TW202128826A - Negative-type photosensitive resin composition and method of manufacturing cured film - Google Patents

Abstract

The subject of the present invention is to provide a negative photosensitive resin composition that can form a cured film with high solvent resistance, a cured film containing a cured product of the negative photosensitive resin composition, and the use of the negative photosensitive resin composition. Method for producing cured film of flexible resin composition. The present invention provides a negative photosensitive resin composition containing a resin (A) with a specific structure and a photopolymerization initiator (B) with a specific structure, a cured film containing a cured product of the negative photosensitive resin composition, And the manufacturing method of the cured film using the said negative photosensitive resin composition.

Description

Negative photosensitive resin composition and method for producing cured film

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

The photosensitive resin composition for displays used in thin-film transistor-type liquid crystal display devices (TFT-LCD), organic light-emitting devices (OLED), touch panels (TSP), etc., causes a curing reaction or light by UV (ultraviolet) irradiation. The method of forming patterns by decomposition reaction is divided into positive photosensitive materials and negative photosensitive materials. In the positive photosensitive material, the UV-irradiated area undergoes a photolysis reaction and dissolves in the developer to form a pattern. In the negative photosensitive material, the UV-irradiated area undergoes a photo-hardening reaction and is not dissolved in the developer solution, and the area not irradiated by the UV is dissolved in the developer solution, thereby forming a pattern.

Regarding the photosensitive resin composition, it is very important to ensure the resistance to the heat treatment applied in the step, as well as the resistance to the chemical etching and gas etching steps. In particular, recently, in order to increase the light efficiency of the display, high transmittance and The characteristic of high refraction. In order to ensure the characteristics of high heat resistance, chemical resistance (etch resistance), high permeability and high refraction of the photosensitive resin composition, the most important thing in the composition constituting the photosensitive material is the structure and characteristics of the adhesive. For this reason, it is actively used to impart photosensitivity to novolac resins, polyimide and other binder resins, including acrylic photosensitive resins, which are representative binder resins for photosensitive resin compositions. Were studied. However, the previously used photosensitive resin compositions using acrylic photosensitive resins and novolac resins have poor heat resistance during high-temperature heat treatment steps above 300°C. Therefore, outgassing may generate impurities, resulting in The pollution of the monitor is serious. Furthermore, there is a problem that the transmittance is reduced due to 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 which is produced using a copolymer of an acrylic compound and an acrylate compound as a binder resin and an acrylate compound as a polyfunctional monomer. However, there is a problem that the solubility difference between the exposed part and the unexposed part is insufficient, so the development characteristics are not excellent, and the binder resin that should remain in the development process is partially dissolved in the developing solution, and it is difficult to obtain a fine pattern below 10 μm.

In addition, Patent Document 2 and Patent Document 3 disclose a photosensitive photoresist composition containing polyimide as a precursor of polyimide and a naphthoquinone diazide compound as a dissolution inhibitor. Thermal stability, but when forming a high-resolution pattern, there is a problem that the dissolution rate difference between the exposed part and the unexposed part is insufficient.

Furthermore, the photosensitive resin composition needs to have good adhesion to the lower layer and the upper layer, and have a wide range of steps that can form high-resolution fine patterns under various step conditions that match the purpose of use. As a photosensitive material, high sensitivity is required Characteristics, therefore, researches to improve such characteristics are actively being carried out.

Regarding the technology to solve the above-mentioned problems, Patent Document 4 discloses a negative photosensitive resin composition and a positive photosensitive resin composition, which use a specific structure with excellent heat resistance and high transmittance and high refraction characteristics. The polymer acts as a binder resin. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 4139391 [Patent Document 2] Japanese Patent Laid-Open No. 52-13315 [Patent Document 3] Japanese Patent Laid-Open No. 62-135824 [Patent Document 4] Japanese Patent Publication No. 2018-531311

[The problem to be solved by the invention]

However, when manufacturing a display, there are cases where different layers are laminated after forming a photosensitive resin layer using a photosensitive resin composition. For example, there are cases where a low-refractive index layer is laminated on a high-refractive index layer formed using a photosensitive resin composition to produce a light extraction film with improved light extraction efficiency. This type of lamination process is carried out using a composition obtained by dissolving components such as resin in a solvent. However, when the high refractive index layer for the low refractive index lamination layer does not have the resistance to the solvent, it may be caused by the lamination process. As a result, there is a concern that the film thickness of the high-refractive-index layer cannot be guaranteed, and the refractive index of the high-refractive-index layer is reduced.

However, when the negative photosensitive resin composition described in Patent Document 4 is used, the formed photosensitive resin layer (cured film) has poor solvent resistance. Therefore, if the above-mentioned build-up process is applied, it cannot be achieved. The problem of the required photosensitive resin layer.

The present invention was made in view of the above problems, and its object is to provide a negative photosensitive resin composition capable of forming a cured film with high solvent resistance, and a cured film containing a cured product of the negative photosensitive resin composition , And a method for producing a cured film using the negative photosensitive resin composition. [Technical means to solve the problem]

In order to achieve the above-mentioned object, the inventors of the present invention have conducted intensive research and found that a negative photosensitive resin composition containing a resin (A) of a specific structure and a photopolymerization initiator (B) of a specific structure can solve the problem. The above problems have completed the present invention. Specifically, the present invention provides the following.

(式(a1)中，R^1a 及R^2a 分別獨立地表示碳原子數1以上20以下且可包含雜原子之烷基、碳原子數6以上20以下且可包含雜原子之芳基、-R^4a SR^5a 或-R^6a C(=O)R^7a ， R^3a 表示碳原子數1以上20以下且可包含雜原子之四價芳香族烴基或脂環族烴基， A表示下述式(a2)所表示之二價基， j1及j2分別獨立地表示1以上6以下之整數， R^4a 表示單鍵、碳原子數1以上10以下之伸烷基、或碳原子數6以上15以下之伸芳基， S表示硫原子， R^5a 表示碳原子數1以上10以下之烷基、或碳原子數6以上15以下之芳基， R^6a 表示單鍵、碳原子數1以上10以下之伸烷基、或碳原子數6以上10以下之伸芳基， R^7a 表示碳原子數1以上10以下之烷基、碳原子數1以上10以下之烯基、或碳原子數6以上15以下之芳基) [化2]

(式(a2)中， R^8a 及R^9a 分別獨立地表示氫原子、羥基、巰基、胺基、硝基、鹵素原子、氰基或烷基， R^10a 及R^11a 分別獨立地表示氫原子、烷基或芳基， k1及k2分別獨立地表示0以上4以下之整數， m1及m2分別獨立地表示0以上3以下之整數) [化3]

(式(b1)中， R^1b 表示氫原子、硝基或一價有機基， R^2b 及R^3b 分別獨立地表示可具有取代基之鏈狀烷基、可具有取代基之環狀有機基、或氫原子，R^2b 與R^3b 亦可相互鍵結而形成環， R^4b 表示一價有機基， R^5b 表示氫原子、可具有取代基之碳原子數1以上11以下之烷基、或可具有取代基之芳基， p為0以上4以下之整數， q為0或1)The first aspect of the present invention is a negative photosensitive resin composition comprising: a resin (A) having a structural unit represented by the following formula (a1), and a photopolymerization represented by the following formula (b1) Starter (B). [化1]

(In formula (a1), R ^1a and R ^2a each independently represent an alkyl group having 1 or more and 20 carbon atoms and which may include heteroatoms, an aryl group having 6 or more and 20 or less carbon atoms and which may include heteroatoms, -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 to 20 carbon atoms and which may contain heteroatoms, A represents the following formula (a2) The indicated divalent group, j1 and j2 each independently represent an integer of 1 to 6 and R ^4a represents a single bond, an alkylene having 1 to 10 carbon atoms, or an aromatic having 6 to 15 carbon atoms S represents a sulfur atom, R ^5a represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms, and R ^6a represents a single bond, an alkylene group with 1 to 10 carbon atoms , Or an aryl group with 6 to 10 carbon atoms, R ^7a represents an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms ) [化2]

(In formula (a2), R ^8a and R ^9a each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, and R ^10a and R ^11a each independently represent a hydrogen atom, Alkyl group or aryl group, k1 and k2 each independently represent an integer from 0 to 4, and m1 and m2 each independently represent an integer from 0 to 3) [化3]

(In formula (b1), R ^1b represents a hydrogen atom, a nitro group or a monovalent organic group, and R ^2b and R ^3b each independently represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, Or a hydrogen atom, R ^2b and R ^3b may be bonded to each other to form a ring, R ^4b represents a monovalent organic group, R ^5b represents a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms, or Substituent aryl group, p is an integer from 0 to 4, q is 0 or 1)

The second aspect of the present invention is a cured film comprising the cured product of the negative photosensitive resin composition of the first aspect.

