JP7370145B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a polyamide resin, a photosensitive resin composition, a dry film, a cured product, and an electronic component.

Polybenzoxazole has excellent heat resistance and electrical insulation properties, so it can be used as surface protective films and interlayer insulation films for electrical materials, such as coating films for semiconductor devices, flexible printed wiring board materials, and heat-resistant insulation interlayer materials. Application to parts is progressing.

Conventionally, in order to form a fine pattern of polybenzoxazole, a photosensitive resin composition containing a polybenzoxazole precursor (also referred to as polyhydroxyamide) and a photosensitizer has been used. As such a photosensitive resin composition, for example, Patent Document 1 describes a positive resist composition composed of a polybenzoxazole precursor and a photosensitive diazoquinone.

Special Publication No. 1-046862 Japanese Patent Application Publication No. 2008-33157

However, the composition described in Patent Document 1 may not have sufficient compatibility between the heat resistance of the cured product and the sensitivity and resolution in photolithography. In addition, in recent years, due to the miniaturization of semiconductor devices and multilayer wiring due to high integration, surface protection films and interlayer insulating films are often formed directly on copper wiring. There is also the problem that a large amount of development residue is generated. Furthermore, in order to prevent cracks, and in order to reduce wafer warpage as semiconductor wafers are becoming larger in area in WLP (wafer level packaging), the cured product must have a low coefficient of linear thermal expansion (i.e. , low CTE) are also required.

In order to solve the above problems, it has been considered to use polybenzoxazole precursors and polyimide precursors (also referred to as polyamic acids), each of which has excellent properties, in combination (see Patent Document 2); However, there were problems in that the stability was poor, the quantitative ratio was quite limited, and the properties tended to change in terms of alkali solubility and heat resistance.

Therefore, the object of the present invention is to obtain a photosensitive resin composition that can form a cured film with high heat resistance and a low coefficient of linear thermal expansion, and has excellent sensitivity and suppression of development residue on copper. Provided is a photosensitive resin composition containing the polyamide resin, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, and an electronic component having the cured product. It's about doing.

The inventors of the present invention, while making intensive studies to achieve the above object, found that by introducing a benzoxazole skeleton when synthesizing a polyamide resin, which is a polybenzoxazole precursor (also referred to as polyhydroxyamide), the cured product Although it is possible to improve heat resistance and lower CTE, on the other hand, we focused on the fact that it becomes difficult to suppress development residues on copper, and further studies were conducted. As a result, if a polyamide resin has an amic acid structure, that is, an imide precursor structure introduced into one molecule in addition to a benzoxazole skeleton and a benzoxazole precursor structure, a photosensitive resin composition containing the polyamide resin can be used. The present inventors have discovered that they are excellent in suppressing development residues on copper while achieving heat resistance and low CTE, and have completed the present invention.

That is, the polyamide resin of the present invention is a reaction product of an amine component and a carboxylic acid component,
The amine component is (A) a diamine component and (B) a dihydroxydiamine component,
The carboxylic acid component is (C) a tri- or tetracarboxylic acid anhydride component and (D) a dicarboxylic acid component,
At least one of the (A) diamine component, (B) dihydroxydiamine component, (C) tri- or tetracarboxylic acid anhydride component, and (D) dicarboxylic acid component has a benzoxazole skeleton,
The reactant is a polyamide resin that has a benzoxazole skeleton in its main chain skeleton, and also has an imide precursor structure and a benzoxazole precursor structure.

The photosensitive resin composition of the present invention is characterized by containing the polyamide resin and a photosensitizer.

The dry film of the present invention is characterized by having a resin layer obtained by coating the photosensitive resin composition on a film and drying it.

The cured product of the present invention is characterized in that it is obtained by curing the resin layer of the photosensitive resin composition or the dry film.

The electronic component of the present invention is characterized by having the cured product.

According to the present invention, a polyamide resin capable of forming a cured film having high heat resistance and a low coefficient of linear thermal expansion, and from which a photosensitive resin composition having excellent sensitivity and suppression of development residue on copper can be obtained; To provide a photosensitive resin composition containing a resin, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, and an electronic component having the cured product. I can do it.

Hereinafter, the components contained in the polyamide resin of the present invention and the photosensitive resin composition of the present invention will be described in detail.

(Polyamide resin)
The polyamide resin of the present invention is a polyamide resin that is a reaction product of an amine component and a carboxylic acid component, wherein the amine component is (A) a diamine component and (B) a dihydroxydiamine component, and the carboxylic acid component is (C ) tri- or tetracarboxylic acid anhydride component and (D) dicarboxylic acid component, the (A) diamine component, (B) dihydroxydiamine component, (C) tri- or tetracarboxylic acid anhydride component, and (D) dicarboxylic acid. At least one of the components has a benzoxazole skeleton, and the reactant is a polyamide resin having a benzoxazole skeleton and an imide precursor structure and a benzoxazole precursor structure. be.

The reaction between the amine component and the carboxylic acid component is not particularly limited as long as a polyamide resin can be obtained, and any reaction may be used as long as the amine component and the carboxylic acid component react to form an amide bond.

In the present invention, the tri- or tetracarboxylic anhydride component (C), which is one of the carboxylic acid components, forms an imide precursor structure through a polyaddition reaction with the amine component. Further, (B) dihydroxydiamine forms a benzoxazole precursor structure through a polycondensation reaction with a carboxylic acid component. That is, the polyamide resin of the present invention is an imide precursor-benzoxazole precursor-amide copolyaddition condensate. The polyamide resin of the present invention may be a random copolymer obtained by reacting components (A) to (D) together, or may be a random copolymer obtained by reacting components (A) to (D) sequentially in any order. It may also be a reacted block copolymer.

The benzoxazole skeleton is included in the main chain skeleton of the polyamide resin. The method of introducing the benzoxazole skeleton is not particularly limited, but for example, a polyamide resin may be synthesized using a compound having a benzoxazole skeleton as any of the components (A) to (D). The ratio of the number of benzoxazole skeletons to the number of amide bonds in the polyamide resin is preferably 0.1 to 20%, more preferably 0.1 to 10%. When the benzoxazole skeleton in the polyamide resin is 0.1% or more, the heat resistance of the resin is improved, and when it is 20% or less, the alkali solubility is not impaired.

The benzoxazole skeleton is not particularly limited, and may be a benzobisoxazole skeleton. Furthermore, as the benzoxazole skeleton, benzoxazole skeletons to which benzene rings are bonded, as shown in general formulas (1-1) to (1-3) described below, can also be suitably used.

