KR20210141515A - Esterdiamine-containing polybenzoxazole precursor, photosensitive resin composition, dry film, cured product and electronic component - Google Patents

Abstract

[Problem] Provision of a photosensitive resin composition containing an esterdiamine-containing polybenzoxazole precursor that achieves high dissolution contrast and is less prone to cracking or warping.
[Solution] The esterdiamine-containing polybenzoxazole precursor of the present invention has at least one of the structures represented by the general formulas (1) and (2) and a structure represented by the following general formula (3).

Description

Esterdiamine-containing polybenzoxazole precursor, photosensitive resin composition, dry film, cured product and electronic component

The present invention relates to an esterdiamine-containing polybenzoxazole precursor (also referred to as polyhydroxyamide), a photosensitive resin composition comprising the esterdiamine-containing polybenzoxazole precursor, and a dry-dry comprising a resin layer formed by the photosensitive resin composition It is related with electronic components, such as a printed wiring board and a semiconductor element which have a film, the hardened|cured material formed with this photosensitive resin composition, and this hardened|cured material as a forming material.

The photosensitive resin composition containing the polybenzoxazole precursor undergoes a cyclization reaction into a benzoxazole ring having a rigid hydroxyamide structure by heating, and also increases the packing density between molecules, so that it is excellent in insulation, heat resistance, mechanical strength, etc. It is widely used in various fields from the point of expressing a characteristic. For example, application to a flexible printed wiring board, a buffer coating film of a semiconductor element, and an insulating film for a redistribution layer of a wafer level package (WLP) is progressing.

Conventionally, in a buffer coating film or an insulating film for a redistribution layer of a wafer level package, instead of a photosensitive resin composition containing a polyimide precursor, a photosensitive containing a polybenzoxazole precursor capable of forming a finer pattern by photolithography is possible. Resin compositions are attracting attention.

As such a photosensitive resin composition, the positive resist composition comprised by the polybenzoxazole precursor as disclosed in patent document 1, and photosensitive diazoquinone is mentioned. Then, such a photosensitive resin composition is applied on a substrate such as a wafer and dried to form a dry coating film, exposed by irradiating an active energy ray to the dried coating film, and then developing to form a desired pattern film, followed by a polybenzoxazole precursor is subjected to a cyclization reaction by heating at about 320° C. to form a cured patterned film of polybenzoxazole.

In addition, in recent semiconductor devices, in response to the demand for high functionality and miniaturization, excellent resolution for realizing finer pattern formation in a buffer coating film or an insulating film for a redistribution layer of a wafer level package, and furthermore, a thin film of a wafer serving as a substrate Suppression of cracks and warpage accompanying this is required.

Japanese Patent Publication No. 1-046862

However, in the composition described in Patent Document 1, the balance of solubility of the exposed part and the solubility resistance of the unexposed part at the time of development, which is necessary for realizing the resolution required for a semiconductor device in recent years, a so-called dissolution contrast is low, There was a problem that it was difficult to form a pattern, and furthermore, suppression of cracks and warpage was insufficient.

This invention was made in order to solve such a subject, It is providing the photosensitive resin composition containing the polybenzoxazole precursor which implement|achieves high melt|dissolution contrast as the objective, and does not generate|occur|produce a crack or curvature easily further.

Moreover, the other objective of this invention is providing electronic components, such as a dry film using the said photosensitive resin composition, a printed wiring board, and a semiconductor element.

As a result of intensive research for the realization of the above object, the present inventors have been able to remarkably improve the dissolution contrast of the photosensitive resin composition by introducing a diamine having an ester structure into the polybenzoxazole precursor, and It found out that stress can be relieved, and came to complete this invention.

That is, the esterdiamine-containing polybenzoxazole precursor of the present invention has at least one of the structures represented by the general formulas (1) and (2) and the structure represented by the following general formula (3).

(in general formulas (1) and (2),

X is a divalent organic group,

Any of R ₁ to R ₄ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 6 to 10 carbon atoms, and 6 carbon atoms to 10 benzyloxy groups, and other R ₁ to R ₄ are hydrogen atoms,

n represents an integer of 1 or more,

In general formula (3),

X is a divalent organic group,

Y is a tetravalent organic group having at least two or more hydroxyl groups,

o represents an integer greater than or equal to 1.)

In the present invention, any of R ₁ or R ₃ is selected from an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 6 to 10 carbon atoms, and a benzyloxy group having 6 to 10 carbon atoms, the other is a hydrogen atom,

It is preferred that R ₂ and R _{4 are hydrogen atoms.}

In this invention, it is preferable that Y in general formula (3) is one or more groups chosen from the following structure.

(In the above structural formula,

Either of * ₁ and * ₂ represents a linkage with an amino group, and the other represents a hydroxyl group.)

In this invention, it is preferable that content (esterdiamine content) of the structure represented by General formula (1) and (2) is 0.1 mol% or more and 10 mol% or less.

The photosensitive resin composition of the present invention comprises a polybenzoxazole precursor and a photosensitizer.

In this invention, it is preferable that a photosensitizer is a naphthoquinonediazide compound.

The dry film of this invention is equipped with the resin layer formed with the said photosensitive resin composition on a film, It is characterized by the above-mentioned.

The cured product of the present invention is characterized in that it is formed of the photosensitive resin composition or the resin layer of the dry film.

The electronic component of this invention, such as a printed wiring board and a semiconductor element, has the said hardened|cured material as a forming material, It is characterized by the above-mentioned.

ADVANTAGE OF THE INVENTION According to the esterdiamine containing polybenzoxazole precursor of this invention, the photosensitive resin composition effective in obtaining the dry coating film which has high dissolution contrast and high temperature pattern retentivity can be provided.

[Esterdiamine-containing polybenzoxazole precursor]

According to the polybenzoxazole precursor having at least one of the structures represented by the following general formulas (1) and (2) and the structure represented by the following general formula (3), the polybenzoxazole precursor of the present invention is, In the photosensitive resin composition containing this, the developability of an unexposed part is obtained without impairing the developability of an exposed part, and in hardened|cured material, it is thought that the amide bond and the ester bond excellent in flexibility relieve|moderate internal stress.

In the general formulas (1) and (2), X is a divalent organic group. Although this organic group may be an aliphatic group or an aromatic group may be sufficient, it is preferable that it is an aromatic group, WHEREIN: On an aromatic ring, it is more preferable to couple|bond with the carbonyl in the said General formula (1) and (2).

