JP7256015B2 - Photosensitive resin compositions, dry films, cured products, and electronic components - Google Patents

Description

The present invention relates to photosensitive resin compositions, dry films, cured products, and electronic parts.

Conventionally, resin compositions containing polybenzoxazole precursors and polyimide precursors as main components have been used as insulating materials for rewiring in semiconductor devices. These polybenzoxazole precursors and polyimide precursors are heated at a high temperature (>350°C) to undergo a cyclization reaction to form benzoxazole rings and imide rings, resulting in a rigid structure. A cured film with excellent chemical resistance and thermal properties can be obtained.

On the other hand, in recent years, a so-called chip-first type fan-out wafer level package construction method has appeared, in which rewiring is formed after sealing a chip with a sealant. Therefore, as an insulating material for rewiring used in such a construction method, a material that can be cured at a temperature of about 220° C. is required from the viewpoint of heat resistance of a sealing material mainly composed of epoxy resin.

However, at such a low temperature, the resin composition containing the polybenzoxazole precursor and the polyimide precursor does not sufficiently progress the cyclization reaction of the polybenzoxazole precursor and the polyimide precursor, resulting in poor chemical resistance and heat resistance. There is a problem that various properties such as properties and mechanical properties such as flexibility are degraded.

On the other hand, in order to solve these problems, various approaches of adding a cross-linking agent such as an epoxy compound to a resin composition containing a polybenzoxazole precursor or a polyimide precursor have been proposed (for example, Patent Document 1). .

JP 2014-111718 A

However, with the resin composition as described in Patent Document 1, for example, when insulating layers and conductor (copper) circuit layers are alternately laminated for rewiring, adhesion between the insulating layers and conductor circuit layers In the long-term reliability test such as the PCBT test, peeling occurs between the insulating layer and the conductor circuit layer.

Therefore, the main object of the present invention is to provide a resin composition that can be cured even at a temperature of about 220° C. while using a polybenzoxazole precursor or a polyimide precursor as the main component of the resin composition, and has adhesion to a conductor circuit such as copper. It is an object of the present invention to provide a resin composition containing a polybenzoxazole precursor or a polyimide precursor as a main component, which is excellent in rewiring and effective for use as, for example, an insulating layer for rewiring.
Another object of the present invention is to provide a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product. .

The inventors of the present invention have made extensive studies to achieve the above object. As a result, in a photosensitive resin composition containing a polybenzoxazole precursor or a polyimide precursor as a main component of the resin composition, by containing a cross-linking agent having an episulfide group, the polybenzoxazole precursor or the polyimide precursor The phenolic hydroxyl group or carboxyl group reacts with the episulfide group of the cross-linking agent to form a thiol group in the cross-linked structure. The discovery led to the completion of the present invention.

That is, the photosensitive resin composition of the present invention is characterized by containing (A) a polybenzoxazole precursor or a polyimide precursor, (B) a photosensitive agent, and (C) a cross-linking agent having an episulfide group. is.

In the photosensitive resin composition of the present invention, (C) the episulfide group-containing cross-linking agent preferably has two or more episulfide groups in one molecule.

In addition, the photosensitive resin composition of the present invention preferably contains (D) a cross-linking agent other than the above (C), and the cross-linking agent (D) more preferably contains an epoxy group.

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

The cured product of the present invention is characterized by being 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 polybenzoxazole precursor or a polyimide precursor is used as a main component of a resin composition, and a poly(polyimide) that can be cured even at a temperature of about 220° C. and has excellent adhesion to a conductor circuit such as copper. A resin composition containing a benzoxazole precursor or a polyimide precursor as a main component can be obtained. Further, according to the present invention, it is possible to provide a resin composition which is excellent in film physical properties such as elongation in addition to such effects. Furthermore, according to the present invention, it is possible to provide a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product.

The photosensitive resin composition of the present invention is characterized by containing (A) a polybenzoxazole precursor or a polyimide precursor, (B) a photosensitive agent, and (C) a cross-linking agent having an episulfide group. .

In particular, in the photosensitive resin composition of the present invention, the episulfide group in the cross-linking agent reacts with the phenolic hydroxyl group or carboxyl group of the polybenzoxazole precursor or polyimide precursor to introduce a thiol group into the crosslinked structure. This thiol group improves the adhesion with the interface of metal such as copper.

Furthermore, since the photosensitive resin composition of the present invention contains a cross-linking agent having an episulfide group, it has excellent low-temperature curability and film physical properties such as elongation. In addition, by containing a cross-linking agent having this episulfide group, it is possible to suppress the problem that the unexposed portion of the coating film swells when the coating film is developed with the positive photosensitive resin composition, and the pattern film is formed. It is also beneficial for formation.

Furthermore, the photosensitive resin composition of the present invention contains (D) a cross-linking agent other than (C) above, particularly a cross-linking agent containing an epoxy group, so that the adhesiveness and elongation with a metal interface such as copper It is possible to further improve film physical properties such as This effect is presumed to be due to the fact that the thiolate anion produced by ring-opening of the episulfide group reacts with the epoxy group, thereby imparting excellent toughness (flexibility).

Each component constituting the photosensitive resin composition of the present invention will be described in detail below.

[(A) Polybenzoxazole precursor or polyimide precursor]
The photosensitive resin composition of the present invention contains (A) a polybenzoxazole precursor or a polyimide precursor. Hereinafter, (A1) polybenzoxazole precursor and (A2) polyimide precursor will be described in detail in this order.

[(A1) Polybenzoxazole precursor]
(A1) The method for synthesizing the polybenzoxazole precursor is not particularly limited, and may be synthesized by a known method. For example, it can be obtained by reacting a dihydroxydiamine as an amine component with a dicarboxylic acid component such as a dicarboxylic acid dichloride, a dicarboxylic acid, or a dicarboxylic acid ester as an acid component.

（式中、Ｘは４価の有機基を示し、Ｙは２価の有機基を示す。ｎは２以上の整数であり、好ましくは１０～２００、より好ましくは２０～７０である。） (A1) The polybenzoxazole precursor is preferably a polyhydroxyamide, preferably a polyhydroxyamide having a repeating structure represented by the following general formula (1).

(Wherein, X represents a tetravalent organic group, Y represents a divalent organic group, n is an integer of 2 or more, preferably 10 to 200, more preferably 20 to 70.)

(A1) When synthesizing the polybenzoxazole precursor by the above synthesis method, in the general formula (1), X is the residue of the dihydroxydiamines, and Y is the residue of the dicarboxylic acid component. be.

Examples of the dihydroxydiamines having the repeating structure include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis(3-amino-4-hydroxy phenyl)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 , 3-hexafluoropropane and the like. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is preferred.

