KR101182248B1 - Positive photosensitive resin composition - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition, the positive photosensitive resin composition comprising: (A) a polybenzoxazole precursor having a repeating unit represented by the following formula (1); (B) a photosensitive diazoquinone compound; (C) silane compound; (D) a phenol compound; And (E) a solvent, wherein one end of the polybenzoxazole precursor is thermally polymerizable derived from a first monocarboxylic acid halide selected from the group consisting of a compound represented by the following Chemical Formulas 2 to 5 and combinations thereof It includes a functional group, and the other end includes a thermopolymerizable functional group derived from a second monocarboxylic acid halide represented by the following formula (6).

[Formula 1]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

(In the above Chemical Formulas 1 to 6, the definition of each substituent is the same as defined in the specification.)

The positive photosensitive resin composition of the present invention can form crosslinks efficiently during thermosetting, thereby lowering the molecular weight of the polymer before curing, and excellent in mechanical properties, resolution, pattern shape, and residue removal property of the film after curing. Hygroscopicity and membrane shrinkage can be lowered.

Positive type, polybenzoxazole, terminal block monomer, alkali aqueous solution, phenolic compound, semiconductor device

Description

Positive photosensitive resin composition {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a positive photosensitive resin composition, and more particularly has a high sensitivity and high resolution, good pattern shape, excellent residue removal properties, low film shrinkage, excellent mechanical properties and final cured film It relates to a positive photosensitive resin composition having low hygroscopicity.

Conventionally, polyimide resins having excellent heat resistance, electrical properties, mechanical properties, and the like have been used for surface protection films and interlayer insulating films of semiconductor devices. This polyimide resin is recently used in the form of a photosensitive polyimide precursor composition, and is easy to apply. After applying the polyimide precursor composition on a semiconductor device, patterning by ultraviolet rays, development, and thermal imidization treatment are performed. It is possible to easily form a surface protective film, an interlayer insulating film and the like. Therefore, it has a feature that a process can be significantly shortened compared with the conventional non-photosensitive polyimide precursor composition.

The photosensitive polyimide precursor composition has a positive type in which the exposed part is dissolved by development and a negative type in which the exposed part is cured. In the positive type, a non-toxic aqueous alkali solution can be used as a developer. The positive photosensitive polyimide precursor composition includes polyamic acid as a polyimide precursor, diazonaphthoquinone as a photosensitive material, and the like. However, the positive photosensitive polyimide precursor composition has a problem in that the carboxylic acid of the polyamic acid used is too soluble in alkali to obtain a desired pattern.

In order to solve this problem, a substance in which a phenolic hydroxyl group is introduced instead of carboxylic acid, such as reacting an alcohol compound having at least one hydroxyl group through an ester bond with polyamic acid (see Japanese Patent Application Laid-Open No. 10-307393), has been proposed. This material has insufficient developability and has a problem of reducing the film or peeling the resin from the substrate.

In another method, a material in which a diazonaptoquinone compound is mixed with a polybenzoxazole precursor (Japanese Patent Laid-Open No. 63-96162) has recently been attracting attention, but especially when the polybenzoxazole precursor composition is actually used, Since the film reduction amount of the unexposed part is large, it is difficult to obtain a desired pattern after development. In order to solve this problem, if the molecular weight of the polybenzoxazole precursor is increased, the film reduction amount of the unexposed part becomes small, but developing residues occur in the exposed part during development, resulting in poor resolution and long developing time of the exposed part. there was.

In order to solve this problem, it is reported that the amount of film reduction of unexposed portions during development is suppressed by adding a specific phenol compound to the polybenzoxazole precursor composition (Japanese Patent Laid-Open No. 9-302221 and Japanese Patent Laid-Open No. 2000). -292913). However, in this method, the effect of suppressing the reduction amount of the unexposed portion is insufficient, and there is a continuous demand for research to increase the film reduction suppression effect without generating development residues.

In addition, since the thermosetting film formed using such a polyimide or polybenzoxazole precursor composition continuously remains in the semiconductor device and acts as a surface protective film, mechanical properties of the film such as tensile strength, elongation and Young's modulus are particularly important factors. . In particular, with the rapid development of semiconductor packaging methods, the mechanical properties of polyimide or polybenzoxazole films used as surface protective films are very important to cope with their development. However, in the case of polyimide or polybenzoxazole precursors that are generally used, such mechanical properties, more specifically, elongation often fall below an appropriate level, and various methods of using various additives or crosslinking during thermal curing to solve this problem. Examples have been reported of using precursor compounds and the like of which structures can occur.

However, in the case of these studies, the mechanical properties represented by elongation can be improved, but the optical properties such as sensitivity and resolution do not reach practical levels, and thus excellent mechanical properties are achieved without bringing down such optical properties. There is an urgent need for research on how to do this.

At the same time, due to the nature of these compositions that must remain as surface protective films on the surface of the semiconductor, these thermosetting films should be particularly excellent in hygroscopicity and chemical resistance. The polyimide and polybenzoxazole thermosets used in general show some degree of hygroscopicity and chemical resistance, but are still of practical value for polybenzoxazole and polyimide precursors made using terminal block monomers. Are not obtained.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having excellent sensitivity and resolution, good pattern shape, and excellent residue removal properties, and particularly, an end-capping monomer having an appropriate reactivity and structure at the end of a molecular chain. By lowering the molecular weight of the polymer by the introduction of the present invention is to provide a positive photosensitive composition capable of optimally maintaining the balance between the solid content and the viscosity in the resin composition, and to exhibit low film shrinkage and excellent film properties after curing.

