JP2016079340A - Resin composition, production method of cured relief pattern, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent adhesiveness to a substrate and showing high photosensitivity when used as a photosensitive resin composition.SOLUTION: The resin composition comprises: (A) 100 parts by mass of at least one resin selected from a group consisting of an alkali-soluble resin and a resin having a polymerizable group in a side chain; and (B) 0.001 to 1 part by mass of an amide compound represented by general formula (1) below. In formula (1), Rand Reach independently represent an alkyl group having 1 to 5 carbon atoms; and Rand Reach independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group may have an ether bond, or Rand Rmay be bonded to form a ring structure.SELECTED DRAWING: None

Description

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

Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these 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 applying the precursor, exposing, developing, and curing. be able to. Such a photosensitive polyimide precursor has a feature that enables significant process shortening compared to a conventional non-photosensitive polyimide.
In recent years, the mounting method of a semiconductor device on a printed wiring board has been changed from the viewpoint of improving the degree of integration and function and reducing the chip size. From conventional mounting methods using metal pins and lead-tin eutectic solder, structures such as BGA (Ball Griped Array) and CSP (Chip Size Packaging) that can be mounted with higher density have come to be used. Yes. In these structures, the polyimide film directly contacts the solder bump. 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 | film | coat is disclosed by adding a thermal crosslinking agent to the composition containing a polyimide precursor (refer patent document 1).
By the way, in recent semiconductor processes, the stepper exposure time has become longer as the wafer size increases. Along with this, from the viewpoint of improving the yield in the exposure process, higher sensitivity of the photosensitive material is required. Further, in the rewiring process, not only the silicon base material but also adhesion to a wiring layer made of copper or the like is required. As a technique for increasing the sensitivity, an improvement method based on the chemical structure of the initiator and the sensitizer is generally used. However, the adhesion to the base may be reduced by the addition of these components. Development of a resin composition having both good adhesion and high photosensitivity is desired.

JP 2003-287889 A

An object of the present invention is to provide a resin composition that has excellent adhesion to a substrate and exhibits high photosensitivity when applied as a photosensitive resin composition.
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, and to complete the present invention. It came. 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 the 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 having 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 each other. Thus, a ring structure may be formed. } The amide compound represented by: 0.001-1 mass part is contained, The resin composition characterized by the above-mentioned.
[2] The component (A) 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 having 5 to 30 carbon atoms, or a saturated aliphatic group having 1 to 4 carbon atoms. } The resin composition as described in [1] which is a polyimide precursor which has a repeating unit represented by these.
[3] R ₅ and R ₆ in the above general formula (2) are each independently a hydrogen atom, the following general formula (3):

{In Formula (3), R <_9> , R < ₁₀ > and R <_11> are respectively independently a hydrogen atom or a C1-C3 monovalent organic group, and m is an integer of 2-10. } Or a monovalent organic group represented by the following general formula (4):
-R ₁₂ (4)
{In 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. . }, And a monovalent organic group represented by the above general formula (3) and 1 represented by the above general formula (4) for all of R ₅ and R _6. the total proportion of valent organic group is 80 mol% or more, and for all of R ₅ and R _6, 1-valent ratio 20 mol% to 80 mol of an organic group represented by the general formula (4) % Of the resin composition according to [2].
[4] R ₅ and R ₆ in the above general formula (2) are each independently a hydrogen atom, the following general formula (3):

{In Formula (3), R <_9> , R < ₁₀ > and R <_11> are respectively independently a hydrogen atom or a C1-C3 monovalent organic group, and m is an integer of 2-10. }, Or a saturated aliphatic group having 1 to 4 carbon atoms, provided that both R ₅ and R ₆ are not hydrogen atoms at the same time, 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 (C) a photosensitizer and is photosensitive.

[7] The following steps:
(1) A coating step of coating the 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) a development step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a heating step of forming a cured relief pattern by heat-treating the relief pattern.
[8] A semiconductor device comprising a cured relief pattern obtained by the method according to [7].

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 in which a resin pattern is formed using the photosensitive resin composition, and a semiconductor device.

  Embodiments of the present invention will be specifically described below. Throughout this specification, when there are a plurality of structures represented by the same symbols in the general formula in a molecule, these may be the same or different from each other.

