terminal encapsulant is added in an amount of 2 to 10 parts by mass, 2 to 5 parts by mass, or 3 to 5 parts by mass based on 100 parts by mass of the compound containing a hydroxy group represented by the above formula (2). You may.

Examples of the end-capping agent include organic acids, organic acid anhydrides, and amic acids.
As the terminal encapsulant, aromatic carboxylic acid anhydride is preferable, and phthalic acid anhydride is mentioned as a specific example. By using the aromatic carboxylic acid anhydride as the terminal sealant, the resin (A) has a particularly excellent effect on the properties of heat resistance, high transmission and high refraction.

When an end sealant is used, the end structure of the resin (A) can be a structure derived from the end sealant.
Further, the terminal structure of the resin (A) is a structure derived from a raw material added in excess among raw materials such as a compound containing a hydroxy group represented by the above formula (2) and a tetracarboxylic dianhydride. obtain.
More specifically, the terminal structure of the resin (A) can be, for example, the following structures 1 to 4, and the mass average molecular weight of the resin (A) can be appropriately controlled. The structures of a plurality of terminals in the molecular chain of the resin constituting the resin (A) may be different from each other.
The following OX for structure 4 is a group formed by the reaction of the hydroxyl group in structure 3 with the terminal encapsulant. Among the following terminal structures, structure 4 is preferable in terms of development characteristics. As the structure 4, a structure having an OX derived from an organic acid anhydride such as a dicarboxylic acid anhydride such as a phthalic acid anhydride or a tetrahydrophthalic acid anhydride is preferable.
Structure 1: A structure in which a hydrogen atom is bonded to the leftmost carbonyloxy group in the structure represented by the formula (a1). Structure 2: Two of the plurality of carboxy groups in the structure 1 are carboxylic acid anhydride groups. Structural structure 3: Structural structure represented by −CHR ^2a − (CH ₂ ) _j2 −O−A−O− (CH ₂ ) _j1 −CH (OH) −R ^1a 4: −CHR ^2a − (CH ₂ ) _j2 -O-A-O- (CH ₂ ) _j1- Structure represented by -CH (OX) -R ^1a

（式（ｂ１）中、
Ｒ^１ｂは、水素原子、ニトロ基又は１価の有機基を表し、
Ｒ^２ｂ及びＲ^３ｂは、それぞれ独立に、置換基を有していてもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子を表し、Ｒ^２ｂとＲ^３ｂとは相互に結合して環を形成してもよく、
Ｒ^４ｂは１価の有機基を表し、
Ｒ^５ｂは、水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基を表し、
ｐは、０以上４以下の整数であり、
ｑは、０又は１である。） <Photopolymerization initiator (B)>
The photopolymerization initiator (B) contained in the negative photosensitive resin composition is a photopolymerization initiator represented by the following formula (b1). The photopolymerization initiator means a component that generates an active species capable of initiating the polymerization of the above-mentioned resin (A) by visible light, ultraviolet rays, far ultraviolet rays, charged particle beams, X-rays and the like.

(In equation (b1),
R ^1b represents a hydrogen atom, a nitro group or a monovalent organic group.
R ^2b and R ^3b independently represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R ^2b and R ^3b are They may combine with each other to form a ring.
R ^4b represents a monovalent organic group
R ^5b represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
p is an integer of 0 or more and 4 or less,
q is 0 or 1. )

In formula (b1), R ^1b is a hydrogen atom, a nitro group or a monovalent organic group. R ^1b is attached to a 6-membered aromatic ring on the fluorene ring in the formula (b1), which is different from the 6-membered aromatic ring attached to the group represented by _{− (CO) q −.} In the formula (b1), the ^{bonding position of R 1b} with respect to the fluorene ring is not particularly limited. When the compound represented by the formula (b1) has 1 or more R ^{1b , one of the 1 or more R 1b} is a fluorene ring because the compound represented by the formula (b1) can be easily synthesized. It is preferable to bind to the 2-position of the inside. If R ^1b is plural, R ^1b may be different even in the same.

When R ^1b is an organic group, R ^1b is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where R ^1b is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a benzoyloxy which may have a substituent. A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent. It has a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like.

When R ^1b is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 6. When R ^1b is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^1b is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples thereof include an n-decyl group and an isodecyl group. When R ^1b is an alkyl group, the alkyl group may contain an ether bond (−O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^1b is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. When R ^1b is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^1b is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, and n. -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octioxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, an isodecyloxy group and the like. When R ^1b is an alkoxy group, the alkoxy group may contain an ether bond (−O−) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When R ^1b is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10 and more preferably 3 to 6. Specific examples of the case where R ^1b is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Specific examples of the case where R ^1b is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group and the like.

When R ^1b is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. Specific examples of the case where R ^1b is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and n. -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^1b is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, and 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ^1b is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. Specific examples of the case where R ^1b is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octioxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^1b is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. When R ^1b is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. Specific examples of the case where R ^1b is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^1b is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. R ^1b is a phenyl group, or when it is naphthyl alkyl group, R ^1b may further have a substituent on the phenyl group, or naphthyl group.

