KR101257696B1 - 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 poly benzoxazole precursor having a repeating unit represented by the following formula (1); (B) a photosensitive diazoquinone compound; (C) a silane compound; (D) a phenol compound; And (E) a solvent.

[Formula 1]

(In Formula 1, the definition of each substituent is the same as described in the specification.)

Positive type, photosensitive polybenzoxazole precursor composition, low temperature hardening, aqueous alkali 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, can be cured at a low temperature, has high sensitivity and high resolution, has a good pattern shape, has high residue removal properties, and has a low film shrinkage ratio, thereby providing excellent final cured film. It relates to a positive photosensitive resin composition having mechanical properties and very low hygroscopicity.

BACKGROUND ART Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, and mechanical properties has been used for a surface protective film and an interlayer insulating film of a semiconductor device. Such polyimide resins have recently been used in the form of photosensitive polyimide precursor compositions, and are easy to apply. After applying the polyimide precursor composition onto a semiconductor device, patterning by ultraviolet rays, development, thermal imidization treatment, and the like are performed. Thus, the surface protective film, the interlayer insulating film and the like can be easily formed. 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 that a desired pattern can not be obtained because the solubility of the carboxylic acid of the polyamic acid used in the alkali is too high.

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 way, 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 improve this problem, if the molecular weight of the polybenzoxazole precursor is increased, the film reduction amount of the unexposed part becomes small, but developing residue (scum) occurs in the exposed part during development, resulting in poor resolution and longer 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 phenolic 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 has been a continuous demand for studies to increase the film reduction suppression effect without generating development residues (scum).

Such conventional photosensitive polyimide or polybenzoxazole is cured at a high temperature around 350 ° C after pattern formation. MRAM (Magnet Resistive RAM), which is the next generation memory device that is emerging these days, is vulnerable to a high temperature process and requires a low temperature curing process. Therefore, there is a need for a material that can be cured at low temperatures at temperatures below 260 ° C. which can be used as surface protective and interlayer insulating films suitable for such new devices. On the other hand, it has been reported that low-temperature curing can be achieved by using a polybenzoxazole precursor polymerized using a thermal acid generator or a monomer having excellent flexibility (Japanese Patent Publication No. 2006-349700 and Japanese Patent Publication 2007-079264).

However, 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 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 in order to cope with their development. In the case of a general low temperature curable photosensitive resin composition, such mechanical properties, more specifically, elongation are often lower than an appropriate level, and heat resistance is generally poor.

In order to solve this problem, in the case of commonly used low temperature curable polyimide or polybenzoxazole precursors, a method of using various additives or a precursor compound having a structure capable of crosslinking upon thermal curing may be used to solve this problem. Examples of use have been reported.

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.

The present invention is capable of low temperature curing, has high sensitivity and high resolution, good pattern shape, high residue removal property, in particular, it is possible to optimally balance the solid content and viscosity of the resin composition, and low film shrinkage after curing It is to provide a positive photosensitive resin composition capable of expressing excellent film properties such as hygroscopicity and chemical resistance.

The present invention is to provide a photosensitive resin film prepared using the positive photosensitive resin composition.

An object of the present invention is to provide a semiconductor device comprising a photosensitive resin film produced using the 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 Formula 1 below; (B) a photosensitive diazoquinone compound; (C) a silane compound; (D) a phenol compound; And (E) a solvent.

According to another embodiment of the invention provides a photosensitive resin film prepared using the photosensitive resin composition.

According to another embodiment of the invention provides a semiconductor device comprising 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.

The positive photosensitive resin composition of the present invention can be cured at a low temperature, and particularly, by introducing a structure having a suitable crosslinkability to the polymer backbone to lower the molecular weight of the polymer, it is possible to optimally maintain a balance between the solid content and the viscosity in the photosensitive resin composition. It has excellent resolution, good pattern shape, high residue removal property, and excellent mechanical properties such as low film shrinkage.

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 only defined by the scope of the claims to be described later.

Unless stated otherwise in the present specification, “4 to 6-valent organic group” or “2 to 6-valent organic group” is an organic group having 4 to 6 functional groups and an organic group having 2 to 6 functional groups. Combines with the functional groups except

In this specification, unless specified otherwise, "substituted" means that at least one hydrogen of the compound is substituted with a substituent selected from the group consisting of halogen, alkyl group, aryl group, alkoxy group, amino group, and alkenyl group.

In the present specification, unless otherwise specified, an "alkyl group" means an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and an "alkoxy group" having an alkoxy group having 1 to 30 carbon atoms, more preferably. Is an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 30 carbon atoms as the "aryl group", more preferably an aryl group having 6 to 18 carbon atoms, and an alkenyl group having 2 to 30 carbon atoms as the "alkenyl group". Preferably, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, more preferably an alkynyl group having 2 to 18 carbon atoms, and an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 2 to 18 carbon atoms The group is more preferably an alkylene group having 1 to 18 carbon atoms, an "arylene group" means an arylene group having 6 to 30 carbon atoms, and more preferably an arylene group having 6 to 18 carbon atoms.