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

{In Formula (1), R ₁ and R ₂ are each an alkyl group having 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 each other. Thus, a ring structure may be formed. } Is contained as an essential component.

[(A) Resin]
(A) resin used for this embodiment is demonstrated.
The resin (A) in this embodiment is at least one resin selected from the group consisting of an alkali-soluble resin and a resin having a polymerizable group in the 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 polyoxazole precursors such as polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzthiazole. (A) resin in this embodiment contains 60 mass% or more of at least 1 sort (s) of resin chosen from the above with respect to all the resins, and it is more preferable to contain 80 mass% or more. (A) resin in this embodiment may contain 100 mass% of at least 1 sort (s) of resin chosen from the above, and may contain other resin as needed.

The weight average molecular weight of these resins is preferably 1,000 or more, and more preferably 5,000 or more as a polystyrene-converted value by gel permeation chromatography from the viewpoint of heat resistance after heat treatment and mechanical properties. The upper limit of this weight average molecular weight is preferably 100,000 or less. When the resin composition of the present embodiment is a photosensitive resin composition, the weight average molecular weight of (A) resin 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. The photosensitive resin can be made into a photosensitive resin composition by using it together with a photosensitizer (C) described later, and is a resin that causes development that is dissolved or undissolved in the subsequent development process. The photosensitive resin is preferably a resin containing a polymerizable group in the side chain. Such a photosensitive resin can be appropriately selected according to desired characteristics and applications that the photosensitive resin composition should have.

The resin species constituting the main skeleton of the resin (A) in the present embodiment is preferably at least one selected from the aforementioned resin group. Among these, since the resin after heat treatment is excellent in heat resistance and mechanical properties, at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polybenzoxazole precursor, and polyimide is more preferable, 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 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 having 5 to 30 carbon atoms, or a saturated aliphatic group having 1 to 4 carbon atoms. }
It is a polyimide precursor which has a structure represented by these. The polyimide precursor represented by the general formula (2) is converted into polyimide by, for example, performing a cyclization treatment by heating at 200 ° C. or higher.
As the monovalent organic group capable of radical polymerization of R ₅ and R ₆ in the general formula (2), the following general formula (3):

{In Formula (3), R <_9> , R < ₁₀ > and R <_11> are respectively independently a hydrogen atom or a C1-C3 monovalent organic group, and m is an integer of 2-10. } It is preferable that it is a monovalent organic group represented by these.
R ₁₀ and R ₁₁ in the general formula (3) are each independently preferably a hydrogen atom or a methyl group, and 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 photosensitive characteristics.

As the monovalent organic group having 5 to 30 carbon atoms of R ₅ and R ₆ in the general formula (2), the following general formula (4):
-R ₁₂ (4)
{In 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 these.
Examples of the aliphatic group having 5 to 30 carbon atoms that may have a hetero atom of R ₁₂ in the general formula (4) include an isopentyl group, a butoxymethyl group, a butyl sulfide methylene group, and a butylaminomethylene group. Others: An aliphatic group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom as a hetero atom can be exemplified. Examples of the aromatic group having 6 to 30 carbon atoms of R ₁₂ include a phenyl group, a benzyl group, and a naphthyl group.
Examples of the saturated aliphatic group having 1 to 4 carbon atoms of R ₅ and R ₆ in the general formula (2) include primary hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, and a butyl group;
Secondary hydrocarbon groups such as isobutyl groups;
A tertiary hydrocarbon group such as a t-butyl group can be exemplified.

As R ₅ and R ₆ in the 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 is based on all of R ₅ and R ₆ . , When the proportion 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 R ₅ and R ₆ are hydrogen atoms at the same time. This is the case.
Such (A) resin works suitably as a polyimide precursor that is cyclized and converted to polyimide by, for example, heat treatment at 200 ° C. or higher.

