TWI886469B - Negative photosensitive resin composition and method for producing the same, and method for producing hardened relief pattern - Google Patents

Abstract

The present invention provides a photosensitive resin composition that exhibits good copper adhesion and does not produce white mud during coating, and a method for producing a hardened relief pattern using the photosensitive resin composition. The negative photosensitive resin composition of the present invention comprises: (A) at least one resin selected from (A1) a polyimide precursor and (A2) a polyimide, (B) a sugar derivative represented by any one of the general formulas (1)-A to (1)-C, (C) a photopolymerization initiator, and (D) a solvent.

Description

Negative photosensitive resin composition and its manufacturing method, and manufacturing method of hardened relief pattern

The present invention relates to a negative photosensitive resin composition and a method for producing a hardened relief pattern.

Previously, polyimide resins, polybenzoxazole resins, phenolic resins, etc. with excellent heat resistance, electrical properties, and mechanical properties were used in insulating materials for electronic parts, and passivation films, surface protection films, and interlayer insulating films for semiconductor devices. Among these resins, photosensitive resin compositions provide a heat-resistant embossed pattern film that can be easily formed by coating, exposing, developing, and curing the composition through thermal imidization. This photosensitive resin composition has the characteristic of being able to significantly shorten the steps compared to previous non-photosensitive materials.

On the other hand, in recent years, from the perspective of increasing integration and computing functions, as well as miniaturization of chip size, the mounting method (package structure) of semiconductor devices on printed wiring boards has also changed. For example, the previous mounting method using metal pins and lead-tin eutectic soldering has been used to achieve higher density mounting, such as BGA (ball grid array) and CSP (chip size package), which have always used a structure in which a polyimide film is directly in contact with the solder bump. Furthermore, a structure such as FO (fan-out) has been proposed, which includes multiple layers of redistribution layers with an area larger than the area of the semiconductor chip on the surface of the semiconductor chip.

Copper is often used for wiring of semiconductor devices, but in packaging structures with larger areas, the stress generated by the difference in thermal expansion coefficients of different materials leads to a decrease in electrical properties caused by the peeling of copper and interlayer insulating materials, which is particularly problematic. Therefore, the material used as the interlayer insulating film is required to have high adhesion to copper.

Furthermore, in recent years, the application of semiconductor devices in automobiles and mobile phones has been extremely significant. Semiconductor devices in this field are required to have high reliability and are tested for operational stability in high temperature environments.

As a means to solve the above-mentioned problem, for example, Patent Document 1 discloses a photosensitive resin composition that can ensure good copper adhesion even in a high temperature environment by adding sugar to a composition containing a polyimide precursor. However, according to the research of the inventors, the photosensitive resin composition containing sugar has the problem of easily generating white turbidity or separation structure when applied to a substrate. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2016-167036

[The problem the invention is trying to solve]

Therefore, the purpose of the present invention is to provide a photosensitive resin composition that exhibits good copper adhesion and does not produce white turbidity during coating, and a method for producing a hardened relief pattern using the photosensitive resin composition. [Technical means for solving the problem]

The inventors of the present invention have discovered that by adding a compound obtained by replacing the hydroxyl group of a sugar with another functional group to a photosensitive resin composition, a photosensitive resin composition showing higher copper adhesion and less likely to produce white mud when applied to a substrate can be obtained, thereby completing the present invention. That is, the present invention is as follows. [1] A negative photosensitive resin composition characterized by comprising: (A) at least one resin selected from (A1) a polyimide precursor and (A2) a polyimide, (B) a sugar derivative represented by any one of the general formulas (1)-A to (1)-C, [Chemical 1] (In the formula, _R1 is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic group which may have a substituent; _R2 to _R4 are a hydrogen atom or a monovalent organic group having 1 to 9 carbon atoms; _R5 is any one of *-CH2 _- OH, *-COOH, * _-CH2 - _N3 , or a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * indicates a bonding position with other parts. Furthermore, any two or more of _R1 to _R4 are hydrogen atoms. However, it is not a combination in which all of _R1 to _R4 are hydrogen atoms and _R5 is * _-CH2 -OH) [Chemistry 2] (In the formula, R ₆ is any one of *-CH ₂ -OH, *-COOH, *-CH ₂ -N ₃ , and a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * indicates a bonding position with other sites) [Chemical 3] (wherein _R7 is any one of *-CH2 _- OH, *-COOH, * _-CH2 - _N3 , and a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * represents a bonding position with other parts) (C) a photopolymerization initiator, and (D) a solvent. [2] The negative photosensitive resin composition as described in [1], wherein in the above-mentioned (B) sugar derivative, _R6 of the above-mentioned formula (1)-B and _R7 of the above-mentioned formula (1)-C are *-CH2 _- OH. [3] The negative photosensitive resin composition as described in [1] or [2], wherein in the above-mentioned (B) sugar derivative, _R2 to _R4 of the above-mentioned formula (1)-A are all hydrogen atoms, and _R5 is *-CH2 _- OH. [4] A negative photosensitive resin composition as described in any one of [1] to [3], wherein _R1 of the sugar derivative (B) is an aromatic group which may have a substituent. [5] A negative photosensitive resin composition as described in any one of [1] to [4], further comprising (E) a heterocyclic compound. [6] A negative photosensitive resin composition as described in any one of [1] to [5], wherein the polyimide precursor (A1) comprises a polyimide precursor having a structural unit represented by the following general formula (2): [Chemical 4] {In formula (2), _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R11 and _R12 are independently a hydrogen atom or a monovalent organic group}. [7] A negative photosensitive resin composition as described in [6], wherein in the above general formula (2), at least one of _R11 and _R12 has a structural unit represented by the following general formula (3): [Chemical 5] {In formula (3), _L1 , _L2 and _L3 are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and _m1 is an integer of 2 to 10}. [8] A negative photosensitive resin composition as described in any one of [1] to [7], wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film. [9] A method for producing a hardened relief pattern, comprising the following steps: (1) applying a negative photosensitive resin composition as described in any one of [1] to [8] on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heating the relief pattern to form a hardened relief pattern. [10] The method for producing a hardened relief pattern as described in [9], wherein the heating treatment in step (4) is a heating treatment at a temperature below 230°C. [11] A method for producing polyimide, comprising the step of curing the negative photosensitive resin composition as described in any one of [1] to [8]. [Effect of the Invention]

According to the present invention, a photosensitive resin composition showing excellent copper adhesion and hardly producing white mud during coating, and a method for producing a hardened relief pattern using the same can be provided.

The following is a detailed description of the embodiment for implementing the present invention (hereinafter referred to as "the present embodiment"). Furthermore, the present invention is not limited to the following present embodiment, and can be implemented in various ways within the scope of its main purpose. Furthermore, throughout this specification, when there are multiple structures represented by the same symbol in the general formula in a molecule, they can be the same or different from each other.

<Negative photosensitive resin composition> The negative photosensitive resin composition of this embodiment comprises: (A) at least one resin selected from (A1) a polyimide precursor and (A2) a polyimide, (B) a sugar derivative represented by any one of the general formulas (1)-A to (1)-C, [Chemical 6] (In the formula, _R1 is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic group which may have a substituent; _R2 to _R4 are a hydrogen atom or a monovalent organic group having 1 to 9 carbon atoms; _R5 is any one of *-CH2 _- OH, *-COOH, * _-CH2 - _N3 , or a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * indicates a bonding position with other parts. Furthermore, any two or more of _R1 to _R4 are hydrogen atoms. However, it is not a combination in which all of _R1 to _R4 are hydrogen atoms and _R5 is * _-CH2 -OH) [Chemistry 7] (In the formula, R ₆ is any one of *-CH ₂ -OH, *-COOH, *-CH ₂ -N ₃ , and a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * indicates a bonding position with other sites) [Chemical 8] (wherein _R7 is any one of *-CH2 _- OH, *-COOH, * _-CH2 - _N3 , and a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * indicates a bonding position with other parts) (C) a photopolymerization initiator, and (D) a solvent.

(A) Resin (A1) Polyimide precursor The (A1) polyimide precursor in this embodiment is a resin component contained in a negative photosensitive resin composition, and is converted into polyimide by applying a thermal cyclization treatment. The (A1) polyimide precursor has no limitation on its structure as long as it is a resin that can be used in a negative photosensitive resin composition, but is preferably not alkali-soluble. By making the polyimide precursor not alkali-soluble, higher chemical resistance can be obtained.

The polyimide precursor is preferably a polyimide having a structure represented by the following general formula (2). [Chemistry 9] {In formula (2), _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R11 and _R12 are independently a hydrogen atom or a monovalent organic group}

Preferably, in the general formula (2), at least one of R ₁₁ and R ₁₂ has a structural unit represented by the following general formula (3): {In formula (3), L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10}.