Examples of the dicarboxylic acid component having the repeating structure include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, and 2,6-naphthalenedicarboxylic acid. , 4,4′-dicarboxybiphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl) Dicarboxylic acids having aromatic rings such as propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2 -Cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid and other aliphatic dicarboxylic acids. Among them, 4,4'-dicarboxydiphenyl ether is preferred.

In the above general formula (1), the tetravalent organic group represented by X may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and two hydroxy groups and two amino groups are at the ortho positions. Positioning on an aromatic ring is more preferred. The tetravalent aromatic group preferably has 6 to 30 carbon atoms, more preferably 6 to 24 carbon atoms. Specific examples of the tetravalent aromatic group include, but are not limited to, the groups shown below, and a known aromatic group that can be contained in the polybenzoxazole precursor is selected depending on the application. do it.

Among the above aromatic groups, the tetravalent aromatic group is preferably a group shown below.

In the above general formula (1), the divalent organic group represented by Y may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and the carbonyl in the above general formula (1) on the aromatic ring. It is more preferable that the The number of carbon atoms in the divalent aromatic group is preferably 6-30, more preferably 6-24. Specific examples of the divalent aromatic group include, but are not limited to, the groups shown below, and a known aromatic group contained in the polybenzoxazole precursor may be selected depending on the application. Just do it.

（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。）

(wherein 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 above aromatic groups, the divalent organic group is preferably a group shown below.

(A1) The polybenzoxazole precursor may contain two or more of the above polyhydroxyamide repeating structures. In addition, (A1) the polybenzoxazole precursor may contain a structure other than the repeating structure of polyhydroxyamide described above, and may contain, for example, a repeating structure of polyamic acid or a benzoxazole structure.

(A1) The number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 1,000 to 100,000, more preferably 5,000 to 50,000. Here, the number average molecular weight is a numerical value measured by gel permeation chromatography (GPC) and converted with standard polystyrene. The weight average molecular weight (Mw) of (A) the polybenzoxazole precursor is preferably 5,000 to 200,000, more preferably 10,000 to 100,000. Here, the weight average molecular weight is a numerical value measured by GPC and converted with standard polystyrene. Mw/Mn is preferably 1-5, more preferably 1-3.

(A1) Polybenzoxazole precursors may be used singly or in combination of two or more.

[(A2) polyimide precursor]
(A2) The method for synthesizing the polyimide precursor is not particularly limited, and may be synthesized by a known method. Examples thereof include resins obtained by reacting a carboxylic anhydride component with an amine component and/or an isocyanate component. The imidization may be performed by thermal imidization, chemical imidization, or a combination thereof.

Examples of the carboxylic anhydride component include tetracarboxylic anhydrides and tricarboxylic anhydrides, but are not limited to these acid anhydrides. Acid anhydride groups that react with amino groups and isocyanate groups and Any compound having a carboxyl group can be used, including its derivatives. Moreover, these carboxylic anhydride components may be used singly or in combination of two or more.

Examples of tetracarboxylic anhydrides include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-bis(trifluoromethyl)pyro mellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride anhydride, 2,2'-difluoro-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 5,5'-difluoro-3,3',4,4'-biphenyltetracarboxylic acid dianhydride anhydride, 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, 6,6′-bis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylic acid 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, 5,5′,6,6′-tetrakis(trifluoromethyl)-3,3′,4,4′ -biphenyltetracarboxylic 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′″-quaterphenyl Tetracarboxylic dianhydride, 3,3'''',4,4''''-kinked phenyl tetracarboxylic 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, 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 acid 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-tetramethylsiloxane dianhydride, 1,3-bis(3,4-dicarboxy Phenyl)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, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, anhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3′,4,4′-bicyclohexyltetracarboxylic 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 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 acid dianhydride, 3,3′-bis(trifluoromethyl)oxy-4,4′-diphthalic dianhydride, 5,5′-bis(trifluoromethyl)oxy-4,4′-diphthalic acid dianhydride anhydride, 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, 3, 3'-difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic dianhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic acid 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, 3,3',6,6'-tetrakis(trifluoro Methyl)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′-diphthal acid 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-perfluoropropylidene-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'-diphthalic 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-(trifluoro methyl)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 bis trimellitate 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) compound), 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-(hexadecamethylene)bis(trimellitate anhydride), 1,18-(octadecamethylene) ) bis(trimellitate anhydride) and the like.

Examples of tricarboxylic anhydrides include trimellitic anhydride and nuclear-hydrogenated trimellitic anhydride.

As the amine component, diamines such as aliphatic diamines and aromatic diamines and polyvalent amines such as aliphatic polyetheramines can be used, but the amines are not limited to these amines. Also, these amine components may be used alone or in combination.

Examples of the diamine include diamines having one benzene nucleus such as p-phenylenediamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, and 2,6-toluenediamine; ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ethers such as diaminodiphenyl ethers, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl , 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenylmethane , 3,3′,5,5′-tetramethyl-4,4′-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4′-diaminobenzanilide, 3,3′-dichlorobenzidine, 3, 3′-dimethylbenzidine (o-tolidine), 2,2′-dimethylbenzidine (m-tolidine), 3,3′-dimethoxybenzidine, 2,2′-dimethoxybenzidine, 3,3′-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4, 4′-dimethoxybenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4 -aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1, 1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-dicarboxy-4,4 Diamines with two benzene nuclei such as '-diaminodiphenylmethane, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene , 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy ) benzene, 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3′-diamino-4-(4-phenyl)phenoxybenzophenone, 3,3′-diamino-4,4′ -di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide) Benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)benzene, 1,3-bis[ Benzene such as 2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene three-nuclear diamines, 3,3′-bis(3-aminophenoxy)biphenyl, 3,3′-bis(4-aminophenoxy)biphenyl, 4,4′-bis(3-aminophenoxy)biphenyl, 4,4 '-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl ] ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenoxy)phenyl]ketone, bis[4-( 3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide , bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4- aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis [3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-( 3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis [4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2- bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1, Benzene nucleus four such as 1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane aromatic diamines such as diamines, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 ,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane and other aliphatic diamines. Examples of polyether amines include ethylene glycol and/or propylene glycol polyvalent amines. Amines having a carboxyl group can also be used as described below.

Examples of amines having a carboxyl group include diaminobenzoic acids such as 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid and 3,4-diaminobenzoic acid, and 3,5-bis(3-aminophenoxy)benzoic acid. , 3,5-bis(4-aminophenoxy)benzoic acid and other aminophenoxybenzoic acids, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-di Carboxybiphenyl compounds such as carboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, 4,4'-diamino-2,2',5,5'-tetracarboxybiphenyl, 3,3' -diamino-4,4'-dicarboxydiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,2-bis[3-amino-4-carboxyphenyl]propane, 2,2-bis [4-amino-3-carboxyphenyl]propane, 2,2-bis[3-amino-4-carboxyphenyl]hexafluoropropane, 4,4'-diamino-2,2',5,5'-tetracarboxy Carboxydiphenylalkanes such as carboxydiphenylmethane such as diphenylmethane, 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino Carboxydiphenyl ether compounds such as -2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxy Diphenylsulfone, 4,4'-diamino-3,3'-dicarboxydiphenylsulfone, 4,4'-diamino-2,2'-dicarboxydiphenylsulfone, 4,4'-diamino-2,2',5 ,5′-tetracarboxydiphenylsulfone and other diphenylsulfone compounds, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane and other bis[(carboxyphenyl)phenyl]alkane compounds, 2 , 2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone and other bis[(carboxyphenoxy)phenyl]sulfone compounds.