In the general formula (2), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably from the viewpoint of achieving both heat resistance and photosensitive properties. , -COOR ₅ group and -CONH- group are bonded to the same aromatic ring, both are in the ortho position with each other, and the other of -COOR ₆ group and -CONH- group is the same aromatic ring A tetravalent aromatic group or a tetravalent alicyclic aliphatic group which are bonded to each other and are ortho to each other. In the former case, the aromatic ring to which -COOR ₅ group is bonded and the aromatic ring to which -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.
The tetravalent organic group represented by X ₁ is more preferably the following formula:

Although the structure represented by each of these is mentioned, it is not limited to these. The structure of X ₁ are may be two or more kinds in combination. X ₁ groups having these structures are preferable in terms of achieving both the heat resistance and the photosensitive characteristics.
In the general formula (2), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive characteristics. Following formula:

{In the above formula, A is, independently, are methyl groups (-CH), ethyl _{(-C 2 H} 5), propyl _(-C 3 _{H 7)} or a butyl group _(-C 4 _{H 9)} . }, But is not limited thereto. Further, the structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having the structure represented by the above formula is preferable in terms of achieving both heat resistance and photosensitive characteristics.

  (A) When a polyimide precursor is used as the resin, examples of a method for imparting a monovalent organic group capable of radical polymerization to the resin include an ester bond type and an ion bond type. The former is a method of introducing a monovalent organic group capable of radical polymerization by an ester bond into the side chain of the polyimide precursor. The latter is based on the reaction between a resin having a carboxyl group and a radically polymerizable compound having an amino group (for example, a (meth) acrylate compound having an amino group), through an ionic bond between the carboxyl group and the amino group, to form a polyimide precursor. In this method, a monovalent organic group capable of radical polymerization is introduced into the side chain of the body. Of these, the ester bond type is preferable.

[Preparation method of polyimide precursor]
Preparation of the ester bond type polyimide precursor is carried out by, for example, firstly tetracarboxylic dianhydride having a desired tetravalent organic group X ₁ and alcohols having a radical polymerizable group (for example, unsaturated double bond). To prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester), and this and a diamine having a desired divalent organic group Y ₁ Obtained by condensation. A saturated aliphatic alcohol may optionally be used in combination with the alcohol having the radical polymerizable group (for example, an unsaturated double bond).

(Preparation of acid / ester)
In this embodiment, examples of the tetracarboxylic dianhydride having a tetravalent organic group X ₁ that are suitably used for preparing an ester bond type polyimide precursor include pyromellitic anhydride and diphenyl ether-3. , 3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic acid Dianhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3 ′, 4,4′-tetracarboxylic dianhydride, 2,2-bis (3 , 4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane, and the like. Is not to be done. In addition, these may be used alone or in combination of two or more.

  In this embodiment, examples of alcohols having a radical polymerizable group that are preferably used for preparing an ester bond type polyimide precursor include 2-acryloyloxyethyl alcohol and 1-acryloyloxy-3-propyl. 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 include 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

Saturated aliphatic alcohols having 1 to 4 carbon atoms are preferred as saturated aliphatic alcohols that can be optionally used together with the alcohols having the radical polymerizable group. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like. The amount of these saturated aliphatic alcohols is preferably 80 mol% or less, more preferably 50 mol% or less, based on the total of alcohols having a radical polymerizable group and saturated aliphatic alcohols. preferable.
The amount of alcohol, the total amount of alcohol relative to the tetracarboxylic acid dianhydride to 1 mole having a tetravalent organic group X _1, preferably to 0.1 to 5 mol, 3 mol More preferably.

Stirring the above suitable tetracarboxylic dianhydride and the above alcohols, preferably in the presence of a basic catalyst such as pyridine, preferably in a suitable reaction solvent at a temperature of 20-50 ° C. for 4-10 hours, By mixing, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester body can be obtained.
The reaction solvent is preferably one that completely dissolves the starting tetracarboxylic dianhydride and alcohol, and the product acid / ester. More preferably, the (A) resin, which is an amide polycondensation product of the acid / ester and diamine, is also a completely soluble solvent. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbonized Hydrogen etc. are mentioned. Specific examples of these are:
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Examples of esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate and the like;
Examples of lactones include γ-butyrolactone and the like;
Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran;
Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, and the like;
Examples of hydrocarbons include hexane, heptane, benzene, toluene, xylene,
Each can be mentioned. These may be used alone or in admixture of two or more as required.