It is preferable that it is 6-30, and, as for carbon number of a divalent organic group, it is more preferable that it is 6-24.

Although the group which has the following structures is mentioned as a divalent organic group, It is not limited to these, It is preferable to change suitably according to a use.

In the structural formula of the divalent organic group, A is a single bond, alkylene, -O-, -CO-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ -, and * represents a linkage to carbonyl.

Among the above, from the viewpoint of obtaining the excellent developability of the photosensitive resin composition and the excellent mechanical properties of the cured film, the divalent organic group is particularly preferably a group having the structure shown below.

In the above general formulas (1) and (2), any of R ₁ to R ₄ , preferably any of R ₁ or R ₃ , particularly preferably R ₃ is an alkyl group having 1 to 12 carbon atoms, carbon number selected from an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 6 to 10 carbon atoms, and a benzyloxy group having 6 to 10 carbon atoms, and other R ₁ to R ₄ is a hydrogen atom.

Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group and a hexyl group.

Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.

Examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a diethylphenyl group, a propylphenyl group, a butylphenyl group, a fluorophenyl group, a pentafluorophenyl group, a chlorophenyl group, a bromophenyl group, and a methyl group. Toxyphenyl group, dimethoxyphenyl group, ethoxyphenyl group, diethoxyphenyl group, methoxybenzyl group, dimethoxybenzyl group, ethoxybenzyl group, diethoxybenzyl group, aminophenyl group, aminobenzyl group, nitrophenyl group, nitrobenzyl group, cya and a nophenyl group, a cyanobenzyl group, a phenethyl group, a phenylpropyl group, a phenylamino group, a diphenylamino group, a biphenyl group and a naphthyl group.

Examples of the phenoxy group having 6 to 10 carbon atoms include a methylphenoxy group, an ethylphenoxy group, a propylphenoxy group, a dimethylphenoxy group, a diethylphenoxy group, a methoxyphenoxy group, an ethoxyphenoxy group, and a dimethoxyphenoxy group.

Examples of the benzyl group having 6 to 10 carbon atoms include a benzyl group, a methylbenzyl group, an ethylbenzyl group, a propylbenzyl group, a dimethylbenzyl group, a methoxybenzyl group, an ethoxybenzyl group, and a methoxybenzyl group.

Examples of the benzyloxy group having 6 to 10 carbon atoms include, as the methylbenzyloxy group, a benzyloxy group, a butylbenzyloxy group, an ethylbenzyloxy group, a propylbenzyloxy group, a dimethylbenzyloxy group, a methoxybenzyloxy group, and an ethoxybenzyloxy group. and the like.

Among the above, from the viewpoint of dissolution contrast of the photosensitive resin composition, high-temperature pattern retention, sensitivity, and coefficient of linear thermal expansion, any of R ₁ to R ₄ is an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, and 6 carbon atoms. It is preferably a benzyl group having to 10 carbon atoms and a benzyloxy group having 6 to 10 carbon atoms, more preferably an aromatic group having 6 to 10 carbon atoms, more preferably a phenyl group, a tolyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group and a diethylphenyl group, , A phenyl group is particularly preferable from the viewpoint of the effect of suppressing the film reduction phenomenon of the unexposed portion and the effect of relieving the internal stress by suppressing the packing effect between molecules in the cured product.

In the said General formula (1) and (2), n is an integer of 1 or more, Preferably it is 1-5, More preferably, it is 1-2.

In the esterdiamine-containing polybenzoxazole precursor of the present invention, the content (esterdiamine content) of the structures represented by the general formulas (1) and (2) is preferably 0.1 mol% or more and 10 mol% or less, and 0.1 mol % or more and 5 mol% or less is preferable. Thereby, the dissolution contrast at the time of image development of the dry coating film formed with the photosensitive resin composition containing the polybenzoxazole precursor of this invention can be improved further.

In the said general formula (3), since X is a divalent organic group, about the preferable aspect, etc., since it is the same as general formula (1) and (2), description is abbreviate|omitted here.

In the said General formula (3), Y is a tetravalent organic group which has at least 2 or more hydroxyl groups. Although this organic group may be an aliphatic group or an aromatic group may be sufficient as this organic group, it is preferable that it is an aromatic group.

Moreover, as for the hydroxyl group with which a tetravalent organic group is equipped, it is preferable that the positional relationship with an amino group turns into an ortho position.

It is preferable that it is 6-30, and, as for carbon number of a tetravalent organic group, it is more preferable that it is 6-24.

Although group which has the following structures is mentioned as a tetravalent organic group, It is not limited to these, It is preferable to change suitably according to a use.

In the structural formula of the tetravalent organic _{group, any of *1} and * ₂ represents a linking part to an amino group, and the other represents a hydroxyl group.

Among the above, it is especially preferable that a tetravalent organic group is group of the structure shown below from a viewpoint of the photosensitivity improvement by light transmittance.

In the said General formula (3), o is an integer of 1 or more, Preferably it is 10-40, More preferably, it is 20-30.

In the esterdiamine-containing polybenzoxazole precursor of the present invention, the content of the structure represented by the general formula (3) is preferably 90 mol% or more and 99.9 mol% or less, and preferably 95 mol% or more and 99.9 mol% or less. . Thereby, the photosensitive resin composition containing the esterdiamine containing polybenzoxazole precursor of this invention can improve the outstanding developer solubility of the exposed part as a dry coating film, and the insulation as a cured film, heat resistance, and mechanical strength.

It is preferable that they are 2,000 or more and 50,000 or less, and, as for the number average molecular weights (Mn) of esterdiamine containing polybenzoxazole precursor, it is more preferable that they are 4,000 or more and 25,000 or less. Thereby, the solubility with respect to an alkali developing solution improves.

Moreover, it is preferable that they are 4,000 or more and 10,000 or less, and, as for the weight average molecular weight (Mw) of a polybenzoxazole precursor, it is more preferable that they are 8,000 or more and 50,000 or less. Thereby, generation|occurrence|production of the crack in hardened|cured material can further be reduced.

Moreover, it is preferable that they are 1 or more and 5 or less, and, as for Mw/Mn, it is more preferable that they are 1 or more and 3 or less.

