JP6935982B2 - Resin composition, method for manufacturing cured relief pattern, and semiconductor device - Google Patents

Description

The present invention provides, for example, an insulating material for electronic components, a resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, a method for producing a cured relief pattern using the resin composition, and a semiconductor. It is about the device.

Conventionally, a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties has been used as an insulating material for electronic components, a passivation film for semiconductor devices, 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 coating, exposing, developing, and thermally imidizing the precursor. be able to. Such a photosensitive polyimide precursor has a feature that the process can be significantly shortened as compared with the conventional non-photosensitive polyimide.

In recent years, the mounting method on a printed wiring board has changed from the viewpoint of improving the degree of integration and function in 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) that can be mounted at a higher density have been used. There is. In these structures, the polyimide film comes into direct contact with the solder bumps. The film in such a bump structure is required to have high heat resistance and chemical resistance.
Therefore, a method for improving the heat resistance of the polyimide film or the polybenzoxazole film by adding a thermal cross-linking agent to the composition containing the polyimide precursor or the polybenzoxazole precursor is disclosed (see Patent Document 1). ).

Further, in the rewiring process in the semiconductor process in recent years, the wiring layer is increasingly thickened 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 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 is peeled off from the end face of the pattern after development. Further, when a conventional polyimide precursor composition using N-methyl-2-pyrrolidone as a main solvent is used, the influence of Benard convection at the time of solvent volatilization becomes large, and there is a problem that the film thickness uniformity of the coating film deteriorates. be.

Japanese Unexamined Patent Publication No. 2003-287889

The present invention is intended to solve the above-mentioned problems of the prior art. Therefore, an object of the present invention is to provide a resin composition that gives 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 cured relief pattern manufacturing method using the resin composition and a semiconductor device.

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

[1] A resin composition containing (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 of carbons 1 to 5, and
R ₂ and R ₃ are hydrocarbon groups that may independently have a hydrogen atom or an ether bond having 1 to 6 carbon atoms, except that R ₂ and R ₃ are the same or different from each other. They may be combined with 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 a 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 general formula (A1), X ₁ is a tetravalent organic group;
Y ₁ is a divalent organic group;
R ₄ and R ₅ independently have 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, and 6 to 30 carbon atoms. It is an aromatic group or a monovalent organic group capable of radical polymerization;
At _{least one of R 4} and R ₅ is a monovalent organic group capable of radical polymerization. }
[4] In the above 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 independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms; q is an integer of 2 to 10. } Is a monovalent organic group, an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or an aromatic group having 6 to 30 carbon atoms, and of R ₄ and R ₅ . The total of the monovalent organic group represented by the above general formula (R1), the aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, and the aromatic group having 6 to 30 carbon atoms for all. In [3], the ratio is 80 mol% or more, and the ratio of the monovalent organic group represented by the above general formula (R1) to all of _{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 independently hydrogen atoms, monovalent organic groups represented by the above general formula (R1), or saturated aliphatic groups having 1 to 4 carbon atoms, however.
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 the general formula (A2), a and b are independently integers of 0 to 2 and never become 0 at the same time;
c and d are independently integers from 0 to 4;
R ₁₆ is an (2 + a + c) valent organic group having 2 to 60 carbon atoms;
R ₁₇ is a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom, a (2 + b + d) valent organic group having 2 to 60 carbon atoms;
_{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 independently monovalent organic groups with 1 to 10 carbon atoms, s is an integer of 0 to 2, and Y ₄ is 1 to 1 carbon atoms. It is a monovalent organic group of 20. } The resin composition according to any one of [1] to [6], further containing the silane compound represented by.
[8] The resin composition according to any one of [1] to [7], wherein the (B) amide compound is 3-methoxy-N, N-dimethylpropionamide.
[9] The resin composition according to any one of [1] to [8], further containing (D) a photosensitizer.

[10] The following steps:
(1) A coating step of applying the resin composition according to any one of [1] to [9] onto a substrate to form a resin layer on the substrate.
(2) An exposure step for exposing the resin layer and
(3) A developing step of developing the exposed resin layer to form a relief pattern, and
(4) A method for producing a cured relief pattern, which comprises passing through a heating step of forming a cured relief pattern by heat-treating the relief pattern in the order described above.
[11] A semiconductor device having a cured relief pattern obtained by the production method according to [10].

According to the present invention, it is possible to obtain a resin composition that gives a film having excellent film thickness uniformity at the time of forming a thick film and excellent adhesion to a substrate after development, and further, a resin using the resin composition. 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 reference numerals in the general formula are present in the 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 above general formula (B1) as essential components. In addition to these, the resin composition of the present invention may further contain one or more selected from the group consisting of (C) silane compound and (D) photosensitizer.

<(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, polybenzoimidazole, and the like. It preferably contains at least one resin selected from the group consisting of polybenzthiazole, phenol resin, epoxy resin, siloxane resin, and acrylic resin.
The weight average molecular weight of these resins (A) is preferably 1,000 or more, more preferably 5,000 or more, as a polystyrene-equivalent value by gel permeation chromatography from the viewpoint of heat resistance after heat treatment and mechanical properties. preferable. The upper limit of the weight average molecular weight is preferably 100,000 or less. When the resin composition of the present embodiment is a photosensitive resin composition, the weight average molecular weight of the resin (A) is more preferably 50,000 or less from the viewpoint of solubility in a developing solution.

In the present embodiment, the resin (A) is preferably an alkali-soluble resin. A photosensitive resin is desirable for forming a relief pattern. By using the photosensitive resin together with the photosensitizer (D) described later, the resin composition of the present embodiment can be made into a photosensitive resin composition, depending on whether it is exposed or unexposed in the exposure process. A resin that causes dissolved or undissolved development in the subsequent developing step. The photosensitive resin is preferably a resin containing a polymerizable group in the side chain. Such a photosensitive resin can be appropriately selected depending on the desired properties and applications that the photosensitive resin composition should have.

The resin type constituting the main skeleton of the resin (A) in the present embodiment is preferably at least one selected from the above-mentioned 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 is excellent in heat resistance and mechanical properties. Used.
From the viewpoint of heat resistance and photosensitivity, the resin (A) which is particularly preferable is the general formula (A1):

{In general formula (A1), X ₁ is a tetravalent organic group;
Y ₁ is a divalent organic group;
R ₄ and R ₅ independently have 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, and 6 to 30 carbon atoms. It is an aromatic group or a monovalent organic group capable of radical polymerization;
At _{least one of R 4} and R ₅ is a monovalent organic group capable of radical polymerization. }, A polymer having a structure represented by (polymer (A1)), the following general formula (A2):

{In the general formula (A2), a and b are independently integers of 0 to 2 and never become 0 at the same time;
c and d are independently integers from 0 to 4;
R ₁₆ is an (2 + a + c) valent organic group having 2 to 60 carbon atoms;
R ₁₇ is a carbon atom, a hydrogen atom, a nitrogen atom, consisting of an oxygen atom and a sulfur atom, a (2 + b + d) valent organic group having 2 to 60 carbon atoms;
_{R 18, R 19, R 20} , and _{R 21} are each independently a monovalent organic group hydrogen atom or a C 1-20. } Is preferably contained at least one resin selected from the group consisting of a polymer having a structure represented by (polymer (A2)) and polyhydroxyamide (polymer (A3)). The ratio of these resins used in the resin composition of the present embodiment is preferably 60% by mass or more, more preferably 80% by mass or more, based on the total amount of the resin (A).