This invention also provides the photosensitive resin film, such as a protective film or an interlayer insulation film manufactured using the said positive photosensitive resin composition.

This invention also provides the semiconductor element containing the photosensitive resin film manufactured using the said positive photosensitive resin composition.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

According to an embodiment of the present invention, (A) polybenzoxazole precursor having a repeating unit represented by the following formula (1); (B) a photosensitive diazoquinone compound; (C) silane compound; (D) a phenol compound; And (E) a solvent, wherein one end of the polybenzoxazole precursor is heated from a first monocarboxylic acid halide selected from the group consisting of a compound represented by the following Chemical Formulas 2 to 5 and combinations thereof It provides a positive photosensitive resin composition comprising a synthetic functional group, and the other end thereof comprises a thermopolymerizable functional group derived from a second monocarboxylic acid halide represented by the following formula (6).

[Formula 1]

(In the formula 1,

X ₁ is an aromatic organic group or a 4 to 6-valent aliphatic organic group ,

X ₂ may be an aromatic organic group or a 2 to 6-valent aliphatic organic group, or may be represented by the following Chemical Formula 7,

Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2 to 6-valent aliphatic organic group,

M ₁ and m ₂ are molar ratios, m ₁ + m ₂ is 100 mol%,

M ₁ is 60 to 100 mol%,

M ₂ is 0 to 40 mol%,

[Formula 7]

In Chemical Formula 7,

R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ are the same or different from each other, and each independently a group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a hydroxy group Is selected from,

R ₃ and R ₄ are the same or different from each other, and each independently a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,

k ₁ is an integer from 1 to 50.)

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

(In Chemical Formulas 2 to 6,

Z ₁ to Z ₅ are the same or different from each other, and each independently a halide,

R ₁₆ to R ₂₂ are the same or different from each other, and are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 10 carbon atoms,

R ₂₃ is selected from the group consisting of an aryl group, a cycloalkyl group, an aryl group substituted with an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group substituted with an alkyl group having 1 to 10 carbon atoms,

n ₈ is an integer from 1 to 9,

n ₉ , n ₁₀ , and n ₁₂ are integers from 1 to 4,

n ₁₁ and n ₁₄ are Is an integer from 1 to 5

n ₁₃ is an integer of 1 to 3.)

According to another embodiment of the present invention, a photosensitive resin film prepared by using the positive photosensitive resin composition is provided.

According to another embodiment of the present invention, there is provided a semiconductor device including a photosensitive resin film prepared using the positive photosensitive resin composition.

Other specific details of embodiments of the present invention are included in the following detailed description.

Positive type photosensitive resin composition of this invention can form bridge | crosslinking at the time of thermosetting, and can maintain the balance of solid content and viscosity in a resin composition optimally by lowering the molecular weight of a polymer before hardening, and after hardening, it is excellent mechanical property It has good resolution, low film shrinkage and hygroscopicity.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Photosensitive resin composition according to an embodiment of the present invention (A) polybenzoxazole precursor (polybenzoxazole precursor) having a repeating unit represented by the formula (1); (B) a photosensitive diazoquinone compound; (C) silane compound; (D) a phenol compound; And (E) a solvent.

Unless stated otherwise in the present specification, "substituted" means that one or more hydrogen atoms in the functional group of the present invention is a halogen atom (F, Br, Cl, or I), hydroxy group, nitro group, cyano group, amino group (-NH ₂ , -NH (R), -N (R ') (R "), R, R' and R" are independently of each other an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine or hydrazone group, carboxyl group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group Mean substituted by one or more substituents selected from the group.

In addition, "alkyl group" means an alkyl group having 1 to 30 carbon atoms, "alkylene group" means an alkylene group having 1 to 30 carbon atoms, "alkenyl group" means an alkenyl group having 2 to 16 carbon atoms, and "alky "Nyl group" means an alkynyl group having 2 to 30 carbon atoms, "alkoxy group" means an alkoxy group having 1 to 30 carbon atoms, "aryl group" means an aryl group having 6 to 30 carbon atoms, "arylene group" means It means an arylene group of 6 to 30, and "heteroaryl group" means a heteroaryl group having 2 to 30 carbon atoms.

In addition, the term "aliphatic organic group" used herein means alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, or alkynyl having 2 to 30 carbon atoms, and "aromatic organic group" means an aryl group having 6 to 30 carbon atoms. Or a heteroaryl group having 2 to 30 carbon atoms.

Hereinafter, each structural component of the positive photosensitive resin composition will be described in detail.

(A) polybenzoxazole precursor

The polybenzoxazole precursor has a repeating unit represented by the following Chemical Formula 1, and one end thereof is derived from a first monocarboxylic acid halide selected from the group consisting of a compound represented by the following Chemical Formulas 2 to 5 and a combination thereof And a thermally polymerizable functional group, the other end of which comprises a thermopolymerizable functional group derived from a second monocarboxylic acid halide represented by the following formula (6).

[Formula 1]

In Formula 1,

X ₁ is an aromatic organic group or a 4 to 6-valent aliphatic organic group ,

X ₂ may be an aromatic organic group or a 2 to 6-valent aliphatic organic group, or may be represented by the following Chemical Formula 7,

Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2 to 6-valent aliphatic organic group,

M ₁ and m ₂ are molar ratios, m ₁ + m ₂ is 100 mol%,

M ₁ is 60 to 100 mol%,

M ₂ is 0 to 40 mol%,

[Formula 7]

In Chemical Formula 7,

R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ are the same or different from each other, and each independently a group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a hydroxy group Is selected from

R ₃ and R ₄ are the same or different from each other, and each independently a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,

k ₁ is an integer from 1 to 50.

