TW202045594A - Ester-diamine-containing polybenzoxazole precursor, photosensitive resin composition, dry film, cured product, and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition including an ester-diamine-containing polybenzoxazole precursor that achieves high dissolution contrast and furthermore is resistant to cracking and warping. This ester-diamine-containing polybenzoxazole precursor is characterized by having a structure represented by general formula (1) and/or (2) and a structure represented by general formula (3).

Description

Polybenzoxazole precursor containing ester diamine, photosensitive resin composition, dry film, cured product and electronic parts

The present invention relates to a polybenzoxazole precursor containing ester diamine (also known as polyhydroxyamide), a photosensitive resin composition containing the polybenzoxazole precursor containing ester diamine, and the photosensitive resin composition A dry film of a resin layer formed of a photosensitive resin composition, a cured product formed of the photosensitive resin composition, and electronic parts such as printed wiring boards and semiconductor elements having the cured product as a forming material.

The photosensitive resin composition containing the polybenzoxazole precursor is heated to cyclize the hydroxyamide structure into a rigid benzoxazole ring, and the filling density between molecules also increases, thereby exhibiting insulation, It has excellent properties such as heat resistance and mechanical strength, so it has been widely used in various fields. For example, it has been used in flexible printed wiring boards or buffer coating films for semiconductor devices, and insulating films for rewiring layers such as wafer level packaging (WLP).

In the past, in the buffer coating film or the insulating film for the rewiring layer of the wafer-level package, instead of the photosensitive resin composition containing the polyimide precursor, the pattern can be formed by finer photolithography A photosensitive resin composition containing a polybenzoxazole precursor has attracted attention. As these photosensitive resin compositions, as disclosed in Patent Document 1, a positive photoresist composition composed of a polybenzoxazole precursor and photosensitive diazoquinone is exemplified. Then, these photosensitive resin compositions are coated on a substrate such as a wafer and dried to form a dry coating film, the dry coating film is irradiated with active energy rays for exposure, and then the desired pattern film is formed by development , By heating the polybenzoxazole precursor at about 320°C to carry out a cyclization reaction, forming a patterned cured film of polybenzoxazole.

In addition, in recent semiconductor devices, along with the requirements for higher performance or miniaturization, the buffer coating film or the insulating film for the rewiring layer of wafer-level packaging is also required to achieve excellent resolution in the formation of finer patterns. Furthermore, it is required to suppress the cracks or warpage accompanying the thinning of the wafer as the substrate. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 1-046862

[The problem to be solved by the invention]

However, in the composition described in Patent Document 1, in order to achieve the resolution required for recent semiconductor devices, it is necessary to reduce the so-called dissolution contrast that is the balance between the solubility of the exposed part and the dissolution resistance of the unexposed part during development. There is a problem that it is difficult to form a fine pattern, and the suppression of cracks or warpage is also insufficient.

The present invention was made in order to solve this problem, and its object is to provide a photosensitive resin composition containing a polybenzoxazole precursor that can achieve high dissolution contrast and is less likely to generate cracks or warpage.

In addition, another object of the present invention is to provide electronic parts such as dry films, printed wiring boards, and semiconductor elements using the photosensitive resin composition. [Means to solve the problem]

As a result of active research to achieve the above-mentioned object, the inventors found that the introduction of a diamine with an ester structure into the polybenzoxazole precursor can significantly improve the dissolution contrast of the photosensitive resin composition, and further reduce the hardening time. The internal stress generated, thus completing the present invention.

(通式(1)及(2)中， X 為2價有機基， R₁ ~R₄ 之任一者為選自碳數1~12之烷基、碳數1~12之烷氧基、碳數6~10之芳香族基、碳數6~10之苯氧基、碳數6~10之苄基及碳數6~10之苄氧基，其以外之R₁ ~R₄ 為氫原子， n表示1以上之整數， 通式(3)中， X為2價有機基， Y為至少具有2以上的羥基之4價有機基， o表示1以上之整數)。That is, the polybenzoxazole precursor containing ester diamine of the present invention is characterized by having at least one of the structures shown in general formulas (1) and (2) and the following general formula (3) structure,

(In general formulas (1) and (2), X is a divalent organic group, and any one of R ₁ to R ₄ is selected from an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, Aromatic groups with 6 to 10 carbons, phenoxy with 6 to 10 carbons, benzyl with 6 to 10 carbons, and benzyloxy with 6 to 10 carbons. The other R ₁ to R ₄ are hydrogen atoms , N represents an integer of 1 or more, in the general formula (3), X is a divalent organic group, Y is a tetravalent organic group having at least 2 or more hydroxyl groups, and o represents an integer of 1 or more).

In the present invention, it is preferable that either R ₁ or R ₃ is selected from the group consisting of aromatic groups having 6 to 10 carbons, phenoxy groups having 6 to 10 carbons, benzyl groups having 6 to 10 carbons, and 6 carbons. ~10 benzyloxy, the other is a hydrogen atom, and R ₂ and R ₄ are hydrogen atoms.

(上述構造式中， ＊₁ 及＊₂ 之任一者表示與胺基之連結部，另一者表示羥基)。In the present invention, in the general formula (3), Y is preferably one or more groups selected from the following structures.

(In the above structural formula, any one of * ₁ and * ₂ represents a connecting portion with an amino group, and the other represents a hydroxyl group).

In the present invention, the content (ester diamine content) of the structure represented by the general formulas (1) and (2) is preferably 0.1 mol% or more and 10 mol% or less.

The photosensitive resin composition of the present invention is characterized by comprising a polybenzoxazole precursor and a photosensitive agent.

In the present invention, the preferred photosensitizer is naphthoquinone diazide (naphthoquinone diazide) compound.

The feature of the dry film of the present invention is that the film is provided with a resin layer formed of the above-mentioned photosensitive resin composition.

The cured product of the present invention is characterized by being formed by the photosensitive resin composition or the resin layer of the dry film.

The electronic component of the present invention such as a printed wiring board or a semiconductor element is characterized by having the above-mentioned cured product as a forming material. [Invention Effect]

The polybenzoxazole precursor containing ester diamine according to the present invention can provide a photosensitive resin composition that effectively obtains a dry coating film with high solubility contrast and high temperature pattern maintenance.

