TW201425474A - Photosensitive resin composition, production method of patterned hardened film using the same and semiconductor device - Google Patents

Abstract

This invention provides a resin composition including the following component (a) to component (c): (a) a polyimide precursor having a structural unit represented by the following general formula (1) (in the general formula (1), A is any one of the tetravalent organic groups represented by the following formula (2a) to formula (2d), B is a divalent organic group represented by the following general formula (3)); (b) an oxime ester compound; (c) a solvent.

Description

Photosensitive resin composition, and a manufacturer of a pattern cured film using the same Method and semiconductor device

The present invention relates to a photosensitive resin composition which exhibits excellent photosensitive characteristics, a method for producing a patterned cured film using the same, and a semiconductor device.

In recent years, as a protective film material of a semiconductor integrated circuit, an organic material having high heat resistance such as a polyimide resin has been widely used. Further, when a pattern is formed on a semiconductor integrated circuit, from the viewpoint of simplification of the steps, the following method is employed: exposure and development are performed using a material imparting photosensitivity, thereby forming a necessary pattern.

A method of imparting photosensitivity to polyimine is a method of introducing a methacryl oxime group via an ester bond or an ionic bond in a polyimide precursor, and using a soluble poly oxime containing a photopolymerizable olefin. a method of using an amine, a method of using a self-sensitizing polyimine, or the like, the self-sensitizing polyimine having a benzophenone skeleton and having an alkane in the ortho position of the aromatic ring to which the nitrogen atom is bonded base. Among them, in the method of introducing a methacryl oxime group via an ester bond or an ionic bond in a polyimide precursor, the degree of freedom in monomer selection is high, and research is prevalent.

However, a method in which a tertiary amine having a methacryl fluorenyl group is added to a polyamic acid and forms a quaternary ammonium salt with a carboxyl group in the poly phthalic acid, and a methacryl oxime group is introduced via an ionic bond, a bond The strength is weak. Therefore, when it is stored at room temperature, there is a problem that the depolymerization of poly-proline is likely to occur, the molecular weight is lowered, and the viscosity is lowered. In addition, there is a problem in that even if the methacrylonitrile groups are crosslinked by photopolymerization by exposure, the effect of lowering the dissolution rate of the polylysine is weak, and thus the photosensitivity is lowered (for example, see Patent Document 1).

On the other hand, with the miniaturization of the semiconductor integrated circuit, it is necessary to lower the dielectric constant of the interlayer insulating film called a low-k (low dielectric constant) layer. In order to lower the dielectric constant, for example, there is a method of applying an interlayer insulating film having a pore structure. However, this method causes a problem of a decrease in mechanical strength. In order to protect such an interlayer insulating film having a weak mechanical strength, there is a method of providing a protective film on the interlayer insulating film.

Further, in a region in which a projecting external electrode called a bump is formed, stress acting on the interlayer insulating film is concentrated, and thick film formation of the protective film is performed in order to prevent the interlayer insulating film from being broken (for example) Requirements such as 5 μm or more or high elastic modulus (for example, 4 GPa or more) are constantly increasing. However, by thickening the protective film and high elastic modulus, the stress of the protective film is increased, and the warpage of the semiconductor wafer is increased, which may cause a problem in transportation or wafer fixing. Therefore, it is desirable to develop a low-stress polyimine resin (for example, refer to Patent Document 2).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-174020

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-2917

When the cured film obtained by heating the resin composition containing the polyimide resin is a thick film, the transmittance of the i-ray (wavelength: 365 nm) used in the exposure step is lowered. As a result, there is a problem that the photosensitive characteristics (sensitivity and resolution) are lowered. Therefore, it is difficult to achieve good photosensitivity and low stress at the same time.

An object of the present invention is to provide a resin composition having excellent photosensitivity and low stress of a cured film formed, and a method for forming a pattern cured film using the same.

According to the invention, the following resin composition and the like are provided.

A resin composition comprising the following components (a) to (c): (a) a polyimine precursor having a structural unit represented by the following formula (1), and (b) an oxime ester compound , (c) solvent,

(In the formula (1), A is any one of the tetravalent organic groups represented by the following formulas (2a) to (2d), and B is a divalent organic group represented by the following formula (3); ¹ and R ² are each independently a hydrogen atom, a monovalent organic group or a group having a carbon-carbon unsaturated double bond, and at least one of R ¹ and R ² is a group having a carbon-carbon unsaturated double bond);

(In the formula (2d), X and Y each independently represent a divalent group or a single bond which is not conjugated to the respective bonded benzene ring);

(In the formula (3), R ³ to R ¹⁰ are each independently hydrogen or a monovalent organic group; wherein R ³ to R ^{10 are} not a halogen atom and a monovalent organic group containing a halogen atom).

2. The resin composition according to the above, wherein the component (b) is a compound represented by the following formula (4), a compound represented by the formula (5) or a compound represented by the formula (6),

(In the formula (4), R ₁₁ and R ₁₂ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or a phenyl group; and R ₁₃ represents H, OH, COOH, O(CH ₂ ). OH, O(CH ₂ ) ₂ OH, COO(CH ₂ )OH or COO(CH ₂ ) ₂ OH);

(In the formula (5), R ₁₄ represents an alkyl group having 1 to 6 carbon atoms, R ₁₅ represents NO ₂ or ArCO (wherein Ar represents an aryl group), and R ₁₆ and R ₁₇ each represent a carbon number of 1 to 12; Alkyl, phenyl or tolyl);

(In the formula (6), R ₁₈ represents an alkyl group having 1 to 6 carbon atoms, R ₁₉ represents an organic group having an acetal bond, and R ₂₀ and R ₂₁ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group or a toluene. base).

3. The resin composition according to 1 or 2, wherein the polyimine precursor of the component (a) further has a structural unit represented by the following formula (7).

(In the formula (7), D is a tetravalent organic group represented by the following formula (8), and B, R ¹ and R ^{2 are the} same as the formula (1));

(In the formula (8), Z is an ether bond (-O-) or a thioether bond (-S-)).

4. The resin composition according to any one of 1 to 3, further comprising a tetrazole derivative or a benzotriazole derivative.

A method of producing a patterned cured film, comprising: applying the resin composition according to any one of 1 to 4 on a substrate and adding a step of drying to form a coating film; a step of exposing the coating film formed in the above step to active light rays in a pattern; and removing the unexposed portion other than the exposed portion by development; and the above steps The pattern obtained in the above is subjected to a heat treatment to form a polyimide film pattern.

