TWI655500B - Resin composition containing polyimide precursor, cured film thereof, method for producing cured film, patterned cured film, method for producing the same, and electronic component - Google Patents

Abstract

A resin composition comprising: (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 ) A compound that generates free radicals by irradiating actinic rays.

Description

Resin composition containing polyimide precursor and its hardened film, method for manufacturing hardened film, patterned hardened film and its manufacturing method, and electronic parts

The present invention relates to a resin composition containing a polyimide precursor suitable as a material for a protective film such as a surface coating film of a semiconductor element, an interlayer insulating film or an insulating film of a thin-film multilayer wiring board, and use thereof Manufacturing method of hardened film and electronic parts.

In recent years, as a protective film material for semiconductor integrated circuits, organic materials having high heat resistance such as polyimide resin have been widely used. A protective film (hardened film) using such a polyimide resin can be applied to a substrate by coating a resin film (the resin film is a polyimide precursor or a resin composition containing the polyimide precursor) It is obtained by drying and forming) heated and hardened.

If the polyimide resin is photosensitive, a patterned resin film (patterned resin film) can be easily formed. By heat curing this patterned resin film, A pattern hardened film (patterned hardened film) can be easily formed.

Now, as a precursor of polyimide, it is known to react an aromatic tetracarboxylic dianhydride with an olefin unsaturated alcohol to synthesize an olefin aromatic tetracarboxylic acid diester, by dehydration condensation using carbodiimides The reaction polymerizes the compound with a diamine, and introduces a photosensitive polyimide precursor through a covalent bond (for example, refer to Patent Document 1).

In addition, a polyimide precursor obtained by bonding an isocyanate compound having a photosensitive group to a polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine (for example, refer to a patent) Literature 2).

These polyimide precursors can be used as a negative photosensitive resin composition. The negative photosensitive resin composition is applied on a substrate in a state of varnish dissolved in an organic solvent and dried. After the film is formed, the exposed portion is irradiated with ultraviolet rays to photocure the exposed portion. An unexposed portion other than the exposed portion is developed and rinsed using an organic solvent, thereby obtaining a concave-convex pattern.

However, in the negative photosensitive resin composition containing the polyimide precursor, difunctional di (meth) acrylate compounds (for example, Refer to Patent Document 2 to Patent Document 5).

The cured film using polyimide resin has increased stress after curing due to thickening and high elastic modulus, and the warpage of semiconductor wafers has become large, which may cause defects during transportation or wafer fixing. Expect to develop hardened films with low stress.

As a method of making the polyimide resin low stress, for example, a method using a polyamide obtained by copolymerizing and condensing a tetracarboxylic acid compound and a phthalic acid compound having a specific functional group (for example, refer to Patent Document 6) .

In addition, with regard to the heat-hardening temperature of the polyimide precursor, the requirement for low-temperature hardening becomes higher. If it is previously, the heat-hardening of the polyimide precursor is performed at a high temperature of about 370 ° C, but a temperature of 300 ° C or less is required. Heat curing (for example, refer to Patent Document 7).

[Prior Art Literature]

[Patent Literature]

[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 Literature 6] International Publication No. 2006/008991

[Patent Document 7] International Publication No. 2009/060380

In the technical field, if it is not a (meth) acrylate compound having more than two functions, cross-linking reaction between polymer chains does not proceed, and it becomes insoluble in an organic solvent used as a developer.

However, as a result of research by the present inventors and others, it has been found that when a monofunctional (meth) acrylate compound is used, it has the same photosensitive characteristics as when a dimethic (meth) acrylate compound or more is used. Photosensitive resin composition and cured film.

The object of the present invention is to provide a novel precursor containing polyimide Resin composition and method of manufacturing a cured film using the same.

The present invention provides the following resin composition, method for producing a cured film using the same, and the like.

1. A resin composition comprising the following components (a), (b) and (c):

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

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

(c) Compounds that generate free radicals by irradiation with actinic rays

(In the formula, 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 base)

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

2. The resin composition according to 1, wherein the resin composition contains 1 to 100 parts by mass of the (b) component relative to 100 parts by mass of the (a) component.

3. The resin composition according to 1 or 2, wherein R ⁶ in the formula (2) is a monovalent organic group that does not contain a (meth) acryloyl group, a hydroxyl group, and an amine group.

4. The resin composition according to any one of 1 to 3, wherein the component (b) is a monofunctional photopolymerizable compound having a molecular weight of 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 a tetravalent organic group represented by the following general formula (2a) to general formula (2e) Any of:

(In 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 they are bound; in the general formula (2e), Z is an ether bond (-O-) or Thioether 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 general formula (6) :

(In the formula, R ¹⁰ to R ¹⁷ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, 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 halogenated alkyl).

8. The resin composition according to any one of 1 to 7, wherein the component (c) is an oxime ester compound.

9. A cured film formed from the resin composition according to any one of 1 to 8.

10. A method for producing a cured film, comprising: a step of applying the resin composition according to any one of 1 to 8 to a substrate and drying to form a coating film; and a step of subjecting the coating film to heat treatment.

11. A pattern hardened film comprising the resin group according to any one of 1 to 8. Formed into something.

12. A method for manufacturing a pattern-cured film, comprising: a step of applying the resin composition according to any one of 1 to 8 to a substrate and drying to form a coating film; irradiating the coating film with actinic light After irradiation, a step of developing to obtain a patterned resin film; a step of performing heat treatment on the patterned resin film.

13. An electronic component comprising the hardened film according to 9 or the patterned hard film according to 11.

The present invention can provide a novel resin composition containing a polyimide precursor and a method for producing a cured film using the same.

1‧‧‧Interlayer insulating layer / Interlayer insulating film

2‧‧‧Al wiring layer / wiring layer

3‧‧‧Insulation layer / insulation film

4‧‧‧Surface protective layer / surface protective film

5‧‧‧Pad pad

6‧‧‧Rewiring layer

7‧‧‧ conductive ball

8‧‧‧core

9‧‧‧Surface coating layer

10‧‧‧ Barrier metal

11‧‧‧collar

12‧‧‧underfill

1 is a schematic cross-sectional view of an embodiment of a semiconductor device using the resin composition of the present invention.

FIG. 2 (a) is a gas chromatogram when thermal decomposition gas chromatography mass spectrometry was performed on the cured film obtained in Example 10. FIG. FIG. 2 (b) is a gas chromatogram when thermal decomposition gas chromatography mass spectrometry is performed on the cured film obtained in Comparative Example 2. FIG.

FIG. 3 (a) is a diagram for measuring outgassing from the cured film of Comparative Example 2 using heating-generated gas mass spectrometry. FIG. 3 (b) is a diagram for measuring outgassing from the cured film of Example 1 using mass spectrometry analysis of gas generated by heating.

Hereinafter, the resin composition of the present invention, a cured film using the resin composition, a method of manufacturing the cured film, and the like, and embodiments of electronic parts will be described in detail. again In the present invention, methacrylate and acrylate are collectively referred to as "(meth) acrylate". Furthermore, methacryloyl and acryloyl are also collectively referred to as "(meth) acryloyl". Methacryloyloxy and acryloyloxy are also referred to as "(meth) acryloyloxy". In addition, the numerical range indicated using "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

<Resin composition>

The resin composition of the present invention contains the following components (a), (b) and (c).

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

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

(c) Compounds that generate free radicals by irradiation with actinic rays

(In the formula, 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 base)

[化 6]

(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 that does not contain a (meth) acryloyl group)

The component (b) of the resin composition of the present invention is a crosslinking agent. In the present invention, the pattern-cured film is obtained by using the above-mentioned configuration without using a multifunctional (meth) acrylate compound. This can suppress outgas generated during the hardening reaction.

