JP2020097747A - Resin composition, manufacturing method of cured relief pattern, and semiconductor device - Google Patents

Abstract

To provide a resin composition providing a coated film excellent in film thickness uniformity in thick film formation and excellent in adhesiveness to a substrate after development.SOLUTION: The resin composition contains (A) 100 pts.mass of a resin having a structure represented by the general formula (A1) in the figure, (B) 1 to 1,000 pts.mass of one or more amide compounds selected from 3-alkoxy-N,N-dimethylpropionamides, and (D) a photoinitiator.SELECTED DRAWING: None

Description

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

BACKGROUND ART Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, and mechanical characteristics has been used for an insulating material for electronic parts, a passivation film for a semiconductor device, a surface protective film, an interlayer insulating film, 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 applying the precursor, exposing, developing, and thermally imidizing by curing. be able to. Such a photosensitive polyimide precursor has a feature that it can significantly reduce the process steps as compared with the conventional non-photosensitive polyimide.

In recent years, a mounting method on a printed wiring board has been changed from the viewpoint of improving the degree of integration and function of a semiconductor device and reducing the chip size. From the conventional mounting method using metal pins and lead-tin eutectic solder, structures such as BGA (ball gripped array) and CSP (chip size packaging) capable of higher density mounting have come to be used. There is. In these structures, the polyimide coating directly contacts the solder bumps. The film in such a bump structure is required to have high heat resistance and chemical resistance.
Then, the method of improving the heat resistance of a polyimide film or a polybenzoxazole film by adding a thermal crosslinking agent to the composition containing a polyimide precursor or a polybenzoxazole precursor is disclosed (see Patent Document 1). ).

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

JP, 2003-287889, A

The present invention seeks to solve the problems of the prior art described above. Therefore, 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. Another object of the present invention is to provide a method for producing a cured relief pattern using the resin composition, and a semiconductor device.

By including a compound having a specific structure in a resin composition for forming a film, the present inventors provide a film having excellent film thickness uniformity during thick film formation and excellent adhesion to a substrate. They have found that they can be obtained and have completed the present invention.
The present invention is as follows.

[1] A resin composition comprising (A) 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.

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

{In the 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 a carbon atom having 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
Hydrogen atom, the following general formula (R1):

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

[5] In the formula (A1),
R ₄ and R ₅ are each independently 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
The resin composition according to [3], wherein both R ₄ and R ₅ are not hydrogen atoms at the same time.
[6] The resin composition according to [1], wherein the resin (A) 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 become 0 at the same time;
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, which is composed 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 monovalent organic group hydrogen atom or 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 1 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], which further contains (D) a photosensitizer.

[10] The following steps:
(1) A coating step of coating the resin composition according to any one of [1] to [9] on a substrate to form a resin layer on the substrate,
(2) an exposure step of exposing the resin layer,
(3) a developing step of developing the resin layer after the exposure to form a relief pattern,
(4) A method for producing a cured relief pattern, characterized by passing through a heating step of forming a cured relief pattern by heating the relief pattern in the order described above.
[11] A semiconductor device having a cured relief pattern obtained by the manufacturing method according to [10].

According to the present invention, it is possible to obtain a resin composition which is excellent in film thickness uniformity when forming a thick film and which gives a film having excellent adhesion to a substrate after development. Further, a resin composition using the resin composition can be obtained. A method for manufacturing a cured relief pattern for forming a pattern and a semiconductor device are provided.

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

<< resin composition >>
The resin composition of the present invention contains (A) a resin and (B) an amide compound represented by the 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) silane compounds and (D) photosensitizers.

<(A) resin>
The resin (A) used in the present invention will be described.
The resin (A) of the present invention includes 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.
From the viewpoint of heat resistance and mechanical properties after heat treatment, the weight average molecular weight of these (A) resins is preferably 1,000 or more, and more preferably 5,000 or more, as a polystyrene conversion value by gel permeation chromatography. 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 used as a photosensitive resin composition, the weight average molecular weight of the resin (A) is more preferably 50,000 or less from the viewpoint of solubility in a developing solution.

In this embodiment, the resin (A) is preferably an alkali-soluble resin. A photosensitive resin is desirable for forming the relief pattern. The photosensitive resin can be used as the photosensitive resin composition of the resin composition of the present embodiment by using this together with the (D) photosensitizer described below. Depending on whether the resin composition is exposed or unexposed in the exposure step, It is a resin that causes dissolved or undissolved development in the subsequent development step. The photosensitive resin is preferably a resin having a polymerizable group in its side chain. Such a photosensitive resin can be appropriately selected according to the desired properties 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 species selected from the above resin group. Among these, at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polybenzoxazole precursor, and polyimide is more preferable because the resin after heat treatment has excellent heat resistance and mechanical properties. Used.
From the viewpoint of heat resistance and photosensitivity, a particularly preferable resin (A) is represented by the general formula (A1):

{In the 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 a carbon atom having 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 having a structure represented by the following (polymer (A1)), the following general formula (A2):

{In general formula (A2), a and b are each independently an integer of 0 to 2 and do not become 0 at the same time;
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, which is composed 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 monovalent organic group hydrogen atom or a C 1-20. } It is preferable that at least one resin selected from the group consisting of a polymer having a structure represented by the following (polymer (A2)) and a polyhydroxyamide (polymer (A3)) is contained. The proportion of these resins used 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 the resin (A).

[Polymer (A1)]
Examples of the radically polymerizable monovalent organic group represented by R ₄ and R ₅ in the general formula (A1) include the following general formula (R1):

{In the 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; and 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 preferably each independently a hydrogen atom or a methyl group, and are preferably hydrogen atoms from the viewpoint of photosensitivity. R ₁₃ is preferably a hydrogen atom or a methyl group. Further, q is preferably an integer of 2 or more and 10 or less, and more preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitivity.

