KR102276251B1 - Resin composition containing polyimide precursor and method for manufacturing cured film using said resin composition - Google Patents

Abstract

The present invention generates radicals by (a) a polyimide precursor having a structural unit represented by the following general formula (1), (b) a compound represented by the following general formula (2), and (c) actinic light irradiation It is an electronic component which has the resin composition containing the compound which says, the cured film or pattern cured film formed from it, the manufacturing method of the hard film using the same, and the said cured film or pattern cured film. (In formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent carbon carbon unsaturated double bond. It is an organic group.) (In formula (2), R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is a monovalent organic group not containing a (meth)acryl group.)

Description

The resin composition containing a polyimide precursor, and the manufacturing method of the cured film using it TECHNICAL FIELD

The present invention relates to a resin composition containing a polyimide precursor suitable as a material such as a protective film such as a surface coating film of a semiconductor element, an interlayer insulating film of a thin film multilayer wiring board, and an insulating film, a method for producing a cured film using the same, and an electronic component.

In recent years, an organic material having high heat resistance, such as a polyimide resin, has been widely applied as a material for a protective film of a semiconductor integrated circuit. The protective film (cured film) using such a polyimide resin can be obtained by heating and hardening the resin film formed by apply|coating and drying a polyimide precursor or the resin composition containing a polyimide precursor on a board|substrate.

If the polyimide resin is photosensitive, it is possible to easily form a patterned resin film (patterned resin film). By heating and hardening such a pattern resin film, a pattern cured film (pattern-formed cured film) can be formed easily.

Conventionally, as a polyimide precursor, an aromatic tetracarboxylic dianhydride is reacted with an olefinically unsaturated alcohol to synthesize an olefin aromatic tetracarboxylic acid diester, and this compound and a diamine are polymerized by a dehydration condensation reaction using carbodiimides to form a covalent bond. A polyimide precursor to which a photosensitive group is introduced is known (for example, refer to Patent Document 1).

Moreover, the polyimide precursor which couple|bonded the isocyanate compound which has a photosensitive group to the polyamic acid obtained by making aromatic tetracarboxylic dianhydride react with aromatic diamine is also known (for example, refer patent document 2).

These polyimide precursors are applied to a substrate in a varnish state dissolved in an organic solvent, dried to form a film, and then used as a negative photosensitive resin composition for photocuring the exposed portion by irradiating ultraviolet rays through a photomask. A relief pattern can be obtained by developing and rinsing unexposed areas other than the exposed areas using an organic solvent.

By the way, in the negative photosensitive resin composition containing the said polyimide precursor, a bifunctional di(meth)acrylate compound has been widely used conventionally as a crosslinking agent at the time of photocuring an exposed part (for example, patent document) 2-5).

Cured films using polyimide resins increase in thickness after curing and increase in modulus of elasticity by increasing the thickness and modulus of elasticity, resulting in increased warpage of semiconductor wafers, which may cause problems during transport or wafer fixation. Development of a cured film with low stress is being desired

As a method of making a polyimide resin low stress, the method of using the polyamide which co-condensed the phthalic acid compound which has a specific functional group to a tetracarboxylic acid compound (for example, patent document 6) is mentioned, for example.

In addition, with respect to the heat curing temperature of the polyimide precursor, the demand for low-temperature curing is increasing. Conventionally, heat curing of the polyimide precursor was performed at a high temperature of about 370° C., but heat curing of 300° C. or less is required. (For example, Patent Document 7).

Patent Document 1: Japanese Patent Laid-Open No. 60-233646 Patent Document 2: Japanese Patent Laid-Open No. 9-188762 Patent Document 3: Japanese Patent Laid-Open No. 6-342211 Patent Document 4: Japanese Patent Laid-Open No. 10-95848 Patent Document 5: Japanese Patent Laid-Open No. 8-286374 Patent Document 6: International Publication No. 2006/008991 Patent Document 7: International Publication No. 2009/060380

Summary of invention

In this technical field, unless it is a (meth)acrylate compound more than bifunctional, crosslinking reaction between polymer chains does not progress, and it has been thought that it does not become insoluble with respect to the organic solvent used as a developing solution.

By the way, as a result of examination of the present inventors, also when using a monofunctional (meth)acrylate compound, it discovered that the photosensitive resin composition and cured film which have the photosensitive characteristic equivalent to the case of using the (meth)acrylate compound more than bifunctional can be obtained. .

The objective of this invention is providing a novel polyimide precursor containing resin composition, and the manufacturing method of a cured film using the same.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the following resin composition, the cured film using the same, etc. are provided.

1. The resin composition containing following (a), (b) and (c) component.

(a) a polyimide precursor having a structural unit represented by the following general formula (1)

(b) a compound represented by the following general formula (2)

(c) a compound that generates radicals by irradiation with actinic light

(Wherein, R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent organic group having a carbon carbon unsaturated double bond. .)

(Wherein, R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is a monovalent organic group not containing a (meth)acryl group.)

2. The resin composition of 1 in which said (b) component contains 1-100 mass parts with respect to 100 mass parts of (a) component.

^{3. The resin composition as described in 1 or 2 whose R<6>} in said Formula (2) is a monovalent organic group which does not contain a (meth)acryl group, a hydroxyl group, and an amino group.

4. The resin composition in any one of 1-3 whose said (b) component is a monofunctional photopolymerizable compound whose molecular weight is 300 or less.

5. The resin composition according to any one of 1 to 4, wherein at least one ^{of R 3} and R ⁴ in the formula (1) is a monovalent organic group having a carbon-carbon unsaturated double bond.

^{6. The resin composition according to any one of 1 to 5, wherein R 1} in the formula (1) is any one of tetravalent organic groups represented by the following general formulas (2a) to (2e).

(In formula (2d), X and Y each independently represent a divalent group or single bond not conjugated to the benzene ring to which each is bonded. In formula (2e), Z is an ether bond (-O-) or It is a sulfide bond (-S-).)

^{7. The resin composition according to any one of 1 to 6, wherein R 2} in the formula (1) is a divalent organic group represented by the following general formula (5) or (6).

(Wherein, R ¹⁰ to R ¹⁷ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and ^{at least one of R 10} to R ¹⁷ is a halogen atom or a halogenated alkyl group. R ¹⁸ and R ¹⁹ are each independently is a halogen atom or a halogenated alkyl group.)

8. The resin composition in any one of 1-7 whose said (c)component is an oxime ester compound.

9. Cured film formed from the resin composition in any one of 1-8.

10. The manufacturing method of a cured film including the process of apply|coating the resin composition in any one of 1-8 on a board|substrate, drying, and forming a coating film, and the process of heat-processing a coating film.

11. A pattern cured film formed from the resin composition in any one of 1-8.

12. A step of applying the resin composition according to any one of 1 to 8 on a substrate and drying it to form a coating film, a step of irradiating the coating film with actinic light, followed by development to obtain a pattern resin film, and heat treatment of the pattern resin film The manufacturing method of the pattern cured film including the process of doing.

13. The electronic component which has the cured film of 9 or the pattern cured film of 11.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a novel polyimide precursor containing resin composition and a cured film using the same can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of one Embodiment of the semiconductor device using the resin composition of this invention.
Fig.2 (a) is a gas chromatogram at the time of performing thermal decomposition gas chromatography mass spectrometry about the cured film obtained in Example 10. (b) is a gas chromatogram at the time of performing thermal decomposition gas chromatography mass spectrometry about the cured film obtained by the comparative example 2.
Fig.3 (a) is the figure which measured the outgas from the cured film of the comparative example 2 using heat generation gas mass spectrometry. (b) is the figure which measured the outgas from the cured film of Example 1 using heat generation gas mass spectrometry.

EMBODIMENT OF THE INVENTION Below, embodiment of the resin composition which concerns on this invention, the cured film using the resin composition, the manufacturing method of a cured film, etc. and an electronic component are demonstrated in detail. In addition, in this invention, a methacrylate and an acrylate are collectively called (meth)acrylate. In addition, a methacryl group and an acryl group are collectively called a (meth)acryl group similarly. A methacryloxy group and an acryloxy group are also called a (meth)acryloxy group. In addition, the numerical range shown using "-" represents a range including the numerical value described before and after "-" as a minimum value and a maximum value, respectively.