In addition to the above, if the heating and curing temperature becomes a low temperature of 300 ° C. or lower, outgassing from the polyimide film increases in a vacuum process such as etching of the electrode portion after the polyimide cured film formation process, due to There is a problem of the chamber being contaminated due to the generation of outgassing. (b) If the component is a monofunctional photopolymerizable compound having a molecular weight of 300 or less represented by formula (2), even if it is a cured film that is cured at a low temperature of 300 ° C. or less, it can suppress The resulting outgassing results in a hardened film with low stress.

(a) Component: Polyimide precursor having a structural unit represented by general formula (1)

The resin composition of the present invention contains (a) a polyimide precursor having a structural unit represented by the following general formula (1).

[化 7]

(In the formula, 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 base)

The resin composition of the present invention can exhibit high i-ray transmittance. Specifically, in a film thickness of 20 μm, the i-ray transmittance is preferably 1% or more, more preferably 10% or more, and still more preferably 15% or more. If it is less than 1%, the i-ray does not reach the deep part, and radicals are not sufficiently generated. Therefore, there is a possibility that the photosensitive characteristics such as resin bleed out from the substrate side of the film during development may deteriorate.

In addition, the i-ray transmittance can be measured by measuring a transmission ultraviolet (UV) spectrum using a U-3310 spectrophotometer (manufactured by Hitachi, Ltd.).

R ¹ in the general formula (1) is a structure derived from, for example, tetracarboxylic dianhydride used as a raw material. The tetracarboxylic dianhydride used is not particularly limited, and from the viewpoint of excellent heat resistance in electronic parts, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid are preferred Acid dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'- Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ash tetracarboxylic dianhydride, 1 , 2,5,6-Naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic 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-2,2'-bis {4- (3,4-dicarboxyphenoxy) phenyl } Propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyl diphthalic dianhydride and other aromatic tetracarboxylic dianhydrides. These can be used alone or in combination of two or more.

As the tetravalent organic group in R ¹ , any of the tetravalent organic groups represented by the following general formula (2a) to general formula (2e) is preferable.

(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 bonded to each. In the general formula (2e), Z is an ether bond (-O-) Or sulfide bond (-S-))

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

[化 9]

(In the formula, R ⁸ is a carbon atom or a silicon atom. R ^{9 is} 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)

Furthermore, R ² in the general formula (1) is a structure derived from, for example, a diamine used as a raw material.

The diamine used in the present invention is not particularly limited, and examples thereof include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl. Phenylbenzene, 4,4'-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4- Aminophenoxyphenyl) phenanthrene, bis (3-aminophenoxyphenyl) phenanthrene, bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) Phenyl] ether, 1,4-bis (4-aminophenoxy) benzene and other diamines with aromatic rings, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5 -Hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4 -Hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl), bis (4-amino-3-hydroxyphenyl) Diamines with hydroxyl and aromatic rings, such as benzene, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,5-di Aminobenzoic 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, 4,4'-diamino-5,5'-dicarboxy-2,2 '-Dimethylbiphenyl and other diamines with carboxyl groups and aromatic rings These can be used alone or in combination of two or more.

The divalent organic group in R ² is preferably a divalent organic group represented by the following general formula (5) or general formula (6).

In the formula, 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 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 (such as a methyl group), a halogenated alkyl group having 1 to 20 carbon atoms (such as a trifluoromethyl group), and 1 to 1 carbon atoms. 20 alkoxy (methoxy, etc.).

The halogen atom is preferably a fluorine atom.

The halogenated alkyl group is preferably a perfluoroalkyl group.

The carbon number of the alkyl group and the halogenated alkyl group is preferably 1 to 6.

For example, R ³ and R ⁴ in the general formula (1) each independently include a hydrogen atom and a carbon number of 1 to 20 (preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 6) The alkyl group, the carbon number of 3-20 (preferably the carbon number is 5-15, more preferably the carbon number is 6-12), the cycloalkyl group or the hydrocarbon group has the carbon number 1-10 (preferably (Meth) acryloxy-containing hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group containing (meth) acryloyloxy is preferably an alkyl group containing (meth) acryloyloxy.

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

Examples of the hydrocarbon group having a carbon number of 1 to 10 and containing (meth) acryloyloxy group include acryloxyethyl group, acryloxypropyl group, acryloxybutyl group, and methacryloxyethyl group Group, methacryloyloxypropyl, methacryloyloxybutyl, etc.

The resin composition of the present invention preferably has at least one of R ³ and R ⁴ having a carbon-carbon unsaturated double bond like (meth) acryloyloxyalkyl, and generating free radicals by irradiation with actinic rays The combination of compounds can cross-link between molecular chains of free radical polymerization.

(a) The component can be synthesized by addition polymerization of tetracarboxylic dianhydride and diamine. Furthermore, it can be synthesized by the following method: after the tetracarboxylic dianhydride represented by formula (10) is converted to a diester derivative, it is converted to the acetyl chloride represented by formula (11), and the formula (12) The indicated diamine reaction. These synthesis methods can be selected from known methods.

(Here, R ¹ ~ R ^{4 are the} same as formula (1))

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

[Chem 12] R ²² -OH (13)

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

In the presence of a double amount of the basic compound relative to the chlorinating agent, a chlorinating agent which is usually 2 molar equivalents to 1 molar of tetracarboxylic acid mono (di) ester is reacted and carried out However, in order to control the molecular weight of the synthesized polyimide precursor, the equivalent weight can also be adjusted appropriately. The equivalent of the chlorinating agent is preferably 1.5 molar equivalent to 2.5 molar equivalent, more preferably 1.6 molar equivalent to 2.4 molar equivalent, and even more preferably 1.7 molar equivalent to 2.3 molar equivalent. In the case of less than 1.5 molar equivalents, the molecular weight of the polyimide precursor is low, so there is a possibility that the low stress after hardening may not be fully exhibited; in the case of more than 2.5 molar equivalents, then There is a large amount of hydrochloride of the basic compound remaining in the polyimide precursor, and the electrical insulation of the hardened polyimide may decrease.

As the basic compound, for example, pyridine, 4-dimethylaminopyridine, triethylamine can be used For the chlorinating agent, 1.5 times to 2.5 times the amount is preferred, 1.7 times to 2.4 times the amount is more preferred, and 1.8 times to 2.3 times the amount is more preferred. If the amount is less than 1.5 times, the molecular weight of the polyimide precursor may become low, and the stress after curing may not be sufficiently reduced; if the amount is more than 2.5 times, the polyimide precursor may be colored.

Moreover, the tetracarboxylic dianhydride and the compound of the general formula (13) can also be reacted in the presence of an alkaline catalyst. Examples of the basic catalyst include 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene.

Among the compounds represented by the general formula (13), the 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 are (meth) acryloyloxyalkyl groups having 1 to 10 carbon atoms in the alkyl group.

Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tertiary butanol, hexanol, cyclohexanol, 2-hydroxyethyl acrylate, methacrylic acid- 2-hydroxyethyl, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc. These can be used alone or in combination of two or more.

The weight average molecular weight of the polyimide precursor is preferably 10,000 to 100,000, more preferably 15,000 to 100,000, and even more preferably 20,000 to 85,000. From the viewpoint of sufficiently reducing the stress after hardening, the weight average molecular weight is preferably 10,000 or more. Self-improving solubility in solvents, preventing stickiness of solutions From the viewpoint of increasing the degree and reducing the operability, it is preferably 100,000 or less. In addition, the weight average molecular weight can be determined by measuring by gel permeation chromatography and converting using a standard polystyrene calibration curve.