The proportion of the imide precursor structure (namely, amic acid structure) possessed by the polyamide resin of the present invention can be adjusted by adjusting the proportion of the (C) tri- or tetracarboxylic acid anhydride component in the carboxylic acid component. The proportion of the tri- or tetracarboxylic anhydride component (C) per 100 mol% of the carboxylic acid component is preferably 1 to 30 mol%, more preferably 1 to 15 mol%. (C) The polyamide resin derived from the tri- or tetracarboxylic acid anhydride component preferably has a carboxyl group equivalent of 1,000 or more, more preferably 2,000 to 5,000.

The proportion of the benzoxazole precursor structure that the polyamide resin of the present invention has can be adjusted by adjusting the proportion of the (B) dihydroxydiamine component in the amine component. The proportion of the dihydroxydiamine component (B) is preferably 70 to 99 mol%, more preferably 80 to 99 mol%, per 100 mol% of the amine component. In addition, the hydroxy group contained in the dihydroxydiamine component (B) is preferably a phenolic hydroxyl group, and the dihydroxydiamine component (B) has a structure in which two hydroxy groups and two amino groups are located at ortho positions on an aromatic ring. It is more preferable to have. The phenolic hydroxyl equivalent of the polyamide resin derived from such dihydroxydiamine component (B) is preferably 600 or less, more preferably 100 to 300.

In the present invention, it is preferable that the diamine component (A) contains a diamine having a benzoxazole skeleton, and having the benzoxazole skeleton further improves heat resistance. The molar ratio of the diamine having a benzoxazole skeleton to the dihydroxydiamine component (B) is preferably 0.1:99.9 to 30:70, and preferably 0.1:99.9 to 15:85. It is more preferable. Further, when the diamine (A) has a benzoxazole skeleton, the molar ratio of the tri- or tetracarboxylic acid anhydride component (C) and the dicarboxylic acid component (D) is 0.1:99.9 to 30:70. The ratio is preferably 0.1:99.9 to 20:80, more preferably 0.1:99.9 to 20:80.

The diamine component (A) is not particularly limited, but in the present invention, the "diamine component (A)" does not include the dihydroxydiamine component (B). Examples of diamines when they are aromatic groups include paraphenylene diamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3 '-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diaminobenzophenone, 4, 4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfoxide, 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-aminophenoxybiphenyl, bis[4-( 4-aminophenoxy)phenyl]ether, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-aminophenyl)propane, 1,1,1,3,3,3-hexa Fluoro-2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-amino-4-methylphenyl) Propane, metaphenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis( Examples of diamines in the case of aliphatic groups include 1,1-methaxylylene diamine, 1,3-propanediamine, tetramethylene diamine, and pentamethylene diamine. , hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 4,4-diaminoheptamethylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylene diamine, hexahydro-4,7 -methanoindanilene dimethylenediamine, tricyclo[6.2.1.02,7]-undecylenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine), and isophoronediamine.

When the diamine component (A) has a benzoxazole skeleton, the diamine component (A) includes 6-amino-2-(4-aminophenyl)benzoxazole, 2-(4-aminophenyl)-5-aminobenzo Diamines corresponding to the general formulas (1-1), (1-2) and (1-3) described below such as oxazole (i.e., the following general formulas (1-1), (1-2) and (1-3) ) has two "direct bonds with the nitrogen atom in general formula (2)" changed to amino groups).

The diamine component (A) may be used alone or in combination of two or more. For example, as the diamine component (A), a diamine having a benzoxazole skeleton and a diamine having no benzoxazole skeleton may be used in combination.

The dihydroxydiamine component (B) includes 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, and bis(3-amino-4-hydroxyphenyl). ) propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3- amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3, Examples include 3-hexafluoropropane. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is preferred. The dihydroxydiamine component (B) may be used alone or in combination of two or more.

As the tri- or tetracarboxylic anhydride component (C), examples of the tricarboxylic anhydride include trimellitic anhydride and nuclear hydrogenated trimellitic anhydride. Examples of the tetracarboxylic anhydride include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, and 3,6-bis(trifluoromethyl)pyromellitic acid. Dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride , 2,2'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride , 6,6'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',5,5',6,6'-hexafluoro-3,3',4 , 4'-biphenyltetracarboxylic dianhydride, 2,2'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, fluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 6,6'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride 2,2',5,5'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, fluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyl Tetracarboxylic dianhydride, and 2,2',5,5',6,6'-hexakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 1, 2,3,4-benzenetetracarboxylic dianhydride, 3,3'',4,4''-terphenyltetracarboxylic dianhydride, 3,3''',4,4'''-quaterphenyltetracarboxylic dianhydride Acid dianhydride, 3,3"",4,4""-quinquephenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4,4'- Diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4' -diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 2,2-bis(3 ,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride (i.e., 4,4'-(hexafluoroisopropylidene)diphthalic anhydride), difluoromethylene- 4,4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3 -hexafluoro-1,3-trimethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4 '-diphthalic dianhydride, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4'-diphthalic dianhydride, thio -4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyl Siloxane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3 ,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2 -propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl] Methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2, 2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]-1,1,1,3, 3,3-hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride , 1,3-bis(3,4-dicarboxyphenoxy)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2, 7,8-phenanthrenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride Anhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetra Carboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethynylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4 , 4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis( cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 3,3'-difluorooxy-4,4'-diphthalic acid Dianhydride, 5,5'-difluorooxy-4,4'-diphthalic dianhydride, 6,6'-difluorooxy-4,4'-diphthalic dianhydride, 3,3',5,5 ',6,6'-hexafluorooxy-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 5,5' -Bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',5 , 5'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride 5,5',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, methyl)oxy-4,4'-diphthalic dianhydride, 3,3'-difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic dianhydride Anhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluorosulfonyl-4,4'-diphthalic dianhydride 3,3'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride Anhydride, 3,3',6,6'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)sulfonyl- 4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3'- Difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6 , 6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluoro-2,2-perfluoro Propylidene-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5' -Bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthal Acid dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',6,6 '-Tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-2,2- Perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4 '-diphthalic dianhydride, 9-phenyl-9-(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis(trifluoromethyl)xanthene-2, 3,6,7-tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 9,9-bis[4- (3,4-dicarboxy)phenyl]fluorene dianhydride, 9,9-bis[4-(2,3-dicarboxy)phenyl]fluorene dianhydride, ethylene glycol bistrimelitate dianhydride, 1,2 -(ethylene)bis(trimellitate anhydride), 1,3-(trimethylene)bis(trimellitate anhydride), 1,4-(tetramethylene)bis(trimellitate anhydride), 1,5-(pentamethylene)bis( trimellitate anhydride), 1,6-(hexamethylene) bis(trimellitate anhydride), 1,7-(heptamethylene) bis(trimellitate anhydride), 1,8-(octamethylene) bis(trimellitate anhydride), 1,9-(nonamethylene)bis(trimellitate anhydride), 1,10-(decamethylene)bis(trimellitate anhydride), 1,12-(dodecamethylene)bis(trimellitate anhydride), 1,16-(hexadeca Examples include methylene)bis(trimellitate anhydride), 1,18-(octadecamethylene)bis(trimellitate anhydride), and the like. The tri- or tetracarboxylic acid anhydride component (C) may be used alone or in combination of two or more.