Specifically, X ₁ is 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) Sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxy Phenyl) -1,1,1,3,3,3-hexafluoropropane, and combinations thereof.

Preferably, X ₁ may be a compound represented by the following Chemical Formula 8 or 9, but is not limited thereto.

[Formula 8]

[Chemical Formula 9]

In Chemical Formulas 8 and 9,

The A ₁ may be selected from the group consisting of O, CO, CR ₈ R ₉ , SO ₂ , S, and a single bond,

R ₈ and R ₉ may be the same or independently selected from hydrogen, and a substituted or unsubstituted alkyl group, preferably R ₈ and R ₉ are fluoroalkyl,

R ₅ to R ₇ are the same or different from each other, and each independently hydrogen, and may be selected from the group consisting of a substituted or unsubstituted alkyl group,

N ₁ may be an integer of 1 to 2,

N ₂ and n ₃ may be the same or different from each other, and may each independently be an integer of 1 to 3.

Typically, the X ₂ may be derived from an aromatic diamine or a silicone diamine, but is not limited thereto.

Specific examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6- Aromatic amines such as naphthalenediamine; Or a compound in which the aromatic ring is substituted with an alkyl group or a halogen atom in the aromatic amine; Bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1, 4-bis (4-aminophenoxy) benzene and the like, but are not limited thereto.

Specific examples of the silicone diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyl Disiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, 1,3-bis (aminopropyl Tetramethyldisiloxane And the like, but is not limited thereto.

In addition, the aromatic diamine monomers may be used alone or in combination, and may be used by mixing the aromatic diamine monomer and the silicone diamine monomer.

Typically, Y ₁ and Y ₂ may be a residue of a derivative of dicarboxylic acid, but is not limited thereto.

Specific examples of the derivatives of the dicarboxylic acid include carbonyl halide derivatives or The active compound which is an active ester type derivative which made dicarboxylic acid and 1-hydroxy-1,2,3-benzotriazole react etc. is mentioned. Specific examples include diphenyloxydicarboxylic acid chloride, bis (phenylcarboxylic acid chloride) sulfone, bis (phenylcarboxylic acid chloride) ether, bis (phenylcarboxylic acid chloride) phenone, phthalic carboxylic acid dichloride, terephthal Rick di chloride, isophthalic carboxylic di chloride, di-carboxylic chloride, oxy diphenyl dicarboxylate benzotriazole, 4, 4'-oxydiphthalic benzo carbonyl chloride, and the compound selected from the group consisting of such as It may include, but is not limited thereto.

More preferably, the Y ₁ and Y ₂ are the same or different from each other, and each independently may be selected from the group consisting of the following formula 10 to 12, but is not necessarily limited thereto.

[Formula 10]

[Formula 11]

[Chemical Formula 12]

In Chemical Formulas 10 to 12,

R ₁₀ to R ₁₃ are the same or different from each other, and each independently hydrogen, and may be selected from the group consisting of a substituted or unsubstituted alkyl group,

N ₄ , n ₆ , and n ₇ may be an integer of 1 to 4, n ₅ may be an integer of 1 to 3,

The A ₂ may be selected from the group consisting of O, CR ₁₄ R ₁₅ , CO, CONH, S, and SO ₂ , wherein R ₁₄ and R ₁₅ are the same or different from each other, and are each independently hydrogen, substituted or It may be selected from the group consisting of an unsubstituted alkyl group, and a fluoroalkyl group.

Specifically, each of the thermopolymerizable functional groups is derived from a mixture of a first monocarboxylic acid halide selected from the group consisting of Formulas 2 to 5 and combinations thereof and a second monocarboxylic acid halide represented by Formula 6 It is desirable to be.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

In Chemical Formulas 2 to 6,

Z ₁ to Z ₅ are the same or different from each other, and each independently a halide,

R ₁₆ to R ₂₂ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms,

R ₂₃ is selected from the group consisting of an aryl group, a cycloalkyl group, an aryl group substituted with an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group substituted with an alkyl group having 1 to 10 carbon atoms,

n ₈ is an integer from 1 to 9,

n ₉ , n ₁₀ , and n ₁₂ are integers from 1 to 4,

n ₁₁ and n ₁₄ are integers from 1 to 5,

n ₁₃ is an integer of 1-3.

In addition, the first monocarboxylic acid halide is preferably a monocarboxylic acid halide having a carbon-carbon multiple bond.

In addition, the halide of the first monocarboxylic acid halide and the second mono carboxylic acid halide is preferably chloride.

In Chemical Formulas 3, 4, and 5, the functional group and carboxylic acid halide substituent having the carbon-carbon multiple bond is more preferably substituted at the para position of the benzene ring.

Representative examples of the first monocarboxylic acid halide include 5-norbornene-2-carboxylic acid halide, 4-namidido benzoyl halide, 4- (2-phenylmaleimido) benzoyl halide, 4- (4 -Phenylethynylphthalimido) benzoyl halide, 4- (3-phenylethynylphthalimido) benzoyl halide, 4-maleimido benzoyl halide, And a combination thereof may be selected, and a representative example of the second monocarboxylic acid halide may be selected from the group consisting of benzoyl halide, cyclohexyl halide, and combinations thereof, It is not limited.