The molar ratio of tetracarboxylic dianhydride to diamine when synthesizing a polyimide precursor is usually carried out at 1.0, and it can also be controlled at a molar ratio of 0.7 to 1.3 for the purpose of controlling molecular weight or terminal residue get on. When the molar ratio is 0.7 or less or 1.3 or more, the molecular weight of the obtained polyimide precursor becomes small, and the low stress after hardening may not be sufficiently exhibited.

The addition polymerization and condensation reaction, as well as the synthesis of diester derivatives and acetyl chloride are preferably carried out in an organic solvent. The organic solvent used is preferably a polar solvent that completely dissolves the synthesized polyimide precursor, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric acid triamine, γ-butyrolactone, etc.

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

(b) Component: the compound represented by the general formula (2)

From the viewpoint of self-negative pattern formability, the resin composition of the present invention contains the compound represented by the following general formula (2) as the component (b). (b) The component reacts with (b) components by unsaturated radicals generated by irradiation of actinic rays, or with the unsaturated double bond of (a) component.

[Chem 13]

(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 that does not contain a (meth) acryloyl group)

R ⁶ in the formula (2) is preferably a monovalent organic group that does not contain a (meth) acryloyl group, a hydroxyl group, or an amine group.

Examples of the monovalent organic group free of (meth) acryloyl group in R ⁶ include a group having a piperidine skeleton, a substituted or unsubstituted aminoalkyl group, a group having a polycyclic hydrocarbon group, and an aromatic hydrocarbon group Group, group having a nitrogen-containing heterocyclic group, linear or branched alkyl polyethylene glycol residue, cyclic alkyl polyethylene glycol residue, substituted or unsubstituted phenyl polyethylene Diol residues, etc.

The compound represented by the general formula (2) can be used without particular limitation, and examples thereof include 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 , (Piperidin-4-yl) methyl (meth) acrylate, 2- (piperidin-4-yl) ethyl (meth) acrylate and other (meth) acrylates containing a piperidine skeleton; ( Aminoethyl meth) acrylate, -N-methylaminoethyl (meth) acrylate, -N, N-dimethylaminoethyl (meth) acrylate, -N- (meth) acrylic acid Ethylaminoethyl, (meth) acrylic acid-N, N-diethylaminoethyl, (meth) acrylic acid aminopropyl ester, (meth) acrylic acid-N-methylaminopropyl ester, (Meth) acrylic acid-N, N-dimethylaminopropyl ester, (Meth) acrylic acid-N-ethylaminopropyl ester, (meth) acrylic acid-N, N-diethylaminopropyl ester and other substituted or unsubstituted (meth) acrylic acid aminoalkyl ester ; (Norborneanyl (meth) acrylate), norbornanyl (meth) acrylate, (meth) acrylic acid, norbornanyl (meth) acrylate, (meth) acrylic acid ) Dicyclopentenyloxyethyl acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, tricyclodecane dimethylol (meth) acrylate, etc. (Meth) acrylates containing polycyclic hydrocarbon groups; (meth) acrylates containing aromatic hydrocarbon groups such as benzyl (meth) acrylate; (meth) acrylic acid-2- (1,2-cyclohexylcarboxyl amide) (Meth) acrylates containing nitrogen-containing heterocyclic groups such as imine) ethyl; 2-ethylhexyl polyethylene glycol mono (meth) acrylate, pentyl polyethylene glycol mono (meth) acrylic acid Ester, isoamyl polyethylene glycol mono (meth) acrylate, neopentyl polyethylene glycol mono (meth) acrylate, hexyl polyethylene glycol mono (meth) acrylate, heptyl polyethylene Alcohol mono (meth) acrylate, octyl polyethylene glycol (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, ten Pentaalkyl polyethylene glycol mono (meth) acrylate, cetyl polyethylene glycol mono (meth) acrylate, heptadecyl polyethylene glycol mono (meth) acrylate, octadecane Straight-chain or branched-chain polyethylene glycol mono (meth) acrylate, nonadecyl polyethylene glycol mono (meth) acrylate, eicosyl polyethylene glycol mono (meth) acrylate Alkyl polyglycol mono (meth) acrylate; Cyclopropyl polyethylene glycol mono (meth) acrylate, cyclobutyl polyethylene glycol mono (meth) acrylate, cyclopentyl polyethylene glycol mono (meth) acrylate, cyclohexyl polyethylene glycol Alcohol mono (meth) acrylate, cycloheptyl polyethylene glycol mono (meth) acrylate, cyclooctyl polyethylene glycol mono (meth) acrylate, cyclononyl polyethylene glycol mono (meth) acrylate ) Cyclic alkyl polyethylene glycol mono (meth) acrylates such as acrylates, cyclodecyl polyethylene glycol mono (meth) acrylates; and substituted nonylphenoxy polyethylene glycol acrylates etc. Or unsubstituted phenyl polyethylene glycol mono (meth) acrylate. These can be used individually or in combination of 2 or more types.

In terms of excellent photohardenability, these are more preferably linear or branched alkyl polyethylene glycol mono (meth) acrylates, (meth) acrylates containing aromatic hydrocarbon groups, containing (Meth) acrylate of polycyclic hydrocarbon group, (meth) acrylate containing nitrogen-containing heterocyclic group, and substituted or unsubstituted phenyl polyethylene glycol mono (meth) acrylate, nonyl Phenoxy polyethylene glycol (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, benzyl (meth) acrylate or (meth) Group) 2- (1,2-cyclohexylcarboxyimide) ethyl acrylate.

Furthermore, the component (b) can also be used in combination with a vinyl-containing compound such as vinyl norbornene and vinyl norbornane.

Among the above, from the viewpoint of suppressing outgassing from the cured film, it is preferable to use a compound having a molecular weight of 300 or less. In more detail, the range of 100 to 300 is preferred, the range of 110 to 300 is more preferred, the range of 120 to 280 is further preferred, the range of 130 to 260 is particularly preferred, and the most preferred is 150 ~ 255 Scope.

From the viewpoint of excellent photocurability, among these, those having a molecular weight of 300 or less and linear hydrocarbons containing an aromatic hydrocarbon group in a linear or branched alkyl polyethylene glycol mono (meth) acrylate are preferred ( Methacrylates, (meth) acrylates containing polycyclic hydrocarbon groups, (meth) acrylates containing nitrogen-containing heterocyclic groups, and substituted or unsubstituted phenyl polyethylene glycol mono ( The molecular weight of the meth) acrylate is 300 or less, more preferably the molecular weight of the nonylphenoxy polyethylene glycol (meth) acrylate is 300 or less, dicyclopentenyl (meth) acrylate Oxyethyl ester, dicyclopentyl (meth) acrylate, benzyl (meth) acrylate or 2- (1,2-cyclohexylcarboxyimide) ethyl (meth) acrylate.

Specifically, for example, preferred is dicyclopentenyloxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, benzyl (meth) acrylate, or (meth) acrylic acid-2- (1,2-cyclohexylcarboxylimide) ethyl ester, preferably 2- (1,2-cyclohexylcarboxylimide) ethyl acrylate.

(b) The component preferably contains 1 to 100 parts by mass relative to (a) 100 parts by mass of the component, more preferably contains 3 to 80 parts by mass, and even more preferably contains 5 parts by mass ~ 50 parts by mass, particularly preferably contains 5 to 25 parts by mass, and extremely preferably contains 5 to 15 parts by mass.

The blending amount when other crosslinking agent is contained is preferably 1 part by mass to 100 parts by mass relative to 100 parts by mass of (a) component, more preferably 2 parts by mass to 75 parts by mass, further More preferably, it is 3 to 50 parts by mass, and particularly preferably 5 to 30 parts by mass. If the blending amount is 1 part by mass or more, good photosensitive characteristics can be imparted.

