JP6427383B2 - Resin composition, method of producing cured relief pattern, and semiconductor device - Google Patents

Description

  The present invention relates to, for example, a resin composition used for forming a relief pattern such as an insulating material of an electronic component, a passivation film in a semiconductor device, a buffer coat film, and an interlayer insulating film, a method of producing a cured relief pattern using the same The present invention relates to a semiconductor device.

Conventionally, polyimide resins having excellent heat resistance, electrical properties, and mechanical properties have been used for insulating materials of electronic components, passivation films of semiconductor devices, surface protective films, interlayer insulating films, and the like. Among the polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by thermal imidization treatment by coating, exposing, developing and curing the precursor. be able to. Such photosensitive polyimide precursors have the feature of enabling significant process reduction as compared to conventional non-photosensitive polyimides.
In recent years, the mounting method of a semiconductor device on a printed wiring board has changed from the viewpoint of improving the degree of integration and functions, and reducing the chip size. From the conventional mounting method using metal pins and lead-tin eutectic solder, structures such as BGA (ball grip array), CSP (chip size packaging), etc., which can be mounted at higher density, have come to be used. There is. In these structures, the polyimide coating directly contacts the solder bumps. The film in such a bump structure is required to have high heat resistance and chemical resistance.

Then, the method of improving the heat resistance of a polyimide membrane is disclosed by adding a thermal crosslinking agent to the composition containing a polyimide precursor (refer patent document 1).
In recent semiconductor processes, the stepper exposure time has become longer as the wafer size has become larger. Along with this, from the viewpoint of improving the yield in the exposure process, it is required to increase the sensitivity of the photosensitive material. In the rewiring process, adhesion to not only the silicon base material but also the wiring layer made of copper or the like is required. As a method for increasing sensitivity, the improvement method by the chemical structure of the initiator and the sensitizer is generally used, but the adhesion to the substrate may be reduced by the addition of these components, which is excellent. It is desired to develop a resin composition in which both adhesion and high photosensitivity are compatible.

JP 2003-287889 A

An object of the present invention is to provide a resin composition which exhibits excellent photosensitivity when applied as a photosensitive resin composition as well as having excellent adhesion to a substrate.
Another object of the present invention is to provide a method for producing a cured relief pattern, in which a resin pattern is formed using the photosensitive resin composition, and a semiconductor device.

  The present inventors have found that a photosensitive resin composition having high photosensitivity and excellent adhesion to a substrate can be obtained by using a compound having a specific amide structure, thereby completing the present invention. It reached. That is, the present invention is as follows.

[1] (A) at least one resin selected from the group consisting of an alkali-soluble resin and a resin having a polymerizable group in a side chain: 100 parts by mass, and (B) the following general formula (1):

{In formula (1), R ₁ and R ₂ are each independently an alkyl group of 1 to 5 carbon atoms,
R ₃ and R ₄ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, provided that this hydrocarbon group may have an ether bond, and R ₃ and R ₄ are bonded To form a ring structure. The amide compound represented by}: 0.001-1 mass part, The resin composition characterized by the above-mentioned.
[2] The component (A) has the following general formula (2):

{In general formula (2), X ₁ is a tetravalent organic group,
Y ₁ is a divalent organic group,
R ₅ and R ₆ are each independently a hydrogen atom, a monovalent organic group capable of radical polymerization, a monovalent organic group, or a saturated aliphatic group having 1 to 4 carbon atoms 5 to 30 carbon atoms. The resin composition according to [1], which is a polyimide precursor having a repeating unit represented by
[3] R ₅ and R ₆ in the above general formula (2) are each independently a hydrogen atom, the following general formula (3):

{Wherein _{(3), R 9, R} 10 and _{R 11} are each independently a monovalent organic group hydrogen atom or 1 to 3 carbon atoms, and m is an integer from 2 to 10. Or a monovalent organic group represented by the general formula (4):
-R ₁₂ (4)
{In the formula (4), R ₁₂ is a monovalent group selected from an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, and an aromatic group having 6 to 30 carbon atoms . A monovalent organic group represented by the above general formula (3) and a compound represented by the above general formula (4) for all of R ₅ and R ₆ The ratio of the total of the valent organic groups is 80 mol% or more, and the ratio of the monovalent organic group represented by the above general formula (4) is 20 mol% to 80 mol with respect to all of R ₅ and R ₆ %, The resin composition as described in [2].
[4] R ₅ and R ₆ in the above general formula (2) are each independently a hydrogen atom, the following general formula (3):

{Wherein _{(3), R 9, R} 10 and _{R 11} are each independently a monovalent organic group hydrogen atom or 1 to 3 carbon atoms, and m is an integer from 2 to 10. Or a saturated aliphatic group having 1 to 4 carbon atoms, provided that R ₅ and R ₆ are not simultaneously hydrogen atoms, as described in [2]. Resin composition.
[5] The resin composition according to any one of [1] to [4], wherein the component (B) is N, N-dimethyl-3- (dimethylamino) propanamide.
[6] The resin composition according to any one of [1] to [5], which further contains a photosensitive agent (C) and is photosensitive.

[7] The following steps:
(1) applying a photosensitive resin composition according to [6] on a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of: heating the relief pattern to form a cured relief pattern.
[8] A semiconductor device comprising the cured relief pattern obtained by the method according to [7].

ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in the adhesiveness with respect to a base material can be obtained. When the resin composition is applied as a photosensitive resin composition, it exhibits high sensitivity while maintaining excellent adhesion.
The present invention further provides a method for producing a cured relief pattern and a semiconductor device, wherein a resin pattern is formed using the photosensitive resin composition.

  Embodiments of the present invention will be specifically described below. Throughout the specification, in the case where a plurality of structures represented by the same symbol in the general formula are present in a molecule, they may be identical to or different from each other.

<Resin composition>
The resin composition of the present embodiment comprises (A) at least one resin selected from the group consisting of an alkali-soluble resin and a resin having a polymerizable group in a side chain, and (B) the following general formula (1):

{In formula (1), R ₁ and R ₂ are each an alkyl group of 1 to 5 carbon atoms,
R ₃ and R ₄ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, provided that this hydrocarbon group may have an ether bond, and R ₃ and R ₄ are bonded To form a ring structure. The amide compound represented by} is contained as an essential component.