[Polybenzoxazole precursor containing ester diamine]

If the polybenzoxazole precursor containing ester diamine of the present invention has at least one of the structures shown in the following general formulas (1) and (2) and the structure shown in the following general formula (3) The polybenzoxazole precursor, the photosensitive resin composition containing it can obtain the development resistance of the unexposed part without impairing the developability of the exposed part, and in the cured product, it is considered that the amide is excellent in flexibility. Bond and ester bond can relax internal stress.

In the above general formulae (1) and (2), X is a divalent organic group. The organic group may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and the aromatic ring is more preferably bonded to the carbonyl group in the above general formulas (1) and (2). The carbon number of the divalent organic group is preferably 6-30, more preferably 6-24. As a divalent organic group, the group which has the following structure is illustrated, but it is not limited to these, It is preferable to change suitably according to a use.

In the structural formula of the above-mentioned divalent organic group, A is selected from single bond, alkylene, -O-, -CO-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -and -C( CH ₃ ) ₂ -, * represents the link with the carbonyl group.

Among the above, based on the excellent developability of the photosensitive resin composition and the excellent mechanical properties of the cured film, the divalent organic group is particularly preferably the basis of the structure shown below.

In the above general formulas (1) and (2), any one of R ₁ to R ₄ is preferably any of R ₁ or R ₃ , and particularly preferably R ₃ is selected from an alkane having 1 to 12 carbon atoms Group, alkoxy group with 1 to 12 carbons, aromatic group with 6 to 10 carbons, phenoxy with 6 to 10 carbons, benzyl with 6 to 10 carbons and benzyloxy with 6 to 10 carbons , The other R ₁ to R ₄ are hydrogen atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, and hexyl. 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 aromatic groups having 6 to 10 carbon atoms include phenyl, tolyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, butylphenyl, Fluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, methoxybenzyl, two Methoxybenzyl, ethoxybenzyl, diethoxybenzyl, aminophenyl, aminobenzyl, nitrophenyl, nitrobenzyl, cyanophenyl, cyanobenzyl, benzene Ethyl, phenylpropyl, phenylamino, diphenylamino, biphenyl, naphthyl, etc. Examples of phenoxy groups with 6 to 10 carbon atoms include methylphenoxy, ethylphenoxy, propylphenoxy, dimethylphenoxy, diethylphenoxy, and methoxyphenoxy. , Ethoxyphenoxy and dimethoxyphenoxy, etc. Examples of benzyl groups with 6 to 10 carbon atoms include benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, dimethylbenzyl, methoxybenzyl, ethoxybenzyl and methoxy Benzyl and others. As the benzyloxy group having 6 to 10 carbon atoms, examples of the methylbenzyloxy group include benzyloxy, methylbenzyloxy, ethylbenzyloxy, propylbenzyloxy, dimethylbenzyloxy, methyl Oxybenzyloxy and ethoxybenzyloxy. Among the above, based on the viewpoints of the solubility contrast of the photosensitive resin composition, high-temperature pattern maintenance, sensitivity, and coefficient of linear thermal expansion, any one of R ₁ to R ₄ is preferably an aromatic group having 6 to 10 carbons, and carbon Phenoxy with 6-10, benzyl with 6-10, and benzyloxy with 6-10, more preferably aromatic with 6-10, more preferably phenyl, tolyl , Methyl phenyl, dimethyl phenyl, ethyl phenyl, and diethyl phenyl, based on the suppression effect of the film loss phenomenon in the unexposed area and the interior caused by the suppression of the intermolecular filling effect of the hardened material From the viewpoint of the stress relaxation effect, phenyl is particularly preferred.

In the above general formulas (1) and (2), n is an integer of 1 or more, preferably 1 to 5, and more preferably 1 to 2.

In the polybenzoxazole precursor containing ester diamine of the present invention, the content (ester diamine content) of the structure represented by the general formulas (1) and (2) is preferably 0.1 mol% or more and 10 mol% % Or less, more preferably 0.1 mol% or more and 5 mol% or less. Thereby, the dissolution contrast during development of the dry coating film formed by the photosensitive resin composition containing the polybenzoxazole precursor of the present invention can be further improved.

In the above-mentioned general formula (3), X is a divalent organic group, and the preferred aspects thereof are the same as those in the general formulas (1) and (2), so the description is omitted here.

In the above general formula (3), Y is a tetravalent organic group having at least two or more hydroxyl groups. The organic group may be an aliphatic group or an aromatic group, but is preferably an aromatic group. In addition, the positional relationship between the hydroxyl group and the amino group of the tetravalent organic group is preferably the ortho position. The carbon number of the tetravalent organic group is preferably 6-30, more preferably 6-24. As a tetravalent organic group, the group which has the following structure is illustrated, but it is not limited to this, It is preferable to change suitably according to a use.

In the structural formula of the above-mentioned tetravalent organic group, any one of * ₁ and * ₂ represents a link with an amino group, and the other represents a hydroxyl group.

Among the above, the tetravalent organic group is particularly preferably the base of the structure shown below, based on the viewpoint that the photosensitivity is improved due to light transmittance.

In the above general formula (3), o is an integer of 1 or more, preferably 10-40, more preferably 20-30.

In the ester diamine-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, more preferably 95 mol% or more Below 99.9 mol%. Thereby, the photosensitive resin composition containing the ester diamine-containing polybenzoxazole precursor of the present invention can improve the excellent developer solubility of the exposed part of the dry coating film and the insulation and heat resistance of the cured film Performance and mechanical strength.

The number average molecular weight (Mn) of the polybenzoxazole precursor containing the ester diamine is preferably 2,000 or more and 50,000 or less, more preferably 4,000 or more and 25,000 or less. This improves the solubility of the alkaline developing solution. In addition, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 4,000 or more and 10,000 or less, more preferably 8,000 or more and 50,000 or less. In this way, the occurrence of cracks in the hardened material can be further reduced. Furthermore, Mw/Mn is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less. In addition, in the present invention, the number average molecular weight and the weight average molecular weight are measured by a gel permeation chromatography (GPC) and converted to standard polystyrene.

The polybenzoxazole precursor containing ester diamine can be made of at least a diamine compound represented by the following general formula (4) and a diamine compound represented by the following general formula (5) and the following general formula (6) ) Is obtained by reacting the dicarboxylic acid component.