<Resin composition>

The resin composition of this invention contains following (a), (b), and (c) component.

(a) a polyimide precursor having a structural unit represented by the following general formula (1)

(b) a compound represented by the following general formula (2)

(c) a compound that generates radicals by irradiation with actinic light

(Wherein, R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent organic group having a carbon carbon unsaturated double bond. .)

(In the formula, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is a monovalent organic group not containing a (meth)acryl group.)

(b) component of the resin composition of this invention is a crosslinking agent. In this invention, a pattern cured film can be obtained by setting it as the said structure, without using a polyfunctional (meth)acrylate compound. Thereby, the outgas which generate|occur|produces at the time of hardening reaction can be suppressed.

In addition to the above, when the heat curing temperature is 300 ° C. or less, the outgas from the polyimide film increases in the vacuum process such as the etching of the electrode part after the polyimide cured film formation process. There is a problem in that the chamber is contaminated by the occurrence. (b) If the component is a monofunctional photopolymerizable compound having a molecular weight of 300 or less, represented by the formula (2), even a cured film cured at a low temperature of 300 ° C. or less can suppress outgas generated when exposed to a vacuum process and a cured film with low stress can be obtained.

(a) Component: Polyimide precursor which has a structural unit represented by General formula (1)

The resin composition of this invention contains the polyimide precursor which has a structural unit represented by (a) following General formula (1).

(Wherein, R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent organic group having a carbon carbon unsaturated double bond. .)

Although the resin composition of the present invention can exhibit high i-ray transmittance, specifically, in a film thickness of 20 µm, i-line transmittance is preferably 1% or more, more preferably 10% or more, and 15% or more. more preferably. When it is lower than 1%, the i-line does not reach the deep part, and radicals are not sufficiently generated. Therefore, there is a possibility that the photosensitive characteristics may be deteriorated, such as the resin protruding from the substrate side of the film during development.

In addition, the i-ray transmittance can be measured by measuring the transmitted UV spectrum using a U-3310 spctrophotometer (manufactured by Hitachi Seisakusho Co., Ltd.).

^R<1> in General formula (1) is a structure derived from the tetracarboxylic dianhydride used as a raw material, for example. The tetracarboxylic dianhydride to be used is not particularly limited, but from the viewpoint of excellent heat resistance for electronic components, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3, 3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3 ,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Carboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis{4 '-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3 ,3,3-hexafluoro-2,2'-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro Aromatics such as -2,2'-bis{4-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic dianhydride, and 4,4'-sulfonyldiphthalic dianhydride The system tetracarboxylic dianhydride is preferred. These can be used individually or in combination of 2 or more types.

As a ^{tetravalent organic group in R<1>} , it is preferable that it is any one of tetravalent organic groups represented by the following general formula (2a) - (2e).

(In the general formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded. In the general formula (2e), Z is an ether bond (-O-) or a sulfide bond (-S-).)

The "divalent group not conjugated with the benzene ring to be bonded" of X and Y in the general formula (2d) is -O-, -S-, or a divalent group represented by the following formula.

(Wherein, R ⁸ is a carbon atom or a silicon atom. R ⁹ is each independently a hydrogen atom or a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

n=3.)

^{In addition, R<2>} in General formula (1) is a structure derived from the diamine used as a raw material, for example.

The diamine used in the present invention is not particularly limited, and for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzizine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone , bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy) Diamine having an aromatic ring such as benzene, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydr Roxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane , bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4- Diamine having a hydroxyl group and an aromatic ring such as amino-3-hydroxyphenyl) hexafluoropropane, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2, 5-diaminoterephthalic acid, bis(4-amino-3-carboxyphenyl)methylene, bis(4-amino-3-carboxyphenyl)ether, 4,4'-diamino-3,3'-dicarboxybiphenyl, and diamines having an aromatic ring and a carboxyl group such as 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl, and these may be used alone or in combination of two or more. also be

As the divalent organic group in R ^2, it is preferred for the divalent organic group represented by the formula (5) or (6).

In the formula, each of R ¹⁰ to R ¹⁷ independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and ^{at least one of R 10} to R ¹⁷ is a halogen atom or a halogenated alkyl group. R ¹⁸ and R ¹⁹ are each independently a halogen atom or a halogenated alkyl group.

Examples of the monovalent organic group of R ¹⁰ to R ¹⁷ include an alkyl group having 1 to 20 carbon atoms (methyl group, etc.), a halogenated alkyl group having 1 to 20 carbon atoms (trifluoromethyl group, etc.), an alkoxy group having an alkyl group having 1 to 20 carbon atoms (methoxy time, etc.).

The halogen atom is preferably a fluorine atom.

The halogenated alkyl group is preferably a perfluoroalkyl group.

It is preferable that carbon number of an alkyl group and a halogenated alkyl group is 1-6.

^{As R 3} and R ⁴ in the general formula (1), for example, each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), 3 carbon atoms A cycloalkyl group or hydrocarbon group having ~20 (preferably 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms) containing a (meth)acryloxy group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) A hydrocarbon group is mentioned. The hydrocarbon group containing a (meth)acryloxy group has a preferable (meth)acryloxy group containing alkyl group.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-decyl group, n-dodecyl group and the like. and examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.

Examples of the hydrocarbon group containing a (meth)acryloxy group having 1 to 10 carbon atoms include acryloxyethyl group, acryloxypropyl group, acryloxybutyl group, methacryloxyethyl group, methacryloxypropyl group, and methacryloxybutyl group. and the like.

In the resin composition of the present invention ^{, at least one of R 3} and R ⁴ has a carbon carbon unsaturated double bond, such as a (meth)acryloxyalkyl group, and in combination with a compound that generates a radical upon irradiation with actinic light, a radical It is preferable to make it possible to crosslink between molecular chains by polymerization.

(a) component can be synthesize|combined by addition polymerization of tetracarboxylic dianhydride and diamine. Moreover, it can synthesize|combine by making tetracarboxylic dianhydride represented by Formula (10) into a diester derivative, converting into the acid chloride represented by Formula (11), and making it react with the diamine represented by Formula (12). Such a synthesis method can be selected from known methods.

(Here, R ¹ to R ⁴ are the same as in Formula (1).)

The tetracarboxylic acid mono(di)ester dichloride represented by the general formula (11) is tetracarboxylic acid dianhydride represented by the general formula (10) and a compound represented by the following general formula (13). It can be obtained by reacting a carboxylic acid mono(di)ester with a chlorinating agent such as thionyl chloride or dichlorooxalic acid.

(R ²² in the formula is an alkyl group, a cycloalkyl group, or a monovalent organic group having a carbon-carbon unsaturated double bond.)

The chlorinating agent is usually carried out by reacting 2 molar equivalents with respect to 1 mole of tetracarboxylic acid mono(di)ester in the presence of a basic compound in an amount of 2 times the amount of the chlorinating agent. In order to control the molecular weight of the synthesized polyimide precursor, You may adjust an equivalent weight appropriately. As an equivalent of a chlorinating agent, 1.5-2.5 molar equivalent is preferable, 1.6-2.4 molar equivalent is more preferable, 1.7-2.3 molar equivalent is still more preferable. When less than 1.5 molar equivalent, since the molecular weight of the polyimide precursor is low, low stress after curing may not be sufficiently expressed. When more than 2.5 molar equivalent, a large amount of hydrochloric acid salt of the basic compound remains in the polyimide precursor. , there is a fear that the electrical insulation of the polyimide after curing may decrease.

As a basic compound, for example, pyridine, 4-dimethylaminopyridine, triethylamine, etc. can be used, It is preferable to use 1.5 to 2.5 times with respect to a chlorinating agent, It is more preferable that it is 1.7 to 2.4 times, It is more preferable, 1.8 It is more preferable that it is ~2.3 times. When it is less than 1.5 times, there exists a possibility that the molecular weight of a polyimide precursor becomes low and the stress after hardening may not fully fall, and when it is more than 2.5 times, there exists a possibility that a polyimide precursor may color.

In addition, you may make tetracarboxylic dianhydride and the compound of General formula (13) react in presence of a basic catalyst. Examples of the basic catalyst include 1,8-diazabicyclo[5.4.0]undeca-7-ene and 1,5-diazabicyclo[4.3.0]nona-5-ene.