When R ^1b is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a fused ring, the number of fused rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperazine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like. Be done. When R ^1b is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^1b is a heterocyclyl carbonyl group, the heterocyclyl group contained in the heterocyclyl carbonyl group is the same as when R ^1b is a heterocyclyl group.

When R ^1b is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon atom. Saturated aliphatic acyl group of number 2 to 21, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenylalkyl which may have a substituent and may have 7 to 20 carbon atoms. Examples thereof include a group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group which may have a substituent and has 11 to 20 carbon atoms, and a heterocyclyl group. .. Specific examples of these suitable organic groups are the same as in R ^1b . Specific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group, and an n-. Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naftylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R 1b} further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having a number of 2 to 7, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. , Dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group and the like. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R 1b} further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 are preferable. When ^{the phenyl group, the naphthyl group, and the heterocyclyl group contained in R 1b} have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, a nitro group or a group represented by ^{R 6b −CO− is preferable as R 1b} in that the sensitivity tends to be improved. R ^6b is not particularly limited as long as it does not interfere with the object of the present invention, and can be selected from various organic groups. Examples of a suitable group as R ^6b include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. A good heterocyclyl group is mentioned. Among these groups, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferable as R ^6b.
Further, a hydrogen atom is preferable as ^{R 1b in} that the transparency tends to be good. If R ^1b is a hydrogen atom and R ^4b is a group represented by the formula (R4-2) described later, the transparency tends to be better.

In the formula (b1), R ^2b and R ^3b are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. R ^2b and R ^3b may be coupled to each other to form a ring. Among these groups, as R ^2b and R ^3b , a chain alkyl group which may have a substituent is preferable. When R ^2b and R ^3b are chain alkyl groups which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^2b and R ^3b are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of cases where R ^2b and R ^3b are chain alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-Pentyl group, Isopentyl group, sec-Pentyl group, tert-Pentyl group, n-Hexyl group, n-Heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Examples thereof include a group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when R ^2b and R ^3b are alkyl groups, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^2b and R ^3b are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as it does not impair the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as in the preferred example when ^{R 1b is a cycloalkyl group.} Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like. Specific examples of the heterocyclyl group are the same as in the preferred example when ^{R 1b is a heterocyclyl group.} When R ^1b is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.

When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of preferred substituents depends on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1-20, preferably 1-10, more preferably 1-6.

When R ^2b and R ^3b are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^2b and R ^3b are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ^2b and R ^3b are chain alkyl groups.

When R ^2b and R ^3b are aromatic hydrocarbon groups, whether the aromatic hydrocarbon group is a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond. , It is preferable that the group is formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.

When R ^2b and R ^3b are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, and more preferably 3 to 10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, Examples thereof include a tetracyclododecyl group and an adamantyl group.

When R ^2b and R ^3b are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, such monocyclic rings, or such monocyclic and benzene rings. Is a heterocyclyl group condensed with. When the heterocyclyl group is a fused ring, the number of fused rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperazine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like. Be done.

R ^2b and R ^3b may be coupled to each other to form a ring. The group consisting of the ring formed by ^{R 2b} and R ^{3b is preferably a cycloalkylidene group.} When R ^2b and R ^3b are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

When ^{the group formed by combining R 2b} and R ^3b is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that may be fused with a cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine. Rings, pyrazine rings, pyrimidine rings and the like can be mentioned.

Examples of suitable groups among ^{R 2b} and R ^3b described above include groups represented by the ^{formula −A 1} −A ^2. In the formula, A ¹ is a linear alkylene group and A ² is an alkoxy group, a cyano group, a halogen atom, an alkyl halide group, a cyclic organic group, or an alkoxycarbonyl group.

The ^{number of carbon atoms of the linear alkylene group of A 1} is preferably 1 to 10, and more preferably 1 to 6. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is an alkyl halide group, the halogen atom contained in the alkyl halide group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The alkyl halide group may be linear or branched, preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as those of the cyclic organic group that ^{R 2b} and R ^{3b have as substituents.} When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are similar to those of the alkoxycarbonyl group that ^{R 2b} and R ^{3b have as substituents.}

Preferable specific examples of R ^2b and R ^3b include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl. Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkyl alkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n Cyanalkyl groups such as −pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl Phenyl such as group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy Carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy Carbonyl ethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-etoki An alkoxycarbonylalkyl group such as a sicarbonyl-n-heptyl group and an 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chlor-n-propyl group, 4-chlor-n-butyl group, 5- Chlor-n-pentyl group, 6-chlor-n-hexyl group, 7-chlor-n-heptyl group, 8-chlor-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4- Bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-tri Examples thereof include a fluoropropyl group and an alkyl halide group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

As R ^2b and R ^3b , the preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-Cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,5,5,5-hepta It is a fluoro-n-pentyl group.

Examples of suitable organic groups for R ^4b include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups and substituents ^{, as in R 1b.} A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent. A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group which may have a group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like. Specific examples of these groups are similar to those described for ^{R 1b.} Further, as R ^4b , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained ^{in R 1b may have.}

Among the organic groups, R ^4b includes an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthio which may have a substituent on the aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups that may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

Further, as R ^4b , a group represented by ^{-A 3-} CO-O-A ^{4 is also preferable.} A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and more preferably an alkylene group. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

Preferred examples of A ⁴ is an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific preferable examples of A ⁴ is methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, n- pentyl group, n- hexyl Examples thereof include a group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group and the like.