In addition, in this invention, a number average molecular weight and a weight average molecular weight are the numerical values converted into standard polystyrene measured by gel permeation chromatography (GPC).

This esterdiamine-containing polybenzoxazole precursor is at least a diamine compound represented by the following general formula (4), a diamine compound represented by the following general formula (5), and a dicarboxylic acid component represented by the following general formula (6) can be obtained by reacting

Z in the said General formula (6) represents a hydroxyl group, a halogen group, or the leaving group containing the cyclic compound comprised from nitrogen, sulfur, carbon, oxygen, and an aromatic ring. Especially, it is preferable that it is a halogen group from a viewpoint of productivity.

_{R 1} to R ₄ , X and Y in the general formulas (4) to (6) are as described above.

Examples of the dicarboxylic acid component satisfying the general formula (6) include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, and 5-chloroisophthalic acid. , 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl) Dica having an aromatic ring, such as sulfone, 2,2-bis(p-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane aliphatic dicarboxyl acids such as carboxylic acid, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid acids, dicarboxylic acid dihalides thereof, and dicarboxylic acid esters thereof. Among them, 4,4'-dicarboxydiphenyl ether (ie, 4,4'-diphenyl ether dicarboxylic acid) and its dihalides are desirable.

This esterdiamine-containing polybenzoxazole precursor is a diamine compound other than the diamine compound represented by the general formulas (4) and (5) (hereinafter referred to as other diamine compounds) within the range that does not impair the characteristic effects and polymerization reactivity. can also be combined.

Examples of other diamine compounds include 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl] Sulfide, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy) C)phenyl]-1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzyl Amine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3 '-diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 3,4'-dia Minodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3' -diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[ 4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane , 1,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, 1,4- Bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-bis[4-(4-aminophenoxy)phenyl ]butane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3-methylphenyl]propane, 2,2-bis[4-(4-aminophenoxy) Si)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2- bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3, 3,3-hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene , 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[ 4-(4-aminophenoxy)phenyl]sulfoxide, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4) -Aminophenoxy)phenyl]ether, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,4 -bis[4-(3-aminophenoxy)benzoyl]benzene, 4,4'-bis[(3-aminophenoxy)benzoyl]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl ]propane, 1,3-bis[4-(3-aminophenoxy)phenyl]propane, 3,4'-diaminodiphenylsulfide, 2,2-bis[3-(3-aminophenoxy)phenyl ]-1,1,1,3,3,3-hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl ]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, bis[4-(3-aminophenoxy)phenyl]sulfoxide, 4,4'-bis[3-(4- Aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α- Dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone, bis[4-{4-(4-aminophenoxy) )phenoxy}phenyl]sulfone, 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy) Phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[ 4-(4-amino-6-fluorophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-methylphenoxy)-α,α-dimethylbenzyl ]benzene, 1,3-bis[4-(4-amino-6-cyanophenoxy)-α,α-dimethylbenzyl]benzene, 3,3′-diamino-4,4′-diphenoxybenzo phenone, 4,4'-diamino-5, 5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino -5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4 '-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3' -diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-dia Mino-5'-biphenoxybenzophenone, 1,3-bis(3-amino-4-phenoxybenzoyl)benzene, 1,4-bis(3-amino-4-phenoxybenzoyl)benzene, 1,3 -bis(4-amino-5-phenoxybenzoyl)benzene, 1,4-bis(4-amino-5-phenoxybenzoyl)benzene, 1,3-bis(3-amino-4-biphenoxybenzoyl) Benzene, 1,4-bis(3-amino-4-biphenoxybenzoyl)benzene, 1,3-bis(4-amino-5-biphenoxybenzoyl)benzene, 1,4-bis(4-amino- Some or all of the hydrogen atoms on the aromatic ring in 5-biphenoxybenzoyl)benzene, 2,6-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile and the aromatic diamine Aromatic diamine substituted with a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxyl group, a cyano group, or a halogenated alkyl group having 1 to 3 carbon atoms or an alkoxyl group in which some or all of the hydrogen atoms of the alkyl group or alkoxyl group are substituted with halogen atoms Etc., 4,4'-methylenebis(cyclohexylamine), isophoronediamine, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-cyclohexanebis(methyl amine), 2,5-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,6-bis(aminomethyl)bicyclo[2,2,1]heptane, 3,8-bis(amino methyl)tricyclo[5,2,1,0]decane, 1,3-diaminoadamantane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-aminocyclohexyl) Hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine and aliphatic diamines such as amine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, and 1,9-nonamethylenediamine. Other diamine compounds may be used independently and may be used 2 or more types.

[Photosensitive resin composition]

The photosensitive resin composition of this invention contains (A) the said esterdiamine containing polybenzoxazole precursor, and (B) a photosensitizer.

By using such an esterdiamine-containing polybenzoxazole precursor in the photosensitive resin composition, the dissolution contrast and internal stress of the dry coating film formed by the photosensitive resin composition can be remarkably improved.

Hereinafter, the component which the photosensitive resin composition of this invention contains is demonstrated in detail.

[(A) Esterdiamine-containing polybenzoxazole precursor]

The photosensitive resin composition of the present invention can significantly improve the dissolution contrast of the formed dry coating film and the internal stress of the cured film by including the esterdiamine-containing polybenzoxazole precursor as described above as a polybenzoxazole precursor.

Moreover, you may use the photosensitive resin composition of this invention in combination with polybenzoxazole precursors other than the said esterdiamine containing polybenzoxazole precursor.

It is preferable that they are 50 mass % or more and 99 mass % or less in a non-volatile component, and, as for content of the esterdiamine containing polybenzoxazole precursor in the photosensitive resin composition, it is more preferable that they are 60 mass % or more and 90 mass % or less. According to the range of such content, the effect of this invention can fully be acquired.

[(B) Photosensitizer]

The photosensitive resin composition of this invention contains a photosensitive agent, for example, a photo-acid generator, a photobase generator, etc. are mentioned. Among these, a photo-acid generator is preferable from a viewpoint of dissolution contrast.

This photosensitizer can be mix|blended in a well-known and customary ratio, For example, with respect to a photo-acid generator, 5-40 mass parts with respect to 100 mass parts of esterdiamine containing polybenzoxazole precursors, Preferably the ratio of 10-30 mass parts. It is preferable to mix with

Moreover, 2 or more types of these photosensitizers may be included.