[Polymer (A1)]
The monovalent organic group capable of radical polymerization of _{R 4} and _{R 5} in formula (A1), under following general formula (R1):

{In the general formula (R1), R ₁₃ , R ₁₄ , and R ₁₅ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms; q is an integer of 2 to 10. } Is preferably a monovalent organic group.
_{The R 14} and R ₁₅ in the general formula (R1) are preferably hydrogen atoms or methyl groups independently of each other, and are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. R ₁₃ is preferably a hydrogen atom or a methyl group. Further, q is preferably 2 or more and 10 or less, and more preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.

In the above general formula (R1), the _{tetravalent organic group represented by X 1} is preferably an organic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive characteristics, and more preferably. ,
One of the ₄ -COOR and -CONH- groups is attached to the same aromatic ring, both are in ortho positions with each other, and _{the other of the 5} -COOR and -CONH- groups is on the same aromatic ring. They are either tetravalent aromatic groups or tetravalent alicyclic aliphatic groups that are attached and both are in ortho positions with each other. In the former case, the aromatic ring to which _{4 -COOR groups are bonded and}
The _{aromatic ring to which the −COOR 5} groups are bonded may be the same aromatic ring or different aromatic rings. The aromatic ring in this context is preferably a benzene ring.
As a tetravalent organic group represented by _{X 1, the following formula:}

The structure represented by each of the above can be mentioned, but the structure is not limited to these. Further, _{the structure of X 1} may be one kind or a combination of two or more kinds. _One X unit having these structures is preferable in that it has both heat resistance and photosensitive characteristics.
In the general formula (R1), 2-valent organic group represented by Y _1, from the viewpoint of achieving both the heat resistance and sensitivity characteristics, is preferably an aromatic group having 6 to 40 carbon atoms, for example, The following formula:

{In the above formula, A is independently a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ) or a butyl group (-C ₄ H ₉ ). be. }, But the structure is not limited to these. Further, _{the structure of Y 1} may be one kind or a combination of two or more kinds. _One Y unit having a structure represented by the above formula is preferable in that it has both heat resistance and photosensitive characteristics.

_{Examples of the saturated aliphatic group having 1 to 4 carbon atoms of R 4} and R ₅ in the above general formula (R1) include a primary hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a 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 a butoxymethyl group, a butyl sulfide methylene group, a butyl amino methylene group and the like; an oxygen atom as a hetero atom. , An aliphatic group containing a nitrogen atom, a sulfur atom, or a phosphorus atom. Examples of the aromatics having 6 to 30 carbon atoms of R ₄ and R ₅ include a phenyl group, a benzyl group, and a naphthyl group.

_{R 4} and _{R 5} in formula (A1), each independently,
A hydrogen atom, 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, or an aromatic group having 6 to 30 carbon atoms. , And a _{monovalent organic group represented by the above general formula (R1) for all of R 4} and R ₅ , an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, and 6 to 6 carbon atoms. The total ratio of the 30 aromatic groups is 80 mol% or more, and the ratio of the monovalent organic group represented by the above general formula (R1) to all of _{R 4} and R _{5 is 20 mol% to 80 mol.} If%; 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, however.
This _{is a case where both R 4} and R ₅ are not hydrogen atoms at the same time.
Such a resin (A) preferably works as a polyimide precursor that is cyclized and converted into polyimide by subjecting it to heat treatment at, for example, 200 ° C. or higher.

When the polymer (A1) is used as the resin (A), examples of a method for imparting a monovalent organic group capable of radical polymerization to the polymer (A1) include an ester bond type and an ionic bond type. The former is a method of introducing a monovalent organic group capable of radical polymerization by an ester bond into the side chain of the polyimide precursor. The latter is 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-bonded type is preferable.

[Method for preparing ester-bonded polymer (A1)]
To prepare the ester-bonded polymer (A1), for example, first, _{a tetracarboxylic acid dianhydride having a desired tetravalent organic group X 1} and an alcohol having a radically polymerizable group (for example, an unsaturated double bond) are prepared. is reacted with a kind, partially esterified tetracarboxylic acid (hereinafter, also referred to as acid / ester) was prepared, this and a divalent amide and diamine having an organic group Y ₁ polycondensation It is obtained by letting it. Saturated fatty alcohols may be optionally used in combination with the alcohols having a radically polymerizable group (for example, an unsaturated double bond).

(Preparation of acid / ester)
_{In the present embodiment, tetracarboxylic acid dianhydrides having a tetravalent organic group X 1} preferably used for preparing an ester-bonded polymer (A1) include, for example, pyromellitic anhydride and diphenyl ether-. 3,3', 4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic Acid dianhydride, diphenylsulfone-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic acid 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 can be used alone or in combination of two or more.

Examples of alcohols having a radically polymerizable group, which are preferably used for preparing an ester-bonded polymer (A1) in the present invention, include 2-acryloyloxyethyl alcohol and 1-acryloyloxy-3-propyl. Alcohol, 2-acrylamide ethyl 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 − Methacylamide ethyl 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.

As the saturated fatty alcohols that can be optionally used together with the alcohols having a radically polymerizable group, saturated aliphatic alcohols having 1 to 4 carbon atoms are preferable. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like. The amount of these saturated fatty alcohols used is preferably 80 mol% or less, more preferably 50 mol% or less, based on the total of alcohols having a radically polymerizable group and saturated aliphatic alcohols. preferable.
The amount of alcohol, the total amount of alcohol relative to the tetracarboxylic acid dianhydride to 1 mole having a tetravalent organic group _{X 1,} preferably 10 to 500 mol%, 100 to 300 mol% Is more preferable.

The above-mentioned suitable tetracarboxylic acid dianhydride and alcohols are mixed by stirring at a temperature of 20 to 50 ° C. for 4 to 10 hours, preferably in the presence of a basic catalyst such as pyridine, preferably in a suitable reaction solvent. As a result, the esterification reaction of the acid anhydride proceeds, and a desired acid / ester compound can be obtained.

As the reaction solvent, those in which the raw material tetracarboxylic dianhydride and alcohols and the acid / ester product as a product are completely dissolved are preferable. More preferably, the polymer (A1), which is an amide polycondensation product of the acid / ester compound and the diamine, is also a solvent that dissolves in the Seki z root. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbides. Hydrogens and the like can be mentioned. Specific examples of these are
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like;
Examples of esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate and the like;
As lactones, for example, γ-butyrolactone and the like;
Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran;
Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene and the like;
As hydrocarbons, for example, hexane, heptane, benzene, toluene, xylene, etc.
Each can be listed. These may be used alone or in combination of two or more, if necessary.

