KR20190049488A - Photosensitive resin composition, dry film, cured product, semiconductor element, printed wiring board, and electronic component - Google Patents

Abstract

The purpose of the present invention is to provide a photosensitive resin composition which can form a cured film with high heat resistance and a low coefficient of linear thermal expansion and is excellent in sensitivity and resolution; a dry film including 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 including the cured product. The photosensitive resin composition of the present invention comprises: a polybenzoxazole precursor (A) which is a polyamide-based resin obtained from a reaction of a diamine component and a dicarboxylic acid component; and a photosensitizer (B), wherein, among polyamide structures of the polybenzoxazole precursor (A), the ratio of a structure represented by general formula (1) is 0.1 to 15%, and the ratio of a structure represented by general formula (2) is 85 to 99.9%.

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.

The application of polybenzoxazole to electronic parts such as a surface protective film or an interlayer insulating film of an electric material, for example, a coating film of a semiconductor element, a flexible printed wiring board material, or a heat resistant insulating interlayer material is excellent in heat resistance and electrical insulating properties It is progressing.

In order to form a fine pattern of polybenzoxazole, a photosensitive resin composition in which a polybenzoxazole precursor and a photosensitizer are blended is conventionally used. As such a photosensitive resin composition, for example, Patent Document 1 discloses a positive resist composition composed of a polybenzoxazole precursor and a photosensitive diazoquinone.

Japanese Patent Publication No. 1-046862

However, in the composition described in Patent Document 1, there are cases in which both of the heat resistance of the cured product and the sensitivity and resolution in photolithography are insufficient. Further, it is required that the coefficient of linear thermal expansion of the cured product is low (that is, low CTE) in view of causing cracks and warpage.

Therefore, an object of the present invention is to provide a photosensitive resin composition capable of forming a cured film having high heat resistance and low thermal expansion coefficient, excellent in sensitivity and resolution, a dry film having a resin layer obtained from the composition, And a semiconductor element having the cured product, a printed wiring board, and an electronic component.

As a result of intensive studies in view of the above, the present inventors have found that by using a polyamide-based resin containing a benzoxazole structure in a specific ratio as a polybenzoxazole precursor, or by using a polyamide-based resin having a benzoxazole structure, The present inventors have found that the above problems can be solved by using a polybenzoxazole precursor in combination with a specific ratio.

That is, the photosensitive resin composition of the present invention is a photosensitive resin composition containing a polybenzoxazole precursor (A), which is a polyamide-based resin obtained from the reaction of a diamine component and a dicarboxylic acid component, and a photosensitizer (B)

Wherein the proportion of the structure represented by the following general formula (1) is 0.1 to 15% and the proportion of the structure represented by the following general formula (2) is 85 to 99.9 %. ≪ / RTI >

(In the general formula (1), P is a residue of a diamine component and is a divalent group having a benzoxazole structure represented by any one of the following general formulas (1-1), (1-2) and (1-3) Is a residue of a dicarboxylic acid component and is a divalent organic group)

(Wherein R ₁ to R _{4 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) R ₅ to R _{9 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is a direct bond to a nitrogen atom in the general formula (1)

(In the general formula (1-2), R ₁₀ to R _{14 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R ₁₅ to R _{19 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is a direct bond with a nitrogen atom in the general formula (1), R ₂₀ and R ₂₁ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(Wherein R ₂₂ to R _{26 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) R ₂₇ to R _{31 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is a direct bond with a nitrogen atom in the general formula (1), R ₃₂ and R ₃₃ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(In the general formula (2), X is a residue of a dihydroxydiamine and is a tetravalent organic group, Y is a residue of a dicarboxylic acid component, and is a divalent organic group)

Another photosensitive resin composition of the present invention is a photosensitive resin composition containing a polyamide resin (? -1) obtained from the reaction of a diamine component and a dicarboxylic acid component, a polybenzoxazole precursor (? -2) As a photosensitive resin composition,

Wherein the polyamide-based resin (? -1) has a structure represented by the following general formula (3)

Wherein the polybenzoxazole precursor (? -2) has a structure represented by the following general formula (4)

Wherein the compounding ratio of the polyamide resin (? -1) and the polybenzoxazole precursor (? -2) is 0.1: 99.9 to 15:85 in terms of mass.

(In the general formula (3), P is a residue of a diamine component and is a divalent group having a benzoxazole structure of any of the following general formulas (3-1), (3-2) and (3-3) Is a residue of a dicarboxylic acid component and is a divalent organic group, and n is an integer of 1 or more)

(3-1), R ₁ to R ₄ are any of a direct bond with a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group or a nitrogen atom in the general formula (3) R ₅ to R _{9 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is a direct bond with a nitrogen atom in the general formula (3)

(In the general formula (3-2), R ₁₀ to R ₁₄ are any of a direct bond with a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, R ₁₅ to R ₁₉ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is a direct bond with a nitrogen atom in the general formula (3), R ₂₀ and R ₂₁ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(Wherein R ₂₂ to R _{26 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) R ₂₇ to R ₃₁ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group and a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is a direct bond with a nitrogen atom in the general formula (3), R ₃₂ and R ₃₃ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(In the general formula (4), X is a residue of a dihydroxydiamine, a quadrivalent organic group, Y is a residue of a dicarboxylic acid component, is a divalent organic group, and m is an integer of 1 or more)

The photosensitive resin composition of the present invention preferably further contains a crosslinking agent. Further, the photosensitive resin composition of the present invention preferably contains a triazole compound having a mercapto group, and it is preferable to use a triazole compound having a mercapto group and a melamine-based crosslinking agent in combination. In the photosensitive resin composition of the present invention, it is preferable that the triazole compound having a mercapto group is 3-mercapto-1,2,4-triazole.

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 capable of forming a cured film having high heat resistance and low thermal expansion coefficient, excellent in sensitivity and resolution, a dry film having a resin layer obtained from the composition, Cargo, a semiconductor device having the cured product, a printed wiring board, and an electronic component.

The photosensitive resin composition of the present invention is a photosensitive resin composition containing a polybenzoxazole precursor (A), which is a polyamide-based resin obtained from the reaction of a diamine component and a dicarboxylic acid component, and a photosensitive resin composition , Wherein the proportion of the structure represented by the general formula (1) is 0.1 to 15% and the proportion of the structure represented by the general formula (2) is 85 (meth) acrylamide in the polyamide structure of the polybenzoxazole precursor (A) (A-1) obtained from the reaction of a diamine component and a dicarboxylic acid component, a polybenzoxazole precursor (? -2) and a photosensitive agent (B) Wherein the polyamide resin (α-1) has a structure represented by the general formula (3) and the polybenzoxazole precursor (α-2) is represented by the general formula (4) , And the poly Deugye resin (α-1), and the polybenzoxazole precursor (α-2) mixing ratio is 0.1 by mass in terms of: 99.9 to 15: 85 is a photosensitive resin composition. Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.

