TW201533157A - Resin composition, cured film and manufacturing method thereof, patterned cured film and manufacturing method thereof, and electronic part - Google Patents

Abstract

This invention provides a resin composition including: (a) a polyimide precursor having a structure unit represented by the following formula (1) and (b) a photo-polymerizable compound having ethyleny unsaturated groups and isocyanuric ring structures. In the formula (1), R1 is a tetravalent organic group, R2 is a divalent organic group. R3 and R4 are independently a hydrogen atom, an alkyl group with a carbon number of 1 to 20, a cycloalkyl group with a carbon number of 3 to 20 or a monovalent organic group having a carbon-carbon unsaturated double bonds, respectively.

Description

Resin composition containing polyimide precursor, method for producing cured film, and electricity Subpart

The present invention relates to a resin composition containing a polyimide precursor, a method for producing a cured film using the resin composition, and an electronic component.

As the semiconductor integrated circuit is miniaturized, an interlayer insulating film called a low dielectric constant (low-k) layer for lowering the dielectric constant is required. Since the low-k layer has a pore structure, there is a problem that mechanical strength is lowered. In order to protect such an interlayer insulating film having a weak mechanical strength, a cured film formed of a polyimide resin is used. The cured film is required to have properties such as thick film formability (for example, 5 μm or more) or high elastic modulus (for example, 4 GPa or more). However, as the thickness is increased and the modulus of elasticity is increased, the stress after hardening increases, and the warpage of the semiconductor wafer becomes large, which causes a problem in transportation or wafer fixing.

As a method of reducing the stress of the cured film formed of the polyimide resin, for example, a method of copolymerizing and condensing a phthalic acid compound having a specific functional group with an acid component is used (for example, Patent Document 1). However, in recent years, hardening at a low temperature has been sought, and the above polyamine has been subjected to low-temperature hardening. In the case of obtaining a cured film having sufficient performance, there is still room for improvement.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] International Publication WO2006/008991

Further, in order to achieve low stress, a fluorine-containing polyimide precursor having a high i-ray transmittance has been studied. However, as a result of investigation by the inventors of the present invention, it has been found that the cured film obtained by heat-hardening the resin composition containing the polyimide precursors is easily swelled by absorbing the organic solvent used in the resist process. The term "swelling" as used herein refers to a phenomenon in which a cured film absorbs a solvent when the polyimide film is immersed in N-methylpyrrolidone at a certain temperature (for example, 70 ° C) for a certain period of time (for example, 20 minutes). Expand the volume.

An object of the present invention is to provide a resin composition which can obtain a cured film having low stress and low swelling even when it is cured at a low temperature of 300 ° C or lower.

According to the present invention, the following resin composition can be provided.

A resin composition comprising the following component (a) and component (b): (a) a polyimide intermediate having a structural unit represented by the following formula (1),

(wherein R ¹ is a tetravalent organic group, and R ² is a divalent organic group; and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, Or a monovalent organic group having a carbon-carbon unsaturated double bond; (b) a photopolymerizable compound having an ethylenically unsaturated group and an iso-cyanuric acid ring structure.

2. The resin composition according to 1, wherein R ² of the above formula (1) is a divalent organic group represented by the following formula (2),

(wherein R ⁵ to R ¹² each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵ to R ¹² is a fluorine atom, a methyl group or a trifluoromethyl group).

3. The resin composition according to the above formula (1), wherein R ² of the above formula (1) is a divalent organic group represented by the following formula (3),

(wherein R ¹³ and R ¹⁴ are each independently a fluorine atom or a trifluoromethyl group).

4. The resin composition according to any one of 1 to 3, wherein the photopolymerizable compound contains a structure represented by the following formula (4).

(wherein R ²⁴ is a hydrogen atom or a methyl group, X is an alkylene group, and n is an integer of 1 to 25).

5. The resin composition according to 4, wherein the photopolymerizable compound is a compound represented by the following formula (5),

(wherein R ²¹ to R ²³ are each independently a monovalent organic group, and at least one is a group represented by the above formula (4)).

In the resin composition according to any one of the above aspects, the component (b) is contained in an amount of from 0.01 part by mass to 50 parts by mass per 100 parts by mass of the component (a).

7. The resin composition according to any one of 1 to 6, which further comprises a compound which generates a radical by irradiation with active light as the component (c).

8. The resin composition according to 7, wherein the compound which generates a radical by irradiation with active light is an oxime ester compound.

9. The resin composition according to any one of 1 to 8, which further comprises a photopolymerizable compound other than the component (b) as the component (e).

10. The resin composition according to 9, wherein the photopolymerizable compound is a (meth)acrylic compound.

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

A method of producing a patterned cured film, comprising the steps of: applying a resin composition according to any one of 1 to 10 onto a substrate and drying to form a coating film; and irradiating the coating film with active light Thereafter, development is performed to obtain a pattern resin film; and the pattern resin film is subjected to heat treatment.

A cured film obtained by the method for producing a cured film according to 11.

A pattern cured film obtained by the method for producing a pattern cured film as described in 12.