The mixing ratio of the first monocarboxylic acid halide monomer and the second monocarboxylic acid halide monomer is preferably 8: 2 to 2: 8. When mixed in the above ratio, the mechanical strength, in particular Young's modulus and elongation of the photosensitive resin film can be significantly improved, which is preferable.

It is preferable that the weight average molecular weight (Mw) of the polybenzoxazole precursor is in the range of 3,000 to 300,000, and when the weight average molecular weight is less than 3,000, sufficient physical properties are not obtained. It is not preferable because solubility becomes low and handling becomes very difficult.

(B) photosensitive diazoquinone compound

As said photosensitive diazoquinone compound, the compound which has a 1, 2- benzoquinone diazide structure or a 1, 2- or a ptoquinone diazide structure can be used preferably. This is a material known from US Pat. Nos. 2,772,975, 2,797,213 and 3,669,658.

Representative examples of the photosensitive diazoquinone compound include compounds represented by the following Chemical Formulas 13 to 16, but are not limited thereto.

[Chemical Formula 13]

(In Chemical Formula 13,

R ₃₁ to R ₃₃ may be the same or different from each other, and may each independently be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

D ₁ to D ₃ may be each independently OQ,

Q may be hydrogen, Formula 14a or Formula 14b, wherein Q may not be hydrogen at the same time,

N ₃₁ to n ₃₃ are the same or different from each other, and each independently an integer of 1 to 3.)

[Formula 14a]

[Formula 14b]

[Formula 15]

(In Chemical Formula 15,

R ₃₄ may be hydrogen or a substituted or unsubstituted alkyl group, preferably the alkyl group may be CH ₃ ,

D ₄ to D ₆ may be OQ,

Q is the same as defined in Formula 13,

N ₃₄ to n ₃₆ are the same or different from each other, and each independently an integer of 1 to 3.)

[Chemical Formula 16]

(In Chemical Formula 16,

A ₃ may be CO or CRR ′ and R is And R 'are the same or different from each other, and each independently may be a substituted or unsubstituted alkyl group,

D ₇ to D ₁₀ may be the same or independently of each other, hydrogen, a substituted or unsubstituted alkyl group, OQ, or NHQ,

Q is the same as defined in Formula 13,

N ₃₇ , n ₃₈ , n ₃₉ , and n ₄₀ are the same or different from each other, and each independently an integer of 1 to 4,

n ₃₇ + n ₃₈ and n ₃₉ + n ₄₀ may be each independently an integer of 5 or less,

However, at least one of D ₇ to D ₈ may be OQ, and one aromatic ring may include 1 to 3 OQs, and the other aromatic ring may include 1 to 4 OQs.)

[Chemical Formula 17]

(In Formula 17,

R ₃₅ to R ₄₂ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₄₁ and n ₄₂ are the same or different from each other, and each independently may be an integer of 1 to 5, more preferably an integer of 2 to 4,

Q is the same as defined in formula 13.)

It is preferable that the content of the said photosensitive diazoquinone compound is 5-100 weight part with respect to 100 weight part of (A) polybenzoxazole precursors. When the content of the photosensitive diazoquinone compound is included in an amount of 5 to 100 parts by weight, the pattern is well formed without residue by exposure, and there is no loss of film thickness during development, and a good pattern can be obtained.

(C) silane compound

The said silane compound can improve the adhesive force of the photosensitive resin composition and a board | substrate.

As the silane compound, one represented by the following formula (18) may be used.

[Chemical Formula 18]

(In Formula 18,

R ₆₁ may be selected from the group consisting of a vinyl group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, and preferably 3- (meth) acryloxypropyl, p-styryl, or 3- (Phenylamino) propyl.

R ₆₂ to R ₆₄ are the same or different from each other, and each independently selected from the group consisting of a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, and halogen, wherein at least one of R ₆₂ to R ₆₄ Is an alkoxy group or halogen, preferably the alkoxy group is an alkoxy group having 1 to 8 carbon atoms, the alkyl group may be an alkyl group having 1 to 20 carbon atoms.

Representative examples of the silane compound include compounds represented by the following Chemical Formulas 19 and 20; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, vinyltris (β-methoxyethoxy) silane; Or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldie Oxysilane; Or a silane compound containing a carbon-carbon unsaturated bond such as trimethoxy [3- (phenylamino) propyl] silane, and most preferably vinyltrimethoxysilane or vinyltriethoxysilane. All.

[Formula 19]

(In Chemical Formula 19,

R ₆₅ is NH ₂ or CH ₃ CONH, R ₆₆ to R ₆₈ are the same or independently of each other, a substituted or unsubstituted alkoxy group, preferably the alkoxy group may be OCH ₃ or OCH ₂ CH ₃ , n ₆₁ may be an integer from 1 to 5.)

[Chemical Formula 20]

(In the above formula (20)

R ₆₉ to R ₇₂ are the same or different from each other, each independently represent a substituted or unsubstituted alkoxy group, preferably OCH ₃ ,

R ₇₃ and R ₇₄ are the same or different from each other, each independently represent a substituted or unsubstituted amino group, preferably NH ₂ or CH ₃ CONH,

N ₆₂ and n ₆₃ may be the same or different from each other, and may each independently be an integer of 1 to 5.)

The content of the silane compound is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the content of the silane compound is within the above range, the adhesion between the upper and lower membrane layers is excellent, there is almost no residual film after development, and the optical properties (transmittance) and mechanical properties (tensile strength, elongation, Young's modulus) of the membrane are preferable.

(D) Phenol compound

The phenolic compound may increase the dissolution rate and sensitivity of the exposed part when developing with an aqueous alkali solution, and serves to enable patterning at high resolution without developing residues during development.