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 photosensitivity. ,
One of the —COOR ₄ group and the —CONH— group is bound to the same aromatic ring, both are in the ortho position to each other, and the other —COOR ₅ group and the —CONH— group are the same aromatic ring. They are bonded to each other and are tetravalent aromatic groups in which they are in the ortho position with each other, or tetravalent alicyclic aliphatic groups. In the former case, an aromatic ring to which a —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:

And the structure represented by each of, but is not limited to. The structure of X ₁ may be one kind or a combination of two or more kinds. The X ₁ group having these structures is preferable in terms of achieving both heat resistance and photosensitivity.
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 photosensitivity. The 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 the structure is not limited thereto. The structure of Y ₁ may be one kind or a combination of two or more kinds. The Y ₁ group having the structure represented by the above formula is preferable in terms of achieving both heat resistance and photosensitivity.

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 methyl group, ethyl group, propyl group and butyl group;
Secondary hydrocarbon groups such as isobutyl group and isopentyl group;
Examples thereof include tertiary hydrocarbon groups such as t-butyl group. 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, butoxymethyl group, butyl sulfide methylene group, butyl amino methylene group, and the like; oxygen atom as a hetero atom And aliphatic groups containing a nitrogen atom, a sulfur atom, or a phosphorus atom. Examples of the aromatic group having 6 to 30 carbon atoms for R ₄ and R ₅ include a phenyl group, a benzyl group and a naphthyl group.

As R ₄ and R ₅ in the above general formula (A1), each independently,
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 general formula (R1) for all 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 ratio of the total of 30 aromatic groups is 80 mol% or more, and the ratio of the monovalent organic group represented by the general formula (R1) to all 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 (A) suitably functions as a polyimide precursor which is cyclized and converted into a polyimide by being subjected to heat treatment at 200° C. or higher.

When the polymer (A1) is used as the resin (A), ester bond type and ionic bond type may be mentioned as a method for imparting a radically polymerizable monovalent organic group to the polymer (A1). The former is a method of introducing a monovalent organic group capable of radical polymerization by an ester bond into a side chain of a polyimide precursor. The latter is a polyimide precursor obtained by reacting a polymer having a carboxyl group with 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. This is a method of introducing a monovalent organic group capable of radical polymerization into the side chain of the body. Of these, the ester bond type is preferred.

[Preparation Method of Ester Bonded Polymer (A1)]
The above ester bond-type polymer (A1) is prepared, for example, by first preparing a tetracarboxylic dianhydride having a desired tetravalent organic group X ₁ and an alcohol having a radical polymerizable group (for example, an unsaturated double bond). A partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester form) is prepared by reacting the same with a diamine, and the diamine having a divalent organic group Y ₁ is subjected to amide polycondensation. It is obtained by Saturated aliphatic alcohols may be optionally used in combination with the alcohols having the radically polymerizable group (for example, unsaturated double bond).

(Preparation of acid/ester form)
In the present embodiment, examples of the tetracarboxylic acid dianhydride having a tetravalent organic group X ₁ that is preferably used for preparing the ester bond-type polymer (A1) include, for example, pyromellitic dianhydride, diphenyl ether- 3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, biphenyl-3,3′,4,4′-tetracarboxylic Acid dianhydride, diphenyl sulfone-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 can be mentioned. It is not limited. In addition, these may be used alone or in a mixture of two or more kinds.

Examples of alcohols having a radically polymerizable group, which are preferably used for preparing the ester bond-type 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- Examples thereof include 3-t-butoxypropyl methacrylate and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

Saturated aliphatic alcohols having 1 to 4 carbon atoms are preferable as the saturated aliphatic alcohols that can be optionally used together with the alcohols having a 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 used is preferably 80 mol% or less, more preferably 50 mol% or less, based on the total amount of the alcohols having a radical polymerizable group and the saturated aliphatic alcohols. preferable.
The amount of the alcohols used is preferably 10 to 500 mol%, and preferably 100 to 300 mol%, as the total amount of the alcohols used with respect to 1 mol of the tetracarboxylic dianhydride having a tetravalent organic group X _1. Is more preferable.

The above-mentioned suitable tetracarboxylic dianhydride and alcohol are mixed with stirring, preferably in the presence of a basic catalyst such as pyridine, in a suitable reaction solvent at a temperature of 20 to 50° C. for 4 to 10 hours. As a result, the esterification reaction of the acid anhydride proceeds, and the desired acid/ester product 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 form and a diamine, is also a solvent that dissolves in the quinz root. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbonization Examples thereof include hydrogens. Specific examples of these are:
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate and the like;
Examples of lactones include γ-butyrolactone and the like;
As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like;
Examples of the 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, etc.
Each can be named. These may be used alone or as a mixture of two or more, if necessary.

(Preparation of polymer (A1))
The acid/ester form (typically in a solution state dissolved in the reaction solvent) is mixed with a suitable dehydration condensing agent, preferably under ice cooling, to mix the acid/ester form with a polyanhydride. It is a thing. Next, a solution obtained by separately dissolving or dispersing a diamine having a divalent organic group Y ₁ suitably used in this embodiment in a solvent is dropped into the solution, and both are subjected to amide polycondensation to obtain the target polymer. (A1) can be obtained. Diaminosiloxanes may be used in combination with the diamines having the divalent organic group Y ₁ .
Examples of the dehydration 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 and the like. The amount of the dehydration condensing agent used is preferably 0.1 to 10 mol, and more preferably 1 to 5 mol, per 1 mol of the acid/ester form.
The reaction between the acid/ester and the dehydration condensing agent is carried out, for example, at −50 to 50° C., preferably −20 to 30° C., for example, 1 minute to 24 hours, preferably 5 minutes to 18 hours.
As described above, the polyanhydride as an intermediate is obtained.

In the present embodiment, examples of diamines containing a divalent organic group Y ₁ that are suitably used for the reaction with polyanhydride include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diamino Benzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 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, 9,9-bis(4-aminophenyl)fluorene, etc.;

And those in which some of the hydrogen atoms on the benzene ring 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 substitution product include, for example, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4. '-Diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc. And a mixture thereof and the like. The diamines are not limited to the above examples.

The diaminosiloxane contains the above divalent organic group Y ₁ in the preparation of 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 and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane. .. The amount of these diaminosiloxanes used is preferably 80 mol% or less, more preferably 50 mol% or less, based on the total amount of the diamines containing the divalent organic group Y ₁ and the diaminosiloxanes. ..