[Polybenzoxazole Precursor (A)]

The polybenzoxazole precursor (A), which is a polyamide-based resin obtained from the reaction of the diamine component and the dicarboxylic acid component, has a structure in which the proportion of the structure represented by the following general formula (1) is 0.1 to 15% , And the proportion of the structure represented by the following general formula (2) is 85 to 99.9%.

(In the general formula (1), P is a residue of a diamine component and is a divalent group having a benzoxazole structure represented by any one of the following general formulas (1-1), (1-2) and (1-3) Is a residue of a dicarboxylic acid component and is a divalent organic group)

(Wherein R ₁ to R _{4 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) R ₅ to R _{9 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is a direct bond to a nitrogen atom in the general formula (1)

(In the general formula (1-2), R ₁₀ to R _{14 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R ₁₅ to R _{19 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is a direct bond with a nitrogen atom in the general formula (1), R ₂₀ and R ₂₁ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(Wherein R ₂₂ to R _{26 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) R ₂₇ to R _{31 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is a direct bond with a nitrogen atom in the general formula (1), R ₃₂ and R ₃₃ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(In the general formula (2), X is a residue of a dihydroxydiamine and is a tetravalent organic group, Y is a residue of a dicarboxylic acid component, and is a divalent organic group)

Here, the ratio in the polyamide structure means that the amide structure containing one diamine component and one dicarboxylic acid component is counted as one, as in the general formula (1), and then the polybenzoxazole precursor (A) Quot; means the ratio of the total amount of amide structure in the polyamide structure contained. In the reaction of the diamine component and the dicarboxylic acid component, 100% of the reaction is completed, and the ratio of the diamine component to the total number of the benzoates of the general formulas (1-1), (1-2) and (1-3) (Molar conversion) of the diamine having an oxazole structure (hereinafter also referred to as " benzoxazole moiety "). The ratio may be obtained by analyzing by NMR or the like. The total number of amide structures in the polyamide structure contained in the polybenzoxazole precursor (A) is preferably 10 to 30, more preferably 15 to 25.

When the proportion of the structure represented by the general formula (1) is less than 0.1%, the heat resistance of the cured product is lowered and the coefficient of linear thermal expansion is also increased. If the ratio exceeds 15%, the sensitivity and resolution are deteriorated. Preferably 1 to 10%.

The polyamide structure of the polybenzoxazole precursor (A) is obtained from the reaction of the diamine component and the dicarboxylic acid component. The diamine component and the dicarboxylic acid component are not particularly limited as long as they are used for the synthesis of polyamide. Examples of the diamine component include diamines and dicarboxylic acid components include dicarboxylic acid, dicarboxylic acid ester, And dihalides of dicarboxylic acids such as chloride.

The structure represented by the above general formula (1) may be continuously repeated in the polybenzoxazole precursor (A), and the number of repeating units is preferably 1 to 5 (provided that when the number of repeats is 1, Which means it is not repeated).

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

R ₁ to R ₄ , R ₅ to R ₉ in the general formula (1-1), R ₁₀ to R ₁₄ , R ₁₅ to R _{19 in} the general formula (1-2) Examples of the organic groups that R ₂₂ to R ₂₆ and R ₂₇ to R ₃₁ in formula (1-3) can take include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 3 to 8 carbon atoms A cycloalkyl group, an aryl group having 6 to 12 carbon atoms, an allyl group, and a trifluoromethyl group.

Examples of the organic groups that R ₂₀ and R _{21 in} the general formula (1-2) and R ₃₂ and R _{33 in} the general formula (1-3) can take are, for example, those having 1 to 3 carbon atoms An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an allyl group, and a trifluoromethyl group.

R ₁ to R ₉ in the general formula (1-1), R ₁₀ to R _{21 in} the general formula (1-2), and R ₂₂ to R in the general formula (1-3) _Examples of the halogen atom which can be taken as ₃₃ include fluorine, chlorine and bromine. Among them, fluorine is preferable from the viewpoint of the transmittance of the polymer.

R ₁ to R ₉ in the general formula (1-1), R ₁₀ to R _{21 in} the general formula (1-2), and R ₂₂ to R in the general formula (1-3) ₃₃ is as sulfonyl group that can be taken, include methyl sulfonyl group, ethyl sulfonyl, propyl sulfonyl and butyl sulfonyl group, octyl sulfonyl group, decyl sulfonyl group, dodecyl sulfonyl group such as 1 to 10 carbon atoms in the alkylsulfonyl group of the have.

Examples of the diamine component represented by P in the general formula (1) include diamines having a benzoxazole structure represented by the following general formulas (5), (6) and (7).

Examples of the dicarboxylic acid component represented by R 'in the above general formula (1) include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5- Phthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxy diphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis ) Sulfone, 2,2-bis (p-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, Alicyclic dicarboxylic acids such as dicarboxylic acid, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid And their dihalides. Among them, 4,4'-dicarboxy diphenyl ether and its dihalide are preferable.

In the general formula (1), the divalent organic group represented by R 'may be an aliphatic group and an aromatic group, but is preferably an aromatic group, more preferably an aromatic group bonded to the carbonyl in the general formula (1). The number of carbon atoms of the bivalent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the bivalent aromatic group include, but are not limited to, the following groups, and a known aromatic group contained in the polybenzoxazole precursor 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 >< RTI ID = 0.0 >

The bivalent organic group is preferably the following group among the above aromatic groups.

The polybenzoxazole precursor (A) may contain two or more kinds of structures represented by the general formula (1).

The amide structure other than the general formula (1) contained in the polyamide structure by the polybenzoxazole precursor (A) is an amide structure represented by the following general formula (2). The ratio of the amide structure of the general formula (1) to the amide structure of the general formula (2) is 0.1: 99.9 to 15:85, preferably 1:99 to 10:90, and 1:99 to 5:95 More preferable.

(Wherein X is a residue of dihydroxydiamine and is a quadrivalent organic group, Y is a residue of a dicarboxylic acid component, and is a divalent organic group.) The structure represented by the general formula (2) The number of repeating units is preferably 10 to 30, more preferably 15 to 25 (provided that, in the case where the number of repeating units is 1, the number of repeating units is continuously and repeatedly set in the polybenzoxazole precursor (A) )

Examples of the dihydroxydiamines represented by X in the general formula (2) include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3 ' (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis -Bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and the like. Among them, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane is preferred.

In the general formula (2), the tetravalent organic group represented by X may be an aliphatic group or an aromatic group, but it is preferably an aromatic group, and it is more preferable that two hydroxyl groups and two amino groups are located in the ortho position on the aromatic ring. The number of carbon atoms of the tetravalent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the tetravalent aromatic group include, but are not limited to, the following groups, and known aromatic groups that may be contained in the polybenzoxazole precursor may be selected depending on the use.

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

The dicarboxylic acid component represented by Y in the general formula (2) is the same as the dicarboxylic acid component represented by R 'in the general formula (1).