An electronic component having a cured film as described in 13 or a patterned cured film as described in 14.

According to the invention, it is possible to provide a resin composition which can obtain a cured film having low stress and low swelling even when it is cured at a low temperature of 300 ° C or lower.

1‧‧‧Interlayer insulation (interlayer insulation film)

2‧‧‧Wiring layer

3‧‧‧Insulation (insulation film)

4‧‧‧Surface protection layer (surface protection film)

5‧‧‧ solder pad

6‧‧‧Rewiring layer

7‧‧‧Electrical ball

8‧‧ ‧ core

9‧‧‧Face coating

10‧‧‧Bound metal

11‧‧‧ collar

12‧‧‧Bottom

Fig. 1 is a schematic cross-sectional view showing an embodiment of an electronic component (semiconductor device) manufactured using the resin composition of the present invention.

Hereinafter, a resin composition of the present invention and a method for producing a cured film using the resin composition will be described. Further, the invention is not limited by the embodiment.

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

[(a) ingredient]

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

(In the formula (1), R ¹ is a tetravalent organic group, and R ² is a divalent organic group; and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a ring having 3 to 20 carbon atoms; An alkyl group or a monovalent organic group having a carbon-carbon unsaturated double bond)

[(b) ingredients]

The photopolymerizable compound having an ethylenically unsaturated group and an iso-cyanuric acid ring structure is previously subjected to heat hardening of an amine precursor at a high temperature of about 370 ° C, but the resin composition of the present invention contains (a) a component and Since both of the components (b) are cured at a low temperature of 300 ° C or lower, a cured film having low stress and being less likely to swell can be obtained. In the case where the component (a) is not used, for example, polybenzoic acid is used. In the case of the azole precursor, even if the component (b) is used in combination, the effect on stress and swelling is low.

Hereinafter, each component of the resin composition of the present invention will be described.

Component (a): Polyimine precursor having a structural unit represented by the following formula (1)

R ¹ in the formula (1) is a structure derived from a tetracarboxylic acid or a dianhydride thereof used as a raw material. From the viewpoint of the stress and the i-ray transmittance of the cured film, R ^{1 is} preferably any one of the groups represented by the following formulas (2a) to (2e).

[Chemistry 7]

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

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

(wherein R ¹² is a carbon atom or a halogen atom; and R ^{13 is} independently a halogen atom such as a hydrogen atom or a fluorine atom)

Among these, R ^{1 is more} preferably derived from pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride. Structure. These may be used alone or in combination of two or more.

In the range where the stress and the i-ray transmittance of the cured film are not lowered, the raw material of R ¹ may be used in combination with the following dianhydride: 3,3',4,4'-benzophenonetetracarboxylic dianhydride. 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4, 9,10-decane tetracarboxylic dianhydride, m-triphenyl-3,3',4,4'-tetracarboxylic dianhydride, conjugated triphenyl-3,3',4,4'-tetracarboxylic acid Anhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro -2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-di Carboxyphenyl) propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-di Carboxyphenoxy)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 the like.

R ² in the formula (1) is a structure derived from a diamine used as a raw material. In the component (a), R ² in the formula (1) is preferably a divalent organic group represented by the following formula (2).

(In the formula (2), R ⁵ to R ¹² each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵ to R ¹² is a fluorine atom, a methyl group or a trifluoromethyl group)

Examples of the monovalent organic group of R ⁵ to R ¹² include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a carbon number of 1 to 10 (preferably having 1 to 6 carbon atoms). Fluoroalkyl.

In the component (a), R ² in the formula (1) is more preferably a divalent organic group represented by the following formula (3). The swelling phenomenon at the time of low-temperature curing tends to occur when a fluorine-containing polyimide precursor having a high i-ray transmittance is used.

(In the formula (3), R ¹³ and R ¹⁴ are each independently a fluorine atom or a trifluoromethyl group)

In the component (a), the ratio of R ² in the formula (1) to the structural unit represented by the formula (3) is preferably from 1 mol% (% by mole) to 100 mol%, more preferably from 10 mol% to 100 mol%, and further It is preferably from 30 mol% to 100 mol%.

Examples of the structure represented by the formula (2) or (3) include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl and 2,2'-bis(fluoro)- 4,4'-diaminobiphenyl, 4,4'-diamino octafluorobiphenyl. These may be used alone or in combination of two or more.

Further, a diamine compound which imparts a structure other than the formulas (2) and (3) can also be used. For example, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'- (or 3,4' -, 3,3'-, 2,4'-, 2,2'-)diaminodiphenyl ether, 4,4'- (or 3,4'-, 3,3'-, 2,4' -, 2, 2'-) diaminodiphenyl fluorene, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-)diamine Diphenyl sulfide, o-toluidine, o-toluidine oxime, 4,4'-methylene-bis(2,6-diethylaniline), 4,4'-methylene-bis (2, 6-diisopropylaniline), 2,4-diamino mesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenone diamine, bis-{4-(4'- Aminophenoxy)phenyl}anthracene, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diamine Diphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl} Anthracene, 2,2-bis(4-aminophenyl)propane, diaminopolyoxyalkylene, and the like. These may be used alone or in combination of two or more.