[(A) resin]
The resin (A) used in the present embodiment will be described.
The (A) resin in the present embodiment is at least one resin selected from the group consisting of an alkali-soluble resin and a resin having a polymerizable group in a side chain.
(A) The resin is, for example, a polyimide precursor such as polyamic acid or polyamic acid ester;
It is preferable to contain at least one resin selected from the group consisting of polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, polyoxazole precursor such as polybenzthiazole, and the like. The resin (A) in the present embodiment preferably contains at least 60% by mass or more, and more preferably 80% by mass or more, of at least one resin selected from the above with respect to the entire resin. The resin (A) in the present embodiment may contain 100% by mass of at least one resin selected from the above, and may contain other resins as necessary.

The weight average molecular weight of these resins is preferably 1,000 or more, more preferably 5,000 or more, as a polystyrene conversion value by gel permeation chromatography, from the viewpoint of heat resistance and mechanical properties after heat treatment. The upper limit of the weight average molecular weight is preferably 100,000 or less. When the resin composition of the present embodiment is used as a photosensitive resin composition, the weight average molecular weight of the resin (A) is more preferably 50,000 or less from the viewpoint of solubility in a developer.
The resin (A) in the present embodiment is desirably a photosensitive resin in order to form a relief pattern. A photosensitive resin can be made into a photosensitive resin composition by using this with the below-mentioned (C) photosensitive agent, It is resin which causes melt | dissolution or undissolved development in a subsequent image development process. The photosensitive resin is preferably a resin containing a polymerizable group in the side chain. Such a photosensitive resin can be suitably selected according to the desired characteristic and use which a photosensitive resin composition should have.

It is preferable that the resin kind which comprises the main frame of resin (A) in this embodiment is at least 1 sort (s) chosen from the above-mentioned resin group. Among these, at least one resin selected from the group consisting of a polyamic acid, a polyamic acid ester, a polyamide, a polybenzoxazole precursor, and a polyimide is more preferable because the resin after heat treatment is excellent in heat resistance and mechanical properties. Particularly preferred is at least one resin selected from the group consisting of polyamic acid and polyamic acid ester which are polyimide precursors.
In the photosensitive resin composition of the present invention, the most preferable (A) resin from the viewpoint of heat resistance and photosensitivity is represented by the following general formula (2):

{In general formula (2), X ₁ is a tetravalent organic group,
Y ₁ is a divalent organic group,
R ₅ and R ₆ are each independently a hydrogen atom, a monovalent organic group capable of radical polymerization, a monovalent organic group, or a saturated aliphatic group having 1 to 4 carbon atoms 5 to 30 carbon atoms. }
The polyimide precursor has a structure represented by The polyimide precursor represented by the said General formula (2) is converted into a polyimide, for example by giving the cyclization process by heating 200 degreeC or more.
The radically polymerizable monovalent organic group of R ₅ and R ₆ in the above general formula (2) includes the following general formula (3):

{Wherein _{(3), R 9, R} 10 and _{R 11} are each independently a monovalent organic group hydrogen atom or 1 to 3 carbon atoms, and m is an integer from 2 to 10. It is preferable that it is a monovalent organic group represented by}.
Each of R ₁₀ and R ₁₁ in the general formula (3) is preferably independently a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of photosensitive properties. R ₉ is preferably a hydrogen atom or a methyl group. Further, m is preferably an integer of 2 or more and 10 or less, more preferably an integer of 2 or more and 4 or less, from the viewpoint of the photosensitive properties.

_{R 5} and _{R 6} in the general formula (2), the monovalent organic group having 5 to 30 carbon atoms, the following general formula (4):
-R ₁₂ (4)
{In the formula (4), R ₁₂ is a monovalent group selected from an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or an aromatic group having 6 to 30 carbon atoms . It is preferable that it is a monovalent organic group represented by}.
Examples of the aliphatic group having 5 to 30 carbon atoms which may have the hetero atom of R ₁₂ in the above general formula (4) include, for example, isopentyl group, butoxymethyl group, butyl sulfide methylene group, butylaminomethylene group and the like And others; aliphatic groups containing an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom as a hetero atom can be mentioned. The aromatic having 6 to 30 carbon atoms R _12, and examples thereof include a phenyl group, a benzyl group, a naphthyl group.
The saturated aliphatic group having 1 to 4 carbon atoms of R ₅ and R ₆ in the general formula (2), for example a methyl group, an ethyl group, a propyl group, a primary hydrocarbon group such as butyl group;
A secondary hydrocarbon group such as isobutyl group;
Tertiary hydrocarbon groups, such as t-butyl group, etc. can be mentioned.

As R ₅ and R ₆ in the above general formula (2), particularly preferably each independently
A hydrogen atom, a monovalent organic group represented by the above general formula (3), or a monovalent organic group represented by the above general formula (4), and the above general formula for all of R ₅ and R ₆ The total ratio of the monovalent organic group represented by the formula (3) and the monovalent organic group represented by the general formula (4) is 80 mol% or more, and all of R ₅ and R ₆ are When the ratio of the monovalent organic group represented by the general formula (4) is 20 mol% to 80 mol%; or
A hydrogen atom, a monovalent organic group represented by the above general formula (3), or a saturated aliphatic group having 1 to 4 carbon atoms, provided that both of R ₅ and R ₆ are hydrogen atoms at the same time; There is no case.
Such a resin (A) suitably functions as a polyimide precursor which is cyclized and converted to a polyimide by heat treatment at, for example, 200 ° C. or higher.

In the above general formula (2), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitivity, and more preferably And one of -COOR ₅ and -CONH- is bonded to the same aromatic ring, both are in the ortho position with each other, and the other of -COOR ₆ and -CONH- is the same aromatic ring Or a tetravalent aromatic group or a tetravalent cycloaliphatic aliphatic group, both of which are in ortho position to each other. In the former case, the aromatic ring to which the -COOR ₅ group is bonded and the aromatic ring to which the -COOR ₆ group is bonded may be the same aromatic ring or different aromatic rings. . The aromatic ring in this context is preferably a benzene ring.
More preferably, the tetravalent organic group represented by X ₁ is represented by the following formula:

The structures represented by each of the above are included, but are not limited thereto. In addition, the structure of X ₁ may be one kind or a combination of two or more kinds. The X ₁ group having such a structure is preferable in that the heat resistance and the photosensitive characteristics are compatible.
In the above general formula (2), the divalent organic group represented by Y ₁ is preferably an aromatic group having a carbon number of 6 to 40, from the viewpoint of achieving both heat resistance and photosensitive properties, for example, Following formula:

{In the above formula, each A is independently methyl (-CH), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ) or butyl (-C ₄ H ₉ ) . The structures represented by each of} can be mentioned, but it is not limited thereto. The structure of Y ₁ may be one kind or a combination of two or more kinds. The Y ₁ group having a structure represented by the above formula is preferable in that both the heat resistance and the photosensitive characteristics are compatible.

