KR20190007387A - Photosensitive resin composition, dry film, cured product, semiconductor element, printed wiring board, and electronic component - Google Patents

Abstract

The present invention provides a photosensitive resin composition having excellent low-temperature curing properties, sensitivity, development contrast and electroless copper plating solution resistance; a dry film having a resin layer obtained from the composition; a cured product of a resin layer of the composition or the dry film; and a semiconductor element, a printed wiring board and an electronic component which have the cured product. The photosensitive resin composition, comprising a polyamic acid ester and a photo base generator comprises a polyamic acid ester which is a complete ester having a repeating structure represented by general formula (A) as the polyamic acid ester, and comprises at least any one of a compound represented by general formula (B), an oxime ester compound and the like as the photo base generator.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a dry film, a cured product, a semiconductor device, a printed circuit board, and an electronic component,

The present invention relates to a photosensitive resin composition, a dry film, a cured product, a semiconductor element, a printed wiring board and an electronic component.

Polyimide has been widely applied to various fields based on excellent properties such as high insulation, heat resistance and high mechanical strength. For example, application to a coating film of a semiconductor device, a flexible printed wiring board, and a heat-resisting insulating interlayer material is proceeding not only in the aerospace field first applied.

Polyimide has a problem in that it is insufficient in thermoplasticity and solubility in an organic solvent and is difficult to process. As a result, polyimide can be obtained by forming a desired pattern film by irradiating a photosensitive resin composition obtained by blending a polyimide precursor such as polyamide acid or polyamide acid ester with a photoreactive compound, after irradiating actinic light, And imidization is carried out by ring closure (for example, Patent Documents 1 and 2).

For example, Patent Document 1 discloses a negative tone composition comprising a polyamide acid ester and a photosensitive base generator. Further, Patent Document 2 describes a base resin composition having a specific structure, and a photosensitive resin composition comprising a base generator and a polymer precursor having a specific structure.

Japanese Patent Application Laid-Open No. 5-197148 Japanese Patent No. 5598031

However, the negative tone composition disclosed in Patent Document 1 is intended to provide a photosensitive polyimide to be used for producing an integrated circuit, and a combination of a polyamide acid ester and various photosensitive base generators such as benzyl carbamate However, depending on the kind of the combination of the polyamide acid ester and the base generator, the sensitivity and the dissolution contrast are lowered. For example, in the composition described in the example of Patent Document 1, it is possible to imidize even at a low temperature, but irradiation with a large amount of active rays is required to form a good pattern, and sensitivity is insufficient.

The photosensitive resin composition described in Patent Document 2 is one that has excellent sensitivity and excellent dissolution contrast regardless of the kind of polymer precursor. In practice, however, depending on the kind of the combination of the polymer precursor and the base generator The sensitivity and the dissolution contrast decrease. For example, in the composition described in the example of Patent Document 2, since the polyamide acid is used as the polymer precursor, imidization proceeds even at the unexposed portion and the solubility in the developer is too high, so that the development contrast is small Loses. Also, the electroless copper plating solution resistance was not sufficient.

BACKGROUND ART [0002] In recent years, there have been various electronic components, such as electronic components and semiconductor devices, which can not withstand a high-temperature process (for example, 350 DEG C) for achieving sufficient imidization. Further, circuit wirings and the like are made more precise, and the yield of circuit wiring or the like due to a high-temperature process is also lowered.

In order to improve the production efficiency, there is a tendency to tackify a base material such as a silicon wafer used for semiconductor manufacturing. When a polyimide film is used as a surface protective film in a semiconductor device, stress is generated at the interface due to the difference in heat shrinkage ratio between the substrate and the polyimide film when the temperature is returned from room temperature to the room temperature. This stress acts in a direction to bend the base material. The larger the diameter of the substrate is, the larger the bending amount of the substrate is. If the amount of bending is excessively large, a problem in the manufacturing process may occur, or cracks may occur in the polyimide film. Therefore, it is preferable to set the heating temperature for obtaining the polyimide film as low as possible.

Therefore, an object of the present invention is to provide a photosensitive resin composition which is excellent in low temperature curability, sensitivity, development contrast and electroless copper plating solution resistance, 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 a cured product thereof, a printed wiring board and an electronic component.

The inventors of the present invention have conducted intensive studies in view of the above, and as a result, found that the above problems can be solved by combining a polyamide acid ester which is a complete ester with a photo-base generator having a specific structure.

That is, the photosensitive resin composition of the present invention is a photosensitive resin composition containing a polyamide acid ester and a photo base generating agent,

Wherein the polyamide acid ester comprises a polyamide acid ester which is a complete ester having a repeating structure represented by the following formula (A)

(Wherein _{A A} is a tetravalent organic group, Y _A is a divalent organic group, R _A1 and R _A2 are each independently a monovalent organic group and may be the same or different from each other, and n is an integer of 1 or more to be.)

As the photobase generator, a quaternary ammonium salt represented by the following general formula (B) or (C), a compound represented by any one of the following general formulas (D) to (H) At least any one of a quaternary ammonium salt, an oxime ester compound, and a compound containing a carbamoyloxyimino group represented by the following general formula (I), which generates a tertiary amine containing at least one atom and an oxygen atom, And the like.

(In the general formula (B), R _B1 and R _B2 are each independently a hydrogen atom or an organic group and may be the same or different.) R _B1 and R _B2 may combine with each other to form a cyclic structure, may include a combination. However, R _B1 and R _B2, at least one of which is an organic group. R _B3 and R _B4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol A nitro group, a nitro group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or an organic group and may be the same or different from each other, R _B5 and R _B6, R _B7 and R _B8 are playing each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol, a nitro group, alcohol pinot group, sulfo group, sulfonate group, phosphorus A phosphino group, a phosphonate group, an amino group , And ammonia coming or an organic group, may be the same or different. R _B5, R _B6, R _B7 and R _B8 are, and optionally, combining two or more of them to form a cyclic structure, comprising a bond of the heteroatom R _B9 is a hydrogen atom or an organic group.)

(C), Z _C is a hydrogen atom or a nitro group, R _C1 , R _C2 , R _C3 and R _C4 are each independently an alkyl group having 1 to 8 carbon atoms, R _C5 is a hydrogen atom or a C1- R _C1 and R _C2 , and R _C3 and R _C4 may form a ring structure with each other.)

( _Wherein R _D1 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, An alkoxy group represented by -OR _D2 , an amino group represented by -NR _D3 R _D4 , an acyl group represented by R _D5 CO-, an acyloxy group represented by R _D6 COO-, an alkylthio group represented by -SR _D7 , R _D2 , R _D5 , R _D6 and R _D7 are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, R _D3 and R _{D4 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms An alkyl group or an aryl group having 6 to 12 carbon atoms, n is an integer of 0 to 7, and Y _D ⁺ is a quaternary ammonia group represented by any of the following formulas (D1) to (D4)

Q _D is a nitrogen atom or a methine group (-CH-), t and u is 2 or 3, w is an integer from 0 to 2, A _D is a hydrogen atom, a hydroxyl group or a halogen atom, R _D8 to _D10 R is C 1 -C An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, R _D1 and CH ₂ -Y _D ⁺ X _D ^- may be bonded to the same benzene ring, do. X _D ^- is a counter anion selected from a borate anion, a phenolate anion and a carboxylate anion.)

( _Wherein R _E1 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, An alkoxy group represented by -OR _E2 , an amino group represented by -NR _E3 R _E4 , an acyl group represented by R _E5 CO-, an acyloxy group represented by R _E6 COO-, an alkylthio group represented by -SR _E7 , or R _E2 , R _E5 , R _E6 and R _E7 are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R _E3 and R _{E4 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms An alkyl group or an aryl group having 6 to 12 carbon atoms, m is an integer of 0 to 9, Y _E ⁺ is a quaternary ammonia group represented by any one of the following formulas (E1) to (E4)

Q _E is a nitrogen atom or a methine group (-CH-), t and u is 2 or 3, w is an integer from 0 to 2, A _E is a hydrogen atom, a hydroxyl group or a halogen atom, R _E8 to _E10 R is C 1 -C An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, R _E1 and CH ₂ -Y _E ⁺ X _E ^- may be bonded to the same benzene ring, do. X _E ^- is a counter anion selected from a borate anion, a phenolate anion and a carboxylate anion.)