The dicarboxylic acid component (D) includes isophthalic acid, terephthalic acid, 5-tert-butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane , dicarboxylic acids with aromatic rings such as 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2- Examples include aliphatic dicarboxylic acids such as cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid, their dicarboxylic acid dihalides, and their dicarboxylic acid esters. Among these, 4,4'-dicarboxydiphenyl ether (ie, 4,4'-diphenyl ether dicarboxylic acid) and its dihalide are preferred. The dicarboxylic acid component (D) may be used alone or in combination of two or more.

The polymer terminal structure of the polyamide resin of the present invention is not particularly limited, and examples include residues of amine components, residues of carboxylic acid components, unsaturated double bonds, hydroxyl groups, and thiol groups.

The polyamide resin of the present invention is preferably a polyamide resin having a repeating structure represented by the following general formula (1) in which an amine component and a carboxylic acid component are bonded through amide bonds.

（一般式（１）中、Ｘはアミン成分の残基であり、Ｙはカルボン酸成分の残基であり、前記アミン成分が、（Ａ）ジアミン成分および（Ｂ）ジヒドロキシジアミン成分であり、前記カルボン酸成分が、（Ｃ）トリまたはテトラカルボン酸無水物成分と（Ｄ）ジカルボン酸成分であり、前記（Ａ）ジアミン成分、（Ｂ）ジヒドロキシジアミン成分、（Ｃ）トリまたはテトラカルボン酸無水物成分および（Ｄ）ジカルボン酸成分の少なくともいずれか一種がベンゾオキサゾール骨格を有する。）

(In general formula (1), X is a residue of an amine component, Y is a residue of a carboxylic acid component, the amine component is (A) a diamine component and (B) a dihydroxydiamine component, and the The carboxylic acid component is (C) a tri- or tetracarboxylic acid anhydride component and (D) a dicarboxylic acid component, and the (A) diamine component, (B) dihydroxydiamine component, and (C) tri- or tetracarboxylic acid anhydride. component and (D) dicarboxylic acid component has a benzoxazole skeleton.)

In general formula (1), X and the two nitrogen atoms on both sides thereof have a structure derived from an amine component, and Y and the two carbonyl groups on both sides thereof have a structure derived from a carboxylic acid component. In general formula (1), (A) diamine component, (B) dihydroxydiamine component, (C) tri- or tetracarboxylic acid anhydride component, and (D) dicarboxylic acid component are each as described above.

The benzoxazole skeleton is preferably a benzoxazole structure represented by any one of the following general formulas (1-1), (1-2) and (1-3).

（一般式（１－１）中、Ｒ_１～Ｒ_４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_５～Ｒ_９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１～Ｒ_４のうちいずれか一つ、および、Ｒ_５～Ｒ_９のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。）

（一般式（１－２）中、Ｒ_１０～Ｒ_１４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_１５～Ｒ_１９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１０～Ｒ_１４のうちいずれか一つ、および、Ｒ_１５～Ｒ_１９のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。Ｒ_２０、Ｒ_２１はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

（一般式（１－３）中、Ｒ_２２～Ｒ_２６は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_２７～Ｒ_３１は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_２２～Ｒ_２６のうちいずれか一つ、および、Ｒ_２７～Ｒ_３１のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。Ｒ_３２、Ｒ_３３はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

(In general formula (1-1), R ₁ to R ₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or nitrogen atoms or carbonyl in general formula (1)) A direct bond with a group, which may be the same or different. R ₅ to R ₉ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or , a direct bond with the nitrogen atom or carbonyl group in general formula (1), and may be the same or different.However, any one of R ₁ to R ₄ , and Any one of R ₅ to R ₉ is either a direct bond to the nitrogen atom in general formula (1) or a direct bond to the carbonyl group in general formula (1).)

(In general formula (1-2), R ₁₀ to R ₁₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or nitrogen atoms or carbonyl in general formula (1)) A direct bond with a group, which may be the same or different. R ₁₅ to R ₁₉ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or , a direct bond with the nitrogen atom or carbonyl group in general formula (1), and may be the same or different.However, any one of R ₁₀ to R ₁₄ , and Any one of R ₁₅ to R ₁₉ is either a direct bond to the nitrogen atom in the general formula (1) or a direct bond to the carbonyl group in the general formula (1). R ₂₀ , _R21 each represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group, and may be the same or different.)

(In general formula (1-3), R ₂₂ to R ₂₆ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or nitrogen atoms or carbonyl in general formula (1)) A direct bond with a group, which may be the same or different. R ₂₇ to R ₃₁ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or , a direct bond with the nitrogen atom or carbonyl group in general formula (1), and may be the same or different.However, any one of R ₂₂ to R ₂₆ , and Any one of R ₂₇ to R ₃₁ is either a direct bond to the nitrogen atom in the general formula (1) or a direct bond to the carbonyl group in the general formula (1). R ₃₂ , _R33 is each a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group, and may be the same or different.)

R ₁ to R ₄ and R ₅ to R ₉ in the general formula (1-1), R ₁₀ to R ₁₄ and R ₁₅ to R ₁₉ in the general formula (1-2), and the general formula (1- R ₂₂ to R ₂₆ and R ₂₇ to R ₃₁ in 3) are preferably a hydrogen atom or a direct bond with a nitrogen atom in general formula (1).

R ₁ to R ₄ and R ₅ to R ₉ in the general formula (1-1), R ₁₀ to R ₁₄ and R ₁₅ to R ₁₉ in the general formula (1-2), and the general formula (1- In 3), R ₂₂ to R ₂₆ and R ₂₇ to R ₃₁ can be, for example, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. group, an aryl group having 6 to 12 carbon atoms, an allyl group, a trifluoromethyl group, and the like.

Examples of organic groups that can be taken by R ₂₀ and R ₂₁ in the general formula (1-2) and R ₃₂ and R ₃₃ in the general formula (1-3) include an alkyl group having 1 to 3 carbon atoms; Examples include an alkoxy group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an allyl group, and a trifluoromethyl group.

Halogens that can be represented by R ₁ to R ₉ in the general formula (1-1), R ₁₀ to R ₂₁ in the general formula (1-2), and R ₂₂ to R ₃₃ in the general formula (1-3) Atoms include fluorine, chlorine, and bromine. Among them, fluorine is preferred in view of the transmittance of the polymer.

