JP2016069498A - Resin composition, manufacturing method of cured relief pattern and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition providing a coated film excellent in film thickness uniformity during forming a thick film and in adhesiveness with a substrate after developing, a manufacturing method of a cured relief pattern forming a resin pattern by using the resin composition and a semiconductor device.SOLUTION: There is provided a resin composition containing 100 pts.mass of (A) resin: polyamide having a polymerizable group in a side chain and 1 to 10,000 pts.mass of (B) an amide compound represented by the formula (B1), where Ris a C1 to 5 alkyl group, Rand Rare each independently H or a hydrocarbon group which may have a C1 to 6 ether bond, but Rand Rmay bind each other to form a ring structure.SELECTED DRAWING: None

Description

  The present invention relates to, for example, an insulating material for electronic parts, a resin composition used for forming a relief pattern such as 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 a semiconductor It relates to the device.

  Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films, and the like. 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 on a printed wiring board has been changed from the viewpoint of improving the degree of integration and functions in a semiconductor device 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 film or a polybenzoxazole film | membrane is disclosed by adding a thermal crosslinking agent to the composition containing a polyimide precursor or a polybenzoxazole precursor (refer patent document 1). ).

  Further, in a rewiring process in a recent semiconductor process, the wiring layer is increased in thickness from the viewpoint of improving reliability. Along with this, it is required to form a thick film of polyimide as an interlayer insulating film. However, when a thick film relief pattern is formed using a conventional polyimide precursor composition, there is a problem that adhesion to the substrate is poor and the film peels off from the pattern end face after development. In addition, when a conventional polyimide precursor composition containing N-methyl-2-pyrrolidone as a main solvent is used, the effect of Benard convection at the time of solvent volatilization increases and the film thickness uniformity of the coating film deteriorates. is there.

JP 2003-287889 A

  The present invention seeks to solve the above-described problems of the prior art. Accordingly, an object of the present invention is to provide a resin composition that provides a film having excellent film thickness uniformity during thick film formation and excellent adhesion to a substrate after development. It is another object of the present invention to provide a cured relief pattern manufacturing method and a semiconductor device which are performed using the resin composition.

By including a compound having a specific structure in a resin composition for forming a film, the present inventors have obtained a film having excellent film thickness uniformity during thick film formation and excellent adhesion to a substrate. As a result, the present invention was completed.
The present invention is as follows.

[1] A resin composition comprising (A) resin: 100 parts by mass, and (B) an amide compound represented by the following general formula (B1): 1 to 10,000 parts by mass.

{Wherein R ₁ is a C 1-5 alkyl group;
R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group that may have an ether bond having 1 to 6 carbon atoms, provided that R ₂ and R ₃ are the same or different from each other. They may be bonded to each other to form a ring structure. }
[2] The resin composition according to [1], wherein the (A) resin is a resin having a polymerizable group in a side chain.
[3] The resin composition according to [1], wherein the (A) resin is a polymer having a structure represented by the following general formula (A1).

{In general formula (A1), X ₁ is a tetravalent organic group;
Y ₁ is a divalent organic group;
R ₄ and R ₅ are each independently a hydrogen atom, a saturated aliphatic group having 1 to 4 carbon atoms, an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or 6 to 30 carbon atoms. An aromatic group or a monovalent organic group capable of radical polymerization; provided that
At least one of R ₄ and R ₅ is a monovalent organic group capable of radical polymerization. }
[4] In the formula (A1),
R ₄ and R ₅ are each independently
A hydrogen atom, the following general formula (R1):

{In General Formula (R1), R ₁₃ , R ₁₄ , and R ₁₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; q is an integer of 2 to 10. }, A monovalent organic group, 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, and R ₄ and R ₅ The total of the monovalent organic group represented by the above general formula (R1) for all, the aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, and the aromatic group having 6 to 30 carbon atoms In [3], the ratio is 80 mol% or more, and the ratio of the monovalent organic group represented by the general formula (R1) to all of R ₄ and R ₅ is 20 mol% to 80 mol%. The resin composition as described.

[5] In the formula (A1),
R ₄ and R ₅ are each independently a hydrogen atom, a monovalent organic group represented by the general formula (R1), or a saturated aliphatic group having 1 to 4 carbon atoms, provided that
The resin composition according to [3], wherein R ₄ and R ₅ are not simultaneously hydrogen atoms.
[6] The resin composition according to [1], wherein the (A) resin is a polymer having a structure represented by the following general formula (A2).

{In General Formula (A2), a and b are each independently an integer of 0 to 2 and do not simultaneously become 0;
c and d are each independently an integer of 0 to 4;
R ₁₆ is a (2 + a + c) -valent organic group having 2 to 60 carbon atoms;
R ₁₇ is a (2 + b + d) -valent organic group having 2 to 60 carbon atoms, consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom;
R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. }
[7] (C) The following general formula (C1):

{In Formula (C1), X ₄ and X ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2 and Y ₄ is 1 to ₃ carbon atoms. 20 monovalent organic groups. } The resin composition as described in any one of [1]-[6] which further contains the silane compound represented by these.
[8] The resin composition according to any one of [1] to [7], wherein the (B) amide compound is 3-methoxy-N, N-dimethylpropionamide.
[9] The resin composition according to any one of [1] to [8], further comprising (D) a photosensitizer.

[10] The following steps:
(1) An application step of applying the resin composition according to any one of [1] to [9] on a substrate and forming a resin layer on the substrate;
(2) an exposure step of exposing the resin layer;
(3) a development step of developing the exposed resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, wherein a heating step of forming a cured relief pattern by heat-treating the relief pattern is passed in the order described above.
[11] A semiconductor device comprising a cured relief pattern obtained by the production method according to [10].

  According to the present invention, it is possible to obtain a resin composition that provides a film having excellent film thickness uniformity during thick film formation and excellent adhesion to a substrate after development, and further using the resin composition to obtain a resin. A method for producing a cured relief pattern for forming a pattern and a semiconductor device are provided.

  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 the present invention comprises (A) a resin and (B) an amide compound represented by the above general formula (B1) as essential components. In addition to these, the resin composition of the present invention may further contain one or more selected from the group consisting of (C) a silane compound and (D) a photosensitizer.

<(A) Resin>
(A) resin used for this invention is demonstrated.
The (A) resin of the present invention comprises polyamic acid (polyamic acid), polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polyoxazole, polyoxazole precursor, polybenzoxazole, polybenzimidazole, It is preferable to contain at least one resin selected from the group consisting of polybenzthiazole, phenol resin, epoxy resin, siloxane resin, and acrylic resin.
The weight average molecular weights of these (A) resins are preferably 1,000 or more, more preferably 5,000 or more, in terms of polystyrene converted by gel permeation chromatography, from the viewpoint of heat resistance after heat treatment and mechanical properties. preferable. The upper limit of the 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 the (A) resin is more preferably 50,000 or less from the viewpoint of solubility in a developer.