(Preparation of polyimide precursor)
An appropriate dehydration condensing agent is added to and mixed with the acid / ester (typically in a solution dissolved in the reaction solvent), preferably under ice-cooling, to convert the acid / ester into a polyanhydride. And Next, a target polyimide is obtained by adding dropwise a solution obtained by dissolving or dispersing a diamine having a divalent organic group Y ₁ suitably used in the present embodiment in a solvent, and subjecting both to amide polycondensation. A precursor can be obtained.
Examples of the dehydrating condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N Examples include '-disuccinimidyl carbonate. The amount of the dehydrating condensing agent to be used is preferably 0.1 to 10 mol, more preferably 1 to 5 mol, relative to 1 mol of the acid / ester.
The reaction between the acid / ester and the dehydrating condensing agent is performed, 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 that are preferably used in the present embodiment include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 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′-diaminodiphenylsulfone, 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-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) ) Benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) Nthracene, 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 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 substituent include 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, and 3,3′-dimethyl-4,4. '-Diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc. And mixtures thereof. 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 various substrates by applying the resin composition in the present embodiment on the substrate, (A) upon preparing the resin, Diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane can also be copolymerized. The amount of the diamino siloxanes, based on the total of the diamines and diamino siloxanes containing divalent organic group Y _1, preferably 80 mol% or less, more preferably 50 mol% or less .
As a usage-amount of diamine, it is preferable to set it as 0.5-2 mol as a total usage-amount of diamine with respect to 1 mol of the quantity converted into the acid / ester body of a polyacid anhydride, 0.8 It is more preferable to set it to -1.6 mol.
The amide polycondensation reaction between the polyanhydride and the diamine is performed at, for example, -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-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off if necessary, and then an appropriate poor solvent (for example, water, fat, etc.) in the solution containing the polymer component. Group lower alcohol, a mixed solution thereof, etc.) to precipitate the polymer component, and further purify the polymer by repeating re-dissolution and re-precipitation operations as necessary, followed by vacuum drying. To isolate the desired polyimide precursor. In order to improve the degree of purification, the polymer solution 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, more preferably 5,000 to 50,000, when measured as a polystyrene-reduced weight average molecular weight by gel permeation chromatography. It is more preferable. 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 monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

[(B) Amide compound]
The (B) amide compound used in this 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 having 1 to 5 carbon atoms, and R ₃ and R ₄ are each independently a hydrogen atom or a hydrocarbon having 1 to 6 carbon atoms. However, this hydrocarbon group may have an ether bond, and R ₃ and R ₄ may be bonded to form a ring structure. } It is a compound represented.
The resin composition of the present embodiment can increase the photosensitivity when applied as a photosensitive resin composition by using such an (B) amide compound.

Generally, in the formation of a relief pattern by crosslinking of radical reaction, the photosensitivity can be adjusted by a combination of a radical initiator and a sensitizer. As a sensitizer, one that accelerates the reaction by rapidly transferring energy from a ground state to a singlet excited state by absorption and then rapidly transferring to a triplet excited state is known. For example, Michler's ketone. The (B) amide compound in this embodiment has almost no absorption at the wavelength of the mercury lamp of the exposure source used in the semiconductor manufacturing process, so the mechanism by which the photosensitivity of the resin composition is increased by adding the compound is unknown. is there. However, it is considered that the (B) amide compound plays the role of a sensitizer by preventing the radicals generated by the (C) photosensitizer described later from being deactivated.
Moreover, the resin composition which is excellent in the adhesiveness with respect to a base material can be obtained by using (B) amide compound. (B) Although the mechanism by which the adhesiveness is improved by the amide compound is not clear, the amide group of the (B) amide compound reacts with both the resin and the substrate (particularly copper), so that the base material and the resin adhere to each other. It is presumed that the performance will be improved.

  Specific examples of the (B) amide compound include, for example, 3- (dimethylamino) propanamide, 3- (diethylamino) propanamide, 3- (dipropylamino) propanamide, 3- (dibutylamino) propanamide, 3 -(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- (ethylmethyl) 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 and the like. However, it is not limited to these. Moreover, in using these, you may use individually by 1 type, or may be used as a 2 or more types of mixture. Among these, N, N-dimethyl-3- (dimethylamino) propanamide is particularly preferable from the viewpoint of adhesion after development of the relief pattern.
(B) The compounding quantity of an amide compound is 0.001-1 mass part with respect to 100 mass parts of (A) resin from a viewpoint of suppressing the dark reaction of a composition, Preferably it is 0.01-0.8 mass. Part, more preferably 0.01 to 0.5 part by mass.

