JP7471480B2 - Resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Description

The present invention relates to a resin composition used to form relief patterns, for example, insulating materials for electronic components, passivation films in semiconductor devices, buffer coat films, interlayer insulating films, and the like, a method for producing a cured relief pattern using the same, and a semiconductor device.

Conventionally, polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used for insulating materials in electronic components, passivation films, surface protective films, and interlayer insulating films in semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursors can easily form heat-resistant relief pattern films by applying the precursor, exposing it to light, developing it, and subjecting it to a thermal imidization treatment by curing. Such photosensitive polyimide precursors have the characteristic of enabling a significant reduction in process times compared to conventional non-photosensitive polyimides.

In recent years, the mounting method for printed wiring boards has changed from the viewpoint of improving the integration density and functionality of semiconductor devices and miniaturizing chip size. Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures such as BGA (ball gripped array) and CSP (chip size packaging), which enable higher density mounting. In these structures, the polyimide film is in direct contact with the solder bump. The film in such a bump structure is required to have high heat resistance and chemical resistance.
Therefore, a method has been disclosed in which the heat resistance of a polyimide film or a polybenzoxazole film is improved by adding a thermal crosslinking agent to a composition containing a polyimide precursor or a polybenzoxazole precursor (see Patent Document 1).

In recent years, in the rewiring process of semiconductor manufacturing, the wiring layer has been increasingly thickened in order to improve reliability. Accordingly, there is a demand for thick polyimide films, which are interlayer insulating films. However, when a thick relief pattern is formed using a conventional polyimide precursor composition, there are problems such as poor adhesion to the substrate and peeling of the film from the pattern end face after development. In addition, when a conventional polyimide precursor composition in which N-methyl-2-pyrrolidone is used as the main solvent, the effect of Benard convection during solvent evaporation becomes large, resulting in poor film thickness uniformity of the coating film.

JP 2003-287889 A

The present invention is intended to solve the problems of the prior art described above. Therefore, an object of the present invention is to provide a resin composition that provides a film that has excellent film thickness uniformity when formed into a thick film and excellent adhesion to the substrate after development. Another object of the present invention is to provide a method for producing a cured relief pattern using the resin composition, and a semiconductor device.

The present inventors discovered that by incorporating a compound having a specific structure into a resin composition for forming a coating, it is possible to obtain a coating that has excellent thickness uniformity when formed into a thick film and excellent adhesion to a substrate, and thus completed the present invention.
The present invention is as follows.

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

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

In the general formula (A1), _X1 is a tetravalent organic group;
_Y1 is a divalent organic group;
R ₄ and R ₅ each independently represent 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 heteroatom, an aromatic group having 6 to 30 carbon atoms, or a monovalent organic group capable of radical polymerization;
At least one of _R4 and _R5 is a monovalent organic group capable of radical polymerization.
[4] In the formula (A1),
_R4 and _R5 are each independently
a hydrogen atom, a group represented by the following general formula (R1):

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

[5] In the formula (A1),
R ₄ and R ₅ each independently represent 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,
The resin composition according to [3], wherein R ₄ and R ₅ are not both 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 each independently represent an integer of 0 to 2, and cannot simultaneously be 0;
c and d are each independently an integer from 0 to 4;
R ₁₆ is a (2+a+c)-valent organic group having 2 to 60 carbon atoms;
R ₁₇ is a (2+b+d)-valent organic group having 2 to 60 carbon atoms and consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom;
R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
[7] (C) The following general formula (C1):

The resin composition according to any one of [1] to [6], further comprising a silane compound represented by the following formula (C1): {In formula (C1), _X4 and _X5 are each independently a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2, and _Y4 is a monovalent organic group having 1 to 20 carbon atoms.}
[8] The resin composition according to any one of [1] to [7], wherein the (B) amide compound is 3-methoxy-N,N-dimethylpropionamide.
[9] The resin composition according to any one of [1] to [8], further comprising (D) a photosensitizer.