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

[Formula 1]

(In the formula 1,

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

X ₂ is an aromatic organic group, a 2-6 valent aliphatic organic group, a 2-6 valent alicyclic organic group, or a functional group having a structure represented by the following general formula (2),

Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group, a 2 to 6-valent aliphatic organic group, or a 2 to 6-valent alicyclic organic group, wherein at least one of Y ₁ and Y ₂ is a crosslinkable functional group Take it,

m and n are the molar ratios respectively, m + n = 100 mol%,

m is 60 to 100 mol%,

n is 0 to 40 mol%,

[Formula 2]

In Formula 2,

R ₁ and R ₂ are the same or different from each other, and each independently, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxy group,

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

k is an integer from 1 to 50.)

Hereinafter, each component will be described in detail.

(A) polybenzoxazole precursor

The polybenzoxazole precursor is a polymer having a repeating unit represented by the following Chemical Formula 1.

[Formula 1]

(In the formula 1,

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

X ₂ is an aromatic organic group, a 2-6 valent aliphatic organic group, a 2-6 valent alicyclic organic group, or a functional group having a structure represented by the following formula (2),

Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group, a 2 to 6-valent aliphatic organic group, or a 2 to 6-valent alicyclic organic group, wherein at least one of Y ₁ and Y ₂ is a crosslinkable functional group Take it,

m and n are the molar ratios of

m + n = 100 mol%,

m is 60 to 100 mol%,

n is 0 to 40 mol%,

[Formula 2]

In Formula 2,

R ₁ and R ₂ are the same or different from each other, and each independently, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxy group,

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 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-hydroxyphenyl ) -1,1,1,3,3,3-hexafluoropropane, or a combination thereof, but is not limited thereto.

Also, preferably, X ₁ may be a compound represented by the following Chemical Formula 3 or 4.

(3)

[Formula 4]

(In Chemical Formulas 3 and 4,

A ₁ is O, CO, CR ₈ R ₉ , SO ₂ , S, or a single bond,

R ₈ and R ₉ are the same or different from each other, and each independently, hydrogen or a substituted or unsubstituted alkyl group, preferably R ₈ and R ₉ are fluoroalkyl groups,

R ₅ to R ₇ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, A hydroxyl group, a carboxylic acid group, or a thiol 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.)

In addition, the X ₂ may be derived from an aromatic diamine, a silicone diamine, an alicyclic diamine, or a combination thereof.

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- Naphthalenediamine, 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 is not limited thereto. In addition, these aromatic diamine monomers can be used individually or in mixture.

Specific examples of the silicone diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, and bis (γ-aminopropyl). Tetramethyldisiloxane, 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.

Specific examples of the alicyclic diamine include, but are not limited to, cyclohexyldiamine, methylenebiscyclohexylamine, and the like.

In addition, the Y ₁ and Y ₂ may be derived from a dicarboxylic acid or a derivative of dicarboxylic acid having a crosslinkable functional group.

The dicarboxylic acid having the crosslinkable functional group is preferably represented by Y (COOH) ₂ (where Y is the same as Y ₁ and Y ₂ of Formula 1, and is an alicyclic or aliphatic organic group having one or more double bonds). Do. In this case, the alicyclic organic group is preferably a C ₃ to C ₂₀ alicyclic organic group, the aliphatic organic group is preferably a C ₂ to C ₂₀ aliphatic organic group, more preferably a C ₂ to C ₁₂ aliphatic organic group. .

Specific examples of the dicarboxylic acid having the crosslinkable functional group include compounds represented by the following formulas (5) to (7), or a combination thereof.

[Chemical Formula 5]

[Formula 6]

[Formula 7]

(In the above formula (7)

R ₁₀ and R ₁₁ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a halogen, wherein the alkyl group is an ethyl group Preferably, the substituted alkyl group is haloalkyl (meaning an alkyl group substituted with halogen).)

Examples of the dicarboxylic acid derivative having a crosslinkable functional group include: i) a carbonyl halide derivative including an alicyclic or aliphatic organic group having one or more double bonds, or ii) an alicyclic or aliphatic organic group having one or more double bonds. The active compound which is an active ester type derivative which made dicarboxylic acid, 1-hydroxy- 1, 2, 3- benzotriazole, etc. which were made to react, is mentioned. Specific examples of the dicarboxylic acid derivative having a crosslinkable functional group include 5-norbornene-2,3-dicarbonyl chloride, bicyclooct-5-ene-2,3-dicarbonyl chloride, and cyclohexene-1. , 2-dicarbonyl chloride, 3-ethyl-cyclohex-4-ene-1,2-dicarbonyl chloride, or a combination thereof.

In addition, as the compound from which Y ₁ and Y ₂ are derived, in addition to the derivative of dicarboxylic acid or dicarboxylic acid having a crosslinkable functional group, a dicarboxylic acid or dicarboxylic acid derivative having no crosslinkable functional group is further used. It may include.