Among the compounds represented by the general formula (13), examples of alcohols include alcohols in which R ²² is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.

Examples of the monovalent organic group having a carbon-carbon unsaturated double bond represented by R ²² include a (meth)acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group.

Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, hexanol, cyclohexanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like. These may be used independently and may mix and use 2 or more types.

It is preferable that it is 10000-100000, as for the weight average molecular weight of a polyimide precursor, it is more preferable that it is 15000-100000, It is still more preferable that it is 20000-85000. From the viewpoint of sufficiently reducing the stress after curing, the weight average molecular weight is preferably 10,000 or more. It is preferable that it is 100000 or less from a viewpoint of improving the solubility with respect to a solvent, and preventing the viscosity of a solution from increasing and handling property falling. In addition, a weight average molecular weight can be measured by the gel permeation chromatography method, and can be calculated|required by converting using a standard polystyrene analytical curve.

The molar ratio of tetracarboxylic dianhydride and diamine at the time of synthesizing the polyimide precursor is usually 1.0, but for the purpose of controlling molecular weight and terminal residues, it may be carried out in a molar ratio in the range of 0.7 to 1.3. When molar ratio is 0.7 or less or 1.3 or more, the molecular weight of the polyimide precursor obtained may become small, and there exists a possibility that the low stress property after hardening may not fully be expressed.

It is preferable to carry out the said addition polymerization and condensation reaction, and the synthesis|combination of a diester derivative and an acid chloride in an organic solvent. As the organic solvent to be used, a polar solvent that completely dissolves the polyimide precursor to be synthesized is preferable, and N-methyl-2-pyrrolidone, N,N-dimethylacetoamide, N,N-dimethylformamide, dimethyl sulfoxide side, tetramethyl urea, hexamethyl phosphate triamide, γ-butyrolactone, and the like.

In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can also be used.

(b) Component: The compound represented by General formula (2)

The resin composition of this invention contains the compound represented by the following general formula (2) as (b) component from a viewpoint of negative pattern formation. (b) A component reacts with the unsaturated double bond which (b) components or (a) component has with the radical which generate|occur|produced by actinic light irradiation.

(In the formula, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is a monovalent organic group not containing a (meth)acryl group.)

^{It is preferable that R<6>} in said Formula (2) is a monovalent organic group which does not contain a (meth)acryl group, a hydroxyl group, and an amino group.

Examples ^{of the monovalent organic group not containing a (meth)acryl group for R 6} include a group having a piperidine skeleton, a substituted or unsubstituted aminoalkyl group, a group having a polycyclic hydrocarbon group, a group having an aromatic hydrocarbon group, and a nitrogen-containing heterocycle. and a group having a tableware, a linear or branched alkyl polyethylene glycol residue, a cyclic alkyl polyethylene glycol residue, and a substituted or unsubstituted phenyl polyethylene glycol residue.

Although it can use especially without limitation as a compound represented by General formula (2), For example, piperidin-4-yl (meth)acrylate, 1-methylpiperidin-4-yl (meth)acrylate , 2,2,6,6-tetramethylpiperidin-4-yl (meth)acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth)acrylate, ( piperidine skeleton-containing (meth)acrylates such as piperidin-4-yl)methyl (meth)acrylate and 2-(piperidin-4-yl)ethyl (meth)acrylate;

Aminoethyl (meth)acrylate, N-methylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N-ethylaminoethyl (meth)acrylate, N,N-diethylamino Ethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N,N-dimethylaminopropyl (meth) acrylate, N-ethylaminopropyl (meth) acrylate, substituted or unsubstituted aminoalkyl (meth)acrylates such as N,N-diethylaminopropyl (meth)acrylate;

Norbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth)acrylates containing polycyclic hydrocarbon groups such as (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and tricyclodecanedimethylol (meth)acrylate;

(meth)acrylates containing aromatic hydrocarbon groups such as benzyl (meth)acrylate;

Nitrogen-containing heterocyclic group-containing (meth)acrylates such as 2-(1,2-cyclohexacarboxyimide)ethyl (meth)acrylate;

2-ethylhexyl polyethylene glycol mono (meth) acrylate, pentyl polyethylene glycol mono (meth) acrylate, isopentyl polyethylene glycol mono (meth) acrylate, neopentyl polyethylene glycol mono (meth) acrylate, hexyl polyethylene glycol mono ( Meth) acrylate, heptyl polyethylene glycol mono (meth) acrylate, octyl polyethylene glycol mono (meth) acrylate, nonyl polyethylene glycol mono (meth) acrylate, decyl polyethylene glycol mono (meth) acrylate, undecyl polyethylene glycol mono (meth) acrylate, dodecyl polyethylene glycol mono (meth) acrylate, tridecyl polyethylene glycol mono (meth) acrylate, tetradecyl polyethylene glycol mono (meth) acrylate, pentadecyl polyethylene glycol mono (meth) acrylate, Hexadecyl polyethylene glycol mono (meth) acrylate, heptadecyl polyethylene glycol mono (meth) acrylate, octadecyl polyethylene glycol mono (meth) acrylate, nonadecyl polyethylene glycol mono (meth) acrylate, icosyl polyethylene glycol mono ( linear or branched alkyl polyethylene glycol mono (meth) acrylates such as meth) acrylate;

Cyclopropyl polyethylene glycol mono (meth) acrylate, cyclobutyl polyethylene glycol mono (meth) acrylate, cyclopentyl polyethylene glycol mono (meth) acrylate, cyclohexyl polyethylene glycol mono (meth) acrylate, cycloheptyl polyethylene glycol mono ( Cyclic alkyl polyethylene glycol mono (meth) acrylates such as meth) acrylate, cyclooctyl polyethylene glycol mono (meth) acrylate, cyclononyl polyethylene glycol mono (meth) acrylate, and cyclodecyl polyethylene glycol mono (meth) acrylate; and substituted or unsubstituted phenyl polyethylene glycol mono (meth) acrylates such as nonylphenoxy polyethylene glycol acrylate. These are used individually or in combination of 2 or more types.

Among them, linear or branched alkyl polyethylene glycol mono(meth)acrylate, aromatic hydrocarbon group-containing (meth)acrylate, polycyclic hydrocarbon group-containing (meth)acrylate, nitrogen-containing heterocyclic group-containing (meth)acrylate, and substituted or unsubstituted phenyl polyethylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl ( Meth)acrylate or 2-(1,2-cyclohexacarboxyimide)ethyl (meth)acrylate is more preferable at the point excellent in photocurability.

Moreover, (b) component can also be used combining with what has vinyl groups, such as vinyl norbornene and vinyl norbornane.

Among the above, it is preferable to use the compound whose molecular weight is 300 or less from a viewpoint of suppressing generation|occurrence|production of the outgas from a cured film. More specifically, it is preferable that it is the range of 100-300, It is more preferable that it is the range of 110-300, It is still more preferable that it is the range of 120-280, It is especially preferable that it is the range of 130-260, It is 150- A range of 255 is highly desirable.

Among them, linear or branched alkyl polyethylene glycol mono (meth) acrylates having a molecular weight of 300 or less, aromatic hydrocarbon group-containing (meth) acrylate, polycyclic hydrocarbon group-containing (meth) acrylate, nitrogen-containing heterocyclic group-containing Among (meth)acrylates and substituted or unsubstituted phenyl polyethylene glycol mono (meth) acrylates, those having a molecular weight of 300 or less, and among nonylphenoxy polyethylene glycol (meth) acrylates having a molecular weight of 300 or less, dicyclophene Tenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate or 2-(1,2-cyclohexacarboxyimide) ethyl (meth) acrylate have excellent photocurability , it is more preferable.

Specifically, for example, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate or 2-(1,2-cyclohexacarboxyimide) ethyl (meth) ) acrylate is preferable, and 2-(1,2-cyclohexacarboxyimide)ethyl acrylate is more preferable.

(b) It is preferable to contain 1-100 mass parts with respect to 100 mass parts of (a) component, as for component, it is more preferable to contain 3-80 mass parts, It is still more preferable to contain 5-50 mass parts, , It is especially preferable to contain 5-25 mass parts, and it is very preferable to contain 5-15 mass parts.