The ratio of R ₁₁ and R ₁₂ in the general formula (2) to hydrogen atoms is preferably 10% or less, more preferably 5% or less, and further preferably 1% or less, based on the total molar number of R ₁₁ and R 12. Furthermore, the ratio of R ₁₁ and R ₁₂ in the general formula ( ₂ ) to monovalent organic groups represented by the general formula (3) is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more, based on the total molar number of R ₁₁ and R _12. From the viewpoint of photosensitivity and storage stability, it is preferred that the ratio of hydrogen atoms and the ratio of organic groups in the general formula (3) are within the above ranges.

In the general formula (2), _n1 is not limited as long as it is an integer of 2 to 150. From the viewpoint of the photosensitivity and mechanical properties of the negative photosensitive resin composition, it is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

In the general formula (2), the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably an aromatic group or an alicyclic aliphatic group in which _-COOR11 and _-COOR12 are adjacent to -CONH-. Specifically, the tetravalent organic group represented by _X1 includes an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, a group having a structure represented by the following general formula (20), but is not limited thereto: [Chemical 11] {wherein, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent alkyl group, and a C1-C10 monovalent fluorine-containing alkyl group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4}. In addition, the structure of _X1 may be one or a combination of two or more. The _X1 group having the structure represented by the above formula (20) is particularly preferred from the viewpoint of having both heat resistance and photosensitivity.

As the _X1 group, among the structures represented by the above formula (20), the tetravalent organic group represented by the following formula is particularly preferred from the viewpoints of the imidization rate during low temperature heating, degassing property, copper adhesion, chemical resistance, etc.: [Chemical 12] {wherein, R6 is at least one selected from the group consisting of a fluorine atom, a monovalent alkyl group having 1 to 10 carbon atoms, and a monovalent fluorine-containing alkyl group having 1 to 10 carbon atoms, and m is an integer selected from 0 to 3}. In the above general formula (1), the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of having both heat resistance and photosensitivity. For example, the structure represented by the following formula (21) can be cited, but it is not limited thereto: [Chemical 13] {wherein, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent alkyl group, and a C1-C10 monovalent fluorine-containing alkyl group, and n is an integer selected from 0 to 4}. In addition, the structure of _Y1 may be one or a combination of two or more. The _Y1 group having the structure represented by the above formula (21) is particularly preferred from the viewpoint of having both heat resistance and photosensitivity.

As the _Y1 group, among the structures represented by the above formula (21), the divalent group represented by the following formula is particularly preferred from the viewpoints of the imidization rate during low temperature heating, degassing property, copper adhesion, chemical resistance, etc.: [Chemical 14] {wherein, R6 is at least one selected from the group consisting of a fluorine atom, a monovalent alkyl group having 1 to 10 carbon atoms, and a monovalent fluorine-containing alkyl group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4}.

In the general formula (3), _L1 is preferably a hydrogen atom or a methyl group, and _L2 and _L3 are preferably hydrogen atoms from the viewpoint of photosensitivity. Furthermore, _m1 is an integer of 2 to 10, preferably an integer of 2 to 4 from the viewpoint of photosensitivity.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (4): {wherein, R ₁₁ , R ₁₂ , and n ₁ are as defined above}.

More preferably, in the general formula (2), at least one of R ₁₁ and R ₁₂ is a monovalent organic group represented by the general formula (3). When the polyimide precursor (A1) contains a polyimide precursor represented by the general formula (4), the chemical resistance is particularly improved.

In one embodiment, from the viewpoint of thermal properties, it is preferred that the polyimide precursor (A1) is a polyimide precursor having a structural unit represented by the following general formula (5): {wherein, R ₁₁ , R ₁₂ , and n ₁ are as defined above}.

More preferably, in the general formula (5), at least one of R ₁₁ and R ₁₂ is a monovalent organic group represented by the general formula (3).

When the polyimide precursor (A1) contains both the structural unit represented by the general formula (4) and the structural unit represented by the general formula (5), there is a tendency that the resolution is particularly improved. For example, the polyimide precursor (A1) may contain a copolymer of the structural unit represented by the general formula (4) and the structural unit represented by the general formula (5), or may be a mixture of the polyimide precursor represented by the general formula (4) and the polyimide precursor represented by the general formula (5).

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (6): {wherein, R ₁₁ , R ₁₂ , and n ₁ are as defined above}.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (7): {wherein, R ₁₁ , R ₁₂ , and n ₁ are as defined above}. When the polyimide precursor (A1) contains a polyimide precursor represented by the general formula (7), the chemical resistance is particularly improved.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (8): {wherein, R ₁₁ , R ₁₂ , and n ₁ are as defined above}. When the polyimide precursor (A1) contains a polyimide precursor represented by the general formula (8), Tg is particularly improved.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (9): {wherein, R ₁₁ , R ₁₂ , and n ₁ are as defined above}. When the polyimide precursor (A1) contains a polyimide precursor represented by the general formula (9), the dielectric constant is particularly improved.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (10): {wherein, R ₁₁ , R ₁₂ , and n ₁ are as defined above}. By making the polyimide precursor (A1) contain a polyimide precursor represented by the general formula (10), the dielectric constant is particularly improved.

(A1) Preparation method of polyimide precursor (A1) The polyimide precursor can be obtained by the following method: First, a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group _X1 is reacted with a photopolymerizable unsaturated double bond alcohol and an optional alcohol without an unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester). Thereafter, the partially esterified tetracarboxylic acid is subjected to amide condensation with a diamine containing the above-mentioned divalent organic group _Y1 .

(Preparation of Acid/Ester) In the present embodiment, the tetracarboxylic dianhydride containing a tetravalent organic group _X1 which is preferably used for preparing the polyimide precursor (A1) is represented by a tetracarboxylic dianhydride containing a structure represented by the above general formula (20), for example, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, -tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably exemplified by: pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but not limited to these. Moreover, these can be used alone or in combination of two or more.

In the present embodiment, the unsaturated dibond alcohols having photopolymerizability which are preferably used for preparing the polyimide precursor (A1) include, for example, 2-acryloxyethyl alcohol, 1-acryloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate ... 2-Hydroxy-3-cyclohexyloxypropyl methacrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

The above-mentioned photopolymerizable unsaturated double bond alcohols may be mixed with a portion of alcohols not having unsaturated double bonds, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, etc.

In addition, as a polyimide precursor, a non-photosensitive polyimide precursor prepared only with the above-mentioned alcohols without unsaturated double bonds can also be mixed with a photosensitive polyimide precursor for use. From the perspective of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor. In the presence of an alkaline catalyst such as pyridine, the above-mentioned preferred tetracarboxylic dianhydride and the above-mentioned alcohols are stirred and dissolved in the solvent described below at a temperature of 20 to 50°C for 4 to 24 hours and mixed, thereby performing an esterification reaction of the acid anhydride to obtain the desired acid/ester.

(Preparation of polyimide precursor) Under ice cooling, a suitable dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc., is added to the above-mentioned acid/ester body (typically, a solution in the following solvent) to prepare a polyanhydride from the acid/ester body. Then, a diamine containing a divalent organic group _Y1 preferably used in the present embodiment which is separately dissolved or dispersed in a solvent is added dropwise thereto to carry out amide condensation, thereby obtaining the target polyimide precursor. As an alternative method, the acid of the acid/ester body is partially acylated with thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the target polyimide precursor.

The diamines containing a divalent organic group _Y1 preferably used in the present embodiment are represented by diamines having a structure represented by the general formula (21), for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl sulfide, 4,4'-diaminobiphenyl '-Diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, Bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine, 9,9 -bis(4-aminophenyl)fluorene, and those in which a portion of the hydrogen atoms on the benzene ring are substituted by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof, but are not limited thereto.

After the amide polycondensation reaction is completed, the water-absorbing byproduct of the dehydration condensation agent coexisting in the reaction solution is filtered and separated as needed, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component, and then the polymer is repeatedly dissolved and reprecipitated to purify the polymer, and vacuum dried to isolate the target polyimide precursor. In order to improve the degree of purification, the polymer solution can also be passed through a column filled with an anion and/or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

The molecular weight of the polyimide precursor (A1) is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000, when measured by a weight average molecular weight converted to polystyrene obtained by gel permeation chromatography. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when the weight average molecular weight is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the embossed pattern is good. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight is obtained based on a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

(A2) Polyimide The (A2) polyimide used in this embodiment is described. The resin component in the photosensitive resin composition is a polyimide resin having a structural unit represented by the following general formula (24). [Chemical 22] {wherein, _X2 is a tetravalent organic group having 6 to 40 carbon atoms, _Y2 is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50}

The resin represented by the general formula (24) does not require chemical changes in the heat treatment step in order to exhibit sufficient film properties, and is therefore particularly suitable for treatment at lower temperatures.

In the general formula (24), the divalent organic group represented by X ₂ and/or the tetravalent organic group represented by Y ₂ preferably contains an aromatic ring structure, and more preferably contains a benzene ring structure, from the viewpoint of heat resistance.