The amount of the diamines used is preferably 50 to 200 mol%, and 80 to 160 mol, as the total amount of the diamines used per 1 mol of the polyacid anhydride converted into the acid/ester form of the raw material. % Is more preferable.
The amide polycondensation reaction of polyanhydride and diamine is carried out, for example, at -50 to 100°C, preferably at -20 to 80°C, for example, for 1 minute to 48 hours, preferably for 5 minutes to 24 hours.

After completion of the amide polycondensation reaction, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent suitable for the solution containing the polymer component (for example, water or fat). Group lower alcohol, a mixed solution thereof, etc.) to deposit a polymer component, and further, if necessary, operations such as re-dissolution and re-precipitation are repeated to purify the polymer, and then vacuum drying is performed. The desired polymer (A1) is isolated. In order to improve the degree of purification, a solution of this polymer may be passed through a column packed by swelling an anion and/or cation exchange resin 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, and 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, mechanical properties are good, when it is 100,000 or less, dispersibility in a developing solution is good, and resolution performance of a relief pattern is good. Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as a developing solvent for gel permeation chromatography. The molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is recommended to be selected from STANDARD SM-105 organic solvent-based standard sample manufactured by Showa Denko KK.

[Polymer (A2)]
The polymer (A2), which is one of the resins (A) in the present embodiment, is a polymer having a structure represented by the above general formula (A2) and can be a polymer having an oxazole ring by heating or a suitable catalyst. It is a thing. When the polymer (A2) is 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, the range is preferably 1 to 1,000, and 3 to 50. The range is more preferable, and the range of 3 to 30 is the 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 kinds of structural units are present in the polymer (A2), the arrangement of the structural units may be block or random.

The polymer (A2) is, for example, a dicarboxylic acid having a structure of R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ ;
It can be obtained by polycondensation with a diamine having an R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure. R _{16 to} R ₂₁ and d to g in these formulas each have the same meaning as in the above 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, and examples of the diamine include, for example, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl and 4,4′-diamino. -3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 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-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 Others such as'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene:
_{R 17 (NH 2) 2 (} OR 19) e (COOR 21) R 17 in _g the following formula groups:

A bisaminophenol compound which is a tetravalent organic group selected from (wherein R19, R21, e and g in the above formula have the same meanings as in the above general formula (A2)) and the like. Can be mentioned.
Among these bisaminophenol compounds, those particularly preferable from the viewpoint 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.
In bis(aminophenol) (for example, R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g in which R ₁₇ is selected from the above formula group), a bond connecting benzene rings to each other. On the other hand, when the meta position is an amino group and the para position is a hydroxyl group, or when the meta position is a hydroxyl group and the para position is an amino group, it does not matter, but solubility in a solvent From the viewpoint of, it is preferable that the meta position is an amino group and the para position is a hydroxyl group.
Further, as a diamine having an R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure, the following structure:

{In the formula, X ₅₂ is a tetravalent organic group having 2 to 60 carbon atoms. } The diamine represented by these 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 developing solution and heat resistance. It is preferable that the structure is different. When X ₅₂ is an aromatic group, it is preferable that the amide bond and the phenolic hydroxyl group bonded to the same aromatic ring be in the ortho position. 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 the above. Examples of the method for producing these diamines include a method of reacting the above-mentioned bisaminophenol with two molecules of nitrobenzoic acid, and subsequently reducing the nitro group to an amino group.
Furthermore, as a diamine having an R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure, the following structure:

{In the formula, Y ₇ is a divalent organic group having 2 to 60 carbon atoms. } It is also possible to use the diamine represented by these. 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 developing solution and heat resistance, it will be described later as an example of the organic group represented by R _16. It is preferably at least one organic group listed in.
Specific preferred examples of such compounds include the following structural groups:

The diamine represented by each of the above. 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 an R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure, a compound having two sets of polyimide precursor structures in the molecule (hereinafter, referred to as “PI precursor in the molecule”). It is also possible to use "a bisaminophenol having a structure"). Examples of such compounds include the structures:

{In the formula, 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. } You may use the diamine represented by these. More specific examples of such compounds include, for example, the following structural groups:

{In the formula, R ₂₂ is hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms. } The diamine represented by each of these is mentioned.
Examples of the method for producing bisaminophenol having a PI precursor structure in the molecule include, for example,
A tetracarboxylic dianhydride, a monocarboxylic acid, a dicarboxylic acid opened by the action of a monoamine, and the like,
An example is a method in which two molecules of an aniline derivative having a hydroxyl group and a nitro group at the ortho positions are condensed with each other and then the nitro group is reduced.

Next, as the diamine having the R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure as a raw material, 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 alkaline developer. Examples of these diamines include aromatic diamines. Aromatic diamines are advantageous from the viewpoint of heat resistance.

Examples of the aromatic diamines include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diamino. Diphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 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-aminophenyl)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-aminobenzyl)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)diphenyl sulfone, 4,4′-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]benzophenone, 4,4′-bis[4-(α,α-dimethyl-4-aminobenzyl) )Phenoxy]diphenyl sulfone, 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 and the like;
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.

_{Then, R 16 (OR 18) d} (COOR 20) f (COOH) for the dicarboxylic acid having the _second structure 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, and so on.
Such a dicarboxylic acid can be advantageously used when adjusting the solubility in an alkali developing solution.
Examples of R ₁₆ in the case of d=f=0 include structures represented by any of the following structure groups.

{In the formula, 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. Is a divalent group
K pieces of L ₁ which is bound to a ring carbon are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an amide group, a urea group, an imido group and a group selected from the group consisting of urethane groups, And k=4. _{}, - (CH 2) n10} - (. Wherein, n ₁₀ is an integer from 1 to 12), and

{In the formula, L ₂ , L ₃ and L ₄ are each independently a hydrogen atom or a methyl group. }.
Among the above, as a typical compound as a dicarboxylic acid having a tricyclodecane skeleton, bis(carboxy)tricyclo[5.2.1.0 ^2,6 ]decane and the like can be mentioned. As a method for producing this compound, for example, the synthesis examples described in International Publication No. 2009/081950 can be exemplified.
As the dicarboxylic acid in the case of d=0 and f=2 in R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , for example, tetracarboxylic dianhydride is 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, benzyl alcohol and the like. Examples of monoamines include butylamine and aniline.
Examples of the tetracarboxylic acid dianhydride include compounds represented by the following chemical formula groups.