As the isocyanate component, diisocyanates such as aromatic diisocyanates and their isomers and polymers, aliphatic diisocyanates, alicyclic diisocyanates and their isomers, and other general-purpose diisocyanates can be used. It is not limited. Also, these isocyanate components may be used alone or in combination.

Examples of diisocyanates include aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, biphenyl diisocyanate, diphenylsulfone diisocyanate, and diphenyl ether diisocyanate, and isomers and polymers thereof, hexamethylene diisocyanate, and isophorone. Aliphatic diisocyanates such as diisocyanate, dicyclohexylmethane diisocyanate and xylylene diisocyanate, or alicyclic diisocyanates and isomers obtained by hydrogenating the above aromatic diisocyanates, or other general-purpose diisocyanates can be mentioned.

The polyimide precursor as component (A2) may have an amide bond. This may be an amide bond obtained by reacting an isocyanate and a carboxylic acid, or may be a bond formed by other reactions. It may also have other bonds consisting of addition and condensation.

(A2) In the synthesis of the polyimide precursor, which is the component, a known and commonly used alkali-soluble polymer, oligomer, or monomer having a carboxyl group and/or an acid anhydride group may be used. It may be a resin obtained by reacting the resins alone or in combination with the carboxylic anhydride component described above with the amine/isocyanate described above.

The polyimide precursor as component (A2) preferably has an acid value of 20 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g. When the acid value is 20 mgKOH/g or more, the solubility in alkali increases during the alkali development step, the developability becomes good, and the degree of cross-linking with the thermosetting component after light irradiation increases. Development contrast can be obtained. Further, when the acid value is 200 mgKOH/g or less, it is possible to suppress so-called heat fogging in the PEB process after light irradiation, which will be described later, and to increase the process margin.

Further, the molecular weight of the polyimide precursor which is the component (A2) is preferably a weight-average molecular weight of 1,000 to 100,000, more preferably 2,000 to 50,000, in consideration of developability and cured film properties. . When this molecular weight is 1,000 or more, sufficient development resistance and cured physical properties can be obtained after exposure and PEB. Moreover, when the molecular weight is 100,000 or less, the alkali solubility increases, and the developability can be improved.

[(B) Photosensitizer]
The photosensitive resin composition of the present invention contains (B) a photosensitive agent. (B) The photosensitive agent is not particularly limited, and a photoacid generator or a photobase generator can be used. A photoacid generator is a compound that generates an acid upon irradiation with light such as ultraviolet light or visible light. It is a compound that produces more than one basic substance. In the present invention, a photoacid generator can be suitably used as the (B) photosensitive agent.

Photoacid generators include naphthoquinonediazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters. , aromatic N-oxyimide sulfonates, aromatic sulfamides, benzoquinonediazosulfonic acid esters, and the like. Preferably, the photoacid generator is a dissolution inhibitor. Among them, a naphthoquinone diazide compound is preferable.

Specific examples of the naphthoquinonediazide compound include tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene naphthoquinonediazide adducts (for example, TS533, TS567, TS583, TS593 manufactured by Sambo Kagaku Kenkyusho Co., Ltd.). ), naphthoquinone diazide adducts of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sambo Kagaku Kenkyusho Co., Ltd.), and 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α ,α-dimethylbenzyl}phenol naphthoquinonediazide adducts (eg, TKF-428 and TKF-528 manufactured by Sambo Kagaku Kenkyusho Co., Ltd.) and the like can be used.

The photobase generator may be either an ionic photobase generator or a non-ionic photobase generator. It is advantageous, so it is preferable. Basic substances include, for example, secondary amines and tertiary amines.

Examples of ionic photobase generators include salts of aromatic component-containing carboxylic acids and tertiary amines, and ionic PBGs WPBG-082, WPBG-167, WPBG-168 and WPBG- manufactured by Wako Pure Chemical Industries, Ltd. 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, nitrobenzylcarbamate groups, and alkoxybenzyls. A compound having a substituent such as a carbamate group is included. As other photobase generators, Wako Pure Chemical Industries, Ltd. WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E)-1-[3-(2 -hydroxyphenyl)-2-propenoyl]piperidine), WPBG-140 (trade name: 1-(anthraquinon-2-yl)ethyl imidazolecarboxylate), WPBG-165 and the like can also be used.

(B) The photosensitive agent may be used alone or in combination of two or more. The blending amount of (B) the photosensitive agent is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the non-volatile component of the polybenzoxazole precursor or polyimide precursor A).

[(C) a cross-linking agent having an episulfide group]
The photosensitive resin composition of the present invention contains (C) a cross-linking agent having an episulfide group. (C) The cross-linking agent having an episulfide group is not particularly limited, and known ones can be used. In particular, it preferably has two or more episulfide groups in one molecule, and more preferably has two episulfide groups from the viewpoint of toughness (flexibility).

(C) The method for synthesizing the cross-linking agent having an episulfide group is not particularly limited. For example, it may be synthesized from an epoxy compound using a sulfurizing agent such as potassium thiocyanate or thiourea. Examples of the (C) cross-linking agent having an episulfide group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, Bisphenol type epoxy resins such as bisphenol Z type epoxy resins, bisphenol A novolac type epoxy resins, phenol novolac type epoxy resins, novolac type epoxy resins such as cresol novolak epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, aryl alkylene type epoxy resins Epoxy resin, tetraphenylolethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, glycidyl meta Acrylate copolymer epoxy resin, copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, epoxy-modified polybutadiene rubber derivative, CTBN-modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl -4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris(2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-Hydroxyethyl)isocyanurate, epoxy resins such as phenoxy resins, and episulfides obtained by converting the epoxy groups of epoxy resins having aromatic rings such as bisphenol-type epoxy resins into alicyclic hydrogenated epoxy resins into episulfide groups. resin.