The number average molecular weight (Mn) of the polybenzoxazole precursor (A) is preferably 5,000 to 100,000, more preferably 8,000 to 50,000. Here, the number average molecular weight is a value measured by Gel Permeation chromatography (hereinafter referred to as " GPC ") and converted into standard polystyrene. The weight average molecular weight (Mw) of the polybenzoxazole precursor (A) is preferably 10,000 to 200,000, more preferably 16,000 to 100,000. Here, the mass average molecular weight is a value measured by GPC and converted into standard polystyrene. Mw / Mn is preferably 1 to 5, more preferably 1 to 3.

The blending amount of the polybenzoxazole precursor (A) is preferably 60 to 90% by mass, more preferably 70 to 90% by mass, based on the entire solid content of the composition.

When the photosensitive resin composition of the present invention contains the polybenzoxazole precursor (A), it is possible to form a cured film having a high heat resistance and a low linear thermal expansion coefficient without mixing a polymer, and is excellent in sensitivity and resolution, Accordingly, two or more polybenzoxazole precursors (A) may be used in combination. In addition, it may be used in combination with a polymer other than the polybenzoxazole precursor (A) within a range that does not impair the effect of the present invention.

[Polyamide resin (? -1)]

The polyamide resin (? -1) obtained from the reaction of the diamine component and the dicarboxylic acid component has a structure represented by the following general formula (3).

(In the general formula (3), P is a residue of a diamine component and is a divalent group having a benzoxazole structure of any of the following general formulas (3-1), (3-2) and (3-3) Is a residue of a dicarboxylic acid component and is a divalent organic group, and n is an integer of 1 or more)

(3-1), R ₁ to R ₄ are any of a direct bond with a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group or a nitrogen atom in the general formula (3) R ₅ to R _{9 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is a direct bond with a nitrogen atom in the general formula (3)

(In the general formula (3-2), R ₁₀ to R ₁₄ are any of a direct bond with a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, R ₁₅ to R ₁₉ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is a direct bond with a nitrogen atom in the general formula (3), R ₂₀ and R ₂₁ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(Wherein R ₂₂ to R _{26 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) R ₂₇ to R ₃₁ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group and a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is a direct bond with a nitrogen atom in the general formula (3), R ₃₂ and R ₃₃ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

The mixing ratio of the polyamide resin (? -1) and the polybenzoxazole precursor (? -2) is 0.1: 99.9 to 15:85 in terms of mass. When the polyamide-based resin (? -1) is less than 0.1, the heat resistance of the cured product is lowered, and the coefficient of linear thermal expansion is also increased. When the polyamide-based resin (? -1) is more than 15, the sensitivity and resolution are deteriorated. Preferably 1:99 to 10:90.

The polyamide resin (? -1) is obtained from the reaction of the diamine component and the dicarboxylic acid component. The diamine component and the dicarboxylic acid component are not particularly limited as long as they are used for the synthesis of polyamide. Examples of the diamine component include diamines and dicarboxylic acid components include dicarboxylic acid, dicarboxylic acid ester, And dihalides of dicarboxylic acids such as chloride.

The n in the general formula (3) is preferably 1 to 20, more preferably 1 to 5.

Each R in Formulas (3-1) to (3-3) is the same as R in Formulas (1-1) to (1-3).

Examples of the diamine component represented by P in the general formula (3) include diamines having a benzoxazole structure represented by any of the following general formulas (5), (6) and (7) .

In the general formula (3), the dicarboxylic acid component represented by R 'is the same as R' in the general formula (1).

The polyamide-based resin (? -1) may contain two or more kinds of structures represented by the general formula (3). May contain a structure other than the structure represented by the general formula (3), and may include, for example, the structure represented by the general formula (2).

The number average molecular weight (Mn) of the polyamide resin (? -1) is preferably 500 to 10,000. The mass average molecular weight (Mw) of the polyamide resin (? -1) is preferably 1,500 to 25,000. Mw / Mn is preferably 1 to 5.

The blending amount of the polyamide-based resin (? -1) is preferably 0.1 to 15% in the resin component, and the thermomechanical characteristics of the cured film can be improved without deteriorating developability.

[Polybenzoxazole Precursor (? -2)]

The polybenzoxazole precursor (? -2) has a structure represented by the following general formula (4).

(Wherein X is a residue of a dihydroxydiamine and is a tetravalent organic group, Y is a residue of a dicarboxylic acid component, and is a divalent organic group, and m is an integer of 1 or more)

In the general formula (4), m is an integer of 1 or more, preferably 10 to 50, and more preferably 20 to 40. [

The dihydroxydiamines represented by X in the general formula (4) are the same as the dihydroxydiamines represented by X in the general formula (2).

In the general formula (4), the tetravalent organic group represented by X is the same as the tetravalent organic group represented by X in the general formula (2).

As the dicarboxylic acid component represented by Y in the general formula (4), the dicarboxylic acid component represented by R 'in the general formula (1) and the dicarboxylic acid component represented by R' It is the same.

The polybenzoxazole precursor (? -2) may contain two or more kinds of structures represented by the general formula (4).

The number average molecular weight (Mn) of the polybenzoxazole precursor (? -2) is preferably 5,000 to 100,000, more preferably 8,000 to 50,000. The weight average molecular weight (Mw) of the polybenzoxazole precursor (? -2) is preferably 10,000 to 200,000, more preferably 16,000 to 100,000. Mw / Mn is preferably 1 to 5, more preferably 1 to 3.

The blending amount of the polybenzoxazole precursor (? -2) is preferably 85 to 99.9% of the resin component, and a pattern with higher resolution can be obtained.

In the photosensitive resin composition of the present invention, two or more kinds of polyamide resin (? -1) and polybenzoxazole precursor (? -2) may be used in combination as necessary. The polymer may be used in combination with a polymer other than the polyamide resin (? -1) and the polybenzoxazole precursor (? -2) within the range not impairing the effect of the present invention. In addition, the polybenzoxazole precursor (? -2) may have a benzoxazole structure, but preferably does not have a benzoxazole structure, so long as the effect of the present invention is not impaired.

[Photosensitive Agent (B)]

The photosensitizer (B) is not particularly limited, and photoacid generators, photopolymerization initiators and photobase generators can be used. The photoacid generator is a compound which generates an acid upon irradiation of light such as ultraviolet rays or visible light. The photopolymerization initiator is a compound which generates radicals or the like by the same light irradiation. Or the molecules are cleaved to generate at least one basic substance. In the present invention, as the photosensitizer (B), a photo acid generator may be suitably used.

Examples of the photo acid generator include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters , Nitrobenzyl esters, aromatic N-oxyimidosulfonates, aromatic sulfamides, benzoquinonediazosulfonic acid esters and the like. The photoacid generator is preferably a dissolution inhibitor. Among them, naphthoquinone diazide compounds are preferred.