In addition, the phenolic compound of the present invention has a functional group capable of thermal polymerization, and can form crosslinks with the (A) polybenzoxazole precursor during thermosetting.

Representative examples of such phenolic compounds include, but are not limited to, those represented by the following Chemical Formulas 21 to 26.

[Chemical Formula 21]

(In the formula (21)

R ₉₁ to R ₉₃ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

R ₉₄ to R ₉₈ are the same or different from each other, and each independently may be selected from the group consisting of hydrogen, OH, and a substituted or unsubstituted alkyl group, preferably the alkyl group may be CH ₃ ,

n ₉₁ may be an integer from 1 to 5.

[Formula 22]

(In Chemical Formula 22,

R ₉₉ to R ₁₀₄ are the same or different from each other, and each independently may be selected from the group consisting of hydrogen, OH, and a substituted or unsubstituted alkyl group,

A ₄ may be CR′R ″ or a single bond, and R ′ and R ″ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group, and preferably the alkyl group is CH Can be ₃ ,

n ₉₂ + n ₉₃ + n ₉₄ and n ₉₅ + n ₉₆ + n ₉₇ are the same or different from each other, and may each independently be an integer of 5 or less.)

(23)

(In Chemical Formula 23,

R ₁₀₅ to R ₁₀₇ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

N ₉₈ , n ₉₉ , and n ₁₀₂ may be the same or different from each other, and each independently an integer of 1 to 5,

N ₁₀₀ and n ₁₀₁ may be the same or different from each other, and may each independently be an integer of 0 to 4.)

≪ EMI ID =

(In Chemical Formula 24,

R ₁₀₈ to R ₁₁₃ are the same or different from each other, and each independently may be selected from the group consisting of hydrogen, OH, and a substituted or unsubstituted alkyl group,

n ₁₀₅ to n ₁₀₆ are the same or different from each other, and each independently may be an integer of 1 to 5,

Provided that n ₁₀₃ + n ₁₀₅ and n ₁₀₄ + n ₁₀₆ are each independently an integer of 5 or less.)

(25)

(In the formula (25)

R ₁₁₄ may be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₁₁₅ to R ₁₁₇ are the same or different from each other, and may each independently be hydrogen or a substituted or unsubstituted alkyl group,

n ₁₀₇ , n ₁₀₉ , and n ₁₁₁ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₁₀₈ , n ₁₁₀ , and n ₁₁₂ are the same or different from each other, and each independently may be an integer of 0 to 4,

Provided that n ₁₀₇ + n ₁₀₈ , n ₁₀₉ + n ₁₁₀ , and n ₁₁₁ + n ₁₁₂ are each independently an integer of 5 or less.)

(26)

(In the above formula (26)

R ₁₁₈ , R ₁₁₉ , and R ₁₂₀ are the same or different from each other, and may each independently be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₁₂₁ to R ₁₂₄ may be the same or different from each other, and may each independently be hydrogen or a substituted or unsubstituted alkoxy group,

n ₁₁₃ , n ₁₁₅ , and n ₁₁₈ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₁₁₄ , n ₁₁₆ , and n ₁₁₇ are the same or different from each other, and each independently 0 to 4 Can be an integer,

n ₁₂₀ may be an integer from 1 to 4,

_{However, n 113 + n 114, n} 115 + n 116, and n _{118 117+} n are each independently an integer of 5 or less.)

The content of the phenol compound is preferably 1 to 30 parts by weight based on 100 parts by weight of the (A) polybenzoxazole precursor. In the above range, there is almost no development residue, and thus an excellent profile can be obtained. The development speed is appropriate, a clear pattern can be obtained, and the mechanical properties of the film after thermosetting are preferable.

(E) solvent

As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl Ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol 3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, etc. can be used. The solvents may be used alone or in combination of two or more thereof.

The content of the solvent is preferably 200 to 900 parts by weight based on 100 parts by weight of the (A) polybenzoxazole precursor. In the above range, a film having a sufficient thickness can be coated, and it is preferable because of excellent solubility and coating property.

(F) Other additives

The photosensitive resin composition of this invention may further contain (F) other additives other than the component of (A)-(D).

The other additives include heat latent acid generators. The heat latent acid generator includes allyl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid; Perfluoroalkyl sulfonic acids such as trifluoromethanesulfonic acid and fluorobutanesulfonic acid; Alkyl sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, butane sulfonic acid; And mixtures thereof.

The heat latent acid generator is a catalyst for the cyclization reaction of the polybenzoxazole precursor, so that the cyclization reaction may proceed smoothly even if the curing temperature is lowered.

In addition, in order to prevent staining of the film thickness or to improve developability, a suitable surfactant or leveling agent may be further used as an additive.

The process of forming a pattern using the positive photosensitive resin composition of this invention is a process of apply | coating a positive photosensitive resin composition on a support substrate; Drying the applied composition to form a photosensitive polybenzoxazole precursor film; Exposing the polybenzoxazole precursor film; Developing the exposed polybenzoxazole precursor film with an aqueous alkali solution to produce a photosensitive resin film; And a step of heat-treating the photosensitive resin film. The said photosensitive resin composition is apply | coated and exposed. The composition and the like in the process of developing a pattern to form a pattern is well known in the art, so detailed description thereof will be omitted.

In addition, another embodiment of the present invention relates to a photosensitive insulating film or a protective film manufactured using the photosensitive resin composition.