The photoacid generator is a compound that generates an acid upon irradiation with light such as ultraviolet rays or visible light, for example, a naphthoquinonediazide compound, a diarylsulfonium salt, a triarylsulfonium salt, a dialkylphenacylsulfonium salt, and a diarylio Donium salt, aryldiazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonic acid ester, nitrobenzyl ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, benzoquinonediazosulfonic acid ester, etc. are mentioned.

Among the above, a naphthoquinonediazide compound is preferable from a viewpoint of dissolution contrast.

As a naphthoquinonediazide compound, specifically, for example, the naphthoquinonediazide adduct of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, Sanbo Chemical Genkyusho) TS533, TS567, TS583, TS593 manufactured by the Company), naphthoquinonediazide adducts of tetrahydroxybenzophenone (eg, BS550, BS570, BS599 manufactured by Sanbo Chemical Corporation) and 4-{4-[1 Naphthoquinonediazide adduct of ,1-bis(4-hydroxyphenyl)ethyl]-α,α-dimethylbenzyl}phenol (eg, TKF-428, TKF-528 manufactured by Sanbo Chemical Corporation) and the like.

A photobase generator is a compound which produces|generates 1 or more types of basic substances (a secondary amine, a tertiary amine, etc.) by molecular structure change or molecular cleavage by light irradiation, such as an ultraviolet-ray or visible light.

As a photobase generator, although an ionic photobase generator may be sufficient and a nonionic photobase generator may be sufficient, an ionic photobase generator is preferable from a viewpoint of the sensitivity of the photosensitive resin composition.

Examples of the ionic photobase generator include salts of aromatic component-containing carboxylic acids and tertiary amines, and commercially available products thereof include WPBG-082, WPBG-167, and WPBG-168 manufactured by Wako Pure Chemical Industries, Ltd. ionic PBG. , WPBG-266 and WPBG-300, and the like.

Examples of the nonionic photobase generator include α-aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzylcarbamate groups, and alkoxybenzylcarba. The compound etc. which have substituents, such as a mate group, are mentioned.

As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N,N'-diethylcarbamate) manufactured by Wako Pure Chemical Industries, Ltd., WPBG-027 (Brand name: (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine ((E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine )), WPBG-140 (trade name: 1-(anthraquinon-2-yl)ethyl imidazolecarboxylate (1-(anthraquinon-2-yl)ethyl imidazolecarboxylate)), WPBG-165, and the like.

[crosslinking agent]

The photosensitive resin composition of this invention may contain a crosslinking agent. By adding a crosslinking agent, sufficient properties of the cured product can be obtained even at low temperature curing at about 220°C. The crosslinking agent is not specifically limited, A well-known and usual crosslinking agent is mentioned.

In the present specification, the crosslinking agent is preferably a compound capable of forming a crosslinked structure by reacting with the phenolic hydroxyl group in the polybenzoxazole precursor.

Here, as a compound that reacts with the phenolic hydroxyl group in the polybenzoxazole precursor, a crosslinking agent having a cyclic ether group such as an epoxy group, a cyclic thioether group such as an episulfide group, and a hydroxyl group to an alkylene group having 1 to 12 carbon atoms such as a methylol group and a crosslinking agent having an alcoholic hydroxyl group to which pseudo-bonded, a compound having an ether bond such as an alkoxymethyl group, a crosslinking agent having a triazine ring structure, and a urea-based crosslinking agent are exemplified.

Among these, a crosslinking agent having a cyclic ether group, particularly an epoxy group, and a crosslinking agent having an alcoholic hydroxyl group, particularly a methylol group bonded to a hydroxyl group are preferable.

A crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that the compounding quantity of the crosslinking agent in the photosensitive resin composition of this invention is 0.1-30 mass parts with respect to 100 mass parts of non-volatile components of a polybenzoxazole precursor. Moreover, 0.1-20 mass parts is more preferable.

(crosslinking agent having an epoxy group)

It is preferable that the photosensitive resin composition of this invention contains the crosslinking agent which has an epoxy group as a crosslinking agent. The crosslinking agent having an epoxy group thermally reacts with the hydroxyl group of the polybenzoxazole precursor to form a crosslinked structure. It is preferable that the functional group number of the crosslinking agent which has an epoxy group is 2-4. When the photosensitive resin composition contains a crosslinking agent having an epoxy group, low-temperature curability is obtained, and the dissolution contrast of the formed dry coating film can be further improved.

Among the crosslinking agents which have an epoxy group, the epoxy compound more than bifunctional which has a naphthalene skeleton is preferable. Not only can an insulating film superior in flexibility and chemical resistance be obtained, but also it is possible to reduce the CTE, which is in a relationship between flexibility and antinomy, so that warpage or cracks in the insulating film can be suppressed. Moreover, a bisphenol A epoxy compound can also be used suitably from a softness|flexibility viewpoint.

(crosslinking agent having a methylol group)

It is preferable that the photosensitive resin composition of this invention contains the crosslinking agent which has a methylol group as a crosslinking agent. As a crosslinking agent which has a methylol group, it is preferable that it has two or more methylol groups, and it is more preferable that it is a compound represented by the following general formula (7).

(In general formula (7), R ^A1 represents an organic group having a valence of 2 to 10. R ^A2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. r represents an integer of 2 to 10.)

In the general formula (7), R ^A1 is preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent.

In the general formula (7), R ^A2 is preferably a hydrogen atom.

In the said General formula (7), it is preferable that it is an integer of 2-4, and, as for r, it is more preferable that it is 2.

Moreover, it is preferable that it has a fluorine atom, and, as for the crosslinking agent which has a phenolic hydroxyl group, it is more preferable that it has a trifluoromethyl group. It is preferable that the said fluorine atom or the said trifluoromethyl group has a 2- to 10-valent organic group represented by ^{R A1 in the said General formula (7), It is preferable that R A1} is a di(trifluoromethyl) methylene group. Moreover, it is preferable to have a bisphenol structure, and, as for the crosslinking agent which has a phenolic hydroxyl group, it is more preferable to have a bisphenol AF structure.