A semiconductor device comprising a pattern cured film obtained by the method for producing a patterned cured film according to 5.

According to the present invention, it is possible to provide a resin composition having excellent photosensitive properties and low stress of the formed cured film, and a method of forming a patterned cured film using the same.

1‧‧‧Interlayer insulation (interlayer insulation film)

2‧‧‧Aluminum (Al) 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‧‧‧Overcoat

10‧‧‧Resistance metal

11‧‧‧ collar

12‧‧‧ bottom packing

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

(resin composition)

The resin composition of the present invention is characterized by containing the following components (a) to (c).

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

(b) oxime ester compound

(c) solvent

(In the formula (1), A is a tetravalent organic group represented by the following formula (2a) to formula (2d), and B is a divalent organic group represented by the following formula (3).

R ¹ and R ² are each independently a hydrogen atom, a monovalent organic group or a group having a carbon-carbon unsaturated double bond, and at least one of R ¹ and R ² is a group having a carbon-carbon unsaturated double bond)

(In the formula (2d), X and Y each independently represent a divalent group or a single bond which is not conjugated to the respective bonded benzene ring)

(In the formula (3), R ³ to R ¹⁰ are each independently hydrogen or a monovalent organic group, except for the case where R ³ to R ¹⁰ are a halogen atom and a monovalent organic group containing a halogen atom)

Hereinafter, each component will be described.

1. (a) Component: Polyimine precursor

The polyimine precursor used in the present invention has a structural unit represented by the above formula (1). A in the formula (1) is a structure derived from a tetracarboxylic dianhydride used as a raw material of a polyimide precursor.

In order to reduce the stress of the cured film obtained from the composition, A is any one of the tetravalent organic groups represented by the following formulas (2a) to (2d).

(In the formula (2d), X and Y each independently represent a divalent group or a single bond which is not conjugated to the respective bonded benzene ring)

Examples of the tetravalent organic-based tetracarboxylic dianhydride represented by the formula (2a) to the formula (2d) include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 4, 4'-biphenyltetracarboxylic dianhydride, tetracarboxylic dianhydride represented by the following formula (9) to formula (15).

In the polymerization of the polyimide precursor, the tetracarboxylic dianhydride may be used singly or in combination of two or more kinds of tetracarboxylic dianhydride. Among these tetracarboxylic dianhydrides, from the viewpoint of low thermal expansion of the cured film, it is preferred to use pyromellitic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride, and formula (9). The tetracarboxylic dianhydride represented by the formula (11) is more preferably pyromellitic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride or tetracarboxylic dianhydride represented by the formula (9). Further, it is preferred to use pyromellitic dianhydride or 4,4'-biphenyltetracarboxylic dianhydride.

B in the formula (1) is a structure derived from a diamine used as a raw material of a polyimide precursor. From the viewpoint of low stress and i-ray transmittance, B is preferably a divalent organic group represented by the following formula (3).

R ³ to R ¹⁰ each independently represent hydrogen or a monovalent group. Here, the case where R ³ to R ¹⁰ are a halogen atom and a monovalent organic group containing a halogen atom is excluded. In the case of a halogen atom or a monovalent organic group containing a halogen atom, there is a concern that a bond between carbon-halogen atoms is cleaved and the cured film is deteriorated when the cured film is subjected to a plasma treatment.

The monovalent group represented by R ³ to R ¹⁰ may, for example, be an alkyl group having 1 to 20 carbon atoms (such as a methyl group) or an alkoxy group having an alkyl group having 1 to 20 carbon atoms (such as a methoxy group).

The diamine of the starting material can be used: 2,2'-dimethylbenzidine, 2,2'-diaminobenzidine, 3,3'-dimethylbenzidine, 3,3'-diaminobenzidine 2,2',3,3'-tetramethylbenzidine, 2,2'-dimethoxybenzidine, 3,3'-dimethoxybenzidine, and the like.

In the polymerization of the polyimide precursor, these diamines may be used singly or in combination of two or more kinds of diamines. From the viewpoint of low stress, among these diamines, 2,2'-dimethylbenzidine, 2,2'-diaminobenzidine, and 3,3'-dimethyl linking are preferably used. Aniline, 3,3'-diaminobenzidine, more preferably 2,2'-dimethylbenzidine.

R ¹ and R ² in the polyimine precursor represented by the formula (1) are each independently a hydrogen atom, a monovalent organic group or a group having a carbon-carbon unsaturated double bond. At least one of R ¹ and R ² is a group having a carbon-carbon unsaturated double bond.

The monovalent organic group may, for example, be an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.

Examples of the group having a carbon-carbon unsaturated double bond include an acryloxyalkyl group having a carbon number of 1 to 10 and a methacryloxyalkyl group.

The polyimine precursor contains a monovalent organic group having a carbon-carbon unsaturated double bond in at least a portion thereof, thereby combining with a radical-generating compound upon irradiation with active light (for example, i-ray exposure), Crosslinking between molecular chains due to polymerization is easy to form a negative resin composition.

Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-decyl group and n-dodecyl group.

Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like.

Examples of the propylene methoxyalkyl group having an alkyl group having 1 to 10 carbon atoms include an acryloxyethyl group, an acryloxypropyl group, and an acryloxybutyl group.

Examples of the methacryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include a methacryloxyethyl group, a methacryloxypropyl group, and a methacryloxy butyl group.

Further, a method of imparting photosensitivity to a polyimide precursor is known in which a tertiary amine compound having a carbon-carbon unsaturated double bond is added to a corresponding polyamine. However, sometimes the carboxyl group in the polyamic acid forms an ionic bond with the tertiary amine, and the state of the ionic bond changes due to the pH value of the varnish or the influence of moisture, and the storage stability is lowered. Therefore, it is preferred that R ¹ and R ² are a group introduced by an ester bond and are not hydrogen. Among them, from the viewpoint of good photosensitivity, R ¹ and R ^{2 are} preferably an acryloxyethyl group, an acryloxybutyl group, a methacryloxyethyl group introduced by an ester bond, Methyl propylene oxy butyl.

From the viewpoint of lowering the stress of the obtained cured film, the polyimine precursor preferably has a structure represented by the formula (1) of 10 mol% or more, more preferably 20 mol, based on all the constituent units. % or more of the structure represented by the formula (1).

The polyimine precursor used in the resin composition of the present invention may have a formula represented by the following formula (7) from the viewpoint of improving the transmittance of the i-ray, improving the adhesion after curing, and improving the mechanical properties. Structure.