(Wherein R _F1 , R _F2 , R _F4 and R _F5 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R _F3 and Ar _F are each independently an aryl group having 6 to 14 carbon atoms Of these, the aryl group may have a substituent. The substituent may be an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, , An alkoxy group represented by -OR _F6 , an amino group represented by -NR _F7 R _F8 , an acyl group represented by R _F9 CO-, an acyloxy group represented by R _F10 COO-, a group represented by -SR _F11 R _F6 , R _F9 , R _F10 and R _F11 each independently represent an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 8 carbon atoms, an aryl group, R and R _{F7 F8} of the circles 12 are each independently hydrogen, , An aryl group or an alkyl group having 6 to 12 carbon atoms having 1 to 8. _F Y ⁺ is a quaternary ammonium come represented by any of the following formula (F1) or (F2).

(In the general formula (G), R _G1 to R _G5 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms A nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by -OR _G6 , an amino group represented by -NR _G7 R _G8 , an acyl group represented by R _G9 CO-, an acyloxy group represented by R _G10 COO-, alkylthio group represented by SR _G11 or an arylthio group. alkyl group, alkenyl group, alkynyl group and aryl group and may have a substituent, and the substituent is the same as above R _G1 to R _G5, these substituents are a cyclic structure, R _G6 , R _G9 , R _G10 and R _G11 each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R _G7 and R _G8 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms the alkyl group or an aryl group of 6 to 12 carbon atoms. Ar group _G Tan The number of 6 to 14, an aryl group, the aryl being optionally of these groups have a substituent, the substituent is the same as above R R _G1 to _G5, these substituents can take the aryl group and ring structure.

Y _G ⁺ is a quaternary ammonia group represented by any of the following formulas (G1) to (G4)

Q _G is a nitrogen atom or a methine group (-CH-), t and u are 2 or 3, w is an integer of 0 to 2, A _G is a hydrogen atom, a hydroxyl group or a halogen atom, and R _G12 to R _G14 , An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms.

(Formula (H) of, Ar _H1 is an aryl group having 6 to 12 carbon atoms, the aromatic rings at least one is the oxygen atom, a sulfur atom of a hydrogen atom, a group is substituted with a substituent containing a nitrogen atom; Ar _H2 carbon atoms An aryl group having 6 to 14 carbon atoms, and a part of the hydrogen atoms in the aryl group is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, , An alkoxy group represented by -OR _H11 , an amino group represented by -NR _H12 R _H13 , an acyl group represented by R _H14 CO-, an acyloxy group represented by R _H15 COO-, a group represented by -SR _H16 R _H1 and R _H2 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, Ar _H1 , R _H1, R _H2 are coupled to each other to form a ring structure May be; R _H3 is an alkyl group having a carbon number of 1 to 18; n is in the case of an integer being, where n = 1 to 4 is four, Ar _H1 is an aryl group having 6 to 12 carbon atoms, and; R _H11, R _H14, R _H15 and _R16 each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms; R _H12 and R _H13 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms; Y _H ⁺ is a quaternary ammonia group represented by any one of the following general formulas (H1) and (H2);

In formula (H1), R _H4 to R _H5 each independently represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which may be bonded to each other to form a ring structure; Q _H is a methylene group (-CH ₂ -) m or a group represented by the general formula (H3); m is an integer of 2 or 3; In the formula (H2), R _H6 to R _H8 each independently represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, In the formula (H3), R _H9 to R _H10 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and may be bonded to each other to form a ring structure.

(Compound (I) of the, _I Y is - (CH ₂₎ m- group, an alicyclic group, an arylene group, - (CH ₂₎ m- group and combines the alicyclic group, - (CH ₂₎ m- group and arylene M is an integer of 2 to 7, and R _I1 is an aromatic group or a substituted alkyl group.

The photosensitive resin composition of the present invention preferably contains the compound represented by the general formula (B) as the photobase generator.

The photosensitive resin composition of the present invention preferably contains a compound represented by the following formula as the photobase generator.

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

The cured product of the present invention is obtained by curing the resin composition of the photosensitive resin composition or the dry film.

The semiconductor device of the present invention is characterized by having the cured product.

The printed wiring board of the present invention is characterized by having the cured product.

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

According to the present invention, there is provided a photosensitive resin composition excellent in low temperature curability, sensitivity, development contrast, and electroless copper plating solution resistance, 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, A semiconductor device having a cured product, a printed wiring board and an electronic component can be provided.

1 is a chart of ¹ H-NMR (in DMSO-d ₆ ) of polyamic acid ester 1 synthesized in Synthesis Example 1. The abscissa represents chemical shift (ppm), and the ordinate represents relative intensity.

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

[Polyamide acid ester]

The photosensitive resin composition of the present invention includes a polyamide acid ester which is a complete ester having a repeating structure represented by the following general formula (A). In the present invention, " completely esterified " means that the polyamide acid ester does not substantially contain an amide acid moiety. That is, the polyamide acid ester which is a complete ester is an ester having an amide acid ester moiety in the repeating structure of the polyamide acid ester of more than 95% (preferably 98% or more, and most preferably 100%), (A so-called partial esterified polyamic acid ester) containing both an amide acid moiety and an amide acid ester moiety as described in Japanese Patent No. 4687938. When the proportion of the amide acid ester is 95% or less, the carboxyl group of the polyamic acid reacts with the base generated from the photobase generator, making it difficult to obtain low-temperature curability and excellent development contrast.

(Wherein _{A A} is a tetravalent organic group, Y _A is a divalent organic group, R _A1 and R _A2 are each independently a monovalent organic group and may be the same or different from each other, and n is an integer of 1 or more to be.)

Here, the organic group is a group containing a carbon atom.

The number average molecular weight of the polyamide acid ester is preferably from 1,000 to 1,000,000, more preferably from 3,000 to 500,000, and still more preferably from 5,000 to 100,000.

In the technical field, a polyimide precursor having an acryloyl group containing, for example, a carbon-carbon double bond is polymerized in the R _A1 and / or R _A2 in the general formula (A) using a radical polymerization initiator Although there are technical ideas, the present invention is different from such technical ideas. From the viewpoint of distinguishing it from the invention of these different technical ideas, it is preferable that R _A1 and R _A2 in the general formula (A) are organic groups not containing a radical polymerizable unsaturated bond, particularly an organic group not containing a carbon carbon double bond Do. Examples of an organic group containing a radical polymerizable unsaturated bond include groups having a vinyl structure such as an alkenyl group, an alkynyl group and a (meth) acryloyl group.

Examples of organic groups that R _A1 and R _A2 may take in the general formula (A) include hydrocarbon groups such as alkyl groups and aryl groups, and groups having heteroatoms. Each of the hydrocarbon group and the group having a hetero atom may be a group having an alicyclic skeleton such as a cycloalkyl group or the like and may not have an alicyclic skeleton. As the group having a hetero atom, a group having an ether structure or an ester structure may be used. From the viewpoint of reducing film loss, the number of carbon atoms of organic _groups that R _A1 and R _A2 can take is preferably 10 or less, more preferably 1 to 4.

In the general formula (A), R _A1 and R _A2 are preferably alkyl groups from the viewpoint of solubility in the synthesis of the polyamide acid ester. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

In the general formula (A), X _A and Y _A are selected from an aromatic group, preferably an aromatic group or an aliphatic group having 6 to 32 carbon atoms, preferably an aliphatic group having 4 to 20 carbon atoms, . X _A and Y _A, it is preferred if the substituents X _A and Y _A are included in the dianhydride and diamine or a diisocyanate, which will be described later used in the production of the polyamic acid ester. When X _A is an aromatic ring and an aliphatic condensed ring, the aromatic anhydride group becomes an aromatic group when bonded to the aromatic ring and becomes an aliphatic group when the acid anhydride group is bonded to the aliphatic ring. The same applies to Y _A , and when the amino group is bonded to the aromatic ring, it is an aromatic group, and when the amino group is bonded to the aliphatic ring, it is an aliphatic group.

In the formula (A), the number of carbon atoms of the tetravalent aromatic group that X _A can take is preferably from 6 to 30, more preferably from 6 to 24. The tetravalent aromatic group is preferably a group having a skeleton including benzene rings such as a benzene skeleton, a biphenyl skeleton, and a biphenyl skeleton. Specific examples of the above-mentioned tetravalent aromatic group include, but are not limited to, the following groups, and known aromatic groups that may be contained in the polyamic acid ester may be selected depending on the use.

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

In the general formula (A), the bivalent aromatic group that Y _A can take is more preferably bonded to the nitrogen atom in the general formula (A) on the aromatic ring. The number of carbon atoms of the bivalent aromatic group is preferably 6 to 30, more preferably 6 to 24. The bivalent aromatic group is preferably a group having a skeleton including a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a biphenyl skeleton. Specific examples of the bivalent aromatic group include, but are not limited to, the following groups, and known aromatic groups contained in the polyamic acid ester may be selected depending on the use.