From the viewpoint of solubility in an organic solvent, it is preferred that at least one of X ₂ and Y ₂ is a group containing a fluorine atom, and it is further preferred that both X ₂ and Y ₂ are groups containing a fluorine atom.

In the general formula (24), the tetravalent organic group represented by _X2 and/or the divalent organic group represented by _Y2 preferably has a structure in which 2 to 6 benzene rings are linked via a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a fluorinated alkylene group, and an ether group. The alkylene group and the fluorinated alkylene group may be in a straight chain or a branched chain.

(A2) Polyimide can be obtained by reacting tetracarboxylic acid, tetracarboxylic dianhydride corresponding thereto, tetracarboxylic diester dichloride, etc., with diamine, diisocyanate compound corresponding thereto, trimethylsilylated diamine, etc. Polyimide can be generally obtained by dehydrating and ring-closing polyamide, which is one of the polyimide precursors, obtained by reacting tetracarboxylic dianhydride with diamine by heating or chemical treatment with an acid or an alkali.

Preferred tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl) ethane dianhydride, bis(3,4-dicarboxyphenyl) methane dianhydride, bis(2,3-dicarboxyphenyl) methane dianhydride, bis(3,4-dicarboxyphenyl) Sulfur dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10- Aromatic tetracarboxylic dianhydrides such as perylenetetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and compounds represented by 3,3',4,4'-diphenylsulfoniumtetracarboxylic dianhydride.

Among them, it is preferred to use pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonate tetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA). These can be used alone or in combination of two or more.

Preferred diamines include 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diaminodiphenylsulfone, 3,3'-dimethylbenzidine, 3,3'-bis(trifluoromethyl) Benzidine, 2,2'-bis(p-aminophenyl)hexafluoropropane, bis(trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydiphenylamine (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane 、2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DFPOB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl)-2,2-bis(trifluoromethyl)- 3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminotoluene trifluoride (3,5-DABTF), 3,5-diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethylbenzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)benzidine (6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenylphosphine (3FCDAM), 3,6-diamino-9,9-diphenylphosphine The compounds represented, etc.

The ratio of diamine to acid dianhydride used is basically 1:1 in terms of molar ratio. Among them, in order to obtain the desired terminal structure, one of them can also be used in excess. Specifically, by using diamine in excess, the end (both ends) of the polyimide (A2) easily becomes an amine group. On the other hand, by using acid dianhydride in excess, the end (both ends) of the polyimide (A2) easily becomes an acid anhydride group. As described above, in this embodiment, polyimide (A2) preferably has an acid anhydride group at its end. Therefore, in this embodiment, it is preferred to use acid dianhydride in excess when synthesizing polyimide (A2).

The terminal amino group and/or anhydride group of the polyimide obtained by polycondensation can also be reacted with a certain reagent to make the terminal of the polyimide have the desired functional group. The molecular weight of the polyimide (A2) is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, and particularly preferably 10,000 to 50,000 when measured by the weight average molecular weight of polystyrene obtained by gel permeation chromatography. When the weight average molecular weight is 5,000 or more, the mechanical properties are good, so it is better. On the other hand, when the weight average molecular weight is 150,000 or less, the dispersibility in the developer and the resolution performance of the relief pattern are good, so it is better. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is obtained based on a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

(B) Sugar derivatives The (B) sugar derivatives used in this embodiment are compounds represented by any one of the following formulas (1)-A to (1)-C. (In the formula, _R1 is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic group which may have a substituent; _R2 to _R4 are a hydrogen atom or a monovalent organic group having 1 to 9 carbon atoms; _R5 is any one of *-CH2 _- OH, *-COOH, * _-CH2 - _N3 , or a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * indicates a bonding position with other parts. Furthermore, any two or more of _R1 to _R4 are hydrogen atoms. However, it is not a combination in which all of _R1 to _R4 are hydrogen atoms and _R5 is * _-CH2 -OH) [Chemistry 24] (In the formula, R ₆ is any one of *-CH ₂ -OH, *-COOH, *-CH ₂ -N ₃ , and a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * indicates the bonding position with other parts) [Chemical 25] (In the formula, _R7 is any one of *-CH2 _- OH, *-COOH, * _-CH2 - _N3 , and a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group. Here, * indicates a bonding position with other parts)

Furthermore, in the above formula (1)-A, when all R ₁ to R ₄ are hydrogen atoms and R ₅ is *-CH ₂ -OH, the compound becomes a monosaccharide rather than a sugar derivative. Therefore, in the present invention, the compound having the above combination is not included in the (B) sugar derivative.

The above R ₁ to R ₅ may form a ring structure with each other, and the ring structure preferably has no hydroxyl group. (B) The sugar derivative may be a hydrate, but preferably is not a hydrate.

By making the (B) sugar derivative any one of _the formulas (1)-A to (1)-C, the whitening of the photosensitive resin composition when applied to the substrate is suppressed. Although the reason is unclear, it is believed that when compared with the _{monosaccharide} of _C6H12O6 , the (B) sugar derivative has a functional group other than a hydroxyl group, thereby improving the compatibility with the resin composition and making it difficult to separate, thereby suppressing the whitening. Among them, from the perspective of copper adhesion, the (B) sugar derivative preferably contains 3 or more hydroxyl groups. Although not bound by theory, it is believed that by having a certain number of hydroxyl groups in the molecule, it can interact with both the substrate side and the resin side, thereby improving the copper adhesion.

When R ₁ in formula (1)-A is an aliphatic hydrocarbon group, examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, etc., preferably methyl.

When R ₁ in formula (1)-A is an aromatic group which may have a substituent, the aromatic group which may have a substituent may be exemplified by the following structures, but is not limited thereto. In the formula, * represents a bonding part with other parts. [Chem. 26]

The monovalent organic group having 1 to 9 carbon atoms in R ₂ to R ₄ of formula (1)-A may have the following structures, but is not limited thereto. In the formula, * represents a bonding site with other sites. [Chem. 27]

R ₆ in formula (1)-B and R ₇ in formula (1)-C are preferably *-CH ₂ -OH.

In formula (1)-A to (1)-C, the monovalent organic group having 7 to 10 carbon atoms and having an aromatic group represented by R ₅ , R ₆ , and R ₇ may have the following structures, but is not limited thereto. In the formula, * represents a bonding site with other sites. [Chem. 28]

(B) The sugar derivative is preferably a compound represented by formula (1)-A, wherein R ₂ to R ₄ of formula (1)-A are all hydrogen atoms and R ₅ is *-CH ₂ -OH.

Examples of the sugar derivative (B) include 2-nitrophenyl β-D-galactopyranoside, 4-nitrophenyl α-D-glucopyranoside, α-D-galacturonic acid hydrate, methyl α-D-galactopyranoside monohydrate, 4-methoxyphenyl 3-O-allyl-β-D-galactopyranoside, 6-azido-6-deoxy-D-galactopyranose, 4-aminophenyl β-D-galactopyranoside, 4-methoxyphenyl 4,6-O-benzylidene-β-D-galactopyranoside, 4-methoxyphenyl 2,6-bis-O-(4-methylbenzoyl)-β-D-galactopyranoside, phenyl β-D-galactopyranoside, 4-methoxyphenyl 3-O-benzyl-β-D-galactopyranoside, 4-methoxyphenyl 2,6-di-O-benzyl-β-D-galactopyranoside, D-galactaldehyde, D-(+)-glucono-1,5-lactone, etc.

(B) The sugar derivative is preferably a compound represented by formula (1)-A, wherein R ₁ of formula (1)-A is represented by the following formula.

Examples of the sugar derivative (B) include 2-nitrophenyl β-D-galactopyranoside, 4-nitrophenyl α-D-glucopyranoside, and 4-nitrophenyl α-D-galactopyranoside.

The molecular weight of the (B) sugar derivative is preferably 200 or more, more preferably 300 or more. If the molecular weight is less than 200, there is a risk of volatility during thermal curing. From the viewpoint of solubility, the molecular weight is preferably less than 1000, more preferably less than 500, and further preferably less than 400.

The amount of the sugar derivative (B) is preferably 0.5 to 20 parts by mass, more preferably 1 to 12 parts by mass, and still more preferably 3 to 6 parts by mass, based on 100 parts by mass of the resin (A). The amount is preferably 0.5 parts by mass or more from the viewpoint of adhesion, and preferably 20 parts by mass or less from the viewpoint of white turbidity during coating.