  In the present embodiment, the (A) resin is preferably an alkali-soluble resin. In order to form a relief pattern, a photosensitive resin is desirable. The photosensitive resin can be used as the photosensitive resin composition of the present embodiment by using this together with the photosensitive agent (D) described later, depending on whether exposure or unexposed in the exposure step, It is a resin that causes dissolution or undissolved development 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. Used.
From the viewpoint of heat resistance and photosensitivity, the (A) resin that is particularly preferable is the general formula (A1)

{In general formula (A1), X ₁ is a tetravalent organic group;
Y ₁ is a divalent organic group;
R ₄ and R ₅ are each independently a hydrogen atom, a saturated aliphatic group having 1 to 4 carbon atoms, an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or 6 to 30 carbon atoms. An aromatic group or a monovalent organic group capable of radical polymerization; provided that
At least one of R ₄ and R ₅ is a monovalent organic group capable of radical polymerization. } (Polymer (A1)) having the structure represented by the following general formula (A2):

{In General Formula (A2), a and b are each independently an integer of 0 to 2 and do not simultaneously become 0;
c and d are each independently an integer of 0 to 4;
R ₁₆ is a (2 + a + c) -valent organic group having 2 to 60 carbon atoms;
R ₁₇ is a (2 + b + d) -valent organic group having 2 to 60 carbon atoms, consisting of carbon atom, hydrogen atom, nitrogen atom, oxygen atom and sulfur atom;
R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. } It is preferable that it contains at least one resin selected from the group consisting of a polymer having a structure represented by (polymer (A2)) and polyhydroxyamide (polymer (A3)). The use ratio of these resins in the resin composition of the present embodiment is preferably 60% by mass or more, and more preferably 80% by mass or more, based on the total amount of (A) resin.

[Polymer (A1)]
As the monovalent organic group capable of radical polymerization of R ₄ and R ₅ in the general formula (A1), and the following general formula (R1):

{In General Formula (R1), R ₁₃ , R ₁₄ , and R ₁₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; q is an integer of 2 to 10. } It is preferable that it is a monovalent organic group represented by these.
R ₁₄ and R ₁₅ in the general formula (R1) are each independently preferably a hydrogen atom or a methyl group, and preferably a hydrogen atom from the viewpoint of photosensitive properties. R ₁₃ is preferably a hydrogen atom or a methyl group. Further, q is preferably an integer from 2 to 10, more preferably an integer from 2 to 4, from the viewpoint of photosensitive properties.

In the general formula (R1), 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. ,
One of -COOR ₄ group and -CONH- group is bonded to the same aromatic ring, both are in the ortho position to each other, and the other of -COOR ₅ group and -CONH- group is the same aromatic ring. It is a tetravalent aromatic group or a tetravalent alicyclic aliphatic group that is bonded and both are ortho to each other. In the former case, an aromatic ring to which —COOR ₄ group is bonded;
The aromatic ring to which the —COOR ₅ 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 (R1), 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, a methyl group _(-CH 3), ethyl group _{(-C 2 H} 5), propyl group _(-C 3 _{H 7)} or a butyl group _(-C 4 _{H 9)} is there. }, 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.

Examples of the saturated aliphatic group having 1 to 4 carbon atoms of R ₄ and R ₅ in the general formula (R1) 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 and isopentyl;
A tertiary hydrocarbon group such as a t-butyl group can be exemplified. Examples of the aliphatic group having 5 to 30 carbon atoms which may have a hetero atom of R ₄ and R ₅ include, for example, a butoxymethyl group, a butyl sulfide methylene group, a butyl aminomethylene group, and the like; an oxygen atom as a hetero atom And an aliphatic group containing a nitrogen atom, a sulfur atom, or a phosphorus atom. Examples of the aromatic group having 6 to 30 carbon atoms of R ₄ and R ₅ include a phenyl group, a benzyl group, and a naphthyl group.

As R ₄ and R ₅ in the general formula (A1),
A hydrogen atom, a monovalent organic group represented by the general formula (R1), 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. , And a monovalent organic group represented by the above general formula (R1) for all of R ₄ and R ₅ , an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, and 6 to 6 carbon atoms The total proportion of 30 aromatic groups is 80 mol% or more, and the proportion of the monovalent organic group represented by the above general formula (R1) with respect to all of R ₄ and R ₅ is 20 mol% to 80 mol. %; Or
A hydrogen atom, a monovalent organic group represented by the above general formula (R1), or a saturated aliphatic group having 1 to 4 carbon atoms, provided that
This is a case where both R ₄ and R ₅ are not hydrogen atoms at the same time.
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.

  (A) When the polymer (A1) is used as the resin, examples of a method for imparting a monovalent organic group capable of radical polymerization to the polymer (A1) include an ester bond type and an ion bond type. The former is a system in which a monovalent organic group capable of radical polymerization by an ester bond is introduced into the side chain of the polyimide precursor. The latter is based on the reaction between a polymer 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 system, 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.

[Method for Preparing Ester-Linked Polymer (A1)]
Preparation of the ester-linked polymer (A1), for example first, alcohol having a desired tetravalent tetracarboxylic acid dianhydride having an organic group X _1, a radical polymerizable group (e.g. an unsaturated double bond) And a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester), and this and a diamine having a divalent organic group Y ₁ are subjected to amide polycondensation. Is obtained. 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 preferably used for preparing the ester bond type polymer (A1) include pyromellitic anhydride, 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. It is not limited. In addition, these may be used alone or in combination of two or more.

  Examples of alcohols having a radical polymerizable group which are preferably used for preparing the ester bond polymer (A1) in the present invention 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-methacryloyloxyethyl alcohol 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2 -Hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like can be mentioned.

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 10 to 500 mol%, 100 to 300 mol% More preferably.

  The above-mentioned suitable tetracarboxylic dianhydrides and alcohols are preferably stirred and mixed in a suitable reaction solvent at a temperature of 20 to 50 ° C. for 4 to 10 hours, preferably in the presence of a basic catalyst such as pyridine. As a result, 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 polymer (A1) which is an amide polycondensation product of the acid / ester and diamine is also a solvent that dissolves in the Seki z root. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbonized Examples thereof include hydrogen. 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 polymer (A1))
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 mix the acid / ester with polyanhydride. It is a thing. Next, a target polymer is obtained by adding dropwise a solution obtained by dissolving or dispersing a diamine having a divalent organic group Y ₁ suitably used in this embodiment in a solvent, and subjecting both to amide polycondensation. (A1) can be obtained. Diaminosiloxanes may be used in combination with the diamine having the divalent organic group Y ₁ .
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.

In the present embodiment, examples of diamines containing a divalent organic group Y ₁ that are preferably used for the reaction with a polyanhydride 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′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diamino Benzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminoben Phenone, 4,4′-diaminodiphenylmethane, 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) anthracene, 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- bis (4-aminophenyl) fluorene;

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.

The diaminosiloxanes contain the divalent organic group Y ₁ when preparing the polymer (A1) for the purpose of improving the adhesion between the coating film formed from the resin composition of the present embodiment and various substrates. Used in combination with diamines. Specific examples of such diaminosiloxanes include 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetraphenyldisiloxane, and the like. it can. 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 .

The amount of the diamine used is preferably 50 to 200 mol%, and preferably 80 to 160 mol as the total amount of the diamine based on 1 mol of the polyacid anhydride converted to the acid / ester form of the raw material. % Is more preferable.
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 mixture thereof, etc.) to precipitate the polymer component, and further purify the polymer by repeating operations such as re-dissolution and re-precipitation as required, followed by vacuum drying. The target polymer (A1) is isolated. 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 polymer (A1) is preferably 1,000 to 100,000, preferably 5,000 to 50,000, when measured as a polystyrene-reduced weight average molecular weight by gel permeation chromatography. More preferably. 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.