(Wherein, A represents a single _{bond, -CH 2 -, -O-, -CO-} , -S-, -SO 2 -, -NHCO-, -C (CF 3) 2 -, -C (CH 3) ₂ -. ≪ / RTI >

When a cured product pattern of the photosensitive resin composition is formed by short-wavelength light, an aliphatic group may be used as X _A and Y _A from the viewpoint of the absorption characteristics of the polymer. Further, for example, when a fluorine-containing group is used as X _A and Y _A , the lowering of the light absorption or the dielectric property can be improved.

In the present invention, it is important that the structure of the polyamide acid ester can be selected depending on the application.

In addition, although the 4-valent of X _A represents only a valence to be bonded to an acid, X _A may have a substituent. Likewise, although the valence of Y _A represents only a valence bond with a bivalent amine, it may have an additional substituent.

The polyamide acid ester can be synthesized by a conventionally known method. For example, an acid anhydride such as 3,3'-benzophenonetetracarboxylic dianhydride is reacted with an alcohol such as ethanol to obtain a half ester. This half ester is converted into diester diacid chloride using thionyl chloride. The polyamide acid ester can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.

The polyamic acid ester may be obtained by reacting the diisocyanate with a diisocyanate such as sophorone to a half ester obtained by reacting the acid anhydride with an alcohol. Further, the polyamide acid ester can be synthesized more easily by the synthesis method using diisocyanate than the above-mentioned synthesis method using diamine.

The acid anhydride which can be used for the synthesis of the polyamide acid ester is preferably a carboxylic acid dianhydride, more preferably a tetracarboxylic acid dianhydride. Examples thereof include those represented by the following general formula.

(Wherein X _A is as defined in general formula (A)).

By using an acid anhydride of the above formula as the starting material for synthesizing the polyamide acid ester, the X _A group in the repeating unit in the polyamic acid ester of the above formula can be easily introduced.

Specific examples of the acid dianhydride applicable to the synthesis of the polyamide acid ester include ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic acid dianhydride Aliphatic tetracarboxylic acid dianhydrides such as water and cyclopentanetetracarboxylic acid dianhydride; Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid dianhydride, 2,3 ', 3 , 4'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride , 2,3 ', 3,4'-biphenyltetracarboxylic dianhydride, 2,2', 6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-di Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis , 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3- 1,1,3,3,3-hexapple Benzoyl benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis Phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride , Bis {4- [3- (1,2-dicarboxy) phenoxy} phenyl} ketone dianhydride, 4 {4- [4- (1,2-dicarboxy) , Bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4'-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis (4 - [(3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4 Phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [ 4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride , Bis [4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} , 3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,1,1,3,3,3-hexafluoro-2,2- Bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride , 1,2,3,4-benzenetetracarboxylic acid dianhydride, 1,2,4,5-benzenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, pyridine tetracarboxylic acid dianhydride, sulfonyldiphthalic anhydride, m-terphenyl -3,3 ', 4,4'-tetracarboxylic acid An aromatic tetracarboxylic acid dianhydride such as an anhydride, p-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro- Dioxo-3-furanyl) naphtho [l, 2-c] furan-l, 3-dione.

Of the above-mentioned acid dianhydrides, tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2 ', 6,6'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Water, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,2,4,5-benzenetetracarboxylic acid dianhydride Water, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) .

In the synthesis of the polyamide acid ester, the acid anhydrides may be used singly or in combination of two or more.

Use of an acid dianhydride to which fluorine is introduced as an acid dianhydride or an acid dianhydride having a backbone skeleton to be used in combination enables adjustment of physical properties such as solubility and thermal expansion ratio without significantly impairing transparency. Further, it is also possible to use an imitative acid dianhydride such as pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 1,4,5,8-naphthalenetetracarboxylic dianhydride , The coefficient of linear thermal expansion of the finally obtained polyimide tends to be small. However, since the improvement of transparency tends to be inhibited, the polyimide may be used in combination with attention to the copolymerization ratio.

Examples of the diamine that can be used for obtaining the polyamide acid ester include diamines represented by the following general formula. However, the following is only an example, and any known one may be used as long as it is not contrary to the object of the present invention.

(Wherein Y _A is as defined in formula (A)).

Examples of the diamine include diamino isophorone (3-aminomethyl-3,5,5-trimethylcyclohexylamine), toluenediamine, 4,4'-methylenediphenyldiamine, hexamethylenediamine, 4,4'- Aniline, and the like.

Examples of the diisocyanate that can be used to obtain the polyamide acid ester include diisocyanates represented by the following general formula. However, the following is only an example, and any known one may be used as long as it is not contrary to the object of the present invention.

(Wherein Y _A is as defined in formula (A)).

Examples of the diisocyanate include diisocyanates such as sphloron (ITI), toluene diisocyanate (TDI), 4,4'-methylene diphenyl (MDI) diisocyanate, 2,2-bis (4-isocyanatophenyl) Hexafluoropropane, hexamethylene diisocyanate (HMDI), and the like.

The polyamide acid esters may be used singly or in combination of two or more. The blending amount of the polyamide acid ester is preferably 50 to 95 mass%, more preferably 60 to 95 mass%, based on the entire solid content of the composition excluding the solvent.

The photosensitive resin composition of the present invention may contain a polyimide precursor other than the polyamide acid ester within a range not to impair the effect of the present invention.

[Photobase generator]

The photosensitive resin composition of the present invention is a photosensitive resin composition comprising a quaternary ammonium salt represented by the general formula (B) or (C), a quaternary ammonium salt represented by the general formulas (D) to (H) A quaternary ammonium salt, an oxime ester compound and a compound containing a carbamoyloxyimino group represented by the general formula (I) which generate a tertiary amine containing at least one nitrogen atom and at least one oxygen atom in the molecule, And one species. Among the above-mentioned photo-base generators, it is preferable to include at least one of a coumaric acid type compound represented by the general formula (B), a quaternary ammonium salt represented by the general formula (D) and an oxime ester compound, From the viewpoint of contrast, it is more preferable to contain a compound of the coumaric acid type represented by the general formula (B), and it is particularly preferable to include the following compound (B-1).

These photobase generators may be used alone or in combination of two or more. The blending amount of the photobase generator is preferably 1 to 20 mass%, more preferably 5 to 15 mass%, based on the whole solid content of the composition excluding the solvent.

[Compounds of the coumaric acid type represented by the general formula (B)

(In the general formula (B), R _B1 and R _B2 are each independently a hydrogen atom or an organic group and may be the same or different.) R _B1 and R _B2 may combine with each other to form a cyclic structure, may include a combination. However, R _B1 and R _B2, at least one of which is an organic group. R _B3 and R _B4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol A nitro group, a nitro group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or an organic group and may be the same or different from each other, R _B5 and R _B6, R _B7 and R _B8 are playing each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol, a nitro group, alcohol pinot group, sulfo group, sulfonate group, phosphorus A phosphino group, a phosphonate group, an amino group , And ammonia coming or an organic group, may be the same or different. R _B5, R _B6, R _B7 and R _B8 are, and optionally, combining two or more of them to form a cyclic structure, comprising a bond of the heteroatom R _B9 is a hydrogen atom or an organic group.)

In the general formula (B), R _B1 and R _B2 are preferably alkyl groups from the viewpoint of the basicity of the generated bases, or form an alkylene chain having a cyclic structure bonded to each other, and the cyclic alkylene chains bonded to each other It is most preferable to form it. The number of carbon atoms constituting the alkyl group or alkylene chain is preferably 1 to 20, more preferably 1 to 8.

In the general formula (B), R _B3 and R _B4 are preferably a hydrogen atom or an alkyl group, and most preferably all hydrogen atoms. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms.

In the general formula (B), R _B5 , R _B6 , R _B7 and R _B8 are preferably a hydrogen atom, an alkyl group or an alkoxy group, and most preferably all hydrogen atoms. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms.

In the general formula (B), R _B9 is preferably a hydrogen atom or an organic group which is a protecting group which can be deprotected by irradiation with electromagnetic waves and / or heating, and most preferably a hydrogen atom.

As the coumaric acid type compound represented by the general formula (B), it is preferable to be the following compound B-1.

By combining the polyamide acid ester and the compound (B-1) in the photosensitive resin composition of the present invention, the exposure sensitivity can be improved and the exposure amount can be further suppressed, and the development contrast is further improved, .

The photosensitive resin composition of the present invention has high sensitivity and can be imidized at a low temperature by the combination of the polyamide acid ester esterified with an alkyl group having 1 to 4 carbon atoms and the compound (B-1) , It is suitable for use in forming a cured product pattern on a substrate having low heat resistance. In addition, since it is excellent in resistance to electroless copper plating solution, it is suitable for use in producing a copper wiring on the cured product, for example, in the use of an insulating material for a rewiring layer.