Z in the above general formula (6) represents a leaving group formed from a hydroxyl group, a halogen group, or a cyclic compound composed of nitrogen, sulfur, carbon, oxygen, and an aromatic ring. Among them, the halogen group is preferred from the viewpoint of productivity. R ₁ to R ₄ , X and Y in the above general formulas (4) to (6) are as described above.

Examples of dicarboxylic acid components satisfying the general formula (6) are isophthalic acid, terephthalic acid, 5-tert-butyl isophthalic acid; 5-bromoisophthalic acid, 5-fluoroisophthalic acid Formic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxydiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenyl Silane, bis(4-carboxyphenyl) sulfide, 2,2-bis(p-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3, Dicarboxylic acids with aromatic rings such as 3-hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Aliphatic dicarboxylic acids such as cyclopentane dicarboxylic acid, these dicarboxylic acid dihalides, these dicarboxylic acid esters, etc. Among them, 4,4'-dicarboxydiphenyl ether (ie, 4,4'-diphenyl ether dicarboxylic acid) is preferred based on the excellent developability of the photosensitive resin composition and the mechanical properties of the cured film. And its dihalides.

The polybenzoxazole precursor containing ester diamine can also be combined with two other diamine compounds represented by the general formulas (4) and (5) without compromising the characteristic effect and polymerization reactivity. Amine compound (hereinafter referred to as other diamine compound). 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] sulfide, 2,2-bis[4-(3-aminophenoxy)phenyl] Propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine , P-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4 ,4'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl sulfide, 3,3'-Diaminodiphenyl sulfene, 3,4'-Diaminodiphenyl Sodium sulfide, 4,4'-diaminodiphenyl sulfene, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diamine Diphenyl benzophenone, 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-aminobenzene) Oxy)phenyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, 1,4-bis[4-(4-aminophenoxy)benzene Yl]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)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy) Yl)-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]sulphonene, bis[4-(4-aminophenoxy)phenyl ] Sulphurite, bis[4-(4-aminophenoxy)phenyl] sulphur, bis[4-(3-amine Phenyloxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,3-bis[4-(4-aminophenoxy)benzyl] Benzene, 1,3-bis[4-(3-aminophenoxy)benzyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzyl]benzene, 4,4'-bis[(3-aminophenoxy)benzyl]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl]propane, 1,3-bis [4-(3-Aminophenoxy)phenyl]propane, 3,4'-diaminodiphenyl sulfene, 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-aminobenzene Oxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, bis[4-(3-aminophenoxy)phenyl] sulfene , 4,4'-bis[3-(4-aminophenoxy)benzyl]diphenyl ether, 4,4'-bis[3-(3-aminophenoxy)benzyl ]Diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4 -Amino-α,α-dimethylbenzyl)phenoxy]diphenyl chrysene, bis[4-{4-(4-aminophenoxy)phenoxy}phenyl] chrysene, 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-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-dimethyl Benzyl]benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone , 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamine 5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone , 3,3'-diamino-4,4'-diphenyloxybenzophenone, 4,4'-diamino-5,5'-diphenyloxybenzophenone, 3 ,4'-diamino-4,5'-diphenyloxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamine 5-biphenyloxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxydi Benzophenone, 1,3-bis(3-amino-4-phenoxybenzyl)benzene, 1,4-bis(3-amino-4-phenoxybenzyl) Benzene, 1,3-bis(4-amino-5-phenoxybenzyl)benzene, 1,4-bis(4-amino-5-phenoxybenzyl)benzene, 1,3-bis(3-amino-4-biphenoxybenzyl)benzene, 1,4-bis(3-amino-4-biphenoxybenzyl)benzene, 1, 3-bis(4-amino-5-biphenoxybenzyl)benzene, 1,4-bis(4-amino-5-biphenoxybenzyl)benzene, 2,6- Part or all of the hydrogen atoms on the aromatic ring of bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile and the above-mentioned aromatic diamines have halogen atoms and carbon number 1~3 alkyl group or alkoxy group, cyano group, or alkyl group or alkoxy group, part or all of the hydrogen atoms of the alkyl group or alkoxy group are substituted by halogen atoms, and the aromatic group substituted by a halogenated group or alkoxy group with 1 to 3 carbon atoms Diamine, etc., 4,4'-methylene bis(cyclohexylamine), isophorone diamine, trans-1,4-diaminocyclohexane, cis-1,4-diamino Cyclohexane, 1,4-Cyclohexane bis(methylamine), 2,5-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,6-bis(aminomethyl) )Bicyclo[2,2,1]heptane, 3,8-bis(aminomethyl)tricyclo[5,2,1,0]decane, 1,3-diamine methane, 2,2 -Bis(4-aminocyclohexyl)propane, 2,2-bis(4-aminocyclohexyl)hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1, 5-Pentamethylene diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine, 1,8-octamethylene diamine, 1,9-nonamethylene Aliphatic diamines such as diamines. Other diamine compounds may be used alone, or two or more kinds may be used.

[Photosensitive resin composition] The photosensitive resin composition of the present invention includes (A) the above-mentioned ester diamine-containing polybenzoxazole precursor and (B) a photosensitizer. By using these ester diamine-containing polybenzoxazole precursors in the photosensitive resin composition, the dissolution contrast and internal stress of the dried coating film formed from the photosensitive resin composition can be significantly improved.

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

[(A) Polybenzoxazole precursor containing ester diamine] The photosensitive resin composition of the present invention contains the aforementioned ester diamine-containing polybenzoxazole precursor as the polybenzoxazole precursor, which can significantly improve the dissolution contrast and curing of the formed dry coating film The internal stress of the membrane. Furthermore, the photosensitive resin composition of the present invention can also be used in combination with polybenzoxazole precursors other than the above-mentioned ester diamine-containing polybenzoxazole precursors. The content of the ester diamine-containing polybenzoxazole precursor in the photosensitive resin composition is preferably 50% by mass or more and 99% by mass or less, more preferably 60% by mass or more and 90% by mass in the non-volatile content the following. With this content range, the effect of the present invention can be fully obtained.