In addition, another embodiment of the present invention relates to a semiconductor device comprising a photosensitive resin film prepared using the photosensitive resin composition, the composition of the present invention is useful for an insulating film, a passivator layer or a buffer coating layer in a semiconductor device Can be used.

That is, the photosensitive resin composition of this invention can also be usefully used also as a surface protection film and an interlayer insulation film of a semiconductor device.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples and Comparative Examples are for illustrative purposes only and are not intended to limit the present invention.

Synthesis Example 1 Synthesis of 4-namidido benzoyl chloride (EC-1)

Add 150 ml of 4-aminobenzoic acid and 9.5 g of 5-norbornene-2,3-dicarboxylic anhydride while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler. Acetic acid was added to make a mixture. The mixture was stirred at room temperature for 1 hour, then heated up to reflux of solvent, followed by further stirring for 12 hours. The temperature of the solution was then lowered to room temperature and the precipitated white solid was filtered and washed three times with cold ethanol. The solid obtained was dried for 12 hours while heating to 100 ° C. under vacuum to produce 4-namidido benzoic acid, and the result of measuring ¹ H-NMR is shown in FIG. 1.

The solid 4-namidido benzoic acid was placed in a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injection device, and a cooler, and 50 g of thionyl chloride was added while passing nitrogen. The solution was heated to thionyl chloride at reflux, followed by further stirring for 4 hours. Subsequently, after lowering the temperature of the solution to room temperature again, all of the thionyl chlorides were removed under vacuum to obtain a white solid. The white solid was washed 5 times with toluene and then dried for 12 hours while heating to 50 ° C. under vacuum to prepare 4-namidido benzoyl chloride terminal block monomer (EC-1), which was measured by ¹ H-NMR. Is shown in FIG. 2.

Synthesis Example 2 Synthesis of 4- (2-phenylethynylphthalimido) benzoyl chloride (EC-2)

Except for changing 9.5 g of 5-norbornene-2,3-dicarboxylic anhydride to 14.5 g of 3-phenylethynylphthalic anhydride, the same procedure as in Synthesis Example 1 was carried out to provide 4- (2-phenylethynyl Phthalimido) benzoylchloride terminal blockade monomer (EC-2) was synthesized.

Synthesis Example 3 Synthesis of 4- (2-phenylmaleimido) benzoylchloride (EC-3)

Except for changing 9.5 g of 5-norbornene-2,3-dicarboxylic anhydride to 10.1 g of 2-phenylmaleic anhydride, it was carried out in the same manner as in Synthesis example 1, and 4- (2-phenylmaleimido) Benzoylchloride terminal blockade monomer (EC-3) was synthesized.

Synthesis Example 4 Synthesis of 4-maleimido benzoyl chloride (EC-4)

Except for changing 9.5 g of 5-norbornene-2,3-dicarboxylic anhydride to 5.7 g of maleic anhydride, the same procedure as in Synthesis Example 1 was carried out to provide 4-maleimido benzoyl chloride terminal block monomer (EC- 4) was synthesized.

Commercially available benzoyl chloride (TCI, Inc.) was used as (EC-5).

Synthesis Example 5 Synthesis of Polybenzoxazole Precursor (PA-1)

2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler 7 g of 3, -hexaflouropropane and 2 g of 1,3-bis (aminopropyl) tetramethyldisiloxane were added, and 72 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. At this time, the content of solids in the obtained solution was 9% by weight.

When the solid was completely dissolved, 3 g of pyridine was added, and 6.3 g of 4,4'-oxydibenzoyl chloride was added to 55 g of N-methyl-2-pyrrolidone (NMP) while maintaining the temperature at 0 to 5 ° C. The solution was slowly added dropwise for 30 minutes. After dropping, the reaction was carried out at a temperature of 0 to 5 ° C. for 1 hour, and the temperature was raised to room temperature, followed by stirring for 1 hour, followed by 0.75 g of 4-namidido benzoyl chloride (EC-1) prepared in Synthesis Example 1 and benzoyl chloride. 0.25 g of (EC-5) was added, followed by stirring for 17 hours to complete the reaction. The reaction mixture was added to water to form a precipitate, and the precipitate was filtered, washed sufficiently with water, and dried under vacuum at a temperature of 80 ° C. for at least 24 hours to prepare a polybenzoxazole precursor (PA-1). ¹ H-NMR of the prepared polybenzoxazole precursor was measured and the results are shown in FIG. 3.

Synthesis Example 6 Synthesis of Polybenzoxazole Precursor (PA-2)

The terminal blockade monomer was carried out in the same manner as in Synthesis Example 5 except for changing the mixture of 0.5 g of 4-namidido benzoyl chloride (EC-1) and 0.5 g of benzoyl chloride (EC-5) prepared in Synthesis Example 1. , Polybenzoxazole precursor (PA-2) was prepared.

Synthesis Example 7 Synthesis of Polybenzoxazole Precursor (PA-3)

The terminal blockade monomer was carried out in the same manner as in Synthesis Example 5 except for changing the mixture of 0.25 g of 4-namidido benzoyl chloride (EC-1) and 0.75 g of benzoyl chloride (EC-5) prepared in Synthesis Example 1. , Polybenzoxazole precursor (PA-3) was prepared.

Synthesis Example 8 Synthesis of Polybenzoxazole Precursor (PA-4)

The terminal blockade monomer was carried out in the same manner as in Synthesis Example 5 except for changing the mixture of 0.4 g of 4-namidido benzoyl chloride (EC-1) and 0.6 g of benzoyl chloride (EC-5) prepared in Synthesis Example 1. , Polybenzoxazole precursor (PA-4) was prepared.