The third aspect of the present invention is a method for manufacturing a cured film, which includes the steps of: coating the negative photosensitive resin composition of the first aspect on a substrate to form a coating film; and Expose the above-mentioned coating film. [Effects of Invention]

According to the present invention, it is possible to provide a negative photosensitive resin composition capable of forming a cured film with high solvent resistance, a cured film containing a cured product of the negative photosensitive resin composition, and the use of the negative photosensitive resin composition. Method for producing cured film of flexible resin composition.

Hereinafter, the present invention will be described in detail. ＜＜Negative 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 also contain an adhesion enhancer (C), a photopolymerizable compound (D), a solvent (S), and other components as needed.

Hereinafter, the essential components or optional components contained in the negative photosensitive resin composition, and the manufacturing method of the negative photosensitive resin composition will be described.

(式(a1)中，R^1a 及R^2a 分別獨立地表示碳原子數1以上20以下且可包含雜原子之烷基、碳原子數6以上20以下且可包含雜原子之芳基、-R^4a SR^5a 或-R^6a C(=O)R^7a ， R^3a 表示碳原子數1以上20以下且可包含雜原子之四價芳香族烴基或脂環族烴基， A表示下述式(a2)所表示之二價基， j1及j2分別獨立地表示1以上6以下之整數， R^4a 表示單鍵、碳原子數1以上10以下之伸烷基、或碳原子數6以上15以下之伸芳基， S表示硫原子， R^5a 表示碳原子數1以上10以下之烷基、或碳原子數6以上15以下之芳基， R^6a 表示單鍵、碳原子數1以上10以下之伸烷基、或碳原子數6以上10以下之伸芳基， R^7a 表示碳原子數1以上10以下之烷基、碳原子數1以上10以下之烯基、或碳原子數6以上15以下之芳基) [化5]

(式(a2)中， R^8a 及R^9a 分別獨立地表示氫原子、羥基、巰基、胺基、硝基、鹵素原子、氰基或烷基， R^10a 及R^11a 分別獨立地表示氫原子、烷基或芳基， k1及k2分別獨立地表示0以上4以下之整數， m1及m2分別獨立地表示0以上3以下之整數)<Resin (A) (binder resin)> The resin (A) has a structural unit represented by the following formula (a1). [化4]

(In formula (a1), R ^1a and R ^2a each independently represent an alkyl group having 1 or more and 20 carbon atoms and which may include heteroatoms, an aryl group having 6 or more and 20 or less carbon atoms and which may include heteroatoms, -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 to 20 carbon atoms and which may contain heteroatoms, A represents the following formula (a2) The indicated divalent group, j1 and j2 each independently represent an integer of 1 to 6 and R ^4a represents a single bond, an alkylene having 1 to 10 carbon atoms, or an aromatic having 6 to 15 carbon atoms S represents a sulfur atom, R ^5a represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms, and R ^6a represents a single bond, an alkylene group with 1 to 10 carbon atoms , Or an aryl group with 6 to 10 carbon atoms, R ^7a represents an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms ) [化5]

(In formula (a2), R ^8a and R ^9a each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, and R ^10a and R ^11a each independently represent a hydrogen atom, Alkyl group or aryl group, k1 and k2 each independently represent an integer from 0 to 4, and m1 and m2 each independently represent an integer from 0 to 3)

From the structure of the above formula (a2), it can be confirmed that the resin (A) has a biphenyl sulfide structure as a basic structure in its structural unit.

In formula (a1), heteroatoms refer to elements other than carbon atoms and hydrogen atoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, and silicon atoms. It may also contain a plurality of these heteroatoms. The hetero atom is preferably a sulfur atom. In this case, it has particularly excellent effects of heat resistance, chemical resistance, high permeability, high refraction, and optical properties.

In formula (a1), the ^{number of carbon atoms of the alkyl groups R 1a} and R ^2a that may contain heteroatoms is 1 or more and 20 or less, preferably 2 or more and 15 or less, more preferably 2 or more and 10 or less. Specific examples of alkyl groups that may contain heteroatoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl Base, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc. The number of carbon atoms of the heteroatom-containing aryl groups R ^1a and R ^2a 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. As a specific example of the aryl group which may contain a hetero atom, a phenyl group, a naphthyl group, a furyl group, a thienyl group, etc. can be mentioned.

^{Specific examples of the alkylene group R 4a having} 1 to 10 carbon atoms include methylene, ethylidene, n-propylidene, isopropylidene and the like. ^{Specific examples of the arylene group R 4a having} 6 to 15 carbon atoms include phenylene, naphthyl, and the like. Specific examples of the alkyl group R ^{5a having} 1 to 10 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc. ^{Specific examples of the aryl group R 5a having} 6 or more and 15 or less carbon atoms include a phenyl group and a naphthyl group. If R ^1a and R ^2a are -R ^4a SR ^5a , they have particularly excellent effects of heat resistance, high transmission and high refraction characteristics.

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

^{The number of carbon atoms of the tetravalent alicyclic hydrocarbon group R 3a} which may contain a hetero atom is 1 or more and 20 or less, preferably 4 or more and 10 or less, more preferably 4 or more and 6 or less. ^{The number of carbon atoms of the tetravalent aromatic hydrocarbon group R 3a} which may contain a hetero atom is 1 or more and 20 or less, preferably 6 or more and 15 or less, more preferably 6 or more and 12 or less. If the structure has such R ^3a , it has excellent effects of heat resistance, high transmission and high refraction characteristics. As a ^{specific example of R 3a} , the tetravalent group derived from the following tetracarboxylic dianhydride can be mentioned.

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

In the formula (a2), R ^8a and びR ^9a are each independently a hydrogen atom, a hydroxyl group (-OH), a mercapto group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ), a halogen atom, and a cyanide group.基 or alkyl. Specific examples of the halogen atoms R ^8a and R ^9a include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. The alkyl group R ^8a and R ^{9a are,} for example, an alkyl group having 1 to 10 carbon atoms. As a specific example, the same group as the alkyl group ^{exemplified by R 5a can be mentioned.} R ^8a and R ^{9a are} preferably hydrogen atoms.

The alkyl group R ^10a and R ^{11a are,} for example, an alkyl group having 1 to 10 carbon atoms. As a specific example, the same group as the alkyl group ^{exemplified by R 5a can be mentioned.} The aryl groups R ^10a and R ^{11a are,} for example, aryl groups having 6 or more and 15 or less carbon atoms. As the specific example, the same group as the aryl group ^{exemplified by R 5a can be mentioned.}

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

The number of structural units represented by formula (a1) included in the resin (A) is not particularly limited. The number of structural units represented by formula (a1) of the resin (A) is, for example, an integer of 1 or more and 30 or less, and preferably an integer of 1 or more and 10 or less. Within this range, it has particularly excellent effects of heat resistance, high transmittance, 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. When it is within this range, it has the following effects: excellent heat resistance, excellent development speed of the photosensitive material, and easy development with a developer, thereby facilitating pattern formation and exhibiting a high residual film rate.