Specific examples of the naphthoquinone diazide compound include a naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, (E.g., TS533, TS567, TS583, TS593 by Kyusho Co., Ltd.), and naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570 and BS599 available from Sanobo Kagaku Kagaku Co., Ltd.).

As the photosensitizer (B), one type may be used alone, or two or more types may be used in combination. The blending amount of the photosensitizer (B) is preferably 3 to 20% by mass, more preferably 5 to 20% by mass, based on the entire solid content of the composition.

(Crosslinking agent)

The photosensitive resin composition of the present invention preferably contains a crosslinking agent, and the strength of the cured film at the time of low-temperature curing is increased by adding a crosslinking agent. The crosslinking agent is not particularly limited and may contain a known crosslinking agent. Among them, a crosslinking agent having a phenolic hydroxyl group, a crosslinking agent having no phenolic hydroxyl group, two or more methylol groups, a melamine crosslinking agent and a urea crosslinking agent are preferable. Further, it is more preferable to use a combination of a crosslinking agent having a phenolic hydroxyl group and a melamine crosslinking agent. By combining a crosslinking agent, the developing property can be adjusted and the strength of the film cured at a low temperature is increased. The mixing ratio of the crosslinking agent having a phenolic hydroxyl group and the melamine crosslinking agent is preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3, more preferably 4: 6 to 6: 4 desirable. It is more preferable to use a combination of a crosslinking agent having a phenolic hydroxyl group and a crosslinking agent having no phenolic hydroxyl group and having at least two methylol groups, and the pattern rectangle at the time of development becomes better and the strength of the cured film increases. The blending ratio of the crosslinking agent having a phenolic hydroxyl group and the crosslinking agent having no a phenolic hydroxyl group and having at least two methylol groups is preferably from 2: 8 to 8: 2 in terms of mass, more preferably from 3: 7 to 7: 3 , And more preferably from 4: 6 to 6: 4. The content of the crosslinking agent is preferably 1.5 to 20% by mass based on the entire solid content of the composition.

(Crosslinking agent having a phenolic hydroxyl group)

The crosslinking agent having a phenolic hydroxyl group is not particularly limited, but it is preferable that the crosslinking agent has two or more hydroxyl groups (including a phenolic hydroxyl group), more preferably two or more phenolic hydroxyl groups, Compound is more preferable.

(In the general formula (A), R ^A1 represents an organic group having 2 to 10 valences, R ^A2 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 10)

In the general formula (A), R ^A1 is preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent.

In the general formula (A), R ^A2 is preferably a hydrogen atom.

In the general formula (A), n is preferably an integer of 2 to 4, more preferably 2.

Further, the crosslinking agent having a phenolic hydroxyl group is preferably one having a fluorine atom, more preferably having a trifluoromethyl group. The fluorine atom or a methyl group as the trifluoromethyl, the general formula (A) preferably has in the R ^A1 represents a 2 to 10-valent organic group and, R ^A1 is preferably (trifluoromethyl) methylene group D. Further, the crosslinking agent having a phenolic hydroxyl group preferably has a bisphenol structure, and more preferably has a bisphenol AF structure.

Specific examples of the crosslinking agent having a phenolic hydroxyl group are preferably the following compounds.

The crosslinking agent having a phenolic hydroxyl group may be used singly or in combination of two or more. The blending amount of the crosslinking agent having a phenolic hydroxyl group is preferably from 1 to 20% by mass, more preferably from 3 to 10% by mass, based on the whole solid content of the composition. With such blending ratio, a composition having more excellent developing properties and better patterning properties after curing can be obtained.

(A crosslinking agent having no phenolic hydroxyl group and having at least two methylol groups)

The cross-linking agent having no phenolic hydroxyl group and having at least two methylol groups preferably has a molecular weight of 100 or more.

The cross-linking agent having no phenolic hydroxyl group and having at least two methylol groups is more preferably a compound represented by the following general formula (B).

(In the general formula (B), n represents an integer of 1 to 10, and when n is 1, R ^B1 represents a methylol group (that is, "-CH ₂ OH") and when n is an integer of 2 to 10, R ^B1 represents an organic group having 2 to 10 valences, R ^B2 independently represents an organic group having 1 to 4 carbon atoms, m1 represents an integer of 1 to 5, and m2 represents an integer of 0 to 4)

In the general formula (B), n is preferably 1.

In the general formula (B), R ^B2 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

As specific examples of the crosslinking agent having no phenolic hydroxyl group and having at least two methylol groups, the following compounds are preferred.

As the crosslinking agent having no phenolic hydroxyl group and having two or more methylol groups, one type may be used alone, or two or more types may be used in combination. The blending amount of the crosslinking agent having no phenolic hydroxyl group and having two or more methylol groups is preferably 1 to 20% by mass based on the whole solid content of the composition. With such blending ratio, a composition having more excellent developing properties and better patterning properties after curing can be obtained.

(Melamine-based crosslinking agent)

The melamine crosslinking agent is not particularly limited as long as it is a crosslinking agent having a melamine structure, but it is preferably a melamine crosslinking agent represented by the following general formula (C).

( ^Wherein R ^C1A , R ^C2A , R ^C3A , R ^C4A , R ^C5A and R ^C6A are each independently an alkylene group having 1 to 3 carbon atoms.) R ^C1B , R ^C2B , R ^C3B , R ^C4B , R ^C5B and R ^C6B is also preferable that each independently represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms)

In the general formula (C), R ^C1A , R ^C2A , R ^C3A , R ^C4A , R ^C5A and R ^C6A are each preferably a methylene group. In addition, R ^{C1B, C2B} R, R ^{C3B, C4B} R, R and R ^{C5B C6B} is more preferably each independently a methyl group or a hydrogen atom.

The melamine-based crosslinking agent may be used alone or in combination of two or more. The blending amount of the melamine-based crosslinking agent is preferably 0.5 to 15% by mass based on the whole solid content of the composition. If it is 0.5 to 15 mass%, the residual film ratio of the unexposed portion can be further increased, and development residue of the exposed portion can be prevented.

(Urea-based cross-linking agent)

The urea-based crosslinking agent is not particularly limited, but is preferably a melamine crosslinking agent represented by the following general formula (D) or (E).

(Wherein R ^D1 and R ^D2 each independently represent a hydrogen atom or a monovalent organic group)

(Wherein R ^E1 each independently represents a hydrogen atom or a monovalent organic group, and R ^E2 represents a divalent organic group)

The urea-based cross-linking agent is preferably an alkylated urea resin, more preferably a 2-imidazolidinone ring. For example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 4,5-dimethoxy-1,3 -Bis (methoxymethyl) imidazolidin-2-one, and the like. Commercially available products include Nigalac MX-270, MX-279 and MX-280 manufactured by Sanwa Chemical Co., Ltd.

As specific compounds of the urea-based crosslinking agent, the following compounds and the like can be used.