  When a polyimide precursor is used as the resin (A), an ester bond type and an ion bond type may be mentioned as a system for providing a monovalent organic group capable of radical polymerization to the resin. The former is a method of introducing a monovalent organic group which can be radically polymerized by an ester bond to the side chain of the polyimide precursor. The latter is a reaction of a resin having a carboxyl group with a radically polymerizable compound having an amino group (for example, a (meth) acrylate compound having an amino group) to form a polyimide precursor via an ionic bond between the carboxyl group and the amino group. It is a method of introducing a monovalent organic group capable of radical polymerization into the side chain of the body. Among these, the ester bond type is preferable.

[Method of preparing polyimide precursor]
The preparation of the ester bond type polyimide precursor may be carried out, for example, by first preparing a tetracarboxylic acid dianhydride having a desired tetravalent organic group X ₁ and an alcohol having a radical polymerizable group (for example, unsaturated double bond) And a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester) are prepared, and then this and an diamine having a desired divalent organic group Y ₁ are used as It is obtained by condensation. A saturated aliphatic alcohol may optionally be used in combination with the above-mentioned alcohol having a radically polymerizable group (for example, unsaturated double bond).

(Preparation of acid / ester)
Examples of tetracarboxylic acid dianhydride having a tetravalent organic group X ₁ suitably used to prepare an ester bond type polyimide precursor in the present embodiment include, for example, pyromellitic anhydride, diphenyl ether-3. , 3 ', 4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic acid Dianhydride, diphenyl sulfone-3,3 ′, 4,4′-tetracarboxylic acid dianhydride, diphenylmethane-3,3 ′, 4,4′-tetracarboxylic acid dianhydride, 2,2-bis (3 And 2,4-phthalic anhydride) propane and 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane, etc. It is not something to be done. In addition, it is possible to use two or more of them in combination, as a matter of course.

  In this embodiment, as alcohols having a radically polymerizable group, which are suitably used to prepare an ester bond type polyimide precursor, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol Alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2 -Hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxye Alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, Examples thereof include 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

As saturated aliphatic alcohol which can be optionally used with alcohol which has the said radically polymerizable group, a C1-C4 saturated aliphatic alcohol is preferable. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like. The amount of the saturated aliphatic alcohol used is preferably 80 mol% or less, more preferably 50 mol% or less, based on the total of the alcohol having a radically polymerizable group and the saturated aliphatic alcohol. preferable.
The amount of alcohol used is preferably 0.1 to 5 moles, more preferably 1 to 3 moles, as the total amount of alcohols used per 1 mole of tetracarboxylic acid dianhydride having tetravalent organic group X _1. It is more preferable to

The above preferred tetracarboxylic acid dianhydrides and the above alcohols are preferably stirred for 4 to 10 hours at a temperature of 20 to 50 ° C., preferably in the presence of a basic catalyst such as pyridine, preferably in a suitable reaction solvent. By mixing, the esterification reaction of the acid anhydride can proceed to obtain the desired acid / ester.
As the above-mentioned reaction solvent, preferred are those capable of completely dissolving tetracarboxylic acid dianhydride and alcohols as raw materials and acid / ester as product. More preferably, (A) resin which is an amide polycondensation product of the acid / ester and diamine is also a solvent which completely dissolves. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbonized Hydrogen etc. are mentioned. Examples of these are
As ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc .;
As esters, for example, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate etc .;
As lactones, for example, γ-butyrolactone etc .;
As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like;
As halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene etc .;
As hydrocarbons, for example, hexane, heptane, benzene, toluene, xylene and the like,
Each can be mentioned. These may be used alone or in combination of two or more, as necessary.

(Preparation of Polyimide Precursor)
A suitable dehydration condensation agent is added to and mixed with the above-mentioned acid / ester (typically in the form of a solution dissolved in the above reaction solvent), preferably under ice cooling, to obtain an acid / ester as a polyanhydride. I assume. Subsequently, a solution obtained by separately dissolving or dispersing a diamine having a divalent organic group Y ₁ suitably used in the present embodiment in a solvent is added dropwise thereto, and the desired polyimide is obtained by subjecting both to amide polycondensation. Precursors can be obtained.
As the above-mentioned dehydration condensation agent, for example, dicyclohexyl carbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N '-Disuccinimidyl carbonate etc. are mentioned. The amount of the dehydration condensation agent to be used is preferably 0.1 to 10 moles, and more preferably 1 to 5 moles, per mole of the acid / ester.
The reaction between the acid / ester and the dehydration condensation agent is carried out, for example, at -50 to 50 ° C, preferably -20 to 30 ° C, for example, for 1 minute to 24 hours, preferably 5 minutes to 18 hours.
As described above, an intermediate polyacid anhydride is obtained.

Examples of diamines having a divalent organic group Y ₁ suitably used in the present embodiment include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl Sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone 3,3'-diaminobenzophenone, 4,4'-dia Minodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4 , 4-bis (3-amino phenoxy) biphenyl, bis [4- (4- amino phenoxy) phenyl] ether, bis [4- (3- amino phenoxy) phenyl] ether, 1, 4- bis (4- amino phenyl ) Benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) Ntracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2, 2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene etc;
And those in which a part of hydrogen atoms on these benzene rings are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen atom or the like;

And mixtures thereof. Specific examples of the substituted compound include, for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4. '-Diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl etc And mixtures thereof and the like. The diamines are not limited to the above examples.

In addition, for the purpose of improving the adhesion between the resin layer formed on the substrate and the various substrates by applying the resin composition according to the present embodiment on the substrate, the preparation of the resin (A), It is also possible to copolymerize diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane. The amount of these diaminosiloxanes used is preferably 80 mol% or less, more preferably 50 mol% or less, with respect to the total of diamines and diaminosiloxanes containing the divalent organic group Y _1. .
The amount of diamines used is preferably 0.5 to 2 moles as the total amount of diamines used relative to 1 mole of the amount of the polyacid anhydride converted to the acid / ester of the raw material, 0.8 It is more preferable to set it as -1.6 mol.
The amide polycondensation reaction of polyacid anhydride and diamines is carried out, for example, at -50 to 100 ° C, preferably -20 to 80 ° C, for example, for 1 minute to 48 hours, preferably 5 minutes to 24 hours.