[Compound represented by the general formula (C)

(C), Z _C is a hydrogen atom or a nitro group, R _C1 , R _C2 , R _C3 and R _C4 are each independently an alkyl group having 1 to 8 carbon atoms, R _C5 is a hydrogen atom or a C1- R _C1 and R _C2 , and R _C3 and R _C4 may form a ring structure with each other.)

The photosensitive resin composition of the present invention preferably contains the following compound (C-1) as a compound represented by the general formula (C).

[Quaternary ammonium salt represented by the general formula (D)] [

( _Wherein R _D1 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, An alkoxy group represented by -OR _D2 , an amino group represented by -NR _D3 R _D4 , an acyl group represented by R _D5 CO-, an acyloxy group represented by R _D6 COO-, an alkylthio group represented by -SR _D7 , R _D2 , R _D5 , R _D6 and R _D7 are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, R _D3 and R _{D4 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms An alkyl group or an aryl group having 6 to 12 carbon atoms, n is an integer of 0 to 7, and Y _D ⁺ is a quaternary ammonia group represented by any of the following formulas (D1) to (D4)

Q _D is a nitrogen atom or a methine group (-CH-), t and u is 2 or 3, w is an integer from 0 to 2, A _D is a hydrogen atom, a hydroxyl group or a halogen atom, R _D8 to _D10 R is C 1 -C An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, R _D1 and CH ₂ -Y _D ⁺ X _D ^- may be bonded to the same benzene ring, do. X _D ^- is a counter anion selected from a borate anion, a phenolate anion and a carboxylate anion.)

The photosensitive resin composition of the present invention preferably contains at least one of the following compounds (D-1) to (D-9) as the compound represented by the general formula (D)

[Quaternary ammonium salt represented by the general formula (E)] [

( _Wherein R _E1 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, An alkoxy group represented by -OR _E2 , an amino group represented by -NR _E3 R _E4 , an acyl group represented by R _E5 CO-, an acyloxy group represented by R _E6 COO-, an alkylthio group represented by -SR _E7 , or R _E2 , R _E5 , R _E6 and R _E7 are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R _E3 and R _{E4 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms An alkyl group or an aryl group having 6 to 12 carbon atoms, m is an integer of 0 to 9, Y _E ⁺ is a quaternary ammonia group represented by any one of the following formulas (E1) to (E4)

Q _E is a nitrogen atom or a methine group (-CH-), t and u is 2 or 3, w is an integer from 0 to 2, A _E is a hydrogen atom, a hydroxyl group or a halogen atom, R _E8 to _E10 R is C 1 -C An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, R _E1 and CH ₂ -Y _E ⁺ X _E ^- may be bonded to the same benzene ring, do. X _E ^- is a counter anion selected from a borate anion, a phenolate anion and a carboxylate anion.)

The photosensitive resin composition of the present invention preferably contains at least one of the following compounds (E-1) to (E-11) as a compound represented by the general formula (E)

[Quaternary ammonium salt of carboxylic acid type represented by general formula (F)] [

(Wherein R _F1 , R _F2 , R _F4 and R _F5 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R _F3 and Ar _F are each independently an aryl group having 6 to 14 carbon atoms Of these, the aryl group may have a substituent. The substituent may be an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, , An alkoxy group represented by -OR _F6 , an amino group represented by -NR _F7 R _F8 , an acyl group represented by R _F9 CO-, an acyloxy group represented by R _F10 COO-, a group represented by -SR _F11 R _F6 , R _F9 , R _F10 and R _F11 each independently represent an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 8 carbon atoms, an aryl group, R and R _{F7 F8} of the circles 12 are each independently hydrogen, , An aryl group or an alkyl group having 6 to 12 carbon atoms having 1 to 8. _F Y ⁺ is a quaternary ammonium come represented by any of the following formula (F1) or (F2).

The photosensitive resin composition of the present invention preferably contains the following compound (F-1) as a compound represented by the general formula (F).

[The quaternary ammonium salt of the sulfonic acid type represented by the general formula (G)] [

(In the general formula (G), R _G1 to R _G5 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms A nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by -OR _G6 , an amino group represented by -NR _G7 R _G8 , an acyl group represented by R _G9 CO-, an acyloxy group represented by R _G10 COO-, alkylthio group represented by SR _G11 or an arylthio group. alkyl group, alkenyl group, alkynyl group and aryl group and may have a substituent, and the substituent is the same as above R _G1 to R _G5, these substituents are a cyclic structure, R _G6 , R _G9 , R _G10 and R _G11 each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R _G7 and R _G8 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms Or an aryl group having 6 to 12 carbon atoms.

Ar _G groups are an aryl group having 6 to 14, and optionally of which the aryl group has a substituent, the substituent is the same as above R R _G1 to _G5, these substituents can take the aryl group and ring structure. Y _G ⁺ is a quaternary ammonia group represented by any of the following formulas (G1) to (G4)

Q _G is a nitrogen atom or a methine group (-CH-), t and u are 2 or 3, w is an integer of 0 to 2, A _G is a hydrogen atom, a hydroxyl group or a halogen atom, and R _G12 to R _G14 , An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms.

The photosensitive resin composition of the present invention preferably contains at least one of the following compounds (G-1) and (G-2) as the compound represented by the general formula (G)

[Boron-containing quaternary ammonium salt represented by the general formula (H)] [

(Formula (H) of, Ar _H1 is an aryl group having 6 to 12 carbon atoms, the aromatic rings at least one is the oxygen atom, a sulfur atom of a hydrogen atom, a group is substituted with a substituent containing a nitrogen atom; Ar _H2 carbon atoms An aryl group having 6 to 14 carbon atoms and a part of the hydrogen atoms in the aryl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, A hydroxyl group, a cyano group, an alkoxy group represented by -OR _H11 , an amino group represented by -NR _H12 R _H13 , an acyl group represented by R _H14 CO-, an acyloxy group represented by R _H15 COO-, or -SR _H16 R _H1 and R _H2 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, Ar _H1 , R _H1 , R _H2 are coupled to each other to form a ring structure May be; R _H3 is an alkyl group having a carbon number of 1 to 18; n is in the case of an integer being, where n = 1 to 4 is four, Ar _H1 is an aryl group having 6 to 12 carbon atoms, and; R _H11, R _H14, R _H15 and _R16 each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms; R _H12 and R _H13 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms; Y _H ⁺ is a quaternary ammonia group represented by any one of the following general formulas (H1) and (H2);

In formula (H1), R _H4 to R _H5 each independently represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which may be bonded to each other to form a ring structure; Q _H is a methylene group (-CH ₂ -) m or a group represented by the general formula (H3); m is an integer of 2 or 3; In the formula (H2), R _H6 to R _H8 each independently represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, In the formula (H3), R _H9 to R _H10 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and may be bonded to each other to form a ring structure.

The cation structure of the photo-base generator represented by the general formula (H) is preferably a cation structure represented by the following formulas (H _CA -1) to (H _CA -12), for example.

Examples of the anion structure of the photo-base generator represented by the general formula (H) include those represented by the following formulas (H _A -1) to (H _A -11).

The photo-base generator represented by the general formula (H) can be produced by a known method. An example is shown by the following chemical reaction formula. A substituents (Ar _H1, R _H1 and R _H2) leaving group (Z _H) is substituted with a compound (E _H) and, quaternary come ammonia (Y _H ⁺⁾ having a corresponding to the photobase generator for the purpose of The corresponding amine (Y _H ) is reacted directly or in a solvent to obtain a cation intermediate in which Z _H ^- is a counter anion. This cationic intermediate and a borate metal salt having a substituent (Ar _H2 , R _H3 ) corresponding to a photobase generator which is produced by a separately known method are subjected to anion exchange in an organic solvent or water to obtain a target photoinitiator Can be obtained.

_{(Wherein, Ar H1, Ar H2, R} H1, R H2, R H3, Y H + is the same as in the general formula (H), Z is a leaving group and, Z _H ^- is a counter anion that is generated by the Tally , Y _H is an amine equivalent to quaternary ammonium, and M _H ⁺ is a metal cation.)