{Wherein, B is _{-CH 2 -, - O -,} - S -, - SO 2 -, - CO -, - NHCO -, - C (CF 3) 2 - selected from the group consisting of -COO- Is a divalent group. }
The dicarboxylic acid in the case where d=0 and f=2 in R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ is obtained by another method including tetracarboxylic dianhydride and bisaminophenol or diamine. The carboxylic acid residue produced by the reaction can also be synthesized by a method of esterifying or amidating with a monoalcohol or a monoamine.
In R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , in the dicarboxylic acid where d=1 or 2 and f=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 the ortho positions in the molecule can be mentioned. Examples of such a dicarboxylic acid include compounds represented by the following formula.

{In the formula, X ₅₃ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ₂₃ are each 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, a bis(aminophenol) having a structure of R ₁₇ (NH ₂ ) ₂ (OH) _{2 or} a structure of R ₁₇ (NH ₂ ) ₂ (OH) is used. An example is a method in which the diaminophenol contained therein is reacted with two molecules of trimellitic acid chloride and then the acid anhydride and 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 thereof, for example, a dicarboxylic acid and thionyl chloride are used to obtain a diacid chloride, and then bisaminophenol (diamine) is allowed to act on the diacid chloride, or a dicarboxylic acid and bisamino acid. Examples thereof include a method of polycondensing phenol (diamine) with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be simultaneously acted on.

The resin (A) in this embodiment is a polyamic acid (polyamic acid), polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polyoxazole, polyoxazole precursor, polybenzoxazole, polybenzimidazole. , Polybenzthiazole, a phenol resin, an epoxy resin, a siloxane resin, and one or more resins selected from the group consisting of acrylic resin, it is preferable to contain 60% by mass or more, relative to the total of (A) resin, It is more preferable to contain 80 mass% or more. More preferably, it contains at least 60% by mass, more preferably at least 80% by mass, of at least one resin selected from the group consisting of the above polymers (A1) and (A2).

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

{In the formula, R ₁ is an alkyl group having 1 to 5 carbon atoms,
R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms and optionally having an ether bond, provided that R ₂ and R ₃ may be the same as each other. They may be different and may be bonded to each other to form a ring structure. } It is a compound represented by.
The resin composition of the present embodiment is a resin composition capable of forming a thick film relief pattern having excellent film thickness uniformity and excellent adhesion to a substrate by using such an (B) amide compound. be able to.
At the time of forming the relief pattern, Benard convection easily occurs in the heating step (about 100° C.) for removing the solvent. In that case, traces of convection remain after the solvent is sufficiently removed, so that 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 become even worse.

Generally, the ease of forming a Benard cell can be expressed by the Marangoni number. It is known that as the film thickness increases, the Marangoni number increases and convection easily occurs. Also, the higher the viscosity, the smaller the Marangoni number and the less likely convection will occur.
In the heating step for removing the solvent when forming the relief pattern, the heating temperature is 140° C. or less in order to suppress the reaction of the added photosensitizer or to prevent the reaction between the base material made of copper and the resin. Is desirable. The boiling point of N-methyl-2-pyrrolidone or the like used as the main solvent of the polyimide precursor or the like is higher than the heating temperature at the time of removing the solvent, and the solvent is likely to remain in the coating film. Therefore, the viscosity at the time of film curing becomes low, and Benard convection tends to occur easily. Then, since the exposure and development steps are carried out with the solvent remaining in the coating film, the resin is likely to be dissolved in the developing solution during development, and thus the relief pattern to be formed tends to be easily peeled off from the end surface. ..

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

Specific examples of the (B) amide compound include, for example, 3-methoxy-propionamide, 3-ethoxy-propionamide, 3-propoxy-propionamide, 3-butoxy-propionamide, 3-(2-methylpropoxy)-propion. Amido, 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-butoxy-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)propanone, 3-butoxy-1-(1-pyrrolidinyl)propanone, 3-butoxy-1-(1-piperidinyl)propanone, 3-butoxy- Examples thereof include 1-(4-morpholinyl)propanone, but are not limited thereto. Further, in using these, one kind or a mixture of two or more kinds may be used.

Among the above-mentioned amides, one or more selected from 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide from the viewpoint of adhesion after development of a relief pattern. Is preferred.
The compounding amount of the amide compound (B) is 1 to 10,000 parts by mass, and preferably 100 to 1,000 parts by mass, relative to 100 parts by mass of the resin (A).

<(C) Silane compound>
In this embodiment, the (C) silane compound optionally used will be described.
The silane compound (C) 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 1 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 the 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:
Wherein _(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, a vinyl Group, a monovalent organic group having at least one substituent selected from the group consisting of an acryloyl group and a methacryloyl group. }
In the case where the cured relief pattern is sputtered, in the general formula (C1), from the viewpoint of suppressing the occurrence of appearance defects such as wrinkles and swelling that may occur on the pattern, and the elongation of the cured film. , Y ₅ is preferably at least one selected from the 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. }
From the viewpoint of suppressing the occurrence of appearance defects such as wrinkles and swelling that may occur on the cured relief pattern when sputtered, Y ₆ in the general formula (C1) is represented by the following general formula (C1) It is preferably at least one selected from the three groups represented by each of the Y ₆ -1) groups.

{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. 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's are the same. Or may be different, and X ₁₇ and X ₁₈ are each independently a divalent group having 1 to 10 carbon atoms. }
Table above as the _{Y 4} is a compound represented by the general formula _(Y 4 -1), from the viewpoint of the adhesion to the substrate of the cured film, each of the following general formula (C1-1) ~ (C1-4) More preferably, one or more selected from the group consisting of

{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. Is a monovalent organic group, and s is an integer of 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;
In formula (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 to 2. }

The alkoxysilyl group-containing silane compound represented by the general formula (C1-1) or (C1-2) is not limited, but 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, 4,8-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-tetra Chloronaphthalene-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-terphenyl tetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride 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-Dicarboxyphenyl)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′-hexafluoroisopropylidene diphthalic acid dianhydride and the like.