  After completion of the amide polycondensation reaction, the water absorption by-product of the dehydration condensation agent coexisting in the reaction solution is separated by filtration if necessary, and a poor solvent suitable for a solution containing a polymer component (for example, water, fat Lower alcohol, its mixed solution, etc.) to precipitate the polymer component, and further, if necessary, repeat the operation such as re-dissolution and re-precipitation operation to purify the polymer, and then vacuum-dry it. Isolate the desired polyimide precursor. In order to improve the degree of purification, the solution of this polymer may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

  The molecular weight of the ester bond type polyimide precursor is preferably 1,000 to 100,000, preferably 5,000 to 50,000, when measured as a polystyrene equivalent weight average molecular weight by gel permeation chromatography. Is more preferred. When the weight average molecular weight is 1,000 or more, the mechanical properties are good, and when it is 100,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as a developing solvent for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodispersed polystyrene. As standard monodispersed polystyrene, it is recommended to select from Showa Denko organic solvent based standard sample STANDARD SM-105.

[(B) amide compound]
The (B) amide compound used in the present embodiment will be described.
(B) The amide compound has the following general formula (1):

{In formula (1), R ₁ and R ₂ are each independently an alkyl group of 1 to 5 carbons, and R ₃ and R ₄ are each independently a hydrogen atom or a hydrocarbon having 1 to 6 carbon atoms And the hydrocarbon group may have an ether bond, and R ₃ and R ₄ may combine to form a ring structure. It is a compound represented by}.
When the resin composition of the present embodiment is applied as a photosensitive resin composition by using such an (B) amide compound, the photosensitivity can be increased.

Generally, in the formation of a relief pattern by crosslinking of a radical reaction, the photosensitivity can be adjusted by a combination of a radical initiator and a sensitizer. As a sensitizer, what accelerates | stimulates reaction is known by energy-transferring to a triplet excited state rapidly, after becoming a singlet excited state from a ground state by light absorption. For example, Michler's ketone. Since the (B) amide compound in this embodiment hardly absorbs the wavelength of the mercury lamp of the exposure source used in the manufacturing process of the semiconductor, the mechanism of increasing the photosensitivity of the resin composition by the addition of the compound is unclear. is there. However, the (B) amide compound is considered to play a role as a sensitizer by preventing the radical generated by the (C) photosensitizer described later from being inactivated.
Moreover, the resin composition which is excellent in the adhesiveness with respect to a base material can be obtained by using the (B) amide compound. Although the mechanism by which the adhesion is improved by (B) the amide compound is not clear, the adhesion between the substrate and the resin is caused by the reaction of the amide group of the (B) amide compound with both the resin and the substrate (particularly copper). It is surmised that the nature is improved.

  (B) Specific examples of the amide compound include, for example, 3- (dimethylamino) propanamide, 3- (diethylamino) propanamide, 3- (dipropylamino) propanamide, 3- (dibutylamino) propanamide, -(Ethylmethylamino) propanamide, 3- (methylpropylamino) propanamide, 3- (methylbutylamino) propanamide, 3- (ethylpropylamino) propanamide, N-methyl-3- (dimethylamino) propane Amide, N-methyl-3- (diethylamino) propanamide, N-methyl-3- (dipropylamino) propanamide, N-methyl-3- (dibutylamino) propanamide, N-methyl-3- (ethyl methyl) Amino) propanamide, N-methyl-3- (methylpropylamino) Lopanamide, N-methyl-3- (methylbutylamino) propanamide, N-methyl-3- (ethylpropylamino) propanamide, N-ethyl-3- (dimethylamino) propanamide, N-ethyl-3- ( Diethylamino) propanamide, N-ethyl-3- (dipropylamino) propanamide, N-ethyl-3- (dibutylamino) propanamide, N-ethyl-3- (ethylmethylamino) propanamide, N-ethyl- 3- (methylpropylamino) propanamide, N-ethyl-3- (methylbutylamino) propanamide, N-ethyl-3- (ethylpropylamino) propanamide, N, N-dimethyl-3- (dimethylamino) Propanamide, N, N-dimethyl-3- (diethylamino) propanamide,

N, N-dimethyl-3- (dipropylamino) propanamide, N, N-dimethyl-3- (dibutylamino) propanamide, N, N-dimethyl-3- (ethylmethylamino) propanamide, N, N -Dimethyl-3- (methylpropylamino) propanamide, N, N-dimethyl-3- (methylbutylamino) propanamide, N, N-dimethyl-3- (ethylpropylamino) propanamide, N, N-diethyl -3- (dimethylamino) propanamide, N, N-diethyl-3- (diethylamino) propanamide, N, N-diethyl-3- (dipropylamino) propanamide, N, N-diethyl-3- (dibutyl) Amino) propanamide, N, N-diethyl-3- (ethylmethylamino) propanamide, N, N-diethyl-3- Methylpropylamino) propanamide, N, N-diethyl-3- (methylbutylamino) propanamide, N, N-diethyl-3- (ethylpropylamino) propanamide, 3- (dimethylamino) -1- (1 -Pyrrolidinyl) -1-propanone, 3- (dimethylamino) -1- (1-piperidinyl) -1-propanone, 3- (dimethylamino) -1- (4-morpholinyl) -1-propanone etc. Not limited to these. Moreover, in using these, you may use individually by 1 type, or you may use as 2 or more types of mixtures. Among the above, N, N-dimethyl-3- (dimethylamino) propanamide is particularly preferable from the viewpoint of adhesion after development of the relief pattern.
The compounding amount of the (B) amide compound is 0.001 to 1 part by mass, preferably 0.01 to 0.8 parts by mass with respect to 100 parts by mass of the (A) resin from the viewpoint of suppressing the dark reaction of the composition. Part, more preferably 0.01 to 0.5 parts by mass.