(C) Photopolymerization Initiator The (C) photopolymerization initiator used in the present embodiment is described below. As the photopolymerization initiator, a photo-free radical polymerization initiator is preferred, and preferably exemplified are: benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, benzophenone derivatives such as fluorenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 9-oxothiophenone, , 2-methyl-9-oxosulfuron , 2-isopropyl-9-oxysulfide , diethyl-9-oxysulfide 9-Oxysulfuron derivatives, benzoyl, benzoyl dimethyl ketal, benzoyl-β-methoxyethyl acetal and other benzoyl derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2 -(o-benzoyl) oxime, 1,3-diphenylpropane-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropane-2-(o-benzoyl) oxime and other oximes, N-phenylglycine and other N-arylglycine, peroxides such as perchlorinated benzoyl, aromatic biimidazoles, titanocene, α-(n-octanesulfonyloxyimino)-4-methoxyphenylacetonitrile and other photoacid generators, but not limited to these. Among the above-mentioned photopolymerization initiators, oximes are more preferred in terms of photosensitivity.

The amount of the photopolymerization initiator (C) is preferably 0.1 to 20 parts by weight, more preferably 1 to 8 parts by weight, and further preferably 1 to 5 parts by weight, relative to 100 parts by weight of the resin (A). The amount is preferably 0.1 parts by weight or more from the viewpoint of photosensitivity or patterning properties, and preferably 20 parts by weight or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

(D) Solvent The (D) solvent used in this embodiment is described. Examples of the solvent include: amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, Diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, phenoxyethylene, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. Among them, from the viewpoint of resin solubility, stability of resin composition, and adhesion to substrate, preferred are N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethyl urea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenylene glycol, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, and tetrahydrofurfuryl alcohol.

Among such solvents, those that completely dissolve the polyimide precursor are particularly preferred, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. In particular, from the viewpoint of in-plane uniformity when the photosensitive resin composition is applied on a substrate, γ-butyrolactone and 3-methoxy-N,N-dimethylpropionamide are preferred.

The solvent may be one or a mixture of two or more solvents. From the viewpoint of appropriately adjusting the stability of the resin composition, two or more solvents are preferred. When two or more solvents are included, from the viewpoint of in-plane uniformity, it is preferred that 50% by weight or more of the solvent is either γ-butyrolactone or 3-methoxy-N,N-dimethylpropionamide, and more preferably γ-butyrolactone.

In the photosensitive resin composition of this embodiment, the amount of solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and further preferably 125 to 500 parts by mass relative to 100 parts by mass of the resin (A). The negative photosensitive resin composition of this embodiment may further contain components other than the above-mentioned components (A) to (D). The components other than components (A) to (D) are not limited, and examples thereof include: (E) heterocyclic compounds, (F) free radical polymerizable compounds, thermal alkali generators, hindered phenol compounds, organic titanium compounds, bonding aids, sensitizers, polymerization inhibitors, etc.

The negative photosensitive resin composition of this embodiment may also contain (E) a heterocyclic compound. Examples of the heterocyclic compound include azole compounds and purine derivatives. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl] ]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole, 5-carboxyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

Among them, preferred are 5-amino-1H-tetrazole, tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole.

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, etc. and their derivatives.

These heterocyclic compounds may be used alone or in the form of a mixture of two or more.

When the photosensitive resin composition contains the (E) heterocyclic compound, the amount thereof is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.5 to 5 parts by mass from the viewpoint of copper adhesion. When the amount of the (E) heterocyclic compound is 0.1 parts by mass or more relative to 100 parts by mass of the (A) resin, the discoloration of copper is suppressed when the photosensitive resin composition of this embodiment is formed on copper. On the other hand, when the amount of the (E) heterocyclic compound is 10 parts by mass or less relative to 100 parts by mass of the (A) resin, excellent copper adhesion is achieved.

(F) Radical polymerizable compound The negative photosensitive resin composition in this embodiment may also contain a (F) radical polymerizable compound to improve the chemical resistance of the hardened relief pattern. In order to obtain good chemical resistance, it is preferred to contain 5 parts by mass or more of the (F) radical polymerizable compound relative to 100 parts by mass of the (A) resin, more preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 40 parts by mass or more. As for the (F) radical polymerizable compound, from the viewpoint of patterning properties, it is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 80 parts by mass or less.

The so-called free radical polymerizable compound (F) in this embodiment is not particularly limited as long as it is a compound that undergoes free radical polymerization reaction by a photopolymerization initiator, and is preferably a (meth)acrylic acid compound, for example, represented by the following general formula (11): [Chemical 30] {In formula (11), X ₁₁ is an organic group, L ₁₁ , L ₁₂ and L ₁₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. _{n 11} is an integer of 1 to 10}. (F) Examples of free radical polymerizable compounds include mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol; mono-, di- or tri-acrylates and methacrylates of glycerol; cyclohexane diacrylate and dimethacrylate; diacrylate and dimethacrylate of 1,4-butanediol; diacrylate and dimethacrylate of 1,6-hexanediol; di- or di-acrylate of neopentyl glycol; Acrylate and dimethacrylate, mono- or di-acrylate and methacrylate of bisphenol A, benzyltrimethacrylate, isobutyl acrylate and isobutyl methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trihydroxymethylpropane triacrylate and methacrylate, di- or tri-acrylate and methacrylate of glycerol, di-, tri- or tetra-acrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds, but not limited to the above. More specifically, the compounds represented by the following formula can be cited, but not limited to the following: [Chemical 31] [Chemistry 32] .

In this specification, when the number of radical polymerizable groups in (F) a radical polymerizable compound is one, it is called monofunctional. When the number of radical polymerizable groups in (F) a radical polymerizable compound is two or more, it is called x-functional groups according to the number x of radical polymerizable groups, and sometimes two or more functional groups are collectively called polyfunctional. The radical polymerizable compound may be monofunctional or difunctional or more. From the viewpoint of chemical resistance, the radical polymerizable compound is preferably trifunctional or more, further preferably tetrafunctional or more, and more preferably hexafunctional or more. On the other hand, from the viewpoint of elongation at break, it is preferably ten-functional or less.

The molecular weight of the (F) radical polymerizable compound is preferably 100 or more, more preferably 200 or more, and more preferably 300 or more. The upper limit is preferably 1000 or less, and more preferably 800 or less. By setting it within the above range, chemical resistance and patterning properties are improved.

It is preferred that at least one of the (F) radical polymerizable compounds used in this embodiment is a radical polymerizable compound having at least one of a hydroxyl group and a urea group.

As a radical polymerizable compound having a hydroxyl group in the molecule, there can be exemplified a structure represented by the following general formula (12): [Chemical 33] {In formula (12), X ₁₁ is an organic group, L ₁₁ , L ₁₂ and L ₁₃ are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. _{n 11} is an integer of 1 to 10, and n ₁₂ is an integer of 1 to 10}. From the viewpoint of free radical reactivity, it is preferred that in the above formula (12), L ₁₁ is a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ are hydrogen atoms. More specifically, the compounds represented by the following formulas can be cited, but are not limited to the following: [Chemical 34] . Chemical resistance becomes particularly good by having a hydroxyl group in the molecular structure. The number of hydroxyl groups in the molecular structure is preferably 1 or more, and more preferably 2 or more. As an upper limit, it is preferably 10 or less, more preferably 6 or less, and more preferably 3 or less. By setting it to the above range, chemical resistance and adhesion to the substrate become good.

The free radical polymerizable compound having a urea group in the molecule can be represented by the following general formula (13): {In formula (13), _X20 , _X21 , _X22 , and _X23 are independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (14), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and at least one of _X20 , _X21 , _X22 , and _X23 is a monovalent organic group having a group represented by the following general formula (14)} [Chemistry 36] {In formula (14), _L11 , _L12 and _L13 are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms}. In view of radical reactivity, it is preferred that in formula (14), _L11 is a hydrogen atom or a methyl group, and _L12 and _L13 are hydrogen atoms.

Examples of the impurity atom in this embodiment include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom.

In formula (13), when _X20 , _X21 , _X22 , and _X23 are monovalent organic groups having 1 to 20 carbon atoms which may contain a heteroatom, it is more preferable to contain an oxygen atom from the viewpoint of developing properties. The carbon number is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it is preferably 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. _X20 , _X21 , _X22 , and _X23 in formula (12) may be mutually bonded to have a ring structure, but from the viewpoint of chemical resistance, it is preferable not to have a ring structure. By making _X20 , _X21 , _X22 , and _X23 mutually bonded to have a ring structure, the freedom of the bonding angle of the urea group is lost, and it is difficult to form a strong hydrogen bond. From the viewpoint of forming a hydrogen bond with other molecules, it is preferred that at least one of _X20 , _X21 , _X22 , and _X23 is a hydrogen atom. On the other hand, from the viewpoint of solubility, the number of hydrogen atoms of _X20 , _X21 , _X22 , and _X23 is preferably 2 or less. Specifically, the compound represented by the following formula can be exemplified: [Chemical 37] .