(c) Ingredient: a compound that generates free radicals by irradiating actinic rays

When at least a part of R ³ and / or R ⁴ in the polyimide precursor of the component (a) is a monovalent organic group having a carbon-carbon unsaturated double bond, if and if actinic rays are irradiated, Compounds that generate free radicals are used together and dissolved in a solvent to make a photosensitive resin composition.

(c) Components include N, N 'such as oxime ester compounds, benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) described later -Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2- Aromatic ketones such as methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-acetone-1, quinones condensed with aromatic rings such as alkylanthraquinone, benzoin alkyl ethers, etc. Benzoin ether compounds, benzoin compounds such as benzoin and alkyl benzoin, and benzoyl derivatives such as benzoyl dimethyl ketal.

In order to provide excellent sensitivity and provide good patterns, the oxime ester compound is preferred among these.

From the viewpoint of obtaining good sensitivity and residual film ratio, the oxime ester compound is preferably 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) The indicated compound.

[化 14]

In formula (7), R and R ₁ respectively 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, preferably one having 1 to 8 carbon atoms Alkyl, cycloalkyl having 4 to 6 carbons, phenyl or tolyl, more preferably alkyl having 1 to 4 carbons, cycloalkyl having 4 to 6 carbons, phenyl or tolyl , Even more preferably methyl, cyclopentyl, phenyl or tolyl.

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, preferably Hydrogen atom, -O (CH ₂ ) OH, -O (CH ₂ ) ₂ OH, -COO (CH ₂ ) OH or -COO (CH ₂ ) ₂ OH, more preferably hydrogen atom, -O (CH ₂ ) ₂ OH or -COO (CH ₂ ) ₂ OH. In addition, the aromatic ring may have a substituent other than R ₂ .

In formula (8), R ₃ independently represents an alkyl group having 1 to 6 carbon atoms, preferably a propyl group.

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

R ₅ and R ₆ each represent an alkyl group having 1 to 12 carbons, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group.

In addition, the aromatic ring may have a substituent other than R ₄ .

In formula (9), R ₇ represents an alkyl group having 1 to 6 carbon atoms, preferably ethyl.

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

R ₉ and R ₁₀ each represent an alkyl group having 1 to 12 carbons, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group.

In addition, the aromatic ring may have a substituent other than R ₈ .

Examples of the compound represented by the formula (7) include compounds represented by the following formula (7-1) and compounds represented by the following formula (7-2). The compound represented by the following formula (7-1) can be used as IRGACURE OXE-01 (BASF) Co., Ltd. made, trade name).

Examples of the compound represented by the formula (8) include compounds represented by the following formula (8-1). This compound is available as DFI-091 (made by Daito Chemix Co., Ltd., trade name).

[Chem 19]

Examples of the compound represented by the formula (9) include compounds represented by the following formula (9-1). It can be obtained as Adeka Optomer N-1919 (made by ADEKA Corporation, trade name).

As other oxime ester compounds, the following compounds are preferably used.

Moreover, the following compound can also be used for (c) component.

(c) The content of the component is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the (a) component, more preferably 0.03 to 20 parts by mass, and even more preferably 0.05 parts by mass ~ 15 parts by mass, especially 0.5 ~ 10 parts by mass. If the blending amount is 0.01 parts by mass or more, the exposed portion is sufficiently cross-linked, and the photosensitive characteristics are further improved. If it is 30 parts by mass or less, the heat resistance of the cured film tends to be further improved.

(d) Ingredient (adhesion aid): organosilane compound

In the resin composition of the present invention, in order to improve the adhesion to a silicon substrate or the like after curing, an organic silane compound may be included as the component (d). Examples of organic silane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-glycidoxypropane Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-propenyloxypropyltrimethoxysilane, 3- Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, triethoxysilane Propylethylamine formate, 3- (triethoxysilyl) propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, 3-triethoxysilane-N- (1,3-dimethylbutylene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 1-isocyanatomethyltrimethylsilane, 1-isocyanatomethyltriethylsilane, 1-isocyanatomethyltripropylsilane, 1-isocyanatomethyltributyl Silane, 1-isocyanatomethyltrimethoxysilane, 1-isocyanatomethyldimethoxymethylsilane, 1-isocyanatomethylmethoxydimethylsilane, 1- Isocyanatomethyltriethoxysilane, 1-isocyanatomethyltripropoxysilane, 1-isocyanatomethyltributoxysilane, 1-isocyanatomethyldiethyl Oxyethylsilane, 3-isocyanatopropyltrimethylsilane, 3-isocyanatopropyltriethylsilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanic acid Propylpropyldimethoxymethylsilane, 3-isocyanatopropylmethoxydimethylsilane, 3-isocyanatopropyltriethoxysilane, 3-iso Cyanopropyl diethoxyethylsilane, 3-isocyanatopropylethoxydiethylsilane, 6-isocyanatohexyltrimethoxysilane, 6-isocyanatohexyldimethyl Oxymethylmethylsilane, 6-isocyanatohexylmethoxydimethylsilane, 6-isocyanatohexyltriethoxysilane, 6-isocyanatohexyldiethoxyethylsilane, 6 -Isocyanatohexylethoxydiethylsilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, N- (hydroxymethyl) -N-methylaminopropyltrimethoxysilane, 7-triethoxysilylpropoxy-5 -Hydroxyflavonoids, N- (3-triethoxysilylpropyl) -4-hydroxybutyramide, 2-hydroxy-4- (3-methyldiethoxysilylpropoxy) diphenyl Ketone, 1,3-bis (4-hydroxybutyl) tetramethyldisilaxane, 3- (N-acetyl-4-hydroxypropoxy) propyltriethoxysilane, hydroxymethyltrisiloxane B Oxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, triethoxysilylpropylethylcarbamate, N- (3-triethoxysilane Propyl) -O-third butyl carbamate and the like. The adjustment amount is adjusted in such a way that the desired effect can be obtained.

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

(e) Ingredient: solvent

In the resin composition of the present invention, a solvent may be used as the component (e) if necessary.

(e) The component is preferably a polar solvent that completely dissolves the polyimide precursor, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-di Methylformamide, dimethylsulfoxide, tetramethylurea, triamine hexamethylphosphate, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, Propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone. These can be used alone or in combination of two or more.

(e) The content of the component is not particularly limited. Generally, it is preferably 50 parts by mass to 1000 parts by mass relative to 100 parts by mass of the component (a), and more preferably 100 parts by mass to 500 parts by mass.

In addition, in order to ensure good storage stability in the resin composition of the present invention, a radical polymerization inhibitor or a radical polymerization inhibitor may be blended. Examples of the radical polymerization inhibitor or radical polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, O-Dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, Cupferron, 2,5-toluquinone, tannic acid, p-benzylaminophenol, nitrosoamines, etc. These can be used alone or in combination of two or more.

As the compounding amount when a radical polymerization inhibitor or a radical polymerization inhibitor is contained, it is preferably 0.01 parts by mass to 30 parts by mass relative to 100 parts by mass of the polyimide precursor, and more preferably 0.01 parts by mass Parts to 10 parts by mass, further preferably 0.05 parts by mass to 5 parts by mass. If the blending amount is 0.01 parts by mass or more, the storage stability is further improved; if it is 30 parts by mass or less, the heat resistance of the cured film is further improved.

The resin composition of the present invention may contain a bifunctional or higher photopolymerizable compound within a range that does not hinder the effects of the present invention. Examples of the photopolymerizable compound having more than two functions include tetraethylene glycol dimethacrylate and the like.