R ³ and R ⁴ in the formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), and 3 to 20 carbon atoms. A cycloalkyl group (preferably having a carbon number of 5 to 15, more preferably 6 to 12 carbon atoms) or a monovalent organic group having a carbon-carbon unsaturated double bond.

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

Examples of the monovalent organic group having a carbon-carbon unsaturated double bond include an organic group having a (meth)acryl fluorenyl group. Specifically, a (meth) acryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms is exemplified. In addition, the "(meth)acryloyl group" means "methacryl fluorenyl group" or "acryloyl fluorenyl group", and the "(meth) propylene fluorenyl group" means "methacryloyloxy group" or "propylene". "Methoxy", "(meth)acrylate" means "methacrylate" or "acrylate".

Examples of the (meth)acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group include (meth)acryloxyethyl, (meth)acryloxypropyl, and (methyl) groups. Acryloxy butyl and the like.

When at least one of R ³ and R ⁴ is a monovalent organic group having a carbon-carbon unsaturated double bond, it is combined with a compound which generates a radical by irradiation with active light, thereby making it possible to utilize freely A photosensitive resin composition which polymerizes to crosslink molecular chains.

The component (a) of the present invention can be synthesized by subjecting tetracarboxylic dianhydride to diamine polymerization. Further, it can be synthesized by converting the tetracarboxylic dianhydride represented by the formula (5) into a diester derivative, and converting it into a hydrazine chloride represented by the formula (6), and formula (7). The diamine represented by the reaction is carried out. The synthesis method can be selected from known methods.

[11]

(In the formulas (5), (6) and (7), R ¹ to R ^{4 are the} same as in the formula (1))

The molecular weight of the polyimine imine precursor of the component (a) is preferably 10,000 to 100,000, more preferably 15,000 to 100,000, still more preferably 20,000 to 85,000, in terms of polystyrene. If the weight average molecular weight is more than 10,000, the stress after hardening can be sufficiently reduced. Further, when it is less than 100,000, the solubility in a solvent can be improved, the viscosity of the solution is reduced, and workability is improved. Further, the weight average molecular weight can be measured by gel permeation chromatography, and can be obtained by conversion using a standard polystyrene calibration curve.

The molar ratio of the tetracarboxylic dianhydride to the diamine in the synthesis of the component (a) is usually 1.0, but it may be a molar ratio in the range of 0.7 to 1.3 for the purpose of controlling the molecular weight or the terminal residue. When the molar ratio is 0.7 or less or 1.3 or more, the molecular weight of the obtained polyimide intermediate precursor is small, and the low stress property after hardening is not sufficiently exhibited.

The heating temperature at which the polyarsenazo precursor of the component (a) of the present invention is heat-treated to convert the oxime to a polyimine is preferably 80 to 300 ° C, more preferably 100. °C ~ 300 ° C, and further preferably 200 ° C ~ 300 ° C. When the temperature is less than 80 ° C, the ruthenium imidization may not sufficiently proceed, and the heat resistance may be lowered. If the temperature is higher than 300 ° C, the semiconductor element may be damaged.

The residual stress of the cured film obtained by applying the polyimine precursor represented by the formula (1) to a substrate and heat-curing the film is preferably 30 MPa when the film thickness of the cured film is 10 μm. Hereinafter, it is more preferably 27 MPa or less, further preferably 25 MPa or less. When the residual stress is 30 MPa or less, when the film is formed so that the film thickness after hardening becomes 10 μm, the warpage of the wafer can be more sufficiently suppressed, and the occurrence of the problem of transporting or adsorbing the fixed wafer can be further suppressed. .

In addition, the residual stress can be measured by measuring the amount of warpage of the wafer using a film stress measuring device FLX-2320 (manufactured by KLA Tencor Co., Ltd.) and converting the stress into a stress.

The cured film obtained in the present invention is formed so that the film thickness after hardening becomes 10 μm, and after the step of applying the resin composition onto a substrate and drying to form a coating film, the thickness of the coating film must be about 20 μm. Therefore, when a photosensitive resin composition is produced by combining with a compound which generates radicals by irradiation with active light, the higher the i-ray transmittance of the resin composition, the better.

Specifically, when the film thickness is 20 μm, the i-ray transmittance is preferably 5% or more, more preferably 8% or more, still more preferably 15% or more. When the amount is less than 5%, the i-ray does not reach the deep portion, and radicals are not sufficiently generated. Therefore, there is a concern that the photosensitive property such as bleeding of the resin from the substrate side of the film during development may be lowered.

Further, the i-ray transmittance can be measured by a transmission ultraviolet (ultraviolet) spectrum using a U-3310spctrophotometer (manufactured by Hitachi, Ltd.).