(Preparation of polymer (A1))
The acid / ester compound (typically in a solution state dissolved in the reaction solvent) is mixed with an appropriate dehydration condensing agent, preferably under ice-cooling, to make the acid / ester compound polyacid anhydride. It is a thing. Then to this, a diamine having a suitably divalent organic group Y ₁ used in the present embodiment separately dropped into the which is dissolved or dispersed in a solvent, by causing both the engaged amide polycondensation, the polymer of interest (A1) can be obtained. With diamines having an organic group Y ₁ of the divalent, it may be used in combination diamino siloxanes.
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. '-Diskosine imidyl carbonate and the like can be mentioned. The amount of the dehydration condensing agent used is preferably 0.1 to 10 mol, more preferably 1 to 5 mol, with respect to 1 mol of the acid / ester compound.
The reaction of the acid / ester with the dehydration condensing agent is carried out at, for example, −50 to 50 ° C., preferably -20 to 30 ° C. for, for example, 1 minute to 24 hours, preferably 5 minutes to 18 hours.
As described above, an intermediate polyacid anhydride is obtained.

In the present embodiment, the diamines containing organic group Y ₁ of the divalent suitably used for the reaction with the polyacid anhydrides, 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 Sulfur, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 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-bis) Aminophenoxy benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4- (4-aminophenoxy) phenyl] 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- (4- (4- (4-)4-) Aminophenoxy) phenyl) hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-trizine sulfone, 9,9-bis (4-aminophenyl) fluorene, etc .;

And some of the hydrogen atoms on these benzene rings are replaced with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogen atoms, etc .;
And a mixture thereof and the like. 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'-dimethitoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc. ; And a mixture thereof and the like. Diamines are not limited to the above examples.

Diamino siloxanes, improved adhesion between the coating and various substrate formed from the resin composition of the present embodiment for the purpose, including organic group Y ₁ of the divalent In the preparation of the polymer (A1) Used in combination with diamines. Examples of such diamino siloxanes, eg if 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and the like 1,3-bis (3-aminopropyl) tetraphenyldisiloxane etc. can. The amount of the diamino siloxanes, based on the total of the diamines and diamino siloxanes containing divalent organic group Y _1, preferably 80 mol% or less, more preferably 50 mol% or less ..

As the amount of diamines used, the total amount of diamines used is preferably 50 to 200 mol%, preferably 80 to 160 mol, based on 1 mol of the amount of the polyacid anhydride converted into the acid / ester form of the raw material. It is more preferable to set it to%.
The amide polycondensation reaction between the polyacid anhydride and the diamines is carried out at, for example, −50 to 100 ° C., preferably -20 to 80 ° C. for, for example, 1 minute to 48 hours, preferably 5 minutes to 24 hours.

After completion of the amide polycondensation reaction, the water-absorbing by-products of the dehydration condensate coexisting in the reaction solution are filtered out as necessary, and then a poor solvent suitable for the solution containing the polymer component (for example, water, fat) is used. Group lower alcohols, mixed solutions thereof, etc.) are added to precipitate the polymer components, and if necessary, the polymer is purified by repeating operations such as redissolution and reprecipitation, and then vacuum-dried. , Isolate the polymer of interest (A1). In order to improve the degree of purification, a solution of this polymer may be passed through a column filled with anions and / or cation exchange resins swollen with an appropriate organic solvent to remove ionic impurities.

The molecular weight of the ester-bonded polymer (A1) is preferably 1,000 to 100,000, preferably 5,000 to 50,000, as measured as a polystyrene-equivalent weight average molecular weight by gel permeation chromatography. More preferably. When the weight average molecular weight is 1,000 or more, the mechanical properties are good, and when it is 100,000 or less, the dispersibility in the developing solution is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the developing solvent for gel permeation chromatography. The molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

[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 an appropriate catalyst. It is a thing. When the polymer (A2) becomes a polymer having an oxazole ring structure, the heat resistance and solvent resistance of the formed film are dramatically improved.
The number of repetitions 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 is preferably in the range of 1 to 1,000 from the viewpoint of developability, and is preferably in the range of 3 to 50. The range is more preferred, most preferably the range of 3-30.
In the polymer (A2), the structural unit represented by the general formula (A2) may be one kind or two or more kinds. If there are two or more structural units in the polymer (A2), an arrangement of the structural units is not good at random in block.

The polymer (A2) is composed of, for example, a dicarboxylic acid having a structure of _{R 16} (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) _{2 and a dicarboxylic acid.}
It can be obtained by polycondensing 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 have the same meanings as in the above general formula (A2), respectively.
First, _{a diamine having an 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 3,3'-dihydroxybenzidine, 3,3'-dihydroxy-4,4'-dihydroxybiphenyl, and 4,4'-diamino. -3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-4-) Hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-amino-4-hydroxyphenyl) 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'-dihydroxy-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, etc .:
_{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 the above (however, 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 bis-aminophenol compounds, those in which R 17} is a tetravalent organic group selected from the above formula group are particularly preferable from the viewpoint of solubility in an alkaline developer and heat resistance.
Bis (aminophenol) _{(e.g., R 17 (NH 2) 2} (OR 19) e (COOR 21) _{that R 17} in the _g structure is selected from the formula group) at the bond joining the benzene rings On the other hand, it does not matter whether the meta position is an amino group and the para position is a hydroxyl group, or the meta position is a hydroxyl group and the para position is an amino group, but the solubility in a solvent is acceptable. From this point of view, 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. } Can also be used as a diamine.
X ₅₂ is not limited as long as it is a tetravalent organic group having a carbon number of 2 to 60, from the viewpoint of solubility and heat resistance in an alkali developing solution, exemplified as preferred organic groups represented by R ₁₇ described above It is preferable that the structure is formed. 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 are at the ortho position of each other. Such a diamine is referred to as (hereinafter, "diamine having a PBO precursor structure in the molecule".
More specifically, as a preferable structure of the diamine having a PBO precursor structure in the molecule, the following structure:

Diamines represented by each of are mentioned. Examples of the method for producing these diamines include a method in which two molecules of nitrobenzoic acid are reacted with the above-mentioned bisaminophenol, and then the nitro group is reduced to an amino 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, Y ₇ is a divalent organic group having 2 to 60 carbon atoms. } Is also possible to use the diamine represented by. _{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 will be described later as an example of the organic group represented by _{R 16 from the viewpoint of solubility in an alkaline developer and heat resistance.} It is preferably at least one organic group listed in.
Specific examples of such compounds include the following structural groups:

Diamines represented by each of are mentioned. These diamines can be obtained, for example, by reacting a dicarboxylic acid dichloride compound with two molecules of nitroaminophenol and then reducing the nitro group to an amino group.
In addition to these, _{as a diamine having 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, “PI precursor in the molecule”. It is also possible to use "bisaminophenol having a structure"). Examples of such compounds include the following structures:

{In the formula, Y ₈ is a tetravalent organic group having 4 to 60 carbon atoms, and R ₂₂ is an independently monovalent hydrocarbon group having 1 to 20 carbon atoms. } May be used. 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. } Can be mentioned as a diamine represented by each of.
As a method for producing bisaminophenol having a PI precursor structure in the molecule, for example,
A dicarboxylic acid ring-opened by reacting a tetracarboxylic dianhydride with a monoalcohol, a monoamine, etc.
A method of reducing the nitro group after condensing two molecules of an aniline derivative having a hydroxyl group and a nitro group at the ortho position can be exemplified.