(C) The structure of the cross-linking agent having an episulfide group is an episulfide compound having a cyclic skeleton such as an aromatic ring, a heterocyclic ring, or an alicyclic skeleton, or an episulfide compound having an acyclic skeleton such as a chain aliphatic. However, an episulfide compound having an alicyclic skeleton or a chain-like aliphatic is preferable, and an episulfide compound having an alicyclic skeleton is more preferable, because a cured product having more excellent toughness (flexibility) can be obtained. Examples of the alicyclic skeleton include cycloalkanes and cycloalkenes, among which cycloalkanes having a ring structure with 4 to 8 carbon atoms are preferred. Examples of the episulfide compound having an alicyclic skeleton include episulfide compounds obtained by replacing the epoxy group of the epoxy compound having an alicyclic skeleton with an episulfide group among the epoxy compounds listed above. Specifically, hydrogenated bisphenol type episulfide resin, hydrogenated novolac type episulfide resin, hydrogenated biphenyl type episulfide resin, hydrogenated biphenyl aralkyl type episulfide resin, hydrogenated arylalkylene type episulfide resin, hydrogenated tetraphenylolethane type episulfide resin. A resin etc. are mentioned. In the above, hydrogenation means adding hydrogen to reduce an aromatic ring (e.g., benzene ring) to form an aliphatic ring (e.g., cyclohexane ring). In the case of using the term "added bisphenol type", it is sufficient that it has a hydrogenated structure, i.e., a structure in which the aromatic ring is substituted with an aliphatic ring, and it is synthesized without hydrogenation. There may be. The episulfide compounds may be used singly or in combination of two or more.

(C) Examples of commercially available cross-linking agents having an episulfide group include TBIS-AHS and TBIS-FXPS manufactured by Taoka Chemical Co., Ltd., and Ogsol CS-500 manufactured by Osaka Gas Chemicals Co., Ltd.

(C) The episulfide equivalent of the crosslinking agent having an episulfide group is preferably 100 to 700 g/eq, more preferably 200 to 450 g/eq. By setting it as such a range, the hardened|cured material excellent in a softness|flexibility and adhesiveness can be obtained.

Further, the amount of (C) a cross-linking agent having an episulfide group is preferably 0.1 to 60 parts by mass with respect to 100 parts by mass of the non-volatile component of the (A) polybenzoxazole precursor or polyimide precursor, It is more preferably 1 to 25 parts by mass. By setting the amount in such a range, it is possible to obtain a cured product which exhibits sufficient adhesion to copper by low-temperature curing, and which is excellent in storage stability and flexibility.

[(D) a cross-linking agent other than the above (C)]
The photosensitive resin composition of the present invention preferably contains (D) a cross-linking agent other than (C). This (D) cross-linking agent other than the above (C) is preferably a compound that reacts with the phenolic hydroxyl group or carboxyl group of the polybenzoxazole precursor or polyimide precursor to form a crosslinked structure. Here, the functional group that reacts with the phenolic hydroxyl group or carboxyl group of the polybenzoxazole precursor or polyimide precursor includes a cyclic ether group such as an epoxy group, a cyclic thioether group other than an episulfide group, and a C1 group such as a methylol group. Examples include alcoholic hydroxyl groups in which hydroxyl groups are bonded to alkylene groups of 1 to 12, and among these, epoxy groups are preferred. By including a cross-linking agent containing an epoxy group, it is possible to further improve film physical properties such as adhesion to a metal interface such as on copper and elongation.

As the cross-linking agent containing an epoxy group, other structures are not particularly limited as long as it is a compound containing an epoxy group. bisphenol type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin, bisphenol A novolak type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. Resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, aryl alkylene type epoxy resins, tetraphenylolethane type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, phenoxy type epoxy resins, dicyclopentadiene type epoxy resins, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, glycidyl methacrylate copolymer epoxy resin, copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, epoxy-modified polybutadiene rubber derivative, CTBN-modified epoxy resin, trimethylol Propane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4′-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether , Tris (2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, epoxy resins such as phenoxy resins, and epoxy resins having aromatic rings such as bisphenol type epoxy resins. Any of cycloaliphatic epoxy resins and the like can be mentioned. The epoxy group-containing (D) crosslinking agent other than (C) may be used alone or in combination of two or more.

A cross-linking agent containing an epoxy group may or may not have a flexible chain in its structure. It is possible to improve the flexibility of the cured product of the photosensitive resin composition of the present invention without having a flexible chain. may not have

Examples of commercially available cross-linking agents containing epoxy groups include EPICLON-860, EXA4850-150, HP-4032D manufactured by DIC Corporation, YX-4000 manufactured by Mitsubishi Chemical Corporation, and TEPIC manufactured by Nissan Chemical Industries, Ltd. -S and the like.

The epoxy equivalent of the cross-linking agent containing epoxy groups is preferably 100 to 500 g/eq.

（式中、Ｒ^２１Ａ、Ｒ^２２Ａ、Ｒ^２３Ａ、Ｒ^２４Ａ、Ｒ^２５ＡおよびＲ^２６Ａはそれぞれ独立に炭素数１～３のアルキレン基であることが好ましい。Ｒ^２１Ｂ、Ｒ^２２Ｂ、Ｒ^２３Ｂ、Ｒ^２４Ｂ、Ｒ^２５ＢおよびＲ^２６Ｂはそれぞれ独立に水素原子、または、炭素数１～３のアルキル基であることが好ましい。） In addition, (D) the cross-linking agent other than (C) preferably has a triazine ring structure, and in the present invention, the elongation of the cured product can be further improved. The cross-linking agent having this triazine ring structure is not particularly limited, but is preferably a cross-linking agent represented by the following general formula (2).

(wherein R ^21A , R ^22A , R ^23A , R ^24A , R 25A and R ^26A are each independently preferably an alkylene group ^having 1 to 3 carbon atoms. R ^21B , R ^22B , R ^23B , R ^24B , R ^25B and R ^26B are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

In general formula (2), each of R ^21A , R ^22A , R ^23A , R ^24A , R ^25A and R ^26A is more preferably a methylene group. Further, R ^21B , R ^22B , R ^23B , R ^24B , R ^25B and R ^26B are more preferably each independently a methyl group or a hydrogen atom.

(D) The cross-linking agents other than (C) may be used singly or in combination of two or more. In addition, the amount of (D) a cross-linking agent other than (C) is preferably 0.01 to 125 parts by mass, more preferably 0 parts by mass with respect to 100 parts by mass of (A) polybenzoxazole precursor or polyimide precursor. .1 to 70 parts by mass. By setting the content within such a range, it is possible to obtain a cured product that exhibits sufficient adhesion to metals such as copper when cured at a low temperature and that has excellent flexibility.