It is preferable to set it as 1-100 mass parts with respect to 100 mass parts of (a) component, as for the compounding quantity in the case of containing another crosslinking agent, It is more preferable to set it as 2-75 mass parts, It is further more preferable to set it as 3-50 mass parts. It is preferable, and it is especially preferable to set it as 5-30 mass parts. A favorable photosensitive characteristic can be provided as a compounding quantity is 1 mass part or more.

(c) A component: The compound which generates a radical by actinic light

^{(a) When at least a part of R 3} and or R ⁴ in the polyimide precursor of the component is a monovalent organic group having a carbon carbon unsaturated double bond, it is used in combination with a compound that generates a radical when irradiated with actinic light, and dissolved in a solvent It can be set as the photosensitive resin composition.

(c) As a component, N,N'- tetraalkyl, such as an oxime ester compound mentioned later, benzophenone, N,N'- tetramethyl-4,4'- diaminobenzophenone (mihiraketone), etc. as a component, for example -4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl Aromatic ketones such as ]-2-morpholino-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, and alkylbenzoin Benzyl derivatives, such as a benzoin compound, such as a benzyl dimethyl ketal, are mentioned.

Among these, in order to be excellent in a sensitivity and to provide a favorable pattern, an oxime ester compound is preferable.

It is preferable that an oxime ester compound is a compound represented by a compound represented by the following formula (7), a compound represented by the following formula (8), or a compound represented by the following general formula (9) from a viewpoint that a favorable sensitivity and a film remaining rate can be obtained Do.

In formula (7), R and R ₁ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, and a phenyl group. Or it is preferably a tolyl group, more preferably a C1-C4 alkyl group, a C4-C6 cycloalkyl group, a phenyl group or a tolyl group, and still more preferably a methyl group, a cyclopentyl group, a phenyl group or a tolyl group.

R ₂ represents a hydrogen atom, -OH, -COOH, -O(CH ₂ )OH, -O(CH ₂ ) ₂ OH, -COO(CH ₂ )OH or -COO(CH ₂ ) ₂ OH, hydrogen atom, -O(CH ₂ )OH, -O(CH ₂ ) ₂ OH, -COO(CH ₂ )OH or -COO(CH ₂ ) ₂ OH, preferably a hydrogen atom, -O(CH ₂ ) ₂ More preferably, it is OH or -COO(CH ₂ ) _{2 OH.} Moreover, you may have substituents other than _{R<2> in an aromatic ring.}

In Formula (8), R<_3> represents a C1-C6 alkyl group each independently, and it is preferable that it is a propyl group.

R ₄ represents -NO ₂ or -C(=O)Ar (here, Ar represents an aryl group), and as Ar, a tolyl group is preferable.

Each of R ₅ and R ₆ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, and is preferably a methyl group, a phenyl group or a tolyl group.

Moreover, you may have substituents other than _{R<4> in an aromatic ring.}

In Formula (9), R<_7> represents a C1-C6 alkyl group, and it is preferable that it is an ethyl group.

R ₈ is an organic group having an acetal bond, and is preferably a substituent corresponding to ^{R 8 in the compound represented by the following formula (9-1).}

Each of R ₉ and R ₁₀ represents an alkyl group, phenyl group or tolyl group having 1 to 12 carbon atoms, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group.

Moreover, you may have substituents other than _{R<8> in an aromatic ring.}

Examples of the compound represented by the formula (7) include a compound represented by the following formula (7-1) and a compound represented by the following formula (7-2). The compound represented by the following formula (7-1) is available as IRGACURE OXE-01 (manufactured by BASF Corporation, trade name).

As a compound represented by said formula (8), the compound represented by following formula (8-1) is mentioned, for example. This compound is available as DFI-091 (manufactured by Daito Chemix Co., Ltd., trade name).

As a compound represented by said formula (9), the compound represented by following formula (9-1) is mentioned, for example. It can be obtained as Adeka Optomer N-1919 (made by ADEKA Corporation, a brand name).

As another oxime ester compound, it is preferable to use the following compound.

Moreover, the following compounds can also be used as (c)component.

(c) As content of component, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of (a) component, It is more preferable that it is 0.03-20 mass parts, It is still more preferable that it is 0.05-15 mass parts, 0.5-10 It is especially preferable that it is a mass part. When a compounding quantity is 0.01 mass part or more, an exposure part fully bridge|crosslinks, a photosensitive characteristic becomes more favorable, and it exists in the tendency for the heat resistance of a cured film to improve more as it is 30 mass parts or less.

(d) component (adhesion aid): organic silane compound

In order to improve the adhesiveness to the silicon substrate etc. after hardening in the resin composition of this invention, you may contain the organosilane compound as (d)component. Examples of the organosilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycy Doxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-ureidepropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, trie Toxysilylpropylethylcarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl -N-(1,3-dimethylbutylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 1-isocyanatomethyltrimethylsilane, 1-isocyanatomethyltriethyl Silane, 1-isocyanatomethyltripropylsilane, 1-isocyanatomethyltributylsilane, 1-isocyanatomethyltrimethoxysilane, 1-isocyanatomethyldimethoxymethylsilane, 1-isocyanatomethyl Methoxydimethylsilane, 1-isocyanatomethyltriethoxysilane, 1-isocyanatomethyltripropoxysilane, 1-isocyanatomethyltributoxysilane, 1-isocyanatomethyldiethoxyethylsilane, 3 -isocyanatopropyltrimethylsilane, 3-isocyanatopropyltriethylsilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropylmethoxydimethylsilane , 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyldiethoxyethylsilane, 3-isocyanatopropylethoxydiethylsilane, 6-isocyanatohexyltrimethoxysilane, 6-isocia Natohexyldimethoxymethylsilane, 6-isocyanatohexylmethoxydimethylsilane, 6-isocyanatohexyltriethoxysilane, 6-isocyanatohexyldiethoxyethylsilane, 6-isocyanatohexylethoxydiethyl Silane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, N,N-bis(2-hydroxyethyl)-N,N-bis(trimethoxysilylpropyl)ethylenediamine, N- (hydroxymethyl)-N-methylaminopropyltrimethoxysilane, 7-triethoxysilylpropoxy-5-hydroxyflavone, N-(3-triethoxysilylpropyl)-4-hydroxybutyramide , 2-hydroxy-4- (3methyldiethoxyl Rylpropoxy)diphenylketone, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane, 3-(N-acetyl-4-hydroxypropyloxy)propyltriethoxysilane, hydroxymethyltriethane Toxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, triethoxysilylpropylethylcarbamate, N-(3-triethoxysilylpropyl)Ot-butylcarbamate, etc. can A compounding quantity is adjusted suitably so that a desired effect may be acquired.

Among these, it is preferable to use bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane.

(e) Ingredient: Solvent

A solvent can be used for the resin composition of this invention as (e) component as needed.

(e) As a component, the polar solvent which melt|dissolves polyimide precursor completely is preferable, For example, N-methyl- 2-pyrrolidone, N,N- dimethylacetamide, N,N- dimethylformamide, dimethyl sulfoxide. Side, tetramethylurea, hexamethyl phosphate triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate , ethyl lactate, and 1,3-dimethyl-2-imidazolidione. These may be used independently and may be used in combination of two or more.

Although it does not specifically limit as content of (e) component, Usually, 50-1000 mass parts is preferable with respect to 100 mass parts of (a) component, and 100-500 mass parts is more preferable.

Moreover, in order to ensure favorable storage stability, you may mix|blend a radical polymerization inhibitor or a radical polymerization inhibitor with the resin composition of this invention. Examples of the radical polymerization inhibitor or radical polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene; Paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tolquinone, tannic acid, parabendylaminophenol, nitrosamines, etc. are mentioned. These may be used independently and may be used in combination of 2 or more types.

As a compounding quantity in the case of containing a radical polymerization inhibitor or a radical polymerization inhibitor, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of polyimide precursors, It is more preferable that it is 0.01-10 mass parts, It is 0.05-5 mass parts more preferably. Storage stability becomes more favorable as a compounding quantity is 0.01 mass part or more, and the heat resistance of a cured film can be improved more in it being 30 mass parts or less.