(In the formula (7), D is a tetravalent organic group represented by the formula (8), and B, R ¹ and R ^{2 are the} same as the formula (1))

(In the general formula (8), Z is an ether bond (-O-) or a thioether bond (-S-))

Examples of the tetracarboxylic dianhydride which forms the structure of the general formula (8) include 4,4'-oxydiphthalic dianhydride and thioether diphthalic anhydride. Combination of polyamidiamine precursors In the case of the above, the tetracarboxylic dianhydride may be used singly or in combination of two. From the viewpoint of adhesion after hardening, 4,4'-oxybisphthalic dianhydride is preferably used.

In the case where the structural unit represented by the formula (1) and the structural unit represented by the formula (7) are contained in the polyimine precursor, the polyimine precursor becomes copolymerized. The copolymer is, for example, a block copolymer or a random copolymer, and is not particularly limited.

The polyimine precursor having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (7) has a low stress and good adhesion. The molar ratio of the formula (1) to the formula (7) [formula (1) / formula (7)] is preferably from 1/9 to 9/1, more preferably from 2/8 to 8/2, and thus preferably 2/8~7/3.

The polyimine precursor of the present invention may have a structural unit represented by the formula (1) and a structural unit other than the structural unit represented by the formula (7). Specific examples thereof include: 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-[iso A structural unit of a tetracarboxylic dianhydride such as a propylene bis[(p-phenylene)oxy]]diphthalic acid 1,2:1',2'-dianhydride.

Further, it can be exemplified by 4,4'-oxybisaniline, 4,4'-diaminodiphenylmethane, 1,4-cyclohexanediamine, 1,3'-bis(3-aminophenoxyl). a structural unit of a diamine such as benzene.

From the viewpoint of the low stress, the tetracarboxylic dianhydride and the diamine are preferably 20 mol% or less, more preferably 10 mol% or less, based on the total amount of the tetracarboxylic dianhydride used as the raw material and the diamine. Further, it is preferred to use only tetracarboxylic dianhydrides and diamines which form the structures of the formulae (1) and (7).

The molecular weight of the polyimine precursor of the present invention is preferably polystyrene. The converted weight average molecular weight is 10,000 to 100,000, more preferably 15,000 to 100,000, and further preferably 20,000 to 85,000. The weight average molecular weight is preferably 10,000 or more from the viewpoint of sufficiently reducing the stress after hardening. Further, from the viewpoint of solubility in a solvent or handleability of a solution, it is preferably 100,000 or less. Further, the weight average molecular weight can be measured by a gel-permeation chromatography method, and can be obtained by conversion using a standard polystyrene calibration curve.

In the case where the polyimide composition of the present invention is used to form a resin composition, it is preferred to contain 20% by mass to 60% by mass of the polyimine precursor in the resin composition, more preferably 25 The polyimine precursor having a mass % to 55% by mass, more preferably 30% by mass to 55% by mass of the polyimine precursor.

The molar ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis of the polyimine precursor of the present invention is usually preferably 1.0, but in order to control the molecular weight or the terminal residue, it can also be in the range of 0.7 to 1.3. Moerbi is used for synthesis. When the molar ratio is from 0.7 to 1.3, the molecular weight of the obtained polyimide intermediate precursor becomes appropriate, and the stress after hardening tends to be sufficiently lowered.

The polyimine precursor of the present invention can be synthesized by the following hydrazine chloride method, that is, after the tetracarboxylic dianhydride as a raw material is derived into a diester derivative represented by the following formula (16), The hydrazine chloride represented by the following formula (17) is converted into a condensed product with a diamine in the presence of a basic compound.

(In the formula (16), E is a tetravalent organic group, and represents a tetravalent group structure containing A of the formula (1) and D in the formula (7), R ¹ and R ² and R in the formula (1) ¹ and R ^{2 are the} same)

(In the formula (17), E is a tetravalent organic group, and represents a tetravalent group structure containing A of the formula (1) and D in the formula (7), R ¹ and R ² and R in the formula (1) ¹ and R ^{2 are the} same)

The diester derivative represented by the formula (16) can be synthesized by using at least 2 mol equivalents or more of an alcohol in the presence of a basic catalyst with respect to 1 mol of tetracarboxylic dianhydride as a raw material. reaction. In the case where the diester derivative represented by the formula (16) is converted into the hydrazine chloride represented by the formula (17), if the unreacted alcohol remains, the chlorinating agent reacts with the unreacted alcohol. It may cause the conversion to ruthenium chloride to not proceed sufficiently. Therefore, the equivalent of the alcohol is preferably from 2.0 moles to 2.5 moles, more preferably from 2.0 moles to 2.3 moles, and even more preferably 2.0 moles, based on 1 mole of the tetracarboxylic dianhydride. ~2.2 molar equivalent.

As the alcohol, an alcohol having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, an acryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms or a carbon number of 1 to 1 may be used. 10 methacryloxyalkyl alcohol.

Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, n-hexanol, cyclohexanol, 2-hydroxyethyl acrylate, and methacrylic acid-2. -hydroxyethyl ester, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, A 4-hydroxybutyl acrylate and the like. These alcohols may be used singly or in combination of two or more.

As the basic catalyst, 1,8-diazabicyclo[5.4.0]deca-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene and the like can be used.

When two or more kinds of tetracarboxylic dianhydrides are used as a raw material, an ester derivative derived from each of the tetracarboxylic dianhydrides may be used in combination. Further, two or more kinds of tetracarboxylic dianhydrides may be mixed in advance and simultaneously derivatized into an ester derivative.

When the diester derivative represented by the formula (16) is converted into the phosphonium chloride represented by the formula (17), a 2 mol equivalent chlorinating agent is usually reacted by 1 mol with respect to the diester derivative. The conversion is carried out, but in order to control the molecular weight of the synthesized polyimide precursor, the equivalent may be appropriately adjusted.

As the chlorinating agent, sulfinium chloride or dichlorooxalic acid can be used, and from the viewpoint of increasing the molecular weight of the formed polyimide precursor and sufficiently reducing the stress after hardening, the equivalent is preferably 1.5 mol equivalents to 2.5. The molar equivalent is more preferably 1.6 mole equivalents to 2.4 mole equivalents, and further preferably 1.7 mole equivalents to 2.3 mole equivalents.