R ₁ to R ₉ in the general formula (1-1), R ₁₀ to R ₂₁ in the general formula (1-2), and R ₂₂ to R ₃₃ in the general formula (1-3) can be taken. Examples of the sulfonyl group include alkylsulfonyl groups having 1 to 10 carbon atoms such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, octylsulfonyl group, decylsulfonyl group, and dodecylsulfonyl group.

In the general formula (1), the X derived from the diamine component (A) and the two nitrogen atoms on both sides thereof have a structure represented by the following general formula (2).

（一般式（２）中、Ｚは（Ａ）ジアミン成分の残基であり、２価の有機基である。）

(In general formula (2), Z is a residue of the diamine component (A) and is a divalent organic group.)

In the general formula (2), the divalent organic group represented by Z may be an aliphatic group or an aromatic group, but is preferably an aromatic group. The number of carbon atoms in the divalent aromatic group is preferably 6 to 30, more preferably 6 to 24.

In the general formula (2), the divalent organic group represented by Z has a benzoxazole structure (provided that R ₁ ~R ₄ , R ₅ ~R ₉ , R ₁₀ ~R ₁₄ , R ₁₅ ~R ₁₉ , R ₂₂ ~R ₂₆ , and R ₂₇ ~R ₃₁ all represent the carbonyl group in general formula (1). A divalent group having a bond (not a direct bond) is preferable.

In the general formula (2), the diamine component represented by Z is a diamine component corresponding to the general formulas (1-1), (1-2), and (1-3) (i.e., the diamine component represented by the general formula (1-1)). ), (1-2) and (1-3) in which the two "direct bonds with the nitrogen atom in general formula (1)" are changed to amino groups).

The ratio of the number of structures represented by the above general formula (2) per 100 mol% of the structure derived from the amine component of the polyamide resin is preferably 1 to 40 mol%, and preferably 1 to 30 mol%. More preferred.

In the general formula (1), the X derived from the dihydroxydiamine component (B) and the two nitrogen atoms on both sides thereof have a structure represented by the following general formula (3).

（一般式（３）中、Ｗは（Ｂ）ジヒドロキシジアミン成分の残基であり、４価の有機基である。）

(In general formula (3), W is a residue of the dihydroxydiamine component (B) and is a tetravalent organic group.)

In the general formula (3), the tetravalent organic group represented by W may be an aliphatic group or an aromatic group, but is preferably an aromatic group, with two hydroxy groups and two amino groups in the ortho position. More preferably, it is located on an aromatic ring. The number of carbon atoms in the tetravalent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the tetravalent aromatic group include the following groups, but are not limited to these. Known aromatic groups that can be included in the polybenzoxazole precursor may be selected depending on the purpose. Bye.

Among the aromatic groups, the tetravalent aromatic group is preferably the following group.

The ratio of the number of structures represented by the above general formula (3) per 100 mol% of the structure derived from the amine component of the polyamide resin is preferably 60 to 99 mol%, and preferably 70 to 99 mol%. More preferred.

In the general formula (1), Y derived from the tri- or tetracarboxylic anhydride component (C) and the two carbonyl groups on both sides thereof have a structure represented by the following general formula (4).

（一般式（４）中、Ｐは（Ｃ）トリまたはテトラカルボン酸無水物成分の残基であり、３価または４価の有機基である。ｊは１または２である。）

(In general formula (4), P is a residue of (C) tri- or tetracarboxylic acid anhydride component and is a trivalent or tetravalent organic group. j is 1 or 2.)

In the above general formula (4), the trivalent or tetravalent organic group represented by P may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and on the aromatic ring, the trivalent or tetravalent organic group represented by the above general formula (4) More preferably, it is bonded to the carbonyl within. The number of carbon atoms in the trivalent or tetravalent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the trivalent or tetravalent aromatic group include, but are not limited to, the following groups. Known aromatic groups contained in the imide precursor may be selected depending on the purpose. Bye.

（式中、Ａは単結合、－ＣＨ_２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ_２－、－ＮＨＣＯ－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基を表す。）

(In the formula, A is a single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ represents a divalent group selected from the group consisting of -)

Among the aromatic groups, the trivalent or tetravalent organic group is preferably the following group.

Per 100 mol% of the structure derived from the carboxylic acid component of the polyamide resin, the ratio of the number of structures represented by the above general formula (4) is preferably 1 to 50 mol%, and 1 to 15 mol%. is more preferable.

In the general formula (1), Y derived from the dicarboxylic acid component (D) and the two carbonyl groups on both sides thereof have a structure represented by the following general formula (5).

（一般式（５）中、Ｑは（Ｄ）ジカルボン酸成分の残基であり、２価の有機基である。）

(In general formula (5), Q is a residue of the dicarboxylic acid component (D) and is a divalent organic group.)

In the general formula (5), the divalent organic group represented by Q may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and the carbonyl group in the general formula (5) is preferably an aromatic group. More preferably, it is combined with. The number of carbon atoms in the divalent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the divalent aromatic group include the following groups, but are not limited to these, and if a known aromatic group contained in the polybenzoxazole precursor is selected depending on the purpose. good.

（式中、Ａは単結合、－ＣＨ_２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ_２－、－ＮＨＣＯ－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基を表す。）

(In the formula, A is a single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ represents a divalent group selected from the group consisting of -)

Among the aromatic groups, the divalent organic group is preferably the following group.

Per 100 mol% of the structure derived from the carboxylic acid component of the polyamide resin, the ratio of the number of structures represented by the above general formula (5) is preferably 50 to 99 mol%, and 85 to 99 mol%. is more preferable.

Examples of the repeating unit of the amide structure possessed by the polyamide resin of the present invention include structural units represented by the following general formulas (6) to (9).

The structural unit represented by the following general formula (6) is a structural unit derived from (A) a diamine component and (C) a tri- or tetracarboxylic acid anhydride component.

（一般式（６）中、Ｚは一般式（２）と同様であり、Ｐおよびｊは一般式（４）と同様である。）

(In general formula (6), Z is the same as in general formula (2), and P and j are the same as in general formula (4).)

As a specific example of the structural unit represented by general formula (6), for example, (A) the diamine component is 6-amino-2-(4-aminophenyl)benzoxazole, and (C) the tri- or tetracarboxylic acid Examples include, but are not limited to, the following structural units in which the anhydride component is 4,4'-(hexafluoroisopropylidene) diphthalic anhydride.

（右側の４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）由来の構造において、アミド結合およびカルボキシル基はメタ位またはパラ位である。）

(In the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) on the right, the amide bond and carboxyl group are at the meta or para position.)

The structural unit represented by the following general formula (7) is a structural unit derived from (A) a diamine component and (D) a dicarboxylic acid component.

（一般式（７）中、Ｚは一般式（２）と同様であり、Ｑは一般式（５）と同様である。）

(In general formula (7), Z is the same as general formula (2), and Q is the same as general formula (5).)