Examples of the silane compound having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, 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 Examples thereof include methyldimethoxysilane and 4-aminobutyldimethylmethoxysilane.
Among the alkoxysilyl group-containing silane compounds represented by the general formula (C1-1), the compounds represented by the following structures are particularly preferable from the viewpoint of the adhesion of the cured film to the substrate.

Among the alkoxysilyl group-containing silane compounds represented by the general formula (C1-2), the compounds represented by the following structures are 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 of a silane compound having an amino group with an isocyanate compound or a carbonate derivative, or a reaction of a silane compound containing an isocyanate group with an amino compound or an alcohol.
When the alkoxysilyl group-containing silane compound represented by the general formula (C1-3) is synthesized by reacting a silane compound having an amino group with an isocyanate compound or a carbonate derivative, the silane compound having an amino group is: The compounds mentioned above may be mentioned.

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, p-tolyl isocyanate. , N-propyl isocyanate, isopropyl isocyanate, ethyl isocyanate, benzyl isocyanate and the like.
Examples of the carbonic acid ester derivative include ethyl chlorocarbonate, methyl chlorocarbonate, n-butyl chlorocarbonate, isobutyl chlorocarbonate, Z-chloride, 2-methoxyethyl chlorocarbonate and the like; di-tbutyl dicarbonate and the like. Carbonic acid dianhydride of. Among these carbonic acid ester derivatives, di-t-butyl dicarbonate is preferable because it does not use a chloride and does not require an operation such as removing a chlorine ion after the reaction. When di-t-butyl dicarbonate is used, the obtained t-butoxycarbonyl group is completely desorbed by baking at about 200° C., and therefore exhibits excellent adhesiveness even at lower temperatures. Therefore, it is preferable.

When the alkoxysilyl group-containing silane compound represented by the general formula (C1-3) is synthesized by reacting an isocyanate group-containing silane compound with an amino compound or an alcohol, the isocyanate group-containing silane compound is, for example, 3- Examples thereof include triethoxysilylpropyl isocyanate, 3-trimethoxysilylpropyl isocyanate, 3-dimethoxymethylsilylpropyl isocyanate, and the amino compounds include, for example, aromatic or aliphatic monoamines and the like;
Examples of the alcohol include monohydric alcohol and the like.
Among the alkoxysilyl group-containing silane compounds represented by the general formula (C1-3), the compounds represented by the following structural groups are particularly preferable from the viewpoint of the 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, trade name manufactured by Shin-Etsu Chemical Co., Ltd.). LS3610, trade name SIU9055.0 manufactured by Azumax Co., Ltd., N-(3-trimethoxysilylpropyl) urea (trade name SIU9058.0 manufactured by Azumax 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 are the 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 is a hydrogen atom or a methyl group, X ₄₅ is a divalent organic group, and X ₄₆ and X ₄₇ are each independently a 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;
In formula (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, And s is an integer of 0 to 2; and X _{44 in the} formula (C1-6) and X ₄₈ in the formula (C1-7) are each independently the following formula group:

Is at least one divalent group selected from 12 types of groups represented by }

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 thereof include phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyldimethoxymethylsilane and N-phenyl-γ-aminopropyldimethoxyethylsilane. Among these, N-phenyl-γ-aminopropyltrimethoxysilane is particularly preferable from the viewpoint of the adhesiveness 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 (manufactured by Azumax Co., Ltd., trade name SLA0598.0), m. -Aminophenyltrimethoxysilane (trade name SLA0599.0 manufactured by Azumax Co., Ltd.), p-aminophenyltrimethoxysilane (trade name SLA0599.1 manufactured by Azumax Co., Ltd.), aminophenyltrimethoxysilane (trade name SLA0599 manufactured by Azumax Co., Ltd. . 2) and the like. Among these, the compounds represented by the following structures are particularly preferable from the viewpoint of the adhesiveness 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 (manufactured by Azumax Co., Ltd., trade name SIT8396.0), 2-(tri). Examples thereof include ethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, and 2-(diethoxysilylmethylethyl)pyridine. Among these, the compounds represented by the following structures are particularly preferable from the viewpoint of the adhesiveness 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 Include, for example, 3-mercaptopropyltrimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd., trade name KBM803, Chisso Corporation, trade name Sila Ace S810, etc.), 3-mercaptopropyltriethoxysilane (Azumax Co., Ltd. trade name. SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (for example, Shin-Etsu Chemical Co., Ltd. trade name LS1375, Azumax Co., Ltd. trade name SIM6474.0, etc.), mercaptomethyltrimethoxysilane (Azumax Co., Ltd. trade name SIM6473). .5C), mercaptomethyltrimethoxysilane (trade name SIM6473.0 manufactured by Azumax Co., Ltd.),

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-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane. Etc.

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 Include, 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 Co., Ltd.), vinyltriethoxysilane, and diethoxymethylvinylsilane;
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 Co., Ltd. product name KBE503), 3-(methacryloxy)propyltri(2-methoxyethoxy)silane, etc.
Each is listed.

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

The amount of the (C) silane compound used in the present invention is preferably in the range of 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass with respect to 100 parts by mass of the (A) resin. The range is from 8 parts by mass to 8 parts by mass. The (C) silane compound listed above may be appropriately selected depending on the type of the substrate, and one type may be used alone or two or more types may be used in combination.
By using the (C) silane compound in the above aspect, a resin composition having excellent adhesion between the substrate and the resin after development can be obtained. As described above, the interaction between the resin (A) and the amide compound (B) suppresses the dissolution of the resin due to the solvation of the developing solution, 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 silane compound (C) undergoes a silane coupling reaction with the base material, and the silane compound (C) interacts with the amide compound (B), so that the silane compound is applied to the interface between the resin and the base material during development. It is presumed that the stress will be more relaxed.