Dicarboxylic acid Y (COOH) ₂ having no crosslinkable functional group, wherein Y is the same as Y ₁ and Y ₂ of Formula 1, and is an aromatic organic group, 2 to 6-valent alicyclic, or 2 to 6-valent aliphatic oil Device) or a derivative of dicarboxylic acid, a compound represented by the following Chemical Formulas 8 to 10, 4,4'-oxydibenzoyl chloride, diphenyloxydicarboxylic acid chloride, bis (phenylcarboxylic acid chloride) Sulfone, bis (phenylcarboxylic acid chloride) ether, bis (phenylcarboxylic acid chloride) phenone, phthalic carboxylic acid dichloride, terephthalic acid dichloride, isophthalic carboxylic acid dichloride, carboxylic acid dichloride, diphenyloxydica Reboxylate benzotriazole or combinations thereof can be used.

[Formula 8]

[Chemical Formula 9]

[Formula 10]

(In Chemical Formulas 8 to 10,

R ₁₂ to R ₁₅ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₅ , n ₆ , and n ₇ are integers from 1 to 3, n ₄ is an integer from 1 to 4,

A ₂ is O, CR ₁₆ R ₁₇ , CO, CONH, S, SO ₂ , or a single bond, wherein R ₁₆ and R ₁₇ are the same or different from each other, and each independently a substituted or unsubstituted alkyl group, hydrogen, or Fluoroalkyl group.)

The crosslinkable functional group-containing repeating unit derived from the dicarboxylic acid or dicarboxylic acid derivative having the crosslinkable functional group may be contained in 10 to 70 mol%, based on 100 mol% of the polybenzoxazole precursor, and 30 to It is preferable to contain in 50 mol%. In the above range, the mechanical properties at the time of thermosetting are excellent, and solubility is also preferable.

In addition, the polybenzoxazole precursor may have a thermopolymerizable functional group derived from the terminal blockade monomer at either or both ends of the molecular chain terminal.

As the terminal blocking monomer, monoamines, monoanhydrides, or monocarboxylic acid halides having carbon-carbon multiple bonds can be used.

Toluidine, dimethylaniline, ethylaniline, aminophenol, aminobenzyl alcohol, aminoindan, aminoacetophenone, or a combination thereof may be used as the monoamines.

Examples of the monoanhydrides include 5-norbornene-2,3-dicarboxylic hydride represented by the following Formula 11, 3,6-epoxy-1,2,3, represented by the following Formula 12, 6-tetrahydrophthalic hydride, isobutenyl succinic hydride, maleic hydride, aconitic anhydride represented by the following formula (13), 3,4,5,6-tetrahydrophthalic 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6, tetrahydrophthalic anhydride Itanic anhydride (IA), citraconicanhydride (CA), 2,3-dimethylmaleicanhydride (DMMA), or combinations thereof And the like.

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

Formulas 14 to 18 are representative examples of thermopolymerizable functional groups derived from monoanhydrides, and such thermopolymerizable functional groups may be crosslinked in a heating process.

 [Formula 14]

(In the above formula (14)

R ₁₈ is H, CH ₂ COOH, or CH ₂ CHCHCH _3. )

[Formula 15]

(In the above formula (15)

R ₁₉ and R ₂₀ are the same or different from each other, and each independently H or CH _3. )

[Chemical Formula 16]

[Chemical Formula 17]

(In the above formula (17)

R ₂₁ is H or CH ₃ and R ₂₂ is CH ₂ or O.

[Chemical Formula 18]

(In the above formula (18)

R ₂₃ and R ₂₄ are the same or different and are each independently H, CH ₃ or OCOCH ₃ ).

As the monocarboxylic acid halides having the carbon-carbon multiple bond, those represented by the following formula (19) may be used.

[Chemical Formula 19]

(In Chemical Formula 19,

R ₂₅ is a substituted or unsubstituted alicyclic group or a substituted or unsubstituted aryl group,

The substituted alicyclic group or substituted aryl group is a substituent selected from a substituted or unsubstituted namidido group, a substituted or unsubstituted alicyclic group, or a fused ring of a substituted or unsubstituted alicyclic group and an aryl group. It may be substituted with, wherein the alicyclic group is most preferably a maleimide group,

Z ₁ is F, Cl, Br, or I)

Specific examples of the monocarboxylic acid halides having a carbon-carbon multiple bond include 5-norbornene-2-carboxylic acid halides represented by the following 20, 4-namidido benzoyl halides represented by the following Formula 21, and represented by the following Formula 22: 4- (4-phenylethynylphthalimido) benzoyl halide, 4- (2-phenylmaleimimido) benzoyl halide represented by the following formula (23), benzoyl halide represented by the following formula (24), represented by the following formula (25) Cyclobenzoyl halide, 4- (3-phenylethynylphthalimido) benzoyl halide, and 4-maleimido benzoyl halide can be preferably used. These can also be used individually or in mixture with each other.