In this embodiment, it is preferred that the radical polymerizable compound (F) has at least one hydroxyl group and at least one urea group in the molecule. The radical polymerizable compound having at least one hydroxyl group and at least one urea group in the molecule can be represented by the following general formula (15): {In formula (15), _X30 , _X31 , _X32 , and _X33 are independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (16), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom; at least one of _X30 , _X31 , _X32 , and _X23 is a monovalent organic group having a group represented by the following general formula (16), and at least one of them is a hydroxyl group} [Chemistry 39] {In formula (16), _L11 , _L12 and _L13 are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms}. In view of radical reactivity, it is preferred that in formula (16), _L11 is a hydrogen atom or a methyl group, and _L12 and _L13 are hydrogen atoms.

In the formula (15), when _X30 , _X31 , _X32 , and _X33 are monovalent organic groups having 1 to 20 carbon atoms which may contain a heteroatom, it is more preferable to contain an oxygen atom from the viewpoint of developing properties. The carbon number is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it is preferably 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. _X30 , _X31 , _X32 , and _X33 in the formula (15) may be mutually bonded to have a ring structure, but from the viewpoint of chemical resistance, it is preferable not to have a ring structure. By bonding _X30 , _X31 , _X32 , and _X33 to each other to form a ring structure, the freedom of the bonding angle of the urea group is lost, and it is difficult to form a strong hydrogen bond. From the viewpoint of forming a hydrogen bond with other molecules, it is preferred that at least one of _X30 , _X31 , _X32 , and _X33 is a hydrogen atom. On the other hand, from the viewpoint of solubility, the number of hydrogen atoms of _X30 , _X31 , _X32 , and _X33 is preferably 2 or less. Specifically, the compound represented by the following formula can be exemplified: [Chemical 40] .

Among the (F) radical polymerizable compounds in the present embodiment, the method for producing the radical polymerizable compound having a urea group is not particularly limited, and it can be obtained, for example, by reacting an isocyanate compound having a radical polymerizable group with an amine-containing compound. When the amine-containing compound contains a functional group such as a hydroxyl group that can react with the isocyanate, it may also contain a compound formed by reacting a part of the isocyanate compound with a functional group such as a hydroxyl group.

The (F) radical polymerizable compound in this embodiment may be used alone or in combination of two or more. By using two or more radical polymerizable compounds in combination, chemical resistance and in-plane uniformity are improved. Although the reason for the improved in-plane uniformity is speculative, it is considered that when only one radical polymerizable compound is added in large amounts, microphase separation occurs with the polyimide precursor or polyimide component in the varnish. Based on the above reasons, when a radical polymerizable compound is used alone, it is preferably 60 parts by mass or less, and more preferably 40 parts by mass or less, relative to 100 parts by mass of the polyimide precursor or polyimide.

When two or more radical polymerizable compounds (F) are used in combination, the number is preferably 6 or less, more preferably 4 or less, from the viewpoint of controlling the crosslinking density.

When a plurality of radical polymerizable compounds are mixed and used, it is preferred that at least one of the plurality of radical polymerizable compounds has a different number of functional groups. When three or more radical polymerizable compounds are used, it is sufficient that at least one of the radical polymerizable compounds has a different number of functional groups, and it is preferred that all the radical polymerizable compounds have different numbers of functional groups. When a plurality of radical polymerizable compounds are used, it is preferred that at least one monofunctional radical polymerizable compound is included from the viewpoint of elongation at break.

When two or more radical polymerizable compounds (F) are mixed for use, it is preferred that at least one radical polymerizable compound containing nitrogen atoms and at least one radical polymerizable compound not containing nitrogen atoms are contained. The radical polymerizable compound containing nitrogen atoms is preferably a radical polymerizable compound containing urea groups. Radical polymerizable compounds containing nitrogen atoms can form strong hydrogen bonds, and thus have excellent chemical resistance. However, if multiple radical polymerizable compounds containing nitrogen atoms are added, a complex hydrogen bond network structure is formed, resulting in insufficient solubility.

Thermal alkali generator The negative photosensitive resin composition of this embodiment may also contain an alkali generator. The so-called alkali generator refers to a compound that generates an alkali by heating. By containing a thermal alkali generator, the imidization of the photosensitive resin composition can be further promoted.

The type of the thermal alkali generator is not particularly limited, and examples thereof include amine compounds protected by a tert-butoxycarbonyl group, and the thermal alkali generator disclosed in International Publication No. 2017/038598. However, the invention is not limited thereto, and other known thermal alkali generators may be used.

Examples of the amine compound protected by the tert-butoxycarbonyl group include, but are not limited to, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, -Propanol, 4-amino-2-methyl-1-butanol, valine alcohol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(iso propylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidol, 2-pyrrolidinolmethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinolmethanol, 3-piperidinolmethanol, 2-piperidinolmethanol, 4-piperidinolethanol, 2-piperidinolethanol, 2-(4-piperidinol) 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxa-tetradecane, 1-aza-15-crown-5, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxa-undecane, or amino acids and their derivatives.

The amount of the hot alkali generator to be added is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the resin (A). The amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization promoting effect, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

In order to suppress discoloration on the copper surface, the negative photosensitive resin composition may also optionally contain a hindered phenol compound. The hindered phenol compound is not limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and the like. tributyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-phenylpropionamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], isocyanuric acid tris-(3,5-di-tert-butyl-4-hydroxybenzyl) ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, etc.

Examples of hindered phenol compounds include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-trisin-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trisin-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trisin-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2 ,6-dimethylbenzyl]-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)- The present invention also includes, but is not limited to, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione.

Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione and the like are particularly preferred.

The amount of the hindered phenol compound to be added is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the resin (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the hindered phenol compound to be added is 0.1 parts by mass or more relative to 100 parts by mass of the resin (A), for example, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, discoloration and corrosion of the copper or a copper alloy can be prevented. On the other hand, when the amount of the hindered phenol compound to be added is 20 parts by mass or less relative to 100 parts by mass of the resin (A), the photosensitivity is excellent.

Organic titanium compound The negative photosensitive resin composition of this embodiment may also contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer with excellent chemical resistance can be formed even when curing at low temperature.

Usable organic titanium compounds include organic chemical substances bonded to titanium atoms via covalent bonds or ionic bonds.

Specific examples of organic titanium compounds are shown in the following I) to VII): I) Titanium chelate compounds: In terms of the storage stability of the negative photosensitive resin composition and the acquisition of good patterns, titanium chelates having two or more alkoxy groups are more preferred. Specific examples are: titanium bis(triethanolamine) diisopropoxide, titanium bis(2,4-pentanedioate) di-n-butanol, titanium bis(2,4-pentanedioate) diisopropoxide, titanium bis(tetramethylpimelic acid) diisopropoxide, titanium bis(ethyl acetylacetate) diisopropoxide, etc.

II) Tetraalkoxy titanium compounds: for example, titanium tetra-n-butoxide, titanium tetraethanol, titanium tetra(2-ethylhexyl)ol, titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethylol, titanium tetramethoxypropoxide, titanium tetramethylphenol, titanium tetra-n-nonoxide, titanium tetra-n-propoxide, titanium tetrastearylol, titanium tetra[bis{2,2-(allyloxymethyl)butanol}], and the like.

III) Titanium cyclopentadienyl compounds: for example, (pentamethylcyclopentadienyl)trimethoxide titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

IV) Monoalkoxy titanium compounds: for example, titanium tri(dioctyl phosphate) isopropylate, titanium tri(dodecylbenzene sulfonate) isopropylate, etc.

V) Titanium oxide compounds: for example, bis(glutaric acid)titanium oxide, bis(tetramethylpimelic acid)titanium oxide, phthalocyanine titanium oxide, etc.

VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

VII) Titanium ester coupling agent: for example, isopropyl tri(dodecylbenzenesulfonyl)titanium ester.

Among them, as an organic titanium compound, from the viewpoint of exerting better chemical resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanocene compounds is preferred. Especially preferred are titanium bis(ethyl acetylacetate)diisopropoxide, titanium tetra-n-butoxide, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

When the organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the resin (A). When the amount thereof is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when the amount thereof is 10 parts by mass or less, excellent storage stability is achieved.

Adhesion aid In order to improve the adhesion between the film formed by using the negative photosensitive resin composition of this embodiment and the substrate, the negative photosensitive resin composition may also optionally contain a adhesion aid. Examples of the bonding aid include γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidyloxypropyl methyl dimethoxysilane, γ-butyl propyl methyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethyl silane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropyl silane, diethoxy-3-glycidyloxypropyl methyl silane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalimide, Silane coupling agents such as formamide, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl trimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, and aluminum-based bonding agents such as tri(ethyl acetylacetate), aluminum tri(acetylacetone), and aluminum diisopropyl acetylacetate.

Among the bonding agents, silane coupling agents are more preferably used in terms of bonding strength. When the photosensitive resin composition contains a bonding agent, the amount of the bonding agent is preferably in the range of 0.5 to 25 parts by weight relative to 100 parts by weight of the resin (A).