Synthesis Example 9 Synthesis of Polybenzoxazole Precursor (PA-5)

A polybenzoxazole precursor (PA-5) was prepared in the same manner as in Synthesis Example 5 except that the terminal blocking monomer was used alone in 1 g of benzoyl chloride (EC-5).

Synthesis Example 10 Synthesis of Polybenzoxazole Precursor (PA-6)

A polybenzoxazole precursor (PA-6) was prepared in the same manner as in Synthesis Example 5 except that no terminal blocking monomer was used.

Synthesis Example 11 Synthesis of Polybenzoxazole Precursor (PA-7)

A polybenzoxazole precursor (PA-7) was prepared in the same manner as in Synthesis Example 5 except that 4 g of 5-norbornene-2,3-dicarboxylic acid anhydride was used as the terminal blocking monomer.

≪ Example 1 >

15 g of the polybenzoxazole precursor (PA-1) prepared in Synthesis Example 5 was dissolved in 35.0 g of γ-butyrolactone (GBL) and 5.0 g of N-methyl-2-pyrrolidone, and expressed by the following Chemical Formula 13a. 3 g of photosensitive diazoquinone, 0.75 g of trimethoxy [3- (phenylamino) propyl] silane of the formula (18a) Filtration was carried out to obtain a positive photosensitive polybenzoxazole precursor composition.

[Formula 13a]

로 치환되어 있고, 나머지 하나는 수소이다.)Wherein _{two of} Q ₁ , Q ₂ , and Q ₃ are

And the other is hydrogen.)

[Formula 18a]

[Formula 22a]

<Example 2>

Positive in the same manner as in Example 1, except that the polybenzoxazole precursor (PA-1) prepared in Synthesis Example 5 was changed to the polybenzoxazole precursor (PA-2) prepared in Synthesis Example 6. A type photosensitive polybenzoxazole precursor composition was obtained.

<Example 3>

Positive type was carried out in the same manner as in Example 1 except that the polybenzoxazole precursor (PA-1) prepared in Synthesis Example 5 was changed to the polybenzoxazole precursor (PA-3) prepared in Synthesis Example 7. The photosensitive polybenzoxazole precursor composition was obtained.

<Example 4>

Positive type was carried out in the same manner as in Example 1 except for changing the polybenzoxazole precursor (PA-1) prepared in Synthesis Example 5 to the polybenzoxazole precursor (PA-4) prepared in Synthesis Example 8. The photosensitive polybenzoxazole precursor composition was obtained.

&Lt; Comparative Example 1 &

Positive type was carried out in the same manner as in Example 1 except for changing the polybenzoxazole precursor (PA-1) prepared in Synthesis Example 5 to the polybenzoxazole precursor (PA-5) prepared in Synthesis Example 9. The photosensitive polybenzoxazole precursor composition was obtained.

Comparative Example 2

Positive type was carried out in the same manner as in Example 1 except for changing the polybenzoxazole precursor (PA-1) prepared in Synthesis Example 5 to the polybenzoxazole precursor (PA-6) prepared in Synthesis Example 10. The photosensitive polybenzoxazole precursor composition was obtained.

&Lt; Comparative Example 3 &

Positive type was carried out in the same manner as in Example 1 except that the polybenzoxazole precursor (PA-1) prepared in Synthesis Example 5 was changed to the polybenzoxazole precursor (PA-7) prepared in Synthesis Example 11. The photosensitive polybenzoxazole precursor composition was obtained.

The composition of each photosensitive polybenzoxazole precursor composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3 is summarized in Table 1 below.

Property measurement

Each of the photosensitive polybenzoxazole precursor compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 was coated on an 8 inch wafer using a Mikasa (1H-DX2) spin coater, and then coated on a hot plate. It heated at 4 degreeC for 4 minutes, and formed the photosensitive polyimide precursor film.

The polyimide precursor film was exposed to 250 ms with an I-line stepper (NSR i10C) manufactured by Nikon Japan, using a mask engraved with a pattern of various sizes on the film, followed by 60 seconds in a 2.38% aqueous tetramethylammonium hydroxide solution at room temperature. After dissolving and removing the exposed part through 2 puddle, it was washed with pure water for 30 seconds. Next, the obtained pattern was cured at 150 ° C / 30 minutes, and further 320 ° C / 30 minutes at an oxygen concentration of 1000 ppm or less using an electric furnace to prepare a film with a pattern.

About the film in which the pattern was formed, the resolution, the film thickness change, the residual film ratio, and the sensitivity were measured.

The resolution of the finished film pattern could be confirmed by an optical microscope, and the film thickness change after preliminary baking, development, and curing was measured using a KMAC (ST4000-DLX) device.

In addition, the reduction rate of the film thickness after development has an effect on the developability and the final film thickness, and the film thickness reduction should be small even during development, and the pre-fired film was measured by 2.38% tetramethylammonium company of AZ-EM. The method was immersed in an aqueous solution of hydroxide (TMAH) for each hour and washed with water, and the residual film rate (thickness after development / thickness, unit%) was calculated by measuring the change in film thickness with time.

After exposure and development, the sensitivity was obtained by determining an exposure time in which a 10 um L / S pattern was formed with a line width of 1 to 1, which was the optimum exposure time, and the resolution was the minimum pattern dimension at the optimum exposure time as the resolution.

As a result of measuring the resolution and sensitivity, the sensitivity of the polybenzoxazole precursor compositions of Examples 1 to 4 and Comparative Examples 1 to 3 was 300 to 350 mJ / cm ² , and the resolution was 3 μm.