As a specific example of the structural unit represented by general formula (7), for example, (A) the diamine component is 6-amino-2-(4-aminophenyl)benzoxazole, and (D) the dicarboxylic acid component is Examples include, but are not limited to, the following structural unit which is 4,4'-diphenyl ether dicarboxylic acid chloride.

The structural unit represented by the following general formula (8) is a structural unit derived from (B) a dihydroxydiamine component and (C) a tri- or tetracarboxylic acid anhydride component.

（一般式（８）中、Ｗは一般式（３）と同様であり、Ｐおよびｊは一般式（４）と同様である。）

(In general formula (8), W is the same as in general formula (3), and P and j are the same as in general formula (4).)

As a specific example of the structural unit represented by general formula (8), for example, (B) dihydroxydiamine component is bis(3-amino-4-hydroxyamidophenyl)hexafluoropropane, and (C) tri- or Examples include, but are not limited to, the following structural units in which the tetracarboxylic anhydride component is 4,4'-(hexafluoroisopropylidene) diphthalic anhydride.

（右側の４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）由来の構造において、アミド結合およびカルボキシル基はメタ位またはパラ位である。）

(In the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) on the right, the amide bond and carboxyl group are at the meta or para position.)

The structural unit represented by the following general formula (9) is a structural unit derived from (B) a dihydroxydiamine component and (D) a dicarboxylic acid component.

（一般式（９）中、Ｗは一般式（３）と同様であり、Ｑは一般式（５）と同様である。）

(In general formula (9), W is the same as in general formula (3), and Q is the same as in general formula (5).)

As a specific example of the structural unit represented by general formula (9), for example, (B) dihydroxydiamine component is bis(3-amino-4-hydroxyamidophenyl)hexafluoropropane, and (D) dicarboxylic acid Examples include, but are not limited to, the following structural units in which the component is 4,4'-diphenyl ether dicarboxylic acid chloride.

The number average molecular weight (Mn) of the polyamide resin of the present invention is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. Here, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene. Further, the weight average molecular weight (Mw) of the polyamide resin of the present invention is preferably 6,000 to 200,000, more preferably 15,000 to 100,000. Here, the weight average molecular weight is a value measured by GPC and converted to standard polystyrene. Mw/Mn is preferably 1-6, more preferably 1-4.

The method for producing a polyamide resin of the present invention is a method for producing a polyamide resin that is a polybenzoxazole precursor having an imide precursor, which comprises a step of reacting an amine component and a carboxylic acid component to synthesize a polyamide resin,
The amine component is (A) a diamine component and (B) a dihydroxydiamine component,
The carboxylic acid component is (C) a tri- or tetracarboxylic acid anhydride component and (D) a dicarboxylic acid component,
At least one of the above (A) diamine component, (B) dihydroxydiamine component, (C) tri- or tetracarboxylic acid anhydride component, and (D) dicarboxylic acid component has a benzoxazole skeleton. be.

In the method for producing a polyamide resin of the present invention, (A) diamine component, (B) dihydroxydiamine component, (C) tri- or tetracarboxylic acid anhydride component, and (D) dicarboxylic acid component are each as described above. .

The method of reacting the amine component and the carboxylic acid component is not particularly limited, and may be synthesized by a known method. For example, (A) diamine component and (B) dihydroxydiamine component are stirred in a solution such as N-methylpyrrolidone, and (C) tri- or tetracarboxylic acid is stirred at a low temperature of 5°C or lower, specifically 0°C. There is a method in which the anhydride component and (D) dicarboxylic acid component are added little by little, and after the carboxylic acid component is dissolved, the mixture is reacted at room temperature for 6 hours or more, and then taken out as a solid using a reprecipitation method or the like.

(Photosensitive resin composition)
The polyamide resin of the present invention may be mixed with other components and used as a resin composition. In addition, by combining it with a photosensitizer to form a photosensitive resin composition, it is possible to form a cured film with excellent sensitivity and suppression of development residue on copper, high heat resistance, and a low coefficient of linear thermal expansion. The amount of the polyamide resin of the present invention is preferably 60 to 95% by mass based on the nonvolatile content of the photosensitive resin composition.

(Photosensitizer)
There are no particular limitations on the photosensitizer, and photoacid generators and photobase generators can be used. A photoacid generator is a compound that generates an acid when irradiated with light such as ultraviolet rays or visible light, and a photobase generator is a compound that changes its molecular structure or cleaves its molecules when irradiated with light. It is a compound that produces more than one type of basic substance. In the present invention, a photoacid generator can be suitably used as the photosensitizer.

Examples of photoacid generators include naphthoquinonediazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, and nitrobenzyl esters. , aromatic N-oxyimidosulfonate, aromatic sulfamide, benzoquinonediazosulfonic acid ester, and the like. Preferably, the photoacid generator is a dissolution inhibitor. Among these, naphthoquinone diazide compounds are preferred.

Specifically, the naphthoquinonediazide compound includes, for example, a naphthoquinonediazide adduct of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593 manufactured by Sanpo Chemical Research Institute). ), naphthoquinonediazide adducts of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Research Institute), and 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α , α-dimethylbenzyl}phenol and naphthoquinone diazide adducts (for example, TKF-428 and TKF-528 manufactured by Sanpo Chemical Research Institute), etc. can be used.

The photobase generator may be either an ionic photobase generator or a nonionic photobase generator, but the ionic photobase generator has higher composition sensitivity and is more effective in forming patterned films. This is preferable because it is advantageous. Examples of the basic substance include secondary amines and tertiary amines.

Examples of ionic photobase generators include salts of aromatic component-containing carboxylic acids and tertiary amines, and ionic PBGs manufactured by Wako Pure Chemical Industries, Ltd. such as WPBG-082, WPBG-167, WPBG-168, and WPBG-. 266, WPBG-300, etc. can be used.

Examples of nonionic photobase generators include α-aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, alkoxybenzyl Examples include compounds having substituents such as carbamate groups. Other photobase generators include WPBG-018 (product name: 9-anthrylmethyl N,N'-diethylcarbamate) and WPBG-027 (product name: (E)-1-[3-(2) manufactured by Wako Pure Chemical Industries, Ltd. -hydroxyphe
nyl)-2-propenoyl]piperidine), WPBG-140 (trade name: 1-(anthraquinon-2-yl)ethyl imidazolecarboxylate), WPBG-165, etc. can also be used.

The photosensitizers may be used alone or in combination of two or more. The blending amount of the photosensitizer is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass, based on the total solid content of the composition.