[(B) Sensitizer] The photosensitive resin composition of the present invention contains a photosensitizer, and examples thereof include photoacid generators and photobase generators. Among these, from the viewpoint of dissolution contrast, a photoacid generator is preferred. The photosensitizer can be formulated in a conventionally used ratio. For example, for photoacid generators, relative to 100 parts by mass of the polybenzoxazole precursor containing ester diamine, preferably 5-40 parts by mass, more preferably 10~ Blended in a proportion of 30 parts by mass. Moreover, these photosensitizers may contain 2 or more types.

The photoacid generator is a compound that generates acid by irradiation with light such as ultraviolet rays or visible light, and examples thereof include naphthoquinonediazide compounds, diarylsulfonates, triarylsulfonates, diarylphenylsulfonates, Diaryl iodonium salt, aryl diazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonic acid ester, nitrobenzyl ester, aromatic N-oxamidosulfonate, aromatic sulfonamide, benzene Quinone diazosulfonate and so on. Among the above, from the viewpoint of dissolution contrast, a naphthoquinonediazide compound is preferred. Specific examples of the naphthoquinone diazide compound include, for example, the naphthoquinone diazide adduct of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (e.g., manufactured by Sanbao Chemical Research Institute) TS533, TS567, TS583, TS593), naphthoquinone diazide adducts of tetrahydroxybenzophenone (e.g. BS550, BS570, BS599 manufactured by Sanbao Chemical Research Institute), and 4-{4-[1,1 -Bis(4-hydroxyphenyl)ethyl)-α,α-dimethylbenzyl)phenol naphthoquinone diazide adduct (e.g. TKF-428, TKF-528 manufactured by Sambo Chemical Research Institute) Wait.

The photobase generator is a compound that produces more than one basic substance (a secondary amine, a tertiary amine, etc.) by irradiating light such as ultraviolet rays or visible light to change the molecular structure or cracking the molecule. In addition, the photobase generator may be an ionic photobase generator or a nonionic photobase generator, but from the viewpoint of the sensitivity of the photosensitive resin composition, an ionic photobase generator is preferred. As the ionic photobase generator, for example, salts of aromatic-containing carboxylic acids and tertiary amines can be used. Examples of commercially available products are WPBG-082, WPBG-167, WPBG- ionic PBG manufactured by Wako Pure Chemical Industries, Ltd. 168, WPBG-266 and WPBG-300, etc. As the nonionic photobase generator, for example, α-aminoacetophenone compounds, oxime ester compounds, or N-formylated aromatic amine groups, N-acylated aromatic amine groups, and nitrobenzylamine can be used. Compounds of substituents such as carbamic acid ester group and alkoxybenzyl carbamate group. As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N,N'-diethyl carbamate) manufactured by Wako Pure Chemical Industries, Ltd., WPBG-027 (trade name: (E)-1-[3-(2-hydroxyphenyl)-2-propenyl]piperidine), WPBG-140 (trade name: 1-(anthraquinone-2-yl) ethyl imidazole carboxylate ) And WPBG-165 etc.

[Crosslinking agent] The photosensitive resin composition of the present invention may contain a crosslinking agent. By adding a cross-linking agent, even if it is hardened at a low temperature of about 220°C, sufficient characteristics of the hardened product can be obtained. The crosslinking agent is not particularly limited, and can be exemplified by conventionally used crosslinking agents. In this specification, the crosslinking agent is preferably a compound that can react with the phenolic hydroxyl group in the polybenzoxazole precursor to form a crosslinked structure. Here, as the compound that reacts with the phenolic hydroxyl group in the polybenzoxazole precursor, there are exemplified crosslinking agents having cyclic ether groups such as epoxy groups, cyclic thioether groups such as epithio groups, and hydroxymethyl A crosslinking agent with an alcoholic hydroxyl group bonded to an alkylene group with 1 to 12 carbon atoms, a compound having an ether bond such as an alkoxymethyl group, a crosslinking agent with a triazine ring structure, and urea Department of cross-linking agent. Among these, crosslinking agents having cyclic ether groups, especially epoxy groups, and crosslinking agents having alcoholic hydroxyl groups, especially methylol groups to which hydroxyl groups are bonded are preferred. A crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more types. The blending amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.1-30 parts by mass relative to 100 parts by mass of the non-volatile content of the polybenzoxazole precursor. Moreover, it is more preferable that it is 0.1-20 mass parts.

[Crosslinking agent with epoxy group] The photosensitive resin composition of the present invention preferably contains a crosslinking agent having an epoxy group as a crosslinking agent. The crosslinking agent with epoxy group reacts thermally with the hydroxyl group of the polybenzoxazole precursor to form a crosslinked structure. The number of functional groups of the epoxy-containing crosslinking agent is preferably 2 to 4. By making the photosensitive resin composition contain a crosslinking agent having an epoxy group, low-temperature curability can be obtained, and the dissolution contrast of the formed dry coating film can be improved. Among the crosslinking agents having an epoxy group, a bifunctional or more epoxy compound having a naphthalene skeleton is preferable. Not only can an insulating film with better flexibility and chemical resistance be obtained, but also a low CTE, which is antithetical to flexibility, can be used to prevent warping or cracking of the insulating film. Furthermore, from the viewpoint of flexibility, a bisphenol A epoxy compound can also be preferably used.

(通式(7)中，R^A1 表示2~10價有機基，R^A2 分別獨立表示氫原子或碳數1~4之烷基，r表示2~10之整數)。(Crosslinking agent having methylol group) The photosensitive resin composition of the present invention preferably contains a crosslinking agent having methylol group as a crosslinking agent. The crosslinking agent having a hydroxymethyl group preferably has two or more hydroxymethyl groups, and more preferably a compound represented by the following general formula (7).

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

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

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

In the above general formula (7), r is preferably an integer of 2 to 4, more preferably 2.

In addition, the crosslinking agent having a phenolic hydroxyl group preferably has a fluorine atom, and more preferably has a trifluoromethyl group. The fluorine atom or the trifluoromethyl group preferred system of the above formula (7) of the R ^A1 2 to 10 having the monovalent organic group, R ^A1 is preferably bis (trifluoromethyl) methylene group. In addition, the crosslinking agent having a phenolic hydroxyl group preferably has a bisphenol structure, and more preferably has a bisphenol AF structure.