Next, as a diamine having a raw material R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure, a diamine in which both e and g are 0 will be described. Such diamines 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 diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylene diamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diamino. Diphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 4,4'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 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-trimethylindan, bis (p-aminophenyl) Phenyloxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-amino) Phenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) ) Phenyloxy] diphenylsulfone, 4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, phenylindandinamine, 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, etc.;
Examples thereof include diamines in which the hydrogen atom of the aromatic nucleus of these aromatic diamines is substituted with a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, a phenyl group and the like.

Next, a dicarboxylic acid having a structure of _{R 16} (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) _{2 will be described.}
In R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , d = f = 0, d = 0 and f = 2, d = 1 or 2 and f = 2 and the like may be satisfied.
Such a dicarboxylic acid can be advantageously used when adjusting the solubility in an alkaline developer.
The R ₁₆ in the case where d = f = 0, include the structures for example represented by any one of the following structure group.

{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. It is a divalent group that is
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 independently hydrogen atoms or methyl groups, respectively. }.
Among the above, typical compounds as dicarboxylic acids having a tricyclodecane skeleton include bis (carboxy) tricyclo [5.2.1.0 ^2,6 ] decane and the like. As a method for producing this compound, for example, a synthetic example described in International Publication No. 2009/081950 pamphlet can be exemplified.
As _{the dicarboxylic acid when d = 0 and f = 2 in R 16} (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , for example, tetracarboxylic acid dianhydride was ring-opened with monoalcohol, monoamine or the like. Dicarboxylic acids can be used. Here, examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like. Examples of monoamines include, for example, butylamine, aniline and the like.
Examples of the above-mentioned tetracarboxylic dianhydride include compounds represented by each of the following chemical formula groups.

{In the formula, B is selected from the group consisting _{of -CH 2-} , _{-O-, -S-, -SO 2-} , -CO-, -NHCO-, -C (CF ₃ ) _{2-, and -COO-.} It is a divalent group to be made. }
As _{the dicarboxylic acid when d = 0 and f = 2 in R 16} (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , as another method, tetracarboxylic acid dianhydride and bisaminophenol or diamine are used. The carboxylic acid residue produced by the reaction can also be synthesized by a method of esterifying or amidating with monoalcohol or monoamine.
In R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ , in the dicarboxylic acid when d = 1 or 2 and f = 2, R ₁₈ can be, for example, hydrogen. Examples of such a dicarboxylic acid include a dicarboxylic acid having two sets of amide bonds and phenolic hydroxyl groups in the ortho position of each other in the molecule. As such a dicarboxylic acid, for example, a compound represented by the following formula can be exemplified.

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

As a method for producing the compound represented by the above formula, for example, 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 of a method in which two molecules of trimellitic acid chloride are reacted with the diaminophenol to be contained, and then the acid anhydride and the alcohol are further reacted.

Polyhydroxyamide, which is a polymer (A3), can be synthesized, for example, by polycondensation of a dicarboxylic acid and a bisaminophenol compound (diamine). A typical method thereof is, for example, a method in which a diacid chloride is obtained using a dicarboxylic acid and thionyl chloride, and then a bisaminophenol (diamine) is allowed to act on the diacid chloride, or a dicarboxylic acid and a bisamino. Examples thereof include a method of polycondensing phenol (diamine) with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act at the same time.

The resin (A) in the present embodiment is polyamic acid (polyamic acid), polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polyoxazole, polyoxazole precursor, polybenzoxazole, polybenzoimidazole. , Polybenzthiazole, phenol resin, epoxy resin, siloxane resin, and one or more resins selected from the group consisting of acrylic resins are preferably contained in an amount of 60% by mass or more based on the total amount of the resin (A). It is more preferable to contain 80% by mass or more. More preferably, it contains at least 60% by mass, more preferably 80% by mass or more of one or more resins selected from the group consisting of the above-mentioned polymer (A1) and polymer (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 of carbons 1 to 5, and
R ₂ and R ₃ are hydrocarbon groups that may independently have a hydrogen atom or an ether bond having 1 to 6 carbon atoms, except that R ₂ and R ₃ may be the same as each other. They may be different or may be combined with each other to form a ring structure. } Is a compound represented by.
By using such an amide compound (B), 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. be able to.
At the time of forming the relief pattern, Benard convection is likely to occur in the heating step (about 100 ° C.) for removing the solvent. Then, even after the solvent is sufficiently removed, convection marks remain, so that the film thickness uniformity of the coating film tends to deteriorate. In particular, when forming a relief pattern of a thick film, the unevenness of the coating film due to Benard convection becomes more severe, so that the film thickness uniformity tends to be further deteriorated.

In general, the ease of formation of Benard cells can be expressed by the Marangoni number. It is known that the thicker the film thickness, the larger the Marangoni number and the easier it is for convection to occur. In addition, the higher the viscosity, the smaller the Marangoni number and the less likely it is that convection will occur.
In the heating step of removing the solvent when forming the relief pattern, the heating temperature is set to 140 ° C. or lower in order to suppress the reaction of the added photosensitizer or to prevent the resin from reacting with the base material made of copper or the like. It is desirable to. The boiling point of N-methyl-2-pyrrolidone or the like used as a main solvent for a polyimide precursor or the like is higher than the heating temperature at the time of removing the solvent, and the solvent tends to remain in the coating film. Therefore, since the viscosity at the time of film curing becomes low, Benard convection tends to occur easily. Then, since the exposure and development steps are performed with the solvent remaining in the coating film, the resin tends to be easily dissolved in the developing solution during development, and therefore the formed relief pattern tends to be easily peeled off from the end face thereof. ..

The (B) amide compound used in this 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 and treated at the same heating temperature, the residual amount of the solvent in the coating film becomes large. However, the resin composition using the (B) amide compound is superior to the resin composition using N-methyl-2-pyrrolidone in the film thickness uniformity of the coating film, and peeling after the relief pattern development is suppressed.
The mechanism by which the (B) amide compound contributes to the uniformity of the film thickness of the coating film is not clear, but the interaction between the (A) resin and the (B) amide compound increases the viscosity at the time of solvent volatilization and Benard. It is presumed that the convection was suppressed. Further, although the mechanism of excellent adhesion of the relief pattern after development is not clear, the dissolution of the resin due to the solvation of the developer was suppressed by the interaction between the resin (A) and the amide compound (B). As a result, it is presumed that the swelling of the relief pattern is suppressed, and as a result, the stress applied to the interface between the base material and the relief pattern is reduced.