(b) Component: Photopolymerizable compound having an ethylenically unsaturated group and an iso-cyanuric acid ring structure

The resin composition of the present invention comprises an ethylenically unsaturated group and isomeric cyanuric acid The photopolymerizable compound having a ring structure is referred to as component (b). It is considered that the photopolymerizable compound functions as a crosslinking agent and remains in the film after curing, whereby a crosslinked structure is formed in the polyimide polyimide cured film, and swelling can be suppressed. Further, the photopolymerizable compound has a function of improving the alignment property of the polyimide film of the polyimide, and can also increase the residual film ratio after curing.

In addition, an aluminum chelate compound is used as an additive for suppressing swelling of the polyimide film. However, when the aluminum chelate compound is cured at a low temperature of, for example, 300 ° C or lower, a sufficient effect cannot be obtained by adding an aluminum chelate compound. By using the component (b) described above, a sufficient swelling suppressing effect can be obtained even at a low temperature of 300 ° C or lower.

The photopolymerizable compound is preferably a triallyl isocyanurate, a triallyl isocyanurate prepolymer, and a compound having a structure represented by the following formula (4).

(In the formula (4), R ²⁴ is a hydrogen atom or a methyl group, X is an alkylene group, and n is an integer of 1 to 25)

The compound having a structure represented by the formula (4) is preferably a compound represented by the following formula (5).

(In the formula (5), R ²¹ to R ²³ are each independently a monovalent organic group, and at least one of them is a group represented by the above formula (4))

As the compound having a structure represented by the formula (4), a compound represented by the following formula (6) can also be used.

(In the formula (6), R ²¹ to R ²³ are each independently a monovalent organic group, and at least one of them is a group represented by the following formula (9))

(In the formula (9), R ²⁴ is a hydrogen atom or a methyl group, X is an alkylene group, Y is an alkylene group, n is an integer of 1 to 25, and m is an integer of 1 to 14)

Examples of the monovalent organic group of the formula (5) and the formula (6) include an alkyl group having 1 to 15 carbon atoms, a glycidyl group, and a vinyl group. The alkyl group having 1 to 15 carbon atoms may have a halogen atom as the 2,3-dibromopropyl group.

The carbon number of the alkyl group of X and Y of the formulae (4) and (9) is not particularly limited, and is preferably an alkylene group having 2 to 7 carbon atoms, more preferably a carbon number of 2 to 4. The alkyl group is further preferably an ethyl group or a propyl group.

n in the formula (4) and the formula (9) is an integer of 1 to 25, preferably an integer of 1 to 20, and more preferably an integer of 1 to 15.

m in the formula (9) is an integer of 1 to 14, preferably an integer of 1 to 6, more preferably an integer of 6.

Specific examples of the photopolymerizable compound as the component (b) include a compound represented by the following formula (10), which is commercially available as A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The content of the component (b) of the resin composition of the present invention is preferably from 1 part by weight to 50 parts by mass, more preferably 1 part by weight based on 100 parts by weight of the component (a), from the viewpoint of the swelling inhibiting property and the film property. The amount is preferably 30 parts by mass to 20 parts by mass.

By setting the content of the component (b) to 1 part by mass or more based on 100 parts by weight of the component (a), swelling of the cured film by the organic solvent can be suppressed, and it is set to 100 parts by weight based on the component (a). When the amount is 50 parts by mass or less, the decrease in the elongation of the cured film can be suppressed.

(c) component: a compound that generates free radicals by active light

The resin composition of the present invention preferably contains a compound which generates a radical by active light as the component (c).

In the case where at least a part of R ³ and or R ⁴ in the formula (1) of the (a) component of the polyimine precursor is a monovalent organic group having a carbon-carbon unsaturated double bond, by using a resin The composition contains the component (c), and the resin composition of the present invention can be made into a photosensitive resin composition.

Examples of the component (c) include the following oxime ester compounds, benzophenone, and N,N'-tetramethyl-4,4'-diaminobenzophenone (micilenone). , N'-tetraalkyl-4,4'-diaminobenzophenone; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 An aromatic ketone such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; an anthracene which is condensed with an aromatic ring such as an alkyl hydrazine; a benzoin compound such as a benzoin alkyl ether, a benzoin compound such as benzoin or an alkyl benzoin; a benzoin derivative such as benzoin dimethyl ketal. These may be used alone or in combination of two or more.

Among these, the oxime ester compound is preferred because it is excellent in sensitivity and can impart a good pattern.

The oxime ester compound is preferably a compound represented by the following formula (9), a compound represented by the following formula (10) or a compound represented by the following formula (11).