Amine (Y _H) Examples of the amine represented by the formula (H _Y -1) {1,8- diazabicyclo [5.4.0] -7-undecene (DBU; "DBU" is manufactured by whether or birth Pro . of a registered trademark)}, the formula _(Y H -2) amine {1,5-diazabicyclo [4,3,0] represented by - -5-nonene (DBN)}, the formula _(Y H -3) (Each symbol is the same as that of the formula (H2). For example, cyclic amines such as 1-azabicyclo [2.2.2] octane, 3-hydroxy-1-azabicyclo [2.2.2] octane and 1,4- diazabicyclo [2.2.2] (Triphenylamine, tri-p-tolylamine and diphenyl p-toluenesulfonate) such as amine (tributylamine, trioctylamine, octyldimethylamine and diisopropylethylamine), trialkenylamine -tolyl-chain amines such as amine, etc.} and the formula _(Y H -4) amine {formula _(Y H -4) of, _H17 R is an alkyl group having 1 to 18 alkyl group, R is a _H18 having 1 to 18 carbon atoms represented by a, An alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms and may be bonded to each other to form a cyclic structure. For example, 1-methylimidazol-3-yl, 1,2-dimethylimidazole Yl, 1-methyl-2-ethylimidazol-3-yl) yl}.

Examples of the leaving group (Z _H ) include a halogen atom (such as a chlorine atom and a bromine atom), a sulfonyloxy group (trifluoromethylsulfonyloxy, 4-methylphenylsulfonyloxy and methylsulfonyloxy), and acyloxy And trifluoromethylcarbonyloxy), and the like. Of these, halogen atoms and sulfonyloxy groups are preferable from the standpoint of ease of production and the like.

In the photosensitive resin composition of the present invention, it is preferable that the quaternary ammonium salt of a boron represented by the general formula (H) contains a quaternary ammonium quaternary ammonium salt having a thioxanthone skeleton.

[Quaternary ammonium salts which generate tertiary amines containing at least one nitrogen atom and at least one oxygen atom in the molecule upon irradiation with actinic rays]

The quaternary ammonium salt is represented by the following structural formula and is a photobase generator that generates a tertiary amine by irradiation with an actinic ray. Wherein Z is an aromatic group having a skeleton such as benzene, benzofuran, naphthalene, anthracene, phenanthrene, and pyrene.

(A _J ⁺ represents a quaternary ammonium group, B _J ^- represents a counter ion, and Z _J represents an aromatic group.)

The photosensitive resin composition of the present invention preferably contains the following compound (J-1) as the quaternary ammonium salt.

[Oxime ester compound]

The oxime ester compound is a compound having the following partial structure (K).

Examples of the oxime ester compound include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], a compound represented by the following formula (K1), 2- (acetyloxyiminoethyl) 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) And an oxime ester compound having a carbazole skeleton such as a compound represented by the formula (K2).

In the general formula (K2), R _K21 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. R _K22 and R _K24 each independently represent a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. R _K23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group When the number of carbon atoms of the alkyl group constituting the alkoxyl group is 2 or more, the alkyl group may be substituted with at least one hydroxyl group, or may have at least one oxygen atom in the middle of the alkyl chain) or a phenoxycarb group. The phenyl group and the benzoyl group may each have a substituent such as an alkyl group on a benzene ring.

Such oxime ester compounds are preferable because they can increase the sensitivity of the photosensitive resin composition of the present invention for exposure for direct imaging, for example, and are excellent in resolution. Further, the oxime ester compound may be a dimer.

The oxime ester compound of the dimer is more preferably a compound represented by the following general formula (K3).

In the general formula (K3), R _K33 represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, or a naphthyl group. R _K31 and R _K32 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a benzofuryl group or a benzothienyl group.

Ar _K3 represents a single bond or an alkylene group having 1 to 10 carbon atoms, a vinylene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furylene group, A di-yl group, a 4,4'-stilbene-diyl group, and a 4,2'-styrene-diyl group.

and n represents an integer of 0 to 1.

As the alkyl group represented by R _K33 , an alkyl group having 1 to 17 carbon atoms is preferable. As the alkoxy group represented by R _K33 , an alkoxy group having 1 to 8 carbon atoms is preferable. The phenyl group represented by R _K33 may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (Preferably having 1 to 8 carbon atoms in the alkyl group) or a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group). Examples of R may have a substituent and naphthyl groups represented by _K33, the substituent, a phenyl group represented by R include groups wherein the substituents and _K33 machangajiin which may have.

The alkyl group represented by R _K31 and R _K32 is preferably an alkyl group having 1 to 17 carbon atoms. The alkoxy group represented by R _K31 and R _K32 is preferably an alkoxy group having 1 to 8 carbon atoms. The phenyl group represented by R _K31 and R _K32 may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkyl An amino group (preferably having 1 to 8 carbon atoms in the alkyl group) or a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group). _K31 and R is naphthyl which may have a substituent group represented by R _K32, can be given as the substituent, R _K31, and _K32 R groups and the substituents in a phenyl group may have machangajiin represented by.

In the general formula (K3), R _K31 and R _K32 are each independently a methyl group or an ethyl group, R _K32 is methyl or phenyl, Ar _K3 is a single bond, a phenylene group, a naphthylene group or a thienylene group, n Is preferably 0.

As the compound represented by the general formula (K3), the following compound (K3-1) is more preferable.

Examples of the oxime ester compound include CGI-325, Irgacure OXE01 (1.2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)]) commercially available from BASF Japan, (ADEKA), 1- (2-methylbenzoyl) -9H-carbazol-3-yl] N-1919, NCI-831, TR-PBG-304, manufactured by Nippon Kagaku Kogyo Kogyo Co., Ltd., and TOE-04-A3 manufactured by Cangzhou Kyo Ryoku Denshi Shinji Co.,

In the photosensitive resin composition of the present invention, it is preferable to include an oxime ester compound having a carbazole skeleton as an oxime ester compound.

As oxime ester compounds, compounds represented by the following general formulas (K4) to (K8) may also be used.

(Formula (K4) of, _K4 X is - (CH ₂₎ n- group, an alicyclic group, an arylene group, - (CH ₂₎ n- group and combines the alicyclic group, - (CH ₂₎ n- group and arylene N is an integer of 2 to 7, and R _K41 is an aromatic group or a substituted alkyl group.

As the oxime ester compound represented by the general formula (K4), it is preferable to include at least any one of the following compounds (K4-1) to (K4-7).

(And the general formula (K5) wherein the organic group D _K5 from 1 to 4-valent organic group, R _K51 is a divalent organic group, R _K52, R _K53 each represent a monovalent organic group, R _K52, R at least one of _K53 M is 0 or 1, and when m is 0, the organic group of D _K5 is not an aromatic group, n is an integer of 1 to 4, and a plurality of R _K51 , R _K52 and R _K53 are each an aromatic group They may be the same or different.)

As the oxime ester compound represented by the general formula (K5), it is preferable to include the following compound (K5-1).

(In the general formula (K6), X _K6 is a tetravalent organic group and n is an integer of 0 to 3. R _K61 is an aromatic group or an alkyl group having 1 or more carbon atoms.)

As the oxime ester compound represented by the general formula (K6), it is preferable to include at least any one of the following compounds (K6-1) and (K6-2).

(Formula (K7) of the, X _K7 is an aryl group having a connecting group Y _K7, n represents an integer of 0 to 3. R _K71 is an aromatic group or an alkyl group having a connecting group Y _K7, Y _K7 is a divalent organic It is a device.)

As the oxime ester compound represented by the general formula (K7), it is preferable to include at least any one of the following compounds (K7-1) to (K7-4).

(In the general formula (K8), X _K8 is a divalent organic group and n is an integer of 1 to 5. R _K81 represents an aromatic group or an alkyl group having 1 or more carbon atoms.)

As the oxime ester compound represented by the general formula (K8), it is preferable to include at least any one of the following compounds (K8-1) and (K8-2). In the following compounds (K8-1) and (K8-2), n represents an integer of 1 to 5.

[Compound containing a carbamoyloxyimino group represented by the general formula (I)

(Compound (I) of the, _I Y is - (CH ₂₎ m- group, an alicyclic group, an arylene group, - (CH ₂₎ m- group and combines the alicyclic group, - (CH ₂₎ m- group and arylene M is an integer of 2 to 7, and R _I1 is an aromatic group or a substituted alkyl group.

The photosensitive resin composition of the present invention may contain a photobase generator other than the photobase generator within a range not to impair the effect of the present invention.

Hereinafter, other components that can be incorporated into the photosensitive resin composition of the present invention will be described.

The solvent usable in the photosensitive resin composition of the present invention is not particularly limited so long as it dissolves polyamide acid ester, photo base generating agent and other additives. Examples include N, N'-dimethylformamide, N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone, N, N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, ? -butyrolactone,? -butyrolactone,? -acetyl-? -butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazolidone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, Phosphoramid, pyridine,? -Butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited. For example, it may be used in a range of 50 to 9000 parts by mass based on 100 parts by mass of the polyamic acid ester, depending on the coating film thickness and viscosity.