[Chemical Formula 20]

[Chemical Formula 21]

[Formula 22]

(23)

≪ EMI ID =

(25)

(In the above formula 20 to 25,

Z ₂ to Z ₇ are the same or different from each other, and each independently F, Cl, Br, or I, preferably Cl.)

In addition, the photosensitive resin composition of the present invention, in addition to the polybenzoxazole precursor having a repeating unit represented by Formula 1 above, a polybenzoxazole precursor having a repeating unit represented by the following Formula 40 having no crosslinkable functional group in the polymer main chain It may further include.

[Formula 40]

In the above formula (40)

X ₁ and X ₂ are the same as defined in Formula 1,

Y ₃ and Y ₄ are the same or different from each other, and each independently an aromatic organic group, a 2 to 6-valent aliphatic organic group, or a 2 to 6-valent alicyclic organic group,

m and n are the same as defined in the formula (1).

At this time, the polybenzoxazole precursor having a repeating unit represented by Formula 40 is (A) a polybenzoxazole precursor having a repeating unit represented by Formula 1 and mixed at a weight ratio of 5: 95 to 70: 30 to be used. It is desirable to be. In the above range, there is an advantage in the good patterning properties and excellent mechanical properties at the time of curing at a suitable mixing ratio.

In the present invention, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably in the range of 3,000 to 300,000. When the weight average molecular weight is in the above range, sufficient physical properties are obtained, solubility in organic solvents is high, and handling is preferable.

(B) photosensitive diazoquinone compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure can be preferably used. These are the materials known by US Pat. Nos. 2,772,975, 2,797,213 and 3,669,658, which are incorporated herein by reference.

Representative examples of the photosensitive diazoquinone compound may include a compound represented by the following Chemical Formulas 26 to 28, but is not limited thereto.

(26)

(In the above formula (26)

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, or Chemical Formula 27-1 or 27-2, 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 27-1]

[Formula 27-2]

(28)

(In Chemical Formula 28,

R ₃₄ is hydrogen or a substituted or unsubstituted alkyl group, D ₄ to D ₆ may be OQ,

Q is the same as defined in Formula 26,

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

[Formula 29]

(In Chemical Formula 29,

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 different from each other and each independently hydrogen, a substituted or unsubstituted alkyl group, OQ, or NHQ,

Q is the same as defined in Formula 26,

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,

Provided that at least one of the D ₇ to D ₈ is OQ, one aromatic ring has an OQ can contain 1 to 3, there is OQ can contain one to four and one of the aromatic ring.)

(30)

(In Chemical Formula 30,

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 26.)

The photosensitive diazoquinone compound is preferably included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the content of the photosensitive diazoquinone compound is within the above range, 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 silane compound can improve adhesion between the photosensitive resin composition and the substrate.

The silane compound represented by the following formula (31) can be used.

(31)

In the formula (31)

R ₆₁ may be a vinyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, preferably 3- (meth) acryloxypropyl, p-styryl, or 3- (phenylamino) propylyl Can be.

R ₆₂ to R ₆₄ are the same as or different from each other, and each independently, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, or a halogen, wherein at least one of R ₆₂ to R ₆₄ is an alkoxy group or a halogen Preferably, the alkoxy group is an alkoxy group having 1 to 8 carbon atoms, and 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 formulas (32) and (33); Silane compounds having an aryl group such as trimethoxy [3- (phenylamino) propyl] silane; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, silane compounds containing carbon-carbon unsaturated bonds, such as p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane; and most preferably The vinyl trimethoxysilane or vinyl triethoxysilane is mentioned.

(32)

(In Chemical Formula 32,

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

(33)

(In Chemical Formula 33,

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

R ₇₃ and R ₇₄ are the same or different from each other, and each independently, 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 silane compound may be used in an amount of 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 to the upper and lower film layers is excellent, and the residual film is not left after development, and mechanical properties such as optical properties (transmittance), tensile strength, elongation and Young's modulus can be improved .

(D) Phenol compound

The phenol group-containing compound can increase the dissolution rate and sensitivity of the exposed portion during development with an aqueous alkali solution, and also serves to pattern at high resolution without a residue during development.

The phenolic compound is capable of crosslinking with the (A) polybenzoxazole precursor upon thermal curing.

Specific examples of the phenolic compound include those represented by the following Chemical Formulas 34 to 39, but are not limited thereto.

[Formula 34]

(In Chemical Formula 34,

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 H, OH, or a substituted or unsubstituted alkyl group, preferably the alkyl group may be CH ₃ ,

n ₉₁ may be an integer from 1 to 5.

(35)

(In Chemical Formula 35,

R ₉₉ to R ₁₀₄ are the same or different from each other, and each independently H, OH, or 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,

Preferably the alkyl group may be CH 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.)

(36)

(In Formula 36,

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.)