[(C) Photosensitizer]
The resin composition of this embodiment functions as a photosensitive resin composition by blending (C) a photosensitive agent.
The (C) photosensitive agent used for the resin composition of this embodiment will be described.
(C) As a photosensitizer, a compound conventionally used as a photopolymerization initiator for UV curing can be arbitrarily selected and used. (C) As a compound that can be suitably used as a photosensitizing agent, for example, benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and fluorenone;
Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone;
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone;
Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal;
Benzoin derivatives such as benzoin and 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-aryl glycines such as N-phenyl glycine;
Peroxides such as benzoyl perchloride;
Aromatic biimidazoles and the like are preferred, but are not limited thereto. In using these, it may be used alone or as a mixture of two or more. Among the above photopolymerization initiators, oximes are more preferable particularly from the viewpoint of photosensitivity.
(C) It is preferable that the compounding quantity of a photosensitizer is 0.1-20 mass parts with respect to 100 mass parts of (A) resin, and 2-15 mass parts is more preferable from a viewpoint of a photosensitivity characteristic. (C) It is excellent in photosensitivity by mix | blending 1 mass part or more with respect to 100 mass parts of (A) resin, and it is excellent in thick film curability by setting it as 20 mass parts or less. 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 the present embodiment is typically used as a resin composition in which the above-described components and optional components further used as necessary are dissolved in a suitable solvent to form a varnish. Therefore, (D) Other components can include solvents, for example, (A) resins other than resins, silane compounds, sensitizers, monomers having photopolymerizable unsaturated bonds, adhesion aids, heat 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 and alcohols.
As the solvent in the resin composition of the present embodiment, it is preferable to use a polar organic solvent from the viewpoint of solubility in the polyimide precursor, among (A) resin resins. 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, Examples include α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and the like. 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 alcohols. Alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond, and specific examples include, for example, methyl alcohol, ethyl alcohol, n -Alkyl alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol;
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;
Examples include dialcohols such as ethylene glycol and propylene glycol. Among these, at least one selected from lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol is preferable. Particularly, 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 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), depending on the desired coating thickness and viscosity of the resin composition. Can be used in a range. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the entire solvent is preferably 5 to 50% by mass, more 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 is good. When the content is 50% by mass or less, the solubility of the resin (A) is good. Become.

The resin composition in the present embodiment may further contain a resin component other than the above-described (A) resin. Examples of the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. 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 the resin (A).
The resin composition in the present 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-tri 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, more preferably in the range of 8 parts by mass or less, with respect to 100 parts by mass of the (A) resin.

A sensitizer can be arbitrarily blended in the resin composition of the present embodiment in order to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene 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, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-fur Nyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or in combination of, for example, 2 to 5 kinds.
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 the relief pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily blended. Such a monomer is preferably a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but examples include diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Mono- or di (meth) acrylates of ethylene glycol or polyethylene glycol;
Mono- or di (meth) acrylates of propylene glycol or polypropylene glycol;
Mono, di or tri (meth) acrylates 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;
Mono or di (meth) acrylate of bisphenol A;
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;
Moreover, compounds such as ethylene oxide or propylene oxide adducts of these compounds can be mentioned.
The compounding amount when the resin composition of the present embodiment contains the monomer having the above-described photopolymerizable unsaturated bond for improving the resolution of the relief pattern is based on (A) 100 parts by mass of the resin. 1 to 50 parts by mass.

In addition, an adhesion aid can be optionally blended for improving the adhesion between the film formed using the negative photosensitive resin composition of the present invention and the substrate. Examples of the adhesion assistant 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;
Examples thereof include aluminum-based adhesion aids such as aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), and ethyl acetoacetate aluminum diisopropylate.
Among these adhesion assistants, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The compounding amount when the resin composition in the present embodiment contains an adhesion assistant is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of (A) resin.