Specific examples of the (B) amide compound include 3-methoxy-propionamide, 3-ethoxy-propionamide, 3-propoxy-propionamide, 3-butoxy-propionamide, 3- (2-methylpropoxy) -propion. Amide, 3-pentyroxy-propionamide, 3-methoxy-N-methylpropionamide, 3-ethoxy-N-methylpropionamide, 3-propoxy-N-methylpropionamide, 3-butoxy-N-methylpropionamide, 3 -(2-Methylpropoxy) -N-methylpropionamide, 3-pentyroxy-N-methylpropionamide, 3-methoxy-N-ethylpropionamide, 3-ethoxy-N-ethylpropionamide, 3-propoxy-N- Ethylpropionamide, 3-butoxy-N-ethylpropionamide, 3- (2-methylpropoxy) -N-ethylpropionamide, 3-pentyroxy-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-pentyroxy-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-pentyroxy-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, but are not limited to, 1- (4-morpholinyl) propanone. Further, in using these, one kind or a mixture of two or more kinds may be used.

Among the above amides, one or more selected from 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide should be used from the viewpoint of post-development adhesion of the relief pattern. Is preferable.
The blending amount of the (B) amide compound is 1 to 10,000 parts by mass, preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the resin (A).

<(C) Silane compound>
In this embodiment, the (C) silane compound arbitrarily 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 independently monovalent organic groups with 1 to 10 carbon atoms, s is an integer of 0 to 2, and Y ₄ is 1 to 1 carbon atoms. It is a monovalent organic group of 20. }
In the general formula (C1), _{Y 4} is preferably a group represented by the following general formula _(Y 4 -1) or _(Y 4 -2).

{Wherein _(Y 4 -1), _{X 6} is a single bond or a divalent organic group having 1 to 10 carbon atoms, and _{Y 5} is amino group, hydroxyl group, carboxyl group, amide group and an alkoxy group, It is 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 It is a monovalent organic group having at least one substituent selected from the group consisting of a group, an acryloyl group and a methacryloyl group. }
In the general formula (C1), from the viewpoint of suppressing the occurrence of appearance defects such as wrinkles and swelling that may occur on the cured relief pattern when the cured relief pattern is sputtered, and from the viewpoint of 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 independently monovalent organic groups having 1 to 20 carbon atoms, and X ₁₀ and X ₁₄ are independently divalent organic groups having 1 to 10 carbon atoms, respectively. Organic groups, X ₁₁ and X ₁₂ are independently monovalent organic groups with 1 to 10 carbon atoms, X ₁₃ is a tetravalent organic group, and s is an integer of 0 to 2. be. }
_{In the general formula (C1), Y 6} is the following general formula (from the viewpoint of suppressing the occurrence of appearance defects such as wrinkles and swelling that may occur on the cured relief pattern when the cured relief pattern is sputtered. Y 6 _-1) is preferably at least one selected from three groups represented by each group.

{In the above equation, 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 from 0 to 5, and if u is 2 to 5, the plurality of X _16s are the same. Or may be different, and X ₁₇ and X ₁₈ are independently divalent groups with 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 the compounds to be used.

{In formula (C1-1), X ₁₉ and X ₂₀ are independently divalent organic groups having 1 to 10 carbon atoms, and X ₂₁ and X ₂₂ are independently having 1 to 10 carbon atoms, respectively. Is a monovalent organic group of, and s is an integer of 0-2;
In formula (C1-2), X ₂₅ and X ₂₇ are independently divalent organic groups having 1 to 10 carbon atoms, and X ₂₆ is a tetravalent organic group, X ₂₃ , X ₂₄ , and so on. X ₂₈ and X ₂₉ are independently monovalent organic groups with 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 -OR ₃₅ (in the formula, R ₃₄ and R ₃₅ are independently monovalent organic groups). It is a monovalent group, X ₃₁ is a divalent organic group having 1 to 10 carbon atoms, X ₃₂ and X ₃₃ are independently monovalent organic groups 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 independently monovalent organic groups, and s is an integer of 0-2. }

The alkoxysilyl group-containing silane compound represented by the general formula (C1-1) or (C1-2) has, but is not limited to, an acid anhydride or an acid dianhydride and an amino group. It can be produced by reacting a silane compound with 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 anhydride, phthalic anhydride and the like. Can be mentioned.

Examples of the acid dianhydride include pyromellitic acid dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, and 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride. 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, naphthalene-2,3,6,7-tetracarboxylic Acid dianhydride, naphthalene-1,2,5,6-tetracarboxylic acid dianhydride, naphthalene-1,2,4,5-tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetra Caroic acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 , 6-Tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic acid dianhydride, 2,6 −Dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetra Chloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic acid dianhydride, 3,3', 4,4'-Diphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyltetracarboxylic acid dianhydride,

3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3" -p-terphenyltetracarboxylic dianhydride, 2,3,3 ", 4 "-P-Terphenyltetracarboxylic acid dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propanedi. 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) sulfonate dianhydride, 1,1-bis (2) , 3-Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic acid dianhydride, perylene- 3,4,9,10-Tetracarboxylic acid dianhydride, Perylene-4,5,10,11-Tetracarboxylic acid dianhydride, Perylene-5,6,11,12-Tetracarboxylic acid dianhydride, phenanthrene -1,2,7,8-tetracarboxylic acid dianhydride, phenanthrene-1,2,6,7-tetracarboxylic acid dianhydride, phenanthrene-1,2,9,10-tetracarboxylic acid dianhydride, Pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride , 4,4'-Hexafluoroisopropyridene diphthalic acid dianhydride and the like.

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

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

There are two types of alkoxysilyl group-containing silane compounds represented by the general formula (C1-3), a urea type and a urethane type. This compound can generally be obtained by reacting a silane compound having an amino group with an isocyanate compound or a carbonic acid ester derivative, or by reacting an isocyanate group-containing silane compound 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 carbonic acid ester derivative, the silane compound having an amino group is selected. The above-mentioned compounds can 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, and p-tolyl isocyanate. , N-propyl isocyanate, isopropyl isocyanate, ethyl isocyanate, benzyl isocyanate and the like.
Examples of the carbonic acid ester derivative include chlorocarbonate ester compounds such as ethyl chlorocarbonate, methyl chlorocarbonate, n-butyl chlorocarbonate, isobutyl chlorocarbonate, Z-chloride, and 2-methoxyethyl chlorocarbonate; di-tbutyl dicarbonate and the like. Carbonated ester dianhydride can be mentioned. Among these carbonic acid ester derivatives, di-t-butyl dicarbonate is preferable because it does not use chloride and does not require an operation such as removing chlorine ions after the reaction. When di-t-butyl dicarbonate is used, the obtained t-butoxycarbonyl group is completely eliminated by calcination at about 200 ° C., so that excellent adhesiveness is exhibited even by calcination at a lower temperature. It is preferable because it can be used.

When the alkoxysilyl group-containing silane compound represented by the general formula (C1-3) is synthesized by the reaction of the isocyanate group-containing silane compound with an amino compound or an alcohol, the isocyanate group-containing silane compound may be, 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;
Examples of the alcohol include monohydric alcohol.
Among the alkoxysilyl group-containing silane compounds represented by the general formula (C1-3), the compounds represented by each of the following structural groups 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 (C1-4) include N- (3-triethoxysilylpropyl) urea (for example, a product name manufactured by Shin-Etsu Chemical Industry Co., Ltd.). LS3610, Azumax Co., Ltd. product name SIU9055.0, etc.), N- (3-trimethoxysilylpropyl) urea (Azumax Co., Ltd. product name SIU9058.0), 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- Examples thereof include (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, and N- (3-tripropoxysilylbutyl) urea. ..