[Polymer (A2)]
The polymer (A2) which is one of the resins (A) in this embodiment is a polymer having a structure represented by the general formula (A2), and can be a polymer having an oxazole ring by heating or an appropriate catalyst. Is. When the polymer (A2) becomes a polymer having an oxazole ring structure, the heat resistance and solvent resistance of the formed film are dramatically improved.
The repeating number of the structural unit represented by the general formula (A2) in the polymer (A2) is not limited as long as it is a positive integer, but from the viewpoint of developability, a range of 1 to 1,000 is preferable, and 3 to 50 The range is more preferable, and the range of 3 to 30 is most preferable.
In the polymer (A2), the structural unit represented by the general formula (A2) may be one type or two or more types. When two or more types of structural units are present in the polymer (A2), the arrangement of the structural units may be either block or random.

The polymer (A2) includes, for example, a dicarboxylic acid having a structure of R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ ,
R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) It can be obtained by polycondensation with a diamine having a _g structure. R _{16 to} R ₂₁ and d to g in these formulas have the same meanings as in the general formula (A2).
First, the diamine having the R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure will be described.

For example, R ₁₉ is a hydrogen atom, and e is 2. Examples of the diamine include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino. -3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-4- Hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- ( 4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino No-3-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′-diamino-4,4′-dihydroxybenzophenone, 4,4′-diamino-3,3 ′ -Dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino -4,6-dihydroxybenzene and others:
_{R 17 (NH 2) 2 (} OR 19) e (COOR 21) R 17 in _g the following formula groups:

A bisaminophenol compound (wherein R19, R21, e, and g in the above formula have the same meanings as in the general formula (A2)), etc. Can be mentioned.
Among these bisaminophenol compounds, those particularly preferable from the viewpoints of solubility in an alkali developer and heat resistance are compounds in which R ₁₇ is a tetravalent organic group selected from the above formula group.
Bis (aminophenol) _{(e.g., R 17 (NH 2) 2} (OR 19) e (COOR 21) _{that R 17} in the _g structure is selected from the formula group) at the bond joining the benzene rings In contrast, the meta position is an amino group and the para position is a hydroxyl group, and the meta position is a hydroxyl group and the para position is an amino group. From this viewpoint, it is preferable that the meta position is an amino group and the para position is a hydroxyl group.
In addition, as a diamine having a R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure, the following structure:

_{{Wherein, X 52} is a tetravalent organic group having 2 to 60 carbon atoms. } Can also be used.
X ₅₂ is not limited as long as it is a tetravalent organic group having 2 to 60 carbon atoms, but is exemplified as a preferable organic group represented by R ₁₇ described above from the viewpoint of solubility in an alkali developer and heat resistance. It is preferable to have a structure. When X ₅₂ is an aromatic group, the amide bond and the phenolic hydroxyl group bonded to the same aromatic ring are preferably in the ortho positions. Such a diamine is hereinafter referred to as “a diamine having a PBO precursor structure in the molecule”.
As a preferable structure of the diamine having a PBO precursor structure in the molecule, more specifically, the following structure:

The diamine represented by each of these is mentioned. Examples of the method for producing these diamines include a method in which the above-described bisaminophenol is reacted with two molecules of nitrobenzoic acid, and then the nitro group is reduced to an amino group.
Furthermore, as a diamine having the R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure, the following structure:

{Wherein, _{Y 7} is a divalent organic group having 2 to 60 carbon atoms. } Can also be used. Y ₇ in the above formula is not limited as long as it is a divalent organic group having 2 to 60 carbon atoms, but from the viewpoint of solubility in an alkali developer and heat resistance, an example of the organic group represented by R ₁₆ will be described later. It is preferable that it is at least 1 type of organic group enumerated by these.
Preferable examples of such compounds are specifically the following structural groups:

The diamine represented by each of these is mentioned. These diamines can be obtained, for example, by reacting a dicarboxylic acid dichloride compound with two molecules of nitroaminophenol and then reducing the nitro group to an amino group.
In addition to these, as a diamine having the structure R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g , a compound having two polyimide precursor structures in the molecule (hereinafter referred to as “PI precursor in the molecule”). Bisaminophenol having a structure ") can also be used. Examples of such compounds include the following structures:

{Wherein Y ₈ is a tetravalent organic group having 4 to 60 carbon atoms, and R ₂₂ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. } May be used. More specific examples of such compounds include the following structural groups:

{In the formula, R ₂₂ represents hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms. }, Diamines represented by each of the above.
As a method for producing a bisaminophenol having a PI precursor structure in the molecule, for example,
Dicarboxylic acid ring-opened by allowing monoalcohol, monoamine, etc. to act on tetracarboxylic dianhydride;
A method of reducing the nitro group after condensing two molecules of an aniline derivative having a hydroxyl group and a nitro group at the ortho positions relative to each other can be exemplified.

Next, as a diamine having a raw material R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure, a diamine in which both e and g are 0 will be described. Such a diamine can be advantageously used for adjusting the solubility in an alkali developer. Examples of these diamines include aromatic diamines. Aromatic diamines are advantageous from the viewpoint of heat resistance.

  Examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-amino) Phenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2 , 4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-amino) Benzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene,

4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) Phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diaminodiphenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4′-bis (4-amino) Phenoxy) diphenylsulfone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4′-diaminobenzophenone, phenylindanediamine, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3 , 3′-dimethyl-4,4′-diaminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) ) Sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- ( 3-aminophenoxy) diphenylsulfone and 4,4′-diaminobenzanilide ;
The diamine etc. which the hydrogen atom of the aromatic nucleus of these aromatic diamine substituted by the chlorine atom, the fluorine atom, the bromine atom, the methyl group, the methoxy group, the cyano group, the phenyl group etc. can be mentioned.

Next, a dicarboxylic acid having a structure of R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ will be described.
In R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , d = f = 0, d = 0 and f = 2, d = 1 or 2, and f = 2.
Such a dicarboxylic acid can be advantageously used when adjusting the solubility in an alkali developer.
Examples of R ₁₆ when d = f = 0 include structures represented by any of the following structural groups.

{Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. A divalent group,
K L ₁ bonded to the ring carbon are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an amide group, a urea group, an imide group, and a urethane group; And k = 4. }, — (CH ₂ ) _n10 — (where n ₁₀ is an integer of 1 to 12), and

{Wherein L ₂ , L ₃ and L ₄ are each independently a hydrogen atom or a methyl group. }.
Among the above, a typical compound as a dicarboxylic acid having a tricyclodecane skeleton includes bis (carboxy) tricyclo [5.2.1.0 ^2,6 ] decane. As a manufacturing method of this compound, the synthesis example described in the international publication 2009/081950 pamphlet can be illustrated, for example.
As the dicarboxylic acid in the case where d = 0 and f = 2 in R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , for example, tetracarboxylic dianhydride was ring-opened with monoalcohol, monoamine or the like. Dicarboxylic acids can be used. Here, examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and benzyl alcohol. Examples of monoamines include butylamine and aniline.
As an example of said tetracarboxylic dianhydride, the compound etc. which are respectively represented by each of the following chemical formula group are mentioned, for example.

{Wherein B is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and —COO—. Divalent group. }
In the case where d = 0 and f = 2 in R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , as another method, tetracarboxylic dianhydride and bisaminophenol or diamine may be used. The carboxylic acid residue produced by the reaction can also be synthesized by a method of esterification or amidation with a monoalcohol or monoamine.
In the dicarboxylic acid where d = 1 or 2 and f = 2 in R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , R ₁₈ can be, for example, hydrogen. As such a dicarboxylic acid, for example, a dicarboxylic acid having two pairs of amide bonds and phenolic hydroxyl groups in ortho positions with each other can be given. Examples of such a dicarboxylic acid include compounds represented by the following formulas.