(Plasticizer)
The photosensitive resin composition of the present invention preferably contains a plasticizer. The plasticizer is not particularly limited as long as it is a compound that improves plasticity. In the present invention, by blending a plasticizer, the cyclization reaction and imidization reaction of (A) the polybenzoxazole precursor or polyimide precursor are promoted, the low-temperature curability is further improved, and the chemical resistance is improved. An excellent cured product can be obtained. Originally, in low-temperature curing at about 220 ° C., the cyclization rate and imidization rate of (A) polybenzoxazole precursor or polyimide precursor are low, and low-temperature curability can be improved by blending a cross-linking agent. , the cyclization rate can be further reduced due to the reaction of the cross-linking agent with the functional groups that undergo cyclization and imidization reactions. Although the detailed mechanism is not clear, in the present invention, the plasticizing action of the plasticizer, that is, the aggregation action between polymer molecular chains is reduced, and the mobility and flexibility between molecular chains are improved, resulting in (A) It is considered that the thermal molecular motion of the polybenzoxazole precursor or polyimide precursor was improved, and the cyclization reaction and imidization reaction were promoted. Moreover, in the present invention, a cured product having excellent flexibility can be obtained by blending a plasticizer. Furthermore, in the present invention, the addition of a plasticizer improves the developability of the exposed area, so that better pattern formation can be achieved by photolithography. The plasticizers may be used singly or in combination of two or more. The plasticizer is preferably a plasticizer that does not cross-link with other ingredients in the composition. Moreover, it is preferable that the plasticizer does not have the function of generating thermal acid.

The plasticizer may be a plasticizer with self-polymerizable groups or a plasticizer without self-polymerizable groups. A (meth)acryloyl group, a vinyl group, an allyl group, etc. are mentioned as a self-polymerizable group. In the present specification, (meth)acryloyl group is a generic term for acryloyl group, methacryloyl group and mixtures thereof, and the same applies to other similar expressions.

The photosensitive resin composition of the present invention can further improve the flexibility of the cured product by containing a plasticizer having a self-polymerizable group. A bifunctional (meth)acrylic compound is preferred as the plasticizer having a self-polymerizable group. The bifunctional (meth)acrylic compound is preferably a compound that does not form a crosslinked structure with other components in the composition. Also, the bifunctional (meth)acrylic compound is preferably a compound that forms a linear structure by self-polymerization.

The bifunctional (meth)acrylic compound is not particularly limited as long as it is a compound having two (meth)acryloyl groups, and specific examples thereof include 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate. , 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate , dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, a diol diacrylate obtained by adding at least one of ethylene oxide and propylene oxide to neopentyl glycol, Glycol diacrylates such as caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A diglycidyl ether acrylic acid adduct , tricyclodecane dimethanol diacrylate, tris(2-hydroxyethyl)isocyanurate diol diacrylate obtained by adding at least one of ethylene oxide and propylene oxide to bisphenol A, hydrogenated dicyclopentadienyl Examples include diacrylates, diacrylates having a cyclic structure such as cyclohexyl diacrylate, isocyanuric acid diacrylates such as isocyanuric acid ethylene oxide-modified diacrylates, bifunctional polyester acrylates, and methacrylates corresponding to these.

Commercially available products include light acrylate 1,6HX-A, 1,9ND-A, 3EG-A, 4EG-A (manufactured by Kyoeisha Chemical Co., Ltd.), HDDA, 1,9-NDA, DPGDA, TPGDA (Daicel). Allnex (trade name), Viscoat #195, #230, #230D, #260, #310HP, #335HP, #700HV, #540 (trade name manufactured by Osaka Organic Chemical Industry Co., Ltd.), Aronix M-208, M -211B, M-215, M-220, M-225, M-240, M-270, M-6200, M-6250, M-6500 (trade names manufactured by Toagosei Co., Ltd.), NK Ester BPE-200, BPE-500, BPE-900 (trade name of Shin-Nakamura Chemical Co., Ltd.) and the like.

Among the bifunctional (meth)acrylic compounds, diol (such as ethylene oxide and propylene oxide) alkylene oxide adduct di(meth)acrylates and bifunctional polyester (meth)acrylates are preferred, and bifunctional polyesters (meth)acrylates are preferred. ) acrylates are more preferred.

As the di(meth)acrylate of the alkylene oxide adduct of the diol, specifically, one obtained by modifying the diol with alkylene oxide and then adding a (meth)acrylate to the terminal thereof is preferable, and a diol having an aromatic ring is more preferable. . Examples thereof include bisphenol A EO (ethylene oxide) adduct diacrylate and bisphenol A PO (propylene oxide) adduct diacrylate. Specific structures of di(meth)acrylates, which are alkylene oxide adducts of diols, are shown below, but are 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.)

Preferred bifunctional polyester (meth)acrylates are M-6200, M-6250 and M-6500 (trade names of Toagosei Co., Ltd.).

The amount of the plasticizer having a self-polymerizable group is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the non-volatile component of the polybenzoxazole precursor, and exhibits sufficient chemical resistance in low-temperature curing. can be done.

The photosensitive resin composition of the present invention can further improve the chemical resistance of the cured product by containing a plasticizer having no self-polymerizable group. Plasticizers having no self-polymerizable group include sulfonamide compounds such as N-butylbenzenesulfonamide and N-ethyl-p-toluenesulfonamide, dimethyl phthalate, diethyl phthalate, and di(2-ethylhexyl phthalate). ), maleate ester compounds such as di(2-ethylhexyl) maleate, trimellitate esters such as tris(2-ethylhexyl) trimellitate, dimethyl adipate, aliphatic dibasic compounds such as dibutyl adipate acid _{esters ,} phosphate esters such as _trimethyl phosphate, _{tris (} butoxyethyl) phosphate, (C6H5O) _2P (O) _OC6H4C ( _CH3 ) _2C6H4OP (O)(OC ₆ H ₅ ) _{2 ,} ether compounds such as aromatic condensed phosphates and crown ethers. Among them, sulfonamide compounds, phthalate compounds, and maleate compounds are preferred.

The sulfonamide compound is preferably a benzenesulfonamide compound represented by the following general formula (3).

（一般式（３）中、Ｒ^３１は、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基またはアミド基であり、Ｒ^３２は、水素原子または有機基であり、ｎは０～５の整数である。ｎが２以上の場合、Ｒ^３１はそれぞれ同じであっても異なっていてもよい。）

(In general formula (3), R ³¹ is an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group or an amido group; R ³² is a hydrogen atom or an organic group; n is 0; is an integer of up to 5. When n is 2 or more, each R ³¹ may be the same or different.)

The maleic acid ester compound is preferably a compound represented by the following general formula (4).

（一般式（４）中、Ｒ^４１およびＲ^４２は、それぞれ独立に水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基またはアミド基であり、Ｒ^４１とＲ^４２は、結合して環を形成してもよい。Ｒ^４３は水素原子または有機基であり、Ｒ^４４は、水素原子または有機基である。）

(In general formula (4), R ⁴¹ and R ⁴² are each independently a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or an amido group, and R ⁴¹ and R ⁴² are , may combine to form a ring, R ⁴³ is a hydrogen atom or an organic group, and R ⁴⁴ is a hydrogen atom or an organic group.)