In the photosensitive resin composition of the present invention, a sensitizer may be further added to improve the light sensitivity. (4'-diethylaminobenzal) cyclopentane, 2,6-bis (4 ', 4'-diethylaminobenzal) cyclopentane, Diethylaminobenzal) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) -4-methylcyclohexanone, 2,6-bis (Diethylamino) chalcone, p-dimethylamino cinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- ( (p-dimethylaminophenylvinylene) isonaphthotriazole, 1,3-bis (p-dimethylaminophenylvinylene) benzothiazole, 2- (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl- Dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylamino N-phenylethanolamine, N-phenyldiethanolamine, Np-diethylaminocoumarin, N-phenylethanolamine, N- N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto (P-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like can be given. From the viewpoint of sensitivity, 4- (1-methylethyl) -9H-thioxanthen-9- Of thioacids are preferably used. These may be used alone or in combination of 2 to 5 kinds. The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the polyamide acid ester.

Further, in the photosensitive resin composition of the present invention, an adhesion assisting agent may be added in order to improve the adhesiveness with a substrate. As the adhesion assisting agent, known adhesives can be used so long as they do not contradict the object of the present invention. For example, there may be mentioned γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane , N- [3- (triethoxysilyl) propyl] phthalamidic acid, reaction product of benzophenonetetracarboxylic dianhydride and (triethoxysilyl) propylamine. The blending amount of the adhesion assisting agent is preferably in the range of 0.5 to 10 parts by mass based on 100 parts by mass of the polyamide acid ester.

A base proliferator may be added to the photosensitive resin composition of the present invention. When forming a thick film pattern, the decomposition ratio of the photo-nucleating agent to the same extent from the surface to the bottom is required. In this case, addition of a base proliferating agent is preferable in order to improve the sensitivity. For example, it is possible to use a base proliferator disclosed in Japanese Patent Application Laid-Open Nos. 2000-237776 and 2006-282657.

In the photosensitive resin composition of the present invention, another photosensitive component that generates an acid by light may be added within a range that does not significantly impair the cured film properties. When a compound having one or more ethylenic unsaturated bonds in the photosensitive resin composition of the present invention is added, a photo-radical generator may be added.

In order to impart processing characteristics and various functions to the photosensitive resin composition of the present invention, various organic or inorganic low molecular weight or high molecular weight compounds may be added. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon and layered silicate, and they may be porous or hollow. Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers and fibers.

The dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film (support). The dry film can be formed by diluting the photosensitive resin composition of the present invention with the organic solvent and adjusting the viscosity to an appropriate viscosity, and then applying the resulting solution to a substrate such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, , A spray coater or the like to a uniform thickness on the carrier film. Thereafter, the applied photosensitive resin composition is dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to form a resin layer. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in the film thickness after drying.

As the carrier film, a plastic film is used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film after the resin layer containing the photosensitive resin composition of the present invention is formed on the carrier film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper and the like can be used. The cover film may be one having a smaller adhesion force between the resin layer and the carrier film when peeling off the cover film.

Next, a method for producing a patterned film as a cured product using the photosensitive resin composition of the present invention will be described. As described in the following production method, the photosensitive resin composition of the present invention can be suitably used as a negative-type photosensitive resin composition.

First, as a step 1, a photosensitive resin composition is coated on a substrate and dried to obtain a coated film. Examples of the method of applying the photosensitive resin composition on a substrate include a method which has been conventionally used for coating a photosensitive resin composition, such as a method of applying by a spin coater, a bar coater, a blade coater, a curtain coater or a screen printing machine, A spray coating method, an ink jet method, or the like can be used. As the drying method of the coating film, a method of drying by heating with a air dryer, an oven or a hot plate, or vacuum drying may be used. The drying of the coating film is preferably performed under the condition that the imidization of the polyamic acid ester in the photosensitive resin composition does not occur. Concretely, natural drying, air drying, or heat drying can be carried out at 20 to 140 ° C for 1 minute to 1 hour. Preferably, drying is performed on a hot plate for 1 to 20 minutes. Vacuum drying is also possible. In this case, the reaction can be carried out at room temperature for 1 minute to 1 hour.

The substrate is not particularly limited and can be widely applied to a silicon wafer, a wiring substrate, various resin, metal, and a passivation protective film of a semiconductor device.

In addition, since imidization can be performed at a low temperature, it is widely applicable to members and materials which are not suitable for high-temperature processing such as substrates for printed wiring boards.

Subsequently, as the step 2, the coating film is directly exposed through a photomask having a pattern or directly. The exposure light beam has a wavelength capable of generating a base by activating the photo-base generator. As described above, the photosensitivity can be adjusted by appropriately using a sensitizer. As the exposure apparatus, a contact aligner, a mirror projection, a stepper, a laser direct exposure apparatus, or the like can be used.

Subsequently, as step 3, heating is carried out to promote imidization of the coating film by the base generated in the coating film. As a result, the base generated in the exposed portion in Step 2 becomes a catalyst, and the polyamide acid ester is partially imidized. The heating time and heating temperature are appropriately changed depending on the polyamic acid ester to be used, the thickness of the coating film, and the type of the photoacid generator. Typically, in the case of a coating film thickness of about 10 mu m, it is about 2 to 10 minutes at 110 to 200 DEG C. [ If the heating temperature is too low, partial imidization can not be efficiently achieved. On the other hand, if the heating temperature is excessively high, the imidization of the unexposed portion progresses and the difference in solubility between the exposed portion and the unexposed portion becomes small, which may cause trouble in pattern formation.

Subsequently, in Step 4, the coating film is treated with a developer. Thereby, a pattern film containing a polyamic acid ester and a partially imidized polyimide can be formed on a substrate.

As the method for development, any known method can be selected from a known photoresist development method, for example, a rotary spray method, a paddle method, a dipping method accompanied by an 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, and organic amines such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide Of quaternary ammonium salts and the like. If necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol or the like or a surfactant can be used as an aqueous solution to which an appropriate amount is added. Thereafter, if necessary, the coating film is rinsed with a rinsing liquid to obtain a pattern film. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, etc. may be used alone or in combination.

As the developing solution, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, Propyleneglycol monomethyl ether acetate, methyl-3-methoxyacetyl acetate, propyleneglycol monomethyl ether acetate, methyl-3-methoxyacetyl chloride, Propionic acid, propionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate, diacetone alcohol and the like may be used.

Thereafter, the pattern film is heated in step 5. The heating temperature is appropriately set so that the polyimide pattern film can be cured. For example, heating is performed at 150 to 300 DEG C for about 5 to 120 minutes in an inert gas. A more preferred range of the heating temperature is 150 to 250 ° C, and a more preferable range is 160 to 220 ° C. The heating is performed by using, for example, a hot plate, an oven, and a heating oven capable of setting a temperature program. 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 the resin composition of the present invention can be suitably used for various applications such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, A variety of known fields and products, etc., which are used. In particular, a wide range of products and products, for example, paints or printing inks, or color filters, films for flexible displays, coating films for semiconductor devices, electronic parts, interlayer insulating films , A coating film of a printed wiring board such as a solder resist, a light circuit, an optical circuit component, an antireflection film, a hologram, an optical member, or a building material.

Particularly, the photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern film formed thereby serves as a permanent film made of polyimide as a component for imparting heat resistance and insulating property. For example, , A film for a flexible display, an insulating material for a passive component, a coating film for a semiconductor device, an interlayer insulating film, a coating film for a printed wiring board such as a solder resist or a coverlay film, a solder dam, Antireflection film, and other optical members or electronic members.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

≪ Synthesis of polyimide precursor >

[Synthesis Example 1: Synthesis of polyamic acid ester 1]

7.76 g (25.0 mmol) of 4,4'-oxydiphthalic dianhydride as an acid dianhydride, 50 mL of methanol and 50 mL of toluene were added to a 300-mL branched flask, and the mixture was refluxed overnight. After refluxing, the solvent was distilled off and vacuum dried to obtain a half ester. Subsequently, 40 mL of ethyl acetate was added to dissolve the half ester. Oxalyl chloride (7.93 g, 62.5 mmol, 2.5 eq.) Was added to the mixture in four portions, and one drop of N, N-dimethylformamide was added thereto. This solution was refluxed for 4 hours, distilled off the solvent, and dried under reduced pressure to obtain diester dichloride.

Oxindianiline (5.01 g, 25.0 mmol), N-methylpyrrolidone (hereinafter referred to as NMP) 60 mL and pyridine (3.96 g, 50.0 mmol) as diamine were added to a 200 mL four- And dissolved. A solution of diester dichloride dissolved in 15 mL of tetrahydrofuran was added dropwise with ice cooling, and the mixture was stirred at room temperature overnight. The obtained solution was injected into ion-exchange water to reprecipitate, washed with methanol, and dried under reduced pressure to obtain polyamic acid ester 1. The weight average molecular weight Mw of the resulting polyamic acid ester was measured by GPC and found to be 100000 in terms of polystyrene. The esterification rate was measured by < 1 > H-NMR and found to be 100% as in Fig.