(Crosslinking agent)
The photosensitive resin composition of the present invention may contain a crosslinking agent. Adding a crosslinking agent increases the strength of the cured film when cured at low temperatures. The crosslinking agent is not particularly limited, and may include any known and commonly used crosslinking agent. The crosslinking agent is preferably a compound that reacts with the phenolic hydroxyl group or carboxyl group of the polyamide resin of the present invention to form a crosslinked structure. Examples of the crosslinking agent include a crosslinking agent having a cyclic ether group such as an epoxy group, a crosslinking agent having a cyclic thioether group such as an episulfide group, a crosslinking agent having a phenolic hydroxyl group, and an alkylene group having 1 to 12 carbon atoms such as a methylol group. Examples include a crosslinking agent having an alcoholic hydroxyl group to which a hydroxyl group is bonded, a crosslinking agent having a triazine ring structure, and a urea-based crosslinking agent. One type of crosslinking agent may be used alone, or two or more types may be used in combination.

((meth)acrylic compound)
The photosensitive resin composition of the present invention may contain a (meth)acrylic compound. The (meth)acrylic compound is not particularly limited as long as it has a (meth)acryloyl group, but a compound having two (meth)acryloyl groups is preferable. Among them, diol (ethylene oxide or propylene oxide) Di(meth)acrylates of alkylene oxide adducts (such as) and bifunctional polyester(meth)acrylates are preferred, and bifunctional polyester(meth)acrylates are more preferred. In addition, in this specification, a (meth)acrylic compound is a term which generically refers to an acrylic compound, a methacrylic compound, and a mixture thereof, and the same applies to other similar expressions.

As the di(meth)acrylate of an alkylene oxide adduct of a diol, specifically, one in which a diol is modified with an alkylene oxide and then a (meth)acrylate is added to the terminal is preferable, and one in which the diol has an aromatic ring is more preferable. . Examples include bisphenol AEO (ethylene oxide) adduct diacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, and the like. A specific structure of di(meth)acrylate, which is an alkylene oxide adduct of diol, is shown below, but the structure is not limited thereto.

（式中、ｍ＋ｎは２以上であり、２～４０であることが好ましく、３．５～２５であることがより好ましい。）

(In the formula, m+n is 2 or more, preferably 2 to 40, more preferably 3.5 to 25.)

As the bifunctional polyester (meth)acrylate, M-6200, M-6250, and M-6500 (trade name manufactured by Toagosei Co., Ltd.) are preferable.

(Sensitizer, adhesive agent, other ingredients)
The photosensitive resin composition of the present invention may contain a known sensitizer to further improve photosensitivity and a silane coupling agent to improve adhesion to the substrate, within a range that does not impair the effects of the present invention. It is also possible to add a known adhesive agent. Furthermore, in order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various other organic or inorganic low-molecular or high-molecular compounds may be blended. For example, surfactants, leveling agents, fine particles, etc. can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon, and layered silicates. Further, various colorants, fibers, plasticizers, thermal acid generators, etc. may be added to the photosensitive resin composition of the present invention.

Furthermore, the photosensitive resin composition of the present invention may contain resin components other than the polyamide resin of the present invention within a range that does not impair the effects of the present invention.

(solvent)
The solvent used in the photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve the polyamide resin of the present invention, the photosensitizer, and other additives. Examples include N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Mention may be made of butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of solvent to be used can be appropriately determined depending on the coating film thickness and viscosity. For example, it can be used in an amount of 50 to 9,000 parts by mass based on 100 parts by mass of the polyamide resin of the present invention.

The photosensitive resin composition of the present invention may be of positive type or negative type.

[Dry film]
The dry film of the present invention has a resin layer obtained by coating and drying the photosensitive resin composition of the present invention.

The dry film of the present invention can be obtained by uniformly applying the photosensitive resin composition of the present invention to a carrier film (supporting film) by an appropriate method using a blade coater, lip coater, comma coater, film coater, etc., and drying. It can be manufactured by forming the above resin layer and preferably laminating a cover film (protective film) thereon. The cover film and the carrier film may be the same film material or may be different films.

In the dry film of the present invention, any film material known for use in dry films can be used for the carrier film and the cover film.

As the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used.

As the cover film, polyethylene film, polypropylene film, etc. can be used, but it is preferable that the adhesive force with the resin layer is smaller than that of the carrier film.

The thickness of the resin layer on the dry film of the present invention is preferably 100 μm or less, more preferably in the range of 5 to 50 μm.

Using the photosensitive resin composition of the present invention, a patterned film, which is a cured product thereof, may be produced by a known and commonly used manufacturing method, for example, a positive photosensitive resin composition containing a photoacid generator as a photosensitizer. In the case of a product, it is manufactured using the following steps.

First, in step 1, a coating film is obtained by applying a photosensitive resin composition onto a substrate and drying it, or by transferring (laminating) a resin layer from a dry film onto the substrate. Methods for applying the photosensitive resin composition onto the substrate include methods conventionally used for applying photosensitive resin compositions, such as spin coaters, bar coaters, blade coaters, curtain coaters, screen printers, etc. A coating method using a spray coater, a spray coating method using a spray coater, an inkjet method, etc. can be used. As a method for drying the coating film, methods such as air drying, heating drying using an oven or hot plate, and vacuum drying are used. Further, it is desirable that the coating film be dried under conditions that do not cause ring closure of the polyamide resin of the present invention in the photosensitive resin composition. Specifically, natural drying, blow drying, or heat drying can be performed at 70 to 140° C. for 1 to 30 minutes. Preferably, drying is performed on a hot plate for 1 to 20 minutes. Vacuum drying is also possible, and in this case it can be carried out at room temperature for 20 minutes to 1 hour.

There are no particular limitations on the substrate on which the coating film of the photosensitive resin composition is formed, and it can be widely applied to semiconductor substrates such as silicon wafers, wiring boards, and substrates made of various resins and metals.

Next, in step 2, the coating film is exposed to light through a patterned photomask or directly. The exposure light used has a wavelength capable of activating a photoacid generator as a photosensitizer and generating acid. Specifically, the exposure light preferably has a maximum wavelength in the range of 350 to 410 nm. As mentioned above, photosensitivity can be adjusted by appropriately blending a sensitizer. As the exposure device, a contact aligner, mirror projection, stepper, laser direct exposure device, etc. can be used.

Subsequently, in step 3, heating may be performed to cyclize a portion of the polyamide resin in the unexposed area. Here, the cyclization rate is about 30%. The heating time and heating temperature are appropriately changed depending on the polyamide resin, the coating film thickness, and the type of photoacid generator used as the photosensitizer.

Next, in step 4, the coating film is treated with a developer. Thereby, the exposed portion in the coating film can be removed to form a patterned film of the photosensitive resin composition of the present invention.

As the method used for development, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. Examples of developing solutions include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Examples include aqueous solutions of quaternary ammonium salts such as . Further, if necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant may be added to these. Thereafter, if necessary, the coating film is washed with a rinsing liquid to obtain a patterned film. As the rinsing liquid, distilled water, methanol, ethanol, isopropyl alcohol, etc. can be used alone or in combination. Further, the above-mentioned solvents may be used as the developer.