<(D) Photosensitizer>
Next, the (D) photosensitizer optionally used in the resin composition of the present embodiment will be described.
As the (D) photosensitizer in the present embodiment, a compound conventionally used as a photopolymerization initiator for UV curing can be arbitrarily selected. Examples of the compound (D) which can be suitably used as the photosensitizer include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, benzophenone derivatives such as fluorenone;
Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone;
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone;
Benzyl derivatives such as benzyl, benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal;
Benzoin, benzoin derivatives such as benzoin methyl ether;

1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propane Dione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, Oximes such as 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime;
N-arylglycines such as N-phenylglycine;
Peroxides such as benzoyl perchloride;
Aromatic biimidazoles and the like are preferable, but 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 in view of photosensitivity.
The compounding amount of the (D) photosensitizer is preferably 0.1 to 20 parts by mass, and more preferably 2 to 15 parts by mass, based on 100 parts by mass of the resin (A). When 1 part by mass or more of the photosensitizer (D) is mixed with 100 parts by mass of the resin (A), photosensitivity is excellent, and when it is 20 parts by mass or less, thick film curability is excellent.

<(E) Other ingredients>
The resin composition in the present embodiment may further contain components other than the above components (A) to (D). The resin composition in the present embodiment is typically used as a varnish-shaped resin composition by dissolving the above-mentioned components and optional components that are further used as necessary in a suitable solvent. Therefore, as the other component (E), a solvent can be mentioned, and for example, a sensitizer, a monomer having a photopolymerizable unsaturated bond, an adhesion aid, a thermal polymerization inhibitor, a crosslinking agent, an azole compound, a hinder. Examples thereof include dephenol compounds.

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

From the viewpoint of improving the storage stability of the resin composition, the solvent preferably contains alcohols. Alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and not having an olefinic double bond. Specific examples include, for example, alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol;
Lactic acid 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 thereof 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 are 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, relative to 100 parts by mass of the resin (A), depending on the desired coating film thickness and viscosity of the resin composition. It can be used in the range of. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, and It is preferably 10 to 30% by 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 good, and when it is 50% by mass or less, the resin (A) is dissolved. Good quality.
The amide compound (B) in the resin composition of the present embodiment includes those that are liquid at room temperature. When the resin composition of the present embodiment contains a liquid (B) amide compound, it may be able to exist as a varnish composition without adding a solvent. In such a case, the resin composition of this embodiment need not contain a solvent, but a solvent may be added.

The resin composition of the present embodiment may optionally contain a sensitizer in order to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis(diethylamino)benzophenone, 2,5-bis(4′-diethylaminobenzal)cyclopentane, 2,6-bis(4′-diethylaminobenzal. ) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin),

3-Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylamino) Examples thereof include styryl)naphtho(1,2-d)thiazole and 2-(p-dimethylaminobenzoyl)styrene. These can be used alone or in combination of, for example, 2 to 5 types.
When the resin composition of the present embodiment contains a sensitizer, the compounding amount thereof is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the resin (A).

Further, in order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be optionally blended. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to the following, and examples thereof include diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. , Ethylene glycol or polyethylene glycol mono- or di(meth)acrylates;
Propylene glycol or polypropylene glycol mono or di(meth)acrylates;
Glycerol mono-, di-, or tri(meth)acrylates;
Cyclohexane di(meth)acrylate;
Di(meth)acrylate of 1,4-butanediol;
Di(meth)acrylate of 1,6-hexanediol;
Neopentyl glycol di(meth)acrylate;
Bisphenol A mono- or di(meth)acrylate;

Benzene trimethacrylate;
Isobornyl (meth)acrylate;
Acrylamide and its derivatives;
Methacrylamide and its derivatives;
Trimethylolpropane tri(meth)acrylate;
Di- or tri(meth)acrylate of glycerol;
Pentaerythritol di-, tri- or tetra(meth)acrylate;
In addition, compounds such as ethylene oxide or propylene oxide adducts of these compounds can be mentioned.

When the resin composition of the present embodiment contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the compounding amount is relative to 100 parts by mass of the resin (A). , 1 to 50 parts by mass is preferable.

In order to improve the adhesiveness between the film formed by using the resin composition of the present embodiment and the substrate, an adhesion aid can be optionally blended. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and 3 -Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl) Succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1 , 4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic hydride, silane cup such as N-phenylaminopropyltrimethoxysilane Other than ring agents;
Aluminum-based adhesion aids such as aluminum tris(ethyl acetoacetate), aluminum tris(acetyl acetonate), and ethyl acetoacetate aluminum diisopropylate can be used.

Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the resin composition in the present embodiment contains an adhesion aid, the compounding amount 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 order to improve the stability of viscosity and photosensitivity of the resin composition, when the resin composition of the present embodiment is stored in a solution containing a solvent, a thermal polymerization inhibitor is optionally added. 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.
The blending amount of the thermal polymerization inhibitor when blended in the resin composition of the present embodiment is preferably in the range of 0.005 to 12 parts by mass with respect to 100 parts by mass of the resin (A).

A cross-linking agent can be optionally added to the resin composition of this embodiment.
The cross-linking agent has a function of cross-linking the resin (A) when the relief pattern formed by using the resin composition of the present embodiment is heat-cured, or the cross-linking agent itself can form a cross-linked network. .. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film.
As such a cross-linking agent, amino resins and their derivatives are preferably used, and among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and their derivatives are preferably used. Particularly preferred are alkoxymethylated urea compounds and alkoxymethylated melamine compounds. Specific examples thereof include MX-290 (manufactured by Nippon Carbide Co.), UFR-65 (manufactured by Nippon Cytec Co., Ltd.), and MW-390 (manufactured by Nippon Carbide Co.).
In consideration of various performances other than heat resistance and chemical resistance, when the resin composition of the present embodiment contains a crosslinking agent, the compounding amount is 0.5 to 20 parts by mass with respect to 100 parts by mass of the resin (A). It is preferably about 10 parts by weight, more preferably about 2 to 10 parts by weight. When the amount is 0.5 part by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 20 parts by mass or less, the storage stability is excellent.