{Wherein X ₅₃ is a trivalent or tetravalent organic group having at least 2 carbon atoms, each R ₂₃ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and , N ₁₁ is an integer of 1 or 2. )

As a method for producing the compound represented by the above formula, for example, the structure of bis (aminophenol) having the structure of R ₁₇ (NH ₂ ) ₂ (OH) _{2 or} the structure of R ₁₇ (NH ₂ ) ₂ (OH) is used. An example is a method in which two molecules of trimellitic acid chloride are reacted with diaminophenol, and then an acid anhydride and an alcohol are further reacted.

  The polyhydroxyamide that is the polymer (A3) can be synthesized, for example, by polycondensation of a dicarboxylic acid and a bisaminophenol compound (diamine). As a typical method, for example, after obtaining diacid chloride using dicarboxylic acid and thionyl chloride, bisaminophenol (diamine) is allowed to act on the diacid chloride, or dicarboxylic acid and bisamino Examples include a method of polycondensing phenol (diamine) with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

  (A) resin in this embodiment is polyamic acid (polyamic acid), polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polyoxazole, polyoxazole precursor, polybenzoxazole, polybenzimidazole It is preferable to contain at least 60% by mass of at least one resin selected from the group consisting of polybenzthiazole, phenol resin, epoxy resin, siloxane resin, and acrylic resin, based on the total amount of the resin (A). It is more preferable to contain 80% by mass or more. More preferably, it is a case where one or more resins selected from the group consisting of the polymer (A1) and the polymer (A2) are contained, preferably 60% by mass or more, more preferably 80% by mass or more.

<(B) Amide compound>
The amide compound (B) used for the resin composition of this embodiment will be described.
(B) The amide compound has the following general formula (B1):

{Wherein R ₁ is a C 1-5 alkyl group;
R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group optionally having an ether bond having 1 to 6 carbon atoms, provided that R ₂ and R ₃ may be the same as each other. They may be different from each other and may be bonded to each other to form a ring structure. } It is a compound represented.
The resin composition of this embodiment is a resin composition that can form a thick film relief pattern that is excellent in film thickness uniformity and excellent in adhesion to a substrate by using such an (B) amide compound. be able to.
When forming a relief pattern, Benard convection is likely to occur in the heating step (approximately 100 ° C.) for removing the solvent. Then, since the trace of convection remains even after the solvent is sufficiently removed, the film thickness uniformity of the coating film tends to deteriorate. In particular, when a thick film relief pattern is formed, the unevenness of the coating film due to Benard convection becomes more severe, and thus the film thickness uniformity tends to be further deteriorated.

In general, the ease of forming a Benard cell can be expressed by the Marangoni number. It is known that the thicker the film thickness, the larger the Marangoni number and the easier the convection occurs. In addition, the higher the viscosity, the smaller the Marangoni number and the less convection occurs.
In the heating process for removing the solvent when forming the relief pattern, the heating temperature is 140 ° C. or lower in order to suppress the reaction of the added photosensitizer or to prevent the base material made of copper or the like from reacting with the resin. It is desirable to make it. N-methyl-2-pyrrolidone or the like used as a main solvent for the polyimide precursor or the like has a boiling point higher than the heating temperature at the time of solvent removal, and the solvent tends to remain in the coating film. Therefore, since the viscosity at the time of film | membrane hardening becomes low, there exists a tendency for a Benard convection to occur easily. And since it passes through exposure and a development process in the state in which the solvent remains in the coating film, the resin is likely to be dissolved in the developer during development, and thus the formed relief pattern tends to peel off from the end face. .

The amide compound (B) used in the present embodiment tends to have a higher boiling point than N-methyl-2-pyrrolidone. Therefore, when the treatment is performed at the same heating temperature when removing the solvent during the relief pattern formation, the residual amount of the solvent in the coating film increases. However, the resin composition using the (B) amide compound is more excellent in film thickness uniformity than the resin composition using N-methyl-2-pyrrolidone, and the peeling after the relief pattern development is suppressed.
Although the mechanism by which (B) the amide compound contributes to the film thickness uniformity of the coating film is not clear, the interaction between (A) resin and (B) amide compound increases the viscosity at the time of solvent volatilization, and Benal It is estimated that convection was suppressed. Moreover, although the mechanism excellent in the adhesiveness of the relief pattern after image development is not certain, dissolution of the resin due to solvation of the developer was suppressed by the interaction between the (A) resin and the (B) amide compound. As a result, the swelling of the relief pattern is suppressed, and as a result, it is estimated that the stress applied to the interface between the base material and the relief pattern is reduced.

  Specific examples of (B) amide compounds include, for example, 3-methoxy-propionamide, 3-ethoxy-propionamide, 3-propoxy-propionamide, 3-butoxy-propionamide, 3- (2-methylpropoxy) -propion Amide, 3-pentyloxy-propionamide, 3-methoxy-N-methylpropionamide, 3-ethoxy-N-methylpropionamide, 3-propoxy-N-methylpropionamide, 3-butoxy-N-methylpropionamide, 3, -(2-Methylpropoxy) -N-methylpropionamide, 3-pentyloxy-N-methylpropionamide, 3-methoxy-N-ethylpropionamide, 3-ethoxy-N-ethylpropionamide, 3-propoxy-N- Ethylpropionamide, 3-but Ci-N-ethylpropionamide, 3- (2-methylpropoxy) -N-ethylpropionamide, 3-pentyloxy-N-ethylpropionamide, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N , N-dimethylpropionamide, 3-propoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 3- (2-methylpropoxy) -N, N-dimethylpropionamide, 3- Pentyloxy-N, N-dimethylpropionamide, 3-methoxy-N, N-diethylpropionamide, 3-ethoxy-N, N-diethylpropionamide,

3-propoxy-N, N-diethylpropionamide, 3-butoxy-N, N-diethylpropionamide, 3- (2-methylpropoxy) -N, N-diethylpropionamide, 3-pentyloxy-N, N-diethyl Propionamide, 3-methoxy-1- (1-pyrrolidinyl) propanone, 3-methoxy-1- (1-piperidinyl) propanone, 3-methoxy-1- (4-morpholinyl) propanone, 3-ethoxy-1- (1 -Pyrrolidinyl) propanone, 3-ethoxy-1- (1-piperidinyl) propanone, 3-ethoxy-1- (4-morpholinyl) propanone, 3-propoxy-1- (1-pyrrolidinyl) propanone, 3-propoxy-1- (1-piperidinyl) propanone, 3-propoxy-1- (4-morpholinyl) propano , 3-butoxy-1- (1-pyrrolidinyl) propanone, 3-butoxy-1- (1-piperidinyl) propanone, 3-butoxy-1- (4-morpholinyl) propanone, and the like, but are not limited thereto. It is not a thing. Moreover, in using these, 1 type or a 2 or more types of mixture may be sufficient.

Among the amides, at least one selected from 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide is used from the viewpoint of adhesion after development of the relief pattern. Is preferred.
(B) The compounding quantity of an amide compound is 1-10,000 mass parts with respect to 100 mass parts of (A) resin, Preferably it is 100-1,000 mass parts.

<(C) Silane compound>
In this embodiment, the (C) silane compound that is optionally used will be described.
The (C) silane compound in the present embodiment is not particularly limited as long as it is an organic compound containing an alkoxysilyl group as represented by the following general formula (C1).