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 (C) include compounds represented by the following general formulas (C1-5) to (C1-7).

{In formula (C1-5), X ₄₀ is a divalent organic group having 1 to 10 carbon atoms, and X ₃₉ , X ₄₁ and X ₄₂ are independently monovalent organic groups having 1 to 10 carbon atoms. Is a group, s is an integer 0-2, and t is an integer 0-5;
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 independently monovalent with 1 to 10 carbon atoms. It is an organic group, s is an integer 0-2, and u is an integer 1-3;
In formula (C1-7), X ₄₉ is a divalent organic group having 1 to 10 carbon atoms, and X ₅₀ and X ₅₁ are independently monovalent organic groups having 1 to 10 carbon atoms. And s is an integer from 0 to 2; and X _{44 in} equation (C1-6) and X ₄₈ in equation (C1-7) are independent of the following equation group:

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

Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (C1-5) include N-phenyl-γ-aminopropyltrimethoxysilane (trade name KBM573 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and N-. Examples thereof include phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyldimethoxymethylsilane, N-phenyl-γ-aminopropyldimethoxyethylsilane and the like. Among these, N-phenyl-γ-aminopropyltrimethoxysilane is particularly preferable from the viewpoint of 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 (trade name SLA0598.0 manufactured by Azumax Co., Ltd.) and 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 compound represented by the following structure 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 (C1-7) include 2- (trimethoxysilylethyl) pyridine (trade name SIT8396.0 manufactured by Azumax Co., Ltd.) and 2- (tri). Examples thereof include ethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine and the like. Among these, the compound represented by the following structure is 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 , For example, 3-mercaptopropyltrimethoxysilane (for example, product name KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., product name Sila Ace S810 manufactured by Chisso Co., Ltd.), 3-mercaptopropyltriethoxysilane (trade name manufactured by Azumax Co., Ltd.). SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (for example, product name LS1375 manufactured by Shin-Etsu Chemical Co., Ltd., product name SIM6474.0 manufactured by Azumax Co., Ltd.), mercaptomethyltrimethoxysilane (trade name SIM6473 manufactured by Azumax Co., Ltd.) .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 And so on.

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

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

The blending 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 with respect to 100 parts by mass of the resin (A), and more preferably 0.5 parts by mass. The range is from part by mass to 8 parts by mass. The (C) silane compounds listed above may be appropriately selected depending on the type of 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-described manner, it is possible to obtain a resin composition having excellent adhesion between the base material and the developed resin. As described above, the interaction between the (A) resin and the (B) amide compound suppresses the dissolution of the resin due to the solvation of the developer and suppresses the swelling of the relief pattern, resulting in the base material and the relief. It is estimated that the stress applied to the interface with the pattern is reduced. Here, the (C) silane compound undergoes a silane coupling reaction with the base material, and the (C) silane compound and the (B) amide compound interact with each other to reach the interface between the resin and the base material during development. It is presumed that the stress is 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. (D) Compounds that can be suitably used as a photosensitizer include, for example, benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone;
Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone;
Thioxantone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethyl thioxanthone;
Benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal;
Benzoin derivatives such as benzoin and benzoin methyl ether;

1-Phenyl-1,2-butandion-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-diphenylpropanthrion-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 imidazoles and the like are preferably mentioned, but are not limited thereto. In using these, one kind or a mixture of two or more kinds may be used. Among the above-mentioned photopolymerization initiators, oximes are more preferable in terms of photosensitivity.
The amount of the photosensitizer (D) to be blended is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and more preferably 2 to 15 parts by mass from the viewpoint of light sensitivity characteristics. When the photosensitizer (D) is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of the resin (A), the photosensitivity is excellent, and when the photosensitizer is blended in an amount of 20 parts by mass or less, the 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 resin composition obtained by dissolving each of the above components and, if necessary, an optional component further used, in a suitable solvent to form a varnish. Therefore, as the other component (E), a solvent can be mentioned, for example, a sensitizer, a monomer having a photopolymerizable unsaturated bond, an adhesion aid, a thermal polymerization inhibitor, a cross-linking agent, an azole compound, and a hinder. Dophenol compounds and the like can be mentioned.

Examples of the solvent include polar organic solvents and alcohols.
As the solvent in the resin composition of the present embodiment, it is preferable to use a polar organic solvent among the resins (A) 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 thereof 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 preferably used are typically alcohols that have an alcoholic hydroxyl group in the molecule and do not have an olefin-based double bond. Specific examples include 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) ethers;
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 ethyl lactate, propylene glycol-1-methyl ether, and propylene glycol-1-ethyl ether are particularly preferable. 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 with respect 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 olefin-based double bond, the content of the alcohol having no olefin-based double bond in the total solvent is preferably 5 to 50% by mass, more preferably. It is preferably 10 to 30% by mass. When the content of the alcohol having no olefin-based double bond is 5% by mass or more, the storage stability of the negative photosensitive resin composition becomes good, and when it is 50% by mass or less, the resin (A) is dissolved. The sex becomes good.
The (B) amide compound in the resin composition of the present embodiment includes those which are in a liquid state at room temperature. When the resin composition of the present embodiment contains a liquid (B) amide compound, it may exist as a varnish-like composition without adding a solvent. In such a case, the resin composition of the present embodiment does not need to contain a solvent, but a solvent may be added.

A sensitizer can be optionally added to the resin composition of the present embodiment in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Milliden 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-Dimethylaminokumarin, 3-ethoxycarbonyl-7-Dimethylaminokumarin, 3-Benzyloxycarbonyl-7-Dimethylaminokumarin, 3-methoxycarbonyl-7-diethylaminokumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-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, for example, in a combination of 2 to 5 types.
When the resin composition of the present embodiment contains a sensitizer, the blending amount 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 the monomer 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) acrylate;
Propylene glycol or polypropylene glycol mono or di (meth) acrylate;
Mono, di, or tri (meth) acrylates of glycerol;
Cyclohexanedi (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 adduct 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 blending amount is based on 100 parts by mass of the resin (A). , 1 to 50 parts by mass is preferable.

An adhesive aid can be optionally blended in order to improve the adhesiveness between the film formed by using the resin composition of the present embodiment and the base material. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3 − Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamide 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, N-phenylaminopropyltrimethoxysilane, etc. Other than ring agent;
Examples thereof include aluminum-based adhesive aids such as aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetone), and ethyl acetoacetate aluminum diisopropylate.

Among these adhesive 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 adhesive aid, the blending 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).