In particular, when the resin composition of the present embodiment is stored in the state of a solution containing a solvent, a thermal polymerization inhibitor is optionally blended in order to improve the stability of the viscosity and 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 etherdiaminetetraacetic 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 blended in the resin composition of the present embodiment.
The crosslinking agent has a function that, when the relief pattern formed using the resin composition of the present embodiment is heat-cured, (A) the resin can be crosslinked or the crosslinking agent itself can form a crosslinked network. It is preferable. 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 preferably used, and among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used. Particularly preferred are alkoxymethylated urea compounds and alkoxymethylated melamine compounds. Specific examples thereof include MX-290 (manufactured by Nippon Carbide), UFR-65 (manufactured by Nippon Cytec), MW-390 (manufactured by Nippon Carbide) and the like.
In consideration of various performances other than heat resistance and chemical resistance, the blending amount when the resin composition in the present embodiment contains a crosslinking agent is 0.5 to 20 masses per 100 mass parts of the resin (A). Part, preferably 2 to 10 parts by weight. When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are expressed, and when it is 20 parts by mass or less, the storage stability is excellent.

  In the case where the substrate to which the resin composition of this embodiment is applied is, for example, a substrate made of copper or a copper alloy, an azole compound can be arbitrarily blended in order to suppress 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, and 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, 5-bis (α, α-dimethyl Tilbenzyl) phenyl] -benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-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 at least one 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.

  When the resin composition in this embodiment contains the azole compound, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and is 0 from the viewpoint of photosensitivity characteristics. More preferable is 5 to 5 parts by mass. 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, copper or a copper alloy surface On the other hand, when the discoloration is suppressed and the amount 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 arbitrarily blended instead of the azole compound or together with the azole compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl. -4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4′-thio-bis (3-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3 -T-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydro Cyphenyl) 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-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanate Nurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3- Proxy-2,6-dimethyl-4-isopropyl-benzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) - trione,

1,3,5-tris (4-tert-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-tert-butyl-3-hydroxy-2,5 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-tert-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-tert-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 and the like are particularly preferred.

  It is preferable that the compounding quantity of a hindered phenol compound is 0.1-20 mass parts with respect to 100 mass parts of (A) resin, and it is more preferable that it is 0.5-10 mass parts from a viewpoint of a photosensitivity characteristic. 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 Discoloration / corrosion of the alloy is prevented, and on the other hand, when the amount is 20 parts by mass or less, the excellent photosensitivity of the resin composition is maintained.

<Method for Manufacturing Cured Relief Pattern and Semiconductor Device>
The present invention also provides a method for producing a cured relief pattern.
To form a cured relief pattern in this embodiment,
(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 a product. In the former case, the component (A) is particularly preferably 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). This is a case where a part is a monovalent organic group capable of radical polymerization.
Such a resin composition functions as a negative photosensitive resin composition, and an effect relief pattern can be easily and efficiently produced.
In any of the above cases, it is preferable that the resin composition further contains (C) a photosensitizer.

In the present embodiment, the cured relief pattern is, for example, the following process:
(1) An application step of applying the above-described negative photosensitive resin composition of the present embodiment on a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer;
(3) a development step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) It can manufacture by the manufacturing method of a hardening relief pattern including the heating process which forms a hardening relief pattern by heat-processing the said relief pattern.
Hereinafter, typical aspects of each process will be described.

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

(2) Exposure process In this process, the photosensitive resin layer formed above is exposed. As the exposure apparatus, for example, a contact aligner, mirror projection, stepper or the like is used. Exposure can be through a photomask or reticle having a pattern, or directly. The light beam used for exposure is, for example, ultraviolet rays.
After the exposure, post-exposure baking (PEB) and / or pre-development baking by any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity. The baking conditions are preferably 40 to 120 ° C. for the temperature and 10 to 240 seconds for the time. However, the baking conditions are limited to these ranges as long as the various characteristics of the negative photosensitive resin composition in the present embodiment are not impaired. Absent.

(3) Development process In this process, the unexposed part of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), a conventionally known photoresist developing method can be selected and used. For example, a rotary spray method, a paddle method, an immersion method with ultrasonic treatment, or the like. Further, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking at any combination of temperature and time may be performed as necessary. The post-development baking temperature can be, for example, 30 to 180 ° C., and the time can be, for example, 1 to 30 minutes.