In addition, the dispersion degree (mass average molecular weight Mw/number average molecular weight Mn) of the resin (A) can be, for example, in the range of 1.0 to 5.0, and preferably in the range of 1.5 to 4.0. When it is within this range, it has the following effects: excellent heat resistance, excellent development speed of the photosensitive material, and easy development with a developer, thereby facilitating pattern formation and exhibiting a high residual film rate.

Furthermore, the mass average molecular weight, number average molecular weight, and dispersion in this specification can be measured by gel permeation chromatography (GPC).

By preparing a negative photosensitive resin composition containing this specific resin (A) and the specific photopolymerization initiator (B) described below in detail, it can be formed as shown in the following examples. Hardened film with high solvent resistance. Moreover, it can be set as the negative photosensitive resin composition excellent also in resolution. In addition, as the resin (A), a resin with a high refractive index or a resin with high functionality such as heat resistance, chemical resistance, and high permeability can be selected. Therefore, a negative photosensitive resin combination containing the resin (A) The material can form a cured film with high refractive index, or a cured film with high functionality such as heat resistance, chemical resistance, and high permeability.

(式(1)中，R^8a ～R^11a 、k1、k2、m1及m2分別與式(a2)中之R^8a ～R^11a 、k1、k2、m1及m2相同，R^12a 及R^13a 分別獨立地表示羥基、硫醇基、胺基、硝基、氰基、包含雜原子之碳原子數1以上20以下之脂肪族烷基或脂環族烷基、或包含雜原子之碳原子數6以上20以下之芳基) [化7]

(式(2)中，R^8a ～R^11a 、k1、k2、m1及m2分別與式(a2)中之R^8a ～R^11a 、k1、k2、m1及m2相同，R^1a 、R^2a 、j1及j2分別與式(a1)中之R^1a 、R^2a 、j1及j2相同)The resin (A) can be produced by the method described in Patent Document 4, for example. Specifically, the resin (A) can be synthesized by synthesizing the hydroxyl-containing compound (monomer) represented by the following formula (2) from the compound represented by the following formula (1), and then combining with tetracarboxylic acid The anhydride undergoes polymerization. [化6]

(In the formula (1), in the ^{R 8a ~ R 11a, k1,} k2, m1 and m2, respectively of formula ^{(a2) R 8a ~ R 11a} , k1, k2, m1 , and the same m2, R ^12a and R ^13a each independently Ground represents a hydroxyl group, a thiol group, an amino group, a nitro group, a cyano group, an aliphatic alkyl group or a cycloaliphatic alkyl group with a heteroatom-containing carbon number of 1 or more and 20 or less, or a heteroatom-containing carbon atom number of 6 or more Aryl groups below 20) [Chemical 7]

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

In formula (1), heteroatoms refer to elements other than carbon atoms and hydrogen atoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, and silicon atoms. It may also contain a plurality of these heteroatoms. For example, R ^12a and R ^13a can also contain heteroatoms in the form of a hydroxyl group, a thiol group, an amine group, a nitro group, or a cyano group.

The number of carbon atoms of the heteroatom-containing aliphatic alkyl group or alicyclic alkyl group R ^12a and R ^13a is 1 or more and 20 or less, preferably 1 or more and 10 or less, more preferably 3 or more and 8 or less, and particularly preferably 3 or more 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 heteroatom-containing aryl groups 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 and 10 or less. R ^12a and R ^{13a are} preferably hydroxyl groups.

As the tetracarboxylic dianhydride, tetracarboxylic dianhydride represented by the following formula (3) may be mentioned.

(式(3)中，R^3a 與式(a1)中之R^3a 相同)[化8]

(Formula (3), the same as R ^3a and formula (A1) R ^3a)

Specific examples of tetracarboxylic dianhydride include: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'- Phenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic 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-di Carboxyphenyl) methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) bis(3,4-dicarboxyphenyl) dianhydride, bis(3,4-dicarboxyphenyl) ether Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl) dianhydride, 9,9-bis[4-(3,4- Dicarboxyphenoxy) phenyl) dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10 -Perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and other aromatic cyclic tetracarboxylic dianhydrides, or 1,2,3,4-cyclobutane Alicyclic tetracarboxylic dianhydride such as tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, or 3,3',4,4'-diphenyl tetracarboxylic dianhydride, etc.

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

Tetracarboxylic dianhydride can also be used based on 100 parts by mass of the hydroxyl-containing compound represented by the above formula (2), for example, 5-40 parts by mass, 10-30 parts by mass, or 10-20 parts by mass.

In the production of the resin (A), for example, a terminal blocking agent may be added after the start of the above-mentioned polymerization reaction to carry out the reaction. With the end-capping agent, it is easy to control the mass average molecular weight of the resin (A). The reaction of the terminal blocking agent (terminal blocking reaction) can be carried out at 100 to 130°C, or 110 to 120°C within 30 minutes to 4 hours, or 1 hour to 3 hours, for example.

The terminal blocking agent can also be added in 2-10 parts by mass, 2-5 parts by mass, or 3-5 parts by mass based on 100 parts by mass of the hydroxyl-containing compound represented by the above formula (2), for example.

The terminal blocking agent may, for example, be an organic acid, an organic acid anhydride, or an amide acid. As a terminal blocking agent, aromatic carboxylic dianhydride is preferable, and as a specific example, phthalic anhydride is mentioned. By using an aromatic carboxylic dianhydride as a terminal blocking agent, the resin (A) has particularly excellent effects of heat resistance, high permeability, and high refractive index.

In the case of using a terminal blocking agent, the terminal structure of the resin (A) may be a structure derived from the terminal blocking agent. In addition, the terminal structure of the resin (A) may be a structure derived from a raw material excessively added to raw materials such as the hydroxyl-containing compound represented by the above formula (2) or tetracarboxylic dianhydride. 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 plurality of terminal structures on the molecular chain of the resin constituting the resin (A) may also be different from each other. Regarding structure 4, the following OX is a group formed by the reaction of the hydroxyl group of structure 3 with the above-mentioned end-capping agent. Among the following terminal structures, the structure 4 is preferable in terms of development characteristics. As structure 4, the structure which has OX derived from organic acid anhydrides, such as dicarboxylic dianhydride, such as phthalic anhydride and tetrahydrophthalic anhydride, is preferable. Structure 1: In the structure represented by formula (a1), the left end of the carbonyloxy group is bonded with a hydrogen atom. Structure 2: The structure in which two of the plural carboxyl groups in structure 1 become carboxylic acid dianhydride groups 3: -CHR ^2a -(CH ₂ ) _j2 -OAO-(CH ₂ ) _j1 -CH(OH)-R ^1a represents the structure structure 4: -CHR ^2a -(CH ₂ ) _j2 -OAO-(CH ₂ ) Structure represented by _j1 -CH(OX)-R ^1a

(式(b1)中， R^1b 表示氫原子、硝基或一價有機基， R^2b 及R^3b 分別獨立地表示可具有取代基之鏈狀烷基、可具有取代基之環狀有機基、或氫原子，R^2b 與R^3b 亦可相互鍵結而形成環， R^4b 表示一價有機基， R^5b 表示氫原子、可具有取代基之碳原子數1以上11以下之烷基、或可具有取代基之芳基， p為0以上4以下之整數， q為0或1)<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 refers to a component that generates active species that can start the polymerization of the resin (A) by visible light, ultraviolet light, extreme ultraviolet light, charged particle beam, X-ray, etc. [化9]

(In formula (b1), R ^1b represents a hydrogen atom, a nitro group or a monovalent organic group, and R ^2b and R ^3b each independently represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, Or a hydrogen atom, R ^2b and R ^3b may be bonded to each other to form a ring, R ^4b represents a monovalent organic group, R ^5b represents a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms, or Substituent aryl group, p is an integer from 0 to 4, q is 0 or 1)

In the formula (b1), R ^1b is a hydrogen atom, a nitro group, or a monovalent organic group. R ^{1b is} bonded to a six-membered aromatic ring on the fluorine ring in formula (b1), and the six-membered aromatic ring is different from the six-membered aromatic ring bonded to the group represented by _{-(CO) q -.} In the formula (b1), ^{the bonding position of R 1b} in the chrysanthemum ring is not particularly limited. When the compound represented by the formula (b1) has one or more R ^1b, it is easy to synthesize the compound represented by the formula (b1). Therefore, it is preferable to make one of the one or more R ^1b and 2 of the 茀 ring Position bonding. When R ^1b is plural, the plural R ^1b may be the same or different.