By the presence of a basic compound in the ruthenium chloride represented by the formula (17) The polyamine imide precursor used in the present invention can be obtained by adding a diamine as a raw material. The basic compound is used for the purpose of capturing hydrogen chloride generated when a hydrazine chloride is reacted with a diamine.

As the basic compound, pyridine, 4-dimethylaminopyridine, triethylamine or the like can be used. With respect to the amount thereof used, it is preferably 1.5 molar equivalents to 2.5 molar equivalents, more preferably 1.7 molar equivalents to 2.4 molar equivalents, and more preferably 1.8 molar equivalents to 2.3 moles, relative to the amount of the chlorinating agent. Ear equivalent. If it is less than 1.5 mol equivalent, the molecular weight of the polyimide precursor may be lowered, and the stress after hardening may not be sufficiently lowered. If it is more than 2.5 mol equivalent, the polyimine precursor may be colored.

Further, in addition to the hydrazine chloride method as described above, the above polyimide precursor may be synthesized by an isoindole imine method or a Dicyclohexylcarbodiimide (DCC) method. In the isoindole imine method, a tetracarboxylic dianhydride as a raw material is polycondensed with a diamine to synthesize polylysine, and after adding trifluoromethyl acetic anhydride to convert to an isoindole, an alcohol compound is added to synthesize it. Polyesterimide precursor of ester linkage. In the DCC method, a diester derivative represented by the formula (16) is reacted with 2 moles of DCC (dicyclohexylcarbodiimide), and then a diamine is added, whereby a polyimide precursor can be obtained. .

The alcohol compound to be used is preferably an alcohol having an alkyl group having a propylene oxyalkyl group having 1 to 10 carbon atoms or an alkyl group having a methacryloxyalkyl group having 1 to 10 carbon atoms. Specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, and methyl group. 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like. The alcohol They may be used singly or in combination of two or more.

In addition, in order to control the molecular weight, a part of the tetracarboxylic dianhydride as a raw material may be converted into an ester compound represented by the formula (18) by reacting with the above-mentioned alcohol compound, and then polycondensation with a diamine may be carried out.

(In the formula (18), G is a tetravalent organic group, and represents a tetravalent structure containing D of the formula (1) and D of the formula (7), and R ²² is the same as R ¹ or R ² in the formula (1) )

The above addition polymerization and condensation reaction or synthesis of a diester derivative or a ruthenium chloride are preferably carried out in an organic solvent. The organic solvent to be used is preferably a polar solvent in which the synthesized polyimine precursor is completely dissolved, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N. , N-dimethylformamide, dimethyl hydrazine, tetramethyl urea, hexamethylphosphonium triamine, γ-butyrolactone, and the like.

2. (b) Component: oxime ester compound

The component (b) is used as a photoinitiator. The component (b) is not particularly limited, and from the viewpoint of obtaining a good sensitivity and a residual film ratio, a compound represented by the following formula (4), a compound represented by the following formula (5), and the following are preferable. Any one of the compounds represented by the formula (6).

In the formula (4), R ₁₁ and R ₁₂ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or a phenyl group, preferably an alkyl group having 1 to 8 carbon atoms and a carbon number of 4; The cycloalkyl group or phenyl group of ~6 is more preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms or a phenyl group, and more preferably a methyl group, a cyclopentyl group or a phenyl group.

R ₁₃ represents H, OH, COOH, O(CH ₂ )OH, O(CH ₂ ) ₂ OH, COO(CH ₂ )OH or COO(CH ₂ ) ₂ OH, preferably 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 (5), R ₁₄ each represents an alkyl group having 1 to 6 carbon atoms, preferably a propyl group.

R ₁₅ represents NO ₂ or ArCO (here, Ar represents an aryl group), and Ar is preferably a tolyl group.

R ₁₆ and R ₁₇ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, and preferably a methyl group, a phenyl group or a tolyl group.

(In the formula (6), R ₁₈ represents an alkyl group having 1 to 6 carbon atoms, preferably an ethyl group.

R ₁₉ is an organic group having an acetal bond, and preferably a substituent corresponding to R ₁₉ of the compound represented by the formula (6-1) below.

R ₂₀ and R ₂₁ 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, more preferably a methyl group.

The compound represented by the following formula (4) is, for example, a compound represented by the following formula (4-1) and a compound represented by the following formula (4-2). The compound represented by the following formula (4-1) can be obtained as IRGACURE OXE-01 (manufactured by BASF Corporation, trade name).

The compound represented by the above formula (5) is, for example, a compound represented by the following formula (5-1). This compound can be obtained as DFI-091 (manufactured by Daito Chemix Co., Ltd., trade name).

The compound represented by the following formula (6) is, for example, a compound represented by the following formula (6-1). It can be obtained as Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., trade name).

Other oxime ester compounds preferably use the following compounds.

These oxime ester compounds may be used singly or in combination of two or more.

Further, in addition to the above-described oxime ester compound as the component (b), a conventionally known person may be added as a photoinitiator.

The content of the component (b) is preferably from 0.1 part by mass to 20 parts by mass, more preferably from 0.1 part by mass to 15 parts by mass, even more preferably from 0.5 to 15 parts by mass, based on 100 parts by mass of the polyimine precursor as the component (a). Parts by mass to 10 parts by mass, especially preferably 0.5 parts by mass to 5 parts The mass fraction is extremely preferably from 1 part by mass to 5 parts by mass. When the amount is 0.1 parts by mass or more, the crosslinking of the exposed portion is more sufficiently performed, and the photosensitive characteristics (sensitivity and resolution) tend to be more excellent. When the amount is 20 parts by mass or less, the cured film can be obtained. The heat resistance is better.

The resin composition of the present invention is excellent in photosensitive characteristics by combining the components (a) and (b), and the stress of the formed cured film is lowered. In particular, the polyimine precursor having the structural unit represented by the general formula (1) as the component (a) and the fluorene represented by the general formula (4) to the general formula (6) as the component (b) When the ester compound is used in combination, since the oxime ester compound represented by the general formulae (4) to (6) exhibits high activity particularly when irradiated with an electron beam such as an i-ray, good photosensitive characteristics can be achieved. Further, in the case of producing a polyimide by heat treatment, there is a characteristic that a low stress is exhibited due to a rigid skeleton.

3. (c) Ingredients: Solvent

The component (c) is preferably a polar solvent in which the polyimine precursor of the component (a) is completely dissolved. Specific examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, tetramethylurea, and hexamethyl Phosphonic triamine, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1 , 3-dimethyl-2-imidazolidinone, N,N'-dimethyl-propenyl urea, and the like. These solvents may be used singly or in combination of two or more.