{In Formula (C1), X ₄ and X ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2 and Y ₄ is 1 to ₃ carbon atoms. 20 monovalent organic groups. }
In the general formula (C1), Y ₄ is preferably a group represented by the following general formula (Y ₄ -1) or (Y ₄ -2).

{In formula (Y ₄ -1), X ₆ is a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₅ is an amino group, a hydroxyl group, a carboxyl group, an amide group, or an alkoxy group. A monovalent group having at least one substituent selected from the group consisting of:
In the formula (Y ₄ -2), X ₇ is a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₆ is an aromatic group having 1 to 20 carbon atoms, a mercapto group, a glycidyl group, or vinyl. A monovalent organic group having at least one substituent selected from the group consisting of a group, an acryloyl group and a methacryloyl group. }
In the general formula (C1), from the viewpoint of suppressing appearance defects such as wrinkles and blisters that may occur on the cured relief pattern when it is sputtered, and from the viewpoint of elongation of the cured film. Y ₅ is preferably at least one selected from five groups represented by each of the following general formula groups.

{In the above formula, X ₈ and X ₉ are each independently a monovalent organic group having 1 to 20 carbon atoms, and X ₁₀ and X ₁₄ are each independently a divalent organic group having 1 to 10 carbon atoms. X ₁₁ and X ₁₂ are each independently a monovalent organic group having 1 to 10 carbon atoms, X ₁₃ is a tetravalent organic group, and s is an integer of 0 to 2. is there. }
In the general formula (C1), Y ₆ is represented by the following general formula (C1) from the viewpoint of suppressing appearance defects such as wrinkles and blisters that may occur on the pattern when the cured relief pattern is sputtered. It is preferably at least one selected from three groups represented by each of the groups Y ₆ -1).

{In the above formula, X ₁₅ is a monovalent organic group having 1 to 20 carbon atoms, t is an integer of 0 to 5, and when t is 2 to 5, a plurality of X ₁₅ are the same. Or X ₁₆ is a hydrogen atom or a methyl group, u is an integer of 0 to 5, and when u is 2 to 5, a plurality of X ₁₆ are the same. Or X ₁₇ and X ₁₈ are each independently a divalent group having 1 to 10 carbon atoms. }
The compound in which Y ₄ is represented by the general formula (Y ₄ -1) is represented by each of the following general formulas (C1-1) to (C1-4) from the viewpoint of adhesion of the cured film to the substrate. One or more selected from the group consisting of the above compounds is more preferred.

{In Formula (C1-1), X ₁₉ and X ₂₀ are each independently a divalent organic group having 1 to 10 carbon atoms, and X ₂₁ and X ₂₂ are each independently 1 to 10 carbon atoms. A monovalent organic group, and s is an integer from 0 to 2;
In formula (C1-2), X ₂₅ and X ₂₇ are each independently a divalent organic group having 1 to 10 carbon atoms, X ₂₆ is a tetravalent organic group, and X ₂₃ , X ₂₄ , X ₂₈ and X ₂₉ are each independently a monovalent organic group having 1 to 10 carbon atoms, and s is an integer of 0 to 2;
In formula (C1-3), X ₃₀ is represented by —NH—R ₃₄ or —O—R ₃₅ (wherein R ₃₄ and R ₃₅ are each independently a monovalent organic group). A monovalent group, X ₃₁ is a divalent organic group having 1 to 10 carbon atoms, X ₃₂ and X ₃₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and s is an integer from 0 to 2;
Wherein _{(C1-4), X 36} is a divalent organic _{group, X 37} and _{X 38} are each independently a monovalent organic group, and s is an integer of 0-2. }

The alkoxysilyl group-containing silane compound represented by the general formula (C1-1) or (C1-2) is not limited, and has, for example, an acid anhydride or an acid dianhydride, and an amino group. It can be produced by reacting a silane compound in an organic solvent at 20 ° C. to 100 ° C. for 30 minutes to 10 hours.
Examples of the acid anhydride include maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic acid, and phthalic anhydride. Can be mentioned.

  Examples of the acid dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic Acid dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetra Carboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 , 6-tetracarboxylic dianhydride, , 8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8 -Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8- Tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyltetracarboxylic dianhydride,

3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3" -p-terphenyltetracarboxylic dianhydride, 2,3,3 ", 4 "-P-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane Anhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis ( 3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2 , 3-Dicarboki Phenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9 , 10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2, 7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, pyrazine-2,3 , 5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4 ′ -Hexafluoro Seo Pro pyridinium diphthalic dianhydride, and the like.

Examples of the silane compound having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylethyl. Dimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropyldiethyl Ethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyl Me Examples include tildimethoxysilane and 4-aminobutyldimethylmethoxysilane.
Among the alkoxysilyl group-containing silane compounds represented by the general formula (C1-1), compounds represented by the following structure are particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

  Among the alkoxysilyl group-containing silane compounds represented by the general formula (C1-2), a compound represented by the following structure is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

The alkoxysilyl group-containing silane compound represented by the general formula (C1-3) includes two types, a urea type and a urethane type. This compound can be generally obtained by a reaction between a silane compound having an amino group and an isocyanate compound or a carbonate derivative, or a reaction between an isocyanate group-containing silane compound and an amino compound or an alcohol.
When the alkoxysilyl group-containing silane compound represented by the general formula (C1-3) is synthesized by a reaction between an amino group-containing silane compound and an isocyanate compound or a carbonic acid ester derivative, Mention may be made of the aforementioned compounds.

Examples of the isocyanate compound include cyclohexyl isocyanate, n-hexyl isocyanate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 1-naphthyl isocyanate, n-octadecyl isocyanate, phenyl isocyanate, m-tolyl isocyanate, and p-tolyl isocyanate. , N-propyl isocyanate, isopropyl isocyanate, ethyl isocyanate, benzyl isocyanate and the like.
Examples of the carbonate ester derivatives include chlorocarbonate compounds such as ethyl chlorocarbonate, methyl chlorocarbonate, n-butyl chlorocarbonate, isobutyl chlorocarbonate, Z-chloride, 2-methoxyethyl chlorocarbonate; di-tbutyl dicarbonate, etc. Of carbonic acid ester dianhydride. Among these carbonic acid ester derivatives, di-t-butyl dicarbonate is preferable because it does not use chlorides and does not require an operation such as removal of chlorine ions after the reaction. When di-t-butyl dicarbonate is used, the resulting t-butoxycarbonyl group is completely eliminated by firing at about 200 ° C., and thus exhibits excellent adhesion even at lower temperatures. This is preferable.

When the alkoxysilyl group-containing silane compound represented by the general formula (C1-3) is synthesized by a reaction of an isocyanate group-containing silane compound with an amino compound or an alcohol, examples of the isocyanate group-containing silane compound include 3- Examples include triethoxysilylpropyl isocyanate, 3-trimethoxysilylpropyl isocyanate, 3-dimethoxymethylsilylpropyl isocyanate, and the amino compound includes, for example, aromatic or aliphatic monoamines;
As said alcohol, monohydric alcohol etc. are mentioned, for example.
Among the alkoxysilyl group-containing silane compounds represented by the general formula (C1-3), compounds represented by each of the following structural groups are particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

  Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (C1-4) include, for example, N- (3-triethoxysilylpropyl) urea (for example, Shin-Etsu Chemical Co., Ltd., trade name). LS3610, trade name SIU9055.0 manufactured by AMAX Co., Ltd.), N- (3-trimethoxysilylpropyl) urea (trade name SIU9058.0 manufactured by AMAX Co., Ltd.), 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-tripropoxysilylethyl) urea, N- (3 -Tripropoxysilylethyl) urea, 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.