The urea-based cross-linking agents may be used singly or in combination of two or more kinds. The blending amount of the urea-based crosslinking agent is preferably 1 to 20% by mass based on the whole solid content of the composition. If it is 1 to 20% by mass, the film strength at the time of low-temperature curing can be improved without adversely affecting the development.

(Thiol compound)

The photosensitive resin composition of the present invention may contain a thiol compound. By containing a thiol compound, the development residue can be reduced. The thiol compound is not particularly limited, and in addition to D, L-dithiothreitol and 2-mercaptoethanol, compounds shown below may be used. Particularly, D, L-dithiothreitol is preferable.

The thiol compound may be used alone or in combination of two or more. The blending amount of the thiol compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the entire solid content of the composition. By setting the above range, it is possible to more reliably suppress occurrence of scum.

The photosensitive resin composition of the present invention preferably contains a triazole compound having a mercapto group. The detailed mechanism is not clear, but the adhesion with the copper substrate is improved and the development residue on the copper can be suppressed.

The triazole compound having a mercapto group is not particularly limited as long as it is a compound having a mercapto group and having a triazole structure. For example, triazole compounds having a mercapto group include 3-mercapto-1,2,4- Sol, 3-mercapto-4-methyl-4H-1,2,4-triazole, and the like. Among them, a compound in which a mercapto group is directly bonded to a triazole ring such as the above-mentioned compound is preferable. The triazole compound having a mercapto group is more preferably a compound represented by the following formula (5), particularly preferably 3-mercapto-1,2,4-triazole.

(In the formula (5), R ₄₁ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom)

The triazole compounds having a mercapto group may be used singly or in combination of two or more. The blending amount of the triazole compound having a mercapto group is preferably 0.1 to 5.0 mass%, more preferably 0.5 to 2.0 mass%, based on the whole solid content of the composition.

Further, according to the present invention, use of a triazole compound having a mercapto group and a melamine-based crosslinking agent makes it possible to both suppress the development residue and develop resistance, even when the development time is prolonged. The term " developability " in the present invention means that the residual film ratio after development is high and the surface of the cured film has no shape or crack.

(Urea compound)

The photosensitive resin composition of the present invention may contain urea compounds. By containing the urea compound, the dissolution rate of the resin can be adjusted and the pattern formability can be improved. The urea compound is not particularly limited and includes, for example, 1,3-diphenyl urea, 1,3-bis [4- (trifluoromethyl) phenyl] urea, N, N'-bis (trimethylsilyl) , 1-acetyl-3-methyl urea, 1-acetyl-2-thiourea, acetyl urea, 1-adamantyl thiourea, 1-allyl 3- (2-hydroxyethyl) Benzene thiourea, benzoyl urea, benzyl urea, 1,3-bis (tert-butoxycarbonyl) thiourea, 1,3-bis (4-chlorophenyl) urea, 1,3-bis (4-fluorophenyl) urea, 1,3- (hydroxymethyl) urea, 1,3-bis (4-methoxyphenyl) urea, urea, butyl urea, N, '-Diphenyl element and the like can be used.

One kind of urea compound may be used alone, or two or more kinds of urea compounds may be used in combination. The blending amount of the urea compound is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, based on the whole solid content of the composition. By setting the thickness in the above range, it is possible to improve the residual film ratio, improve the developing property of the thick photoresist film on the metal substrate, and obtain a better pattern shape after development.

(Silane coupling agent)

The photosensitive resin composition of the present invention may contain a silane coupling agent. By containing the silane coupling agent, adhesion with the silicon substrate can be improved. The silane coupling agent is preferably a silane coupling agent having an arylamino group and a silane coupling agent having at least two trialkoxysilyl groups. From the viewpoint of excellent resolution, it is more preferable to be a silane coupling agent having an arylamino group.

The silane coupling agent having an arylamino group will be described. Examples of the aryl group of the arylamino group include aromatic hydrocarbon groups such as phenyl group, tolyl group and xylyl group, condensed polycyclic aromatic groups such as naphthyl group, anthracenyl group and phenanthrenyl group, aromatic heterocyclic groups such as thienyl group and indolyl group have.

The silyl coupling agent having an arylamino group is preferably a compound having a group represented by the following general formula (F).

(Wherein R ^F1 to R ^F5 each independently represent a hydrogen atom or an organic group)

In the general formula (F), it is preferable that R ^F1 to R ^F5 are hydrogen atoms.

In the silane coupling agent having an arylamino group, it is preferable that the silicon atom and the arylamino group are bonded by an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.

Specific examples of the silane coupling agent having an arylamino group are preferably the compounds shown below.

Next, the silane coupling agent having two or more trialkoxysilyl groups will be described. The trialkoxysilyl groups of the silane coupling agent having two or more trialkoxysilyl groups may be the same or different, and the alkoxy groups of these groups may be the same or different. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Among them, a methoxy group and an ethoxy group are preferable.

The silane coupling agent having two or more trialkoxysilyl groups preferably has at least two silicon atoms bonded to an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.

Specific examples of the silane coupling agent having two or more trialkoxysilyl groups are preferably the following compounds.

The silane coupling agent may be used singly or in combination of two or more kinds. The silane coupling agent having an arylamino group as described above and a silane coupling agent other than the silane coupling agent having two or more trialkoxysilyl groups may be contained.

The blending amount of the silane coupling agent is preferably 1 to 15% by mass based on the whole solid content of the composition. If it is 1 to 15% by mass, the development residue of the exposed portion can be prevented.

A solvent may be added to the photosensitive resin composition of the present invention. The solvent is not particularly limited so long as it dissolves the polybenzoxazole precursor (A), the photosensitizer (B), and other optional additives. Specific examples of the solvent include N, N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, -Butyrolactone,? -Acetyl-? -Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, Formamide, 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 may be in the range of 50 to 9000 parts by mass based on 100 parts by mass of the polybenzoxazole precursor (A), depending on the coating film thickness and viscosity.

In the photosensitive resin composition of the present invention, known sensitizers, adhesion aids, and the like may be blended to the extent that the effects of the present invention are not impaired.

The photosensitive resin composition of the present invention may further contain various organic or inorganic low molecular weight or high molecular weight compounds for imparting processing characteristics and various functions. For example, 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. In the photosensitive resin composition of the present invention, various coloring agents, fibers and the like may be blended.

[Dry Film]

The dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention.

The dry film of the present invention can be obtained by uniformly applying the photosensitive resin composition of the present invention to a carrier film (support film) by a suitable method using a blade coater, a lip coater, a comma coater, a film coater, And a cover film (protective film) is laminated thereon. The cover film and the carrier film may be the same film material or different films may be used.

In the dry film of the present invention, the film material of the carrier film and the cover film may be any of those known for use in a dry film.

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

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

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

The photosensitive resin composition of the present invention is preferably a positive type. Using the photosensitive resin composition of the present invention, the patterned film as a cured product thereof is produced, for example, as follows. In the following production method, the polybenzoxazole precursor (A) is included. However, the case where the polybenzoxazole precursor (A-2) is contained in the polyamide resin to be.