Preferable specific examples of the group represented by −A ³ −CO—O—A ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n. -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group and the like.

（式（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^７ｂ及びＲ^８ｂはそれぞれ有機基であり、ｒは０〜４の整数であり、Ｒ^７ｂ及びＲ^８ｂがベンゼン環上の隣接する位置に存在する場合、Ｒ^７ｂとＲ^８ｂとが互いに結合して環を形成してもよく、ｓは１〜８の整数であり、ｔは１〜５の整数であり、ｕは０〜（ｔ＋３）の整数であり、Ｒ^９ｂは有機基である。） ^{Although R 4b} has been described above, the group represented by the following formula (R4-1) or (R4-2) is preferable as ^{R 4b.}

(In formulas (R4-1) and (R4-2), R ^7b and R ^8b are organic groups, respectively, r is an integer of 0 to 4, and R ^7b and R ^8b are adjacent positions on the benzene ring. R ^7b and R ^8b may combine with each other to form a ring, where s is an integer of 1 to 8, t is an integer of 1 to 5, and u is 0 to (t + 3). ), And R ^9b is an organic group.)

^{Examples of organic groups for R 7b} and R ^{8b in} formula (R4-1) are the same as for R ^1b . As R ^7b , an alkyl group or a phenyl group is preferable. When R ^7b is an alkyl group, the number of carbon atoms thereof is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ^7b is most preferably a methyl group. When R ^7b and R ^8b are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (R4-1) in which R ^7b and R ^8b form a ring include a naphthalene-1-yl group and 1,2,3. Examples thereof include 4-tetrahydronaphthalene-5-yl group. In the above formula (R4-1), r is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the above formula (R4-2), R ^9b is an organic group. Examples of the organic group include groups similar to the organic group described for ^{R 1b.} Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R ^9b , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the above formula (R4-2), t is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (R4-2), u is 0 to (t + 3), and an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, and 0 is particularly preferable. In the above formula (R4-2), s is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In the formula (b1), R ^5b is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As the ^{substituent which may be possessed when R 5b} is an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. Further, ^{as the substituent which may be possessed when R 5b} is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

In the formula (b1), ^{as R5b} , a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified. Of these, a methyl group or a phenyl group is more preferable.

The content of the photopolymerization initiator (B) is preferably 0.001 to 30 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the total solid content of the negative photosensitive resin composition. Is more preferable, and 0.5 to 10 parts by mass is further preferable.
The content of the photopolymerization initiator (B) is preferably 0.1 to 50% by mass, preferably 0.5 to 30% by mass, based on the total of the resin (A) and the photopolymerization initiator (B). It is more preferably mass%, and even more preferably 0.5-10 mass%.

The photopolymerization initiator (B) represented by the formula (b1) may be used alone or in combination of two or more, and when two or more thereof are used, the following (i) to (iii) are preferable.
(I) ^{Combination of a compound in which R 1b} is a hydrogen atom and a compound in which R ^1b is a nitro group (ii) A compound in which R ^4b is a formula (R4-1) and a compound in which R ^4b is a formula (R4-2). Combination with compound (iii) ^{Sensitivity and permeation of cured product among compounds in which R 4b} is of formula (R4-1) or formula (R4-2) and R ^4b is an alkyl group having 1 to 4 carbon atoms. From the viewpoint of improving characteristics such as rate, the combination of (i) above is preferable, and the combination satisfying (i) and (ii) or (iii) is more preferable.

The compounding ratio (mass ratio) of each compound based on the combination of (i) to (iii) may be appropriately adjusted according to the desired characteristics such as sensitivity. For example, 1:99 to 99: 1 is preferable, 10:90 to 90:10 is more preferable, and 30:70 to 70; 30 is even more preferable.

Preferable specific examples of the compound represented by the formula (b1) include the following compounds 1 to 41.

The negative photosensitive resin composition may contain a polymerization initiator other than the photopolymerization initiator (B).
Examples of the polymerization initiator other than the photopolymerization initiator (B) include an oxime ester compound other than the photopolymerization initiator (B), a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, and α-. Examples thereof include diketone compounds, polynuclear quinone compounds, phosphine compounds, and triazine compounds.

Examples of the oxime ester compound other than the photopolymerization initiator (B) include 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (0-acetyloxime). ), 1,3-octanedione-1 [(4-phenylthio) phenyl] 2-benzoyl-oxime and the like.

Examples of the acetophenone-based compound include α-hydroxyketone-based compounds, α-aminoketone-based compounds, and compounds other than these.

Specific examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane. Examples thereof include -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like, and specific examples of α-aminoketone compounds include. Examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like. Specific examples of the compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and the like.
These acetophenone compounds can be used alone or in admixture of two or more. By using these acetophenone compounds, it is possible to further improve the strength of the thin film.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-. Biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis ( 2-Chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4, 4', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'-tetraphenyl- 1,2'-biimidazole and the like can be mentioned.