[Plasticizer]

It is preferable that the photosensitive resin composition of this invention contains a plasticizer. In the present invention, the thermal molecular motion of the polybenzoxazole precursor is improved by reducing the plasticizing action of the plasticizer, that is, the aggregation action between the polymer molecular chains, and the mobility and flexibility between the molecular chains are improved, and the cyclization reaction is promoted. It is thought that low-temperature hardenability is provided by becoming. The plasticizer is not particularly limited as long as it is a compound that improves plasticity, and an ether compound such as a bifunctional (meth)acrylic compound, a sulfonamide compound, a phthalic acid ester compound, a maleic acid ester compound, an aliphatic dibasic acid ester, a phosphoric acid ester, a crown ether, etc. can be heard Especially, it is preferable that it is a bifunctional (meth)acryl compound. It is preferable that a bifunctional (meth)acrylic compound is a compound which does not form a crosslinked structure with the other component in a composition. Moreover, it is preferable that a bifunctional (meth)acrylic compound is a compound which forms a linear structure by self-polymerization from a viewpoint of further relieve|moderating the internal stress of hardened|cured material. As a compounding quantity of the plasticizer in the photosensitive resin composition of this invention, it is preferable that it is 3-40 mass parts with respect to 100 mass parts of non-volatile components of a polybenzoxazole precursor.

Among the bifunctional (meth)acrylic compounds, di(meth)acrylate and bifunctional polyester (meth)acrylate of an alkylene oxide adduct (such as ethylene oxide and propylene oxide) of diol are preferable, and bifunctional Polyester (meth)acrylate is more preferable.

As di(meth)acrylate of the alkylene oxide adduct of diol, it is preferable specifically, what added (meth)acrylate to the terminal after alkylene oxide modification|denaturation of diol, and what has an aromatic ring to diol is more preferable. . For example, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol APO (propylene oxide) adduct diacrylate, etc. are mentioned. Although the specific structure of the di(meth)acrylate of the alkylene oxide adduct of diol is shown to the following general formula (8), it is not limited to this.

In general formula (8), p+q is 2 or more, it is preferable that it is 2-40, and it is more preferable that it is 3.5-25.

(thermal acid generator, sensitizer, adhesive, other ingredients)

In the photosensitive resin composition of the present invention, within a range not impairing the effects of the present invention, a known thermal acid generator for accelerating the cyclization reaction of a polybenzoxazole precursor, a known sensitizer for improving photosensitivity, a substrate and A well-known adhesive agent, such as a silane coupling agent, etc. may be further mix|blended in order to improve the adhesiveness of . In addition, in order to provide processing characteristics and various functionalities to the photosensitive resin composition of this invention, you may mix|blend various organic or inorganic low molecular weight or high molecular compounds. For example, surfactants, leveling agents, microparticles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon, and layered silicate. Moreover, you may mix|blend various coloring agents, a fiber, etc. with the photosensitive resin composition of this invention.

[solvent]

The photosensitive resin composition of this invention may contain the solvent. The solvent is not particularly limited as long as it can dissolve the respective components, for example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N' -Dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N- cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether, and the like.

Content of the solvent in the photosensitive resin composition is not specifically limited, Although it is preferable to change suitably according to the use, For example, 50 with respect to 100 mass parts of esterdiamine containing polybenzoxazole precursors contained in the photosensitive resin composition. It can be set as 9000 mass parts or more and 9000 mass parts or more.

Moreover, the photosensitive resin composition may contain 2 or more types of solvents.

[Dry Film]

The dry film of this invention is equipped with a film (for example, a support (carrier) film), and the resin layer formed using the said photosensitive resin composition on this film. Moreover, the dry film may further be equipped with the film (so-called protective film) to protect (cover) on the resin layer formed on the film.

(film)

The film is not particularly limited. For example, a film containing a thermoplastic resin such as a polyester film such as polyethylene terephthalate and polyethylene naphthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film may be used. can

Among these, the viewpoints of heat resistance, mechanical strength, handleability, etc. to a polyethylene terephthalate are preferable. Moreover, the laminated body of these films can also be used as a film.

In addition, the thermoplastic resin film as described above is preferably a film stretched in the uniaxial direction or the biaxial direction from the viewpoint of improving the mechanical strength.

Although the thickness in particular of a film is not restrict|limited, For example, it can be 10-150 micrometers.

(resin layer)

A resin layer is formed using the said photosensitive resin composition, The thickness is not specifically limited, Although it is preferable to change suitably according to a use, it can be set as 1 micrometer or more and 150 micrometers or less, for example.

The resin layer can be formed by coating the photosensitive resin composition on the film to a uniform thickness by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. have.

In addition, in another embodiment, a resin layer can be formed by apply|coating and drying the photosensitive resin composition on a protective film.

(protective film)

In the present invention, it is preferable to laminate a peelable protective film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer.

The peelable protective film is not particularly limited as long as the adhesive force between the resin layer and the protective film becomes smaller than the adhesive force between the resin layer and the film when the protective film is peeled, and for example, a polyethylene film, a polytetrafluoroethylene film, A polypropylene film, a surface-treated paper, etc. can be used.

Although the thickness of a protective film is not specifically limited, For example, it can be 10 micrometers or more and 150 micrometers or less.

[Cured material]

The cured product of the present invention is characterized in that it is formed using the photosensitive resin composition. In addition, the thing in which the pattern is formed (henceforth, it may be called a pattern film in some cases) may be sufficient as this hardened|cured material.

Hereinafter, the manufacturing method of the hardened|cured material of this invention is demonstrated.

[First step]

The manufacturing method of the hardened|cured material of this invention includes the process of forming a dry coating film by apply|coating a photosensitive resin composition on a base material, forming a coating film, drying this, or transferring a resin layer from the said dry film onto a base material.

The coating method of the photosensitive resin composition on the substrate is not particularly limited, and for example, a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., a method of spray coating with a spray coater, and inkjet law, and the like.

As a drying method of a coating film, methods, such as air drying, heat drying by oven or a hot plate, and vacuum drying, are used.

In addition, it is preferable to perform drying of a coating film on the conditions in which ring closure of the polyimide precursor in the photosensitive resin composition does not occur.

Specifically, it is preferable to perform natural drying, air drying, or heat drying at 70 to 140°C for 1 to 30 minutes. Moreover, since the operation method is simple, it is preferable to perform drying for 1 to 20 minutes using a hotplate.