First, as a step 1, a coating film is obtained by applying a photosensitive resin composition on a base material and drying it, or by transferring (laminating) a resin layer onto a base material from a dry film. Examples of the method of applying the photosensitive resin composition on a substrate include a method conventionally used for coating a photosensitive resin composition, for example, a method of applying by a spin coater, a bar coater, a blade coater, a curtain coater, 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 carried out under the condition that the ring-opening of the polybenzoxazole precursor (A) in the photosensitive resin composition does not occur. Concretely, natural drying, air drying, or heat drying can be carried out at 70 to 140 ° C for 1 to 30 minutes. Preferably, drying is performed on a hot plate for 1 to 20 minutes. Vacuum drying is also possible. In this case, the reaction can be carried out at room temperature for 20 minutes to 1 hour.

The substrate is not particularly limited and can be widely applied to a substrate including a semiconductor substrate such as a silicon wafer, a wiring substrate, various resins, and metals.

Subsequently, as the step 2, the above coating film is directly exposed through a photomask having a pattern. The exposure light beam has a wavelength capable of activating a photo acid generator as a photosensitizer (B) to generate an acid. Specifically, the exposure light preferably has a maximum wavelength in the range of 350 to 410 nm. As described above, when sensitizer is appropriately used, the light sensitivity can be adjusted. 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 a step 3, a part of the polybenzoxazole precursor (A) in the unexposed portion may be closed by heating. Here, the waste rate is about 30%. The heating time and the heating temperature are appropriately changed according to the polybenzoxazole precursor (A), the thickness of the coating film and the type of the photo acid generator as the photosensitizer (B).

Subsequently, as a step 4, the coating film is treated with a developing solution. Thus, the patterned film of the photosensitive resin composition of the present invention can be formed by removing the exposed portion in the coated film.

As a method for use in the development, any one of a conventionally known developing method of a photoresist, for example, a rotary spray method, a paddle method, a dipping method accompanied by an ultrasonic treatment, and the like can be selected. 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 Quaternary ammonium salts and the like. If necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol or the like or a surfactant may be added thereto. 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, isopropyl alcohol, etc. may be used alone or in combination. The solvent may be used as the developing solution.

Thereafter, as the step 5, the pattern film is heated to obtain a cured coating film (cured product). At this time, the polybenzoxazole precursor (A) may be cyclized to obtain polybenzoxazole. The heating temperature is appropriately set so that the pattern film of polybenzoxazole can be cured. For example, heating is carried out at 150 to 350 DEG C for about 5 to 120 minutes in an inert gas. A more preferred range of the heating temperature is 180 to 320 占 폚. 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 is suitably used as a coating material, a printing ink or an adhesive, or a forming material of a display device, a semiconductor device, an electronic part, an optical part or a building material. Specifically, as a material for forming a display device, it can be used as a layer forming material and an image forming material in a color filter, a film for a flexible display, a resist material, an alignment film, and the like. As a material for forming the semiconductor device, a resist material, a layer forming material such as a buffer coating film, and the like can be used. As the material for forming the electronic component, it can be used as a sealing material or a layer forming material in a printed wiring board, an interlayer insulating film, a wiring coating film and the like. As the material for forming the optical component, it can be used as an optical material and a layer forming material, such as a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, and the like. The building material can be used for paints, coatings, and the like.

The photosensitive resin composition of the present invention is mainly used as a pattern forming material and the pattern film thus formed serves as a permanent film containing polybenzoxazole as a component for imparting heat resistance and insulation, A protective film for a flip chip device, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, an insulating material for a passive component, a solder resist or a coverlay film, etc. Protective films for printed wiring boards, liquid crystal alignment films, and the like.

The method for producing the photosensitive resin composition of the present invention is not particularly limited, but a photosensitive resin composition containing a polybenzoxazole precursor (A), which is a polyamide resin obtained from the reaction of the diamine component and a dicarboxylic acid component, with a photosensitizer (B) In the case of the resin composition production method, the diamine can be suitably prepared by using a diamine component having a benzoxazole structure represented by any one of the following general formulas (5), (6) and (7). The production of a photosensitive resin composition containing a polyamide resin (? -1), a polybenzoxazole precursor (? -2) and a photosensitive agent (B) obtained from the reaction of the diamine component and the dicarboxylic acid component Method can be suitably produced by using a diamine component having a benzoxazole structure represented by any one of the following general formulas (5), (6) and (7) as the diamine.

(Formula (5) of, R ₁ to R ₄ will any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, may be the same or different search. R ₅ to R ₉ is Any one of R ₁ to R ₄ and any one of R ₅ to R _{9 may} be the same or different and may be the same or different from each other and is preferably a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, Is an amino group)

(Formula (6) of, R ₁₀ to R ₁₄ is a search even will any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, sulfonyl group or amino group, may be the same or different. R ₁₅ to R ₁₉ is Any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R _{19 may} be the same or different from each other and may be the same or different from each other and is preferably a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, R ₂₀ and R ₂₁ are each independently a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group and may be the same or different)

(Formula (7) of, R ₂₂ to R ₂₆ will any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, may be the same or different search. R ₂₇ to R ₃₁ is Provided that any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R _{31 may} be the same or different from each other, R ₃₂ and R ₃₃ are each independently a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group and may be the same or different)

<Examples>

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. In the following, &quot; part &quot; and &quot;% &quot; are on a mass basis unless otherwise specified.

(Synthesis of polybenzoxazole precursor A-1) (benzooxazole moiety 10%)

Methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer and a thermometer, to which 10.29 g (28.1 mmol) of bis (3-amino-4-hydroxyphenyl) Aminophenyl) -5-aminobenzoxazole (0.70 g, 3.12 mmol) were dissolved with stirring. Thereafter, the flask was immersed in an ice bath, 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was added over 10 minutes while maintaining the inside of the flask at 0 to 5 ° C , And the mixture was stirred in an ice bath for 30 minutes. Thereafter, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance: 18.2 M? 占 ㎝ m), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone and added to 1 L of ion-exchanged water. The precipitated individual was recovered and dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the carboxyl group end. The weight average molecular weight determined by GPC standard standard polystyrene conversion was 31,700.

(Synthesis of polybenzoxazole precursor A-2) (benzoxazole part 5%)

Methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer and a thermometer, and 10.86 g (29.65 mmol) of bis (3-amino-4-hydroxyphenyl) Aminophenyl) -5-aminobenzoxazole (0.7 g, 1.55 mmol) were dissolved with stirring. Thereafter, the flask was immersed in an ice bath, 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was added over 10 minutes while maintaining the inside of the flask at 0 to 5 ° C , And the mixture was stirred in an ice bath for 30 minutes. Thereafter, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance: 18.2 M? 占 ㎝ m), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone and added to 1 L of ion-exchanged water. The precipitated individual was recovered and dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the carboxyl group end. The weight average molecular weight determined by GPC standard standard polystyrene conversion was 33,700.