The resin composition of this invention may contain the photopolymerizable compound more than bifunctional in the range which does not impair the effect of this invention. As a photopolymerizable compound more than bifunctional, tetraethylene glycol dimethacrylate etc. are mentioned.

As a compounding quantity in the case of containing a photopolymerizable compound more than bifunctional, it is preferable that it is 1-10 mass parts with respect to 100 mass parts of polyimide precursors, It is more preferable that it is 1-8 mass parts, It is still more preferable that it is 1-5 mass parts Do.

In addition, the resin composition of the present invention may substantially consist of the above components (a) to (c) and optionally at least one of component (d), component (e), a radical polymerization inhibitor and a radical polymerization inhibitor, Moreover, you may consist only of such a component. "Consisting substantially" means that the said component is 95 mass % or more, or 98 mass % or more with respect to the whole composition.

<The manufacturing method of a cured film and a pattern cured film>

The cured film of this invention is formed from the resin composition mentioned above.

In addition, the pattern cured film of this invention is a pattern cured film formed with the resin composition mentioned above.

The manufacturing method of the pattern cured film of this invention apply|coats the above-mentioned resin composition on a board|substrate and dries to form a coating film, After irradiating actinic light to the coating film formed in the said process, the process of developing and obtaining a pattern resin film, and a step of heat-treating the patterned resin film.

Hereinafter, each process of the manufacturing method of a pattern cured film is demonstrated first.

The manufacturing method of the pattern cured film of this invention includes the process of apply|coating the above-mentioned resin composition on a board|substrate, drying it, and forming a coating film. As a method of apply|coating a resin composition on a base material, the dipping method, the spraying method, the screen printing method, and the spin coating method are mentioned, for example. As a base material, a silicon wafer, a metal substrate, a ceramic substrate etc. are mentioned, for example.

In a drying process, a coating film without adhesiveness can be formed by heating and removing a solvent. The drying process can use apparatuses, such as a PMC Co., Ltd. product, DATAPLATE (Digital Hotplate), 90-130 degreeC is preferable as a drying temperature, and 100-400 second is preferable as a drying time.

The manufacturing method of the patterned cured film of this invention includes the process of developing and obtaining a patterned resin film, after irradiating actinic light to the coating film formed in the said process. Thereby, the resin film in which the desired pattern was formed can be obtained.

Although the resin composition of this invention is suitable for i-ray exposure, as an actinic light to irradiate, an ultraviolet-ray, a deep ultraviolet-ray, a visible light, an electron beam, X-ray, etc. can be used.

The developer is not particularly limited, but a flame retardant solvent such as 1,1,1-trichloroethane, an aqueous sodium carbonate solution, an aqueous alkali solution such as an aqueous solution of tetramethylammonium hydroxide, N,N-dimethylformamide, and dimethyl good solvents such as sulfoxide, N,N-dimethylacetoamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, and acetate esters, these good solvents and lower alcohols; A mixed solvent with poor solvents, such as water and an aromatic hydrocarbon, etc. are used. After development, rinsing is performed with a poor solvent or the like as necessary.

The manufacturing method of the pattern cured film of this invention includes the process of heat-processing a pattern resin film.

For this heat treatment, an apparatus such as a vertical diffusion furnace made by Koyo Lindbergh can be used, and it is preferable to carry out at a heating temperature of 80 to 400°C, and the heating time is preferably 5 to 300 minutes. According to this process, imidation of the polyimide precursor in a resin composition can advance, and the pattern cured film containing polyimide resin can be obtained.

Moreover, 250-300 degreeC is more preferable, and, as for heating temperature, 260-290 degreeC is still more preferable. Moreover, as for heat time, 120 to 280 minutes are more preferable, and 180 to 270 minutes are still more preferable.

The manufacturing method of the cured film of this invention includes the process of apply|coating a resin composition on a board|substrate, drying it, and forming a coating film, and the process of heat-processing a coating film. The process of forming a coating film and the process of heat-processing can be carried out similarly to the manufacturing method of the said pattern cured film. The cured film in which pattern formation is not carried out may be sufficient as the cured film of this invention.

The cured film or pattern cured film of the present invention obtained in this way can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer, etc. of a semiconductor device.

1 is a schematic cross-sectional view of a semiconductor device having a redistribution structure according to an embodiment of the present invention.

The semiconductor device of this embodiment has a multilayer wiring structure. An Al wiring layer 2 is formed on the interlayer insulating layer (interlayer insulating film) 1, and an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed thereon, and further protecting the surface of the device A layer (surface protective film) 4 is formed. A redistribution layer 6 is formed from the putt portion 5 of the wiring layer 2, and extends to the upper portion of the core 8, which is a connection portion with an external connection terminal, such as a conductive ball 7 formed of solder, gold, or the like. have. Further, on the surface protective layer 4 , a cover coat layer 9 is formed. The redistribution layer 6 is connected to the conductive ball 7 through the barrier metal 10 , but a collar 11 is provided to hold the conductive ball 7 . When a package having such a structure is mounted, in order to further relieve stress, there is a case through the underfill 12 .

The cured film or pattern cured film of the present invention can be used for so-called package applications such as the cover coat layer 9 of the above embodiment, the core 8 for rewiring, the collar 11 for balls such as solder, and the underfill 12. have.

The cured film or pattern cured film of the present invention is excellent in adhesiveness to a metal layer or an encapsulant, etc., is excellent in copper migration resistance, and has a high stress relaxation effect. Therefore, the cured film or pattern cured film of the present invention is excellent. A semiconductor element to have becomes a thing excellent in reliability.

The electronic component of the present invention is not particularly limited except for having a cover coat using the cured film or pattern cured film of the present invention, a core for rewiring, a ball collar such as solder, an underfill used for flip chips, etc. It can take a branch structure.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

Synthesis Example 1 (Synthesis of pyromellitic acid-hydroxyethyl methacrylate diester)

In a 0.5 liter poly bottle, 43.624 g (200 mmol) of pyromellitic dianhydride, 54.919 g (401 mmol) of 2-hydroxyethyl methacrylate, and 0.220 g of hydroquinone, dried for 24 hours with a dryer at 160° C. After dissolving in 394 g of rolidone, adding a catalytic amount of 1,8-diazabicycloundecene, stirring at room temperature (25°C) for 24 hours, esterification was carried out, and pyromellitic acid-hydroxyethyl methacrylate A diester (PMDA(HEMA)) solution was obtained.

Synthesis Example 2 (Synthesis of 3,3'-4,4'-biphenyltetracarboxylic acid diester)

In a 0.5 liter poly bottle, 30.893 g (105 mmol) of 3,3'-4,4'-biphenyltetracarboxylic dianhydride and 28.833 g (210 mmol) of 2-hydroxyethyl methacrylate dried at 160°C for 24 hours ) and 0.110 g of hydroquinone were dissolved in 239 g of N-methylpyrrolidone, a catalytic amount of 1,8-diazabicycloundecene was added, and then stirred at room temperature (25° C.) for 24 hours to perform esterification. , 3,3'-4,4'-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester (s-BPDA (HEMA)) solution was obtained.

Synthesis Example 3 (Synthesis of 4,4'-oxydiphthalic acid diester)

In a 0.5 liter poly bottle, 49.634 g (160 mmol) of 4,4'-oxydiphthalic acid, 44.976 g (328 mmol) of 2-hydroxyethyl methacrylate, and 0.176 g of hydroquinone dried for 24 hours with a dryer at 160 ° C. After dissolving in 378 g of methylpyrrolidone, adding a catalytic amount of 1,8-diazabicycloundecene, stirring at room temperature (25° C.) for 48 hours to effect esterification, 4,4'-oxydi A solution of phthalic acid-hydroxyethyl methacrylate diester (ODPA (HEMA)) was obtained.