(In the formula (9), 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 preferably an alkyl group having 1 to 8 carbon atoms; a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, more preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, and further preferably a methyl group. , cyclopentyl, phenyl or tolyl; R ₂ represents H, OH, COOH, O(CH ₂ )OH, O(CH ₂ ) ₂ OH, COO(CH ₂ )OH or COO(CH ₂ ) ₂ OH, Preferred is H, O(CH ₂ )OH, O(CH ₂ ) ₂ OH, COO(CH ₂ )OH or COO(CH ₂ ) ₂ OH, more preferably H, O(CH ₂ ) ₂ OH or COO ( CH ₂ ) ₂ OH)

(In the formula (10), R ₃ represents an alkyl group having 1 to 6 carbon atoms, preferably a propyl group; and R ₄ represents NO ₂ or ArCO (wherein Ar represents a substituted or unsubstituted aryl group), R is preferably a tolyl group; R ₅ and R ₆ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group)

(In the formula (11), R ₇ represents an alkyl group having 1 to 6 carbon atoms, preferably an ethyl group; and R ₈ is an organic group having an acetal bond, preferably represented by the following formula (11-1); a compound having a substituent corresponding to R ₈ ; in addition, a benzene ring in which R ⁸ is substituted may have a more substituent; and R ₉ and R ₁₀ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group; , preferably methyl, phenyl or tolyl, more preferably methyl)

The compound represented by the following formula (9), for example, a compound represented by the following formula (9-1) and a compound represented by the following formula (9-2). In the above, the compound represented by the following formula (9-1) can be obtained by IRGACURE OXE-01 (manufactured by BASF Corporation, trade name).

The compound represented by the above formula (10) is, for example, a compound represented by the following formula (10-1). This compound can be obtained by DFI-091 (manufactured by DAITO CHEMIX Co., Ltd., trade name).

The compound represented by the above formula (11) is, for example, a compound represented by the following formula (11-1). It can be obtained by Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., trade name).

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

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

The content in the case of containing the component (c) is preferably 0.01 parts by mass to 30 parts by mass, more preferably 0.05 parts by mass to 15 parts by mass, even more preferably 0.1% by mass based on 100 parts by mass of the component (a). ~10 parts by mass. When the amount is 0.01 parts by mass or more, the exposed portion is sufficiently crosslinked, and the photosensitive property is further improved. When the amount is 30 parts by mass or less, the heat resistance of the cured film tends to be further improved.

(d) Ingredients: Solvent

The resin composition of the present invention may further contain a solvent as the component (d).

As the component (d), that is, a solvent, it is preferred to completely dissolve the pole of the polyimide precursor. The solvent may, for example, be N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, tetramethylurea, Hexamethylphosphonium triamine, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate , 1,3-dimethyl-2-imidazolidinone, and the like.

These solvents may be used singly or in combination of two or more.

The content of the component (d) of the resin composition of the present invention is preferably 50 parts by mass to 500 parts by mass, more preferably 80 parts by mass to 400 parts by mass, even more preferably 100% by mass based on 100 parts by weight of the component (a). ~300 parts by mass.

(e) component: photopolymerizable compound other than component (b)

The resin composition of the present invention may contain a photopolymerizable compound other than the component (b) as the component (e). Examples of the photopolymerizable compound include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and trimethylol. Propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, (A) 2-hydroxyethyl acrylate, 1,3-(methyl) propylene oxy-2-hydroxypropane, methylene bis acrylamide, N,N-dimethyl decylamine, N-hydroxyl Acrylamide and the like. These may be used singly or in combination of two or more.

The amount of the photopolymerizable compound is preferably from 1 part by mass to 100 parts by mass, more preferably from 10 parts by mass to 75 parts by mass, even more preferably from 100 parts by mass to 100 parts by mass of the component (a). It is set to 30 parts by mass to 50 parts by mass. When the amount is 1 part by mass or more, more excellent photosensitivity can be imparted, and if it is 100 parts by mass or less, the heat resistance of the cured film can be further improved.

In addition to the above components (a) to (e), the resin composition of the present invention may contain a radical polymerization inhibiting agent or a radical polymerization inhibitor in order to ensure good storage stability.

Specific examples thereof include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, and Dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, cupferron, 2,5-methylphenylhydrazine, tannic acid, p-benzylaminophenol , nitrosamine compounds, and the like. These may be used singly or in combination of two or more.

The content in the case where the resin composition contains a radical polymerization inhibiting agent or a radical polymerization inhibitor is preferably 0.01 parts by mass to 30 parts by mass, more preferably 0.01 parts by mass, per 100 parts by mass of the component (a). 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass. When the amount is 0.01 parts by mass or more, the storage stability is further improved, and when the amount is 30 parts by mass or less, the heat resistance of the cured film can be further improved.

In order to further improve the adhesion to the cured ruthenium substrate or the like, the resin composition of the present invention may further contain an organic decane compound.

Examples of the above organodecane compound include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, and γ-shrinkage. Glyceroxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-(meth)acryloxypropyltrimethoxydecane, 3-ureidopropyltriethoxylate Baseline, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, ethylamino Triethoxy decyl propyl formate, 3-(triethoxydecyl)propyl succinic anhydride, phenyl triethoxy decane, phenyl trimethoxy decane, N-phenyl-3-aminopropyl Base three Oxaloxane, 3-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

The content of the organic decane compound may be appropriately adjusted so as to obtain a desired effect.

<Method for Producing Cured Film and Pattern Cured Film>

The residual stress of the cured film obtained by applying the composition of the present invention to a substrate and heat-hardening is preferably 30 MPa or less, and more preferably 27 MPa or less, when the film thickness of the cured film is 10 μm. More preferably, it is 25 MPa or less. When the residual stress is 30 MPa or less, when the film is formed so that the film thickness after hardening becomes 10 μm, the warpage of the wafer can be more sufficiently suppressed, and the occurrence of the problem of transporting or adsorbing the fixed wafer can be further suppressed. .