When the substrate to which the resin composition of the present embodiment is applied is, for example, a substrate made of copper or a copper alloy, an azole compound can be optionally added in order to suppress discoloration of the copper surface. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole and 4-t-butyl-. 5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, 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-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl- 2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,

Hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- Methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like can be mentioned. 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 the present embodiment contains the azole compound, the compounding amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the resin (A), and is 0 from the viewpoint of photosensitivity characteristics. It is more preferably 0.5 to 5 parts by mass. When the compounding amount of the azole compound with respect to 100 parts by mass of the (A) resin is 0.1 parts by mass or more, when the resin composition of the present embodiment is formed on copper or a copper alloy, Discoloration is suppressed, while when it is 10 parts by mass or less, excellent photosensitivity of the resin composition is maintained.

In order to suppress the discoloration of the copper surface, a hindered phenol compound may be optionally blended in place 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-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4 ,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3- t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2- Thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],

N,N' hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2, 2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3, 5-di-t-butyl-4-hydroxybenzyl)-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, 1 ,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-Tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-Tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)- Trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione , 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

1,3,5-Tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)- Trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H ,5H)-Trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H ,3H,5H)-Trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4. 6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2, 4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2, 4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine- Examples include 2,4,6-(1H,3H,5H)-trione, but are not limited thereto. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-Trione and the like are particularly preferable.

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

<<Method for producing cured relief pattern>>
The present invention also provides a method of making a cured relief pattern.
To form a cured relief pattern in this embodiment,
(A) A resin composition satisfying at least one of the case where the resin has a polymerizable group in its side chain and the case where the resin composition contains a crosslinking agent may be used. preferable. Such a resin composition functions as a negative photosensitive resin composition, and it becomes possible to easily and efficiently produce an effect relief pattern.
In any of the above cases, the resin composition preferably further contains (D) a photosensitizer.

The method of manufacturing the effect relief pattern according to the present embodiment includes, for example, the following steps:
(1) A coating step of coating the negative photosensitive resin composition described above on a substrate to form a resin layer on the substrate,
(2) an exposure step of exposing the resin layer,
(3) a developing step of developing the resin layer after the exposure to form a relief pattern,
(4) A heating step 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 above resin layer is a photosensitive resin layer.
Hereinafter, typical aspects of each of the above steps will be described.

(1) Coating Step In this step, the negative photosensitive resin composition is coated on the 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 printer or the like may be used for coating, or a spray coater may be used for spray coating.
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, and vacuum drying are used. When the resin (A) contained in the resin composition to be used is composed of the polymer (A1), the coating film is dried under the condition that imidization of the polymer (A1) does not occur. Is desirable. Specifically, when air drying or heat drying is performed, the drying can be performed at 20° C. to 140° C. for 1 minute to 1 hour. As described above, the photosensitive resin layer can be formed on the substrate.

(2) Exposure step In this step, the photosensitive resin layer formed above is exposed. As the exposure device, for example, a contact aligner, a mirror projection, a stepper or the like is used. The exposure can be done through a patterned photomask or reticle, or directly. The light beam used for exposure is, for example, ultraviolet light.
After the exposure, for the purpose of improving the photosensitivity, a post-exposure bake (PEB) and/or a pre-development bake may be performed at any combination of temperature and time, if necessary. 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 it does not impair the various characteristics of the negative photosensitive resin composition in the present embodiment. ..

(3) Development Step In this step, the unexposed portion of the photosensitive resin layer after exposure is removed by development. As a developing method for developing the photosensitive resin layer after exposure (irradiation), a conventionally known developing method for photoresist can be selected and used. For example, there are a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. In addition, after development, for the purpose of adjusting the shape of the relief pattern and the like, a post-development baking may be performed at an arbitrary combination of temperature and time, if necessary. The temperature of the post-development bake can be, for example, 30 to 180° C., and the time can be, for example, 1 to 30 minutes.

The developer used for the development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and a 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 and the like 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, the ratio of the poor solvent to the good solvent is preferably adjusted according to the solubility of the polymer in the negative photosensitive resin composition. Further, each solvent may be used in combination of two or more kinds, for example, several kinds.

(4) Heating Step In this step, the relief pattern obtained by the above development is heated to diffuse the photosensitive component. When the resin (A) contained in the resin composition to be used is composed of the polymer (A1), it can be converted into a cured relief pattern composed of polyimide by imidizing the resin in this step.
As a method of heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising type oven capable of setting a temperature program can be selected. The heating can be performed, for example, at 200° C. to 400° C. for 30 minutes to 5 hours. Air may be used as an 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 above-mentioned semiconductor device can be a semiconductor device having, for example, a base material which 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 using a semiconductor element as a substrate and including the method for manufacturing a cured relief pattern described above as a part of the process. The semiconductor device of the present embodiment has a semiconductor device having a cured relief pattern formed by the above-described method for producing a cured relief pattern, for example, a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip-chip device protective film, and a bump structure. It can be manufactured by forming it as a protective film of the device or the like and combining it with a known semiconductor device manufacturing method.

The negative photosensitive resin composition of the present embodiment, in addition to the application to the semiconductor device as described above, for interlayer insulation of multilayer circuits, cover coat of flexible copper clad board, solder resist film, liquid crystal alignment film, etc. Is also useful.

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 KK Trade name Shodex 805M/806M in-line standard monodisperse polystyrene: Showa Denko KK 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. As a result, a coating film having the average film thickness shown 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. The film thickness was measured using a Nanospec 5100 optical film thickness meter (manufactured by Nanometrics). The film thickness uniformity of the photosensitive resin composition was estimated from the following formula.
Uniformity of film thickness [%]=(maximum film thickness at 39 points after coating-minimum film thickness at 39 points after coating)/average film thickness at 39 points Selection criteria for measuring points: outer peripheral edge of wafer Except for the area of 10 mm, the measurement points were 39 points which were set concentrically at equal intervals from the rest of the area.

(3) Evaluation of Adhesion with Substrate A negative type 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 through a reticle with a test pattern by an i-line stepper NSR2005i8A (manufactured by Nikon Corporation) to irradiate with energy of 300 mJ/cm ² . Next, the coating film after exposure was spray-developed using cyclopentanone as a developing solution using a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan). Then, the coating film after development was rinsed with propylene glycol methyl ether acetate to remove the unexposed portion by development to obtain a relief pattern.
Regarding the obtained pattern, the fine line pattern shape of 2 to 30 μm width of the exposed portion was observed under an optical microscope, and the fine line pattern of the minimum width without peeling was less than 16 μm, the adhesion was “good”, and 16 μm or more The adhesiveness was evaluated as "poor".