Synthesis Example 4 (Synthesis of Polymer 1)

In a 0.5 liter flask equipped with a stirrer and a thermometer, 195.564 g of the PMDA (HEMA) solution obtained in Synthesis Example 1 and 58.652 g of the ODPA (HEMA) solution obtained in Synthesis Example 3 were put, and then, thereafter, under ice cooling, tea chloride 25.9 g (217.8 mmol) of O'Neil was dripped using the dropping funnel so that the reaction solution temperature might be maintained at 10 degrees C or less. After completion|finish of dripping of thionyl chloride, reaction was performed under ice cooling for 2 hours, and the solution of the acid chloride of PMDA (HEMA) and ODPA (HEMA) was obtained. Then, using a dropping funnel, 31.696 g (99.0 mmol) of 2,2'-bis(trifluoromethyl)bendizine, 34.457 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone N-methyl The 90.211 g solution of pyrrolidone was dripped, being careful not to exceed 10 degreeC by the temperature of the reaction solution by ice cooling. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester. The weight average molecular weight calculated|required by standard polystyrene conversion was 34,000. This is polymer 1 (pyromellitic acid-hydroxyethyl methacrylate diester/4,4'-oxydiphthalic acid-hydroxyethyl methacrylate diester/2,2'-bis(trifluoromethyl)bendizine axis polymer (PMDA/ODPA/TFMB)). 1 g of Polymer 1 was dissolved in 1.5 g of N-methylpyrrolidone, applied by spin coating on a glass substrate, heated for 180 seconds on a hot plate at 100° C. to volatilize the solvent, and a coating film having a thickness of 20 μm was formed. At this time, the i-ray transmittance of the obtained coating film was 30%.

Synthesis Example 5 (Synthesis of Polymer 2)

In a 0.5 liter flask equipped with a stirrer and a thermometer, 282.125 g of the s-BPDA (HEMA) solution obtained in Synthesis Example 2 was put, and then 25.9 g (217.8 mmol) of thionyl chloride was added under ice cooling with a reaction solution temperature of 10° C. or less. was dropped using a dropping funnel to maintain After completion|finish of dripping of thionyl chloride, stirring was performed under ice cooling for 1 hour, and the solution of s-BPDA(HEMA) chloride was obtained. Then, using a dropping funnel, 31.696 g (99.0 mmol) of 2,2'-bis(trifluoromethyl)bendizine, 34.457 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone N-methyl The 90.211 g solution of pyrrolidone was dripped, being careful not to exceed 10 degreeC by the temperature of the reaction solution by ice cooling. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester. The weight average molecular weight calculated|required by standard polystyrene conversion was 85,000. Polymer 2 (3,3'-4,4'-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester/2,2'-bis(trifluoromethyl)bendizine condensation polymer (BPDA/TFMB)) do it with 1 g of polymer 2 was dissolved in 1.5 g of N-methylpyrrolidone, applied by spin coating on a glass substrate, heated for 180 seconds on a hot plate at 100° C. to evaporate the solvent, and a coating film having a thickness of 20 μm was formed. At this time, the i-ray transmittance of the obtained coating film was 60%.

Synthesis Example 6 (Synthesis of Polymer 3)

In a 0.5 liter flask equipped with a stirrer and a thermometer, 244.455 g of the PMDA (HEMA) solution obtained in Synthesis Example 1 was put, and thereafter, 25.9 g (217.8 mmol) of thionyl chloride was added under ice cooling to keep the reaction solution temperature at 10°C or less. It was dripped using the dropping route so that it might be. After completion|finish of dripping of thionyl chloride, stirring was performed under ice cooling for 1 hour, and the solution of PMDA (HEMA) chloride was obtained. Then, using a dropping funnel, 31.696 g (99.0 mmol) of 2,2'-bis(trifluoromethyl)bendizine, 34.457 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone N-methyl The 90.211 g solution of pyrrolidone was dripped, being careful not to exceed 10 degreeC by the temperature of the reaction solution by ice cooling. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester. The weight average molecular weight calculated|required by standard polystyrene conversion was 32,000. Let this be polymer 3 (pyromellitic acid-hydroxyethyl methacrylate diester/2,2'-bis(trifluoromethyl)bendizine condensation polymer (PMDA/TFMB)). 1 g of Polymer 3 was dissolved in 1.5 g of N-methylpyrrolidone, applied by spin coating on a glass substrate, heated for 180 seconds on a hot plate at 100° C. to volatilize the solvent, and a coating film having a thickness of 20 μm was formed. At this time, the i-ray transmittance of the obtained coating film was 17%.

Synthesis Example 7 (Synthesis of Polymer 4)

In a 0.5 liter flask equipped with a stirrer and a thermometer, 169.275 g of the s-BPDA (HEMA) solution obtained in Synthesis Example 2 and 72.7776 g of ODPA (HEMA) solution obtained in Synthesis Example 3 were placed, and then, 25.9 thionyl chloride 25.9 were cooled under ice. g (217.8 mmol) was added dropwise using a dropping funnel so that the temperature of the reaction solution was maintained at 10°C or lower. After completion|finish of dripping of thionyl chloride, stirring was performed under ice cooling for 1 hour, and the solution of the chloride of s-BPDA (HEMA) and ODPA (HEMA) was obtained. Then, using a dropping funnel, and then using a dropping funnel, 21.017 g (99.0 mmol) of 2,2'-dimethylbendizine, 34.457 g (435.6 mmol) of pyridine, and 0.076 g (0.693 mmol) of hydroquinone The 59.817 g solution of N-methylpyrrolidone was dripped, being careful that the temperature of the reaction solution does not exceed 10 degreeC by ice-cooling. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester. The weight average molecular weight calculated|required by standard polystyrene conversion was 35,000. Polymer 4 (3,3'-4,4'-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester/4,4'-oxydiphthalic acid-hydroxyethyl methacrylate diester/2,2' -Dimethylbendizine condensation polymer (BPDA/ODPA/DMB)). 1 g of polymer 4 was dissolved in 1.5 g of N-methylpyrrolidone, applied by spin coating on a glass substrate, heated for 180 seconds on a hot plate at 100° C. to evaporate the solvent, and a coating film having a thickness of 20 μm was formed. At this time, the i-ray transmittance of the obtained coating film was 8%.

Synthesis Example 8 (Synthesis of Polymer 5)

In a 0.5 liter flask equipped with a stirrer and a thermometer, 181.944 g of the ODPA (HEMA) solution obtained in Synthesis Example 3 was put, and thereafter, 25.9 g (217.8 mmol) of thionyl chloride was added under ice-cooling to maintain the reaction solution temperature at 10°C or less. It was dripped using the dropping route so that it might be. After completion of the dropwise addition of thionyl chloride, the mixture was stirred under ice cooling for 1 hour to obtain a solution of ODPA (HEMA) chloride. Then, using a dropping funnel, a solution of 21.017 g (99.0 mmol) of 2,2'-dimethylbendizine, 34.457 g (435.6 mmol) of pyridine, and 59.817 g of N-methylpyrrolidone of 0.076 g (0.693 mmol) of hydroquinone was added dropwise, being careful that the temperature of the reaction solution did not exceed 10°C by ice-cooling. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester. The weight average molecular weight calculated|required by standard polystyrene conversion was 35,000. Let this be polymer 5 (4,4'-oxydiphthalic acid-hydroxyethyl methacrylate diester/2,2'-dimethylbendizine condensation polymer (ODPA/DMB)). 1 g of polymer 5 was dissolved in 1.5 g of N-methylpyrrolidone, applied by spin coating on a glass substrate, heated for 180 seconds on a hot plate at 100° C. to volatilize the solvent, and a coating film having a thickness of 20 μm was formed. At this time, the i-ray transmittance of the obtained coating film was 40%.

The conditions for measuring the weight average molecular weight of polymers 1 to 5 in terms of standard polystyrene by GPC method are as follows, and solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (for 0.5 mg of polymer) volume ratio)] was measured using 1 mL of the solution.

Measuring device: Detector: L4000UV manufactured by Hitachi Seisakusho Co., Ltd.

A pump: L6000 made by Hitachi Seisakusho

C-R4A Chromatopac manufactured by Shimadzu Corporation

Measurement conditions: Column　Gelpack　GL-S300MDT-5×2

Eluent: THF/DMF=1/1 (volume ratio)

LiBr (0.03 mol/L), H ₃ PO ₄ (0.06 mol/L)

Flow rate: 1.0 mL/min, Detector: UV270 nm

The i-ray transmittance of the polymers 1 to 5 was measured using a U-3310 Spectrophotometer (manufactured by Hitachi, Ltd.).