Among the above biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4) -Dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole and the like are preferable, and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'is particularly preferable. -Bimidazole.

<Adhesion enhancer (C)>
The adhesion enhancer (C) is a component having an action of improving the adhesive force with the substrate, and is, for example, a reactive functional group such as a carboxyl group, a (meth) acryloyl group, a vinyl group, an isocyanate group, an epoxy group, and a mercapto group. A silane coupling agent having a group is preferable. Specifically, for example, trimethoxysilyl benzoic acid, 3-((meth) acryloyloxy) propyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, (3-isocyanatopropyl) triethoxysilane, 3- One or more selected from glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
In addition, in this specification, "(meth) acryloyl" means both "acryloyl" and "methacryloyl". Further, "(meth) acrylic rate" means both "acrylate" and "methacrylate", and "(meth) acrylic" means both "acrylic" and "methacryl".

Examples of the adhesion enhancer (C) include isocyanate-based compounds, epoxy-based compounds, (meth) acrylate-based compounds, vinyl compounds, and mercapto-based compounds, although some of the above silane coupling agents overlap, and epoxy is more preferable. It is a system compound. Examples of the epoxy compound include an organic silane compound having an epoxy group, and more specific examples thereof include an alkoxysilane having an epoxy group and having 1 or more and 5 or less carbon atoms.

The content of the adhesion enhancer (C) is, for example, 0 to 10 parts by mass, 0.01 to 10 parts by mass, 0.02 to 1 part by mass, or 0. The amount is preferably 05 to 0.1 parts by mass, and within this range, there is an excellent effect on the adhesive force with the substrate.

<Photopolymerizable compound (D)>
The negative photosensitive resin composition may or may not contain the photopolymerizable compound (D).
The photopolymerizable compound (D) is not particularly limited, and examples thereof include a crosslinkable compound having an ethylenically unsaturated bond.
A crosslinkable compound having an ethylenically unsaturated bond is generally a crosslinkable unit having at least two or more ethylene-based double bonds, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and the like. Triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylroll propanetriacrylate, trimethylroll propanetrimethacrylate. , Tetramethylroll Propane Tetraacrylate, Tetramethylroll Propane Tetramethacrylate, Pentaerythritol Triacrylate, Pentaerythritol Trimethacrylate, Pentaerythritol Tetraacrylate, Pentaerythritol Tetramethacrylate, Dipentaerythritol Pentaacrylate, Dipentaerythritol Pentamethacrylate, Dipentaerythritol Multi-action of hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate and their poly (poly-) compounds (polyethylene glycol diacrylate) Sex (meth) acrylic monomers and oligomers;
A polyester (meth) acrylate obtained by reacting a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid with a (meth) acrylic acid, a compound having a polyol group and two isocyanate groups. Polyurethane (meth) acrylate obtained by reacting with (meth) acrylic acid after the reaction;
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, Examples thereof include an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as an aliphatic or alicyclic epoxy resin, an amine epoxy resin, or a dihydroxybenzene type epoxy resin with (meth) acrylic acid. Further, in consideration of exposure sensitivity and the like, it is preferable to use a polyfunctional (meth) acrylic monomer as the photopolymerizable compound (D).

When the photopolymerizable compound (D) is contained, the photopolymerizable compound (D) is preferably contained in an amount of 0.1 to 200 parts by mass, preferably 1 to 30 parts by mass, based on 100 parts by mass of the resin (A). It is more preferable that it is contained in 5 to 10 parts by mass, and it is more preferable that it is contained in 5 to 10 parts by mass.

<Solvent (S)>
Examples of the solvent (S) include an organic solvent and water. The organic solvent is an acetate-based, ether-based, glycol-based, ketone-based, alcohol-based, carbonate-based or other organic solvent used in a general negative photosensitive resin composition, and dissolves the resin (A). There is no particular limitation as long as it allows. Examples of the organic solvent include propylene glycol monomethyl ether acetate (PEGMEA), ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, and 3 -Ethoxypropionic acid, N, N-dimethylacetamide, N-methylpyrrolidone (NMP), N-methylcaprolactam and the like can be mentioned.

The content of the solvent (S) is, for example, 20 to 95 parts by mass, preferably 30 to 90 parts by mass, and more preferably 50 to 80 parts by mass with respect to 100 parts by mass of the negative photosensitive resin composition. Within this range, thin film formation is easy even if a conventional coating method is used, and a thin film having a desired thickness can be easily obtained after coating.

<Other ingredients>
The negative photosensitive resin composition may contain an additive, if necessary. Examples of such additives include stabilizers, heat crosslinkers, photocuring accelerators, surfactants, base quenchers, antioxidants, adhesive aids, defoamers, etc., which can be used alone as needed. Alternatively, it can be mixed and used.

Surfactants are components that have the effect of improving coating properties, coating properties, uniformity, and stain removal on substrates. Examples of the surfactant include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant, and a silicon-based surfactant is preferable. Examples of the silicon-based surfactant include polyether-modified polysiloxane, and more specific examples thereof include polyether-modified polydimethylsiloxane.

The content of the surfactant is, for example, 0.01 to 5 parts by mass, 0.02 to 1 part by mass, or 0.05 to 0.1 parts by mass based on 100 parts by mass of the resin (A). Is preferable.