(Synthesis of polybenzoxazole precursor R-1) (benzooxazole moiety 30%)

Methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer and a thermometer, to which 8.00 g (21.8 mmol) of bis (3-amino-4-hydroxyphenyl) Aminophenyl) -5-aminobenzoxazole (2.0 g, 9.32 mmol) were dissolved with stirring. Thereafter, the flask was immersed in an ice bath, 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was added over 10 minutes while maintaining the inside of the flask at 0 to 5 ° C , And the mixture was stirred in an ice bath for 30 minutes. Thereafter, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance: 18.2 M? 占 ㎝ m), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone and added to 1 L of ion-exchanged water. The precipitated individual was recovered and dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the carboxyl group end. The weight average molecular weight determined by GPC standard standard polystyrene conversion was 28,200.

(Synthesis of polybenzoxazole precursor R-2) (benzooxazole moiety 0%)

212 g of N-methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer and a thermometer, and 60.52 g (165.22 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved with stirring. Thereafter, the flask was immersed in an ice bath, and 53.02 g (179.65 mmol) of 4,4-diphenyl ether dicarboxylic acid chloride was added in 5 g portions over 30 minutes while maintaining the inside of the flask at 0 to 5 ° C And stirred in an ice bath for 30 minutes. Thereafter, stirring was continued at room temperature for 5 hours. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance: 18.2 M? 占 ㎝ m), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone and added to 1 L of ion-exchanged water. The precipitated solid was recovered and dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor (R-2) having the following repeating structure at the carboxyl group end. The polybenzoxazole precursor (R-2) had a number average molecular weight (Mn) of 13,100, a weight average molecular weight (Mw) of 32,100 and Mw / Mn of 2.45.

The polybenzoxazole precursors A-1, A-2, R-1 and A-3 described later have an amide structure having the following benzoxazole structure and other amide structures in the polyamide structure. The polybenzoxazole precursor R-2 has the following other amide structure in the polyamide structure.

An amide structure having a benzoxazole structure

ㆍ Other amide structures

(Example 1)

(Property evaluation)

100 parts by mass of the polybenzoxazole precursor A-1 and 10 parts by mass of the diazonaphthoquinone compound were dissolved in 300 parts by mass of? -Butyrolactone and then filtered through a 0.2 占 퐉 filter to obtain a varnish of photosensitive resin composition. The varnish was coated on a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 캜 for 30 minutes to obtain a coating film having a thickness of about 30 탆. Subsequently, the silicon wafer with the coated film was heated in an oven at 150 占 폚 for 30 minutes, 250 占 폚 for 30 minutes, and 320 占 폚 for 30 minutes. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis).

(Pattern making)

The varnish was coated on a 6-inch silicon wafer by using a spin coater and dried at 120 DEG C for 3 minutes on a hot plate to obtain a coating film having a thickness of about 5 mu m. The obtained coating film was subjected to i-line exposure at 300 to 600 mJ / cm &lt; 2 &gt; through a mask having a pattern of 1 to 30 mu m drawn thereon. After exposure, the resist film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds and rinsed with water to obtain a pattern of a positive cured film.

(Evaluation of unexposed portion retention rate)

The film thickness of the cured film after development was measured, and the ratio of the film thickness before development to the unexposed film residual ratio was obtained.

Remaining film ratio = (film thickness after development / 占 퐉) / (film thickness before development / 占 퐉) 占 100

(Evaluation of sensitivity and resolution)

The size of the minimum pattern that can be patterned without scumming by observing the pattern after development with an electron microscope (SEM " JSM-6010 ") is referred to as resolution (L (탆) / S (탆)), .

(Example 2)

The evaluation was conducted in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to A-2.

(Comparative Example 1)

The evaluation was conducted in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to R-1.

When the developability evaluation was carried out, the exposed portions were not dissolved in the developer and no pattern was obtained.

(Comparative Example 2)

The evaluation was conducted in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to R-2.

When the developability was evaluated, all of the unexposed portions of the exposed portions were dissolved in the developer, and no pattern was obtained.

(Synthesis of polybenzoxazole precursor A-3) (2% of benzoxazole part)

Methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer and a thermometer, to which 11.21 g (30.6 mmol) of bis (3-amino-4-hydroxyphenyl) Aminophenyl) -5-aminobenzoxazole (0.145 g, 0.644 mmol) were dissolved with stirring. The flask was then immersed in an ice bath and 10.10 g (34.2 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was added over 10 minutes while maintaining the flask at 0-5 &lt; 0 &gt; C , And the mixture was stirred in an ice bath for 30 minutes. Thereafter, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance: 18.2 M? 占 ㎝ m), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone and added to 1 L of ion-exchanged water. The precipitated individual was recovered and dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the carboxyl group end. The weight average molecular weight determined by GPC standard standard polystyrene conversion was 34,500.

(Example 3)

100 parts by weight of polybenzoxazole precursor A-2, 10 parts by weight of diazonaphthoquinone compound and 5 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573) were added to 300 parts by weight of? -Butyrolactone And the mixture was filtered through a 0.2 mu m filter to obtain a varnish of a photosensitive resin composition. The varnish was coated on a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 캜 for 30 minutes to obtain a coating film having a thickness of about 30 탆. Subsequently, the silicon wafer with the coated film was heated in an oven at 150 占 폚 for 30 minutes and at 250 占 폚 for 30 minutes. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis).

Separately, the varnish was coated on a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 ° C for 30 minutes to obtain a coating film having a thickness of about 5 μm. The obtained coating film was subjected to i-line exposure at 300 to 600 mJ / cm &lt; 2 &gt;. After exposure, the resist film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds and rinsed with water to obtain a pattern of a positive cured film.

(Example 4)

Except that TML-BPAF-MF was added in an amount of 10 parts by mass.

(Example 5)

Evaluation was carried out in the same manner as in Example 3 except that the polybenzoxazole precursor was changed to A-3 and 10 parts by mass of MX270 (produced by Sanwa Chemical Co., Ltd.) was added.

(Example 6)

, 5 parts by mass of TML-BPAF-MF (Honshu Kagaku), and 5 parts by mass of MW390 (Sanwa Chemical) were added.

(Example 7)

100 parts by mass of polybenzoxazole precursor A-3, 10 parts by mass of diazonaphthoquinone compound, 5 parts by mass of TML-BPAF-MF, 5 parts by mass of 1,4-benzene dimethanol, 5 parts by mass of methoxysilane (KBM-573) was dissolved in 300 parts by mass of? -Butyrolactone and then filtered through a 0.2 占 퐉 filter to obtain a varnish of photosensitive resin composition. The varnish was coated on a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 캜 for 30 minutes to obtain a coating film having a thickness of about 30 탆. Subsequently, the silicon wafer with the coated film was heated in an oven at 150 占 폚 for 30 minutes, 250 占 폚 for 30 minutes, and 320 占 폚 for 30 minutes. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis). Separately, the varnish was coated on a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 ° C for 30 minutes to obtain a coating film having a thickness of about 5 μm. The obtained coating film was subjected to i-line exposure at 300 to 600 mJ / cm &lt; 2 &gt;. After exposure, the resist film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds and rinsed with water to obtain a pattern of a positive cured film.