In formula (C1), a _{group Y 4} is represented by _(Y 4 -2), one of _{Y 6} in the _(Y 4 -2) is of the general formula _(Y 6 -1) Examples of the compound represented by the formula include compounds represented by the following general formulas (C1-5) to (C1-7).

{In Formula (C1-5), X ₄₀ is a divalent organic group having 1 to 10 carbon atoms, and X ₃₉ , X _41, and X ₄₂ are each independently a monovalent organic group having 1 to 10 carbon atoms. A group, s is an integer from 0 to 2 and t is an integer from 0 to 5;
In formula (C1-6), X ₄₃ represents a hydrogen atom or a methyl group, X ₄₅ represents a divalent organic group, and X ₄₆ and X ₄₇ each independently represent a monovalent monovalent group having 1 to 10 carbon atoms. An organic group, s is an integer from 0 to 2 and u is an integer from 1 to 3;
Wherein _{(C1-7), X 49} is a divalent organic group having 1 to 10 carbon _{atoms, X 50} and _{X 51} are each independently a monovalent organic group having 1 to 10 carbon atoms, S is an integer of 0 to 2; and X _{44 in} formula (C1-6) and X ₄₈ in formula (C1-7) are each independently the following group of formulas:

And at least one divalent group selected from 12 types of groups represented by each of the above. }

  Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (C1-5) include N-phenyl-γ-aminopropyltrimethoxysilane (trade name KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.), N- Examples include phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyldimethoxymethylsilane, N-phenyl-γ-aminopropyldimethoxyethylsilane, and the like. Among these, N-phenyl-γ-aminopropyltrimethoxysilane is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

  Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (C1-6) include 3- (m-aminophenoxy) propyltrimethoxysilane (trade name SLA0598.0 manufactured by Amax Co., Ltd.), m -Aminophenyltrimethoxysilane (trade name SLA0599.0, manufactured by AMAX Co., Ltd.), p-aminophenyltrimethoxysilane (trade name SLA0599.1, manufactured by AMAX Co., Ltd.), aminophenyltrimethoxysilane (trade name SLA0599, manufactured by AMAX Co., Ltd.) .2) and the like. Among these, a compound represented by the following structure is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

  Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (C1-7) include 2- (trimethoxysilylethyl) pyridine (trade name SIT8396.0 manufactured by Amax Co., Ltd.), 2- (tri And ethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine and the like. Among these, a compound represented by the following structure is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

In the formula (C1), a group _{Y 4} is represented by the general formula _(Y 4 -2), and as the _{compound Y 6} in the general formula _(Y 4 -2) has a mercapto group, specifically For example, 3-mercaptopropyltrimethoxysilane (for example, trade name KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Silaace S810, manufactured by Chisso Corporation), 3-mercaptopropyltriethoxysilane (trade name, manufactured by Amax Corporation) SIM647475.0), 3-mercaptopropylmethyldimethoxysilane (for example, trade name LS1375, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SIM6474.0, etc.), mercaptomethyltrimethoxysilane (trade name: SIM6473, manufactured by AMAX Co., Ltd.) .5C), mercaptomethyltrimethoxysilane Run (trade name SIM6473.0, manufactured by Amax Max)

3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercapto Chill methoxy dipropoxy silane, 4-mercaptobutyl trimethoxysilane, 4-mercapto-butyl triethoxysilane, 4-mercapto-butyl tripropoxysilane, and the like.

In the formula (C1), a group _{Y 4} is represented by the general formula _(Y 4 -2), and as the _{compound Y 6} in the general formula _(Y 4 -2) has a glycidyl group, specifically For example, 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Silicone, trade name KBE403), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and the like;
Specific examples of the compound in which Y ₆ has a vinyl group include vinyltrimethoxysilane (trade name KBE1003 manufactured by Shin-Etsu Silicone), vinyltriethoxysilane, diethoxymethylvinylsilane, and the like;
Examples of the compound in which Y ₆ has an acryloyl group include 3-acryloxypropyltrimethoxysilane and the like;
Examples of the compound in which Y ₆ has a methacryloyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane ( Shin-Etsu Silicone brand name KBE503), 3- (methacryloxy) propyltri (2-methoxyethoxy) silane, etc.
Each is listed.

  Among the many silane compounds described above, from the viewpoint of suppressing occurrence of appearance defects such as wrinkles and blisters that may occur on the cured relief pattern when it is sputtered, the above general formula ( A silane compound represented by each of C1-1) to (C1-7) is preferable, and from the viewpoint of the elongation of the obtained cured film, the silane compound is represented by the above general formulas (C1-1) to (C1-4). More preferred are silane compounds.

The amount of the (C) silane compound used in the present invention is preferably in the range of 0.1 to 10 parts by mass, more preferably 0.5 to 100 parts by mass of the (A) resin. It is the range of 8 parts by mass or more. The (C) silane compounds listed above may be appropriately selected depending on the type of the substrate, and may be used alone or in combination of two or more.
By using the (C) silane compound in the above-described manner, a resin composition having excellent adhesion between the substrate and the developed resin can be obtained. As described above, the interaction between the (A) resin and the (B) amide compound suppresses the dissolution of the resin due to the solvation of the developer and suppresses the swelling of the relief pattern. It is estimated that the stress applied to the interface with the pattern is reduced. Here, the (C) silane compound undergoes a silane coupling reaction with the base material, and the (C) silane compound and the (B) amide compound interact with each other, so that it is applied to the interface between the resin and the base material during development. It is estimated that the stress is more relaxed.

<(D) Photosensitive agent>
Next, the (D) photosensitive agent that is optionally used in the resin composition of the present embodiment will be described.
As the photosensitive agent (D) in the present embodiment, a compound conventionally used as a photopolymerization initiator for UV curing can be arbitrarily selected. (D) Examples of compounds that can be suitably used as a photosensitizer include 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, one kind or a mixture of two or more kinds may be used. Among the above photopolymerization initiators, oximes are more preferable particularly from the viewpoint of photosensitivity.
(D) It is preferable that the compounding quantity of a photosensitive agent 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. (D) It is excellent in photosensitivity by mix | blending 1 mass part or more with respect to 100 mass parts of (A) resin, and it will be excellent in thick film curability by mix | blending 20 mass parts or less.

<(E) Other ingredients>
The resin composition in the present embodiment may further contain components other than the components (A) to (D). 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, (E) Other components can include solvents, for example, sensitizers, monomers having photopolymerizable unsaturated bonds, adhesion assistants, thermal polymerization inhibitors, crosslinking agents, azole compounds, hinders. A dophenol compound etc. can be mentioned.

Examples of the solvent include polar organic solvents and alcohols.
As a solvent in the resin composition of this embodiment, it is preferable to use a polar organic solvent among the (A) resins, 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, 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 an alcohol. The alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and having no olefinic double bond. Specific examples include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-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, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable, and particularly ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, And propylene glycol-1- (n-propyl) ether is more preferred.

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. 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 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 negative photosensitive resin composition is improved. When the content is 50% by mass or less, (A) the resin is dissolved. Good.
In addition, the (B) amide compound in the resin composition of this embodiment includes what is liquid at normal temperature. When the resin composition of this embodiment contains a liquid (B) amide compound, it may exist as a varnish-like composition without adding a solvent. In such a case, although the resin composition of this embodiment does not need to contain a solvent, you may add a solvent.