[Formula 37]

(In Chemical Formula 37,

R ₁₀₈ to R ₁₁₃ are the same or different and are each independently hydrogen, OH, or a substituted or unsubstituted alkyl group,

n ₁₀₃ to n ₁₀₆ may be the same or different from each other and may each independently be an integer of 1 to 4,

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

(38)

(In Formula 38,

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

R ₁₁₅ to R ₁₁₇ may be 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 may be the same or different from each other and may each independently be an integer from 1 to 5,

n ₁₀₈ , n ₁₁₀ , and n ₁₁₂ are the same or different and each independently can be an integer from 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.)

[Chemical Formula 39]

(In Formula 39,

R ₁₁₈ , R ₁₁₉ , and R ₁₂₀ may be 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 each independently, hydrogen, or a substituted or unsubstituted alkoxy group,

n _113, n ₁₁₅ , and n ₁₁₈ are the same or different and are each independently an integer of 1 to 5,

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

n ₁₁₉ may be an integer of 1 to 4,

Provided that n ₁₁₃ + n ₁₁₄ , n ₁₁₅ + n ₁₁₆ , and n ₁₁₇ + n ₁₁₈ are each independently an integer of 5 or less.)

The phenolic compound is preferably used in 1 to 30 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the content of the phenolic compound is in the above range, it does not cause a decrease in sensitivity during development, and moderately increases the dissolution rate of the non-exposed part to obtain a good pattern, and does not cause precipitation during freezing storage, thus showing excellent storage stability. It is preferable.

(E) Solvent

The solvent is an organic solvent, preferably N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethyl acetate, 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 Or the like may be used, but the present invention is not limited thereto. The solvent may be used alone or in combination.

The solvent is preferably used at 50 to 500 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the content of the solvent is in the above range, it is possible to coat a film of sufficient thickness, it is preferable because of excellent solubility and coating properties.

(G) other additives

The photosensitive resin composition of this invention can further contain the (G) other additive.

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 may smoothly proceed with the cyclization reaction even if the curing temperature is lowered as a catalyst for the dehydration reaction of the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor and the cyclization reaction.

Moreover, in order to prevent the film | membrane of a film thickness, or to improve developability, you may further use a suitable surfactant or reveling agent as an additive.

The step of forming a pattern using the positive photosensitive resin composition of the present invention includes a step of applying 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 heating the photosensitive resin film. Process conditions for applying the photosensitive resin composition, exposing and developing the pattern, and the like are well known in the art, so detailed description thereof will be omitted.

According to another embodiment of the present invention, there is provided a photosensitive resin film prepared using the positive photosensitive resin composition. Preferable examples of the photosensitive resin film include an insulating film or a protective film. In addition, according to another embodiment of the present invention, there is provided a semiconductor device comprising a photosensitive resin film prepared using the photosensitive resin composition of the present invention. The composition of the present invention can be usefully used for an insulating film, a passivation layer, or a butter coating layer in a semiconductor device. That is, the composition of the present invention can be usefully used as a surface protective film and an interlayer insulating film of a semiconductor device.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments of the present invention, and the present invention is not limited to the following Examples.

Synthesis Example 1 Synthesis of Polybenzoxazole Precursor (PBO-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 17.4 g of 3-hexafluoropropane, 0.9 g of 1,3-bis (aminopropyl) tetramethyldisiloxane, and 280 g of N-methyl-2-pyrrolidone (NMP) were added to dissolve it. In the solution obtained at this time, solid content was 9 weight%.

When the solid is completely dissolved, 9.9 g of pyridine is added and 11.0 g of 5-norbornene-2,3-dicarbonyl chloride is maintained at 0 to 5 ° C. and 110 g of N-methyl-2-pyrrolidone (NMP). The dissolved 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 reaction was terminated by raising the temperature to room temperature and stirring for 3 hours. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate. The precipitate was filtered and thoroughly washed with water, and then dried under vacuum at a temperature of 80 ° C. for at least 24 hours to produce polybenzoxazole. Precursor (PBO-1) was prepared. The weight average molecular weight of the polybenzoxazole precursor (PBO-1) obtained at this time is 9,800.

Synthesis Example 2 Synthesis of Polybenzoxazole Precursor (PBO-2)

11.0 g of 5-norbornene-2,3-dicarbonylchloride was changed to 1.5 g of 4,4'-oxydibenzoyl chloride and 9.9 g of 5-norbornene-2,3-dicarbonyl chloride. Was carried out in the same manner as in Synthesis example 1 to prepare a polybenzoxazole precursor (PBO-2). The weight average molecular weight of the polybenzoxazole precursor (PBO-2) obtained at this time is 9,750.

Synthesis Example 3 Synthesis of Polybenzoxazole Precursor (PBO-3)

Except for changing 11.0 g of 5-norbornene-2,3-dicarbonyl chloride to 4.4 g of 4,4'-oxydibenzoyl chloride and 7.7 g of 5-norbornene-2,3-dicarbonyl chloride Was carried out in the same manner as in Synthesis example 1 to prepare a polybenzoxazole precursor (PBO-3). The weight average molecular weight of the polybenzoxazole precursor (PBO-3) obtained at this time is 9,900.