When the resin composition of the present embodiment is stored in a solution containing a solvent, a thermal polymerization inhibitor is optionally added in order to improve the stability of the viscosity and photosensitivity of the resin composition. be able to. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N) -Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.
The amount of the thermal polymerization inhibitor 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 the present embodiment.
The cross-linking agent has a function that (A) the resin can be cross-linked or the cross-linking agent itself can form a cross-linking network when the relief pattern formed by using the resin composition of the present embodiment is heat-cured. .. The cross-linking agent can further enhance the heat resistance and chemical resistance of the cured film.
As such a cross-linking agent, an amino resin and a derivative thereof are preferably used, and among them, a urea resin, a glycol urea resin, a hydroxyethylene urea resin, a melamine resin, a benzoguanamine resin, and derivatives thereof are preferably used. Particularly preferred are an alkoxymethylated urea compound and an alkoxymethylated melamine compound. Specific examples thereof include MX-290 (manufactured by Nippon Carbide Co., Ltd.), UFR-65 (manufactured by Nippon Cytec Co., Ltd.), MW-390 (manufactured by Nippon Carbide Co., Ltd.), and the like.
In consideration of various performances other than heat resistance and chemical resistance, when the resin composition of the present embodiment contains a cross-linking agent, the blending amount is 0.5 to 20 mass by mass with respect to 100 parts by mass of the resin (A). It is preferably parts, more preferably 2 to 10 parts by mass. When the blending amount is 0.5 parts 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 blended in order to suppress discoloration of the copper surface. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-. 5-Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxy Phenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5 -Bis (α, α-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- Examples thereof include methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferred is one or more selected from triltriazole, 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 blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and is 0 from the viewpoint of light sensitivity characteristics. .5 to 5 parts by mass is more preferable. When the blending amount of the azole compound (A) with respect to 100 parts by mass of the resin is 0.1 parts by mass or more, when the resin composition of the present embodiment is formed on a copper or a copper alloy, the surface of the copper or the copper alloy Discoloration is suppressed, while when it is 10 parts by mass or less, the excellent photosensitivity of the resin composition is maintained.

In order to suppress discoloration of the copper surface, a hindered phenol compound can be optionally blended in place of or in combination with the azole compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-). 4-Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-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- (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'hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2, 2'-methylene-bis (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrax [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)- Trion, 1,3,5-Tris [4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion , 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-2,4,5-(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- 2,4,6- (1H, 3H, 5H) -trione and the like can be mentioned, but the present invention is not limited thereto. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) ) -Trione and the like are particularly preferable.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. preferable. When the blending amount of the hindered phenol compound (A) with respect to 100 parts by mass of the resin 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 Discoloration and corrosion of the alloy are prevented, while when the amount is 20 parts by mass or less, the excellent photosensitivity of the resin composition is maintained.

<< Manufacturing method of cured relief pattern >>
The present invention also provides a method for producing a cured relief pattern.
To form a cured relief pattern in this embodiment
(A) It is possible to use a resin composition that satisfies at least one of the cases where the resin is a resin containing a polymerizable group in its side chain and the case where the resin composition contains a cross-linking agent. preferable. Such a resin composition functions as a negative type photosensitive resin composition, and an effect relief pattern can be easily and efficiently produced.
In any of the above cases, it is preferable that the resin composition further contains (D) a photosensitizer.

The method for producing the effect relief pattern in the present embodiment is, for example, the following step:
(1) A coating step of applying the above-mentioned negative photosensitive resin composition on a substrate and forming a resin layer on the substrate.
(2) An exposure step for exposing the resin layer and
(3) A developing step of developing the exposed resin layer to form a relief pattern, and
(4) It is characterized in that it goes through a heating step of forming a cured relief pattern by heat-treating the relief pattern 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, a negative photosensitive resin composition is applied onto a substrate, and if necessary, dried thereafter 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 method of applying a screen printing machine or the like, a method of spraying the coating with a spray coater.
If necessary, the photosensitive resin layer can be dried. As the 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 made of the polymer (A1), the coating film is dried under conditions such that imidization of the polymer (A1) does not occur. Is desirable. Specifically, when air-drying or heat-drying is performed, 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 apparatus, for example, a contact aligner, a mirror projection, a stepper, or the like is used. Exposure can be done through a photomask or reticle with a pattern, or directly. The light rays used for exposure are, for example, ultraviolet rays.
After exposure, post-exposure bake (PEB) and / or pre-development bake may be applied at any combination of temperature and time, if necessary, for the purpose of improving light sensitivity and the like. The range of the baking conditions is preferably 40 to 120 ° C. and 10 to 240 seconds, but is not limited to this range as long as it does not inhibit various properties 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 developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), a conventionally known developing method for a photoresist can be selected and used. For example, a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. Further, after development, post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern. The temperature of the bake after development can be, for example, 30 to 180 ° C., and the time can be, for example, 1 to 30 minutes.

As the developing solution used for development, a good solvent for the photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a 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, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Further, two or more kinds of each solvent, for example, several kinds can be used in combination.

(4) Heating step In this step, the relief pattern obtained by the above development is heated to dilute the photosensitive component. When the resin (A) contained in the resin composition used is made of the polymer (A1), it can be converted into a cured relief pattern made of polyimide by imidizing the resin in this step.
As a method of heat curing, various methods such as a hot plate method, an oven method, and a temperature rise type oven in which a temperature program can be set 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 the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.
As described above, the effect relief pattern can be manufactured.
<< Semiconductor device >>
The present invention also provides a semiconductor device having a cured relief pattern obtained by the method for producing a cured relief pattern of the present invention described above.
The above-mentioned semiconductor device can be, for example, a semiconductor device having a base material which is a semiconductor element and a cured relief pattern formed on the base material by the above-mentioned cured relief pattern manufacturing method.

The semiconductor device can be manufactured, for example, by using a semiconductor element as a base material and including the above-mentioned method for manufacturing a cured relief pattern as a part of a process. The semiconductor device of the present embodiment has a cured relief pattern formed by the above-mentioned cured relief pattern manufacturing method, for example, a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, and a semiconductor having a bump structure. It can be manufactured by forming it as a protective film or the like of the device and combining it with a known manufacturing method of a semiconductor device.

The negative photosensitive resin composition of the present embodiment is applied to semiconductor devices as described above, and is also used for interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like. 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 characteristics 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 a gel permeation chromatography method (standard polystyrene conversion) under the following conditions.
Column: Showa Denko Co., Ltd. Brand name Shodex 805M / 806M Series standard monodisperse polystyrene: Showa Denko Co., Ltd. Shodex STANDARD SM-105
Developing solvent: N-methyl-2-pyrrolidone Detector: Showa Denko brand name Shodex RI-930

(2) Evaluation of film thickness uniformity 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 from the wafer according to the following criteria. The film thickness measurement was performed using a Nanospec 5100 optical film thickness measuring machine (manufactured by Nanometrics). The film thickness uniformity of the photosensitive resin composition was estimated from the following formula.
Film thickness uniformity [%] = (maximum film thickness of 39 points after coating-minimum film thickness of 39 points after coating) / average film thickness of 39 points Selection criteria for measurement points: Outer edge of wafer The measurement points were 39 points set concentrically at equal intervals from the entire remaining area except for the area of 10 mm.

(3) Evaluation of Adhesion to Base Material A negative photosensitive resin composition was spin-coated on a 6-inch silicon wafer to remove the solvent to form a coating film. This coating film was exposed to energy of ^{300 mJ / cm 2} by an i-line stepper NSR2005i8A (manufactured by Nikon Corporation) via a reticle with a test pattern. Next, the coating film after exposure was spray-developed using a developer (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan) using cyclopentanone as a developing solution. Next, the developed coating film was rinsed with propylene glycol methyl ether acetate to develop and remove the unexposed portion to obtain a relief pattern.
Regarding the obtained pattern, the shape of the fine line pattern having a width of 2 to 30 μm in the exposed part was observed under an optical microscope, and the fine line pattern having the minimum width of less than 16 μm without peeling was regarded as “good” and the adhesion was 16 μm or more. Those were evaluated as "poor" adhesion.