<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.
This reaction mixture was allowed to cool to room temperature after the end of heat generation due to the reaction, and allowed to stand for 16 hours.

Next, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture under ice cooling over 40 minutes while stirring, and subsequently 4,4′-diaminodiphenyl ether (DADPE) was added. ) A suspension of 93.0 g of γ-butyrolactone in 350 ml was added over 60 minutes while stirring. Further, stirring was 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 this reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction liquid was put into 3 liters of ethyl alcohol to generate a precipitate composed of a crude polymer. 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 obtained 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 described above. The reaction was carried out in the same manner as in the method described in 1, to obtain a 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 the polymer (2) obtained in the above-mentioned production example, a photosensitive resin composition was prepared by the following method and evaluated. (A) 50 g of the polymer (1) as the resin and 50 g of the polymer (2) were dissolved in 200 g of 3-methoxy-N,N-dimethylpropionamide as the (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 above-mentioned method.

<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 give 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, the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed and developed, and the exposed fine line was adhered at 12 μm or more, and the adhesion was “good”.

<Example 3>
To the resin composition of Example 2, 1 g of N-[3-(triethoxysilyl)propyl]phthalamic acid (C) as a silica compound was added 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, the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed and developed, and the exposed fine line was adhered at 10 μm or more, and the adhesion was “good”.

<Example 4>
Example 3 was repeated except that the amount of 3-methoxy-N,N-dimethylpropionamide as the amide compound (B) was changed to 1 g and 199 g of N-methyl-2-pyrrolidone was added as the solvent. A negative photosensitive resin composition was prepared in the same manner as in.
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, the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed and developed, and the exposed fine lines were in close contact with each other at 14 μm or more, and the adhesion was “good”.

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

<Example 6>
Example 3 except that the compounding amount of 3-methoxy-N,N-dimethylpropionamide as the amide compound (B) was changed to 100 g and 100 g of N-methyl-2-pyrrolidone was added as the solvent in Example 3. A negative photosensitive resin composition was prepared in the same manner as in.
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, the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed and developed, and the exposed fine line was adhered at 12 μm or more, and the adhesion was “good”.

<Example 7>
Negative photosensitive resin composition was prepared in the same manner as in Example 3 except that the compounding amount of 3-methoxy-N,N-dimethylpropionamide (B) 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>
Negative photosensitive resin composition was prepared in the same manner as in Example 3 except that the compounding amount of 3-methoxy-N,N-dimethylpropionamide (B) 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 (B) instead of 3-methoxy-N,N-dimethylpropionamide, 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 of 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, the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed and developed, and the exposed fine lines were in close contact with each other at 14 μm or more, and the adhesion was “good”.

<Comparative Example 1>
A resin composition was prepared by dissolving 50 g of polymer (1) as a resin (A) and 50 g of polymer (2) in 200 g of N-methyl-2-pyrrolidone.
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>
6 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime as a photosensitizer (D) and N-[as a silica compound (C) were added to the resin composition of Comparative Example 1. A negative photosensitive resin composition was prepared by adding 3-(triethoxysilyl)propyl]phthalamic acid (1 g).
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, the resin composition was applied to a silicon wafer according to the method described above, dried, exposed and developed, and then the exposed fine line of the exposed portion had a thickness of 20 μm or more, and the adhesiveness was “poor”.

The above results are summarized in the table below.

In the above table, the upward arrow indicates that the type and amount of the blended component corresponding to the relevant column is the same as the above column.
The abbreviations of the respective components have the following meanings.
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-Propanedion-2-(O-ethoxycarbonyl)-oxime E1:N-methyl-2-pyrrolidone

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be suitably used in the field of photosensitive materials useful in the production of electric/electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (12)

(A) Resin: 100 parts by mass,
(B) One or more amide compounds selected from 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide: 1 to 1,000 parts by mass, and (D) photopolymerization Contains a photosensitizer that is an initiator,
The resin composition, wherein the resin (A) is a polymer having a structure represented by the following general formula (A1).

{In the 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 a carbon atom having 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 the 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; and q is an integer of 2 to 10. } A monovalent organic group represented by or a saturated aliphatic group having 1 to 4 carbon atoms, provided that
The resin composition according to claim 1, wherein at least one of R ₄ and R ₅ is a monovalent organic group represented by the general formula (R1). (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 1 carbon atoms. 20 monovalent organic groups. } The resin composition of Claim 1 or 2 which further contains the silane compound represented by these. The resin composition according to any one of claims 1 to 3, wherein the (B) amide compound is 3-methoxy-N,N-dimethylpropionamide. X ₁ in the general formula (A1) is the following formula:

The resin composition according to any one of claims 1 to 4, which is selected from a tetravalent group represented by each. Y ₁ in the general formula (A1) is represented by the 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. } The resin composition according to any one of claims 1 to 5, which is selected from a divalent group represented by each. X ₁ in the general formula (A1) is the following formula:

Is a tetravalent group represented by
Y ₁ is the following formula:

The resin composition according to any one of claims 1 to 6, which is a divalent group represented by. The resin composition according to any one of claims 1 to 7, wherein the photosensitizer (D) contains an oxime. The resin composition according to any one of claims 1 to 8, wherein the compounding amount of the (D) photosensitizer is 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin. Further containing a solvent,
The solvent is N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α- 10. One or more selected from acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone is contained in any one of claims 1 to 9. The resin composition described. The following steps:
(1) A coating step of coating the resin composition according to any one of claims 1 to 10 on a substrate to form a resin layer on the substrate,
(2) an exposure step of exposing the resin layer,
(3) a developing step of developing the resin layer after the exposure to form a relief pattern,
(4) A method for producing a cured relief pattern, characterized by passing through a heating step of forming a cured relief pattern by heating the relief pattern in the order described above. A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to claim 11.