The developer used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent. 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 and the like are preferable. ;
As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water are preferable. When mixing and using a good solvent and a poor solvent, 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. Also, two or more of each solvent, for example, several types may be used in combination.

(4) Heating step In this step, the relief pattern obtained by the development is heated to diffuse 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 made of polyimide by imidizing the resin in this step. .
As a method of heat curing, various methods such as a method using a hot plate, a method using an oven, a method using a temperature rising type oven capable of setting a temperature program can be selected. Heating can be performed, for example, at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. As an atmospheric 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 semiconductor device can be, for example, a semiconductor device having a base material that is a semiconductor element and a cured relief pattern formed on the base material by the above-described method for producing a cured relief pattern.
The semiconductor device can be manufactured, for example, by a method using a semiconductor element as a base material and including the above-described method for manufacturing a cured relief pattern as part of the process. The semiconductor device according to the present embodiment has a cured relief pattern formed by the method for producing a cured relief pattern, for example, a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film, and a bump structure. It can be manufactured by forming it as a protective film of the semiconductor device it has and combining it with a known method for manufacturing a semiconductor device.

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

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In Examples, Comparative Examples, and Production Examples, the 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 the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement is a trade name Shodex 805M / 806M series manufactured by Showa Denko KK
As standard monodisperse polystyrene, Showa Denko Co., Ltd. Shodex STANDARD SM-105,
The developing solvent is N-methyl-2-pyrrolidone,
The detector used was a trade name Shodex RI-930 manufactured 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, and then heated and dried at 100 ° C. for 4 minutes to form a 10 μm thick coating film. This coating film was irradiated and exposed through a reticle with a test pattern with an i-line stepper NSR2005i8A (Nikon Corp.) with an exposure dose varied in the range of 50 to 600 mJ / cm ² energy. The exposed coating film is spray-developed with cyclopentanone using a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) and then rinsed with propylene glycol methyl ether acetate to remove unexposed portions. Development and removal were performed to obtain a relief pattern of a polyimide precursor. Next, the wafer on which this relief pattern was formed was placed in a temperature rising program curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan), and heat-treated at 350 ° C. for 2 hours under a nitrogen atmosphere, A cured relief pattern of polyimide having a thickness of 5 μm was obtained. The film thickness of the cured relief pattern was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor).

About the obtained pattern, the pattern shape and the width | variety of the pattern part were observed under the optical microscope. When the area of the opening of the 10 μm pattern is 1/2 or more of the corresponding pattern mask opening area and there is no peeling,
A case where the area of the opening is less than ½ of the corresponding pattern mask opening area, or a case where there is peeling is defined as “bad”.
At this time, the minimum exposure amount at which a “good” pattern was obtained was defined as photosensitivity.

(3) Adhesive evaluation with a base material The photosensitive resin composition was spin-coated on a copper substrate, and heated and dried at 100 ° C. for 4 minutes to form a 10 μm-thick photosensitive resin layer coating film. The copper substrate on which this coating film was formed was placed in a temperature rising programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan), and at 200 ° C. for 1 hour in a nitrogen atmosphere, followed by 250 ° C. A cured resin coating film having a thickness of 5 μm was obtained by heat treatment (curing) for 2 hours.
About the film | membrane after curing, according to the cross-cut method of JISK5600-5-6 specification, the adhesive characteristic between a copper substrate / cured resin coating film was evaluated based on the following references | standards.
“Very good”: When the number of lattices of the cured resin coating film adhered to the substrate is 100 “Good”: When the number of lattices of the cured resin coating film adhered to the substrate is 80 to 99 “ “Yes”: When the number of lattices of the cured resin coating film adhered to the substrate is 50 to 79 “Bad”: When the number of lattices of the cured resin coating film adhered to the substrate is 20 to 49 “Very 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. Next, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 81.5 g of pyridine was added with stirring at room temperature to obtain a reaction mixture.
The reaction mixture was allowed to cool to room temperature after completion of the exothermic reaction, and 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 was added 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, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added.
The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction liquid was thrown into 3 liters of ethyl alcohol, and the deposit which consists of a crude polymer was produced | generated. The produced crude polymer was collected by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution is dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate is collected by filtration and then vacuum dried to obtain a resin (A1) that is a polyimide precursor as a powder. It was.
When the molecular weight of this resin (A1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