[Plasticizer] The photosensitive resin composition of the present invention preferably contains a plasticizer. In the present invention, it is believed that the plasticizing effect of the plasticizer is to reduce the aggregation between polymer molecular chains, improve the mobility and flexibility between molecular chains, and increase the thermal molecular motion of the polybenzoxazole precursor. , To promote the cyclization reaction, and can impart low-temperature hardenability. The plasticizer is not particularly limited as long as it is a compound capable of improving plasticity, and examples include bifunctional (meth)acrylic compounds, sulfonamide compounds, phthalate compounds, maleate compounds, and aliphatic compounds. Dibasic acid esters, phosphate esters, crown ethers and other ether compounds. Among them, bifunctional (meth)acrylic compounds are preferred. The bifunctional (meth)acrylic compound is preferably a compound that does not form a crosslinked structure with other components in the composition. In addition, from the viewpoint that the internal stress of the cured product is more relaxed, the bifunctional (meth)acrylic compound is preferably a compound that forms a linear structure by self-polymerization. The compounding amount of the plasticizer in the photosensitive resin composition of the present invention is preferably 3 to 40 parts by mass relative to 100 parts by mass of the nonvolatile content of the polybenzoxazole precursor.

Among the bifunctional (meth)acrylic compounds, the di(meth)acrylate of the alkylene oxide adduct of the glycol (such as ethylene oxide or propylene oxide) or the bifunctional polyester (meth) Base) acrylate, more preferably a bifunctional polyester (meth)acrylate.

The di(meth)acrylate as the alkylene oxide adduct of the diol is specifically preferably one in which a (meth)acrylate is added to the terminal after modifying the diol with alkylene oxide, more preferably Those who have an aromatic ring in the diol. Examples include bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, and the like. The specific structure of the di(meth)acrylate of the alkylene oxide adduct of diol is shown by the following general formula (8), but it is not limited to this.

In the general formula (8), p+q is 2 or more, preferably 2-40, more preferably 3.5-25.

(Thermal acid generator, sensitizer, adhesion agent, other ingredients) In the photosensitive resin composition of the present invention, the conventional thermal acid generator used to promote the cyclization reaction of the polybenzoxazole precursor can also be formulated to increase the light Conventional sensitizers for sensitivity, or conventional adhesives such as silane coupling agents to improve adhesion to the substrate. Furthermore, in order to impart processing characteristics or various functional properties to the photosensitive resin composition of the present invention, various other organic or inorganic low molecular or high molecular compounds may be formulated. For example, surfactants, leveling agents, fine particles, etc. can be used. The microparticles include organic microparticles such as polystyrene and polytetrafluoroethylene, and inorganic microparticles such as silica, carbon, and layered silicate. In addition, various coloring agents, fibers, etc. may be blended in the photosensitive resin composition of the present invention.

[Solvent] The photosensitive resin composition of this invention may contain a solvent. The solvent is not particularly limited as long as it can dissolve the above-mentioned components. For example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene Dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl -2-pyrrolidone, dimethyl sulfoxide, hexamethylsulfonamide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether, etc.

The solvent content of the photosensitive resin composition is not particularly limited, and it is preferable to change it appropriately according to its use, but for example, relative to 100 mass of the ester diamine-containing polybenzoxazole precursor contained in the photosensitive resin composition Parts can be from 50 parts by mass to 9000 parts by mass. In addition, the photosensitive resin composition may contain two or more kinds of solvents.

[Dry film] The dry film of the present invention includes a film (for example, a support (carrier) film) and a resin layer formed on the film using the photosensitive resin composition. Furthermore, the dry film may be provided with a protective (covering) film (so-called protective film) on the resin layer formed on the film.

(membrane) The film is not particularly limited, and polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyimide films, polypropylene films, and polyimide films can be used. Films made of thermoplastic resins such as vinyl films. Among these, from the viewpoints of heat resistance, mechanical strength, and handling properties, polyethylene terephthalate is preferred. In addition, a laminate of these films can also be used as a film.

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

The thickness of the film is not particularly limited, but may be, for example, 10 to 150 μm.

(Resin layer) The resin layer is formed using the above-mentioned photosensitive resin composition, and its thickness is not particularly limited, and is preferably changed appropriately according to the application, but it may be, for example, 1 μm or more and 150 μm or less.

The resin layer is made of chipped wheel coater, plate coater, lip die coater, bar coater, blade coater, reverse roll coater, rotary die coater, gravure coater And the spray coater coats the photosensitive resin composition with a uniform thickness on the film, and then it is dried to form. In other embodiments, the resin layer can be formed by coating and drying the photosensitive resin composition on the protective film.

(Protective film) In the present invention, for the purpose of preventing dust from adhering to the surface of the resin layer, etc., it is preferable to laminate a peelable protective film on 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 is lower than the adhesive force between the resin layer and the film when the protective film is peeled off. For example, polyethylene film and polytetrafluoroethylene film can be used. , Polypropylene film and surface-treated paper, etc.

The thickness of the protective film is not particularly limited, but may be, for example, 10 μm or more and 150 μm or less.

[Hardened material] The cured product of the present invention is characterized by being formed using the above-mentioned photosensitive resin composition. In addition, the cured product may be patterned (hereinafter referred to as patterned film as appropriate). Hereinafter, the method of manufacturing the cured product of the present invention will be explained.

[Step 1] The method for producing a cured product of the present invention includes coating a photosensitive resin composition on a substrate to form a coating film, and drying it, or transferring a resin layer from the dry film to the substrate to form a dried Steps of coating.

The method of applying the photosensitive resin composition to the substrate is not particularly limited, and examples include spin coaters, bar coaters, blade coaters, curtain coaters, and screen printing. Machine coating method, spray coating method with spray coater, and inkjet method.

As the drying method of the coating film, air drying, heating drying by an oven or hot plate, vacuum drying, etc. are used. In addition, drying of the coating film is desirably performed under conditions that do not cause ring closure of the polyimide precursor in the photosensitive resin composition. Specifically, natural drying, air blowing drying or heat drying can be carried out at 70~140°C for 1~30 minutes. In addition, since the operation method is simple, it is preferable to use a hot plate for drying for 1 to 20 minutes. In addition, vacuum drying is also possible. In this case, it can be carried out at room temperature for 20 minutes to 1 hour.

The transfer of the dry film to the substrate is preferably carried out under pressure and heating using a vacuum laminator or the like. By using these vacuum laminators, when using a circuit-forming substrate, even if the surface of the circuit substrate has irregularities, the resin layer of the dry film can be filled in the irregularities of the circuit substrate under vacuum, so no bubbles will be mixed in It can also improve the hole-filling properties of the recesses on the substrate surface.