(Example 8)

Except that the polybenzoxazole precursor was changed to A-2, 1 part by mass of dithiothreitol and 1 part by mass of diphenyl ether were added, and TML-BPAF-MF and 1,4-benzene dimethanol were not added The evaluation was carried out in the same manner as in Example 7. [

(Example 9)

100 parts by mass of the polybenzoxazole precursor A-2, 10 parts by mass of the diazonaphthoquinone compound, 1 part by mass of mercaptotriazole and 5 parts by mass of KBM-573 were dissolved in 300 parts of? -Butyrolactone, Followed by filtration to obtain a varnish of a photosensitive resin composition. The varnish was coated on a 6-inch silicon wafer using a spin coater and dried on a hot plate at 110 占 폚 for 30 minutes to obtain a coating film having a thickness of about 30 占 퐉. Subsequently, the silicon wafer with the coated film was heated in an oven at 150 占 폚 for 30 minutes and at 320 占 폚 for 30 minutes. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis). The residual film ratio, resolution, and sensitivity were evaluated in the same manner as described above.

(Example 10)

Measurement and evaluation were conducted in the same manner as in Example 9 except that the polybenzoxazole precursor was changed to A-3.

(Example 11)

Except that 5 parts by mass of MW390 was added as a melamine compound.

(Pattern making)

Each of the compositions of Examples 9 to 11 was coated on a 5-inch Cu sputtered silicon wafer using a spin coater and dried on a hot plate at 110 占 폚 for 3 minutes to obtain a coating film having a thickness of about 5 占 퐉. The obtained coating film was subjected to i-line exposure at 500 to 800 mJ / cm &lt; 2 &gt; through a mask having a pattern of 1 to 30 mu m drawn thereon. After exposure, the resist film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 80 seconds and rinsed with water to obtain a pattern of a positive cured film.

(Developability)

The developed L / S = 20 mu m / 20 mu m pattern was observed with an electron microscope (SEM " JSM-6010 ") and the developability was evaluated according to the following criteria.

?: The residual film ratio after development is 90% or more, and the surface of the patterned cured film has no shape or cracks.

?: The residual film ratio after development is 80% or more and less than 90%, and the surface of the cured film has no shape or cracks.

X: Remaining film ratio is less than 80% or the surface of the cured film has a shape or a crack.

(Development residue)

After development, the pattern of L / S = 20 mu m / 20 mu m was observed with an electron microscope (SEM " JSM-6010 ") and the presence or absence of development residue was checked. A case where the residue-free portion had a narrow pattern was rated as &amp; cir &amp; and a case where the residue was present was evaluated as x.

From the results shown in the above table, it can be seen that the photosensitive resin composition of the present invention can form a cured film having high heat resistance and low thermal expansion coefficient, and excellent in sensitivity and resolution.

Claims (9)

As a photosensitive resin composition containing a polybenzoxazole precursor (A), which is a polyamide-based resin obtained from the reaction of a diamine component and a dicarboxylic acid component, and a photosensitizer (B)
Wherein the proportion of the structure represented by the following general formula (1) is 0.1 to 15% and the proportion of the structure represented by the following general formula (2) is 85 to 99.9 %. &Lt; / RTI &gt;

(In the general formula (1), P is a residue of a diamine component and is a divalent group having a benzoxazole structure represented by any one of the following general formulas (1-1), (1-2) and (1-3) Is a residue of a dicarboxylic acid component and is a divalent organic group)

(Wherein R ₁ to R _{4 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) R ₅ to R _{9 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is a direct bond to a nitrogen atom in the general formula (1)

(In the general formula (1-2), R ₁₀ to R _{14 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R ₁₅ to R _{19 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is a direct bond with a nitrogen atom in the general formula (1), R ₂₀ and R ₂₁ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(Wherein R ₂₂ to R _{26 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) R ₂₇ to R _{31 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (1) , Any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is a direct bond with a nitrogen atom in the general formula (1), R ₃₂ and R ₃₃ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(In the general formula (2), X is a residue of a dihydroxydiamine and is a tetravalent organic group, Y is a residue of a dicarboxylic acid component, and is a divalent organic group) 1. A photosensitive resin composition comprising a polyamide resin (? -1) obtained from the reaction of a diamine component and a dicarboxylic acid component, a polybenzoxazole precursor (? -2) and a photosensitive agent (B)
Wherein the polyamide-based resin (? -1) has a structure represented by the following general formula (3)
Wherein the polybenzoxazole precursor (? -2) has a structure represented by the following general formula (4)
Wherein the compounding ratio of the polyamide resin (? -1) and the polybenzoxazole precursor (? -2) is 0.1: 99.9 to 15:85 in terms of mass.

(In the general formula (3), P is a residue of a diamine component and is a divalent group having a benzoxazole structure of any of the following general formulas (3-1), (3-2) and (3-3) Is a residue of a dicarboxylic acid component and is a divalent organic group, and n is an integer of 1 or more)

(3-1), R ₁ to R ₄ are any of a direct bond with a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group or a nitrogen atom in the general formula (3) R ₅ to R _{9 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is a direct bond with a nitrogen atom in the general formula (3)

(In the general formula (3-2), R ₁₀ to R ₁₄ are any of a direct bond with a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, R ₁₅ to R ₁₉ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is a direct bond with a nitrogen atom in the general formula (3), R ₂₀ and R ₂₁ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(Wherein R ₂₂ to R _{26 each} represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) R ₂₇ to R ₃₁ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group and a direct bond with a nitrogen atom in the general formula (3) , Any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is a direct bond with a nitrogen atom in the general formula (3), R ₃₂ and R ₃₃ are each a hydrogen atom, Each of which may be the same or different from a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group)

(In the general formula (4), X is a residue of a dihydroxydiamine, a quadrivalent organic group, Y is a residue of a dicarboxylic acid component, is a divalent organic group, and m is an integer of 1 or more) The photosensitive resin composition according to claim 1 or 2, further comprising a crosslinking agent. The photosensitive resin composition according to claim 1 or 2, further comprising a triazole compound having a mercapto group. A dry film having a resin layer obtained by applying the photosensitive resin composition according to claim 1 or 2 to a film and drying the film. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2, or a resin film of a dry film having a resin layer obtained by applying the photosensitive resin composition to a film and drying the film. A semiconductor device having the cured product according to claim 6. A printed wiring board having the cured product according to claim 6. An electronic part having the cured product according to claim 6.