It is preferable to contain 40% by mass to 80% by mass of the solvent in the resin composition, more preferably 45% by mass to 75% by mass of the solvent, and more preferably 45%. Mass %~70% by mass of solvent.

4. Other ingredients

When the photosensitive resin composition of the present invention is used on a copper substrate, it is preferred to contain a tetrazole derivative or a benzotriazole derivative from the viewpoint of preventing development residue from occurring in the unexposed portion.

The tetrazole derivatives may, for example, be 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetra Azole, 5,5'-bis-1H-tetrazole, 1-methyl-5-ethyl-tetrazole, 1-methyl-5-mercapto-tetrazole, 1-carboxymethyl-5-mercapto-tetra Oxazole and the like. Among these tetrazole derivatives, 1H-tetrazole or 5-amino-1H-tetrazole is preferred.

The benzotriazole derivative may, for example, be benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriene Oxazole, mercaptobenzoxazole. Among these benzotriazole derivatives, benzotriazole is preferred.

The tetrazole derivative or the benzotriazole derivative may be used alone or in combination of two or more. The derivatives are usually used in an amount of from 0.1 part by weight to 10 parts by weight per 100 parts by weight of the component (A), and in a total amount of from 0.1 part by weight to 10 parts by weight in combination of two or more. More preferably, it is in the range of 0.2 part by weight to 5 parts by weight.

In the resin composition of the present invention, an organic decane compound may be contained in order to improve the adhesion to the ruthenium substrate or the like after curing. The organodecane compound may, for example, be γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane or γ-glycidyloxy. Propyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-propyleneoxypropyltrimethoxydecane, 3 -ureidopropyltriethoxy Baseline, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, triethoxydecane Propyl ethyl urethane, 3-(triethoxydecyl)propyl succinic anhydride, phenyl triethoxy decane, phenyl trimethoxy decane, N-phenyl-3-amino Propyltrimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane and so on.

In the case of the content of the organic decane compound, the content is preferably set to 0.1 part by mass to 20 parts by mass, based on 100 parts by mass of the polyimide precursor, from the viewpoint of the adhesion after curing. The amount is preferably 0.5 parts by mass to 15 parts by mass, and more preferably 0.5 parts by mass to 10 parts by mass.

In the resin composition of the present invention, an addition polymerizable compound may be formulated as needed. Examples of the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate. Ester, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate Ester, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidine Ketone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-propenyloxy-2-hydroxypropane, 1,3-methylpropenyloxy-2-hydroxypropane, Methylene dipropylene fluorene Amine, N,N-dimethyl methacrylamide, N-methylol acrylamide, and the like. These addition polymerizable compounds may be used singly or in combination of two or more.

The content in the case of containing the addition polymerizable compound is preferably in the range of 100 parts by mass of the polyimide precursor, from the viewpoint of the solubility in the developer and the heat resistance of the obtained cured film. The amount is preferably from 1 part by mass to 100 parts by mass, more preferably from 1 part by mass to 75 parts by mass, and further preferably from 1 part by mass to 50 parts by mass.

Further, in the resin composition of the present invention, a radical polymerization inhibiting agent or a radical polymerization inhibitor may be formulated in order to secure good storage stability. Examples of the radical polymerization inhibiting agent or the radical polymerization inhibitor include p-methoxyphenol, diphenyl p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcin, and o Dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, Cupferron, 2,5-toluidine (2,5-toluquinone) ), citric acid, p-benzylaminophenol, nitrosamines, and the like. These compounds may be used singly or in combination of two or more.

The content in the case of containing a radical polymerization inhibiting agent or a radical polymerization inhibitor, with respect to the storage stability of the resin composition and the heat resistance of the obtained cured film, relative to the mass of the polyimide intermediate 100 The content is preferably from 0.01 part by mass to 30 parts by mass, more preferably from 0.01 part by mass to 10 parts by mass, even more preferably from 0.05 part by mass to 5 parts by mass.

Further, the resin composition of the present invention may substantially contain at least one of the above components (a) to (c) and the other components described above, or may be Contains these ingredients. The term "substantially contained" means that the composition mainly contains at least one of the components (a) to (c) and the other components described above, and for example, the components are 95% by mass or more or 98 based on the total amount of the raw materials. More than % by mass.

(pattern hardening film, method of manufacturing a pattern cured film, semiconductor device)

The pattern cured film of the present invention is obtained by heating the above-described resin composition of the present invention. The pattern cured film of the present invention is preferably used as a protective layer of a Low-k material as an interlayer insulating film. Examples of the Low-k material include porous ceria, benzocyclobutene, hydrogen sesquioxanes, polyallyl ether, and the like.

The method for producing a pattern cured film of the present invention comprises the steps of: applying a resin composition of the present invention onto a substrate and drying it to form a coating film; and irradiating the coating film formed in the above step with active light to expose the pattern a step of removing the unexposed portion other than the exposed portion by development; and a step of heat-treating the pattern obtained in the above step to form a polyimide film.

Examples of the method of applying the resin composition of the present invention to a substrate include a dipping method, a spray method, a screen printing method, and a spin coating method. Examples of the substrate include a germanium wafer, a metal substrate, a ceramic substrate, and the like. Since the resin composition of the present invention can form a low-stress cured film, it can be preferably applied to a large-diameter tantalum wafer of 12 Å or more.

After the resin composition is applied onto the substrate, the solvent is removed (dried) by heating, whereby a coating film (resin film) having less adhesiveness can be formed. Further, the heating temperature during drying is preferably from 80 ° C to 130 ° C, and the drying time is preferably from 30 seconds to 300 seconds. Drying is preferably carried out using a device such as a hot plate.

Then, by drawing a mask having a desired pattern, the method obtained by the above method The coating film illuminates the active light and is exposed in a pattern. The resin composition of the present invention is suitable for i-ray exposure, and the active light to be irradiated may be ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays or the like.

Then, the unexposed portion is dissolved and removed by using a suitable developer, whereby a desired pattern resin film can be obtained. The developer is not particularly limited, and a flame retardant solvent such as 1,1,1-trichloroethane, an aqueous alkaline solution such as a sodium carbonate aqueous solution or a tetramethylammonium hydroxide solution, or N,N-dimethyl group can be used. Good solvents such as decylamine, dimethyl hydrazine, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetate, etc. A mixed solvent of a good solvent and a poor solvent such as a lower alcohol, water or an aromatic hydrocarbon. After development, it is necessary to perform rinsing and washing with a poor solvent (for example, water, ethanol, 2-propanol).