Further, vacuum drying is also possible, and in this case, it can be carried out at room temperature for 20 minutes to 1 hour.

The transfer of the dry film onto the substrate is preferably performed under pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, when a circuit-formed substrate is used, even if the circuit board surface has irregularities, the resin layer of the dry film is filled in the irregularities of the circuit board under vacuum conditions. The hole filling properties of the recesses are also improved.

As the base material, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin Materials such as copper-clad laminates for high-frequency circuits using polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc. are used. Copper-clad laminates of all grades (FR-4, etc.), other metal substrates, polyimide films, polyethylene A terephthalate film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, etc. are mentioned.

[Second process]

Then, the coating film is exposed by irradiating an active energy ray selectively through a photomask having a pattern or non-selectively without passing through the photomask.

For the active energy ray, for example, (B) a photosensitive agent having a wavelength capable of activating the photosensitizer is used. Specifically, it is preferable that the maximum wavelength of the active energy ray is in the range of 350 to 410 nm.

Although the exposure amount varies depending on the film thickness and the like, it is generally within the range of 10 to 1000 mJ/cm 2 , and preferably 20 to 800 mJ/cm 2 .

As the exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. are mounted, and any device that irradiates ultraviolet rays in the range of 350 to 450 nm is sufficient, and direct drawing A device (eg, a laser direct imaging device that draws an image with a laser directly by means of CAD data from a computer) can also be used.

[Third process]

This process is performed as needed, and you may ring-close a part of polyimide precursor of an unexposed part by heating a coating film for a short time. Here, the exchange rate is about 30%. Heating time and heating temperature are changed suitably according to the kind of polyimide precursor, a coating film thickness, and the kind of (B) photosensitive agent.

[Fourth process]

Then, a pattern film can be obtained by processing the coating film after the said exposure with a developing solution, and removing the exposed part in a coating film.

In this process, arbitrary methods can be selected from the conventionally known photoresist developing method, for example, a rotation spray method, a paddle method, the immersion method with ultrasonic treatment, etc.

Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia; organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine; tetramethylammonium hydroxide; tetrabutylammonium hydroxide; aqueous solutions such as quaternary ammonium salts of

Moreover, you may add water-soluble organic solvents, such as methanol, ethanol, and isopropyl alcohol, and surfactant in an appropriate amount to these as needed.

Thereafter, if necessary, the coating film is washed with a rinsing solution to obtain a patterned film.

As a rinse liquid, distilled water, methanol, ethanol, isopropyl alcohol, etc. can be used individually or in combination. Moreover, you may use the said solvent as a developing solution.

[Step 5]

Next, the pattern film is heated to obtain a cured coating film (cured product).

According to this heating process, the polybenzoxazole precursor contained in the photosensitive resin composition cyclizes and turns into polybenzoxazole.

It is preferable to adjust heating conditions suitably, For example, in the temperature of 150 degreeC or more and less than 350 degreeC, it can set in about 5 minutes - 120 minutes.

For heating, for example, a hot plate, an oven, and an elevated temperature oven capable of setting a temperature program can be used.

A heating atmosphere (gas), air, or an inert gas such as nitrogen or argon may be used.

[purpose]

The use of the photosensitive resin composition of this invention is not specifically limited, For example, it is used suitably as a forming material, such as a paint, a printing ink, an adhesive agent, a display apparatus, a semiconductor element, an electronic component, an optical component, and a building material.

Specifically, as a forming material of a display device, the layer forming material and image forming material in a color filter, the film for flexible displays, a resist material, an orientation film, etc. are mentioned.

As a forming material of a semiconductor element, the layer forming material in a resist material, a buffer coat film, the insulating film for redistribution layers of a wafer level package (WLP), etc. is mentioned.

As a forming material of an electronic component, the sealing material and layer forming material in a printed wiring board, an interlayer insulating film, a wiring coating film, etc. are mentioned.

Moreover, as a forming material of an optical component, the optical material and layer forming material in a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, etc. are mentioned.

Moreover, as a building material, it can be used for a paint, a coating agent, etc.

The photosensitive resin composition of the present invention can be mainly used as a pattern forming material, and in particular, a surface protective film, a buffer coating film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, and a bump structure for semiconductor devices, display devices and light emitting devices. It can use suitably as a protective film of the device which has, the interlayer insulating film of a multilayer circuit, the insulating material for passive components, the protective film of printed wiring boards, such as a soldering resist and a coverlay film, and a liquid crystal aligning film, etc.

Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the examples. In addition, in the following, everything referred to as "part" and "%" is a mass basis, unless otherwise stated.

(Reference Example 1: Synthesis of polybenzoxazole precursor A-1)

In a 0.5 liter flask equipped with a stirrer and a thermometer, 0.489 g (1.61 mmol) of (2-phenyl-4-aminophenyl)-4-aminobenzoate (PHBPAA) represented by the following formula (a) and the following formula (b) 28.02 g (76.5 mmol) of the bis(3-amino-4-hydroxyphenyl)hexafluoropropane represented by , was charged and dissolved with stirring in 215 g of N-methylpyrrolidone.

Thereafter, the flask was immersed in an ice bath, and 25.29 g (85.7 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride represented by the following formula (c) was added as a solid while maintaining the inside of the flask at 0 to 5° C. It was added over 10 minutes, and stirred in an ice bath for 30 minutes.

After that, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value of 18.2 MΩ·cm), and the precipitate was recovered. Then, the obtained solid was melt|dissolved in 420 mL of acetone, and it injected|thrown-in to 1 L of ion-exchange water. The precipitated individual was collected and dried under reduced pressure to obtain a polybenzoxazole precursor containing carboxyl group-terminal ester diamine represented by the following formula. The weight average molecular weight calculated|required by GPC method standard polystyrene conversion was 31,000.

In addition, content of the ester diamine in ester diamine containing polybenzoxazole precursor was 2 mol%.

(Reference Example 2: Synthesis of polybenzoxazole precursor A-2)

In a 0.5 liter flask equipped with a stirrer and a thermometer, 0.474 g (1.56 mmol) of PHBPAA and 10.88 g (29.7 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane were charged, and N-methylpi It stirred and melt|dissolved in 85 g of rollidone.

Then, the flask is immersed in an ice bath, and while maintaining the inside of the flask at 0 to 5 ° C., 10.09 g (34.2 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride is added as a solid over 10 minutes, The mixture was stirred in an ice bath for 30 minutes.