Examples of the stabilizer include a heat stabilizer and a light stabilizer.

As the heat stabilizer, a heat stabilizer that can be generally used for a negative photosensitive resin composition can be used, and the heat stabilizer is not particularly limited, but for example, of a cured product (organic film) to be formed. Examples thereof include a heat stabilizer capable of suppressing a decrease in permeability during the post-heat treatment step and increasing the permeability of the residual organic film. Examples of the heat stabilizer include a phenol-based heat stabilizer, a phosphite-based heat stabilizer, and a lactone-based heat stabilizer. Preferred heat stabilizers include, for example, compounds represented by the following formulas (4) to (6).

As the light stabilizer, a light stabilizer that can be generally used for a negative photosensitive resin composition can be used, and for example, the light resistance of the cured product (for example, an organic insulating film) to be formed is maximized. Examples of light stabilizers that can be used. Examples of the light stabilizer include a benzotriazole-based light stabilizer, a triazine-based light stabilizer, a benzophenone-based light stabilizer, a hindered aminoether-based light stabilizer, and a hindered amine-based light stabilizer.

<< Manufacturing method of negative photosensitive resin composition >>
The negative photosensitive resin composition can be produced by a general method, for example, by mixing each of the above components and filtering using a filter if necessary.

≪Manufacturing method of cured film and cured film≫
The negative photosensitive resin composition can be used to produce a cured film that can be used for displays such as TFT-LCDs, OLEDs, and touch screen panels. The cured film produced may be patterned, if desired.
A method for producing a cured film using the negative photosensitive resin composition will be described below.

First, the negative photosensitive resin composition is applied onto a substrate to form a coating film.
The substrate on which the coating film is formed is not particularly limited, and conventionally known substrates can be used, and examples thereof include a silicon substrate, a glass substrate, and a substrate having a metal surface. As the metal species constituting the metal surface, copper, gold, and aluminum are preferable, and copper is more preferable.
Further, in the negative type photosensitive resin composition, since the heating temperature can be lowered when forming the cured film, a substrate having low heat resistance can be used. Examples of the substrate having low heat resistance include a flexible substrate (for example, a flexible substrate). Examples of the flexible substrate include plastic substrates, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimide; polycarbonate; polyamide; polyacetal; polyphenylene oxide; polyphenylene sulfide; polyether sulfone; polyether ether. Ketone; homopolymer of norbornene-based monomer (additional polymer, ring-opening polymer, etc.), copolymer of norbornene-based monomer and olefin-based monomer such as copolymer of norbornene and ethylene (additional polymer, ring-opening polymer, etc.) Cyclic olefin copolymers such as), cyclic polyolefins such as derivatives thereof; (meth) acrylic resins such as vinyl polymers (eg, polymethylmethacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resins (eg) ABS resin), etc.); Vinylidene-based polymer (for example, polyvinylidene chloride, etc.); Cellulous resin such as triacetyl cellulose (TAC); Epoxy resin; Phenolic resin; Melamine resin; Uria resin; Maleimide resin; Silicone, etc. Examples include a plastic substrate made of a plastic material.

The method for applying the negative photosensitive resin composition is not particularly limited, and a known method may be used. For example, coating methods such as spin coating, dip coating, roll coating, screen coating, spray coating, flow coating, screen printing, inkjet, and drop casting can be mentioned.

The film thickness of the coating film to be formed varies depending on the coating method, the concentration of the solid content of the negative photosensitive resin composition, the viscosity, etc., and is not particularly limited, but usually, the film thickness is 0.5 to 100 μm after drying. Can be applied so as to become.

If necessary, the coating film may be dried. The drying method is not particularly limited, and examples thereof include a method of volatilizing the solvent by vacuum, infrared irradiation, or heating.

Next, the coating film is exposed. In the exposure process, energy rays such as excimer laser, far ultraviolet rays, ultraviolet rays, visible rays, electron beams, X-rays or g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), h-rays (wavelength 405 nm) or mixed rays thereof. Irradiate. For the exposure, an exposure method such as a contact type, a proximity type, or a projection type may be used.
The energy dose to be irradiated varies depending on the composition of the negative photosensitive resin composition, but is, for example, 140 mJ / cm ² or less, preferably 5 to 100 mJ / cm ² , and more preferably 10 to 60 mJ / cm ² .
By exposing the coating film, a curing reaction occurs and a cured product (cured film) is formed.

The exposure may be a regioselective exposure. Regioselective exposure is performed, for example, through a negative mask. By performing regioselective exposure, a patterned cured film can be formed.

When the coating film is exposed in a regioselective manner, a cured film patterned in a desired shape can be obtained by developing the coating film after exposure with a developing solution.
The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used.
The developer is appropriately selected according to the composition of the negative photosensitive resin composition. An alkaline aqueous solution may be used as the developer, but this is more environmentally friendly and economical than an organic solvent. Examples of the alkaline developing solution include an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide, and an amine-based aqueous solution such as ammonia, ethylamine, propylamine, diethylamine and triethylamine.