For example, the pattern obtained as described above is heated at 80 ° C to 400 ° C for 5 minutes to 300 minutes, whereby the polyimide precursor contained in the resin composition can be imidized to obtain a pattern cured film. In the step of the heat treatment, in order to suppress oxidative degradation of the polyimide by heating, it is preferred to use a hardening furnace which can be cured at a low oxygen concentration of 100 ppm or less. For example, an inert gas oven can be used. Or a vertical diffusion furnace for heat treatment.

[Example of use of cured film or patterned cured film]

The cured film or pattern-hardened film of the present invention thus obtained can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer, or the like of a semiconductor device.

Fig. 1 is a schematic cross-sectional view showing a semiconductor device having a rewiring structure according to an embodiment of the present invention. Semiconductor device of this embodiment It has a multilayer wiring structure. An aluminum (Al) wiring layer 2 is formed on the interlayer insulating layer (interlayer insulating film) 1, and an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed on the upper portion thereof, thereby forming a surface protective layer of the element. (surface protective film) 4. The pad portion 5 of the wiring layer 2 is formed with a rewiring layer 6 extending to the upper portion of the core portion 8, and the core portion 8 is a conductive ball formed of solder, gold or the like as an external connection terminal. The connection part of 7. Further, an overcoat 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 order to further alleviate the stress when installing the package of such a structure, an under fill 12 is sometimes interposed.

In the case of a semiconductor device using copper in the above-mentioned rewiring layer 6, a photosensitive composition using IRGACURE OXE-01 (trade name, manufactured by BASF Corporation) may be formed. When the film is cured, a polyimide residue is generated in the opening. It is presumed that the reason is that on copper, a specific oxime ester compound generates a radical during prebaking, and the unexposed portion is also hardened. This can be suppressed by including a tetrazole derivative or a benzotriazole derivative in the photosensitive resin composition.

It is presumed that the photosensitive resin composition contains a tetrazole derivative or a benzotriazole derivative, and a tetrazole derivative or a benzotriazole derivative forms a film on copper to prevent active metal surface and resin composition from being directly By contact, it is possible to suppress decomposition or radical polymerization of an unnecessary photoinitiator in the unexposed portion, and to secure photosensitivity on the copper substrate.

The cured film or the patterned cured film of the present invention can be used for a so-called packaging application such as a cover coat material, a core material for rewiring, a ball collar material such as solder, or an underfill material.

The cured film or the patterned cured film of the present invention is excellent in adhesion to a metal layer or a sealant, and the like, and is excellent in copper migration resistance and high in stress relaxation effect, and thus has the cured film or pattern hardening of the present invention. The reliability of the semiconductor element of the film is extremely excellent.

The semiconductor device of the present invention has a pattern cured film obtained by the production method of the present invention. Examples of the semiconductor device include a logic (Logic) semiconductor device such as a microprocessor unit (MPU), or a memory such as a dynamic random access memory (DRAM) or a NAND flash memory (memory). ) is a semiconductor device or the like.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples.

Example 1 to Example 12, Comparative Example 1 to Comparative Example 6

(1) Synthesis of polyglycolate (polyimine precursor)

The tetracarboxylic dianhydride 1 shown in Table 1 or Table 2 is 2 equivalents of 2-hydroxyethyl methacrylate relative to tetracarboxylic dianhydride 1, and the catalyst amount of 1,8-dia nitrogen Heterobicyclo[5.4.0]undec-7-ene (DBU) is dissolved in N-methyl-2-pyrrolidone in an amount of 4 times the mass ratio of tetracarboxylic dianhydride 1 at room temperature The mixture was stirred for 48 hours to obtain an ester solution 1.

Further, if necessary, the tetracarboxylic dianhydride component 2 shown in Table 1 is relative to the tetracarboxylic acid. The dianhydride 2 is 2 equivalents of 2-hydroxyethyl methacrylate and the amount of catalyst DBU is dissolved in N-methyl-2- in an amount of 4 times the tetracarboxylic dianhydride 2 by mass ratio. The pyrrolidone was stirred at room temperature for 48 hours to obtain an ester solution 2.

After the ester solution 1 and the ester solution 2 were mixed, the mixture was cooled in an ice bath, and 2.2 eq. of ruthenium chloride was added dropwise to the total amount of the tetracarboxylic dianhydride 1 and the tetracarboxylic dianhydride 2. The hydrazine chloride solution was prepared by stirring for 1 hour.

Further, it is prepared to dissolve twice the equivalent amount of pyridine of the diamine 1 and the optional diamine 2 and sulfinium chloride shown in Table 1 in a mass ratio of four times that of the diamine 1 and the diamine 2. A solution of methyl-2-pyrrolidone was added dropwise to the above-prepared hydrazine chloride solution while cooling on one side in an ice bath. After the completion of the dropwise addition, the reaction liquid droplets were added to distilled water, and the resulting precipitate was separated by filtration and collected, washed several times with distilled water, and then vacuum dried to obtain a polyamidate.

(2) Preparation of photosensitive resin composition

100 parts by mass of polyperurethane [(a) component], 20 parts by mass of tetraethylene glycol dimethacrylate, and light-initiated light generated by irradiation of active rays as shown in Table 1 or Table 2 The amount of the component (the component (b)) was adjusted to 150 parts by mass of the N-methyl-2-pyrrolidone [(c) component] until it was uniformly dissolved, and then subjected to pressure filtration using a 1 μm filter. Resin composition.

(Measurement of weight average molecular weight)

The weight average molecular weight of the obtained polyphthalate was determined by a gel permeation chromatography (GPC) method in terms of standard polystyrene. In addition, the measurement conditions of the weight average molecular weight by the GPC method are as follows.

0.5 mg of the polymer was measured using a solution of 1 [ml of a solvent [Tetrahydrofuran (THF) / Dimethylformamide (DMF) = 1 / 1 (volume ratio)].

Measuring device: detector 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

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

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

Flow rate: 1.0 ml/min, detector: ultraviolet (Ultraviolet, UV) 270 nm

(Measurement of i-ray transmittance)

The following articles were prepared and the transmittance at 365 nm was measured: 100 parts by mass of the obtained polyphthalate was dissolved in 150 parts by mass of N-methyl-2-pyrrolidone, and the obtained polyphthalate solution was spin-coated. The glass plate was heat-treated at 100 ° C for 3 minutes on a hot plate to form a coating film having a film thickness of 20 μm. The measurement of the i-ray transmittance was carried out by a cast film method using a visible ultraviolet spectrophotometer U-3310 manufactured by Hitachi High-Technologies. When the transmittance was 20% or more, it was evaluated as H, and when the transmittance was 10% or more and less than 20%, it was evaluated as M, and when the transmittance was less than 10%, it was evaluated as L.