In addition, after the pattern was formed, the mixture was heated at 120 ° C. for 30 minutes in a nitrogen atmosphere, and then heated up to 320 ° C. for 1 hour, and heated at 320 ° C. for 1 hour to produce a cured film.

Mechanical properties (tensile strength, elongation, and Young's modulus) and hygroscopicity of the cured film were measured, and are shown in Table 2 below.

After curing, the mechanical properties of the film were immersed in a 2% HF solution for 30 minutes in a film-covered silicon wafer to separate the film, and cut into 6.0 cm × 1.0 cm ribbon pieces to measure the mechanical properties. After the preparation, it was measured using a universal testing machine (instron series IX).

In addition, the hygroscopicity of the thermosetting film was measured according to JIS-K6911.

Referring to Table 2, it can be seen that the cured film prepared by curing the photosensitive resin compositions of Examples 1 to 4 shows excellent mechanical properties and low hygroscopicity compared to Comparative Examples 1 to 3.

In addition, in Comparative Example 2 using 5-norbornene-2,3-dicarboxylic acid anhydride, which is known to have thermal crosslinkability, as the terminal blocking monomer, it was confirmed that the hygroscopicity was low but the mechanical properties were remarkably inferior.

In summary, according to Examples 1 to 4 of the present invention, a thick film having remarkably excellent mechanical properties and hygroscopic resistance can be produced as compared with Comparative Examples 1 to 3. In addition, since Examples 1 to 4 of the present invention show the same optical characteristics as those of Comparative Examples 1 to 3, the present invention can easily form a semiconductor interlayer insulating film or a surface protective film having good patternability and at the same time having excellent mechanical properties. It could be confirmed that it could be formed.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

1 is a graph showing the ¹ H-NMR structure of 4-namidido benzoic acid prepared in Synthesis Example 1 of the present invention.

2 is a graph showing the ¹ H-NMR structure of 4-namidido benzoyl chloride (EC-1) prepared in Synthesis Example 1 of the present invention.

3 is a graph showing the ¹ H-NMR structure of the polybenzoxazole precursor (PA-1) prepared in Synthesis Example 5 of the present invention.

Claims (7)

(A) polybenzoxazole precursor having a repeating unit represented by the following formula (1); (B) a photosensitive diazoquinone compound; (C) silane compound; (D) a phenol compound; And (E) a solvent, One end of the polybenzoxazole precursor includes a thermopolymerizable functional group derived from a first monocarboxylic acid halide selected from the group consisting of a compound represented by the following Chemical Formulas 2 to 5 and a combination thereof, and the other end is A positive photosensitive resin composition comprising a thermopolymerizable functional group derived from a second monocarboxylic acid halide represented by the following formula (6). [Formula 1]

(In the formula 1, X ₁ is an aromatic organic group or a 4 to 6-valent aliphatic organic group , X ₂ may be an aromatic organic group or a 2 to 6-valent aliphatic organic group, or may be represented by Formula 7 below. Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2 to 6-valent aliphatic organic group, M ₁ and m ₂ are molar ratios, m ₁ + m ₂ is 100 mol%, M ₁ is 60 to 100 mol%, M ₂ is 0 to 40 mol%, [Formula 7]

In Chemical Formula 7, R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ are the same or different from each other, and each independently a group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a hydroxy group Is selected from R ₃ and R ₄ are the same or different from each other, and each independently a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, k ₁ is an integer from 1 to 50.) [Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

(In Chemical Formulas 2 to 6, Z ₁ to Z ₅ are the same or different from each other, and each independently a halide, R ₁₆ to R ₂₂ are the same or different from each other, and are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 10 carbon atoms, R ₂₃ is selected from the group consisting of an aryl group, a cycloalkyl group, an aryl group substituted with an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group substituted with an alkyl group having 1 to 10 carbon atoms, n ₈ is an integer from 1 to 9, n ₉ , n ₁₀ , and n ₁₂ are integers from 1 to 4, n ₁₁ and n _{14 are} integers _from 1 to 5 n ₁₃ is an integer of 1 to 3.) The method of claim 1, The first monocarboxylic acid halide is 5-norbornene-2-carboxylic acid halide, 4-nadimido benzoyl halide, 4- (4-phenylethiniphthalimido) benzoyl halide, 4- (3-phenyl Ethylniphthalimido) benzoyl halide, 4- (2-phenylmaleimido) benzoyl halide, 4-maleimido benzoyl halide, and combinations thereof, The second monocarboxylic acid halide is selected from the group consisting of benzoyl halide or cyclohexyl halide, and combinations thereof. The method of claim 1, The positive photosensitive resin composition of claim 1, wherein the mixing ratio of the first monocarboxylic acid halide monomer and the second monocarboxylic acid halide monomer is 8: 2 to 2: 8. The method of claim 1, The polybenzoxazole precursor is a positive photosensitive resin composition having a weight average molecular weight (Mw) of 3,000 to 300,000. The method of claim 1, The resin composition is Based on 100 parts by weight of the (A) polybenzoxazole precursor 5 to 100 parts by weight of the (B) photosensitive diazoquinone compound; 0.1 to 30 parts by weight of the (C) silane compound; 1 to 30 parts by weight of the (D) phenol compound; And 200 to 900 parts by weight of the solvent (E) Positive photosensitive resin composition comprising a. The photosensitive resin film formed using the positive photosensitive resin composition of any one of Claims 1-5. The semiconductor element containing the photosensitive resin film of Claim 6.

Images