As the compounding amount when containing a difunctional or more photopolymerizable compound, it is preferably 1 part by mass to 10 parts by mass relative to 100 parts by mass of the polyimide precursor, and more preferably 1 part by mass to 8 parts The parts by mass, further preferably 1 part by mass to 5 parts by mass.

In addition, the resin composition of the present invention may include at least one of the components (a) to (c) and any of the components (d), (e), a radical polymerization inhibitor and a radical polymerization inhibitor It is substantially formed and may contain only these components. The “substantially formed” means that the component is 95% by mass or more or 98% by mass or more with respect to the entire composition.

<Manufacturing method of cured film and patterned cured film>

The cured film of the present invention is formed of the above resin composition.

Furthermore, the pattern-cured film of the present invention is a pattern-cured film formed from the resin composition.

The method for manufacturing a pattern-cured film of the present invention includes the steps of applying the above resin composition on a substrate and drying to form a coating film; irradiating the coating film formed by the above steps with actinic rays and then developing The step of obtaining a patterned resin film; the step of performing heat treatment on the patterned resin film.

Hereinafter, each step of the method for manufacturing the pattern cured film will be described first.

The method for producing a pattern cured film of the present invention includes the steps of applying the above resin composition on a substrate and drying to form a coating film. Examples of the method of applying the resin composition to the substrate include a dipping method, a spray method, a screen printing method, and a spin coating method. Examples of the base material include silicon wafers, metal substrates, and ceramic substrates.

In the drying step, the solvent is removed by heating, thereby forming a non-adhesive coating film. For the drying step, a device such as DATAPLATE (Digital Hotplate) manufactured by PMC Co., Ltd. can be used. The drying temperature is preferably 90 ° C to 130 ° C, and the drying time is preferably 100 seconds to 400 seconds.

The method for manufacturing a pattern cured film of the present invention includes a step of obtaining a patterned resin film by irradiating the coating film formed by the above steps with actinic rays and then developing it. Thereby, a resin film formed with a desired pattern can be obtained.

The resin composition of the present invention is suitable for i-ray exposure, and as actinic rays irradiated, ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays can be used Wait.

The developer is not particularly limited, and flame retardant solvents such as 1,1,1-trichloroethane, alkaline aqueous solutions such as sodium carbonate aqueous solution and tetramethylammonium hydroxide aqueous solution, and N, N-dimethylformamide can be used. Good solvents such as amine, dimethyl sulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc. Mixed solvents of solvents and poor solvents such as lower alcohols, water, aromatic hydrocarbons, etc. After development, if necessary, rinse with a poor solvent.

The method for manufacturing a pattern cured film of the present invention includes a step of subjecting a pattern resin film to heat treatment.

The heat treatment may use a device such as a vertical diffusion furnace manufactured by Koyo Lindberg, preferably at a heating temperature of 80 ° C to 400 ° C, and the heating time is preferably 5 minutes to 300 minutes. By this step, the polyimide precursor in the resin composition is subjected to imidization to obtain a pattern-cured film containing the polyimide resin.

In addition, the heating temperature is more preferably 250 ° C to 300 ° C, and even more preferably 260 ° C to 290 ° C. Moreover, the heating time is more preferably 120 minutes to 280 minutes, and even more preferably 180 minutes to 270 minutes.

The method for producing a cured film of the present invention includes: a step of applying a resin composition on a substrate and drying to form a coating film; and a step of heating the coating film. The step of forming a coating film and the step of performing heat treatment may be the same as the method of manufacturing the pattern-cured film. The cured film of the present invention may be a patterned cured film.

The cured film or patterned cured film of the present invention obtained as described above can be used as It is used for surface protection layers, interlayer insulating layers, redistribution layers, etc. of semiconductor devices.

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 A1 wiring layer 2 is formed on the interlayer insulating layer (interlayer insulating film) 1, an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed on the upper part, and a surface protective layer (surface protective film) 4 of the device is further formed . The redistribution layer 6 is formed from the pad portion 5 of the wiring layer 2 and extends to the upper portion of the core 8 of the connection portion of the conductive ball 7 formed of solder, gold, or the like as an external connection terminal. Further, a surface coating layer 9 is formed on the surface protective layer 4. The redistribution layer 6 is connected to the conductive ball 7 via the barrier metal 10, and a collar 11 is provided to hold the conductive ball 7. When installing a package of this structure, in order to further relax the stress, the underfill 12 may be used.

The cured film or patterned cured film of the present invention can be used in so-called packaging applications such as the surface coating layer 9, the core 8 for rewiring, the ball collar 11 for solder, and the underfill 12.

The cured film or patterned cured film of the present invention has excellent adhesion to a metal layer, a sealant, etc., and is excellent in copper migration resistance, and also has a high stress relaxation effect. Therefore, a semiconductor element including the cured film or patterned cured film of the present invention Reliability becomes excellent.

The electronic component of the present invention includes a surface coating using the cured film or patterned cured film of the present invention, a ball collar for rewiring, solder, etc., an underfill used in a flip chip, etc., and There are no special restrictions, and various structures can be used.

[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these.

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

In a 0.5-liter plastic bottle, pyromellitic dianhydride 43.624g (200mmol), 2-hydroxyethyl methacrylate 54.919g (401mmol) and p-benzene, dried in a 160 ° C dryer for 24 hours 0.220 g of diphenol was dissolved in 394 g of N-methylpyrrolidone, and after adding a catalyst amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25 ° C.) for 24 hours to perform esterification. The pyromellitic acid-hydroxyethyl methacrylate diester (PMDA (HEMA)) solution was obtained.

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

In a 0.5 liter plastic bottle, 30.893g (105mmol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and methacrylic acid-2- 28.833g (210mmol) of hydroxyethyl ester and 0.110g of hydroquinone were dissolved in 239g of N-methylpyrrolidone, after adding a catalyst amount of 1,8-diazabicycloundecene, at room temperature ( 25 ° C) After stirring for 24 hours, esterification was performed to obtain a 3,3 ', 4,4'-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester (s-BPDA (HEMA)) solution.

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

In a 0.5-liter plastic bottle, 49.634g (160mmol) of 4,4'-oxydiphthalic acid and 44.976g of 2-hydroxyethyl methacrylate were dried in a 160 ° C dryer for 24 hours. 328mmol) and hydroquinone 0.176g dissolved in N-methyl To 378 g of pyrrolidone, after adding 1,8-diazabicycloundecene in a catalyst amount, stirring was carried out at room temperature (25 ° C) for 48 hours to perform esterification to obtain 4,4′-oxodiane Phthalic acid-hydroxyethyl methacrylate diester (ODPA (HEMA)) solution.

Synthesis Example 4 (Synthesis of Polymer 1)

In a 0.5 liter flask equipped with a stirrer and a thermometer, put 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, and then use dropwise addition under ice cooling In the funnel, 25.9 g (217.8 mmol) of thionyl chloride was added dropwise to maintain the temperature of the reaction solution at 10 ° C. or lower. After the dropwise addition of thionyl chloride, the reaction was carried out under ice cooling for 2 hours to obtain a solution of PMDA (HEMA) and ODPA (HEMA) in acetyl chloride. Secondly, using a dropping funnel under ice cooling, pay attention to the temperature of the reaction solution does not exceed 10 ℃ while adding 2,2'-bis (trifluoromethyl) benzidine 31.696g (99.0mmol), pyridine 34.457g (435.6mmol ), Hydroquinone 0.076g (0.693mmol) N-methylpyrrolidone 90.211g solution. The reaction liquid was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure, thereby obtaining a polyamide. The weight average molecular weight calculated by standard polystyrene conversion was 34,000. It is used as polymer 1 (pyromellitic acid-hydroxyethyl methacrylate diester / 4,4'-oxydiphthalic acid-hydroxyethyl methacrylate diester / 2,2'-bis (tri Fluoromethyl) benzidine polycondensate (PMDA / ODPA / TFMB)). 1 g of polymer 1 was dissolved in 1.5 g of N-methylpyrrolidone, applied on a glass substrate by spin coating, and heated on a 100 ° C. hot plate for 180 seconds to volatilize the solvent to form a thickness It is a 20μm coating film. At this time, the i-ray transmittance of the obtained coating film was 30%.