(Evaluation of photosensitive characteristics)

The obtained photosensitive resin composition was applied onto a 6-inch wafer by a spin coating method, and dried on a hot plate at 100 ° C for 3 minutes to form a coating film having a film thickness of 10 μm. The coating film is interposed mask using an i-ray stepper FPA-3000iW Canon (Canon) Co. manufactured to 50mJ / cm ² in units of a predetermined pattern irradiation ^{50mJ / cm 2 ~ 500mJ / cm} i 2 of Ray, exposure. Further, the unexposed coating film having the same thickness was immersed in cyclopentanone, and the time until twice the time until complete dissolution was set as the development time, and the exposed wafer was immersed in cyclopentanone for immersion development. After that, it was rinsed with isopropyl alcohol. The minimum exposure amount of the coating film of the exposure portion at this time is less than 10% of the initial film thickness as the sensitivity, and the minimum value of the mask size of the square hole-shaped opening portion is evaluated as the resolution. .

Those having a sensitivity of 300 mJ/cm ² or less were evaluated as ○, those having a sensitivity of more than 300 mJ/cm ² and 500 mJ/cm ² or less were evaluated as Δ, and those having a sensitivity of more than 500 mJ/cm ² were evaluated as ×. The degree of resolution of 10 μm or less was evaluated as ○, the resolution of more than 10 μm and 30 μm or less was evaluated as Δ, and the resolution of more than 30 μm was evaluated as ×.

(Measurement of residual stress)

The obtained photosensitive resin composition was applied onto a 6-inch wafer having a thickness of 625 μm, and was spin-coated so as to have a film thickness of 10 μm after curing. It was heat-hardened at 375 ° C for 1 hour under a nitrogen atmosphere using a vertical diffusion furnace manufactured by Kobayashi Lindberg to obtain a polyimide film (cured 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. When the stress is 30 MPa or less, it is evaluated as ○, and when the stress is more than 30 MPa and 35 MPa or less, it is evaluated as Δ, and when the stress is more than 35 MPa, it is evaluated as ×.

(Evaluation of chemical resistance)

The tantalum wafer with a cured film prepared for the measurement of the residual stress was immersed in N-methyl pyrrolidinone (NMP) at 70 ° C for 20 minutes, and then washed with pure water to adhere thereto. After the moisture on the surface of the cured film is wiped off, it is air-dried. The rate of change of the film thickness of the cured film after air drying to the initial film thickness is within ±10%, and is evaluated as ○, and the rate of change is greater than ±10% and ±20% or less, and the rate of change is greater than ±20%. The evaluation is ×.

The measurement results are shown in Table 1 or Table 2.

In Tables 1 and 2, the numerical values in the parentheses of the photoinitiator indicate the mass parts of the photoinitiator relative to 100 parts by mass of the polyphthalate.

In addition, the abbreviation in the table indicates the following compound, and the mass in the bracket is the amount of the raw material added.

. Polyimine precursor material

PMDA: pyromellitic dianhydride

s-BPDA: 4,4'-biphenyltetracarboxylic dianhydride

MMXDA: 9,9'-dimethyl-2,3,6,7-dibenzopyrantetracarboxylic dianhydride

ODPA: 4,4'-oxydiphthalic anhydride

TFDB: 2,2'-bis(trifluoromethyl)benzidine

DMAP: 2,2'-dimethylbenzidine

. Photoinitiator

Compound 1: IRCAC OXE-01, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzylidene), manufactured by BASF肟)

Compound 2: IRKAC (OXGA-02) OXE-02, 1-[6-(2-methylbenzhydryl)-9-ethyl-9H-carbazol-3-yl], manufactured by BASF Corporation Ethyl ketone O-acetyl hydrazine

Compound 3: 4,4'-bis(diethylamino)benzophenone

Compound 4: bis[4-(2-hydroxy-2-methylpropenyl)phenyl]methane

Compound 5: bis(η ⁵ -cyclopentadienyl) bis[2,6-difluoro-3-(1H-pyrrol-1-yl)]phenyltitanium

In Examples 1 to 12 using a photoinitiator having an oxime ester structure, excellent photosensitivity was exhibited, whereas in Comparative Example 1, using benzophenone type photoinitiator, benzene was used. In Comparative Example 2 of the ethyl ketone type photoinitiator and Comparative Example 3 using the titanocene type photoinitiator, the photosensitive characteristics were lowered. Further, in Examples 1 to 12 in which PMDA, s-BPDA, and MMXDA were used as the tetracarboxylic dianhydride, low stress was exhibited, whereas in Comparative Example 6 using only ODPA, high stress was exhibited. Further, in Examples 1 to 12 in which DMAP having a monovalent organic group having no fluorine atom or fluorine atom was used as the diamine, it was found that good chemical liquid resistance was exhibited, and in contrast, it was used. In Comparative Example 4 and Comparative Example 5 in which the diamine TFDB having a trifluoromethyl group was found to have a low chemical resistance.

Example 13 [Preparation and Evaluation of Photosensitive Resin Composition]

100 parts by mass of the polyglycolate [(a) component], 20 parts by mass of tetraethylene glycol dimethacrylate, and 1-[4-(phenylthio)benzene, which are the same as those of Examples 5 to 9. 3 parts by weight of -1,2-octanedione 2-(O-benzhydrylhydrazine) and 3 parts by weight of benzotriazole in N-methyl-2-pyrrolidone [(c) component] 150 After stirring in a mass part until it was uniformly dissolved, it was subjected to pressure filtration using a 1 μm filter to obtain a resin composition. The resin composition obtained was evaluated in the same manner as in Example 1 to Example 12 except that the residue on the copper substrate was evaluated by the following method. The results are shown in Table 3.