After that, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 700 mL of ion-exchanged water (resistance value of 18.2 MΩ·cm), and the precipitate was recovered. Then, the obtained solid was melt|dissolved in 420 mL of acetone, and it injected|thrown-in to 1 L of ion-exchange water. The precipitated individual was collected and dried under reduced pressure to obtain a polybenzoxazole precursor containing esterdiamine at the terminal of a carboxyl group. The weight average molecular weight calculated|required by GPC method standard polystyrene conversion was 26,900.

In addition, content of esterdiamine in esterdiamine containing polybenzoxazole precursor was 5 mol%.

(Reference Example 3: Synthesis of polybenzoxazole precursor A-3)

In a 0.5 liter flask equipped with a stirrer and a thermometer, 10.0 g (27.3 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 1500 g of N-methylpyrrolidone.

Then, the flask is immersed in an ice bath, and while maintaining the inside of the flask at 0 to 5 ° C., 8.78 g (29.8 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride is added as a solid over 10 minutes, The mixture was stirred in an ice bath for 30 minutes.

After that, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 700 mL of ion-exchanged water (resistance value of 18.2 MΩ·cm), and the precipitate was recovered. Then, the obtained solid was melt|dissolved in 420 mL of acetone, and it injected|thrown-in to 1 L of ion-exchange water. The precipitated individual was collected and dried under reduced pressure to obtain a polybenzoxazole precursor having a carboxyl group terminal. The weight average molecular weight calculated|required by GPC method standard polystyrene conversion was 29,500, the number average molecular weight was 11,600, and PDI was 2.54.

<Example 1-1>

Polybenzoxazole precursor A-1 (100 parts by mass) and diazonaphthoquinone compound A (10 parts by mass, manufactured by Sanbo Chemical Industries, Ltd., TKF-428, photosensitizer) obtained in Reference Example 1 were γ- After melt|dissolving in butyrolactone (300 mass parts), it filtered with a 0.2 micrometer filter and obtained the varnish A-1 of the photosensitive resin composition.

<Example 1-2>

Except having changed the polybenzoxazole precursor A-1 into the polybenzoxazole precursor A-2, it carried out similarly to Example 1-1, and obtained the varnish A-2 of the photosensitive resin composition.

<Comparative Example 1-1>

Except having changed the polybenzoxazole precursor A-1 into the polybenzoxazole precursor A-3, it carried out similarly to Example 1-1, and obtained the varnish A-3 of the photosensitive resin composition.

<<Evaluation of elongation rate >>

The varnishes A-1, A-2 and A-3 obtained in Examples 1-1 to 1-2 and Comparative Example 1-1 were applied on a 6-inch silicon wafer using a spin coater, respectively, and applied on a hot plate. It dried at 110 degreeC for 3 minutes, and obtained the coating film with a film thickness of about 30 micrometers. Subsequently, the silicon wafer with a coating film was heated at 150 degreeC/30min and 320 degreeC/60min using oven.

The obtained cured film was peeled from a silicon wafer, elongation was measured from the tensile test using EZ-SX by Shimadzu Corporation, and it evaluated based on the following evaluation criteria. Table 1 summarizes the evaluation results.

(Evaluation standard)

(double-circle): The elongation rate was 15 % or more.

(circle): Elongation rate was 10 % or more and less than 15 %.

x: The elongation rate was less than 10 %.

<<Evaluation of glass transition temperature>>

The glass transition temperature (Tg) of the cured film obtained in elongation evaluation was measured by TMA (thermomechanical analysis), and it evaluated based on the following evaluation criteria. Table 1 summarizes the evaluation results.

(Evaluation standard)

(double-circle): The glass transition temperature was 300 degreeC or more.

(circle): The glass transition temperature was 250 degreeC or more and less than 300 degreeC.

x: The glass transition temperature was less than 250 degreeC.

<<Evaluation of internal stress>>

The varnishes A-1, A-2 and A-3 obtained in Examples 1-1 to 1-2 and Comparative Example 1-1 were applied on a 6-inch silicon wafer using a spin coater, respectively, and applied on a hot plate. It dried at 110 degreeC for 3 minutes, and obtained the coating film with a film thickness of about 6 micrometers. Subsequently, the silicon wafer with a coating film was heated at 150 degreeC/30min and 320 degreeC/60min using oven.

From the curvature radius obtained from the change of the curvature amount of the silicon wafer before and behind cured film formation, internal stress was measured using Formula (1), and it evaluated based on the following evaluation criteria. Table 1 summarizes the evaluation results.

(Evaluation standard)

(double-circle): The internal stress was less than 25 MPa.

(circle): The internal stress was 25 MPa or more and less than 30 MPa.

x: The internal stress was 30 MPa or more.

<<Evaluation of dissolution contrast>>

The varnishes A-1, A-2, and A-3 obtained in Examples 1-1 to 1-2 and Comparative Example 1-1 were coated on a 6-inch silicon wafer using a spin coater, and 110 on a hot plate. It was dried at °C for 3 minutes, and a coating film having a film thickness of about 8 µm was obtained. With respect to the obtained coating film, i-line exposure was performed through a mask, and the exposed part and the unexposed part were made in the same board|substrate. After exposure, it developed for 120 second with the 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, rinsed with water, and the pattern of the positive type cured film was obtained.

The exposure part development speed and the unexposed part development speed|rate until the film thickness of an exposure part became 0 were calculated|required. Contrast was computed from the following formula, and the following reference|standard evaluated. Table 1 summarizes the evaluation results.

(Evaluation standard)

(double-circle): Contrast was 100 or more.

(circle): Contrast was 20 or more and less than 100.

x: The dissolution rate ratio was less than 20.

<<Sensitivity evaluation>>

The varnishes A-1, A-2, and A-3 obtained in Examples 1-1 to 1-2 and Comparative Example 1-1 were applied on a silicon wafer with a spin coater, and the hot plate was used at 110° C. for 3 minutes. It heat-dried and obtained the coating film with a film thickness of about 8 micrometers.

The obtained coating film was irradiated with broad light through a photomask having a pattern using a high-pressure mercury lamp (with an i-line filter). In addition, the exposure amount was raised by 50 mJ/cm<2>, and it performed in the range of 100-1000 mJ/cm<2> after photomask transmission.