[Synthesis Example 2: Synthesis of polyamide acid ester 2]

The procedure of Synthesis Example 1 was repeated except that 4,4'-oxydiphthalic dianhydride was changed to 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride as an acid dianhydride to obtain a polyamic acid ester 2 Were synthesized. The weight average molecular weight Mw of the resulting polyamic acid ester was measured by GPC and found to be 30000 in terms of polystyrene. The esterification rate was determined by < 1 > H-NMR to be 100%.

[Synthesis Example 3: Synthesis of polyamide acid ester 3]

Polyamide acid ester 3 was synthesized in the same manner as in Synthesis Example 1 except that 4,4'-oxydiphthalic acid dianhydride was changed to pyromellitic acid dianhydride as an acid dianhydride. The weight average molecular weight Mw of the resulting polyamic acid ester was measured by GPC and found to be 20,000 in terms of polystyrene. The esterification rate was determined by < 1 > H-NMR to be 100%.

[Synthesis Example 4: Synthesis of polyamide acid ester 4]

Polyamide acid ester 4 was synthesized in the same manner as in Synthesis Example 1 except that the addition amount of oxalyl chloride was changed to 1.9 eq. The weight average molecular weight Mw of the resulting polyamic acid ester was measured by GPC and found to be 100000 in terms of polystyrene. The esterification rate was 96% as determined by < 1 > H-NMR.

[Comparative Synthesis Example 1: Synthesis of partially esterified polyamic acid ester R-1]

4,4'-oxydianiline (4.87 g, 24.3 mmol) and 100 mL of NMP were added to a 300 mL two-necked flask under a nitrogen flow, and the mixture was stirred until the 4,4'-oxydianiline completely dissolved. 4,4'-oxydiphthalic dianhydride (7.76 g, 25.0 mmol) was further added thereto, followed by stirring at room temperature overnight. After stirring, N, N-dimethylformamide dimethylacetal (5.96 g, 50.0 mmol) was diluted with 10 mL of NMP, and the mixture was reacted at 40 DEG C for 3 hours. The resulting solution was poured into ion-exchange water, subjected to suction filtration, washed with methanol, and dried under reduced pressure to obtain a partially esterified polyamide acid ester R-1. The weight average molecular weight Mw of the obtained partially esterified polyamide acid ester was measured by GPC and found to be 75000 in terms of polystyrene. The esterification ratio was 70% as determined by < 1 > H-NMR.

[Comparative Synthesis Example 2: Synthesis of polyamic acid R-2]

4,4'-oxydianiline (4.87 g, 24.3 mmol) and 100 mL of NMP were added to a 300 mL two-necked flask under a nitrogen flow, and the mixture was stirred until the 4,4'-oxydianiline completely dissolved. 4,4'-oxydiphthalic dianhydride (7.76 g, 25.0 mmol) was further added thereto, followed by stirring at room temperature overnight. The resulting solution was poured into ion-exchange water, subjected to suction filtration, washed with methanol, and dried under reduced pressure to obtain polyamic acid R-2. The weight average molecular weight Mw of the obtained polyamic acid was measured by GPC and found to be 16000 in terms of polystyrene.

(Method for calculating esterification rate)

The esterification rate of the polyamic acid ester 1 was calculated by ¹ H-NMR (in DMSO-d ₆ ). On the chart, the integral value A of the methyl ester peak near 3.8 ppm based on the integral value 14 of the aromatic proton in the repeating structure of the polyamic acid ester and the theoretical value 6 of the integral value were calculated.

Esterification rate = 100 x A / 6

As for the esterification ratios of the polyamide acid esters 2 to 4 and the partially esterified polyamic acid ester R-1, the integral value of the aromatic proton in the repeating structure of the polyamide acid ester and the integral value of the proton And calculated from the integral value.

[Examples 1 to 10, Comparative Examples 1 to 3]

The photosensitive resin compositions of the examples and comparative examples were obtained by blending the polyimide precursor, photo base generator, and solvent obtained above at the compounding ratios (mass ratio) shown in the following table. The performance of each composition was evaluated. The evaluation method is as follows.

(Imidation completion temperature)

Each of the above compositions was spin-coated on a silicon wafer to a thickness of 5 mu m after drying, and dried on a hot plate at 100 DEG C for 5 minutes. The obtained dried film was subjected to broad exposure at 10 J / cm ² by means of a high-pressure mercury lamp using a desk-top type exposure apparatus of San-Ai Den-Ze Co., The silicon wafer was heated on a hot plate set at a predetermined temperature for 5 minutes, and then the infrared spectroscopy was measured. The imidization rate was calculated by the following formula.

In the above formula, I ₁₃₈₀ is a peak area derived from CN stretching vibration which increases with progress of imidization, and I ₁₅₀₀ is a peak area derived from C = C stretching vibration of an aromatic ring which is not changed before and after the reaction. samp. is a cured sample of the Examples and Comparative Examples, and imide is a standard cured sample. Standard cured samples were prepared by heating the dried film on a hot plate at 300 ° C for 1 hour. The imidization rate was calculated in accordance with the above formula, and the temperature at which it became 100% was defined as the imidization completion temperature.

(Sensitivity)

Each of the above compositions was spin-coated on a silicon wafer to a thickness of 5 mu m after drying, and dried on a hot plate at 100 DEG C for 5 minutes. A pattern mask for resist evaluation was closely adhered to the obtained dried film, and a predetermined amount of broad exposure was performed by a high-pressure mercury lamp using a desk-top type exposure apparatus made by Sanyo Denki Seisakusho Co., Ltd. Subsequently, heating was carried out at 120 ° C for Examples 1 to 10 in Comparative Examples 1 to 3 and post-exposure for 10 minutes at 160 ° C in a Yamato Kagaku Oven, and immersion phenomenon was observed with a mixed developer of NMP: ethanol = 1: , And the polyimide pattern obtained by rinsing with ion-exchanged water was observed with a JEOL-made scanning electron microscope to define the minimum exposure amount capable of forming a pattern of L / S = 20/20 占 퐉 as the sensitivity.

(Development contrast)

Each of the above compositions was spin-coated on a silicon wafer to a thickness of 5 mu m after drying, and dried on a hot plate at 100 DEG C for 5 minutes. A mask was placed on a half of the obtained dried film, and broad exposure of 10 J / cm ² was carried out by a high-pressure mercury lamp using a desk-top type exposure apparatus of San Ai Denki Seisakusho Co., Subsequently, heating was carried out at 120 ° C for Examples 1 to 10 in Comparative Examples 1 to 3 and post-exposure for 10 minutes at 160 ° C in a Yamato Kagaku Oven, and immersion phenomenon was observed with a mixed developer of NMP: ethanol = 1: , And rinsed with ion-exchanged water. The development contrast was calculated from the film thickness before and after development of the exposed and unexposed portions of the obtained film by the following formula.

A development contrast of 10 or more was defined as & cir &

(Electroless copper plating solution resistance)

Each of the above compositions was spin-coated on a silicon wafer to a thickness of 5 mu m after drying, and dried on a hot plate at 100 DEG C for 5 minutes. The obtained dried film was subjected to broad exposure at 10 J / cm ² by means of a high-pressure mercury lamp using a desk-top type exposure apparatus of San-Ai Den-Ze Co., This silicon wafer was heated on a hot plate at 160 캜 for 5 minutes and then immersed in an electroless copper plating solution (Thru Cup PEA made by Uemura Kogyo Co., Ltd.) heated at 36 캜 for 20 minutes. And those on the silicon wafer were defined as x.

· Repeated structure of polyamide acid ester 1

· Repeated structure of polyamide acid ester 2

· Repeated structure of polyamide acid ester 3

· Photobase generator 1 (corresponding to the compound represented by formula (B))

Second photobase generator (corresponding to the quaternary ammonium salt represented by formula (D))

· Photobase generator (corresponding to oxime ester compound)

· Photochemical generator R-3

As is clear from the results shown in Table 1, the compositions of Examples 1 to 10 of the present invention were excellent in sensitivity, development contrast, and electroless copper plating solution resistance, . In particular, from the comparison of Examples 1 to 3 and Example 10, it was found that the higher the esterification rate of the amide acid ester moiety was, the lower the temperature curability and the excellent development contrast were obtained. On the other hand, Comparative Examples 1 and 2 in which the polyimide precursor was changed to a partial ester or polyamic acid required 200 占 폚 to complete the imidization, and the sensitivity and development contrast were poor, which was dissolved in the electroless copper plating solution. Comparative Example 3 in which the photo-base generator was changed to a compound having a known carbamate skeleton showed the same performance as Examples 1 to 9 in terms of imidization completion temperature and electroless copper plating solution resistance. However, The contrast was poor and the energy required for pattern formation was 5000 J / cm ² .