The silane coupling agent is not limited, and examples thereof include: 3-butylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace S810), 3-butylpropyltriethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-butylpropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd.: trade name SIM6474.0), butylmethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), butylmethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0), 3-butylpropyldiethoxymethoxysilane, 3-butylpropylethoxydimethoxysilane, 3-butyl Propyltripropoxysilane, 3-butylpropyldiethoxypropoxysilane, 3-butylpropylethoxydipropoxysilane, 3-butylpropyldimethoxypropoxysilane, 3-butylpropylmethoxydipropoxysilane, 2-butylethyltrimethoxysilane, 2-butylethyldiethoxymethoxysilane, 2-butylethylethoxydimethoxysilane 2-Benzylethyltripropoxysilane, 2-Benzylethyltripropoxysilane, 2-Benzylethylethoxydipropoxysilane, 2-Benzylethyldimethoxypropoxysilane, 2-Benzylethylmethoxydipropoxysilane, 4-Benzylbutyltrimethoxysilane, 4-Benzylbutyltriethoxysilane, 4-Benzylbutyltripropoxysilane, and the like.

The silane coupling agent is not limited, and examples thereof include N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea 、N-(3-ethoxydimethoxysilylpropyl)urea、N-(3-tripropoxysilylpropyl)urea、N-(3-diethoxypropoxysilylpropyl)urea、N-(3-ethoxydipropoxysilylpropyl)urea、N-(3-dimethoxypropoxysilylpropyl)urea、N-(3-methoxydipropoxysilylpropyl)urea、N-(3-trimethoxysilylethyl)urea、N-(3-ethoxydimethoxysilylethyl)urea、 N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy) Propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), etc.

Examples of the silane coupling agent include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidyloxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra- -n-butoxysilane, tetra-isobutoxysilane, tetra-tert-butoxysilane, tetra(methoxyethoxysilane), tetra(methoxy-n-propoxysilane), tetra(ethoxyethoxysilane), tetra(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]diol Sulfide, Bis[3-(triethoxysilyl)propyl]tetrasulfide, Di-tert-butoxydiethoxysilane, Di-isobutoxyaluminoxytriethoxysilane, Phenylsilanetriol, Methylphenylsilanediol, Ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, Diphenylsilanediol, Dimethoxydiphenylsilane, Diethoxydiphenylsilane, Dimethoxydi-p-tolylsilane, Ethylmethylphenylsilaneol, n-propylmethylphenylsilane The present invention also includes, but is not limited to, diphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethyl-isopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like.

The silane coupling agents listed above may be used alone or in combination. Among the silane coupling agents listed above, preferred from the viewpoint of storage stability are phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent having a structure represented by the following formula: [Chemical 41] .

When a silane coupling agent is used, the amount thereof is preferably 0.01 to 20 parts by weight relative to 100 parts by weight of the resin (A).

Sensitizer The negative photosensitive resin composition of this embodiment may also contain a sensitizer to increase the photosensitivity. Examples of the sensitizer include: michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminochalcone, Methylaminocinnamylene dihydroindanone, p-dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7 -diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-Phenylbenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-benzimidazole, 1-phenyl-5-benzyltetrazol, 2-benzylthiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These can be used alone or in combination of 2 to 5 types, for example.

When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount thereof is preferably 0.1 to 25 parts by weight relative to 100 parts by weight of the resin (A).

Polymerization Inhibitor In addition, the negative photosensitive resin composition of the present embodiment may also optionally contain a polymerization inhibitor to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition, especially when stored in a solution containing a solvent. As polymerization inhibitors, hydroquinone, N-nitrosodiphenylamine, tert-butyl o-o-catechol, phenothiocyanate, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, etc. can be used.

<Method for manufacturing hardened relief pattern and semiconductor device> The method for manufacturing hardened relief pattern of this embodiment comprises the following steps: (1) applying the negative photosensitive resin composition of this embodiment on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the resin layer; (3) developing the exposed resin layer to form a relief pattern; (4) heating the relief pattern to form a hardened relief pattern.

(1) Resin layer forming step In this step, the negative photosensitive resin composition of the present embodiment is applied to the substrate, and then dried as needed to form a photosensitive resin layer. As the coating method, a method previously used for coating a photosensitive resin composition can be used, such as a coating method using a rotary coater, a rod coater, a blade coater, a curtain coater, a screen printer, etc., a spray coating method using a spray coater, etc.

(2) Exposure step In this step, an exposure device such as a contact aligner, mirror projection, or stepper is used to expose the resin layer formed above through a patterned mask or a reticle or directly using an ultraviolet light source.

(3) Relief pattern forming step In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from previously known photoresist developing methods, such as a rotary spray method, a liquid coating method, and an immersion method accompanied by ultrasonic treatment. In addition, after development, post-development baking at any combination of temperature and time can be performed as needed for the purpose of adjusting the shape of the relief pattern.

As a developer for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferred. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. As a poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a good solvent and a poor solvent are mixed and used, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more solvents may be used in combination, for example, a combination of several solvents.

(4) Hardened relief pattern forming step In this step, the relief pattern obtained by the above-mentioned development is subjected to heat treatment to evaporate the photosensitive component, and the (A1) polyimide precursor is imidized, thereby converting it into a hardened relief pattern containing polyimide. As a method of heat treatment, various methods can be selected, such as a method using a heating plate, a method using an oven, and a method using a temperature-raising oven with a settable temperature control program. The heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. The temperature of the heat treatment is preferably below 230°C, more preferably below 200°C, and further preferably below 180°C. As the atmosphere gas during heat curing, air can be used, or inert gases such as nitrogen and argon can be used.

<Polyimide> The polyimide of this embodiment can be produced by curing a negative photosensitive resin composition. In addition, another aspect of the present invention also provides a method for producing a polyimide cured film comprising the following steps: imidizing the negative photosensitive resin composition described above to form a cured polyimide with an imidization rate of 80 to 100%. The structure of the polyimide contained in the cured relief pattern formed by the polyimide precursor composition is represented by the following general formula (17). [Chemistry 42] {In the above general formula (17), X ₁ and Y ₁ are the same as X ₁ and Y ₁ in the general formula (2), and m is a positive integer}

For the same reason, the preferred X ₁ and Y ₁ in the general formula (2) are also preferred in the polyimide having the structure represented by the general formula (17). In the general formula, the number of repeating units m is not particularly limited and can be an integer of 2-150.

<Semiconductor device> In this embodiment, a semiconductor device having a hardened relief pattern obtained by the above-mentioned method for manufacturing a hardened relief pattern is also provided. Therefore, a semiconductor device having a substrate as a semiconductor element and a hardened relief pattern of polyimide formed on the substrate by the above-mentioned method for manufacturing a hardened relief pattern can be provided. In addition, it can also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-mentioned method for manufacturing a hardened relief pattern of this embodiment as a part of the steps.

Semiconductor devices can be manufactured by using the hardened embossed pattern formed by the manufacturing method of the hardened embossed pattern of this embodiment as a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device with a bump structure, and combining it with a known manufacturing method for semiconductor devices.

<Display device> In this embodiment, a display device is provided, which has a display element and a hardened film disposed on the upper part of the display element, and the hardened film is the hardened relief pattern mentioned above. Here, the hardened relief pattern can be directly connected to the display element and laminated thereon, or can be laminated on the display element with another layer in between. For example, as the hardened film, there can be cited: surface protection film, insulating film, and flattening film of TFT (thin-film transistor) liquid crystal display element and color filter element, protrusion for MVA (Multi-Domain Vertical Alignment) type liquid crystal display device, and partition wall for cathode of organic EL (Electroluminescence) element.

The negative photosensitive resin composition of this embodiment is preferably used for forming an insulating member or an interlayer insulating film. In addition to the application in the semiconductor device as described above, the negative photosensitive resin composition of this embodiment can also be used for interlayer insulating films of multilayer circuits, cover coatings of flexible copper foils, solder resists, and liquid crystal alignment films. [Example]

Hereinafter, the present embodiment will be specifically described by way of examples, but the present embodiment is not limited thereto. In the examples, comparative examples, and preparation examples, the physical properties of the polyimide precursor or the negative photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured using gel permeation chromatography (converted to standard polystyrene) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40°C Column: 2 Shodex KD-806M in series, or Shodex 805M/806M in series, manufactured by Showa Denko Co., Ltd. Standard monodisperse polystyrene: Shodex STANDARD SM-105, manufactured by Showa Denko Co., Ltd. Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL/min.

(2) Preparation of hardened relief pattern on Cu A 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm) was sputter-coated with 200 nm thick titanium (Ti) and 400 nm thick copper (Cu) in sequence using a sputtering device (L-440S-FHL model, manufactured by CANON ANELVA). Then, a photosensitive resin composition prepared by the following method was spin-coated on the wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO), and pre-baked at 110°C for 180 seconds using a hot plate to form a coating film of about 8.5 μm thickness. Using a photomask with a test pattern, the coating was irradiated with i-rays at an energy of 50 to 650 mJ/ ^cm2 by Prisma GHI (manufactured by Ultratech). Then, using cyclopentanone as a developer, the coating was spray-developed with a coating developer (D-Spin 60A, manufactured by SOKUDO) for 1.4 times the time until the unexposed part was completely dissolved and disappeared, and then washed with propylene glycol methyl ether acetate by rotary spray for 10 seconds to obtain a relief pattern on Cu.