The dried coating film after exposure was developed using 2.38% TMAH aqueous solution, rinsed with water, and a positive patterned film was formed.

The exposure amount from which the exposed part did not completely elute was made into the minimum exposure amount, and the following evaluation criteria evaluated. Table 1 summarizes the evaluation results.

(Evaluation standard)

(double-circle): The minimum exposure amount was less than 400 mJ/cm<2>.

(circle): The minimum exposure amount was 400 mJ/cm<2> or more and less than 700 mJ/cm<2>.

x: The minimum exposure amount was 700 mJ/cm<2> or more.

As is clear from the evaluation result shown in said Table 1, in an Example, it has confirmed that it has a high glass transition temperature, elongation, melt|dissolution contrast, and a sensitivity, and has a low internal stress.

<Example 2-1>

Polybenzoxazole precursor A-1 (100 parts by mass) obtained in Reference Example 1, diazonaphthoquinone compound A (10 parts by mass, manufactured by Sanbo Chemical Industries, Ltd., TKF-428, photosensitizer) and bifunctional A (meth)acrylic compound (10 parts by mass, manufactured by Toagosei Co., Ltd., M-6250, a plasticizer) was dissolved in γ-butyrolactone (300 parts by mass), filtered through a 0.2 μm filter, and varnish B-1 of the photosensitive resin composition got

<Example 2-2>

Polybenzoxazole precursor A-1 (100 parts by mass) obtained in Reference Example 1, diazonaphthoquinone compound A (10 parts by mass, manufactured by Sanbo Chemical Industries, Ltd., TKF-428, photosensitizer) and bifunctional After the above epoxy compound (10 parts by mass, manufactured by DIC, HP-4032D, crosslinking agent) was dissolved in γ-butyrolactone (300 parts by mass), it was filtered with a 0.2 μm filter to obtain varnish C-1 of the photosensitive resin composition.

<Example 2-3>

Polybenzoxazole precursor A-1 (100 parts by mass) obtained in Reference Example 1, diazonaphthoquinone compound A (10 parts by mass, manufactured by Sanbo Chemical Industries, Ltd., TKF-428, photosensitizer) and the following formula After dissolving TM-BIP-A (10 parts by mass, crosslinking agent) represented by (d) in γ-butyrolactone (300 parts by mass), it was filtered with a 0.2 µm filter to obtain varnish D-1 of the photosensitive resin composition.

<<Evaluation of glass transition temperature>>

While changing the varnish to the varnishes B-1, C-1, and D-1 obtained in Examples 2-1 to 2-3, heating of the silicon wafer with a coating film by oven is 150 degreeC/30 minute, 220 The glass transition temperature was measured by the method similar to the above-mentioned method except having changed to °C/60 min, and it evaluated based on the same evaluation criteria. Table 2 summarizes the evaluation results.

<<Evaluation of internal stress>>

While changing the varnish to the varnishes B-1, C-1, and D-1 obtained in Examples 2-1 to 2-3, heating of the silicon wafer with a coating film by oven is 150 degreeC/30 minute, 220 The internal stress was measured by the method similar to the above-mentioned method except having changed to °C/60min, and it evaluated based on the same evaluation criteria. Table 2 summarizes the evaluation results.

<<Evaluation of dissolution contrast>>

Except having changed the varnish into the varnishes B-1, C-1, and D-1 obtained in Examples 2-1 to 2-3, the contrast was calculated|required by the method similar to the above-mentioned method, and it was based on the same evaluation criteria. evaluated on the basis of Table 2 summarizes the evaluation results.

<<Sensitivity evaluation>>

Except having changed the varnish into the varnishes B-1, C-1 and D-1 obtained in Examples 2-1 to 2-3, a sensitivity is calculated|required by the method similar to the above-mentioned method, and it is based on the same evaluation criteria. evaluated on the basis of Table 2 summarizes the evaluation results.

As is clear from the evaluation results shown in Table 2, in each Example, it has been confirmed that even curing at a low temperature has a high glass transition temperature and a high dissolution contrast, and has a low internal stress.

Claims (10)

It has at least one of the structures represented by following General formula (1) and (2), and the structure represented by following General formula (3), The esterdiamine containing polybenzoxazole precursor characterized by the above-mentioned.

(in general formulas (1) and (2),
X is a divalent organic group,
Any of R ₁ to R ₄ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 6 to 10 carbon atoms, and 6 carbon atoms to 10 benzyloxy groups, and other R ₃ to R ₆ are hydrogen atoms,
n represents an integer of 1 or more,
In general formula (3),
X is a divalent organic group,
Y is a tetravalent organic group having at least two or more hydroxyl groups,
o represents an integer greater than or equal to 1.) According to claim 1,
any of R ₁ or R ₃ is selected from an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 6 to 10 carbon atoms and a benzyloxy group having 6 to 10 carbon atoms, and the other is a hydrogen atom ego,
An esterdiamine-containing polybenzoxazole precursor, wherein _{R 2} and R _{4 are hydrogen atoms.} 3. The method of claim 1 or 2,
In the general formula (3), Y is an aromatic group, an esterdiamine-containing polybenzoxazole precursor. 4. The method according to any one of claims 1 to 3,
An esterdiamine-containing polybenzoxazole precursor, wherein Y in the general formula (3) is one or more groups selected from the following structures.

(In the above structural formula,
Either of * ₁ and * ₂ represents a linkage with an amino group, and the other represents a hydroxyl group.) 5. The method according to any one of claims 1 to 4,
The polybenzoxazole precursor containing esterdiamine whose content (ester diamine content) of the structure represented by the said General formula (1) and (2) is 0.1 mol% or more and 10 mol% or less. The photosensitive resin composition containing the esterdiamine containing polybenzoxazole precursor in any one of Claims 1-5, and a photosensitive agent. 7. The method of claim 6,
The photosensitive agent is a naphthoquinone diazide compound, the photosensitive resin composition. On a film, the resin layer formed with the photosensitive resin composition of Claim 6 or 7 is provided, The dry film characterized by the above-mentioned. It is formed of the resin layer of the photosensitive resin composition of Claim 6 or 7, or the dry film of Claim 8, The hardened|cured material characterized by the above-mentioned. An electronic component comprising the cured product according to claim 9 as a forming material.