Example 14 [Preparation and Evaluation of Photosensitive Resin Composition]

100 parts by mass of the polyglycolate [(a) component], 20 parts by mass of tetraethylene glycol dimethacrylate, and 1-[4-(phenylthio)benzene, which are the same as those of Examples 5 to 9. 3 parts by weight of -1,2-octanedione 2-(O-benzylidene fluorene) and 3 parts by weight of tetrazole in 150 parts by mass of N-methyl-2-pyrrolidone [(c) component] After stirring until it was uniformly dissolved, the mixture was filtered under pressure using a 1 μm filter to obtain a resin composition. The resin composition obtained was evaluated in the same manner as in Example 1 to Example 12 except that the residue on the copper substrate was evaluated by the following method. The results are shown in Table 3.

Example 15 [Preparation and Evaluation of Photosensitive Resin Composition]

100 parts by weight of the same polyamine amide ester, 20 parts by weight of tetraethylene glycol dimethacrylate, 2 parts by weight of the compound represented by the above formula (4-2), and benzo with the same Examples 5 to 9. 3 parts by weight of triazole was stirred in 150 parts by weight of N-methyl-2-pyrrolidone until it was uniformly dissolved, and then subjected to pressure filtration using a 1 μm filter to obtain a photosensitive resin composition. The resin composition obtained was evaluated in the same manner as in Example 1 to Example 12 except that the residue on the copper substrate was evaluated by the following method. The results are shown in Table 3.

Example 16 [Preparation and Evaluation of Photosensitive Resin Composition]

100 parts by weight of the same polyamine amide ester, 20 parts by weight of tetraethylene glycol dimethacrylate, 2 parts by weight of the compound represented by the above formula (4-2), and tetrazole, which are the same as those in Examples 5 to 9. 3 parts by weight of a mixture of 150 parts by weight of N-methyl-2-pyrrolidone until it was uniformly dissolved, and then subjected to pressure filtration using a 1 μm filter, thereby obtaining a feeling Light resin composition. The resin composition obtained was evaluated in the same manner as in Example 1 to Example 12 except that the residue on the copper substrate was evaluated by the following method. The results are shown in Table 3.

(Evaluation of residue on copper substrate)

A copper substrate prepared for the measurement of the residue on the copper substrate (a pattern-hardened film was formed on the copper substrate by the same method as the evaluation of the photosensitive characteristics described above) was used in a vertical diffusion furnace manufactured by Koyo Limdberg in a nitrogen atmosphere. The film was heat-hardened at 375 ° C and 300 ° C for 1 hour to obtain a patterned polyimide film (hardened film). After immersing for 5 minutes in the Cu oxide film removal solution Z-200 (manufactured by World Metal Co., Ltd.) for 2 minutes by an O ₂ ashing apparatus (manufactured by Yamaha Scientific Co., Ltd.), After washing with pure water, the moisture adhering to the surface of the cured film is wiped off and air-dried. The residue of the pattern opening was observed using a scanning electron microscope (SEM) manufactured by Hitachi High-Technologies Co., Ltd., and the presence of the polyimide residue in the opening was evaluated as ○. The case where the residue was confirmed was evaluated as ×.

For the compositions prepared in Examples 1 to 12, the residue on the copper substrate was also evaluated. The results are shown in Table 4.

As is apparent from Table 4, when benzotriazole or tetrazole was added to the resin composition of the present invention, no development residue was generated on the copper substrate.

[Industrial availability]

The resin composition of the present invention can be used for a protective film material or a pattern film forming material of an electronic component such as a semiconductor device.

The embodiments and/or the embodiments of the present invention have been described in detail above, but those skilled in the art will be able to practice the embodiments and/or implementations without departing from the novel teachings and effects of the invention. There are many changes to the examples. Accordingly, such various modifications are intended to be included within the scope of the present invention.

The contents of the documents described in the present specification and the Japanese Patent Application Laid-Open No.

1‧‧‧Interlayer insulation (interlayer insulation film)

2‧‧‧Aluminum (Al) 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‧‧‧Overcoat

10‧‧‧Resistance metal

11‧‧‧ collar

12‧‧‧ bottom packing

Claims (6)

A resin composition comprising the following components (a) to (c): (a) a polyimine precursor having a structural unit represented by the following formula (1); (b) an oxime ester compound; c) solvent; (In the formula (1), A is any one of the tetravalent organic groups represented by the following formulas (2a) to (2d), and B is a divalent organic group represented by the following formula (3); ¹ and R ² are each independently a hydrogen atom, a monovalent organic group or a group having a carbon-carbon unsaturated double bond, and at least one of R ¹ and R ² is a group having a carbon-carbon unsaturated double bond); (In the formula (2d), X and Y each independently represent a divalent group or a single bond which is not conjugated to the respective bonded benzene ring); (In the formula (3), R ³ to R ¹⁰ are each independently hydrogen or a monovalent organic group; wherein R ³ to R ^{10 are} not a halogen atom and a monovalent organic group containing a halogen atom). The resin composition according to the first aspect of the invention, wherein the component (b) is a compound represented by the following formula (4), a compound represented by the formula (5) or a compound represented by the formula (6) compound of, (In the formula (4), R ₁₁ and R ₁₂ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or a phenyl group; and R ₁₃ represents H, OH, COOH, O(CH ₂ ). OH, O(CH ₂ ) ₂ OH, COO(CH ₂ )OH or COO(CH ₂ ) ₂ OH); (In the formula (5), R ₁₄ represents an alkyl group having 1 to 6 carbon atoms, R ₁₅ represents NO ₂ or ArCO (wherein Ar represents an aryl group), and R ₁₆ and R ₁₇ each represent a carbon number of 1 to 12; Alkyl, phenyl or tolyl); (In the formula (6), R ₁₈ represents an alkyl group having 1 to 6 carbon atoms, R ₁₉ represents an organic group having an acetal bond, and R ₂₀ and R ₂₁ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group or a toluene. base). The resin composition according to claim 1, wherein the polyimine precursor of the component (a) further has a structural unit represented by the following formula (7). (In the formula (7), D is a tetravalent organic group represented by the following formula (8), and B, R ¹ and R ^{2 are the} same as the formula (1)); (In the formula (8), Z is an ether bond (-O-) or a thioether bond (-S-)). The resin composition according to any one of claims 1 to 3, further comprising a tetrazole derivative or a benzotriazole derivative. A method for producing a patterned cured film, comprising the steps of: applying a resin composition according to any one of claims 1 to 4 to a substrate and drying the film to form a coating film; a step of exposing the active film to the active light and patterning; removing the unexposed portion other than the exposed portion by development; and heat-treating the pattern obtained in the above step to form a polyimide The steps of the pattern. A semiconductor device comprising a pattern cured film obtained by the method for producing a patterned cured film according to claim 5 of the patent application.