Synthesis Example 5 (Synthesis of Polymer 2)

282.125g of the s-BPDA (HEMA) solution obtained in Synthesis Example 2 was placed in a 0.5-liter flask equipped with a stirrer and a thermometer, and thereafter, a dropping funnel was used to keep the temperature of the reaction solution below 10 ° C under ice cooling 25.9 g (217.8 mmol) of thionyl chloride was added dropwise. After the dropwise addition of thionyl chloride was completed, stirring was carried out for 1 hour under ice cooling to obtain a solution of s-BPDA (HEMA) chloride. Secondly, using a dropping funnel under ice cooling, pay attention to the temperature of the reaction solution does not exceed 10 ℃ while adding 2,2'-bis (trifluoromethyl) benzidine 31.696g (99.0mmol), pyridine 34.457g (435.6mmol ), Hydroquinone 0.076g (0.693mmol) N-methylpyrrolidone 90.211g solution. The reaction liquid was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure, thereby obtaining a polyamide. The weight average molecular weight calculated by standard polystyrene conversion was 85,000. It is used as polymer 2 (3,3 ', 4,4'-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester / 2,2'-bis (trifluoromethyl) benzidine polycondensate (BPDA / TFMB)). 1 g of polymer 2 was dissolved in 1.5 g of N-methylpyrrolidone, applied on a glass substrate by spin coating, and heated on a 100 ° C. hot plate for 180 seconds to volatilize the solvent to form a thickness It is a 20μm coating film. At this time, the i-ray transmittance of the obtained coating film was 60%.

Synthesis Example 6 (Synthesis of Polymer 3)

244.455 g of the PMDA (HEMA) solution obtained in Synthesis Example 1 was placed in a 0.5-liter flask equipped with a stirrer and a thermometer, and then dropped under ice cooling using a dropping funnel to keep the temperature of the reaction solution at 10 ° C or lower Add 25.9 g (217.8 mmol) of thionyl chloride. After the dropwise addition of thionyl chloride, proceed under ice cooling for 1 hour Stirring, to obtain a solution of PMDA (HEMA) chloride. Secondly, using a dropping funnel under ice cooling, pay attention to the temperature of the reaction solution does not exceed 10 ℃ while adding 2,2'-bis (trifluoromethyl) benzidine 31.696g (99.0mmol), pyridine 34.457g (435.6mmol ), Hydroquinone 0.076g (0.693mmol) N-methylpyrrolidone 90.211g solution. The reaction liquid was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure, thereby obtaining a polyamide. The weight average molecular weight calculated by standard polystyrene conversion was 32,000. This was used as polymer 3 (pyromellitic acid-hydroxyethyl methacrylate diester / 2,2′-bis (trifluoromethyl) benzidine polycondensate (PMDA / TFMB)). 1 g of polymer 3 was dissolved in 1.5 g of N-methylpyrrolidone, applied on a glass substrate by spin coating, and heated on a 100 ° C. hot plate for 180 seconds to volatilize the solvent to form a thickness It is a 20μm coating film. At this time, the i-ray transmittance of the obtained coating film was 17%.

Synthesis Example 7 (Synthesis of Polymer 4)

169.275 g of the s-BPDA (HEMA) solution obtained in Synthesis Example 2 and 72.7776 g of the ODPA (HEMA) solution obtained in Synthesis Example 3 were placed in a 0.5-liter flask equipped with a stirrer and a thermometer, and then used under ice cooling The dropping funnel added 25.9 g (217.8 mmol) of thionyl chloride dropwise to maintain the temperature of the reaction solution at 10 ° C. or lower. After the dropwise addition of thionyl chloride was completed, stirring was performed for 1 hour under ice cooling to obtain a chloride solution of s-BPDA (HEMA) and ODPA (HEMA). Secondly, using a dropping funnel, under ice cooling, pay attention to the temperature of the reaction solution does not exceed 10 ℃ while adding 2,2'-dimethylbenzidine 21.017g (99.0mmol), pyridine 34.457g (435.6mmol), Resorcinol 0.076g (0.693mmol) N-A 59.817g of pyrrolidone. The reaction liquid was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure, thereby obtaining a polyamide. The weight average molecular weight calculated by standard polystyrene conversion was 35,000. It is used as polymer 4 (3,3 ', 4,4'-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester / 4,4'-oxydiphthalic acid-hydroxyethyl methacrylate Diester / 2,2'-dimethylbenzidine polycondensate (BPDA / ODPA / DMB)). 1 g of polymer 4 was dissolved in 1.5 g of N-methylpyrrolidone, applied on a glass substrate by spin coating, and heated on a 100 ° C. hot plate for 180 seconds to volatilize the solvent to form a thickness It is a 20μm coating film. At this time, the i-ray transmittance of the obtained coating film was 8%.

Synthesis Example 8 (Synthesis of Polymer 5)

181.944 g of the ODPA (HEMA) solution obtained in Synthesis Example 3 was placed in a 0.5-liter flask equipped with a stirrer and a thermometer, and then dropped under ice cooling using a dropping funnel to keep the temperature of the reaction solution at 10 ° C or lower Add 25.9 g (217.8 mmol) of thionyl chloride. After the dropwise addition of thionyl chloride, the mixture was stirred under ice cooling for 1 hour to obtain a solution of ODPA (HEMA) chloride. Secondly, using a dropping funnel under ice-cooling. Make sure that the temperature of the reaction solution does not exceed 10 ° C. While adding 2,2'-dimethylbenzidine 21.017g (99.0mmol), pyridine 34.457g (435.6mmol), p-benzene A solution of 0.076 g (0.693 mmol) of diphenol in N-methylpyrrolidone 59.817 g. The reaction liquid was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure, thereby obtaining a polyamide. The weight average molecular weight calculated by standard polystyrene conversion was 35,000. It is used as polymer 5 (4,4'-oxydiphthalic acid-hydroxyethyl methacrylate diester / 2,2'-dimethylbenzidine polycondensate (ODPA / DMB)). 1 g of polymer 5 was dissolved in 1.5 g of N-methylpyrrolidone, applied on a glass substrate by spin coating, and heated on a 100 ° C. hot plate for 180 seconds to volatilize the solvent to form a thickness It is a 20μm coating film. At this time, the i-ray transmittance of the obtained coating film was 40%.

The measurement conditions of the weight average molecular weight of the polymer 1 to the polymer 5 calculated by the standard polystyrene conversion of the GPC method are as follows, and the solvent [tetrahydrofuran (THF) / dimethyl) relative to 0.5 mg of the polymer is used. Formamide (DMF) = 1/1 (volume ratio)] was measured with a solution of 1 mL.

Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.

Pump: L6000 manufactured by Hitachi, Ltd.