In addition, the residual stress can be measured by measuring the amount of warpage of the wafer using a film stress measuring device FLX-2320 (manufactured by KLA Tencor Co., Ltd.) and converting the stress into a stress.

The pattern cured film of the present invention is a pattern cured film formed of the above resin composition. The pattern cured film of the present invention is formed when the resin composition contains the component (c).

Further, the method for producing a pattern cured film of the present invention comprises the steps of: applying the resin composition onto a substrate and drying it to form a coating film; and after irradiating the coating film with active light, developing the pattern to obtain a pattern resin film And heat-treating the above-mentioned patterned resin film.

Hereinafter, each step of the method for producing a pattern cured film will be described.

The method for producing a pattern hardened film of the present invention comprises the steps of: the above resin The composition is applied onto a substrate and dried to form a coating film. Examples of the method of applying the resin composition onto the substrate include a dipping method, a spray method, a screen printing method, a spin coating method, and the like. Examples of the substrate include a silicon wafer, a metal substrate, and a ceramic substrate. Since the resin composition of the present invention can form a low-stress cured film, it can be suitably used for a large-diameter tantalum wafer of 12 inches or more.

By removing the solvent by heating in the drying step, a non-adhesive coating film can be formed. The drying step can be carried out using a device such as a DATAPLATE (Digital Hotplate, manufactured by PMC Co., Ltd.) as a drying temperature, preferably 90 ° C to 130 ° C, and as a drying time, preferably 100 seconds to 400 seconds.

The method for producing a pattern cured film of the present invention comprises the steps of: subjecting the coating film formed in the above step to active light rays, and then developing to obtain a pattern resin film. Thereby, a resin film which forms a desired pattern can be obtained. The resin composition of the present invention is suitably used for i-ray exposure, but as the active light to be irradiated, ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays or the like can be used.

The developer is not particularly limited, and an alkaline aqueous solution such as a flame retardant solvent such as 1,1,1-trichloroethane, an aqueous solution of sodium carbonate or an aqueous solution of tetramethylammonium hydroxide can be used, N,N-dimethyl Good solvent such as carbamide, dimethyl hydrazine, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetate, etc. A mixed solvent of such a good solvent and a poor solvent such as a lower alcohol, water or an aromatic hydrocarbon. After the development, it is washed with a poor solvent or the like as needed.

The method for producing a pattern cured film of the present invention includes a step of heat-treating the pattern resin film.

This heat treatment can use a vertical diffusion furnace (Koyo Lindbergh (KOYO) The apparatus of LINDBERG) is preferably carried out at a heating temperature of 80 ° C to 300 ° C, and the heating time is preferably 5 minutes to 300 minutes. By this step, the polyimide precursor in the resin composition can be imidized to obtain a patterned cured film containing a polyimide resin.

Further, the cured film of the present invention is a cured film formed of the above resin composition. That is, the cured film of the present invention may be a cured film which is not patterned.

The cured film or patterned cured film of the present invention obtained in this manner can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer, and the like of a semiconductor device.

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

The semiconductor device of the present embodiment has a multilayer wiring structure. An A1 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 on the upper portion thereof, and a surface protective layer of the element is further formed (surface protection) Membrane) 4. The rewiring layer 6 is formed from the pad portion 5 of the wiring layer 2, and extends to a connection portion with a conductive ball (ball) formed of solder, gold or the like as an external connection terminal, that is, a core (core) ) The upper part of 8. Further, a cover coat layer 9 is formed on the surface protective layer 4. The rewiring layer 6 is connected to the conductive ball 7 via a barrier metal 10, and a collar 11 is provided to hold the conductive ball 7. In the case of installing a package of such a structure, in order to further alleviate the stress, there is also a case where an underfill 12 is interposed.

The cured film or the patterned cured film of the present invention can be used for the top coat material, the core material for rewiring, the ball collar material such as solder, and the base rubber of the above-described embodiment.

The electronic component of the present invention has a surface coating layer using a cured film or a pattern cured film of the present invention, a core for rewiring, a ball collar for solder, and the like, and a flip chip (flip) The primer used in the chip or the like is not particularly limited, and various structures can be employed.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples.

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

In a 0.5 L polymer bottle, 43.624 g (200 mmol) of pyromellitic dianhydride and 54.919 g (401 mmol) of 2-hydroxyethyl methacrylate were dried in a dryer at 160 ° C for 24 hours, and 0.220 g of benzenediol was dissolved in 394 g of N-methylpyrrolidone, and after adding 1,8-diazabicycloundecene in a catalytic amount, the mixture was stirred at room temperature (25 ° C) for 24 hours to carry out esterification. Thereby, a solution of pyromellitic acid-hydroxyethyl methacrylate diester was obtained. This solution was made into a solution of pyromellitic dianhydride (PMDA) (hydroxyethyl methacrylate (HEMA)).