In general formulas (3) and (4) and general formulas (5) and (6) described later, the organic group is a group containing a carbon atom. Examples of organic groups include alkyl groups having 1 to 12 carbon atoms, which may be linear or branched.

The amount of the plasticizer having no self-polymerizable group is preferably 1 to 50 parts by mass, more preferably 10 to 50 parts by mass, with respect to 100 parts by mass of the non-volatile component of the polybenzoxazole precursor. preferable. If the blending amount is 1 part by mass or more, the plasticizing effect is likely to appear, and if it is 50 parts by mass or less, the properties of the resulting cured film are not impaired.

In the present invention, it is preferable to use a plasticizer having a self-polymerizable group and a plasticizer having no self-polymerizable group in combination, and a cured product having excellent flexibility and chemical resistance can be obtained.

(Thermal acid generator)
The photosensitive resin composition of the present invention preferably contains a thermal acid generator. Although the detailed mechanism is not clear, when the thermal acid generator is blended in the present invention, it acts as a catalyst for the cyclization reaction and imidization reaction of (A) the polybenzoxazole precursor or the polyimide precursor, resulting in a low-temperature reaction. The cyclization reaction and imidization reaction are accelerated, and a cured product having better chemical resistance and heat resistance can be obtained. One of the thermal acid generators may be used alone, or two or more thereof may be used in combination.

The thermal acid generator is not particularly limited as long as it generates acid by heat. Examples of the acid generated include sulfonic acid, carboxylic acid, acetic acid, hydrochloric acid, nitric acid, bromic acid, and iodic acid. From the viewpoint of cyclization efficiency, strong acids are preferred, such as benzenesulfonic acid and p-toluene. Sulfonic acids such as arylsulfonic acids such as sulfonic acids, perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, camphorsulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid is preferred. These acids are blended into the photosensitive resin composition as thermal acid generators, for example, as salts such as onium salts or as compounds latent by covalent bonds such as imidosulfonates.

Specific examples of thermal acid generators include sulfonic acid ester compounds, sulfonimide compounds, sulfonium salts, 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, benzothiazolium salts, ammonium salts, phosphonium salts, sulfonate and the like. Among these, sulfonic acid ester compounds and sulfonates are preferred. The thermal acid generator is preferably a compound that generates a strong acid (acid dissociation constant pKa in water is 0 or less) by heat.

Sulfonic acid ester compounds include ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, 2-isopropoxyethyl methanesulfonate, cyclohexyl 4-methylbenzenesulfonate, (1R,2S,5R)- 5-methyl-2-(propan-2-yl)cyclohexyl 4-methylbenzenesulfonic acid, phenyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, 2-phenyl p-toluenesulfonate Ethyl, n-propyl p-toluenesulfonate, n-butyl p-toluenesulfonate, t-butyl p-toluenesulfonate, n-hexyl p-toluenesulfonate, n-heptyl p-toluenesulfonate, p-toluene n-octyl sulfonate, 2-methoxyethyl p-toluenesulfonate, propargyl p-toluenesulfonate, 3-butynyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, perfluorobutanesulfone Ethyl acid, methyl perfluorobutanesulfonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, trimethylsulfonium methylsulfate, tri-p-sulfonium trifluoromethane sulfonate, trimethylsulfonium trifluoromethanesulfonate, pyridinium-p-toluenesulfonate, ethyl perfluorooctanesulfonate, 1,4-butanesultone, 2,4-butanesultone, 1,3-propanesultone, phenol red, bromocresol green, bromocresol purple and the like.

As the sulfonic acid ester compound, a compound represented by the following general formula (5) is preferable.

（一般式（５）中、Ｒ^５１は、水素原子またはアルキル基を表し、Ｒ^５２は、水素原子または有機基を表す。）

(In general formula (5), R ⁵¹ represents a hydrogen atom or an alkyl group, and R ⁵² represents a hydrogen atom or an organic group.)

The alkyl group that R ⁵¹ can take may be linear or branched. Also, the number of carbon atoms is preferably 1-10, more preferably 1-6.

The organic group that R ⁵² can take may be linear or branched, and may have a cyclic structure. The number of carbon atoms is preferably 1-16, more preferably 1-11.

As the sulfonate, a compound represented by the following general formula (6) is preferable.

（一般式（６）中、Ｒ^６１は水素原子またはアルキル基を表し、Ｒ^６２、Ｒ^６３はそれぞれ独立に水素原子または有機基を表す。Ｒ^６２とＲ^６３は結合して環を形成してもよい。）

(In general formula (6), R ⁶¹ represents a hydrogen atom or an alkyl group, and R ⁶² and R ⁶³ each independently represent a hydrogen atom or an organic group. R ⁶² and R ⁶³ combine to form a ring is also good.)

The alkyl group that R ⁶¹ can take may be linear or branched. The number of carbon atoms is preferably 1-10, more preferably 1-6.

The organic group that R ⁶² and R ⁶³ can take may be linear or branched.

Among thermal acid generators, those that generate acid at 120 to 220° C. are preferred. In the case of a thermal acid generator that generates acid at 120° C. or higher, the reaction does not easily proceed during prebaking, and development residue is less likely to occur. Further, thermal acid generators that generate acid at 150 to 220° C. are preferred. The generation of acid can be confirmed at the weight loss temperature by TG-DTA.

The amount of the thermal acid generator is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the non-volatile component of the polybenzoxazole precursor. More preferably, it is 1 to 3 parts by mass.

(Sensitizer, adhesion agent, other ingredients)
In the photosensitive resin composition of the present invention, a known sensitizer for further improving photosensitivity, a silane coupling agent for improving adhesion to a substrate, etc., within a range that does not impair the effects of the present invention. A known adhesion agent or the like can also be blended. In addition, various organic or inorganic low-molecular-weight or high-molecular-weight compounds may be added to the photosensitive resin composition of the present invention in order to impart processing properties and various functionalities. For example, surfactants, leveling agents, fine particles and the like can be used. Fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon, and layered silicate. In addition, various colorants, fibers, and the like may be added to the photosensitive resin composition of the present invention.

(solvent)
The solvent used in the photosensitive resin composition of the present invention includes (A) a polybenzoxazole precursor or polyimide precursor, (B) a photosensitive agent, and (C) a cross-linking agent having an episulfide group, and other components. It is not particularly limited as long as it dissolves. Examples include N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, 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 according to the coating film thickness and viscosity. For example, it can be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of (A) polybenzoxazole precursor or polyimide precursor.

The photosensitive resin composition of the present invention is preferably of positive type.

[Dry film]
The dry film of the present invention has a resin layer obtained by applying the photosensitive resin composition of the present invention to a film (for example, a support (carrier) film) and then drying the film. This resin layer is used by laminating so as to be in contact with the substrate.