Synthesis Example 4 Synthesis of Polybenzoxazole Precursor (PBO-4)

Except for changing 11.0 g of 5-norbornene-2,3-dicarbonyl chloride to 7.4 g of 4,4'-oxydibenzoyl chloride and 5.5 g of 5-norbornene-2,3-dicarbonyl chloride Was carried out in the same manner as in Synthesis example 1 to prepare a polybenzoxazole precursor (PBO-4). The weight average molecular weight of the obtained P polybenzoxazole precursor (PBO-4) is 9,175.

Synthesis Example 5 Synthesis of Polybenzoxazole Precursor (PBO-5)

Except for changing 11.0 g of 5-norbornene-2,3-dicarbonyl chloride to 10.3 g of 4,4'-oxydibenzoyl chloride and 3.3 g of 5-norbornene-2,3-dicarbonyl chloride Was carried out in the same manner as in Synthesis example 1 to prepare a polybenzoxazole precursor (PBO-5). The weight average molecular weight of the polybenzoxazole precursor (PBO-5) obtained at this time is 9,200.

Synthesis Example 6 Synthesis of Polybenzoxazole Precursor (PBO-6)

Except for changing 11.0 g of 5-norbornene-2,3-dicarbonyl chloride to 13.3 g of 4,4'-oxydibenzoyl chloride and 1.1 g of 5-norbornene-2,3-dicarbonyl chloride Was carried out in the same manner as in Synthesis example 1 to prepare a polybenzoxazole precursor (PBO-6). The weight average molecular weight of the polybenzoxazole precursor (PBO-6) obtained at this time was 9,805.

Synthesis Example 7 Synthesis of Polybenzoxazole Precursor (PBO-7)

A polybenzoxazole precursor (PBO) was prepared in the same manner as in Synthesis Example 1 except that 11.0 g of 5-norbornene-2,3-dicarbonyl chloride was changed to 14.8 g of 4,4'-oxydibenzoyl chloride. -7) was prepared. The weight average molecular weight of the polybenzoxazole precursor (PBO-7) obtained at this time was 9,340.

Synthesis Example 8 Synthesis of Polybenzoxazole Precursor (PBO-8)

While passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector, and a cooler 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexaflouropropane 17.4 g, 1,3-bis (aminopropyl) tetramethyldisiloxane 0.86 g was added and 280 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the solution obtained at this time, solid content was 9 weight%.

When the solid was completely dissolved, 9.9 g of pyridine was added to the solution, and 13.3 g of 4,4'-oxydibenzoyl chloride was maintained at 0 to 5 ° C. with N-methyl-2-pyrrolidone (NMP). 142 g of the dissolved solution was slowly added dropwise to the solution for 30 minutes. After dropping, the reaction was carried out at a temperature of 0 to 5 ° C. for 1 hour, and 1.6 g of 5-norbornene-2-carboxylic acid chloride was added thereto, followed by stirring at room temperature for 2 hours to terminate the reaction. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and washed sufficiently with water. The drying was performed for 24 hours or more under a temperature of 80 ° C. and a vacuum to prepare a polybenzoxazole precursor (PBO-8). The weight average molecular weight of the polybenzoxazole precursor (PBO-8) obtained at this time is 9,100.

≪ Example 1 >

15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 was dissolved in 35.0 g of γ-butyrolactone (GBL), and 3 g of a photosensitive diazoquinone having the structure of Formula 26a was used as a silane coupling agent. 0.75 g of trimethoxy [3- (phenylamino) propyl] silane having a structure of Chemical Formula 31a and 0.75 g of a phenolic compound of Chemical Formula 35a were added thereto, dissolved, and filtered through a 0.45 μm fluorine resin filter to form a positive photosensitive resin composition. Got.

Formula 26a]

(In the above formula, two of Q ₁ , Q ₂ and Q ₃ are substituted with the following formula 27-1, and the other is hydrogen.)

[Formula 27-1]

[Formula 31a]

<Example 2>

The procedure of Example 1 was repeated except that 15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 was changed to 15 g of the polybenzoxazole precursor (PBO-2) synthesized in Synthesis Example 2. The photosensitive resin composition was obtained.

<Example 3>

The procedure of Example 1 was repeated except that 15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 was changed to 15 g of the polybenzoxazole precursor (PBO-3) synthesized in Synthesis Example 3. The photosensitive resin composition was obtained.

<Example 4>

15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 was changed to 15 g of the polybenzoxazole precursor (PBO-4) synthesized in Synthesis Example 4 The photosensitive resin composition was obtained.

<Example 5>

The procedure of Example 1 was repeated except that 15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 was changed to 15 g of the polybenzoxazole precursor (PBO-5) synthesized in Synthesis Example 5. The photosensitive resin composition was obtained.

<Example 6>

The procedure of Example 1 was repeated except that 15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 was changed to 15 g of the polybenzoxazole precursor (PBO-6) synthesized in Synthesis Example 6. The photosensitive resin composition was obtained.