When R ^1b is an organic group, R ^1b is not particularly limited as long as it does not interfere with the purpose of the present invention, and can be appropriately selected from various organic groups. Suitable examples when 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, which may have a substituent The phenyl group, the phenoxy group which may have a substituent, the benzyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzyloxy group which may have a substituent, and the benzene which may have a substituent Alkyl, naphthyl which may have substituents, naphthyloxy which may have substituents, naphthyloxycarbonyl which may have substituents, naphthoxycarbonyl which may have substituents, naphthyloxycarbonyl which may have substituents Group, naphthylalkyl which may have substituents, heterocyclic group which may have substituents, heterocyclic carbonyl which may have substituents, amino group substituted by 1 or 2 organic groups, 𠰌line-1-yl , And piper-1-yl and so on.

When R ^1b is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-6. In addition, when R ^1b is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R ^1b is an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl , Isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl Base, and isodecyl, etc. In addition, when R ^1b is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups with ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When R ^1b is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-6. In addition, when R ^1b is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R ^1b is an alkoxy group include: methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, second butoxy group, Tertiary butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy Oxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. In addition, when R ^1b is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include: methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy Group, propoxyethoxyethoxy, and methoxypropoxy, etc.

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

When R ^1b is a saturated aliphatic oxy group or saturated aliphatic oxy group, the saturated aliphatic oxy group or saturated aliphatic oxy group preferably has 2-21 carbon atoms, more preferably 2-7. Specific examples when R ^1b is a saturated aliphatic acyl group include: acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentanyl group, 2,2-dimethylpropane group Nyl, n-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-thirteen, n-fourteen醯基, pentadecyl, and hexadecyl, etc. Specific examples when R ^1b is a saturated aliphatic oxy group include: acetoxy, propoxy, n-butoxy, 2-methylpropoxy, n-pentoxy, 2,2-Dimethylpropionyloxy, n-hexyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n- Dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy, etc.

When R ^1b is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, more preferably 2-7. Specific examples when R ^1b is an alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl , Second butoxycarbonyl, third butoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, second pentoxycarbonyl, third pentoxycarbonyl, n-hexoxycarbonyl, n-heptyloxy Carbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxy Group carbonyl and so on.

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

When R ^1b is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing more than one N, S, O, or the monocyclic ring is condensed with each other, or the monocyclic ring and a benzene ring are condensed的heterocyclic group. When the heterocyclic group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, azole, isoazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine , Damp, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoindole Quinoline, quinazoline, quinoline, quinazoline, quinoline, piperidine, piperidine, quinoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R ^1b is a heterocyclic group, the heterocyclic group may further have a substituent.

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

When R ^1b is an amine group substituted with one or two organic groups, suitable examples of the organic group include: an alkyl group with 1 to 20 carbon atoms, and a cycloalkyl group with 3 to 10 carbon atoms. , Saturated aliphatic acyl groups with 2 to 21 carbon atoms, phenyl groups that may have substituents, benzyl groups that may have substituents, phenylalkyl groups with 7 to 20 carbon atoms that may have substituents, Substituent naphthyl group, optionally substituted naphthylmethyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, heterocyclic group, and the like. The specific examples of these suitable organic groups are the same as ^{R 1b.} As specific examples of the amino group substituted with one or two organic groups, there may be mentioned: methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, Isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decyl Amino, phenylamino, naphthylamino, acetamino, acrylamido, n-butyramido, n-pentanamido, n-hexamido, n-heptanamido, n-octamido Amino, n-decanoylamino, benzylamino, α-naphthylamino, β-naphthylamino, and the like.

Examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in R ^1b further have a substituent include: an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, and alkyl group with 1 to 6 carbon atoms A monoalkylamino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a linolin-1-yl group, a piperidine-1-yl group, a halogen, a nitro group, a cyano group, and the like. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^1b further have a substituent, the number of the substituent is not limited within a range that does not interfere with the purpose of the present invention, and it is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^1b have plural substituents, the plural substituents may be the same or different.

Among the groups described above, in terms of the tendency to increase sensitivity, R ^{1b is} preferably a nitro group or a ^{group represented by R 6b -CO-.} R ^6b is not particularly limited as long as it does not interfere with the purpose of the present invention, and it can be selected from various organic groups. Suitable examples of the group 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 heterocyclic group which may have a substituent. As R ^6b , among these groups, 2-tolyl, thien-2-yl, and α-naphthyl are particularly preferred. In addition, since the transparency tends to become better, R ^{1b is} preferably a hydrogen atom. Furthermore, if R ^1b is a hydrogen atom and R ^4b is a group represented by the following formula (R4-2), the transparency tends to be better.

In the formula (b1), R ^2b and R ^3b are each a linear alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^2b and R ^3b may be bonded to each other to form a ring. Among these groups, R ^2b and R ^{3b are} preferably a chain alkyl group which may have a substituent. When R ^2b and R ^3b are a chain alkyl group 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 without substituents, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Specific examples when R ^2b and R ^3b are chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Base, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, iso Nonyl, n-decyl, and isodecyl, etc. In addition, when R ^2b and R ^3b are an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of alkyl groups with ether bonds in the carbon chain include: methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxy Ethoxyethyl, and methoxypropyl, etc.

When R ^2b and R ^3b are chain alkyl groups having substituents, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. 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 substitution that the alkyl group may have is not particularly limited as long as it does not interfere with the purpose of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Among them, a fluorine atom, a chlorine atom, and a bromine atom are preferred. The cyclic organic group may, for example, be a cycloalkyl group, an aromatic hydrocarbon group, or a heterocyclic group. As a specific example of a cycloalkyl group, it is the same as a suitable example when ^{R1b is a cycloalkyl group.} Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. Specific examples of the heterocyclic group are the same as the suitable examples when ^{R 1b is a heterocyclic group.} When R ^1b is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1-10, more preferably 1-6.

When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies according to the number of carbon atoms of 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 a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. The cyclic organic group may, for example, be an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic 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, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by bonding a plurality of benzene rings via carbon-carbon bonds, or a group formed by condensation of a plurality of benzene rings . When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 Below, 1 is particularly preferred. Preferred specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl.

When R ^2b and R ^3b are an aliphatic cyclic hydrocarbon group, 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 it is preferably 3-20, more preferably 3-10. Examples of monocyclic cyclic hydrocarbon groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, nordoxyl, isooxyl, tricyclononyl, Tricyclodecyl, tetracyclododecyl, adamantyl, etc.

When R ^2b and R ^3b are heterocyclic groups, the heterocyclic group is a five-membered or six-membered monocyclic ring containing more than one N, S, O, or the monocyclic rings, or the monocyclic ring and the benzene ring A heterocyclic group formed by condensation. When the heterocyclic group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, azole, isoazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrrole, pyrimidine , Damp, benzofuran, benzothiophene, indole, isoindole, indole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoindole Quinoline, quinazoline, quinoline, quinazoline, quinoline, piperidine, piperidine, quinoline, piperidine, tetrahydropyran, and tetrahydrofuran, etc.

R ^2b and R ^3b may be bonded to each other to form a ring. The group including ^{the ring formed by R 2b} and R ^3b is preferably a cycloalkylene group. When R ^2b and R ^{3b are} bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a five-membered ring to a six-membered ring, and more preferably a five-membered ring.