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

In a 0.5 L polymer bottle, 49.634 g (160 mmol) of 4,4'-oxydiphthalic acid and 44.976 g of 2-hydroxyethyl methacrylate were dried in a dryer at 160 ° C for 24 hours. 328 mmol) and 0.176 g of hydroquinone were dissolved in 378 g of N-methylpyrrolidone, and after adding 1,8-diazabicycloundecene in a catalytic amount, the mixture was stirred at room temperature (25 ° C) for 48 hours. The esterification was carried out to obtain a 4,4'-oxydiphthalic acid-hydroxyethyl methacrylate diester solution. This solution was set as a 4,4'-oxydiphthalic anhydride (ODPA) (HEMA) solution.

Synthesis Example 3 (Synthesis of Polymer 1)

In a 0.5 L flask equipped with a stirrer and a thermometer, the mixture was placed in a flask. 195.564 g of a pyromellitic dianhydride (HEMA) solution obtained in Example 1 and 58.652 g of a 4,4'-oxydiphthalic anhydride (HEMA) solution obtained in Synthesis Example 2, followed by cooling in a water bath Next, 25.9 g (217.8 mmol) of sulfite chlorine was added dropwise using a dropping funnel so that the temperature of the reaction solution was kept at 10 degrees or less. After the completion of the dropwise addition of sulfoxide, the reaction was carried out for 2 hours under cooling in a water bath to obtain ruthenium chloride of pyromellitic dianhydride (HEMA) and 4,4'-oxydiphthalic anhydride (HEMA). Solution. Then, using a dropping funnel, it was cooled in a water bath, and while the temperature of the reaction solution did not exceed 10 ° C, 2,2'-bis(trifluoromethyl)benzidine 31.696 g (99.0 mmol) and pyridine 34.457 were added dropwise. A solution of g (435.6 mmol) and hydroquinone 0.076 g (0.693 mmol) of N-methylpyrrolidone 90.211 g. The reaction liquid was added dropwise to distilled water, and the precipitate was collected by filtration and collected, and dried under reduced pressure, whereby a polyphthalate was obtained. The weight average molecular weight determined by standard polystyrene conversion was 34,000. This was designated as Polymer 1. 1 g of the polymer 1 was dissolved in 1.5 g of N-methylpyrrolidone, and applied to a glass substrate by spin coating, and heated on a hot plate at 100 ° C for 180 seconds to evaporate the solvent. A coating film having a thickness of 20 μm was formed. At this time, the obtained coating film had an i-ray transmittance of 30%.

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

Measuring device: L4000UV manufactured by Hitachi, Ltd.

Pump: L6000 manufactured by Hitachi, Ltd.

C-R4A Chromatopac manufactured by Shimadzu Corporation

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

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

LiBr (0.03mol/L), H3PO4 (0.06mol/L)

Flow rate: 1.0 mL/min, detector: UV 270 nm

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

Example 1 to Example 6 and Comparative Example 1 to Comparative Example 4

Each of the components (a), (b), (c), and (e) was dissolved in N-methylpyrrolidone in the formulation shown in Table 1, and a resin composition was prepared and evaluated by the following method. Resolution, residual stress, and swelling ratio. The results are shown in Table 1.

In addition, in Table 1, the number in the brackets of each of the components (b) and (c) indicates the amount of addition (parts by mass) with respect to 100 parts by mass of the component (a). Further, N-methylpyrrolidone was used as the solvent, and the amount used was 1.5 times (150 parts by mass) based on 100 parts by mass of the component (a).

(Evaluation of photosensitive characteristics (resolution))

The prepared resin composition was applied onto a 6-inch wafer by a spin coating method, and heated on a hot plate at 100 ° C for 3 minutes to volatilize the solvent to obtain a coating film having a film thickness of 10 μm. This coating film was immersed in a mixed solvent of γ-butyrolactone: butyl acetate = 7:3 until completely dissolved, and twice the time was set as the development time. The coating film obtained by the same method was exposed to an i-ray conversion of 300 mJ/cm ² using an i-ray stepper FPA-3000iW (manufactured by Canon Inc.) via a photomask. The wafer was immersed in γ-butyrolactone: butyl acetate = 7:3 for puddle development, and then rinsed with cyclopentanone. The minimum value of the mask size of the analyzed line and space pattern was evaluated as the resolution.

(Measurement of residual stress)

The obtained resin composition was applied onto a 6-inch wafer by a spin coating method, and heated on a hot plate at 100 ° C for 3 minutes to volatilize the solvent to obtain a coating film having a film thickness of 10 μm after hardening. . The coating film was heat-hardened at 270 ° C for 4 hours under a nitrogen atmosphere using a vertical diffusion furnace (manufactured by KOYO LINDBERG) to obtain a polyimide film. The residual stress of the hardened polyimide film was measured at room temperature using a film stress measuring device FLX-2320 (manufactured by KLA Tencor Co., Ltd.).