C-R4A Chromatopac manufactured by Shimadzu Corporation

Measuring conditions: Gelpack GL-S300MDT-5 × 2

Dissolution solution: THF / DMF = 1/1 (volume ratio)

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

Flow rate: 1.0mL / min, detector: UV270nm

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

<Example 1 to Example 9, Comparative Example 1>

The components (a) to (c) and the adhesion aid were dissolved in N-methylpyrrolidone in the formulation shown in Table 1 to prepare a resin composition.

In Table 1, parentheses in the columns of (b) component, (c) component and adhesion aid The numbers inside indicate the added amount (parts by mass) relative to 100 parts by mass of the component (a). Furthermore, N-methylpyrrolidone was used as a solvent, and the amount of use was 1.5 times (150 parts by mass) relative to 100 parts by mass of the component (a).

In addition, in the examples, as the component (c), the following 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl oxime)] ( IRGACURE OXE-01 manufactured by BASF Corporation).

Furthermore, as the adhesion aid, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane (manufactured by Gelest Corporation, SIB-1140) was used.

Regarding the resin compositions prepared in the examples and comparative examples, the results of measuring the photosensitive characteristics (film residual ratio, resolution) at the time of film formation are shown in Table 1. The evaluation method is as follows.

(Evaluation of photosensitive characteristics (residual film ratio, resolution))

The resin composition was coated on a 6-inch silicon wafer by spin coating, and heated on a 100 ° C hot plate for 3 minutes to evaporate the solvent to obtain a coating film with a film thickness of 10 μm. This coating film was immersed in a mixed solvent of γ-butyrolactone: butyl acetate = 7: 3 to twice the time until completely dissolved as the development time. The coating film obtained by the same method was exposed to 200 mJ / cm ² in terms of i-rays through a photomask using an i-ray stepper FPA-3000iW manufactured by Canon Inc. The wafer was immersed in γ-butyrolactone: butyl acetate = 7: 3, and after the immersion development at the development time, rinse and wash with cyclopentanone. The residual film rate of the exposed part at this time was evaluated. Here, the residual film ratio can be calculated by the method of the following formula (1).

The minimum value of the mask size of the line and the gap pattern can be evaluated as an analysis when the obtained coating film is exposed to 400 mJ / cm ² in terms of i-rays through the photomask by the same method as described above degree.

In Table 1, component (a) is the 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, the component (b) 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: Dicyclopentyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513M)

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

b5: Acrylic acid-2- (1,2-cyclohexylcarboxyimide) ethyl ester (East Asia Synthetic Co., Ltd. (Made by the company, M-140)

b ': Tetraethylene glycol dimethacrylate (made by Sartomer Co., Ltd., TEGDMA)

As shown in Table 1, the resin compositions of Examples 1 to 9 have a monofunctional (meth) acrylate as the component (b), but they also have tetraethylenedioxide which is not inferior to Comparative Example 1 using difunctional The pattern of the resin composition of alcohol dimethacrylate.

<Example 10 to Example 13, Comparative Example 2>

However, the cured film using polyimide resin has a thicker film and a higher modulus of elasticity. Therefore, the stress after curing increases, and the warpage of the semiconductor wafer increases, which may cause defects during transportation or wafer fixing. Case.

The inventors of the present invention faced the problem that if the heating and curing temperature becomes a low temperature of 300 ° C. or lower, in the vacuum process such as the etching of the electrode portion after the polyimide cured film forming process, the Increased outgassing. If outgassing occurs during the step, the chamber is contaminated, which is a problem. From the viewpoint of generation of outgassing, the forms shown in the following Examples 10 to 12 are preferred.

Example 10

(A) 1100 parts by mass of polymer and (b) 2- (1,2-cyclohexylcarboxyimide) ethyl acrylate (manufactured by Toya Synthetic Co., Ltd., M-140, molecular weight of 251) 10 parts by mass , (C) 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl oxime)] (IRGACURE OXE-01 manufactured by BASF Corporation) 2 parts by mass, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane (manufactured by Gelest Corporation) SIB-1140) 3 parts by mass were dissolved in N-methylpyrrolidone (150 parts by mass of solvent) to prepare a resin composition.

Regarding the prepared resin composition, the photosensitive characteristics (remaining film ratio, resolution) at the time of film formation and the stress and outgas generation amount after curing were measured according to the following evaluation method.

(Evaluation of photosensitive characteristics (residual film ratio, resolution))

The resin composition was coated on a 6-inch silicon wafer by spin coating, and heated on a 100 ° C hot plate for 3 minutes to evaporate the solvent to obtain a coating film with a film thickness of 10 μm. This coating film was immersed in a mixed solvent of γ-butyrolactone: butyl acetate = 7: 3 to twice the time until completely dissolved as the development time. The coating film obtained by the same method was exposed to 200 mJ / cm ² in terms of i-rays through a photomask using an i-ray stepper FPA-3000iW manufactured by Canon Inc. The wafer was immersed in γ-butyrolactone: butyl acetate = 7: 3, and after the immersion development at the development time, rinse and wash with cyclopentanone. The residual film ratio of the exposed part at this time was evaluated and found to be 92%. In addition, the residual film ratio can be calculated by the film thickness after development with respect to the film thickness before development.

The minimum value of the mask size of the line and the gap pattern can be evaluated as an analysis when the obtained coating film is exposed to 400 mJ / cm ² in terms of i-rays through the photomask by the same method as described above Degree, the result is 8 μm.

(Measurement of residual stress)

The resin composition was coated on a 6-inch silicon wafer by spin coating, and heated on a hot plate at 100 ° C. for 3 minutes to evaporate the solvent to obtain a coating film with a thickness of 10 μm after curing. Using a vertical diffusion furnace made by Koyo Lindbergh, This was heat-cured under a nitrogen atmosphere at 270 ° C for 4 hours to obtain a polyimide film (cured film). The residual stress of the cured polyimide film was measured at room temperature using a thin-film stress measuring device FLX-2320 manufactured by KLA Tencor Co., Ltd. The result was 22 MPa.

(Thermal decomposition gas chromatography mass spectrometry analysis)

In the same manner as the measurement of the residual stress, a polyimide film was prepared, and a sample for thermal decomposition gas chromatography mass spectrometry was obtained. Using a Tekmar 7000HT head space sampler to heat the sample at 270 ° C / 30min, the generated gas is introduced into GC / MS (Shimadzu Corporation, model: GC / MS QP-2010, carrier gas) : Helium, 1.0mL / min, column: HP-5MS, oven (Oven): After heating at 40 ℃ for 5 minutes, the temperature is raised to 280 ℃ at a rate of 15 ℃ / min, interface temperature: 280 ℃, ion source Temperature: 250 ° C, sample injection volume: 0.1 mL) and analysis. The measurement results are shown in Fig. 2 (a). The sum of the peak area values was taken as the total amount of outgassing. The sum of the peak area values is 38,375,993. When the value of the sum of the peak area values of Comparative Example 2 described later is set to 1, it becomes about 0.26, and the outgassing is sufficiently reduced.

Example 11

Example 1, except that 1,2-octanedione (c), 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl oxime)] was changed to the following compound 10 Prepare and evaluate a resin composition in the same manner.

[化 25]

In Example 11, the residual film rate was 95%, the resolution was 7 μm, and the residual stress was 22 MPa. The sum of the peak area values in the thermal decomposition gas chromatography mass spectrometry analysis was 58,315,432, and when the sum of the peak area values of Comparative Example 2 described later was set to 1, it was about 0.39, and the outgassing was sufficiently reduced.

Example 12

A resin composition was prepared and evaluated in the same manner as in Example 10 except for further adding 5 parts by mass of tetraethylene glycol dimethacrylate (made by Sadopol Co., Ltd., TEGDMA).