Claims (8)

A photosensitive resin composition comprising a polyamide acid ester and a photo base generating agent,
Wherein the polyamide acid ester comprises a polyamide acid ester which is a complete ester having a repeating structure represented by the following formula (A)

(Wherein _{A A} is a tetravalent organic group, Y _A is a divalent organic group, R _A1 and R _A2 are each independently a monovalent organic group and may be the same or different from each other, and n is an integer of 1 or more to be.)
As the photobase generator, a quaternary ammonium salt represented by the following general formula (B) or (C), a compound represented by any one of the following general formulas (D) to (H) At least any one of quaternary ammonium salts, oxime ester compounds, and compounds containing a carbamoyloxyimino group represented by the following general formula (I), which generate tertiary amines each containing one or more atoms and oxygen atoms, Wherein the photosensitive resin composition is a photosensitive resin composition.

(In the general formula (B), R _B1 and R _B2 are each independently a hydrogen atom or an organic group and may be the same or different.) R _B1 and R _B2 may combine with each other to form a cyclic structure, may include a combination. However, R _B1 and R _B2, at least one of which is an organic group. R _B3 and R _B4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol A nitro group, a nitro group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or an organic group and may be the same or different from each other, R _B5 and R _B6, R _B7 and R _B8 are playing each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol, a nitro group, alcohol pinot group, sulfo group, sulfonate group, phosphorus A phosphino group, a phosphonate group, an amino group , And ammonia coming or an organic group, may be the same or different. R _B5, R _B6, R _B7 and R _B8 are, and optionally, combining two or more of them to form a cyclic structure, comprising a bond of the heteroatom R _B9 is a hydrogen atom or an organic group.)

(C), Z _C is a hydrogen atom or a nitro group, R _C1 , R _C2 , R _C3 and R _C4 are each independently an alkyl group having 1 to 8 carbon atoms, R _C5 is a hydrogen atom or a C1- R _C1 and R _C2 , and R _C3 and R _C4 may form a ring structure with each other.)

( _Wherein R _D1 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, An alkoxy group represented by -OR _D2 , an amino group represented by -NR _D3 R _D4 , an acyl group represented by R _D5 CO-, an acyloxy group represented by R _D6 COO-, an alkylthio group represented by -SR _D7 , R _D2 , R _D5 , R _D6 and R _D7 are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, R _D3 and R _{D4 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms An alkyl group or an aryl group having 6 to 12 carbon atoms, n is an integer of 0 to 7, and Y _D ⁺ is a quaternary ammonia group represented by any of the following formulas (D1) to (D4)

Q _D is a nitrogen atom or a methine group (-CH-), t and u is 2 or 3, w is an integer from 0 to 2, A _D is a hydrogen atom, a hydroxyl group or a halogen atom, R _D8 to _D10 R is C 1 -C An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, R _D1 and CH ₂ -Y _D ⁺ X _D ^- may be bonded to the same benzene ring, do. X _D ^- is a counter anion selected from a borate anion, a phenolate anion and a carboxylate anion.)

( _Wherein R _E1 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, An alkoxy group represented by -OR _E2 , an amino group represented by -NR _E3 R _E4 , an acyl group represented by R _E5 CO-, an acyloxy group represented by R _E6 COO-, an alkylthio group represented by -SR _E7 , or R _E2 , R _E5 , R _E6 and R _E7 are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R _E3 and R _{E4 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms An alkyl group or an aryl group having 6 to 12 carbon atoms, m is an integer of 0 to 9, Y _E ⁺ is a quaternary ammonia group represented by any one of the following formulas (E1) to (E4)

Q _E is a nitrogen atom or a methine group (-CH-), t and u is 2 or 3, w is an integer from 0 to 2, A _E is a hydrogen atom, a hydroxyl group or a halogen atom, R _E8 to _E10 R is C 1 -C An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, R _E1 and CH ₂ -Y _E ⁺ X _E ^- may be bonded to the same benzene ring, do. X _E ^- is a counter anion selected from a borate anion, a phenolate anion and a carboxylate anion.)

(Wherein R _F1 , R _F2 , R _F4 and R _F5 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R _F3 and Ar _F are each independently an aryl group having 6 to 14 carbon atoms Of these, the aryl group may have a substituent. The substituent may be an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, , An alkoxy group represented by -OR _F6 , an amino group represented by -NR _F7 R _F8 , an acyl group represented by R _F9 CO-, an acyloxy group represented by R _F10 COO-, a group represented by -SR _F11 R _F6 , R _F9 , R _F10 and R _F11 each independently represent an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 8 carbon atoms, an aryl group, R and R _{F7 F8} of the circles 12 are each independently hydrogen, , An aryl group or an alkyl group having 6 to 12 carbon atoms having 1 to 8. _F Y ⁺ is a quaternary ammonium come represented by any of the following formula (F1) or (F2).

(In the general formula (G), R _G1 to R _G5 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms A nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by -OR _G6 , an amino group represented by -NR _G7 R _G8 , an acyl group represented by R _G9 CO-, an acyloxy group represented by R _G10 COO-, alkylthio group represented by SR _G11 or an arylthio group. alkyl group, alkenyl group, alkynyl group and aryl group and may have a substituent, and the substituent is the same as above R _G1 to R _G5, these substituents are a cyclic structure, R _G6 , R _G9 , R _G10 and R _G11 each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R _G7 and R _G8 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms the alkyl group or an aryl group of 6 to 12 carbon atoms. Ar group _G Tan The number of 6 to 14, an aryl group, being optionally aryl of these groups have a substituent, the substituent is the same as above R _G1 to R _G5, these substituents can take the aryl group and ring structure. Y _G ⁺ is to A quaternary ammonium nitrogen represented by any one of formulas (G1) to (G4)

Q _G is a nitrogen atom or a methine group (-CH-), t and u are 2 or 3, w is an integer of 0 to 2, A _G is a hydrogen atom, a hydroxyl group or a halogen atom, and R _G12 to R _G14 , An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms.

(Formula (H) of, Ar _H1 is an aryl group having 6 to 12 carbon atoms, the aromatic rings at least one is the oxygen atom, a sulfur atom of a hydrogen atom, a group is substituted with a substituent containing a nitrogen atom; Ar _H2 carbon atoms An aryl group having 6 to 14 carbon atoms and a part of the hydrogen atoms in the aryl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, A hydroxyl group, a cyano group, an alkoxy group represented by -OR _H11 , an amino group represented by -NR _H12 R _H13 , an acyl group represented by R _H14 CO-, an acyloxy group represented by R _H15 COO-, or -SR _H16 R _H1 and R _H2 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, Ar _H1 , R _H1 , R _H2 are coupled to each other to form a ring structure May be; R _H3 is an alkyl group having a carbon number of 1 to 18; n is in the case of an integer being, where n = 1 to 4 is four, Ar _H1 is an aryl group having 6 to 12 carbon atoms, and; R _H11, R _H14, R _H15 and _R16 each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms; R _H12 and R _H13 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms; Y _H ⁺ is a quaternary ammonia group represented by any one of the following general formulas (H1) and (H2);

In formula (H1), R _H4 to R _H5 each independently represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which may be bonded to each other to form a ring structure; Q _H is a methylene group (-CH ₂ -) m or a group represented by the general formula (H3); m is an integer of 2 or 3; In the formula (H2), R _H6 to R _H8 each independently represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, In the formula (H3), R _H9 to R _H10 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and may be bonded to each other to form a ring structure.

(Compound (I) of the, _I Y is - (CH ₂₎ m- group, an alicyclic group, an arylene group, - (CH ₂₎ m- group and combines cycloaliphatic group, - (CH ₂₎ m- group and arylene M is an integer of 2 to 7, and R _I1 is an aromatic group or a substituted alkyl group. The photosensitive resin composition according to claim 1, wherein the photo-base generator is a compound represented by formula (B). The photosensitive resin composition according to claim 2, wherein the photo-base generator is a compound represented by the following formula.

A dry film having a resin layer obtained by applying the photosensitive resin composition according to claim 1 to a film and drying the film. A cured product obtained by curing a resin layer of the photosensitive resin composition according to any one of claims 1 to 3 or the dry film according to claim 4. A semiconductor device having the cured product according to claim 5. A printed wiring board characterized by having the cured product according to claim 5. An electronic part having the cured product according to claim 5.

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