The coated film after exposure may be heated (post-exposure bake (PEB) or post-bake). The heating temperature is not particularly limited, but is, for example, 80 ° C. or higher and 250 ° C. or lower, preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. or higher and 150 ° C. or lower, and further preferably 85 ° C. or higher and 100 ° C. or lower. When a substrate with low heat resistance is used, it is difficult to use a substrate with low heat resistance because heating at a high temperature may adversely affect the substrate, but a substrate with low heat resistance is used by heating at a low temperature. be able to.
When the coating film is exposed in a regioselective manner, the heating (PEB) is preferably performed after the step of exposing the coating film and before the step of developing it.
When a substrate having high heat resistance is used, it is further heated at 80 ° C. or higher and 250 ° C. or lower after the developing step after the PEB step or after the developing step without performing the PEB step after exposure (post-baking). ) May be performed.

Since the cured film (cured product) produced by the above-mentioned production method is formed by using the above-mentioned negative photosensitive resin composition, it has high solvent resistance. The cured film formed by using the negative photosensitive resin composition has high resistance to organic solvents such as propylene glycol monomethyl ether acetate (PEGMEA) and N-methylpyrrolidone (NMP). Therefore, it is suitable for applications in which a laminated material is produced by forming another layer on the cured film using a composition in which a component such as a resin is dissolved in a solvent, or an application in which an adhesive containing a solvent is applied. Used for.

Further, since the negative photosensitive resin composition has excellent resolution, it is possible to produce a patterned cured film having a fine pattern. For example, it is possible to produce a patterned cured film having a fine pattern having a line width of 20 μm or less, preferably 10 μm or less.

Further, by using the negative photosensitive resin composition containing the resin (A), a cured film having a high refractive index and a cured film having high functionality such as heat resistance, chemical resistance, and high permeability can be obtained. Can be manufactured. For example, a cured film having a high refractive index becomes a light extraction film having excellent light extraction efficiency by forming a laminate with a low refractive index film. In addition, the cured film having excellent heat resistance can minimize the taper angle and outgassing.

Such a cured film or a patterned cured film may be, for example, a semiconductor element, an LCD element, an OLED element, a solar cell element, a flexible display element, a touch screen manufacturing element, a nanoimprint lithography element, or the like. It can be applied to the fabrication of devices and coating materials.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[Synthesis Example 1]
(Monomer synthesis)
1st step: 2,2'-((((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxylan) synthesis

Step A: After setting a reflux condenser and a thermometer in a three-necked flask, 42.5 g of 9,9-bisphenol fluorene was added, and 220 mL of 2- (chloromethyl) oxylane was quantified and then injected. After adding 100 mg of tetrabutylammonium bromide, stirring was started and the temperature was raised to 90 ° C. After confirming that the content of the unreacted product was less than 0.3%, distillation was carried out under reduced pressure.

Step B: After lowering the temperature to 30 ° C., dichloromethane was injected and NaOH was gradually added. After confirming that the product content was 96% or more by high performance liquid chromatography (HPLC) method, 5% HCl was added dropwise to terminate the reaction. The reaction product was extracted and layer-separated, and then the organic layer was washed with water and washed until it became neutral. The organic layer was dried in nuclease ₄ and then distilled under reduced pressure in a rotary evaporator to concentrate. Dichloromethane was added to the concentrated product and stirred while raising the temperature to 40 ° C., and methanol was added, and then the temperature of the solution was lowered and the mixture was stirred. After filtering the produced solid, it was vacuum dried at room temperature to obtain 52.7 g (yield 94%) of a white solid powder, and the structure thereof was confirmed by ^{1 1 H NMR.}

¹ H NMR in CDCl ₃ : 7.75 (2H), 7.36 to 7.25 (6H), 7.09 (4H), 6.74 (4H), 4.13 (2H), 3.89 (2H), 3.30 (2H), 2.87 (2H), 2.71 (2H).

2 steps: 3,3'-(((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (1- (phenylthio) propan-2-ol) (BTCP Monomer) synthesis

After setting the reflux condenser and the thermometer in the three-necked flask, the one-step reaction product (1000 g), 524 g of thiophenol, and 617 g of ethanol were added and stirred. 328 g of triethylamine was gradually added dropwise to the reaction solution. After confirming that the starting material had disappeared by high performance liquid chromatography (HPLC), the reaction was terminated. After the reaction was completed, ethanol was distilled under reduced pressure to remove it. The organic matter was dissolved in dichloromethane, washed with water, and then the dichloromethane was removed by vacuum distillation. The concentrated organic matter was dissolved in ethyl acetate, an ether solvent was added dropwise, and the mixture was stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g (yield 64%) of pale yellow oil, and its structure was confirmed by 1 H NMR.

¹ H NMR in CDCl ₃ : 7.82 (2H), 7.38-6.72 (20H), 6.51 (4H), 4.00 (2H), 3.97 (2H), 3.89 (2H), 3.20 (2H), 3.01 (2H), 2.64 (2H).