The residual film rate was 95%, the resolution was 7 μm, and the residual stress was 22 MPa. The sum of the peak area values in the thermal decomposition gas chromatography mass spectrometry analysis was 67,924,419, and when the sum of the peak area values of Comparative Example 2 described later is set to 1, it becomes about 0.45, and the outgassing is sufficiently reduced.

Example 13

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

The residual film rate was 89%, the resolution was 8 μm, and the residual stress was 24 MPa. The sum of the peak area values in the thermal decomposition gas chromatography mass spectrometry analysis is 424,225,722, and when the sum of the peak area values of Comparative Example 2 described later is set to 1, it increases to about 2.84 times, and the outgassing increases.

Comparative example 2

It was prepared in the same manner as in Example 10 except that (b) acrylic acid-2- (1,2-cyclohexylcarboxyimide) ethyl ester was changed to tetraethylene glycol dimethacrylate (molecular weight: 306). The resin composition was evaluated.

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

Examples 10 to 12 are excellent in patternability, and the amount of outgas generation is small.

Experimental example

The cause of contamination of the chamber in the case where the cured film after low-temperature curing was used in a vacuum process such as etching of the electrode portion was investigated, and an experiment was conducted to measure outgas generated from the polyimide film.

In Example 10 and Comparative Example 2, a polyimide film was produced in the same manner as the measurement of residual stress, and the cured film was 15 ° C. for 1 minute using a thermal decomposition device (FRONTIER LAB PY2020D, Frontier Lab Co., Ltd.) After the temperature was raised to 375 ° C, the generated gas was introduced into GC / MS (manufactured by Agilent Technologies Co., Ltd., model: GC / MS 5973 MSD, carrier gas: helium, 0.9mL / min, column: UADTM-2.5N, oven: 350 ° C).

The measurement results of Comparative Example 2 are shown in FIG. 3 (a). The dotted line indicates Polymer 1, and the solid line indicates TEGDMA.

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

The TEGDMA in the cured film of Comparative Example 2 vaporized at around 300 ° C, but M-140 in the cured film of Example 10 did not substantially vaporize at 300 ° C or higher.

If the existing curing temperature is about 370 ° C, the curing temperature is higher than the glass transition temperature of the cured film. Therefore, the cured film temporarily becomes a gum-like region, and the crosslinking agent is released as outgassing. When the curing temperature is lower than the glass transition temperature of the cured film, the cured film becomes a glass state, and the outgassing component is encapsulated in the cured film. If the film is exposed to high vacuum, the encapsulated crosslinking agent is generated as outgassing ingredient.

Experimental example

The cause of contamination of the chamber in the case where the cured film after low-temperature curing was used in a vacuum process such as etching of the electrode portion was investigated, and an experiment was conducted to measure outgas generated from the polyimide film.

In Example 1 and Comparative Example 2, a polyimide film was prepared in the same manner as the measurement of residual stress, and the cured film was 15 ° C. for 1 minute using a thermal decomposition device (FRONTIER LAB PY2020D, Frontier Lab Co., Ltd.) After the ratio was raised to 375 ° C, the generated gas was introduced into GC / MS (manufactured by Agilent Technologies Co., Ltd., model: GC / MS 5973 MSD, carrier gas: helium, 0.9mL / min, column: UADTM-2.5N, Oven: 350 ° C).

The measurement results of Comparative Example 2 are shown in FIG. 3 (a). The dotted line indicates Polymer 1, and the solid line indicates TEGDMA.

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

TEGDMA in the cured film of Comparative Example 2 was vaporized at around 300 ° C, and M-140 in the cured film of Example 1 was substantially not vaporized when it was 300 ° C or higher.

If the existing curing temperature is about 370 ° C, the curing temperature is higher than the glass transition temperature of the cured film. Therefore, the cured film temporarily becomes a gum-like region, and the crosslinking agent is released as outgassing. When the curing temperature is lower than the glass transition temperature of the cured film, the cured film becomes a glass state, and the outgassing component is encapsulated in the cured film. If the film is exposed to high vacuum, the encapsulated crosslinking agent is generated as outgassing ingredient.

[Industry availability]

The resin composition of the present invention can be used in so-called packaging applications such as surface coating materials forming electronic parts such as semiconductor devices, core materials for rewiring, solder collars, underball materials, and the like.

Several embodiments and / or embodiments of the present invention are described in detail above, but those skilled in the art can easily deviate from these exemplary embodiments without substantially deviating from the novel instructions and effects of the present invention. And / or embodiments with numerous changes. Therefore, these numerous changes are included in the scope of the present invention.

The contents of the Japanese application specification that became the basis of Paris priority in this application are all incorporated herein.

Claims (14)

A resin composition comprising the following components (a), (b) and (c): (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 represented by the following formula (7),

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 carbon-carbon unsaturated double bond. Valence 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 containing no (meth) acryloyl group,

In formula (7), R and R ₁ respectively 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 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. A resin composition comprising the following components (a), (b) and (c): (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), which is selected from (meth) acrylates containing a piperidine skeleton, substituted or unsubstituted aminoalkyl (meth) acrylates, (methyl ) Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, (methyl) Benzyl acrylate, (meth) acrylate containing polycyclic hydrocarbon groups, linear or branched alkyl polyethylene glycol mono (meth) acrylate, cyclic alkyl polyethylene glycol mono (meth) More than one of the group consisting of acrylate and phenyl polyethylene glycol mono (meth) acrylate; (c) Compounds that generate free radicals by irradiation with actinic rays,

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 carbon-carbon unsaturated double bond. Valence 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 that does not contain a (meth) acryloyl group. The resin composition according to item 1 or 2 of the patent application range, wherein the resin composition contains 1 part by mass to 100 parts by mass relative to 100 parts by mass of the (a) component. b) Ingredients. The resin composition as described in item 1 or item 2 of the patent application scope, wherein R ⁶ in the formula (2) is a monovalent organic group free of (meth) acryloyl, hydroxyl and amine groups . The resin composition according to item 1 or 2 of the patent application, wherein the component (b) is a monofunctional photopolymerizable compound having a molecular weight of 300 or less. The resin composition as described in item 1 or item 2 of the patent application scope, 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. The resin composition according to item 1 or item 2 of the patent application scope, wherein R ¹ in the formula (1) is a tetravalent organic group represented by the following general formula (2a) to general formula (2e) Any of:

In 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 they are bound; in general formula (2e), Z is an ether bond (-O-) or sulfur Ether bond (-S-). The resin composition according to item 1 or item 2 of the patent application scope, wherein R ² in the formula (1) is a divalent organic group represented by the following general formula (5) or general formula (6) :

In formula (5) and formula (6), R ¹⁰ to R ¹⁷ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, at least one of R ¹⁰ to R ¹⁷ is a halogen atom or a halogenated alkyl group; R ¹⁸ and R ^{19 is} each independently a halogen atom or a halogenated alkyl group. The resin composition as described in item 2 of the patent application, wherein the component (c) is an oxime ester compound. A cured film formed from the resin composition as described in any one of patent application items 1 to 9. A method for manufacturing a cured film, comprising: applying the resin composition as described in any one of patent application items 1 to 9 to a substrate and drying to form a coating film; and coating The step of heat treatment of the membrane. A pattern-cured film formed from the resin composition as described in any one of patent application items 1 to 9. A method for manufacturing a pattern hardened film, comprising: applying the resin composition as described in any one of patent application items 1 to 9 to a substrate, and drying to form a coating film; After the coating film is irradiated with actinic rays, a step of developing to obtain a patterned resin film; and a step of subjecting the patterned resin film to heat treatment. An electronic component comprising the cured film as described in item 10 of the patent application range or the pattern cured film as described in item 12 of the patent application range.