<Examples 1 to 9, Comparative Example 1>

(a) Component - (c) The component and adhesion|attachment adjuvant were melt|dissolved in N-methylpyrrolidone by the compounding shown in Table 1, and the resin composition was prepared.

In Table 1, the number in parentheses of each column of (b) component, (c) component, and adhesion aid shows the addition amount (mass part) with respect to 100 mass parts of (a) component. In addition, N-methylpyrrolidone was used as a solvent, and the usage-amount used all 1.5 times (150 mass parts) with respect to 100 mass parts of (a) component.

Moreover, as (c)component in an Example, following 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl oxime)] (BASF Corporation IRGACURE OXE) -01) was used.

In addition, as an adhesion aid, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane (Gelest Co., Ltd. product, SIB-1140) was used.

About the resin composition prepared by the Example and the comparative example, the result of having measured the photosensitive characteristic (remaining film rate, resolution) at the time of film-forming is shown in Table 1. The evaluation method is as follows.

(Evaluation of photosensitive characteristics (remaining film rate, resolution))

The said resin composition was apply|coated according to the spin coating method on a 6-inch silicon wafer, and it heated for 3 minutes on a 100 degreeC hotplate, the solvent was volatilized, and the coating film with a film thickness of 10 micrometers was obtained. This coating film was immersed in a mixed solvent of γ-butyrolactone:butyl acetate = 7:3 and twice the time until completely dissolved was set as the developing time. ^{200 mJ/cm<2>} exposure was performed to the coating film obtained by the same method through a photomask in conversion of i line|wire using Canon Co., Ltd. product i-line stepper FPA-3000iW. The wafer was immersed in γ-butyrolactone:butyl acetate = 7:3, paddle-developed at the above-mentioned development time, and then rinsed with cyclopentanone. The residual film ratio of the old part at this time was evaluated. Here, the remaining film rate was computed by the method of following formula (1).

The minimum value of the mask dimension of the line-and-space pattern which arose when ^{400 mJ/cm<2> was} exposed to the obtained coating film in i-line conversion through a photomask by the above method was evaluated as resolution.

In Table 1, (a) component is a following compound.

P1: Polymer 1 synthesized in Synthesis Example 4 (PMDA/ODPA/TFMB)

P2: Polymer 2 synthesized in Synthesis Example 5 (BPDA/TFMB)

P3: Polymer 3 synthesized in Synthesis Example 6 (PMDA/TFMB)

P4: Polymer 4 synthesized in Synthesis Example 7 (BPDA/ODPA/DMB)

P5: Polymer 5 synthesized in Synthesis Example 8 (ODPA/DMB)

In Table 1, (b) component is a compound represented by the following structural formula.

b1: Nonylphenoxy polyethylene glycol acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-318A, n (average value) = 8)

b2: dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512M)

b3: dicyclofentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513M)

b4: Benzyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., BzMA)

b5: 2-(1,2-cyclohexacarboxyimide) ethyl acrylate (manufactured by Toagosei Co., Ltd., M-140)

b': tetraethylene glycol dimethacrylate (manufactured by Sutma Co., Ltd., TEGDMA)

As shown in Table 1, even if the resin composition of Examples 1-9 uses a monofunctional (meth)acrylate as (b) component, the bifunctional tetra of Comparative Example 1 It has pattern properties comparable to that of a resin composition using ethylene glycol dimethacrylate.

<Examples 10-13, Comparative Example 2>

By the way, as for the cured film using polyimide resin, the stress after hardening may increase by thickening and making a high elastic modulus, the curvature of a semiconductor wafer becomes large, and a problem may arise at the time of conveyance and wafer fixation.

MEANS TO SOLVE THE PROBLEM When heat-hardening temperature becomes 300 degrees C or less and low temperature, vacuum processes, such as etching of an electrode part, after a polyimide cured film formation process WHEREIN: The subject that the outgas from a polyimide film increases. If outgas is generated during the process, it becomes a problem because the chamber is contaminated. From a viewpoint of outgassing, the aspect shown to the following Examples 10-12 is preferable.

Example 10

(a) 100 parts by mass of Polymer 1, (b) 10 parts by mass of 2-(1,2-cyclohexacarboxyimide)ethyl acrylate (M-140, molecular weight 251, manufactured by Toagosei Co., Ltd.), (c) ) of 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (BASF Corporation IRGACURE OXE-01) in 2 parts by mass, bis(2- 3 mass parts of hydroxyethyl)-3-aminopropyl triethoxysilane (Gelest Co., Ltd. product, SIB-1140) was melt|dissolved in N-methylpyrrolidone (150 mass parts of solvents), and the resin composition was prepared.

About the prepared resin composition, the photosensitive characteristic (remaining film rate, resolution) at the time of film-forming, the stress after hardening, and the amount of outgassing were measured according to the following evaluation method.

(Evaluation of photosensitive characteristics (remaining film rate, resolution))

The said resin composition was apply|coated according to the spin coating method on a 6-inch silicon wafer, and it heated for 3 minutes on a 100 degreeC hotplate, the solvent was volatilized, and the coating film with a film thickness of 10 micrometers was obtained. This coating film was immersed in a mixed solvent of γ-butyrolactone:butyl acetate = 7:3 and twice the time until completely dissolved was set as the developing time. ^{200 mJ/cm<2>} exposure was performed to the coating film obtained by the same method through the photomask in i line|wire conversion using the Canon Corporation i line|wire stepper FPA-3000iW. The wafer was immersed in γ-butyrolactone:butyl acetate = 7:3, and after paddle development at the above development time, rinse-cleaning was performed with cyclopentanone. It was 92 % when the remaining-film rate of the exposure part at this time was evaluated. In addition, the remaining film ratio was computed with the film thickness after image development with respect to the film thickness before image development.

^{When the obtained coating film was exposed to 400 mJ/cm 2 in} i-line conversion through a photomask in the same manner as described above, the minimum value of the mask dimension of the line-and-space pattern generated as a resolution was evaluated as 8 µm.

(Measurement of residual stress)

The obtained resin composition was applied on a 6-inch silicon wafer by a spin coating method, heated on a hot plate at 100° C. for 3 minutes, and the solvent was volatilized to obtain a coating film having a film thickness of 10 µm after curing. This was heat-cured for 4 hours at 270 degreeC in nitrogen atmosphere using the vertical diffusion furnace made from Koyo Lindbergh, and the polyimide film (cured film) was obtained. The residual stress of the polyimide film after curing was 22 MPa when measured at room temperature using KLATencor Co., Ltd. thin film stress measuring apparatus FLX-2320.

(Pyrolysis Gas Chromatography Mass Spectrometry)

A polyimide membrane was created similarly to the measurement of the said residual stress, and the sample for thermal decomposition gas chromatography mass spectrometry was obtained. The sample was heated to 270°C/30min using a Tekmar 7000HT headspace sampler, and the generated gas was GC/MS (manufactured by Shimadzu Corporation, model number: GC/MSQP-2010, carrier gas: helium, 1.0 mL/min). , Column: HP-5MS, Oven: After heating at 40°C for 5 minutes, the temperature is raised to 280°C at a rate of 15°C/min, interface temperature: 280°C, ion source temperature: 250°C, sample injection volume: 0.1 mL) was analyzed. The measurement result is shown in FIG.2(a). The sum of each peak area value was made into the total amount of outgas. The sum of the peak area values is 38, 375, and 993, and when the value of the sum of the peak area values of the comparative example 2 mentioned later is set to 1, it became about 0.26, and the outgas was fully reduced.

Example 11

In the same manner as in Example 10, except that 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] of (c) was changed to the following compound, the resin A composition was prepared and evaluated.

In Example 11, the residual film rate was 95%, the resolution was 7 micrometers, and the residual stress was 22 MPa. The sum of the peak area values in pyrolysis gas chromatography mass spectrometry is 58, 315, and 432, and when the value of the sum of the peak area values of Comparative Example 2 to be described later is 1, it is about 0.39, and the outgas is sufficiently reduced was becoming

Example 12

A resin composition was prepared and evaluated in the same manner as in Example 10 except that 5 parts by mass of tetraethylene glycol dimethacrylate (manufactured by Sutma Co., Ltd., TEGDMA) was further added.