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

Examples of suitable groups in ^{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, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the straight-chain extended alkyl group A ¹ is preferably 1-10, more preferably 1-6. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1-10, more preferably 1-6. 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 a halogenated alkyl group, the halogen atom contained in the halogenated alkyl 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 halogenated alkyl group may be linear or branched, and is preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as 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 the same as those of the alkoxycarbonyl group that ^{R 2b} and R ^{3b have as substituents.}

Suitable specific examples of R ^2b and R ^3b include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3-methoxy n-propyl, 4-methoxy n-butyl, 5-methoxy n-pentyl, 6-methoxy n-hexyl, 7-methoxy n-heptyl, 8-methoxy n Octyl, 2-ethoxyethyl, 3-ethoxy n-propyl, 4-ethoxy n-butyl, 5-ethoxy n-pentyl, 6-ethoxy n-hexyl, 7-ethoxy N-heptyl and 8-ethoxy n-octyl and other alkoxyalkyl groups; 2-cyanoethyl, 3-cyano n-propyl, 4-cyano n-butyl, 5-cyano n-pentyl , 6-cyano n-hexyl, 7-cyano n-heptyl, and 8-cyano n-octyl and other cyanoalkyl groups; 2-phenylethyl, 3-phenyl n-propyl, 4-phenyl n-butyl Phenylalkyl groups such as 5-phenyl n-pentyl, 6-phenyl n-hexyl, 7-phenyl n-heptyl, and 8-phenyl n-octyl; 2-cyclohexyl ethyl, 3-cyclohexyl N-propyl, 4-cyclohexyl n-butyl, 5-cyclohexyl n-pentyl, 6-cyclohexyl n-hexyl, 7-cyclohexyl n-heptyl, 8-cyclohexyl n-octyl, 2-cyclopentyl ethyl , 3-cyclopentyl n-propyl, 4-cyclopentyl n-butyl, 5-cyclopentyl n-pentyl, 6-cyclopentyl n-hexyl, 7-cyclopentyl n-heptyl, and 8-cyclopentyl Cycloalkylalkyl groups such as n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl n-propyl, 4-methoxycarbonyl n-butyl, 5-methoxycarbonyl n-pentyl, 6-methoxycarbonyl n-hexyl, 7-methoxycarbonyl n-heptyl, 8-methoxycarbonyl n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl n-propyl, 4- Alkoxy groups such as ethoxycarbonyl n-butyl, 5-ethoxycarbonyl n-pentyl, 6-ethoxycarbonyl n-hexyl, 7-ethoxycarbonyl n-heptyl, and 8-ethoxycarbonyl n-octyl Carbonyl carbonyl alkyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl Base, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-pentyl, 6-bromo-hexyl, 7-bromo-heptyl, 8-bromo-octyl, 3 ,3,3-Trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl and other halogenated alkyl groups.

As R ^2b and R ^3b , suitable groups mentioned above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2 -Cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5 ,5-Heptafluoro-n-pentyl.

Examples of suitable organic groups R ^4b include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, and saturated aliphatic acyl groups in the same way ^{as R 1b.} An oxy group, a phenyl group that may have a substituent, a phenoxy group that may have a substituent, a benzyl group that may have a substituent, a phenoxycarbonyl group that may have a substituent, and a benzyloxy group that may have a substituent , Phenylalkyl which may have substituents, naphthyl which may have substituents, naphthyloxy which may have substituents, naphthyloxy which may have substituents, naphthoxycarbonyl which may have substituents, which may have Substituent naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, amine group substituted by 1 or 2 organic groups , 𠰌line-1-yl, piper-1-yl and so on. The specific examples of these bases are the same as those described ^{for R 1b.} Moreover, 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 included in ^{R 1b may have.}

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

Moreover, as R ^4b , the group represented by ^{-A 3} -CO-OA ^{4 is also preferable.} A ³ is a divalent organic group, preferably a divalent hydrocarbon group, 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, and is preferably linear. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1-10, more preferably 1-6, and particularly preferably 1-4.

As preferred examples of the A ^4, include: an alkyl group having a carbon number of 1 to 10 carbon atoms, aralkyl of 7 to 20, carbon atoms, and an aromatic hydrocarbon group of 6 to 20. Suitable specific examples of A ⁴ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl Group, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, etc.

Suitable specific examples of the group represented by -A ³ -CO-OA ⁴ include: 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl , 2-n-butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3- Methoxycarbonyl n-propyl, 3-ethoxycarbonyl n-propyl, 3-n-propoxycarbonyl n-propyl, 3-n-butoxycarbonyl n-propyl, 3-n-pentoxycarbonyl n-propyl , 3-n-hexyloxycarbonyl n-propyl, 3-benzyloxycarbonyl n-propyl, and 3-phenoxycarbonyl n-propyl, etc.

(式(R4-1)及(R4-2)中，R^7b 及R^8b 分別為有機基，r為0～4之整數，於R^7b 及R^8b 存在於苯環上相鄰之位置之情形時，R^7b 與R^8b 亦可相互鍵結而形成環，s為1～8之整數，t為1～5之整數，u為0～(t＋3)之整數，R^9b 為有機基)Although R ^4b has been described above, R ^{4b is} preferably a group represented by the following formula (R4-1) or (R4-2). [化10]

(In formulas (R4-1) and (R4-2), R ^7b and R ^8b are organic groups, respectively, r is an integer of 0-4, when R ^7b and R ^8b exist in adjacent positions on the benzene ring When R ^7b and R ^8b can be bonded to each other to form a ring, s is an integer of 1 to 8, t is an integer of 1 to 5, u is an integer of 0 to (t+3), and R ^9b is an organic group)

The examples of the organic groups of ^{R 7b} and R ^8b in the formula (R4-1) are the same as those of ^{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 is preferably 1-10, more preferably 1-5, particularly preferably 1-3, most preferably 1. That is, R ^{7b is} most preferably a methyl group. When R ^7b and R ^{8b are} bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (R4-1), that is, the group in which R ^7b and R ^8b form a ring include naphth-1-yl and 1,2,3,4-tetralin- 5-based etc. In the above formula (R4-1), r is an integer of 0-4, preferably 0 or 1, and more preferably 0.

In the above formula (R4-2), R ^9b is an organic group. As the organic group, the same group as the organic group explained ^{for R 1b can be mentioned.} Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1-10, more preferably 1-5, and particularly preferably 1-3. Preferred examples of R ^{9b include} methyl, ethyl, propyl, isopropyl, butyl, etc. Among them, methyl is more preferred.

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

In the formula (b1), R ^5b is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. As ^{the substituent which may be possessed when R 5b} is an alkyl group, preferred ones include a phenyl group and a naphthyl group. Moreover, as a ^{substituent which may be possessed when R 5b} is an aryl group, preferable examples include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (b1) ^{, preferred examples of R 5b} include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, tolyl group, naphthyl group, etc. Among them, more preferred is a methyl group or a phenyl group.

The content of the photopolymerization initiator (B) is preferably 0.001 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably, relative to 100 parts by mass of the total solid components of the negative photosensitive resin composition It is 0.5-10 parts by mass. In addition, the content of the photopolymerization initiator (B) relative to the total of the resin (A) and the photopolymerization initiator (B) is preferably 0.1-50% by mass, more preferably 0.5-30% by mass, and more Preferably it is 0.5-10 mass %.

The photopolymerization initiator (B) represented by the formula (b1) may be used alone, or two or more types may be used. When two or more types are used, the following (i) to (iii) are preferred. (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) Combination of a compound in which R ^4b is a compound of formula (R4-1) and R ^4b is a compound of formula (R4-2) ) R ^4b is a compound of formula (R4-1) or formula (R4-2) and R ^4b is a compound of a C1-C4 alkyl group, in terms of improving the sensitivity and the transmittance of the cured product, etc. In other words, the combination of (i) above is preferred, and the combination of (i), and (ii) or (iii) above is more preferred.

The compounding ratio (mass ratio) of each compound in the combination of (i) to (iii) above may be appropriately adjusted according to characteristics such as target sensitivity. For example, it is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, and still more preferably 30:70 to 70:30.