(Measurement of swelling rate)

The obtained resin composition was applied onto a 6-inch wafer by a spin coating method, and heated on a hot plate at 100 ° C for 3 minutes to volatilize the solvent to obtain a coating film having a film thickness of 10 μm after hardening. . The coating film was heat-hardened at 270 ° C for 4 hours under a nitrogen atmosphere using a vertical diffusion furnace (manufactured by KOYO LINDBERG) to obtain a polyimide film. The polyimide film prepared on the substrate was immersed in N-methylpyrrolidone at 70 ° C and heated for 20 minutes. The sample (sample) immersed in N-methylpyrrolidone was washed with distilled water, and the film thickness was measured. The swelling ratio (%) was calculated from the change in film thickness before and after the N-methylpyrrolidone immersion.

In Table 1, the component (b) is as follows.

A9300 (Ethoxylated isocyanuric acid triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)

In Table 1, the component (c) is the following compound.

C1:1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzylidene fluorenyl)] (manufactured by BASF Corporation, trade name "IRGACURE OXE-01" ")

C2: Adeka Arkls NCI-930 (made by ADEKA Co., Ltd., trade name)

In Table 1, the component (e) is tetraethylene glycol dimethacrylate.

Further, the aluminum chelate A(w) is tris(acetonitrile)aluminum (manufactured by KAWAKEN FINE CHEMICAL).

In the examples, the compound having an isomeric cyanuric acid skeleton is added to the rigid polyimide containing fluorine, and the swelling ratio is 10% or less in a state of maintaining a low stress of 30 MPa or less. On the other hand, in the comparative example, when the composition does not contain the compound having a hetero-cyanuric acid skeleton, the fluorine-containing polyimide has a large swelling ratio of 20% or more. Further, in Comparative Example 3 and Comparative Example 4, although the aluminum chelate compound was added, the curing temperature was low, and thus the chemical solution resistance improving effect was not obtained.

[Industrial availability]

The resin composition of the present invention can be used to form an electron of a semiconductor device or the like So-called packaging applications such as a face coating material for a part, a core material for rewiring, a ball collar material such as solder, and a primer.

The embodiments and/or the embodiments of the present invention are described in detail above, but the embodiments and/or embodiments of the present invention are susceptible to the embodiments and/or embodiments of the present invention without departing from the novel teachings and effects of the present invention. Apply a variety of changes. Accordingly, such various modifications are intended to be included within the scope of the present invention.

The entire contents of the documents described in the specification and the Japanese Patent Application, which is the priority of the Paris Convention of the present application, are incorporated herein by reference.

Claims (15)

A resin composition comprising the following component (a) and component (b): (a) a polyimide intermediate having a structural unit represented by the following formula (1), (wherein R ¹ is a tetravalent organic group, and R ² is a divalent organic group; and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, Or a monovalent organic group having a carbon-carbon unsaturated double bond; (b) a photopolymerizable compound having an ethylenically unsaturated group and an iso-cyanuric acid ring structure. The resin composition of the above formula (1), wherein R ² of the above formula (1) is a divalent organic group represented by the following formula (2), (wherein R ⁵ to R ¹² each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵ to R ¹² is a fluorine atom, a methyl group or a trifluoromethyl group). The resin composition according to the above formula (1), wherein R ² of the above formula (1) is a divalent organic group represented by the following formula (3), (wherein R ¹³ and R ¹⁴ are each independently a fluorine atom or a trifluoromethyl group). The resin composition according to the first or second aspect of the invention, wherein the photopolymerizable compound comprises a structure represented by the following formula (4), (wherein R ²⁴ is a hydrogen atom or a methyl group, X is an alkylene group, and n is an integer of 1 to 25). The resin composition according to claim 4, wherein the photopolymerizable compound is a compound represented by the following formula (5). (wherein R ²¹ to R ²³ are each independently a monovalent organic group, and at least one is a group represented by the above formula (4)). The resin composition according to the first or second aspect of the invention, wherein the component (b) is contained in an amount of from 0.01 part by mass to 50 parts by mass per 100 parts by mass of the component (a). The resin composition according to claim 1 or 2, further comprising a compound which generates a radical by irradiation with active light as the component (c). The resin composition according to claim 7, wherein the compound which generates a radical by irradiation with active light is an oxime ester compound. The resin composition according to claim 1 or 2, further comprising a photopolymerizable compound other than the component (b) as the component (e). The resin composition according to claim 9, wherein the light is the light The polymerizable compound is a (meth)acrylic compound. A method for producing a cured film, comprising the steps of: applying a resin composition according to any one of claims 1 to 10 to a substrate and drying to form a coating film; The coating film is heat treated. A method for producing a patterned cured film, comprising the steps of: applying a resin composition according to any one of claims 1 to 10 to a substrate and drying to form a coating film; After the coating film is irradiated with the active light, development is performed to obtain a pattern resin film; and the pattern resin film is subjected to heat treatment. A cured film obtained by the method for producing a cured film according to claim 11 of the patent application. A pattern hardening film obtained by the method for producing a pattern cured film according to claim 12 of the patent application. An electronic component having a cured film as described in claim 13 or a patterned cured film according to claim 14 of the patent application.