[(C) Photosensitizer]
The resin composition of the present embodiment functions as a photosensitive resin composition by blending the photosensitive agent (C).
The photosensitive agent (C) used for the resin composition of the present embodiment will be described.
As the photosensitizer (C), any compound conventionally used as a photopolymerization initiator for UV curing can be selected and used. (C) Compounds which can be suitably used as a photosensitizer, for example, benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyl diphenyl ketone, dibenzyl ketone, fluorenone and the like;
Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and the like;
Thioxanthone derivatives such as thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, diethyl thioxanthone and the like;
Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal and the like;
Benzoin derivatives such as benzoin, benzoin methyl ether;

1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propane Dione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, Oximes such as 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime;
N-arylglycines such as N-phenylglycine;
Peroxides such as benzoylperchloride;
Although aromatic biimidazoles etc. are mentioned preferably, it is not limited to these. In using them, they may be used alone or as a mixture of two or more. Among the above-mentioned photopolymerization initiators, oximes are more preferable particularly in light of photosensitivity.
It is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of (A) resin, and, as for the compounding quantity of (C) photosensitive agent, 2-15 mass parts is more preferable from a viewpoint of a photosensitivity characteristic. By adding 1 part by mass or more of (C) a photosensitizer to 100 parts by mass of (A) resin, it becomes excellent in photosensitivity, and by making the compounding amount of 20 parts by mass or less, it is excellent in thick film curability. Become.

[(D) Other components]
The resin composition in the present embodiment may further contain components other than the components (A) to (C). The resin composition in this embodiment is typically used as a resin composition in which the above-described components and optional components further used as required are dissolved in a suitable solvent to make a varnish. Therefore, as the (D) other components, solvents can be mentioned, and for example, resins other than (A) resins, silane compounds, sensitizers, monomers having a photopolymerizable unsaturated bond, adhesion assistants, thermal A polymerization inhibitor, a crosslinking agent, an azole compound, a hindered phenol compound, etc. can be mentioned.

Examples of the solvent include polar organic solvents, alcohols and the like.
As the solvent in the resin composition of the present embodiment, it is preferable to use a polar organic solvent from among the resins (A), particularly from the viewpoint of solubility in the polyimide precursor. Specifically, for example, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like can be mentioned. These can be used alone or in combination of two or more.

From the viewpoint of improving the storage stability of the resin composition, the solvent preferably contains an alcohol. Alcohols which can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and having no olefinic double bond, and specific examples thereof include methyl alcohol, ethyl alcohol, n -Alkyl alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol and the like;
Lactate esters such as ethyl lactate;
Propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- ( Propylene glycol monoalkyl ethers such as n-propyl) ether;
Monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether;
2-hydroxyisobutyric acid esters;
Dialcohols such as ethylene glycol and propylene glycol can be mentioned. Among these, one or more selected from lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters and ethyl alcohol are preferable, and in particular, ethyl lactate, propylene glycol-1-methyl ether, propylene One or more selected from glycol-1-ethyl ether and propylene glycol-1- (n-propyl) ether are more preferable.

  The above solvent is, for example, in the range of 30 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass, with respect to 100 parts by mass of the resin (A) according to the desired coating thickness and viscosity of the resin composition. It can be used in the range. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the whole solvent is preferably 5 to 50% by mass, and more preferably Preferably it is 10-30 mass%. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the resin composition becomes good, and when it is 50% by mass or less, the solubility of the resin (A) becomes good. Become.

The resin composition in the present embodiment may further contain a resin component other than the (A) resin described above. Examples of the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, acrylic resin and the like. The compounding amount of these resin components is preferably in the range of 20 parts by mass or less with respect to 100 parts by mass of (A) resin.
The resin composition in this embodiment can contain a silane compound in order to further improve the adhesion of the formed film. The silane compound is not particularly limited as long as it is an organic compound containing an alkoxysilyl group. For example, the following formula:

N- (3-triethoxysilylpropyl) urea, N- (3-trimethoxysilylpropyl) urea, N- (3-diethoxymethoxysilylpropyl) urea, N- (3- Ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3- Dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-trimethoxysilylpropyl) urea Propoxysilylethyl) urea, N- (3-tripropoxysilylethyl) Rare, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) Urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea and the like can be mentioned, and it is preferable to use one or more selected from these.
The compounding amount of the silane compound in the present embodiment is preferably in the range of 10 parts by mass or less, and more preferably in the range of 8 parts by mass or less, with respect to 100 parts by mass of the (A) resin.

In the resin composition of the present embodiment, a sensitizer can be optionally blended in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, 2,6-bis (4′-diethylaminobenzal) ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnana Myrylene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis (4'-dimethyl) Aminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7 -Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N- Phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoate isoamyl, diethylaminobenzoate isoamyl, 2-mercaptobenzimidazole, 1-fu Nyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,1 2-d) Thiazole, 2- (p-dimethylamino benzoyl) styrene, etc. are mentioned. These can be used alone or in combination of, for example, 2 to 5 types.
It is preferable that the compounding quantity in case a resin composition contains a sensitizer is 0.1-25 mass parts with respect to 100 mass parts of (A) resin.

Moreover, in order to improve the resolution of a relief pattern, the monomer which has a photopolymerizable unsaturated bond can be mix | blended arbitrarily. As such a monomer, a (meth) acrylic compound which undergoes a radical polymerization reaction by a photopolymerization initiator is preferable, and it is not particularly limited to the following, for example, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and the like , Mono- or di (meth) acrylates of ethylene glycol or polyethylene glycol;
Propylene glycol or polypropylene glycol mono or di (meth) acrylate;
Mono-, di- or tri (meth) acrylate of glycerol;
Cyclohexane di (meth) acrylate;
Di (meth) acrylate of 1,4-butanediol;
Di (meth) acrylate of 1,6-hexanediol;
Di (meth) acrylate of neopentyl glycol;
Bisphenol A mono- or di (meth) acrylates;
Benzene trimethacrylate;
Isobornyl (meth) acrylate;
(Meth) acrylamide and its derivatives;
Trimethylolpropane tri (meth) acrylate;
Di- or tri (meth) acrylate of glycerol;
Di-, tri-, or tetra (meth) acrylates of pentaerythritol;
And compounds such as ethylene oxide or propylene oxide adducts of these compounds.
When the resin composition of the present embodiment contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the compounding amount is 100 parts by mass of (A) resin. And 1 to 50 parts by mass.