(Manufacture of resin (A) (binder resin)) Production of resin A1

After setting the reflux condenser and the thermometer in the three-necked flask, 200 g of BTCP monomer synthesized in two steps dissolved in 50% propylene glycol methyl ether acetate (PGMEA) solvent was added, and the temperature was raised to 115 ° C. After dropping 31.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride at 115 ° C., the mixture was stirred while maintaining 115 ° C. for 6 hours. After adding 7.35 g of phthalic anhydride and stirring for another 2 hours, the reaction was terminated. After cooling, a solution of resin A1 having a mass average molecular weight of 3,500 g / mol and a dispersity of 2.2 was obtained.

[Synthesis Example 2]
(Manufacturing of resin (A)) Manufacture of resin A2

After setting the reflux condenser and the thermometer in the three-necked flask, 200 g of BTCP monomer synthesized in two steps dissolved in 50% PGMEA solvent was added, and the temperature was raised to 115 ° C. After dropping 28.4 g of 3,3', 4,4'-benzophenonetetracarboxylic dianhydride at 115 ° C., the mixture was stirred while maintaining 115 ° C. for 6 hours. After adding 7.35 g of phthalic anhydride and stirring for another 2 hours, the reaction was terminated. After cooling, a solution of resin A2 having a mass average molecular weight of 5,000 g / mol and a dispersity of 2.4 was obtained.

Compound 6 was used as the photopolymerization initiator (B).

[Example 1]
93 parts by mass of resin A1 as resin (A), 5.6 parts by mass of compound 6 as photopolymerization initiator (B), and 3-glycidoxypropyltrimethoxysilane as adhesion enhancer (C). 0.93 parts by mass and 0.13 parts by mass of a siloxane-based surfactant (polyester-modified polydimethylsiloxane, BYK-310, manufactured by Big Chemie) as a surfactant so that the solid content concentration becomes 20% by mass. , Dissolved in propylene glycol monomethyl ether acetate (PEGMEA) as a solvent (S) to produce a negative photosensitive resin composition.

[Example 2]
A negative photosensitive resin composition was produced in the same manner as in Example 1 except that the blending amount of the adhesion enhancer (C) was changed to 3 times by mass.

[Example 3]
A negative photosensitive resin composition was produced in the same manner as in Example 1 except that the blending amount of the adhesion enhancer (C) was changed to 5 times by mass.

[Example 4]
Negative photosensitive in the same manner as in Example 3 except that 3- (methacryloyloxy) propyltrimethoxysilane was used as the adhesion enhancer (C) instead of 3-glycidoxypropyltrimethoxysilane. A sex resin composition was produced.

[Example 5]
85 parts by mass of resin A1 as resin (A), 5 parts by mass of compound 6 as photopolymerization initiator (B), and 3 parts of 3-glycidoxypropyltrimethoxysilane as adhesion enhancer (C). 0.2 parts by mass, 0.2 parts by mass of a siloxane-based surfactant (polyester-modified polydimethylsiloxane, BYK-310, manufactured by Big Chemie) as a surfactant, and dipentaerythritol hexaacrylate as a photopolymerizable compound (D). A negative photosensitive resin composition was produced by dissolving 6.5 parts by mass in propylene glycol monomethyl ether acetate (PEGMEA) as a solvent (S) so that the solid content concentration was 20% by mass.

[Comparative Example 1]
A method similar to that of Example 3 except that an oxime ester-based photopolymerization initiator having the structure of the following formula, which does not correspond to the formula (b1), was used instead of the compound 6 as the photopolymerization initiator (B). A negative photosensitive resin composition was produced in the above.

[Comparative Example 2]
Instead of compound 6 as the photopolymerization initiator (B), an oxime ester-based photopolymerization initiator (1,2-octanedione, 1- [4- (phenylthio) phenyl] −, 2 that does not correspond to the formula (b1)) A negative photosensitive resin composition was produced in the same manner as in Example 3 except that − (o-benzoyloxime), Irgacure OXE01, BASF Japan Co., Ltd. was used.

[Comparative Example 3]
A negative photosensitive resin composition was produced in the same manner as in Comparative Example 1 except that the resin A2 was used instead of the resin A1 as the resin (A).

[Comparative Example 4]
A negative photosensitive resin composition was produced in the same manner as in Comparative Example 2 except that the resin A2 was used instead of the resin A1 as the resin (A).

[Evaluation of solvent resistance]
After applying each of the negative photosensitive resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 on a substrate made of polyethylene terephthalate (PET) to a spin coater at 800 to 900 rpm for 15 seconds. A coating film having a film thickness of 5 μm was formed by drying on a hot plate at 85 ° C. for 180 seconds.
The dried coating film was irradiated with ultraviolet rays using a proximity exposure machine (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) with an exposure gap of 25 μm. The exposure amount was 30 mJ / cm ² .
A cured film was obtained by post-baking the exposed coating film at 85 ° C. for 300 seconds.
The obtained cured film was immersed in propylene glycol monomethyl ether acetate (PEGMEA) at 26 ° C. for 300 seconds.
The cured film before and after immersion was observed with a 5000 times scanning electron microscope (SEM), and the solvent resistance was evaluated according to the following criteria.
Evaluation was also made using N-methylpyrrolidone (NMP) as the solvent to be immersed.
Evaluation was also performed in which the post-baking condition was set to 100 ° C. for 300 seconds.
The results are shown in Table 1.
Further, the negative type photosensitive resin composition obtained in Example 5 was subjected to the same solvent resistance evaluation as described above except that post-baking was not performed. The results are described as Example 6.
(PEGMEA)
〇: No change in the cured film before and after immersion ×: Change in the cured film before and after immersion (NMP)
〇: The rate of change in the thickness of the cured film before and after immersion is less than 10% ×: The rate of change in the thickness of the cured film before and after immersion is 10% or more