As a substrate, for example, a printed wiring board or a flexible printed wiring board in which a circuit is formed with copper, etc., can be used. Paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/ Non-woven epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin. Polyethylene. Polyphenylene oxide, polyphenylene oxide. Cyanate ester and other high-frequency circuits with copper-clad laminates and other materials, copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide films, and polyethylene terephthalate Film, polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer board, etc.

[Step 2] Secondly, the above-mentioned coating film is exposed by selectively irradiating active energy rays through a patterned photomask, or not through the photomask instead of selectively irradiating it.

The active energy rays use, for example, those with a wavelength that can activate the photoacid generator as the (B) photosensitizer. Specifically, the active energy rays are preferably those whose maximum wavelength falls within the range of 350 to 410 nm. The amount of exposure varies with the thickness of the film, but generally can be 10~1000mJ/cm ² , preferably in the range of 20~800mJ/cm ² . As the exposure machine used for the above-mentioned active energy ray irradiation, if it is equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, mercury arc lamp, etc., the device irradiates ultraviolet rays in the range of 350 to 450 nm, and direct drawing can also be used. Device (for example, a direct laser imaging device that directly draws an image with a laser using CAD data from a computer).

[Step 3] This step is carried out as needed. By heating the coating in a short time, a part of the polyimide precursor in the unexposed part can be partially closed. Here, the closed loop rate is about 30%. The heating time and heating temperature are appropriately changed according to the type of polyimide precursor, the thickness of the coating film, and the type of (B) photosensitive agent.

[Step 4] Secondly, the above-mentioned exposed coating film is treated with a developer solution to remove the exposed part of the coating film, thereby obtaining a patterned film. In this step, any method can be selected from the conventionally known photoresist development methods, such as rotary spray method, liquid coating method, dipping method accompanied by ultrasonic treatment, etc.

Examples of developing solutions include inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and tetramethylammonium hydroxide. , Aqueous solutions of quaternary ammonium salts such as tetrabutylammonium hydroxide. Furthermore, if necessary, water-soluble organic solvents or surfactants such as methanol, ethanol, isopropanol, etc. may be added in appropriate amounts.

Subsequently, as needed, the coating film is washed with a cleaning solution to obtain a patterned film. As the cleaning liquid, distilled water, methanol, ethanol, isopropanol, etc. can be used alone or in combination. In addition, the above-mentioned solvents can also be used as a developing solution.

[Step 5] Next, the patterned film is heated to obtain a cured coating film (cured product). Through this heating step, the polybenzoxazole precursor contained in the photosensitive resin composition undergoes a cyclization reaction to become polybenzoxazole.

The heating conditions are preferably adjusted appropriately, for example, it can be set at a temperature above 150°C but less than 350°C for about 5 minutes to 120 minutes. For heating, for example, a hot plate, an oven, and a temperature-rising oven with a temperature schedule can be set. The heating environment (gas) can be under air or under inert gas such as nitrogen and argon.

[use] The use of the photosensitive resin composition of the present invention is not particularly limited, and it can be suitably used as, for example, coatings, printing inks, adhesives, display devices, semiconductor elements, electronic parts, optical parts, and building materials.

Specifically, as a forming material of a display device, it is used as a layer forming material and an image forming material in color filters, flexible display films, photoresist materials, alignment films, and the like. Examples of materials for forming semiconductor elements include photoresist materials, buffer coating films, insulating films for rewiring layers of wafer level packaging (WLP), and other layer forming materials. Examples of materials for forming electronic parts include sealing materials and layer forming materials in printed wiring boards, interlayer insulating films, and wiring coating films. In addition, examples of materials for forming optical parts include optical materials or layer forming materials in holograms, optical waveguides, optical circuits, optical circuit parts, and anti-reflection films. Furthermore, as a building material, it can be used for paint, coating agent, etc.

The photosensitive resin composition of the present invention is mainly used as a pattern forming material, and can be particularly used as a surface protection film, buffer coating film, interlayer insulating film, and rewiring insulation for semiconductor devices, display devices, and light-emitting devices. Films, protective films for flip-chip devices, protective films for devices with bump structures, interlayer insulating films for multilayer circuits, insulating materials for passive components, protective films for printed wiring boards such as solder resist or overlaminate films, and liquid crystal alignment Film etc. [Example]

Hereinafter, the present invention will be explained in more detail using examples, but the present invention is not limited to the examples. In addition, the following "parts" and "%" are quality standards unless otherwise specified.

(Reference Example 1: Synthesis of polybenzoxazole precursor A-1) In a 0.5 liter flask equipped with a stirrer and a thermometer, the (2-phenyl-4-amino group) represented by the following chemical formula (a) Phenyl)-4-aminobenzoate (PHBPAA) 0.489g (1.61mmol) and bis(3-amino-4-hydroxyphenyl)hexafluoropropane represented by the following chemical formula (b) 28.02g ( 76.5 mmol) and dissolved in 215 g of N-methylpyrrolidone with stirring. Subsequently, the flask was immersed in an ice bath, while keeping the inside of the flask at 0~5°C, 25.29g (85.7mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride represented by the following chemical formula (c) The solid was added directly over 10 minutes, and stirred in an ice bath for 30 minutes.

Subsequently, stirring was continued for 18 hours at room temperature. The stirred solution is poured into 1 liter of ion-exchange water (specific resistance 18.2MΩ･cm), and the precipitate is recovered. Subsequently, the obtained solid was dissolved in 420 mL of acetone and poured into 1 liter of ion exchange water. After recovering the precipitated solid, it was dried under reduced pressure to obtain an ester diamine-containing polybenzoxazole precursor at the carboxyl end shown in the following chemical formula. The weight average molecular weight calculated by GPC method standard polystyrene conversion was 31,000. In addition, the ester diamine content in the polybenzoxazole precursor containing ester diamine is 2 mol%.