The wafer having the relief pattern formed on Cu was heated at 230° C. for 2 hours in a nitrogen atmosphere using a programmed temperature curing furnace (VF-2000, manufactured by Koyo Lindberg), thereby obtaining a hardened relief pattern including a resin having a thickness of about 4 to 8 μm on Cu.

(3) Evaluation of chemical resistance A chemical solution prepared by mixing the following weight ratios: Dimethyl sulfoxide: 98% Tetramethylammonium hydroxide pentahydrate: 2% was heated to 50°C, and the embossed pattern produced by the method in (2) above was immersed in the heated chemical solution for 10 minutes, washed with running water for 30 minutes, and air-dried. Thereafter, the film surface was visually observed using an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage caused by the chemical solution, such as cracks, and/or the rate of change in film thickness before and after the chemical solution treatment. Chemical resistance was evaluated based on the following criteria. ○: No cracking or other problems occurred, and the film thickness variation rate was less than 10% △: No cracking or other problems occurred, and the film thickness variation rate was more than 10% and less than 15% ×: Cracking or other problems occurred, or the film thickness variation rate was more than 15%

(4) Evaluation of turbidity during coating The film immediately after coating using the method (2) above was visually observed and the degree of turbidity was evaluated. The evaluation criteria are as follows. ○: No turbidity was observed at all. △: Slight turbidity was observed only at the periphery. ×: Turbidity was observed also at areas other than the periphery, or precipitates were observed when observed at 100 times using an optical microscope.

(5) Evaluation of copper adhesion Using a sputtering device (L-440S-FHL, manufactured by CANON ANELVA), 200 nm thick titanium (Ti) and 400 nm thick copper (Cu) were sputtered on a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm). Then, a photosensitive resin composition was spin-coated on the wafer in such a way that the thickness of the film after curing became about 8 μm, and after drying, it was fully exposed and heated at 230°C for 2 hours in a nitrogen atmosphere using a programmed temperature-rising curing furnace (VF-2000, manufactured by Koyo Lindberg) to obtain a hardened relief pattern (thermally cured polyimide coating). For the film after heat treatment, the bonding characteristics between the copper substrate and the hardened resin coating were evaluated based on the following criteria according to the cross-cut method of JIS K 5600-5-6 standard. ○: The number of grids of the hardened resin coating attached to the substrate is 80 or more to 100 △: The number of grids of the hardened resin coating attached to the substrate is 40 or more to less than 80 ×: The number of grids of the hardened resin coating attached to the substrate is less than 40

Preparation Example 1: (A) Synthesis of polyimide precursor A1 124.0 g of 4,4'-oxydiphthalic anhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic anhydride (BPDA) were added to a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added, and the mixture was stirred at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After the exotherm caused by the reaction ended, the reaction mixture was cooled to room temperature and left for 16 hours.

Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 200 mL of γ-butyrolactone was added to the reaction mixture while stirring for 20 minutes, and then a solution prepared by suspending 93.0 g of 4,4'-oxydiphenylamine (ODA) in 350 mL of γ-butyrolactone was added while stirring for 30 minutes. After stirring at room temperature for 4 hours, 30 mL of ethanol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The obtained precipitate was separated by filtration and then vacuum dried to obtain a powdered polymer (polyimide precursor A1). The molecular weight of polyimide precursor A1 was determined by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 24,000.

Preparation Example 2: (A) Synthesis of polyimide precursor A2 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used to replace 124.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) in Preparation Example 1. The same method as described in the above Preparation Example 1 was used to obtain a polymer (polyimide precursor A2). The molecular weight of the polyimide precursor A2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 24,000.

Preparation Example 3: (A) Synthesis of polyimide precursor A3 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) was used to replace 124.0 g of 4,4'-oxydiphthalic anhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic anhydride (BPDA) in Preparation Example 1. The reaction was carried out in the same manner as described in the above-mentioned Preparation Example 1 to obtain a polymer (polyimide precursor A3). The molecular weight of the polyimide precursor A3 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.

Preparation Example 4: (A) Synthesis of polyimide precursor A4 Except for using 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Preparation Example 3, the same method as described in the above-mentioned Preparation Example 1 was used to obtain polymer (A4). The molecular weight of polymer (A4) was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.

Preparation Example 5: (A) Synthesis of polyimide precursor A5 Except for using 48.1 g of p-phenylenediamine (p-PD) instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Preparation Example 3, the reaction was carried out in the same manner as described in the above-mentioned Preparation Example 1 to obtain polymer (A5). The molecular weight of polymer (A5) was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 19,000.

Preparation Example 6: (A) Synthesis of polyimide precursor A6 62.0 g of 4,4'-oxyphthalic anhydride (ODPA) and 65.4 g of pyromellitic anhydride (PMDA) were used instead of 155.1 g of 4,4'-oxyphthalic anhydride (ODPA) in Preparation Example 4. The same method as described in the above-mentioned Preparation Example 1 was used to obtain polymer (A6). The molecular weight of polymer (A6) was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

Preparation Example 7: (A) Synthesis of polyimide precursor A7 182.5 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Preparation Example 3. The reaction was carried out in the same manner as described in the above-mentioned Preparation Example 1 to obtain polymer (A7). The molecular weight of polymer (A7) was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 25,000.

Preparation Example 8: (A) Synthesis of polyimide precursor A8 260.3 g of 4,4'-(4,4'-isopropyldiphenyloxy)phthalic anhydride (BPADA) was used instead of 155.1 g of 4,4'-oxyphthalic anhydride (ODPA) in Preparation Example 4. The same reaction method as described in the above-mentioned Preparation Example 1 was used to obtain polymer (A8). The molecular weight of polymer (A8) was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 25,000.

Preparation Example 9: (A) Synthesis of polyimide A9 Into a 3 L glass separable flask equipped with a stirring device and a stirring blade, 64.1 g (0.20 mol) of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 97.7 g (0.22 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 500 g of DMAc were added and stirred to dissolve TFMB and 6FDA in DMAc. Then, the mixture was stirred continuously at room temperature for 12 hours under a nitrogen flow to carry out a polymerization reaction to obtain a polyimide solution.

After adding 16 g of pyridine to the obtained polyamide solution, 82 g of acetic anhydride was added dropwise at room temperature. Thereafter, the liquid temperature was further maintained at 20 to 100° C. and stirred for 24 hours to carry out the imidization reaction, thereby obtaining a polyimide solution.

In a 5 L container, the obtained polyimide solution was added to 1,000 g of methanol while stirring to precipitate the polyimide resin. Thereafter, the solid polyimide resin was filtered and separated using a vacuum filter, and then washed with 1,000 g of methanol. Then, it was dried at 100°C for 24 hours using a vacuum dryer, and then dried at 200°C for 3 hours. By the above operation, a polyimide powder having an anhydride group at the end, namely polymer (A-11), was obtained. The molecular weight of polymer A-11 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 25,000.

<Example 1> Using polyimide precursor A1, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. A1 as (A) resin: 100 g, B1 as (B) sugar derivative: 2-nitrophenyl β-D-pyranosyl galactoside (manufactured by Tokyo Chemical Industry Co., Ltd.) 6 g, and C1 as (C) photopolymerization initiator: TR-PBG-3057 (manufactured by TRONLY Co., Ltd.) 3 g were dissolved in a mixed solvent of γ-butyrolactone (hereinafter referred to as GBL): 80 g and dimethyl sulfoxide (hereinafter referred to as DMSO): 20 g. The viscosity of the obtained solution was adjusted to about 40 poise by adding a necessary amount of a solution of GBL:DMSO = 80:20 to prepare a photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 1.

<Examples 2 to 22, Comparative Examples 1 to 5> The same photosensitive resin composition as in Example 1 was prepared with the formulation ratio shown in Table 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. (A) Resin, (B) Sugar Derivative, (C) Photopolymerization Initiator, (D) Solvent, (E) Heterocyclic Compound, (F) Free Radical Polymerization Compound listed in Table 1 are shown below.