Suitable specific examples of the compound represented by the formula (b1) include the following compounds 1 to 41. [化11]

[化12]

Furthermore, the negative photosensitive resin composition may contain a polymerization initiator other than the photopolymerization initiator (B). As polymerization initiators other than the photopolymerization initiator (B), for example, oxime ester-based compounds, biimidazole-based compounds, benzoin-based compounds, and acetophenone other than the photopolymerization initiator (B) may be mentioned. -Based compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, phosphine-based compounds, tri-ketone-based compounds, etc.

Examples of oxime ester compounds other than the photopolymerization initiator (B) include: 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl ]-1-(0-acetyloxime), 1,3-octanedione-1[(4-phenylthio)phenyl]2-benzyloxime and the like.

As the acetophenone compound, for example, an α-hydroxyketone compound, an α-aminoketone compound, and compounds other than these may be mentioned.

Specific examples of α-hydroxy ketone compounds include 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy- 2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, etc., as α-amino group Specific examples of the ketone compound include: 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌olinylpropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-𠰌olinylphenyl)-butanone-1, etc., as specific examples of compounds other than these include 2,2-dimethoxyacetophenone, 2, 2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, etc. These acetophenone-based compounds can be used alone or in combination of two or more kinds. By using these acetophenone compounds, the strength of the film can be further improved.

In addition, as a specific example of the biimidazole-based compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl) -1,2'-Biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(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.

Among the above-mentioned 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-trichlorobenzene Yl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc., especially 2,2'-bis(2,4-dichlorophenyl)-4,4' ,5,5'-Tetraphenyl-1,2'-biimidazole.

＜Adhesion enhancer (C)＞ The adhesion enhancer (C) is a component that has the effect of improving the adhesion to the substrate. For example, it preferably has reactivity such as carboxyl group, (meth)acryloyl group, vinyl group, isocyanate group, epoxy group, mercapto group, etc. Functional silane coupling agent. Specifically, for example, it is selected from the group consisting of trimethoxysilyl benzoic acid, 3-((meth)acryloyloxy)propyltrimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane , (3-isocyanatopropyl)triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 2-(3 ,4-Epoxycyclohexyl) ethyl trimethoxy silane one or more. Furthermore, in this specification, "(meth)acryloyl" means both "acryloyl" and "methacryloyl". In addition, "(meth)acrylate" refers to both "acrylate" and "methacrylate", and "(meth)acrylic" refers to both "acrylic" and "methacrylic".

The adhesion enhancer (C) partially overlaps the above-mentioned silane coupling agent, and examples thereof include isocyanate-based compounds, epoxy-based compounds, (meth)acrylate-based compounds, vinyl-based compounds, and mercapto-based compounds, more preferably It is an epoxy compound. As the epoxy-based compound, for example, an organosilane compound having an epoxy group may be mentioned. As a more specific example, an alkoxysilane having 1 to 5 carbon atoms having an epoxy group may be mentioned.

The content of the adhesion enhancer (C) is based on 100 parts by mass of the resin (A), for example, 0-10 parts by mass, preferably 0.01-10 parts by mass, 0.02-1 parts by mass, or 0.05-0.1 parts by mass , If it is within this range, it has the effect of excellent adhesion to 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 for example, a crosslinkable compound having an ethylenically unsaturated bond may be mentioned. The crosslinkable compound having ethylenically unsaturated bonds is generally a crosslinkable unit having at least two ethylene double bonds, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethyl Acrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetra Methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, two Pentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, phenolphthalein based epoxy diacrylate and these poly (poly-) compounds (poly Ethylene glycol diacrylate) and other multi-action (meth)acrylic monomers and oligomers; Polyester prepolymer obtained by condensation of polyols with monobasic acid or polybasic acid and (meth)acrylic acid to obtain polyester (meth)acrylate; make polyol group and have 2 isocyanate groups After the compound reacts, it reacts with (meth)acrylic acid to obtain polyurethane (meth)acrylate; Make bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin Resin, polycarboxylate polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin and other epoxy resins react with (meth)acrylic acid And the obtained epoxy (meth)acrylate resin. Moreover, 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 0.1 to 200 parts by mass, and more preferably 1 to 30 parts by mass relative to 100 parts by mass of the resin (A), More preferably, it contains 5-10 mass parts.

＜Solvent (S)＞ As the solvent (S), an organic solvent or water may be mentioned. As the organic solvent, any organic solvents such as acetate, ether, glycol, ketone, alcohol, and carbonate used in general negative photosensitive resin compositions can be used as long as the resin (A) The dissolved organic solvent is not particularly limited. Examples of organic solvents 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, 3-ethoxypropionate, N,N-dimethylacetamide, N-methylpyrrolidone ( NMP), N-methylcaprolactam, etc.

The content of the solvent (S) relative to 100 parts by mass of the negative photosensitive resin composition 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. Within this range, even if the previous coating method is used, a thin film can be easily formed, and a thin film of a desired thickness can be easily obtained after coating.

＜Other ingredients＞ The negative photosensitive resin composition may also contain additives as needed. As examples of such additives, there are stabilizers, thermal crosslinking agents, light hardening accelerators, surfactants, alkali quenchers, antioxidants, bonding aids, defoamers, etc., which can be used alone or in combination as needed.

Surfactant is a component that has the effect of improving the coating property and coating property, uniformity and decontamination of the substrate. As the surfactant, for example, a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant may be mentioned, and a silicon-based surfactant is preferable. As the silicon-based surfactant, for example, polyether-modified polysiloxane may be mentioned, and as a more specific example, polyether-modified polydimethylsiloxane may be mentioned.

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

The stabilizer may, for example, be a heat stabilizer or a light stabilizer.

The heat stabilizer can be a heat stabilizer commonly used in negative photosensitive resin compositions, and is not particularly limited. For example, the following heat stabilizers can be used in the subsequent heat treatment step of the formed cured product (organic film) It suppresses the decrease in permeability and improves the permeability of the residual organic film. The heat stabilizer may, for example, be a phenol-based heat stabilizer, a phosphite-based heat stabilizer, and a lactone-based heat stabilizer. As a preferable heat stabilizer, the compound represented by following formula (4)-(6) can be mentioned, for example.

[化13]

[化14]

[化15]

As the light stabilizer, a light stabilizer generally used in a negative photosensitive resin composition can be used. For example, the following light stabilizer can be exemplified, which can maximize the light resistance of the formed cured product (for example, an organic insulating film). The light stabilizer may, for example, be a benzotriazole-based light stabilizer, a triazole-based light stabilizer, a benzophenone-based light stabilizer, a hindered amino ether-based light stabilizer, and a hindered amine-based light stabilizer.

＜＜Method for manufacturing negative photosensitive resin composition＞＞ The above-mentioned negative photosensitive resin composition can be produced by a general method, for example, it can be produced by mixing the above-mentioned components and filtering with a filter as necessary.

＜＜Cure film and curing film manufacturing method＞＞ The above-mentioned negative photosensitive resin composition can be used to produce a cured film that can be used in displays such as TFT-LCD, OLED, and touch panels. The produced hardened film can also be patterned as needed. Hereinafter, the method of manufacturing a cured film using the negative photosensitive resin composition mentioned above is demonstrated.

First, the negative photosensitive resin composition is applied on a substrate to form a coating film. The substrate on which the coating film is formed is not particularly limited, and previously known ones can be used, for example, a silicon substrate, a glass substrate, or a substrate with a metal surface. As the type of metal constituting the metal surface, copper, gold, and aluminum are preferred, and copper is more preferred. In addition, the above-mentioned negative photosensitive resin composition can lower the heating temperature when forming a cured film, and therefore, a substrate with low heat resistance can be used. As a substrate with low heat resistance, for example, a substrate having flexibility (for example, a substrate having flexibility) may be mentioned. As a flexible substrate, a plastic substrate can be cited, which is composed of, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene terephthalate (PEN); Amine; polycarbonate; polyamide; polyacetal; polyphenylene ether; polyphenylene sulfide; Polymers, etc.), copolymers of norene and ethylene and other copolymers of norene-based monomers and olefin-based monomers (addition polymers or cyclic olefin copolymers such as ring-opening polymers, etc.), these Cyclic polyolefins such as derivatives; vinyl polymers (for example, (meth)acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resins) (ABS resin), etc.); vinylidene-based polymers (for example, polyvinylidene chloride, etc.); cellulose resins such as triacetyl cellulose (TAC); epoxy resins; phenol resins; melamine resins; urea resins ; Maleic imide resin; silicone and other plastic materials.