(Reference example 2: Synthesis of polybenzoxazole precursor A-2) In a 0.5 liter flask equipped with a stirrer and a thermometer, add 0.474 g (1.56 mmol) of PHBPAA and 10.88 g (29.7 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane to N-methylpyrrole. Stir and dissolve in 85 g of pyridone. Then the flask was immersed in an ice bath, while keeping the inside of the flask at 0~5°C, 10.09g (34.2mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was directly added as a solid for 10 minutes. Stir for 30 minutes in an ice bath. Subsequently, stirring was continued for 18 hours at room temperature. The stirred solution was poured into 700 mL of ion exchange water (specific resistance 18.2MΩ･cm), and the precipitate was recovered. Subsequently, the obtained solid was dissolved in 420 mL of acetone and poured into 1 liter of ion exchange water. After recovering the precipitated solid, it is dried under reduced pressure to obtain a polybenzoxazole precursor containing ester diamine at the carboxyl end. The weight average molecular weight calculated by GPC method standard polystyrene conversion is 26,900. In addition, the ester diamine content in the polybenzoxazole precursor containing ester diamine is 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 was immersed in an ice bath, while keeping the inside of the flask at 0~5°C, 8.78g (29.8mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was added directly as a solid for 10 minutes. Stir for 30 minutes in an ice bath. Subsequently, stirring was continued for 18 hours at room temperature. The stirred solution was poured into 700 mL of ion exchange water (specific resistance 18.2MΩ･cm), and the precipitate was recovered. Subsequently, the obtained solid was dissolved in 420 mL of acetone and poured into 1 liter of ion exchange water. After recovering the precipitated solid, it is dried under reduced pressure to obtain a polybenzoxazole precursor containing ester diamine at the carboxyl end. The weight average molecular weight calculated by GPC standard polystyrene conversion is 29,500, the number average molecular weight is 11,600, and the PDI is 2.54.

<Example 1-1> The polybenzoxazole precursor A-1 (100 parts by mass) and the diazonaphthoquinone compound A (10 parts by mass, manufactured by Sanbao Chemical Industry Co., Ltd., TKF-428, photosensitizer) obtained in Reference Example 1 above were dissolved After γ-butyrolactone (300 parts by mass), it was filtered with a 0.2 μm filter to obtain varnish A-1 of the photosensitive resin composition.

<Example 1-2> Except that the polybenzoxazole precursor A-1 was changed to the polybenzoxazole precursor A-2, the varnish A-2 of the photosensitive resin composition was obtained in the same manner as in Example 1-1.

<Comparative Example 1-1> Except that the polybenzoxazole precursor A-1 was changed to the polybenzoxazole precursor A-3, the varnish A-3 of the photosensitive resin composition was obtained in the same manner as in Example 1-1.

＜＜Evaluation of elongation＞＞ The varnishes A-1, A-2 and A-3 obtained in the above Examples 1-1~1-2 and Comparative Example 1-1 were coated on a 6-inch silicon wafer using a spin coater to heat The board was dried at 110°C for 3 minutes to obtain a coating film with a thickness of about 30 μm. Next, use an oven to heat the silicon wafer with the coating film at 150℃/30min and 320℃/60min. The obtained cured film was peeled from the silicon wafer, and the elongation was measured by a tensile test using EZ-SX manufactured by Shimadzu Corporation. The evaluation was performed based on the following evaluation criteria. The evaluation results are summarized in Table 1. (Evaluation criteria) ◎: The elongation is 15% or more. ○: The elongation is 10% or more and less than 15%. ×: The elongation rate is less than 10%.

＜＜Glass transition temperature evaluation＞＞ The cured film obtained in the evaluation of elongation was evaluated based on the following evaluation criteria by measuring the glass transition temperature (Tg) by TMA (thermomechanical analysis). The evaluation results are summarized in Table 1. (Evaluation criteria) ◎: The glass transition temperature is 300°C or higher. ○: The glass transition temperature is 250°C or higher and less than 300°C. ×: The glass transition temperature did not reach 250°C.

(評價基準) ◎：內部應力未達25MPa。 〇：內部應力25MPa以上且未達30MPa。 ×：內部應力為30MPa以上。＜＜Evaluation of internal stress＞＞ The varnishes A-1, A-2 and A-3 obtained in the above Examples 1-1~1-2 and Comparative Example 1-1 were applied to 6 inches using a spin coater. The silicon wafer was dried on a hot plate at 110°C for 3 minutes to obtain a coating film with a thickness of about 6μm. Next, use an oven to heat the silicon wafer with the coating film at 150℃/30min and 320℃/60min. The radius of curvature obtained from the change in the amount of warpage of the silicon wafer before and after the cured film was formed was measured using the formula (1) and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.

(Evaluation Criteria) ⊚: The internal stress is less than 25 MPa. ○: The internal stress is 25 MPa or more and less than 30 MPa. ×: The internal stress is 30 MPa or more.

(評價基準) ◎：對比度為100以上。 〇：對比度為20以上且未達100。 ×：溶解速度比未達20。＜＜Evaluation of dissolution contrast＞＞ The varnishes A-1, A-2 and A-3 obtained in the above Examples 1-1 to 1-2 and Comparative Example 1-1 were applied to 6-inch silicon using a spin coater The wafer was dried on a hot plate at 110°C for 3 minutes to obtain a coating film with a thickness of about 8μm. The obtained coating film was subjected to i-line exposure through a mask, and an exposed part and an unexposed part were made in the same substrate. After exposure, it was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 120 seconds, and washed with water to obtain a pattern of a positive cured film. The development speed of the exposed part and the development speed of the unexposed part until the film thickness of the exposed part became 0 were calculated|required, the contrast was calculated by the following formula, and the following criteria were used for evaluation. The evaluation results are summarized in Table 1.

(Evaluation Criteria) ⊚: The contrast is 100 or more. ○: The contrast is 20 or more and less than 100. ×: The dissolution rate ratio is less than 20.

＜＜Sensitivity evaluation＞＞ The varnishes A-1, A-2 and A-3 obtained in the above Examples 1-1 to 1-2 and Comparative Example 1-1 were coated on the silicon wafer using a spin coater , Heat and dry on a hot plate at 110°C for 3 minutes to obtain a coating film with a thickness of about 8μm. For the obtained coating film, a high-pressure mercury lamp (with an i-line filter) was used to irradiate wide-area light through a photomask with a pattern. In addition, the amount of exposure is gradually increased at 50 mJ/cm ² , and after the mask passes through, the exposure is performed in the range of 100 to 1000 mJ/cm ² . The dried coating film after exposure is developed with 2.38% TMAH aqueous solution and washed with water to form a positive pattern film. The exposure amount at which the exposed part was not eluted at all was regarded as the minimum exposure amount, and the evaluation was performed based on the following evaluation criteria. The evaluation results are summarized in Table 1. (Evaluation Criteria) ⊚: The minimum exposure amount did not reach 400 mJ/cm ² . ○: The minimum exposure is 400 mJ/cm ² or more and less than 700 mJ/cm ² . ×: The minimum exposure amount is 700 mJ/cm ² or more.