&Lt; Example 7 >

15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 and 7.5 g of the polybenzoxazole precursor (PBO-5) synthesized in Synthesis Example 5 and the polybenzoxazole precursor (PBO synthesized in Synthesis Example 7) -7) Except having changed into 7.5g, it carried out similarly to Example 1 and obtained the photosensitive resin composition.

&Lt; Comparative Example 1 &

The procedure of Example 1 was repeated except that 15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 was changed to 15 g of the polybenzoxazole precursor (PBO-7) synthesized in Synthesis Example 7. The photosensitive resin composition was obtained.

Comparative Example 2

The procedure of Example 1 was repeated except that 15 g of the polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 was changed to 15 g of the polybenzoxazole precursor (PBO-8) synthesized in Synthesis Example 8. The photosensitive resin composition was obtained.

&Lt; Comparative Example 3 &

7.5 g of polybenzoxazole precursor (PBO-7) synthesized in Synthesis Example 7 and 15 g of polybenzoxazole precursor (PBO-1) synthesized in Synthesis Example 1 and polybenzoxazole precursor (PBO) synthesized in Synthesis Example 8 -8) It carried out similarly to Example 1 except having changed to 7.5 g, and obtained the photosensitive resin composition.

The compositions of Examples 1 to 7 and Comparative Examples 1 to 3 are summarized in Table 1 below.

[Table 1]

&Lt; Evaluation of physical properties &

The photosensitive polybenzoxazole precursor composition prepared according to Examples 1 to 7 and Comparative Examples 1 to 3 was coated on an 8-inch wafer by using a Mikasa spin coater, and then coated on a hot plate at 120 ° C. , And heated for 4 minutes to form a photosensitive polyimide precursor film.

After exposure to 250ms with I-line stepper (NSR i10C) manufactured by Nikon Japan, using a mask engraved with a pattern of various sizes on the polyimide precursor film, 60 seconds in a 2.38% aqueous tetramethylammonium hydroxide solution at room temperature After dissolving and exposing the exposed portion through a puddle, it was washed with pure water for 30 seconds. Subsequently, the pattern thus obtained was cured at an oxygen concentration of 1000 ppm or less at 150 캜 for 30 minutes and further at 320 캜 for 30 minutes by using an electric furnace to produce a patterned film.

Sensitivity was determined to be the optimal exposure time by obtaining an exposure time in which a 10 um L / S pattern was formed with a line width of 1 to 1 after exposure and development, and the resolution was measured using the minimum pattern dimension at the optimum exposure time as the resolution. . The resolution could be confirmed by an optical microscope.

In addition, the reduction rate of the film thickness after development has an effect on the developability and the final film thickness, which also requires a small decrease in the film thickness during development, which is 2.38% tetramethylammonium hydroxide (TMAH) The method of immersing in an aqueous solution and rinsing with water was developed, and the residual film ratio (thickness after development / thickness, unit%) was calculated by measuring the change in film thickness with time, and is shown in Table 2 below.

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 prepare a cured film.

In addition, in order to measure the mechanical properties of the film after curing, the silicon wafer covered with the film after curing was immersed in a 2% HF solution for 30 minutes to separate the film, and then cut into a ribbon piece of 6.0 cm * 1.0 cm. Specimens were prepared to measure. The specimens were measured for mechanical properties such as tensile strength, elongation, and Young's modulus with an universal material tester (instron series IX), and the results are shown in Table 2 below.

[Table 2]

Referring to Table 2, the photosensitive resin composition of Examples 1 to 7 using the polybenzoxazole precursor containing a crosslinkable structure in the polymer backbone is compared with the photosensitive resin composition of Comparative Examples 1 to 3 when the photosensitive resin film is prepared. It was confirmed that the excellent mechanical properties, especially elongation.

In addition, the photosensitive resin compositions of Examples 1 to 7 had much better mechanical properties than Comparative Example 3, which used 5-norbornene-2,3-dicarboxylic anhydride, which is known to have a double bond and was thermally crosslinkable, as a terminal block monomer. Physical properties were shown.

Moreover, it was confirmed that the case where the photosensitive resin film was manufactured using the photosensitive resin composition of Examples 1-7 was excellent also in the residual film rate compared with the case where the photosensitive resin composition of Comparative Examples 1-3 was used.

Therefore, when using the polybenzoxazole precursor containing a crosslinkable structure in the polymer backbone as in Examples 1 to 7, it was confirmed that a thick film excellent in mechanical properties and also excellent in terms of residual film ratio.