A1: The polyimide precursor described in Preparation Example 1 A2: The polyimide precursor described in Preparation Example 2 A3: The polyimide precursor described in Preparation Example 3 A4: The polyimide precursor described in Preparation Example 4 A5: The polyimide precursor described in Preparation Example 5 A6: The polyimide precursor described in Preparation Example 6 A7: The polyimide precursor described in Preparation Example 7 A8: The polyimide precursor described in Preparation Example 8 A9: The polyimide described in Preparation Example 9

B1: 2-nitrophenyl β-D-galactopyranoside (manufactured by Tokyo Chemical Industry Co., Ltd.) B2: 4-nitrophenyl α-D-glucopyranoside (manufactured by Tokyo Chemical Industry Co., Ltd.) B3: α-D-galacturonic acid hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) B4: Methyl α-D-galactopyranoside monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) B5: D-galactaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) B6: α-D-galacturonic acid hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) B1': Xylitol (manufactured by Tokyo Chemical Industry Co., Ltd.) B2': L-(+)-arabinose (manufactured by Tokyo Chemical Industry Co., Ltd.) B3': D-erythrococcolic acid lactone (manufactured by Tokyo Chemical Industry Co., Ltd.) B4': D-(-)-arabinose (manufactured by Tokyo Chemical Industry Co., Ltd.) B5': D-(+)-glucose (manufactured by Tokyo Chemical Industry Co., Ltd.)

C1: TR-PBG-3057 (manufactured by TRONLY) D1: γ-Butyrolactone (manufactured by Mitsubishi Chemical) D2: Dimethyl sulfoxide (manufactured by Toray Fine Chemical) E1: 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry) E2: 8-azaadenine (manufactured by Tokyo Chemical Industry) F1: NK ESTER 4G (manufactured by Shin-Nakamura Chemical Industry) F2: NK ESTER A-9300 (manufactured by Shin-Nakamura Chemical Industry) F3: NK ESTER A-TMMT (manufactured by Shin-Nakamura Chemical Industry)

[Table 1] (A) Polyimide Precursor (B) Sugar derivatives (C) Photopolymerization initiator (D) Solvent (E) Heterocyclic compounds (F) Radical polymerizable compound Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Embodiment 1 A1 100 B1 6 C1 3 D1/D2 80/20 Embodiment 2 A1 100 B2 6 C1 3 D1/D2 80/20 Embodiment 3 A1 100 B3 11 C1 3 D1/D2 80/20 Embodiment 4 A1 100 B4 12 C1 3 D1/D2 80/20 Embodiment 5 A1 100 B5 6 C1 3 D1/D2 80/20 Embodiment 6 A1 100 B6 6 C1 3 D1/D2 80/20 Embodiment 7 A1 100 B1 3 C1 3 D1/D2 80/20 Embodiment 8 A1 100 B1 6 C1 3 D1/D2 80/20 E1 1 Embodiment 9 A1 100 B1 20 C1 3 D1/D2 80/20 E2 0.5 Embodiment 10 A1 100 B1 6 C1 3 D1/D2 80/20 E1/E2 1/0.5 Embodiment 11 A1 100 B1 6 C1 3 D1/D2 80/20 E1/E2 1/0.5 F1 8 Embodiment 12 A1 100 B1 6 C1 3 D1/D2 80/20 E1/E2 1/0.5 F2 40 Embodiment 13 A1 100 B1 6 C1 3 D1/D2 80/20 E1/E2 1/0.5 F3 15 Embodiment 14 A1 100 B1 6 C1 3 D1/D2 80/20 E1/E2 1/0.5 F1/F2 20/40 Embodiment 15 A2/A3 50/50 B1 6 C1 3 D1/D2 80/20 Embodiment 16 A3 100 B1 6 C1 3 D1/D2 80/20 Embodiment 17 A4 100 B1 6 C1 3 D1/D2 80/20 Embodiment 18 A5 100 B1 6 C1 3 D1/D2 80/20 Embodiment 19 A6 100 B1 6 C1 3 D1/D2 80/20 Embodiment 20 A7 100 B1 6 C1 3 D1/D2 80/20 Embodiment 21 A8 100 B1 6 C1 3 D1/D2 80/20 Embodiment 22 A9 100 B1 6 C1 5 D1/D2 80/20 E1/E2 1/0.5 F1/F2 20/40 Comparative example 1 A1 100 B1' 6 C1 3 D1/D2 80/20 E2 0.5 Comparative example 2 A1 100 B2' 6 C1 3 D1/D2 80/20 E2 0.5 Comparative example 3 A1 100 B3' 6 C1 3 D1/D2 80/20 E2 0.5 Comparative example 4 A1 100 B4' 6 C1 3 D1/D2 80/20 E2 0.5 Comparative example 5 A1 100 C1 3 D1/D2 80/20 E2 0.5

[Table 2] Evaluation results copper adhesion White mud during painting Chemical resistance Embodiment 1 △ ○ △ Embodiment 2 △ ○ △ Embodiment 3 △ △ △ Embodiment 4 △ △ △ Embodiment 5 △ △ △ Embodiment 6 △ △ △ Embodiment 7 △ ○ △ Embodiment 8 ○ ○ △ Embodiment 9 ○ ○ △ Embodiment 10 ○ ○ △ Embodiment 11 ○ ○ △ Embodiment 12 ○ ○ ○ Embodiment 13 ○ ○ ○ Embodiment 14 ○ ○ ○ Embodiment 15 △ ○ △ Embodiment 16 △ ○ △ Embodiment 17 △ ○ △ Embodiment 18 △ ○ △ Embodiment 19 △ ○ △ Embodiment 20 △ ○ △ Embodiment 21 △ ○ △ Embodiment 22 △ △ △ Comparative example 1 △ × △ Comparative example 2 △ × △ Comparative example 3 △ × △ Comparative example 4 △ × △ Comparative example 5 × ○ △

As shown in Table 1 and Table 2, the negative photosensitive resin composition of Example 1 had a copper adhesion of △, a white turbidity evaluation during coating of ○, and a chemical resistance of △. The photosensitive resin compositions of Examples 2 to 22 were all evaluated as follows: copper adhesion, white turbidity during coating, and chemical resistance were all △ or above.

In comparison examples 1 to 4, the white turbidity during coating was evaluated as ×, and in comparison example 5, the copper adhesion was ×. [Industrial applicability]

By using the photosensitive resin composition of the present invention, a coating film that is not prone to whitening during the coating step can be obtained, and a hardened relief pattern with excellent copper adhesion and chemical resistance can be obtained. The present invention can be preferably used in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multi-layer wiring substrates.

Claims (11)

A negative photosensitive resin composition comprising: (A) at least one resin selected from (A1) a polyimide precursor and (A2) a polyimide, (B) a sugar derivative represented by any one of the general formulas (1)-A to (1)-C, [Chemical 1] (In the formula, _R1 is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic group which may have a substituent; _R2 to _R4 are a hydrogen atom or a monovalent organic group having 1 to 9 carbon atoms; _R5 is any one of *-CH2 _- OH, *-COOH, * _-CH2 - _N3 , or a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group; here, * indicates a bonding position with other parts; and any two or more of _R1 to _R4 are hydrogen atoms; however, it is not a combination in which all of _R1 to _R4 are hydrogen atoms and _R5 is * _-CH2 -OH) [Chemistry 2] (In the formula, R ₆ is any one of *-CH ₂ -OH, *-COOH, *-CH ₂ -N ₃ , and a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group; here, * indicates the bonding position with other parts) [Chemical 3] (wherein _R7 is any one of *-CH2 _- OH, *-COOH, * _-CH2 - _N3 , and a monovalent organic group having 7 to 10 carbon atoms and having an aromatic group; here, * indicates a bonding position with other parts) (C) a photopolymerization initiator, and (D) a solvent. The negative photosensitive resin composition of claim 1, wherein in the sugar derivative (B), R ₆ of the formula (1)-B and R ₇ of the formula (1)-C are *-CH ₂ -OH. The negative photosensitive resin composition of claim 1, wherein in the sugar derivative (B), all of R ₂ to R ₄ in the formula (1)-A are hydrogen atoms, and R ₅ is *-CH ₂ -OH. The negative photosensitive resin composition of claim 1, wherein R ₁ of the sugar derivative (B) is an aromatic group which may have a substituent. The negative photosensitive resin composition of claim 1 further comprises (E) a heterocyclic compound. The negative photosensitive resin composition of claim 1, wherein the polyimide precursor (A1) comprises a polyimide precursor having a structural unit represented by the following general formula (2): {In formula (2), _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R11 and _R12 are independently a hydrogen atom or a monovalent organic group}. The negative photosensitive resin composition of claim 6, wherein in the above general formula (2), at least one of R ₁₁ and R ₁₂ has a structural unit represented by the following general formula (3): {In formula (3), L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10}. The negative photosensitive resin composition of claim 1, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film. A method for producing a hardened embossed pattern, comprising the following steps: (1) applying a negative photosensitive resin composition as described in any one of claims 1 to 8 on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a embossed pattern; (4) heating the embossed pattern to form a hardened embossed pattern. A method for manufacturing a hardened embossed pattern as claimed in claim 9, wherein the heat treatment in the above step (4) is a heat treatment below 230°C. A method for producing polyimide comprises hardening the negative photosensitive resin composition of any one of claims 1 to 8.