As understood from the evaluation results shown in Table 1 above, in the examples, it was confirmed that it has high glass transition temperature, elongation, dissolution contrast, and sensitivity, and low internal stress.

<Example 2-1> The polybenzoxazole precursor A-1 (100 parts by mass) and the naphthoquinone diazide compound A (10 parts by mass, manufactured by Sanbao Chemical Industry Co., Ltd., TKF-428, photosensitizer) obtained in the above Reference Example 1 And a bifunctional (meth)acrylic compound (10 parts by mass, manufactured by Toagosei Co., Ltd., M-6250, plasticizer) was dissolved in γ-butyrolactone (300 parts by mass) and filtered with a 0.2μm filter to obtain photosensitivity Varnish B-1 of resin composition.

<Example 2-2> The polybenzoxazole precursor A-1 (100 parts by mass) and the naphthoquinone diazide compound A (10 parts by mass, manufactured by Sanbao Chemical Industry Co., Ltd., TKF-428, photosensitizer) obtained in the above Reference Example 1 And a bifunctional or higher epoxy compound (10 parts by mass, manufactured by DIC, HP-4032D, crosslinking agent) was dissolved in γ-butyrolactone (300 parts by mass), and filtered with a 0.2μm filter to obtain a photosensitive resin Composition varnish C-1.

<Example 2-3> The polybenzoxazole precursor A-1 (100 parts by mass) and the diazonaphthoquinone compound A (10 parts by mass, manufactured by Sambo Chemical Industry Co., Ltd.) obtained in the above Reference Example 1 TKF-428, sensitizer) and TM-BIP-A (10 parts by mass, crosslinking agent) represented by the following chemical formula (d) are dissolved in γ-butyrolactone (300 parts by mass), and then filtered with 0.2μm Filter to obtain varnish D-1 of the photosensitive resin composition.

＜＜Glass transition temperature evaluation＞＞ Except that the varnish was changed to the varnishes B-1, C-1 and D-1 obtained in Examples 2-1~2-3, and the heating of the silicon wafer with the coating film by the oven was changed to 150℃/30min Except for 220°C/60min, the glass transition temperature was measured by the same method as above, and the evaluation was performed based on the same evaluation criteria. The evaluation results are summarized in Table 2.

＜＜Evaluation of internal stress＞＞ Except that the varnish was changed to the varnishes B-1, C-1 and D-1 obtained in Examples 2-1~2-3, and the heating of the silicon wafer with the coating film by the oven was changed to 150℃/30min Except for 220°C/60min, the internal stress is measured by the same method as above, and the evaluation is based on the same evaluation criteria. The evaluation results are summarized in Table 2.

＜＜Evaluation of dissolution contrast＞＞ Except that the varnish was changed to the varnishes B-1, C-1, and D-1 obtained in Examples 2-1 to 2-3, the contrast was determined by the same method as described above, and the evaluation was performed based on the same evaluation criteria. The evaluation results are summarized in Table 2.

＜＜Sensitivity evaluation＞＞ Except that the varnish was changed to the varnishes B-1, C-1, and D-1 obtained in Examples 2-1 to 2-3, the sensitivity was determined by the same method as described above and evaluated based on the same evaluation criteria. The evaluation results are summarized in Table 2.

As understood from the evaluation results shown in Table 2 above, in each example, it was confirmed that the glass transition temperature and the dissolution contrast were high even at low temperature, and the internal stress was low.

Claims (10)

A polybenzoxazole precursor containing ester diamine, characterized in that it has at least one of the structures shown in the following general formulas (1) and (2) and the structure shown in the following general formula (3) ,

(In general formulas (1) and (2), X is a divalent organic group, and any one of R ₁ to R ₄ is selected from an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, Aromatic groups with 6 to 10 carbons, phenoxy with 6 to 10 carbons, benzyl with 6 to 10 carbons, and benzyloxy with 6 to 10 carbons. The other R ₁ to R ₄ are hydrogen atoms , N represents an integer of 1 or more, in the general formula (3), X is a divalent organic group, Y is a tetravalent organic group having at least 2 or more hydroxyl groups, and o represents an integer of 1 or more). For example, the polybenzoxazole precursor containing ester diamine of claim 1, wherein any one of R ₁ or R ₃ is selected from an aromatic group with 6 to 10 carbons, and a phenoxy with 6 to 10 carbons Group, benzyl group with 6 to 10 carbons, and benzyloxy group with 6 to 10 carbons, the other is a hydrogen atom, and R ₂ and R ₄ are hydrogen atoms. Such as the polybenzoxazole precursor containing ester diamine of claim 1 or 2, wherein, in the general formula (3), Y is an aromatic group. Such as the ester diamine-containing polybenzoxazole precursor of any one of claims 1 to 3, wherein, in the general formula (3), Y is a group selected from 1 or more of the following structures,

(In the above structural formula, any one of * ₁ and * ₂ represents a connecting portion with an amino group, and the other represents a hydroxyl group). The polybenzoxazole precursor containing ester diamine according to any one of claims 1 to 4, wherein the content (ester diamine content) of the structure represented by the aforementioned general formulas (1) and (2) is 0.1 mol% or more and 10 mol% or less. A photosensitive resin composition comprising the ester diamine-containing polybenzoxazole precursor according to any one of claims 1 to 5 and a photosensitive agent. The photosensitive resin composition of claim 6, wherein the photosensitizer is a naphthoquinone diazide (naphthoquinone diazide) compound. A dry film characterized by having a resin layer formed of the photosensitive resin composition of claim 6 or 7 on the film. A hardened product characterized by being formed of the photosensitive resin composition of Claim 6 or 7 or the resin layer of the dry film of Claim 8. An electronic component characterized by having a hardened product as in Claim 9 as a forming material.