The coating method of the said negative photosensitive resin composition is not specifically limited, A well-known method can also be used. For example, coating methods such as spin coating, dip coating, roll coating, screen coating, spray coating, flow coating, screen printing, inkjet, and drip injection can be mentioned.

The film thickness of the formed coating film varies depending on the coating method, the concentration of the solid component of the negative photosensitive resin composition, the viscosity, etc., and is not particularly limited, but it can usually be dried so that the film thickness becomes 0.5～ Coating is carried out in a method of 100 μm.

The coating film can also be dried as needed. The drying method is not particularly limited, and a method of volatilizing the solvent by vacuum, infrared irradiation, or heating may be mentioned.

Then, the coating film is exposed. In the exposure step, irradiate excimer laser, extreme ultraviolet, ultraviolet, visible light, electron beam, X-ray or g-ray (wavelength 436 nm), i-ray (wavelength 365 nm), h-ray (wavelength 405 nm) or the The energy lines of mixing light and so on. In the exposure, exposure methods such as contact type, proximity type, and projection type can also be used. The amount of energy rays to be irradiated varies depending on the composition of the negative photosensitive resin composition. For example, it is 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 to light, a curing reaction occurs to form a cured product (cured film).

The exposure can also be position selective exposure. Position selective exposure is performed, for example, via a negative mask. By performing position selective exposure, a patterned cured film can be formed.

In the case of position-selective exposure of the coating film, the exposed coating film is developed by a developer, whereby a cured film patterned into a desired shape can be obtained. The development method is not particularly limited, and for example, a dipping method, a spray method, etc. can be used. The developer is appropriately selected according to the composition of the negative photosensitive resin composition. An alkaline aqueous solution can also be used as a developer, which is more environmentally friendly and economical than organic solvents. Examples of alkaline developers include aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide, ammonia, ethylamine, propylamine, diethylamine, trimethylammonium hydroxide, etc. Amine-based aqueous solutions such as ethylamine.

It is also possible to heat the coated film after exposure (post-exposure bake (PEB) or post-bake). The heating temperature is not particularly limited. For example, it is 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 still more preferably 85°C or higher and 100°C or lower. In the case of using a substrate with low heat resistance, heating at a high temperature may cause adverse effects on the substrate. Therefore, it is difficult to use a substrate with low heat resistance. However, by heating at a low temperature, a substrate with low heat resistance can be used. In the case of position-selective exposure of the coating film, the above heating (PEB) is preferably performed after the step of exposing the coating film and before the development step. In the case of using a substrate with high heat resistance, it is also possible to perform the development step after the PEB step, or after the PEB step after the exposure and the development step, and then heat at a temperature above 80°C and below 250°C (post-baking) bake).

The cured film (cured product) manufactured by the above-mentioned manufacturing method is formed using the above-mentioned negative photosensitive resin composition, and therefore 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 the following applications: using a composition obtained by dissolving components such as resin in a solvent to form another layer on the above-mentioned cured film to produce a laminate material; or applying an adhesive containing a solvent.

In addition, the above-mentioned negative photosensitive resin composition has excellent resolution. Therefore, a patterned cured film having a fine pattern can be produced. For example, it is possible to produce a patterned cured film having a fine pattern with a line width of 20 μm or less, preferably 10 μm or less.

In addition, by using the negative photosensitive resin composition containing the resin (A), a cured film having a high refractive index or a cured film having high functionality such as heat resistance, chemical resistance, and high permeability can be produced. For example, a cured film with a high refractive index is made into a laminate with a low refractive index film to become a light extraction film with excellent light extraction efficiency. In addition, the cured film with excellent heat resistance can minimize the taper angle and outgassing.

Such a cured film or patterned cured film can be applied to semiconductor devices, LCD devices, OLED devices, solar battery devices, flexible display devices, touch screen manufacturing devices, or nanoimprints, for example. Manufacture of components for lithography and other components, or coating materials. [Example]

Hereinafter, the present invention will be described in further detail with examples, but the present invention is not limited to these examples. [Synthesis Example 1] (Synthesis of monomers) Phase 1: Synthesis of 2,2'-((((9H-茀-9,9-diyl)bis(4,1-phenylene))bis(oxy) ))Bis(methylene))bis(ethylene oxide) [Chemical 16]

Step A: After installing a reflux condenser and a thermometer in a three-necked flask, put 42.5 g of 9,9-bisphenolic acid and 220 mL of 2-(chloromethyl)ethylene oxide quantitatively and then inject it. After adding 100 mg of tetrabutylammonium bromide, stirring was started, and the temperature was increased to 90°C. After confirming that the content of unreacted material has not reached 0.3%, vacuum distillation is performed.

Step B: After lowering the temperature to 30°C, inject dichloromethane and slowly add NaOH. After confirming that the product was over 96% by high performance liquid chromatography (HPLC), 5% HCl was added dropwise to terminate the reaction. After extracting the reactant and performing layer separation, the organic layer was washed with water and washed until it became neutral. After drying the organic layer with MgSO ₄ , it was concentrated by distillation under reduced pressure with a rotary evaporator. Add dichloromethane to the concentrated product, while raising the temperature to 40°C, stirring and adding methanol, then lowering the temperature of the solution and stirring. After filtering the generated solid, vacuum drying was performed at room temperature to obtain 52.7 g of white solid powder (yield 94%), and the ^{structure was confirmed by 1} H NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance).

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).

Phase 2: Synthesis of 3,3'-(((9H-茀-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(1-(phenylthio) Propan-2-yl) (BTCP monomer) [化17]

After installing a reflux condenser and a thermometer in a three-necked flask, put the reactant (1000 g) of the first stage, 524 g of thiophenol, and 617 g of ethanol, and stir. 328 g of triethylamine was slowly added dropwise to the reaction solution. After confirming the disappearance of the starting material by high performance liquid chromatography (HPLC), the reaction was terminated. After the reaction was completed, ethanol was distilled under reduced pressure for removal. After the organic matter was dissolved in dichloromethane, the dichloromethane was removed by distillation under reduced pressure after washing with water. After the concentrated organic matter was dissolved in ethyl acetate, ether solvent was added dropwise and 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).

(Manufacturing of resin (A) (binder resin)) Manufacturing of resin A1 [化18]

After installing a reflux condenser and a thermometer in a three-necked flask, put 200 g of the BTCP monomer synthesized in the second stage dissolved in 50% propylene glycol methyl ether acetate (PGMEA) solvent, and raise the temperature to 115°C. After adding 3,3',4,4'-biphenyltetracarboxylic dianhydride 31.1 g dropwise at 115°C, the mixture was maintained at 115°C for 6 hours and stirred. After adding 7.35 g of phthalic anhydride and further stirring for 2 hours, the reaction was terminated. After cooling, a solution of resin A1 with a mass average molecular weight of 3,500 g/mol and a dispersion degree of 2.2 was obtained.

[Synthesis Example 2] (Production of Resin (A)) Production of Resin A2 [Chemical 19]

After installing a reflux condenser and a thermometer in a three-necked flask, put 200 g of the BTCP monomer synthesized in the second stage dissolved in 50% PGMEA solvent, and raise the temperature to 115°C. After dropping 28.4 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride at 115°C, the mixture was maintained at 115°C for 6 hours and stirred. After adding 7.35 g of phthalic anhydride and further stirring for 2 hours, the reaction was terminated. After cooling, a solution of resin A2 with a mass average molecular weight of 5,000 g/mol and a degree of dispersion of 2.4 was obtained.