[Evaluation of resolution]
After applying each of the negative photosensitive resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 on a substrate made of polyethylene terephthalate (PET) to a spin coater at 800 to 900 rpm for 15 seconds. A coating film having a film thickness of 5 μm was formed by drying on a hot plate at 85 ° C. for 180 seconds.
A proximity exposure machine (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) was used on the dried coating film via a negative mask having an exposure gap of 25 μm and a pattern having a width of 10 μm. It was irradiated with ultraviolet rays. The exposure amount was 30 mJ / cm ² .
The exposed coating film was baked (PEB) at 85 ° C. for 300 seconds and then developed with a 2.38 mass% TMAH aqueous solution at 26 ° C. for 30 seconds to obtain a cured film.
The obtained cured film was observed with a 5000 times scanning electron microscope (SEM), and the case where a pattern having a width of 10 μm was formed was evaluated as 0, and the case where a pattern with a width of 10 μm was not formed was evaluated as ×. And said.
The results are shown in Table 1.
Further, with respect to the negative photosensitive resin composition obtained in Example 5, the resolution was evaluated in the same manner as described above except that PEB was not performed. The results are described as Example 6.

According to Examples 1 to 6, a negative photosensitive resin composition containing a resin (A) having a structural unit represented by the formula (a1) and a photopolymerization initiator (B) represented by the formula (b1). It can be seen that the product has excellent solvent resistance. It can also be seen that these negative photosensitive resin compositions are also excellent in resolution.

On the other hand, according to Comparative Examples 1 to 4, the negative photosensitive resin composition contains the resin (A) having the structural unit represented by the formula (a1), but the photopolymerization initiation represented by the formula (b1) is carried out. It can be seen that the solvent resistance is inferior to that of Examples 1 to 6 when the agent (B) is not contained. It can also be seen that the resolution is also worse than in Examples 1 to 6.

Claims (9)

A negative photosensitive resin composition containing a resin (A) having a structural unit represented by the following formula (a1) and a photopolymerization initiator (B) represented by the following formula (b1).

(In the formula (a1), R ^1a and R ^2a are each independently an alkyl group having 1 or more and 20 or less carbon atoms and may contain a hetero atom, and 6 or more and 20 or less carbon atoms and heteroatoms. Represents an aryl group that may be included, -R ^4a SR ^5a or -R ^6a C (= O) R ^7a .
R ^3a represents a tetravalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 1 or more and 20 or less carbon atoms and may contain a heteroatom.
A represents a divalent group represented by the following formula (a2).
j1 and j2 each independently represent an integer of 1 or more and 6 or less.
R ^4a represents a single bond, an alkylene group having 1 or more and 10 or less carbon atoms, or an arylene group having 6 or more and 15 or less carbon atoms.
S represents a sulfur atom
R ^5a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
R ^6a represents a single bond, an alkylene group having 1 or more and 10 or less carbon atoms, or an arylene group having 6 or more and 10 or less carbon atoms.
R ^7a represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. )

(In equation (a2),
R ^8a and R ^9a independently represent a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group or an alkyl group.
R ^10a and R ^11a independently represent a hydrogen atom, an alkyl group or an aryl group, respectively.
k1 and k2 independently represent integers of 0 or more and 4 or less, respectively.
m1 and m2 independently represent integers of 0 or more and 3 or less. )

(In equation (b1),
R ^1b represents a hydrogen atom, a nitro group or a monovalent organic group.
R ^2b and R ^3b independently represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R ^2b and R ^3b are They may combine with each other to form a ring.
R ^4b represents a monovalent organic group
R ^5b represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
p is an integer of 0 or more and 4 or less,
q is 0 or 1. ) The negative photosensitive resin composition according to claim 1, further comprising an adhesion enhancer (C). A cured film comprising a cured product of the negative photosensitive resin composition according to claim 1 or 2. A step of applying the negative photosensitive resin composition according to claim 1 or 2 onto a substrate to form a coating film.
A method for producing a cured film, which comprises a step of exposing the coating film. The method for producing a cured film according to claim 4, further comprising a step of exposing the coating film and then heating the coating film after the exposure. The step of exposing the coating film is a step of exposing the coating film in a regioselective manner.
The method for producing a cured film according to claim 4, further comprising a step of developing the coating film after exposure. The method for producing a cured film according to claim 6, further comprising a step of heating the coating film after the exposure after the step of exposing the coating film and before the step of developing the coating film. The method for producing a cured film according to claim 5 or 7, wherein the heating temperature in the step of heating the coating film after the exposure is 85 ° C. or higher and 100 ° C. or lower. The method for producing a cured film according to any one of claims 4 to 8, wherein the substrate is a flexible substrate.