Thereafter, in step 5, the patterned film is heated to obtain a cured coating film (cured product). At this time, the benzoxazole precursor structure and the imide precursor structure are cyclized to obtain a benzoxazole skeleton and an imide skeleton. The heating temperature is appropriately set so that the patterned film of the photosensitive resin composition can be cured. For example, heating is performed in an inert gas at 150° C. or higher and lower than 350° C. for about 5 to 120 minutes. A more preferable heating temperature range is 180 to 320°C. Heating is performed, for example, by using a hot plate, an oven, or a heating oven in which a temperature program can be set. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

The use of the photosensitive resin composition of the present invention is not particularly limited, and for example, it can be suitably used as a paint, printing ink, or adhesive, or as a forming material for display devices, semiconductor devices, electronic components, optical components, or building materials. used. Specifically, as a material for forming a display device, it can be used as a layer-forming material or an image-forming material, such as a color filter, a flexible display film, a resist material, an alignment film, and the like. Further, as a material for forming a semiconductor device, it can be used as a resist material, a layer forming material such as a buffer coat film, and the like. Further, as a material for forming electronic components, it can be used as a sealing material or a layer forming material for printed wiring boards, interlayer insulating films, wiring coating films, etc. Furthermore, as a material for forming optical components, it can be used as an optical material or a layer forming material for holograms, optical waveguides, optical circuits, optical circuit components, antireflection films, and the like. Furthermore, as a building material, it can be used as a paint, a coating agent, etc.

The photosensitive resin composition of the present invention is mainly used as a pattern forming material, and the patterned film formed thereby has heat resistance and insulation properties as a permanent film made of a polymer having a benzoxazole skeleton and an imide skeleton. Because it functions as an imparting component, it is particularly useful as a surface protective film for semiconductor devices, display devices, and light emitting devices, interlayer insulating films, rewiring insulating films, protective films for flip-chip devices, and protective films for devices with bump structures. It can be suitably used as an interlayer insulating film for multilayer circuits, an insulating material for passive components, a protective film for printed wiring boards such as a solder resist or a coverlay film, and a liquid crystal alignment film. In particular, it is suitable for use as an insulating film in contact with copper wiring or aluminum wiring.

EXAMPLES Hereinafter, the present invention will be explained in more detail using examples, but the present invention is not limited to the following examples. In addition, in the following, "parts" and "%" are all based on mass unless otherwise specified.

(Synthesis of polyamide resin)
Polyamide resins A-1 to A-5, R-1, which are polybenzoxazole precursors, and polyamide resin R-2, which is a polyimide precursor, were synthesized as follows. The amine component and carboxylic acid component of each polyamide resin, as well as their mole percentages, are listed in Table 1 below.

(Example 1-1: Synthesis of polyamide resin A-1)
Into a 0.5 liter flask equipped with a stirrer and a thermometer, 70 g of N-methylpyrrolidone was charged, and 8.50 g (23.2 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 6- 0.581 g (2.58 mmol) of amino-2-(4-aminophenyl)benzoxazole (O-BO) was dissolved with stirring. After that, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 1.25 g (2.81 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added as a solid. Added over 10 minutes and stirred in ice bath for 15 minutes. Subsequently, 7.46 g (25.3 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) was added as a solid, and the mixture was stirred in an ice bath for 30 minutes. Stirring was then continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyamide resin (A-1) which is a 10% partially benzoxazolized 10% imide precursor-polybenzoxazole precursor having the following repeating structure. The weight average molecular weight (Mw) determined by GPC standard polystyrene conversion was 31,400. Further, the number average molecular weight (Mn) was 9,900, and the Mw/Mn was 3.17.

（右側の４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）由来の構造において、アミド結合およびカルボキシル基はメタ位またはパラ位である。）

（右側の４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）由来の構造において、アミド結合およびカルボキシル基はメタ位またはパラ位である。）

(In the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) on the right, the amide bond and carboxyl group are at the meta or para position.)

(In the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) on the right, the amide bond and carboxyl group are at the meta or para position.)

(Example 1-2: Synthesis of polyamide resin A-2)
Into a 0.5 liter flask equipped with a stirrer and a thermometer, 130 g of N-methylpyrrolidone was charged, and 8.50 g (23.2 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 6- 2.24 g (10.0 mmol) of amino-2-(4-aminophenyl)benzoxazole (O-BO) was dissolved with stirring. After that, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 3.75 g (8.4 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added as a solid. Added over 10 minutes and stirred in ice bath for 15 minutes. Subsequently, 12.44 g (42.2 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) was added as a solid, and the mixture was stirred in an ice bath for 30 minutes. Stirring was then continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyamide resin (A-2) which is a 50% partially benzoxazolized 50% imide precursor-polybenzoxazole precursor. The weight average molecular weight determined by GPC standard polystyrene conversion was 19,400. Further, the number average molecular weight (Mn) was 7,600, and the Mw/Mn was 2,55.

(Example 1-3: Synthesis of polyamide resin A-3)
Into a 0.5 liter flask equipped with a stirrer and a thermometer, 70 g of N-methylpyrrolidone was charged, and 8.50 g (23.2 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 6- 0.581 g (2.58 mmol) of amino-2-(4-aminophenyl)benzoxazole (O-BO) was dissolved with stirring. After that, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 0.8719 g (2.81 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) was added as a solid over 10 minutes. Stir in an ice bath for 15 minutes. Subsequently, 7.46 g (25.3 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) was added as a solid, and the mixture was stirred in an ice bath for 30 minutes. Stirring was then continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyamide resin (A-3) which is a 10% partially benzoxazolized 10% imide precursor-polybenzoxazole precursor. The weight average molecular weight determined by GPC standard polystyrene conversion was 27,300. Further, the number average molecular weight (Mn) was 10,600, and the Mw/Mn was 2.58.

(Example 1-4: Synthesis of polyamide resin A-4)
Into a 0.5 liter flask equipped with a stirrer and a thermometer, 70 g of N-methylpyrrolidone was charged, and 8.50 g (23.2 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 6- 0.581 g (2.58 mmol) of amino-2-(4-aminophenyl)benzoxazole (O-BO) was dissolved with stirring. After that, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 0.8719 g (2.81 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride (BPDA) was added as a solid. The mixture was added over 10 minutes and stirred in an ice bath for 15 minutes. Subsequently, 7.46 g (25.3 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) was added as a solid, and the mixture was stirred in an ice bath for 30 minutes. Stirring was then continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyamide resin (A-4) which is a 10% partially benzoxazolized 10% imide precursor-polybenzoxazole precursor. The weight average molecular weight determined by GPC standard polystyrene conversion was 30,200. Further, the number average molecular weight (Mn) was 11,400, and the Mw/Mn was 2.65.