As the photopolymerization initiator (B), compound 6 was used. [化20]

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

[Example 2] Except having changed the blending amount of the adhesion enhancer (C) to 3 times the mass part, the negative photosensitive resin composition was produced by the same method as in Example 1.

[Example 3] Except having changed the compounding amount of the adhesion enhancer (C) to 5 times the mass part, the negative photosensitive resin composition was produced by the same method as in Example 1.

[Example 4] Use 3-(methacryloxy)propyltrimethoxysilane instead of 3-glycidoxypropyltrimethoxysilane as the adhesion enhancer (C), except for this, the same method as in Example 3 The negative photosensitive resin composition is produced.

[Example 5] 85 parts by mass of resin A1 as resin (A), 65 parts by mass of compound as photopolymerization initiator (B), and 3-glycidoxypropyltrimethoxysilane 3 as adhesion enhancer (C) Parts by mass, 0.2 parts by mass of a silicone-based surfactant (polyester-modified polydimethylsiloxane, BYK-310, BYK-Chemie) as a surfactant, and 0.2 parts by mass as a photopolymerizable compound (D ) 6.5 parts by mass of dipentaerythritol hexaacrylate is dissolved in propylene glycol monomethyl ether acetate (PEGMEA) as the solvent (S) so that the solid content concentration becomes 20% by mass to produce a negative photosensitive resin composition Things.

[Comparative Example 1] The oxime ester-based photopolymerization initiator of the structure not belonging to the following formula of the formula (b1) was used instead of the compound 6 as the photopolymerization initiator (B). Otherwise, the same as in Example 3 The negative photosensitive resin composition was produced in the same way. [化21]

[Comparative Example 2] Use an oxime ester-based photopolymerization initiator (1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(ortho-benzyl oxime), which does not belong to the formula (b1), Irgacure OXE01, BASF Japan Co., Ltd.), except that the compound 6 as the photopolymerization initiator (B) was replaced, the negative photosensitive resin composition was produced in the same manner as in Example 3.

[Comparative Example 3] Except for using resin A2 instead of resin A1 as the resin (A), the negative photosensitive resin composition was produced in the same manner as in Comparative Example 1.

[Comparative Example 4] Except for using resin A2 instead of resin A1 as the resin (A), the negative photosensitive resin composition was produced in the same manner as in Comparative Example 2.

[Evaluation of Solvent Resistance] The negative photosensitive resin composition obtained from Examples 1 to 5 and Comparative Examples 1 to 4 was applied to the polymer by using a spin coater at 800 to 900 rpm for 15 seconds. On the substrate of ethylene phthalate (PET), it was dried on a hot plate at 85°C for 180 seconds to form a coating film with a thickness of 5 μm. The exposure gap was set to 25 μm, and a proximity exposure machine (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.) was used to irradiate the dried coating film with ultraviolet rays. The exposure level is set to 30 mJ/cm ² . The cured film was obtained by post-baking the coated film after exposure 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 by a scanning electron microscope (SEM) at 5000 times, and the solvent resistance was evaluated according to the following criteria. The evaluation of N-methylpyrrolidone (NMP) as the impregnating solvent was also carried out. The evaluation was also performed with the post-baking conditions set to 100°C for 300 seconds. The results are shown in Table 1. In addition, regarding the negative photosensitive resin composition obtained in Example 5, the solvent resistance was evaluated in the same manner as described above, except that post-baking was not performed. The result is described as Example 6. (PEGMEA) ○: There is no change in the cured film before and after immersion ×: There is a change in the cured film before and after immersion (NMP) ○: The change rate of the thickness of the cured film before and after immersion is less than 10% ×: The change in the thickness of the cured film before and after immersion Rate above 10%

[Evaluation of resolution] The negative photosensitive resin composition obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was applied to the polymer by using a spin coater at 800 to 900 rpm for 15 seconds. On the substrate of ethylene phthalate (PET), it was dried on a hot plate at 85°C for 180 seconds to form a coating film with a thickness of 5 μm. Set the exposure gap to 25 μm, and irradiate the dried coating film with ultraviolet rays using a proximity exposure machine (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.) through a negative mask with a pattern of 10 μm in width. . The exposure level is set to 30 mJ/cm ² . The exposed coating film was baked (PEB) at 85°C for 300 seconds, and then developed in a 2.38% by mass TMAH aqueous solution at 26°C for 30 seconds to obtain a cured film. The obtained cured film was observed by a scanning electron microscope (SEM) at 5000 times. When a pattern with a width of 10 μm was formed, it was evaluated as ○, and when a pattern with a width of 10 μm was not formed, it was evaluated as ×. The results are shown in Table 1. In addition, regarding 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 result is described as Example 6.

[Table 1] Solvent resistance evaluation Resolution evaluation PEGMEA NMP 85°C 100°C 85°C 100°C Example 1 ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ ○ Example 6 ○ ○ ○ ○ ○ Comparative example 1 X X X X X Comparative example 2 X X X X X Comparative example 3 X X X X X Comparative example 4 X X X X X

According to Examples 1 to 6, it can be seen that the negative photosensitive resin composition comprising the resin (A) having the structural unit represented by the formula (a1) and the photopolymerization initiator (B) represented by the formula (b1) Excellent solvent resistance. In addition, it can be seen that the resolution of these negative photosensitive resin compositions is also excellent.

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 does not contain the photopolymerization initiator represented by the formula (b1) In the case of agent (B), the solvent resistance is inferior to Examples 1 to 6. It can also be seen that the resolution is also inferior to those of Examples 1-6.

Claims (9)

A negative photosensitive resin composition comprising: a resin (A) having a structural unit represented by the following formula (a1), and a photopolymerization initiator (B) represented by the following formula (b1); [化1]

(In formula (a1), R ^1a and R ^2a each independently represent an alkyl group having 1 or more and 20 carbon atoms and which may include heteroatoms, an aryl group having 6 or more and 20 or less carbon atoms and which may include heteroatoms, -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 to 20 carbon atoms and which may contain heteroatoms, A represents the following formula (a2) The indicated divalent group, j1 and j2 each independently represent an integer of 1 to 6 and R ^4a represents a single bond, an alkylene having 1 to 10 carbon atoms, or an aromatic having 6 to 15 carbon atoms S represents a sulfur atom, R ^5a represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms, and R ^6a represents a single bond, an alkylene group with 1 to 10 carbon atoms , Or an aryl group with 6 to 10 carbon atoms, R ^7a represents an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms ); [化2]

(In formula (a2), R ^8a and R ^9a each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, and R ^10a and R ^11a each independently represent a hydrogen atom, Alkyl group or aryl group, k1 and k2 each independently represent an integer from 0 to 4, and m1 and m2 each independently represent an integer from 0 to 3); [化3]

(In formula (b1), R ^1b represents a hydrogen atom, a nitro group or a monovalent organic group, and R ^2b and R ^3b each independently represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, Or a hydrogen atom, R ^2b and R ^3b may be bonded to each other to form a ring, R ^4b represents a monovalent organic group, R ^5b represents a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms, or For the substituted aryl group, p is an integer of 0 or more and 4 or less, and q is 0 or 1). The negative photosensitive resin composition of claim 1, which further contains an adhesion enhancer (C). A cured film comprising the cured product of the negative photosensitive resin composition of claim 1 or 2. A method for manufacturing a cured film, comprising the following steps: coating the negative photosensitive resin composition of claim 1 or 2 on a substrate to form a coating film; and Expose the above-mentioned coating film. The method for manufacturing a cured film of claim 4, which includes the step of heating the coated film after the exposure after the step of exposing the coated film. The method for manufacturing a cured film of claim 4, wherein the step of exposing the coating film is a step of selectively exposing the coating film, and It further includes a step of developing the above-mentioned coated film after exposure. The method for producing a cured film according to claim 6, which includes the step of heating the coating film after the exposure after the step of exposing the coating film and before the development step. 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 more and 100°C or less. The method for manufacturing a cured film of claim 4, wherein the above-mentioned substrate is a flexible substrate.