Moreover, an adhesion | attachment adjuvant can be arbitrarily mix | blended in order to improve the adhesiveness of the film | membrane and base material which are formed using the negative photosensitive resin composition of this invention. Examples of adhesion assistants include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) ) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene- 1,4-bis (N- [3- Other Li triethoxysilyl] propyl amide) 2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinate nick anhydride, N- phenyl-aminopropyltrimethoxysilane coupling agent such as a silane;
Aluminum-based adhesion aids such as aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate and the like can be mentioned.
Among these adhesion assistants, it is more preferable to use a silane coupling agent from the viewpoint of adhesion. When the resin composition in this embodiment contains an adhesion | attachment adjuvant, the range of 0.5-25 mass parts is preferable with respect to 100 mass parts of (A) resin.

In the case where the resin composition of the present embodiment is stored particularly in the state of a solution containing a solvent, a thermal polymerization inhibitor is optionally blended to improve the stability of the viscosity and the photosensitivity of the resin composition. be able to. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2 , 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl- N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.
As a compounding quantity of the thermal-polymerization inhibitor in the case of mix | blending with the resin composition of this embodiment, the range of 0.005-12 mass parts is preferable with respect to 100 mass parts of (A) resin.

A crosslinking agent can be arbitrarily mix | blended with the resin composition of this embodiment.
The crosslinking agent has the function of crosslinking the resin (A) when heat curing the relief pattern formed using the resin composition of the present embodiment, or the crosslinking agent itself can form a crosslinked network. Is preferred. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the negative photosensitive resin composition.

As such a crosslinking agent, amino resins and derivatives thereof are suitably used. Among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are suitably used. Particularly preferred are alkoxymethylated urea compounds and alkoxymethylated melamine compounds. As the specific example, MX-290 (made by Nippon Carbide Co., Ltd.), UFR-65 (made by Nippon Cytec Co., Ltd.), MW-390 (made by Nippon Carbide Co., Ltd.) etc. are mentioned, for example.
In consideration of various properties other than heat resistance and chemical resistance, the compounding amount in the case where the resin composition in the present embodiment contains a crosslinking agent is 0.5 to 20 mass with respect to 100 mass parts of (A) resin. It is preferably part, more preferably 2 to 10 parts by mass. When the compounding amount is 0.5 parts by mass or more, good heat resistance and chemical resistance develop, while when it is 20 parts by mass or less, the storage stability is excellent.

  When the substrate to which the resin composition of the present embodiment is applied is, for example, a substrate made of copper or a copper alloy, an azole compound can be optionally blended in order to suppress the discoloration of the copper surface. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-Dimethyltriazole, 4,5-Diethyl-1H-triazole, 1H-benzotriazole, 2- (5-Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,3 5-bis (α, α-dime Ethylbenzyl) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole , 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5 -Methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl -1H-tetrazole, 5-amino-1H Tetrazole, 1-methyl -1H- tetrazole, and the like. Particularly preferred is one or more selected from tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or as a mixture of two or more.

  The compounding amount when the resin composition in the present embodiment contains the azole compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, and from the viewpoint of light sensitivity characteristics, 0 0.5-5 mass parts is more preferable. When the compounding quantity with respect to 100 mass parts of (A) resin of an azole compound is 0.1 mass part or more, when the resin composition of this embodiment is formed on copper or a copper alloy, Discoloring is suppressed, while when it is 10 parts by mass or less, the excellent photosensitivity of the resin composition is maintained.

  In order to suppress discoloration of the copper surface, a hindered phenol compound can be optionally blended in place of the azole compound or together with the azole compound. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl-3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3) -Tert-Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydro) Ciphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-) Butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanate Nulate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-bis) Proxy-2,6-dimethyl-4-isopropyl-benzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) - trione,

1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4- (1-ethylpropyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -Trione, 1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H)- Trione, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4) Phenylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,5,5 6-trimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-) Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-) Ethyl 3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,

1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione, 1,3,5-tris (4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H) , 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H) , 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H) , 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydride) Carboxymethyl-2-methylbenzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) - but trione, etc., but is not limited thereto. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) )-Trione etc. are particularly preferred.

  The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. preferable. When the compounding quantity with respect to 100 mass parts of (A) resin of a hindered phenol compound is 0.1 mass part or more, for example, when the resin composition of this embodiment is formed on copper or a copper alloy, copper or copper Discoloring and corrosion of the alloy are prevented, while when it is 20 parts by mass or less, the excellent photosensitivity of the resin composition is maintained.

<Method of Manufacturing Hardened Relief Pattern and Semiconductor Device>
The invention also provides a method of making a cured relief pattern.
In order to form a cured relief pattern in the present embodiment,
(A) A resin composition satisfying at least one of the case where the resin is a resin containing a monovalent organic group capable of radical polymerization in its side chain, and the case where the resin composition contains a crosslinking agent It is preferable to use In the former case, particularly preferably, the component (A) is a polyimide precursor having a repeating unit represented by the general formula (2), and at least one of R ₅ and R _{6 in} the formula (2) It is a case where a part is a radically polymerizable monovalent organic group.
Such a resin composition functions as a negative photosensitive resin composition, and it becomes possible to easily and efficiently produce an effect relief pattern.
In any of the above cases, the resin composition preferably further contains (C) a photosensitizer.

In the present embodiment, the cured relief pattern may be, for example, the following steps:
(1) a coating step of coating the negative photosensitive resin composition of the present embodiment described above on a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) It can manufacture by the manufacturing method of hardened | cured relief pattern including the heating process of forming hardened | cured relief pattern by heat-processing the said relief pattern.
Hereinafter, typical embodiments of each step will be described.

(1) Coating Step In this step, the negative photosensitive resin composition is coated on a substrate and, if necessary, dried to form a photosensitive resin layer.
As the substrate, for example, a substrate made of silicon, silicon nitride, silicon oxide, aluminum, nickel, titanium, copper, a copper alloy or the like can be used.
As a coating method, the method conventionally used for coating of the photosensitive resin composition can be used. For example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine or the like, or a method of spray coating with a spray coater.
If necessary, the photosensitive resin layer can be dried. As a drying method, for example, methods such as air drying, heat drying with an oven or a hot plate, vacuum drying and the like are used. Moreover, when (A) resin contained in the resin composition to be used consists of a polyimide precursor (polyamic acid ester), the drying of the said coating film does not cause imidation of this polyimide precursor. It is desirable to do on condition. Specifically, when air drying or heat drying is performed, drying can be performed at 20 ° C. to 140 ° C. under the conditions of 1 minute to 1 hour.
Thus, the photosensitive resin layer can be formed on the substrate.