The dry film of the present invention is formed by uniformly applying the photosensitive resin composition of the present invention to the film by an appropriate method such as a blade coater, lip coater, comma coater, film coater, etc., and drying to form the above resin layer. and preferably by laminating a film (so-called protective (cover) film) thereon. The protective film and the support film may be made of the same film material or may be made of different films.

In the dry film of the present invention, any film materials known for use in dry films can be used as film materials for the support film and the protective film.
As the support film, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used.
As the protective film, a polyethylene film, a polypropylene film, or the like can be used, but a film having a weaker adhesion to the resin layer than the support film is preferred.

The film 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.

[Cured product]
The cured product of the present invention is obtained by curing the above-described photosensitive resin composition of the present invention through predetermined steps. The pattern film, which is the cured product, may be produced by a known and commonly used production method. For example, in the case of (B) a positive photosensitive resin composition containing a photoacid generator as a photosensitive agent, the following steps manufacture.

First, as step 1, a coating film is obtained by coating and drying a photosensitive resin composition on a substrate, or by transferring a resin layer from a dry film onto the substrate. The method for applying the photosensitive resin composition onto the substrate includes methods conventionally used for applying photosensitive resin compositions, such as spin coaters, bar coaters, blade coaters, curtain coaters, screen printers, and the like. a method of applying with a spray coater, a method of spraying with a spray coater, an inkjet method, or the like. As a method for drying the coating film, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used. Moreover, it is desirable to dry the coating film under conditions that do not cause cyclization of the polybenzoxazole precursor in the photosensitive resin composition. Specifically, natural drying, air drying, or heat drying can be performed at 70 to 140° C. for 1 to 30 minutes. Drying is preferably carried out on a hot plate for 1-20 minutes. Vacuum drying is also possible, and in this case, it can be carried out at room temperature for 20 minutes to 1 hour.
The substrate on which the coating film of the photosensitive resin composition is formed is not particularly limited, and can be widely applied to semiconductor substrates such as silicon wafers, wiring substrates, various resins, metals, and the like.

Next, as step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light used has a wavelength capable of activating the photoacid generator as the photosensitizer (B). Specifically, the exposure light preferably has a maximum wavelength in the range of 350 to 440 nm. As described above, photosensitivity can be adjusted by appropriately blending a sensitizer. As an exposure device, a contact aligner, mirror projection, stepper, laser direct exposure device, or the like can be used.

Next, as step 3, the coating film is treated with a developer. As a result, the exposed portions in the coating film can be removed to form a pattern film of the photosensitive resin composition of the present invention.

As a method used for development, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like. Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia; organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine; tetramethylammonium hydroxide and tetrabutylammonium hydroxide. and aqueous solutions of quaternary ammonium salts such as If necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol or isopropyl alcohol or a surfactant may be added. After that, the coating film is washed with a rinsing liquid as necessary to obtain a pattern film. Distilled water, methanol, ethanol, isopropyl alcohol and the like can be used alone or in combination as the rinse liquid. Moreover, you may use the said solvent as a developer.

Thereafter, in step 4, the pattern film is heated to obtain a cured coating film (cured product). This heating cyclizes the polybenzoxazole precursor to obtain polybenzoxazole. The heating temperature is appropriately set so that the pattern film of the photosensitive resin composition can be cured. For example, heating is performed at 150° C. or more and less than 350° C. for about 5 to 120 minutes in an inert gas. A more preferable range of heating temperature is 180 to 250°C. Since the photosensitive resin composition of the present invention contains (C) a naphthalene-type epoxy compound, cyclization is promoted, and the heating temperature can be less than 250°C, and further 220°C or less. Heating is performed by using, for example, a hot plate, an oven, or a temperature-programmable oven. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

Applications of the photosensitive resin composition of the present invention are not particularly limited. 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, or the like. In addition, 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. Furthermore, as a material for forming electronic parts, it can be used as a sealing material or a layer forming material for a printed wiring board, an interlayer insulating film, a wiring coating film, and the like. Furthermore, as a material for forming optical parts, it can be used as an optical material or a layer forming material for holograms, optical waveguides, optical circuits, optical circuit parts, antireflection films, and the like. Furthermore, as building materials, it can be used for paints, coating agents, and the like.

The photosensitive resin composition of the present invention is mainly used as a pattern forming material, and the pattern film formed by it functions as a component that imparts heat resistance and insulation as a permanent film made of, for example, polybenzoxazole. Therefore, it is particularly suitable for surface protective films of semiconductor devices, display devices and light-emitting devices, interlayer insulating films, insulating films for rewiring, protective films for flip chip devices, protective films for devices having a bump structure, and interlayer insulation for multilayer circuits. It can be suitably used as films, insulating materials for passive components, protective films for printed wiring boards such as solder resists and coverlay films, liquid crystal alignment films, and the like. In particular, the photosensitive resin composition of the present invention is suitable as a material for forming laminated layers, such as an interlayer insulating film and a rewiring insulating film, because the cured product thereof has excellent chemical resistance.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples. In the following description, "parts" and "%" are based on mass unless otherwise specified.

(Synthesis of polybenzoxazole precursor (A1))
40.3 g (0.11 mol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet. ) and 1500 g of N-methyl-2-pyrrolidone were added and dissolved completely. While maintaining the temperature of the solution at 0 to 20°C, 35.4 g (0.12 mmol) of diphenyl ether-4,4'-dicarboxylic acid dichloride was added. After that, the temperature of the reaction system was returned to room temperature and stirred for 6 hours. After that, 1.8 g (0.1 mol) of pure water was added, and the mixture was further reacted at 40° C. for 1 hour. After completion of the reaction, the reaction solution was added dropwise to 2000 g of ion-exchanged water. The precipitate was collected by filtration, washed, and dried in vacuum to obtain a polybenzoxazole precursor (A1). The polystyrene-equivalent weight-average molecular weight and number-average molecular weight were 32,000 and 12,200, respectively, measured by GPC. "Polybenzoxazole precursor" is hereinafter also referred to as "PBO precursor".

(Synthesis of polyimide precursor (A2))
Into a 150 mL screw vial was added a stir bar, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) 5.54 g (13.50 mmol), 4,4′-diaminodiphenyl ether (ODA) 3. .30 g (16.48 mmol) was added and completely dissolved in 43 mL of γ-butyrolactone under an environment of 20° C. and a relative humidity of 20%. After that, 8.38 g (27.01 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) was gradually added and reacted at room temperature for 16 hours. Then, 0.889 g (6.00 mmol) of phthalic anhydride was added and reacted at room temperature for 8 hours to obtain a γ-butyrolactone solution (A3) of a polyimide precursor. The polystyrene-equivalent weight-average molecular weight and number-average molecular weight were 23,900 and 8,500, respectively, measured by GPC. "Polyimide precursor" is hereinafter also referred to as "PI precursor".