(Example 1-5: Synthesis of polyamide resin A-5)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 70 g of N-methylpyrrolidone was charged, and 8.50 g (23.2 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 2- 0.581 g (2.58 mmol) of (4-aminophenyl)-5-aminobenzoxazole (N-BO) was dissolved with stirring. After that, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 1.25 g (2.81 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added as a solid. Added over 10 minutes and stirred in ice bath for 15 minutes. Subsequently, 7.46 g (25.3 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) was added as a solid, and the mixture was stirred in an ice bath for 30 minutes. Stirring was then continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyamide resin (A-5) which is a 10% partially benzoxazolized 10% imide precursor-polybenzoxazole precursor. The weight average molecular weight determined by GPC standard polystyrene conversion was 29,700. Further, the number average molecular weight (Mn) was 11,800, and the Mw/Mn was 2.52.

(Reference Example 1-1: Synthesis of polyamide resin R-1)
212 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and 60.52 g (165.22 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was stirred. Dissolved. After that, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 53.02 g (179.65 mmol) of 4,4-diphenyletherdicarboxylic acid chloride (DEDC) was added as a solid in 5 g portions over 30 minutes. and stirred in an ice bath for 30 minutes. Thereafter, stirring was continued for 5 hours at room temperature. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyamide resin (R-1) which is a polybenzoxazole (PBO) precursor having the following repeating structure at the carboxyl group end. The weight average molecular weight (Mw) determined by GPC standard polystyrene conversion was 32,100. Further, the number average molecular weight (Mn) was 13,100, and the Mw/Mn was 2.45.

(Reference Example 1-2: Synthesis of polyamide resin R-2)
212 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and 9.29 g (46.4 mmol) of 4,4-diaminodiphenyl ether (ODA) was dissolved therein with stirring. After that, the flask was immersed in an ice bath, and while keeping the inside of the flask at 0 to 5°C, 24.8 g (50.6 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added, and the mixture was heated to room temperature. Stirring was continued for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value: 18.2 MΩ·cm), and the precipitate was collected. Thereafter, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion-exchanged water. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyamide resin (R-2), which is a polyimide (PI) precursor having the following repeating structure at the carboxyl group end. The weight average molecular weight determined by GPC standard polystyrene conversion was 31,400. Further, the number average molecular weight (Mn) was 12.500 and Mw/Mn was 2.5.

(Preparation of photosensitive resin composition)
Each component was added in the proportions (parts by mass) shown in Table 2 below, and γ-butyrolactone was added in an amount of 30% by mass based on the polyamide resin to completely dissolve it to form a varnish.

(Sensitivity evaluation, development residue evaluation, and measurement of residual film rate in unexposed areas)
The varnish prepared above was applied onto a copper sputtered silicon substrate using a spin coater and dried on a hot plate at 110° C. for 3 minutes to obtain a 12 μm thick dry film of the photosensitive resin composition. The dried film was irradiated with i-line at an exposure dose of 0 to 1000 mJ/cm ² . After exposure, the film was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 80 seconds and rinsed with water to obtain a positive pattern.
- Sensitivity evaluation The exposure amount that was able to develop the surface of the sputtered copper substrate is listed in the table.
・Evaluation of development residue The above pattern was rated ○ if it was developed without any residue, and if there was a residue it was rated ×.
-Measurement of unexposed area remaining film rate The unexposed area film thickness of the above pattern was compared before and after development to calculate the remaining film rate.

(Tg, CTE evaluation)
The varnish prepared above was spin-coated onto a silicon wafer and heated at 110° C. for 3 minutes. Thereafter, the film was heated in an inert gas oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) at 110°C for 10 minutes in a nitrogen atmosphere, then held at 150°C for 30 minutes, and then heated at 320°C for 60 minutes to thicken the film. A cured film of 40 μm was obtained. Next, the cured film was peeled off using a PCT device at 121° C. and 100% RH for 60 minutes, and then CTE and Tg were measured using TMA Q400 (TA Instruments).

※膨潤により測定不可

*Measurement not possible due to swelling

<Photosensitizer>
Naphthoquinone diazide compound (TKF-428 manufactured by Sanpo Chemical Research Institute)

ＨＰ４０３２Ｄ（ＤＩＣ社製）

ＴＭ－ＢＩＰ－Ａ（旭有機材工業社製）

<Crosslinking agent>
MW390 (manufactured by Sanwa Chemical Co.)

HP4032D (manufactured by DIC)

TM-BIP-A (manufactured by Asahi Yokuzai Kogyo Co., Ltd.)

<Acrylic compound>
Aronix M-6250 (bifunctional polyester acrylate, manufactured by Toagosei Co., Ltd.)

From the results shown in Table 2 above, by using the polyamide resin of the present invention, a cured film with high heat resistance and a low coefficient of linear thermal expansion can be formed, and it is possible to improve sensitivity and suppress development residue on copper substrates. It can be seen that an excellent photosensitive resin composition can be obtained.

(Evaluation of Tg and CTE of cured film obtained by low temperature curing)
For Examples 2-6 to 2-9, the varnish prepared above was spin-coated onto a silicon wafer and heated at 110° C. for 3 minutes. Thereafter, the film was heated in an inert gas oven (CLH-21CD-S manufactured by Koyo Thermosystem Co., Ltd.) at 110°C for 10 minutes in a nitrogen atmosphere, then held at 150°C for 30 minutes, and then heated at 220°C for 60 minutes to thicken the film. A cured film of 40 μm was obtained. Next, the cured film was peeled off using a PCT device at 121° C. and 100% RH for 60 minutes, and then CTE and Tg were measured using TMA Q400 (TA Instruments).

From the results shown in Table 3 above, it can be seen that by using the polyamide resin of the present invention, it is possible to form a cured film with high heat resistance and a low coefficient of linear thermal expansion even when cured at a low temperature. .

Claims (5)

It is a polyamide resin that is a reaction product of an amine component and a carboxylic acid component,
The amine component is (A) a diamine component and (B) a dihydroxydiamine component,
The carboxylic acid component is (C) a tri- or tetracarboxylic acid anhydride component and (D) a dicarboxylic acid component,
The diamine component (A) has a benzoxazole skeleton,
A polyamide resin having a benzoxazole skeleton as a main chain skeleton as a reactant, and having an imide precursor structure and a benzoxazole precursor structure. A photosensitive resin composition comprising the polyamide resin according to claim 1 and a photosensitizer. A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 2 onto a film and drying it. A cured product obtained by curing the photosensitive resin composition according to claim 2 or the resin layer of the dry film according to claim 3 . An electronic component comprising the cured product according to claim 4 .