Moreover, as a result of the optical characteristic measurement of the photosensitive resin composition of Examples 1-7 and Comparative Examples 1-3, the sensitivity showed the value of 300-350 mJ / cm <^2> , and the resolution was 3 micrometers. Accordingly, it can be confirmed that Examples 1 to 7 can be produced as a photosensitive resin film having good patterning properties and at the same time having excellent mechanical properties by maintaining the optical properties equivalent to those of the photosensitive resin films of Comparative Examples 1 to 3. there was.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

Claims (15)

 (A) poly benzoxazole precursor having a repeating unit represented by the following formula (1); (B) a photosensitive diazoquinone compound; (C) a silane compound; (D) a phenol compound; And (E) Solvent Positive photosensitive resin composition comprising a. [Formula 1]

(In the formula 1, X ₁ is an aromatic organic group or a 4-6 valent aliphatic organic group, X ₂ is an aromatic organic group, a 2-6 valent aliphatic organic group, a 2-6 valent alicyclic organic group, or a functional group having a structure represented by the following general formula (2), Y ₁ and Y ₂ are derived from dicarboxylic acid or a derivative of dicarboxylic acid, at least one having a crosslinkable functional group, The dicarboxylic acid having a crosslinkable functional group or a derivative of dicarboxylic acid is iii) Y (COOH) ₂ (wherein Y in Formula 1 is the same as Y ₁ and Y ₂ , an alicyclic having one or more double bonds or Dicarboxylic acid having a crosslinkable functional group represented by an aliphatic organic group), ii) a carbonyl halide derivative comprising an alicyclic or aliphatic organic group having at least one double bond, or iii) an alicyclic having at least one double bond Or an active compound which is an active ester derivative obtained by reacting dicarboxylic acid containing an aliphatic organic group with 1-hydroxy-1,2,3-benzotriazole, or a combination thereof, m and n are the molar ratios of m + n = 100 mol%, m is 60 to 100 mol%, n is 0 to 40 mol%, [Formula 2]

In Formula 2, R ₁ to R ₂ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxy group, 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 is an integer from 1 to 50.) delete delete The method of claim 1, The dicarboxylic acid or derivative of the dicarboxylic acid having the crosslinkable functional group is a compound represented by the following Chemical Formulas 5 to 7, 5-norbornene-2,3-dicarbonyl chloride, bicyclooct-5-ene- Positive type 2,3-dicarbonylchloride, cyclohexene-1,2-dicarbonylchloride, 3-ethyl-cyclohex-4-ene-1,2-dicarbonylchloride, or a combination thereof Photosensitive resin composition. [Chemical Formula 5]

[Formula 6]

[Formula 7]

(In the above formula (7) R ₁₀ and R ₁₁ are the same or different and are each independently hydrogen and a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, or halogen.) The method of claim 1, The polybenzoxazole precursor further comprises a residue derived from dicarboxylic acid or a derivative of dicarboxylic acid having no crosslinkable functional group. The method of claim 1, The crosslinkable functional group-containing repeating unit is contained in 10 to 70 mol% with respect to 100 mol% of polybenzoxazole precursor. The method of claim 1, The polybenzoxazole precursor is derived from a terminal blockade monomer selected from one or both of the molecular chain ends, monoamines, monoanhydrides, monocarboxylic acid halides having carbon-carbon multiple bonds, and combinations thereof. Positive type photosensitive resin composition which has a thermopolymerizable functional group to become. delete The method of claim 7, wherein Monocarboxylic acid halides having a carbon-carbon multiple bond are 5-norbornene-2-carboxylic acid halides represented by the following Formula 20, 4-namidido benzoyl halides represented by the following Formula 21, 4- represented by the following Formula 22: (4-phenylethynylphthalimido) benzoyl halide, 4- (2-phenylmaleicimido) benzoyl halide represented by the following formula (23), benzoyl halide represented by the following formula (24), cyclo benzoyl represented by the following formula (25) Positive type photosensitive resin composition which is a halide, 4- (3-phenylethynylphthalimido) benzoyl halide, or 4-maleimido benzoyl halide, or a combination thereof. [Chemical Formula 20]

[Chemical Formula 21]

[Formula 22]

(23)

&Lt; EMI ID =

(25)

(In Formula 20 to Formula 25, Z ₂ to Z ₇ are the same or different from each other, and each independently F, Cl, Br, or I.) 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, Said photosensitive resin composition is a positive photosensitive resin composition which further contains the polybenzoxazole precursor which has a repeating unit represented by following formula (40) which does not contain a crosslinkable functional group in a principal chain. [Formula 40]

(In Formula 40, X ₁ and X ₂ are the same as defined in Formula 1, Y ₃ and Y ₄ are the same or different from each other, and each independently an aromatic organic group, a 2 to 6-valent aliphatic organic group, or a 2 to 6-valent alicyclic organic group, m and n are the same as defined in Formula 1.) 12. The method of claim 11, The photosensitive resin composition comprises a polybenzoxazole precursor having a repeating unit represented by Formula 40 and a polybenzoxazole precursor having a repeating unit represented by Formula 1 at a weight ratio of 5:95 to 70:30. In positive type photosensitive resin composition. 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 dizoquinone 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 50 to 500 parts by weight of the solvent (E) Positive photosensitive resin composition comprising a. The photosensitive resin film manufactured using the positive photosensitive resin composition of any one of Claims 1, 4-7, or 9-13. The semiconductor element containing the photosensitive resin film of Claim 14.