<Manufacturing example 1>
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 liter volume separable flask. Then, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 81.5 g of pyridine was added with stirring at room temperature to obtain a reaction mixture.
The reaction mixture was allowed to cool to room temperature after the end of heat generation due to the reaction, and allowed to stand for another 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE). ) 93.0 g suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. Further, stirring was continued at room temperature for 2 hours, 30 ml of ethyl alcohol was added, and the mixture was stirred for 1 hour, and then 400 ml of γ-butyrolactone was added.
The precipitate formed in this reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was poured into 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the 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.

<Manufacturing example 2>
Production Example 1 described above, except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride. 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 and evaluated by the following method. 50 g of the polymer (1) and 50 g of the polymer (2) as the resin (A) were dissolved in 200 g of the 3-methoxy-N, N-dimethylpropionamide as the (B) amide compound to prepare a resin composition.
The film thickness uniformity of this resin composition was 4.5% when it was applied onto a silicon wafer and dried according to the above method.

<Example 2>
To the resin composition of Example 1, (D) 6 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime as a photosensitizer was added to obtain a negative photosensitive resin composition. Prepared.
The film thickness uniformity of this resin composition when it was applied to a silicon wafer and dried according to the above method was 4.3%. Further, after the resin composition was applied to a silicon wafer according to the above method, dried, exposed and developed, the thin lines of the exposed portion were in close contact with each other 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 as a (C) silica compound was added to prepare a negative photosensitive resin composition.
The film thickness uniformity of this resin composition when it was applied to a silicon wafer and dried according to the above method was 4.4%. Further, after the resin composition was applied to a silicon wafer according to the above method, dried, exposed and developed, the thin lines of the exposed portion were in close contact with each other at 10 μm or more, and the adhesion was “good”.

<Example 4>
In Example 3, the blending amount of 3-methoxy-N and N-dimethylpropionamide as the (B) amide compound was changed to 1 g, and 199 g of N-methyl-2-pyrrolidone was added as a solvent. In the same manner as above, a negative photosensitive resin composition was prepared.
The film thickness uniformity of this resin composition when it was applied to a silicon wafer and dried according to the above method was 7.1%. Further, after the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed and developed, the thin lines of the exposed portion were in close contact with each other at 14 μm or more, and the adhesion was “good”.

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

<Example 6>
In Example 3, the blending amount of 3-methoxy-N and N-dimethylpropionamide as the (B) amide compound was changed to 100 g, and 100 g of N-methyl-2-pyrrolidone was added as a solvent. In the same manner as above, a negative photosensitive resin composition was prepared.
The film thickness uniformity of this resin composition when it was applied to a silicon wafer and dried according to the above method was 6.3%. Further, after the resin composition was applied to a silicon wafer according to the above method, dried, exposed and developed, the thin lines of the exposed portion were in close contact with each other at 12 μm or more, and the adhesion was “good”.

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

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

<Example 9>
In Example 3, 100 g of 3-butoxy-N, N-dimethylpropionamide was used as the (B) amide compound 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 the above was added.
The film thickness uniformity of this resin composition when it was applied to a silicon wafer and dried according to the above method was 7.2%. Further, after the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed and developed, the thin lines of the exposed portion were in close contact with each other at 14 μm or more, and the adhesion was “good”.

<Comparative example 1>
(A) A resin composition was prepared by dissolving 50 g of the polymer (1) and 50 g of the polymer (2) as a resin in 200 g of N-methyl-2-pyrrolidone.
The film thickness uniformity of this resin composition was 8.2% when it was applied to a silicon wafer and dried according to the above method.

<Comparative example 2>
In the resin composition of Comparative Example 1, (D) 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime as a photosensitive agent (6 g), and (C) N- [as a silica compound. A negative photosensitive resin composition was prepared by adding 1 g of 3- (triethoxysilyl) propyl] phthalamic acid.
The film thickness uniformity of this resin composition when it was applied to a silicon wafer and dried according to the above method was 8.1%. Further, after the resin composition was applied to a silicon wafer according to the above method, dried, exposed and developed, the fine line of the exposed portion that was in close contact was 20 μm or more, and the adhesion 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 compounding ingredients corresponding to the relevant column are the same as those in the above column.
The abbreviations for each component 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-Propanedione-2- (O-ethoxycarbonyl) -oxime E1: N-methyl-2-pyrrolidone

The resin composition of the present invention can be suitably used in the field of photosensitive materials useful for producing electrical and 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 10,000 parts by mass, and (D) photopolymerization. Contains a photosensitizer, which is an initiator,
(A) the resin, have a structure represented by the following general formula (A1), and
A resin composition comprising a polymer having a polystyrene-equivalent weight average molecular weight of 5,000 to 100,000 by gel permeation chromatography.

{In general formula (A1), X ₁ is a tetravalent organic group;
Y ₁ is a divalent organic group;
R ₄ and R ₅ independently have 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, and 6 to 30 carbon atoms. It is an aromatic group or a monovalent organic group capable of radical polymerization;
At _{least one of R 4} and R ₅ is a monovalent organic group capable of radical polymerization. } In the above formula (A1)
R ₄ and R ₅ are independently hydrogen atoms, the following general formula (R1):

{In the general formula (R1), R ₁₃ , R ₁₄ , and R ₁₅ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms; q is an integer of 2 to 10. } Is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms, however.
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 above general formula (R1). (C) The following general formula (C1):

{In formula (C1), X ₄ and X ₅ are independently monovalent organic groups with 1 to 10 carbon atoms, s is an integer of 0 to 2, and Y ₄ is 1 to 1 carbon atoms. It is a monovalent organic group of 20. The resin composition according to claim 1 or 2, further containing the silane compound represented by. 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 the tetravalent groups represented by each of the above. Wherein _{Y 1} in the general formula (A1) is a compound represented by the following formula:

{In the above formula, A is independently a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ) or a butyl group (-C ₄ H ₉ ). be. } The resin composition according to any one of claims 1 to 5, which is selected from the divalent groups represented by each of the above. _{X 1} in the general formula (A1) is the following formula:

It 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 (D) photosensitizer contains oximes. The resin composition according to any one of claims 1 to 8, wherein the blending amount of the (D) photosensitizer is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) resin. Contains more solvent,
The solvent is N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α- One of claims 1 to 9, which comprises one or more selected from acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone. The resin composition described. The following steps:
(1) A coating step of applying the resin composition according to any one of claims 1 to 10 onto a substrate to form a resin layer on the substrate.
(2) An exposure step for exposing the resin layer and
(3) A developing step of developing the exposed resin layer to form a relief pattern, and
(4) A method for producing a cured relief pattern, which comprises passing through a heating step of forming a cured relief pattern by heat-treating 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.