(2) Exposure process At this process, the photosensitive resin layer formed above is exposed. As the exposure apparatus, for example, a contact aligner, a mirror projection, a stepper or the like is used. It can be exposed directly through a photomask or reticle having a pattern. The light beam used for exposure is, for example, ultraviolet light.
After exposure, post exposure bake (PEB) and / or post development bake may be performed according to any combination of temperature and time as needed for the purpose of improving photosensitivity and the like. The baking conditions are preferably 40 to 120 ° C. as temperature, and 10 seconds to 240 seconds as time, but are limited to this range as long as they do not inhibit various properties of the negative photosensitive resin composition in the present embodiment. Absent.

(3) Development Step In this step, the unexposed area of the photosensitive resin layer after exposure is removed by development. As a development method for developing the photosensitive resin layer after exposure (irradiation), a conventional development method of photoresist can be selected and used. For example, a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like. In addition, after development, post-development baking may be performed according to any combination of temperature and time as needed, for the purpose of adjusting the shape of the relief pattern and the like. The post-development bake temperature can be, for example, 30 to 180 ° C., and the time can be, for example, 1 to 30 minutes.

As a developing solution to be used for development, a good solvent for the photosensitive resin composition, or a combination of the good solvent and the poor solvent is preferable. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone etc. are preferable. ;
As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the resin (A) in the negative photosensitive resin composition. In addition, two or more types of each solvent, for example, several types may be used in combination.

(4) Heating Step In this step, the relief pattern obtained by the above development is heated to dilute the photosensitive component. Furthermore, when (A) resin contained in the resin composition to be used consists of a polyimide precursor, it can be converted into a cured relief pattern consisting of polyimide by imidating this resin in this step. .
As a method of heat curing, various methods can be selected such as using a hot plate, using an oven, and using a temperature rising oven capable of setting a temperature program. Heating can be performed, for example, at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. As the atmosphere gas at the time of heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
The present invention also provides a semiconductor device having a cured relief pattern obtained by the method for producing a cured relief pattern of the present embodiment described above.
The above-mentioned semiconductor device can be, for example, a semiconductor device having a substrate which is a semiconductor element, and a cured relief pattern formed on the substrate by the method for producing a cured relief pattern described above.
The semiconductor device can be manufactured by, for example, a method using a semiconductor element as a base material and including the above-described method of manufacturing a cured relief pattern as a part of the process. The semiconductor device of this embodiment includes, for example, a surface protection film, an interlayer insulation film, an insulation film for rewiring, a protection film for a flip chip device, and a bump structure. The semiconductor device can be manufactured by forming it as a protective film or the like of a semiconductor device having the semiconductor device and combining it with a known semiconductor device manufacturing method.

  The resin composition of the present embodiment is useful for applications such as interlayer insulation of multilayer circuits, cover coats of flexible copper clad plates, solder resist films, liquid crystal alignment films, etc. in addition to the application to the semiconductor device as described above. It is.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In Examples, Comparative Examples, and Production Examples, physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each photosensitive resin was measured by gel permeation chromatography (in terms of standard polystyrene). The column used for the measurement is Showa Denko trade name Shodex 805M / 806M series,
Choose Shodex STANDARD SM-105 manufactured by Showa Denko KK as standard monodispersed polystyrene,
The developing solvent is N-methyl-2-pyrrolidone,
The detector used was Shodex RI-930 made by Showa Denko.

(2) Photosensitivity evaluation (Examples 6 to 10 and Comparative Examples 2 and 3)
A negative photosensitive resin composition using a polyimide precursor as a photosensitive resin was spin-coated on a 6 inch silicon wafer, heated at 100 ° C. for 4 minutes and dried to form a 10 μm thick coating film. The coating film was exposed to light through a reticle with a test pattern using an i-line stepper NSR2005i8A (manufactured by Nikon Corporation) with a variable exposure amount in the range of 50 to 600 mJ / cm ² energy. The coated film after exposure is spray developed with cyclopentanone using a developing machine (D-SPIN type 636, Dainippon Screen Mfg., Japan) and then rinsed with propylene glycol methyl ether acetate to give an unexposed area. The development was removed to obtain a relief pattern of the polyimide precursor. Next, the wafer on which the relief pattern is formed is placed in a programmed temperature curing furnace (VF-2000, manufactured by Koyo Lindberg, Japan), and heat treated at 350 ° C. for 2 hours in a nitrogen atmosphere. A cured relief pattern of 5 μm thick polyimide was obtained. The film thickness measurement of a hardening relief pattern was performed using Tencor P-15 type | mold level difference meter (made by KLA Atecor Co., Ltd.).

About the obtained pattern, the pattern shape and the width of the pattern portion were observed under an optical microscope. The case where the area of the opening of the 10 μm pattern is 1/2 or more of the corresponding pattern mask opening area and no peeling is regarded as “good”,
The case where the area of the opening was less than 1/2 of the corresponding pattern mask opening area or the case where there was peeling was regarded as "defective".
At this time, the minimum exposure amount at which a “good” pattern can be obtained was taken as the light sensitivity.

(3) Evaluation of Adhesion to Substrate The photosensitive resin composition was spin-coated on a copper substrate, heated at 100 ° C. for 4 minutes, and dried to form a coating film of a photosensitive resin layer having a thickness of 10 μm. The copper substrate on which this coating film is formed is placed in a programmed temperature curing furnace (VF-2000, manufactured by Koyo Lindberg, Japan), and is kept under nitrogen atmosphere at 200 ° C. for 1 hour, and then at 250 ° C. By heating (curing) for 2 hours, a 5 μm thick cured resin film was obtained.
About the film | membrane after curing, the adhesion | attachment characteristic between a copper substrate / hardened resin coating film was evaluated based on the following references | standards according to the cross-cut method of JISK5600-5-6 specification.
"Very good": when the number of grids of the cured resin coating adhered to the substrate is 100 "good": when the number of grids of the cured resin coating adhered to the substrate is 80 to 99 Yes: When the number of grids of the cured resin coating adhered to the substrate is 50 to 79 "Defect": When the number of grids of the cured resin coating adhered to the substrate is 20 to 49 Extremely bad ": When the number of grids of the cured resin coating adhered to the substrate is less than 20

<Production Example 1> (Synthesis of (A) Resin (Resin (A1)))
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 liter separable flask. Then, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 81.5 g of pyridine was added while stirring at room temperature to obtain a reaction mixture.
The reaction mixture was allowed to cool to room temperature after the end of the reaction exotherm and was allowed to stand for an additional 16 hours.
Next, while stirring the reaction mixture under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone is added thereto over 40 minutes, followed by 4,4'-diamino A suspension of 93.0 g of diphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes. Stirring was further continued at room temperature for 2 hours, and 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added.
The precipitate formed in the reaction mixture was filtered off and removed to obtain a reaction solution.
The resulting reaction solution was poured into 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer. The resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution is dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate is collected by filtration and vacuum dried to obtain a resin (A1) as a polyimide precursor as a powder. The
When the molecular weight of this resin (A1) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.