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

<Example 1>
Using the resin (A1) and the resin (A2) obtained in the above production examples, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) 50 g of resin (A1) as a resin and 50 g of resin (A2) B, and (B) 0.001 g of N, N-dimethyl-3- (dimethylamino) propanamide as an amide compound were used as N- The resin composition was dissolved in 199.999 g of methyl-2-pyrrolidone.
Using this resin composition, the adhesion with the substrate was evaluated according to the method described above, and the adhesion was “OK”.
<Examples 2 to 5 and Comparative Example 1>
In Example 1, the blending amounts of (B) N, N-dimethyl-3- (dimethylamino) propanamide as the amide compound and N-methyl-2-pyrrolidone as the solvent are shown in Table 1, respectively. A resin composition was prepared in the same manner as in Example 1 except that the procedure was changed as described above.
In Comparative Example 1, the (B) amide compound was not used.
Using each of these compositions, the adhesion to the substrate was evaluated according to the method described above. The evaluation results are shown in Table 1.

<Examples 6 to 10 and Comparative Example 2>
(C) 6-g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime as a photosensitizer was further added to the resin compositions of Examples 1 to 5 and Comparative Example 1, respectively. By doing so, a negative photosensitive resin composition was prepared.
Using each of these resin compositions, photosensitivity and adhesion to the substrate were evaluated according to the above-described methods. 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 (B) as an amide compound to the resin composition of Comparative Example 2.
Using this composition, an attempt was made to evaluate photosensitivity according to the method described above. However, the 10 μm pattern did not open, and the evaluation could not be performed. This is thought to be because the coating film was gelled.
Moreover, when the adhesiveness with a base material was measured according to the above-mentioned method using the composition, the adhesiveness was “very good”.

In the said table | surface, the upward arrow shows that the kind and quantity of a mixing | blending component applicable to the said column are the same as the upper column. Further, “-” indicates that the component corresponding to the column was not blended.
Abbreviations for each component have the following meanings.
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 in the field of photosensitive materials useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (8)

(A) At least one resin selected from the group consisting of an alkali-soluble resin and a resin having a polymerizable group in the 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 having 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 each other. Thus, a ring structure may be formed. } The amide compound represented by: 0.001-1 mass part is contained, The resin composition characterized by the above-mentioned. The component (A) 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 having 5 to 30 carbon atoms, or a saturated aliphatic group having 1 to 4 carbon atoms. } The resin composition of Claim 1 which is a polyimide precursor which has a repeating unit represented by these. R ₅ and R ₆ in the general formula (2) are each independently a hydrogen atom, the following general formula (3):

{In Formula (3), R <_9> , R < ₁₀ > and R <_11> are respectively independently a hydrogen atom or a C1-C3 monovalent organic group, and m is an integer of 2-10. } Or a monovalent organic group represented by the following general formula (4):
-R ₁₂ (4)
{In 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. . }, And a monovalent organic group represented by the above general formula (3) and 1 represented by the above general formula (4) for all of R ₅ and R _6. the total proportion of valent organic group is 80 mol% or more, and for all of R ₅ and R _6, 1-valent ratio 20 mol% to 80 mol of an organic group represented by the general formula (4) The resin composition according to claim 2, which is%. R ₅ and R ₆ in the general formula (2) are each independently a hydrogen atom, the following general formula (3):

{In Formula (3), R <_9> , R < ₁₀ > and R <_11> are respectively independently a hydrogen atom or a C1-C3 monovalent organic group, and m is an integer of 2-10. The monovalent organic group represented by this, or a C1-C4 saturated aliphatic group, provided that both of R ₅ and R ₆ are not hydrogen atoms at the same time. Resin composition.   The resin composition according to any one of claims 1 to 4, wherein the component (B) is N, N-dimethyl-3- (dimethylamino) propanamide.   (C) The resin composition as described in any one of Claims 1-5 which further contains a photosensitizer and is photosensitive. The following steps:
(1) An application step of applying the photosensitive resin composition according to claim 6 on a substrate to form a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer;
(3) a development step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a heating step of forming a cured relief pattern by heat-treating the relief pattern.   A semiconductor device comprising a cured relief pattern obtained by the method according to claim 7.