(Examples 1-8 and Comparative Examples 1-7)
Each component shown in Table 1 was blended in the ratio shown in Table 1 with respect to 100 parts by mass of the polybenzoxazole precursor (A1) or polyimide precursor (A2) synthesized above, and Examples 1 and 3 to 8 were used. , For Comparative Examples 1 and 2 to 7, polybenzoxazole precursor (A1), for Example 2 and Comparative Example 2, 30 parts by weight of γ-butyrolactone with respect to 100 parts by weight of polyimide precursor (A2) was added and completely dissolved to obtain a varnish of a photosensitive resin composition. In addition, all compounding amounts in Table 1 are compounding amounts in terms of non-volatile components.

The photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 7 thus obtained were evaluated for elongation, adhesion and sensitivity. These results are also shown in Table 1.

(elongation rate evaluation)
The varnish was applied onto a silicon wafer using a spin coater and dried at 110° C. for 3 minutes to obtain a dry film of the photosensitive resin composition. After that, in an inert gas oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.), in a nitrogen atmosphere, it was heated at 110°C for 10 minutes, held at 150°C for 30 minutes, and further heated to 220°C to 60°C. After heating for 1 minute, a cured film having a thickness of 45 μm was obtained.
The cured film thus obtained was peeled off under the conditions of 121° C., 100% RH, and 60 minutes using a PCT device, and then fractured by a tensile test using EZ-SX manufactured by Shimadzu Corporation. Elongation was measured. The evaluation criteria were as follows.
A: Breaking elongation was 20% or more.
◯: Breaking elongation was 19 to 10%.
Δ: Breaking elongation was 9 to 1%.
x: A self-supporting film was not obtained.

(Adhesion evaluation)
Copper was sputtered onto a silicon wafer to prepare a substrate (hereinafter referred to as a copper sputtered substrate) having a metal material layer formed thereon with a thickness of 200 to 500 nm. The varnish was applied on a copper sputtered substrate using a spin coater and then dried at 110° C. for 3 minutes using a hot plate to obtain a dry film (12 μm) of the photosensitive resin composition. Next, in an inert gas oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.), in a nitrogen atmosphere, the mixture was heated at 110°C for 10 minutes, held at 150°C for 30 minutes, and further heated to 220°C. After heating for 60 minutes, a cured film having a thickness of 10 μm was obtained.
Using a single-edged blade, the cured film thus obtained was cut in a grid pattern of 100 squares at intervals of 1 mm, and subjected to PCT treatment for 100 hours under saturation conditions of 121° C. and 2 atm using a PCT apparatus. , the number of squares peeled out of 100 squares was measured by peeling off with "Cellotape" (registered trademark). The evaluation criteria were as follows.
A: The number of peeled pieces was 0.
◯: The number of peeled pieces was 1.
Δ: The number of peeled pieces was 2 to 9.
x: The number of peeled pieces was 10 or more.

(Sensitivity evaluation)
For Example 1, Examples 3-8, Comparative Examples 1 and 3-7, the varnish was applied onto a copper sputtered substrate using a spin coater and dried on a hot plate at 110° C. for 3 minutes. , A dry film of a photosensitive resin composition with a thickness of 12 μm was irradiated with i-rays at an exposure amount of 0 to 1000 mJ / cm ² , and then developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 80 seconds. and rinsed with water to obtain a positive pattern.
Further, for Example 2 and Comparative Example 2, the varnish was applied on a copper sputtered silicon substrate using a spin coater and dried on a hot plate at 110° C. for 3 minutes to obtain a photosensitive resin composition having a thickness of 9 μm. The dried film was irradiated with i-rays 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 50 seconds and rinsed with water to obtain a positive pattern.
For the positive pattern thus obtained, the film thickness at each exposure dose was measured using an optical film thickness meter, and the exposure dose at which development was possible without scum was taken as the sensitivity. In addition, those that could not be developed at 1000 mJ/cm ² were evaluated as x.

（＊５）：田岡化学工業（株）製ＴＢＩＳ-ＡＨＳ

（＊６）：田岡化学工業（株）製ＴＢＩＳ-ＦＸＰＳ

（＊７）：ＤＩＣ（株）製ＥＰＩＣＬＯＮ－８６０
（＊８）：（株）三和ケミカル製ニカラックＭＷ３９０
（＊９）：（株）東亞合成製アロニックスＭ６２５０
（＊１０）：（株）三和ケミカル製ニカラックＭＸ－２７０
（＊１１）：本州化学工業（株）製ＴＭＬ－ＢＰＡＦ－ＭＦ
（＊１２）：信越化学工業（株）製ＫＢＭ－５７３ (*1): the aforementioned polybenzoxazole precursor (A1)
(*2): the aforementioned polyimide precursor (A2)
(*3): TKF-428 manufactured by Sambo Kagaku Kenkyusho Co., Ltd. (B1 below)
(*4): TKF-525 manufactured by Sambo Kagaku Kenkyusho Co., Ltd. (B2 below)

(*5): TBIS-AHS manufactured by Taoka Chemical Co., Ltd.

(*6): TBIS-FXPS manufactured by Taoka Chemical Co., Ltd.

(*7): EPICLON-860 manufactured by DIC Corporation
(*8): Nikalac MW390 manufactured by Sanwa Chemical Co., Ltd.
(*9): Aronix M6250 manufactured by Toagosei Co., Ltd.
(*10): Nikalac MX-270 manufactured by Sanwa Chemical Co., Ltd.
(*11): TML-BPAF-MF manufactured by Honshu Chemical Industry Co., Ltd.
(*12): KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

From the results shown in the above table, the photosensitive resin composition of the present invention can be cured even at a low temperature of about 220 ° C. while using a polybenzoxazole precursor or a polyimide precursor as the main component of the resin composition, and It can be seen that a resin composition having excellent adhesion to conductor circuits such as copper can be obtained, and that the resin composition has excellent film physical properties such as elongation.

Claims (6)

(A) a polybenzoxazole precursor or polyimide precursor, (B) a photosensitive agent, and (C) a cross-linking agent having an episulfide group ,
(C) the cross-linking agent having an episulfide group has two or more episulfide groups in one molecule,
The amount of the (C) cross-linking agent having an episulfide group is 0.1 to 60 parts by mass with respect to 100 parts by mass of the non-volatile component of the (A) polybenzoxazole precursor or polyimide precursor,
A photosensitive resin composition which is used by being laminated on a conductor circuit . 2. The photosensitive resin composition according to claim 1, further comprising (D) a cross-linking agent other than (C). 3. The photosensitive resin composition according to claim 2 , wherein the (D) cross-linking agent other than the (C) contains an epoxy group. A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to any one of claims 1 to 3 on a film and drying the composition. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 3 or the resin layer of the dry film according to claim 4 . An electronic component comprising the cured product according to claim 5 .