<Production Example 2> ((A) Synthesis of Resin)
Production Example 1 except that 147.1 g of 3,3′4,4′-biphenyltetracarboxylic acid dianhydride was used instead of 155.1 g of 4,4′-oxydiphthalic acid dianhydride in Production Example 1 described above The reaction was carried out in the same manner as described in 1 to obtain a resin (A2).
The molecular weight of this resin (A2) was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was 22,000.

Example 1
The photosensitive resin composition was prepared by the following method using the resin (A1) and the resin (A2) obtained in the above-mentioned Production Example, and the prepared composition was evaluated. (A) 50 g of a resin (A1) as a resin and 50 g of a resin (A2) B, and (B) 0.001 g of N, N-dimethyl-3- (dimethylamino) propanamide as an amide compound, N- as a solvent It was dissolved in 199.999 g of methyl-2-pyrrolidone to make a resin composition.
When the adhesiveness with a base material was evaluated according to the above-mentioned method using this resin composition, the adhesiveness was "OK".
Examples 2 to 5 and Comparative Example 1
In Example 1 above, the compounding amounts of N, N-dimethyl-3- (dimethylamino) propanamide as the (B) amide compound and N-methyl-2-pyrrolidone as the solvent are described in Table 1 respectively. A resin composition was prepared in the same manner as in Example 1 except that the composition was changed as follows.
In Comparative Example 1, the (B) amide compound was not used.
Each of these compositions was used to evaluate the adhesion to the substrate according to the method described above. The evaluation results are shown in Table 1.

Examples 6 to 10 and Comparative Example 2
Further, 6 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime as a photosensitizer (C) is further added to the resin compositions of Examples 1 to 5 and Comparative Example 1 above. Thus, a negative photosensitive resin composition was prepared.
Each of these resin compositions was used to evaluate photosensitivity and adhesion to a substrate according to the method described above. The evaluation results are shown in Table 1.

Comparative Example 3
A negative photosensitive resin composition was prepared by further adding 2 g of N, N-dimethyl-3- (dimethylamino) propanamide as the (B) amide compound to the resin composition of Comparative Example 2.
Using this composition, evaluation of photosensitivity was tried according to the above-mentioned method, but the 10 μm pattern did not open and evaluation could not be made. It is considered that the coating film has gelled.
Moreover, when adhesiveness with a base material was measured according to the above-mentioned method using this composition, adhesiveness was "very favorable."

In the above-mentioned table, the upward arrow shows that the kind and quantity of a combination ingredient applicable to the field concerned are the same as an upper column. Moreover, "-" shows that the component equivalent to the said column was not mix | blended.
The abbreviation of each component has the following meaning, respectively.
A1: Resin (A1)
A2: Resin (A2)
B1: N, N-Dimethyl-3- (dimethylamino) propanamide C1: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime D1: N-methyl-2-pyrrolidone

  The resin composition of the present invention can be suitably used, for example, in the field of photosensitive materials useful for producing electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (7)

(A) the following general formula (2):

{In general formula (2), X ₁ is a tetravalent organic group,
Y ₁ is a divalent organic group,
R ₅ and R ₆ are each independently a hydrogen atom, a monovalent organic group capable of radical polymerization, a monovalent organic group, or a saturated aliphatic group having 1 to 4 carbon atoms 5 to 30 carbon atoms. Polyimide precursor having a repeating unit represented by} : 100 parts by mass, and (B) the following general formula (1):

{In formula (1), R ₁ and R ₂ are each independently an alkyl group of 1 to 5 carbon atoms,
R ₃ and R ₄ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, provided that this hydrocarbon group may have an ether bond, and R ₃ and R ₄ are bonded To form a ring structure. The amide compound represented by}: 0.001-1 mass part, The resin composition characterized by the above-mentioned. R ₅ and R ₆ in the general formula (2) are each independently a hydrogen atom, and the following general formula (3):

{Wherein _{(3), R 9, R} 10 and _{R 11} are each independently a monovalent organic group hydrogen atom or 1 to 3 carbon atoms, and m is an integer from 2 to 10. Or a monovalent organic group represented by the general formula (4):
-R ₁₂ (4)
{In the formula (4), R ₁₂ is a monovalent group selected from an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, and an aromatic group having 6 to 30 carbon atoms . A monovalent organic group represented by the above general formula (3) and a compound represented by the above general formula (4) for all of R ₅ and R ₆ The ratio of the total of the valent organic groups is 80 mol% or more, and the ratio of the monovalent organic group represented by the above general formula (4) is 20 mol% to 80 mol with respect to all of R ₅ and R ₆ % and a resin composition according to claim 1. R ₅ and R ₆ in the general formula (2) are each independently a hydrogen atom, and the following general formula (3):

{Wherein _{(3), R 9, R} 10 and _{R 11} are each independently a monovalent organic group hydrogen atom or 1 to 3 carbon atoms, and m is an integer from 2 to 10. Monovalent organic group represented by}, or a saturated aliphatic group having 1 to 4 carbon atoms, provided that never both R ₅ and R ₆ are not hydrogen atoms at the same time, according to claim 1 Resin composition. The resin composition according to any one of claims 1 to 3 , wherein the component (B) is N, N-dimethyl-3- (dimethylamino) propanamide. The resin composition according to any one of claims 1 to 4 , which further comprises (C) a photosensitizer and is photosensitive. The following steps:
(1) applying a photosensitive resin composition according to claim 5 on a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of: heating the relief pattern to form a cured relief pattern. A semiconductor device comprising a cured relief pattern obtained by the method according to claim 6 .