  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 ′ Dimethylamino benzal) acetone, 1,3-bis (4'-diethylamino benzal) acetone, 3,3'-carbonyl - bis (7-diethylamino coumarin),

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-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethyl) Tilaminostyryl) 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 the resin composition of this embodiment 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;
Acrylamide and its derivatives;
Methacrylamide and derivatives thereof;
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 order to improve the adhesion between the film formed using the resin composition of the present embodiment and the base material, an adhesion assistant can be arbitrarily blended. Examples of the adhesion assistant include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3 -Methacryloxypropyl dimethoxymethylsilane, 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-to Other 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 the resin (A).

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. . The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film.
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 of this 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, 4-t-butyl- 5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxy Phenyltriazole, 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) Rubenzyl) 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- Examples include methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole. 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 in a mixture of two or more.

  When the resin composition of 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, 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-hydroxy) Phenyl) propionate], 2,2-thio - diethylene bis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate],

N, N ′ hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 2, 2′-methylene-bis (4-ethyl-6-tert-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3 5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, , 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-phenyl Njiru) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) - trione,

1,3,5-tris (4-t-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-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-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like, but are not limited thereto. Absent. 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 producing cured relief pattern >>
The present invention also provides a method for producing a cured relief pattern.
To form a cured relief pattern in this embodiment,
(A) Use of a resin composition satisfying at least one of the case where the resin is a resin containing a polymerizable group in its side chain and the case where the resin composition contains a crosslinking agent preferable. 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 (D) a photosensitizer.

The manufacturing method of the effect relief pattern in the present embodiment includes, for example, the following steps:
(1) An application step of applying the above-described negative photosensitive resin composition on a substrate and forming a resin layer on the substrate;
(2) an exposure step of exposing the resin layer;
(3) a development step of developing the exposed resin layer to form a relief pattern;
(4) A heating process of forming a cured relief pattern by heat-treating the relief pattern is performed in the order described above. When the resin composition used functions as a negative photosensitive resin composition, the resin layer is a photosensitive resin layer.
Hereinafter, typical aspects of each of the above steps 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. As a drying method, methods such as air drying, heat drying using 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 polymer (A1), the said coating film is dried on the conditions that imidation of this polymer (A1) does not occur. It is desirable. 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. The exposure can be performed 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 range of the baking conditions is preferably a temperature of 40 to 120 ° C. and a time of 10 seconds to 240 seconds, but is not limited to this range as long as the various characteristics of the negative photosensitive resin composition in the present embodiment are not impaired. .

(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, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable and poor. As the solvent, 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 polymer 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. When (A) resin contained in the resin composition to be used consists of a polymer (A1), it can convert into the cured relief pattern which consists of a polyimide by imidating this resin in this process.
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. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.
The effect relief pattern can be manufactured as described above.
<< Semiconductor Device >>
The present invention also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention.
The semiconductor device described above can be a semiconductor device having, for example, a base material that is a semiconductor element and a cured relief pattern formed on the base material by the above-described cured relief pattern manufacturing method.

  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 of the present embodiment is a semiconductor having a cured relief pattern formed by the above-described cured relief pattern manufacturing method, for example, a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film, or a bump structure. It can be manufactured by forming it as a protective film of the device and combining it with a known method for manufacturing a semiconductor device.

  The negative photosensitive resin composition of this embodiment is used for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, liquid crystal alignment films, etc., in addition to application to semiconductor devices as described above. Is also useful.

  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) under the following conditions.
Column: Showa Denko Co., Ltd. Trade name Shodex 805M / 806M Series Standard monodisperse polystyrene: Showa Denko Co., Ltd. Shodex STANDARD SM-105
Developing solvent: N-methyl-2-pyrrolidone Detector: Showa Denko brand name Shodex RI-930

(2) Film thickness uniformity evaluation A negative photosensitive resin composition using a polyimide precursor as a photosensitive resin is spin-coated on a 6-inch silicon wafer, and then heated at 100 ° C. for 5 minutes to remove the solvent. Thus, a coating film having an average film thickness described in Table 1 was formed. Next, the film thickness (T1) of this coating film was measured at 39 points selected on the wafer according to the following criteria. Film thickness measurement was performed using a Nanospec 5100 optical film thickness measuring machine (manufactured by Nanometrics). The film thickness uniformity of the photosensitive resin composition was estimated from the following formula.
Film thickness uniformity [%] = (maximum film thickness after application 39 points−minimum film thickness after application 39 points) / average film thickness of 39 points Measurement point selection criteria: Wafer peripheral edge The measurement points were 39 points that were concentrically set at equal intervals from the entire remaining region except for the 10 mm region.

(3) Adhesive evaluation with substrate The negative photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and the solvent was removed to form a coating film. This coating film was exposed to 300 mJ / cm ² of energy by an i-line stepper NSR2005i8A (Nikon Corp.) through a reticle with a test pattern. Subsequently, the exposed coating film was spray-developed using cyclopentanone as a developer and using a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan). Next, the developed coating film was rinsed with propylene glycol methyl ether acetate, and the unexposed portion was developed and removed to obtain a relief pattern.
About the obtained pattern, the fine line pattern shape of 2-30 micrometers width | variety of an exposure part is observed under an optical microscope, and the thing of the size of the fine line pattern of the minimum width | variety without peeling is less than 16 micrometers, and adhesiveness is "good", and it is 16 micrometers or more Were evaluated as adhesion "bad".

<Production Example 1>
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 another 16 hours.

Next, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4′-diaminodiphenyl ether (DADPE). ) A suspension of 93.0 g in γ-butyrolactone 350 ml was added over 60 minutes with stirring. 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 was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain a powdery polymer (1).
When the molecular weight of this polymer (1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

<Production Example 2>
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. Reaction was performed in the same manner as described in 1 to obtain polymer (2).
When the molecular weight of this polymer (2) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Example 1>
Using the polymer (1) and polymer (2) obtained in the above-mentioned production examples, a photosensitive resin composition was prepared by the following method and evaluated. (A) 50 g of polymer (1) as resin and 50 g of polymer (2) were dissolved in 200 g of 3-methoxy-N, N-dimethylpropionamide as (B) amide compound to obtain a resin composition.
This resin composition had a film thickness uniformity of 4.5% when applied on a silicon wafer and dried according to the method described above.

<Example 2>
To the resin composition of Example 1, 6 g of (D) 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime as a photosensitizer was added to obtain a negative photosensitive resin composition. Prepared.
This resin composition had a film thickness uniformity of 4.3% when applied to a silicon wafer and dried according to the method described above. Further, after the resin composition was applied to a silicon wafer according to the above-mentioned method and dried, and exposed and developed, the exposed fine line was in close contact at 12 μm or more, and the adhesion was “good”.

<Example 3>
1 g of N- [3- (triethoxysilyl) propyl] phthalamic acid (C) as a silica compound was added to the resin composition of Example 2 to prepare a negative photosensitive resin composition.
This resin composition had a film thickness uniformity of 4.4% when applied to a silicon wafer and dried according to the method described above. Further, after the resin composition was applied to a silicon wafer according to the method described above, dried, exposed and developed, the exposed fine line was in close contact at 10 μm or more, and the adhesion was “good”.