The remaining film ratio was 95%, the resolution was 7 µm, and the residual stress was 22 MPa. The sum of the peak area values in pyrolysis gas chromatography mass spectrometry is 67, 924, and 419, and when the value of the sum of the peak area values of Comparative Example 2 to be described later is 1, it is about 0.45, and the outgas is sufficiently reduced. .

Example 13

(b) 2- (1,2-cyclohexacarboxyimide) ethyl acrylate to nonylphenoxy polyethylene glycol acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-318A, n (average value) = 8, molecular weight 625) A resin composition was prepared and evaluated in the same manner as in Example 10 except for changing to .

The remaining film ratio was 89%, the resolution was 8 µm, and the residual stress was 24 MPa. The sum of the peak area values in pyrolysis gas chromatography mass spectrometry is 424, 225, and 722, and when the value of the sum of the peak area values of Comparative Example 2 to be described later is 1, it increases by about 2.84 times, and the outgas increases did.

Comparative Example 2

A resin composition was prepared in the same manner as in Example 10 except that 2-(1,2-cyclohexacarboxyimide)ethyl acrylate of (b) was changed to tetraethylene glycol dimethacrylate (molecular weight 306), evaluated.

The remaining film ratio was 92%, the resolution was 8 µm, and the residual stress was 22 MPa. The measurement result of pyrolysis gas chromatography mass spectrometry is shown in FIG.2(b). The sum of the peak area values was 149, 526, and 749.

Examples 10-12 were excellent in pattern property, and there was little amount of generation of an outgas.

Experimental example

In order to investigate the cause of contamination of the chamber at the time of using the cured film after low temperature hardening for vacuum processes, such as etching of an electrode part, the experiment which measures the outgas which comes out from a polyimide film was performed.

In Example 10 and Comparative Example 2, a polyimide film was prepared in the same manner as in the measurement of residual stress, and the cured film was thermally decomposed (FRONTIER LAB PY2020D, manufactured by Frontier Laboratories Co., Ltd.) for 1 minute After the temperature was raised to 375°C at a rate of 15°C, the generated gas was GC/MS (manufactured by Agilent Technologies, Ltd., model number: GC/MS 5973 MSD, carrier gas: helium, 0.9 mL/ min, column: UADTM-2.5N, Oven: 350°C) and analyzed.

The measurement result of Comparative Example 2 is shown to Fig.3 (a). The dashed line represents Polymer 1, and the solid line represents TEGDMA.

The measurement result of Example 10 is shown to FIG.3(b). The dashed line represents Polymer 1, and the solid line represents M-140.

Although TEGDMA in the cured film of Comparative Example 2 was gasified at around 300°C, M-140 in the cured film of Example 10 was hardly gasified at 300°C or higher.

At the conventional curing temperature of about 370 ° C., since the curing temperature is higher than the glass transition temperature of the cured film, the cured film becomes a rubber-like region once and releases the crosslinking agent as an outgas, all of which is gasified, so there is no problem, When the curing temperature is lower than the glass transition temperature of the cured film, the cured film remains in a glassy state and contains an outgas component in the cured film. Therefore, when this film is exposed to a high vacuum, the contained crosslinking agent is generated as an outgas component. It is assumed that discarded

Experimental example

In order to investigate the cause of contamination of the chamber at the time of using the cured film after low temperature hardening for vacuum processes, such as etching of an electrode part, the experiment which measures the outgas which comes out from a polyimide film was performed.

In Example 1 and Comparative Example 2, a polyimide film was prepared in the same manner as in the measurement of residual stress, and the cured film was heated at 15°C for 1 minute using a thermal decomposition device (FRONTIER LAB PY2020D, manufactured by Frontier Labs, Inc.). After the temperature was raised to 375°C at a rate, the generated gas was GC/MS (manufactured by Azirent Technology, Ltd., model number: GC/MS 5973 MSD, carrier gas: helium, 0.9 mL/min, column: UADTM-2.5N) , Oven: 350°C) and analyzed.

The measurement result of Comparative Example 2 is shown to Fig.3 (a). The dashed line represents Polymer 1, and the solid line represents TEGDMA.

The measurement result of Example 1 is shown in FIG.3(b). The dashed line represents Polymer 1, and the solid line represents M-140.

Although TEGDMA in the cured film of Comparative Example 2 was gasified at around 300°C, M-140 in the cured film of Example 1 was hardly gasified at 300°C or higher.

At the conventional curing temperature of about 370 ° C., since the curing temperature is higher than the glass transition temperature of the cured film, the cured film becomes a rubber-like region once and releases the crosslinking agent as an outgas, all gasification is not a problem, but the curing temperature is When it is lower than the glass transition temperature of a cured film, a cured film remains in a glassy state, and since an outgas component will be contained in a cured film, when this film is exposed to high vacuum, it is estimated that the contained crosslinking agent will generate|occur|produce as an outgas component. .

Industrial Applicability

The resin composition of the present invention can be used for so-called package applications, such as a cover coating material for forming electronic components such as semiconductor devices, a core material for rewiring, a color material for balls such as solder, and an underfill material.

Although some embodiments and/or examples of the present invention have been described in detail above, those skilled in the art can make many changes to these illustrative embodiments and/or examples without departing substantially from the novel teachings and effects of the present invention. It is easy to add Accordingly, many of these modifications are included within the scope of the present invention.

All the content of the Japanese application specification which becomes the basis of the Paris Convention priority claim of this application is used here.

Claims (14)

The resin composition containing following (a), (b), and (c) component.
(a) a polyimide precursor having a structural unit represented by the following general formula (1)
(b) as a compound represented by the following general formula (2), dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxy At least one compound selected from the group consisting of ethyl (meth) acrylate, benzyl (meth) acrylate, and nitrogen-containing heterocyclic group-containing (meth) acrylate
(c) a compound represented by the following formula (7)

(Wherein, R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent organic group having a carbon carbon unsaturated double bond. .)

(Wherein, R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is a monovalent organic group not containing a (meth)acryl group.)

(In formula (7), R and R ₁ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group,
R ₂ represents a hydrogen atom, -OH, -COOH, -O(CH ₂ )OH, -O(CH ₂ ) ₂ OH, -COO(CH ₂ )OH or -COO(CH ₂ ) ₂ OH.) According to claim 1,
The resin composition in which the said (b) component contains 1-100 mass parts with respect to 100 mass parts of (a) component. According to claim 1,
^R<6> in said Formula (2) is a (meth)acryl group, a hydroxyl group, and the resin composition which is a monovalent organic group which does not contain an amino group. According to claim 1,
The resin composition in which the said (b) component is a monofunctional photopolymerizable compound whose molecular weight is 300 or less. According to claim 1,
^{The resin composition, wherein at least one of R 3} and R ⁴ in the formula (1) is a monovalent organic group having a carbon-carbon unsaturated double bond. According to claim 1,
^{The resin composition in which R<1>} in said Formula (1) is any one of the tetravalent organic groups represented by the following general formula (2a) - (2e).

(In formula (2d), X and Y each independently represent a divalent group or single bond not conjugated to the benzene ring to which each is bonded. In formula (2e), Z is an ether bond (-O-) or It is a sulfide bond (-S-).) According to claim 1,
^{The resin composition wherein R 2} in the formula (1) is a divalent organic group represented by the following general formula (5) or (6).

(Wherein, R ¹⁰ to R ¹⁷ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and ^{at least one of R 10} to R ¹⁷ is a halogen atom or a halogenated alkyl group. R ¹⁸ and R ¹⁹ are each independently is a halogen atom or a halogenated alkyl group.) delete The cured film formed from the resin composition in any one of Claims 1-7. The manufacturing method of a cured film including the process of apply|coating the resin composition in any one of Claims 1-7 on a board|substrate, drying it, and forming a coating film, and the process of heat-processing a coating film. The pattern cured film formed from the resin composition in any one of Claims 1-7. A step of applying the resin composition according to any one of claims 1 to 7 on a substrate and drying it to form a coating film, a step of irradiating the coating film with actinic light and then developing to obtain a pattern resin film; The manufacturing method of a pattern cured film including the process of heat-processing. The electronic component which has the cured film of Claim 9. The electronic component which has the pattern cured film of Claim 11.

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