<Example 4>
Example 3 is the same as Example 3 except that the amount of (B) 3-methoxy-N, N-dimethylpropionamide as the amide compound was changed to 1 g and 199 g of N-methyl-2-pyrrolidone was added as a solvent. In the same manner as described above, a negative photosensitive resin composition was prepared.
This resin composition had a film thickness uniformity of 7.1% when applied to a silicon wafer and dried according to the method described above. Further, after the resin composition was applied to a silicon wafer according to the method described above, dried, exposed and developed, the exposed fine line was in contact at 14 μm or more, and the adhesion was “good”.

<Example 5>
In Example 3, the amount of 3-methoxy-N, N-dimethylpropionamide (B) as the amide compound was changed to 10 g, and 190 g of N-methyl-2-pyrrolidone was added as a solvent. In the same manner as described above, a negative photosensitive resin composition was prepared.
This resin composition had a film thickness uniformity of 6.9% when applied to a silicon wafer and dried according to the method described above. Further, after the resin composition was applied to a silicon wafer according to the method described above, dried, exposed and developed, the exposed fine line was in contact at 14 μm or more, and the adhesion was “good”.

<Example 6>
In Example 3, Example 3 except that (B) the amount of 3-methoxy-N, N-dimethylpropionamide as an amide compound was changed to 100 g and 100 g of N-methyl-2-pyrrolidone was added as a solvent. In the same manner as described above, a negative photosensitive resin composition was prepared.
This resin composition had a film thickness uniformity of 6.3% when applied to a silicon wafer and dried according to the method described above. Further, after the resin composition was applied to a silicon wafer according to the above-mentioned method and dried, and exposed and developed, the exposed fine line was in close contact at 12 μm or more, and the adhesion was “good”.

<Example 7>
In Example 3, a negative photosensitive resin composition was obtained in the same manner as in Example 3 except that the amount of (B) 3-methoxy-N, N-dimethylpropionamide as the amide compound was changed to 1,000 g. Was prepared.
This resin composition had a film thickness uniformity of 3.8% when applied to a silicon wafer and dried according to the method described above.

<Example 8>
In Example 3, a negative photosensitive resin composition was obtained in the same manner as in Example 3 except that the amount of (B) 3-methoxy-N, N-dimethylpropionamide as the amide compound was changed to 10,000 g. Was prepared.
The composition had a film thickness uniformity of 2.1% when applied to a silicon wafer and dried according to the method described above.

<Example 9>
In Example 3, 100 g of 3-butoxy-N, N-dimethylpropionamide was used as the amide compound instead of 3-methoxy-N, N-dimethylpropionamide as the amide compound, and N-methyl-2-pyrrolidone was used as the solvent. A negative photosensitive resin composition was prepared in the same manner as in Example 3 except that 100 g was added.
This resin composition had a film thickness uniformity of 7.2% when applied to a silicon wafer and dried according to the method described above. Further, after the resin composition was applied to a silicon wafer according to the method described above, dried, exposed and developed, the exposed fine line was in contact at 14 μm or more, and the adhesion was “good”.

<Comparative Example 1>
(A) 50 g of the polymer (1) as a resin and 50 g of the polymer (2) were dissolved in 200 g of N-methyl-2-pyrrolidone to obtain a resin composition.
This resin composition had a film thickness uniformity of 8.2% when applied to a silicon wafer and dried according to the method described above.

<Comparative Example 2>
In the resin composition of Comparative Example 1, (D) 6 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime as a photosensitizer and (C) N- [ 3- (Triethoxysilyl) propyl] phthalamic acid (1 g was added to prepare a negative photosensitive resin composition.
This resin composition had a film thickness uniformity of 8.1% when applied to a silicon wafer and dried according to the method described above. Further, after the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed and developed, the exposed exposed fine line was 20 μm or more, and the adhesion was “poor”.

  The above results are summarized in the following table.

In the said table | surface, the upward arrow shows that the kind and quantity of a compounding component applicable to the said column are the same as the upper column.
Moreover, the abbreviation of each component has the following meaning, respectively.
A1: Polymer (1)
A2: Polymer (2)
B1: 3-methoxy-N, N-dimethylpropionamide B2: 3-butoxy-N, N-dimethylpropionamide C1: N- [3- (triethoxysilyl) propyl] phthalamic acid D1: 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) -oxime E1: 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 (11)

(A) Resin: 100 mass parts, (B) Amide compound represented by the following general formula (B1): 1-10,000 mass parts The resin composition characterized by the above-mentioned.

{Wherein R ₁ is a C 1-5 alkyl group;
R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group that may have an ether bond having 1 to 6 carbon atoms, provided that R ₂ and R ₃ are the same or different from each other. They may be bonded to each other to form a ring structure. }   The resin composition according to claim 1, wherein the (A) resin is a resin having a polymerizable group in a side chain. The resin composition according to claim 1, wherein the resin (A) is a polymer having a structure represented by the following general formula (A1).

{In general formula (A1), X ₁ is a tetravalent organic group;
Y ₁ is a divalent organic group;
R ₄ and R ₅ are each independently a hydrogen atom, a saturated aliphatic group having 1 to 4 carbon atoms, an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or 6 to 30 carbon atoms. An aromatic group or a monovalent organic group capable of radical polymerization; provided that
At least one of R ₄ and R ₅ is a monovalent organic group capable of radical polymerization. } In the formula (A1),
R ₄ and R ₅ are each independently
A hydrogen atom, the following general formula (R1):

{In General Formula (R1), R ₁₃ , R ₁₄ , and R ₁₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; q is an integer of 2 to 10. }, A monovalent organic group, 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, and R ₄ and R ₅ The total of the monovalent organic group represented by the above general formula (R1) for all, the aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, and the aromatic group having 6 to 30 carbon atoms The ratio is 80 mol% or more, and the ratio of the monovalent organic group represented by the general formula (R1) to all of R ₄ and R ₅ is 20 mol% to 80 mol%. The resin composition as described. In the formula (A1),
R ₄ and R ₅ are each independently a hydrogen atom, a monovalent organic group represented by the general formula (R1), or a saturated aliphatic group having 1 to 4 carbon atoms, provided that
The resin composition according to claim 3, wherein R ₄ and R ₅ are not simultaneously hydrogen atoms. The resin composition according to claim 1, wherein the (A) resin is a polymer having a structure represented by the following general formula (A2).

{In General Formula (A2), a and b are each independently an integer of 0 to 2 and do not simultaneously become 0;
c and d are each independently an integer of 0 to 4;
R ₁₆ is a (2 + a + c) -valent organic group having 2 to 60 carbon atoms;
R ₁₇ is a (2 + b + d) -valent organic group having 2 to 60 carbon atoms, consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom;
R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. } (C) The following general formula (C1):

{In Formula (C1), X ₄ and X ₅ are each independently a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2 and Y ₄ is 1 to ₃ carbon atoms. 20 monovalent organic groups. } The resin composition as described in any one of Claims 1-6 which further contains the silane compound represented by these.   The resin composition according to any one of claims 1 to 7, wherein the (B) amide compound is 3-methoxy-N, N-dimethylpropionamide.   (D) The resin composition according to any one of claims 1 to 8, further comprising a photosensitizer. The following steps:
(1) Applying the resin composition according to any one of claims 1 to 9 on a substrate, and forming a resin layer on the substrate;
(2) an exposure step of exposing the resin layer;
(3) a development step of developing the exposed resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, wherein a heating step of forming a cured relief pattern by heat-treating the relief pattern is passed in the order described above.   A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to claim 10.