[10] The steps of:
(1) A coating step of coating a substrate with the resin composition according to any one of items [1] to [9] to form a resin layer on the substrate;
(2) an exposure step of exposing the resin layer to light;
(3) a development step of developing the exposed resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the steps of: (a) subjecting the relief pattern to a heat treatment to form a cured relief pattern; and (b) heating the relief pattern in the order described above.
[11] A semiconductor device having a cured relief pattern obtained by the manufacturing method according to [10].

According to the present invention, it is possible to obtain a resin composition that provides a film that has excellent thickness uniformity when formed into a thick film and excellent adhesion to the substrate after development, and further provides a method for producing a cured relief pattern that forms a resin pattern using the resin composition, and a semiconductor device.

The present invention will be described in detail below. Throughout this specification, when a molecule contains multiple structures represented by the same symbol in a general formula, these may be the same or different.

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

<(A) Resin>
The resin (A) used in the present invention will be described.
The resin (A) of the present invention preferably contains at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polyoxazole, polyoxazole precursor, polybenzoxazole, polybenzimidazole, polybenzothiazole, phenolic resin, epoxy resin, siloxane resin, and acrylic resin.
The weight average molecular weight of these (A) resins 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 and mechanical properties after heat treatment. The upper limit of the weight average molecular weight is preferably 100,000 or less. When the resin composition of the present embodiment is used as a photosensitive resin composition, the weight average molecular weight of the (A) resin is more preferably 50,000 or less, from the viewpoint of solubility in a developing solution.

In this embodiment, the (A) resin is preferably an alkali-soluble resin. In order to form a relief pattern, it is desirable that the resin be a photosensitive resin. The photosensitive resin can be used together with the (D) photosensitizer described below to make the resin composition of this embodiment a photosensitive resin composition, and is a resin that causes development of dissolution or non-dissolution in the subsequent development step depending on whether it is exposed or unexposed in the exposure step. The photosensitive resin is preferably a resin that contains a polymerizable group in the side chain. Such a photosensitive resin can be appropriately selected depending on the desired properties and application that the photosensitive resin composition should have.

In the present embodiment, the resin species constituting the main skeleton of the resin (A) 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 preferably used because the resin after heat treatment has excellent heat resistance and mechanical properties.
From the viewpoint of heat resistance and photosensitivity, a particularly preferred (A) resin is a resin represented by the general formula (A1):

In the general formula (A1), _X1 is a tetravalent organic group;
_Y1 is a divalent organic group;
R ₄ and R ₅ each independently represent 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 heteroatom, an aromatic group having 6 to 30 carbon atoms, 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 (polymer (A1)) having a structure represented by the following general formula (A2):

In the general formula (A2), a and b each independently represent an integer of 0 to 2, and cannot simultaneously be 0;
c and d are each independently an integer from 0 to 4;
R ₁₆ is a (2+a+c)-valent organic group having 2 to 60 carbon atoms;
R ₁₇ is a (2+b+d)-valent organic group having 2 to 60 carbon atoms and consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom;
R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. It is preferable that the resin composition contains at least one resin selected from the group consisting of a polymer having a structure represented by the following formula (polymer (A2)): and polyhydroxyamide (polymer (A3)). The proportion of these resins used in the resin composition of this embodiment is preferably 60% by mass or more, and more preferably 80% by mass or more, based on the total amount of resin (A).

[Polymer (A1)]
The radically polymerizable monovalent organic group of _R4 and _R5 in the above general formula (A1) is preferably a group represented by the following general formula (R1):

{In general formula (R1), R ₁₃ , R ₁₄ , and R ₁₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; and q is an integer of 2 to 10.} is preferable.
In the general formula (R1), _R14 and _R15 are each preferably independently a hydrogen atom or a methyl group, and from the viewpoint of photosensitive properties, preferably a hydrogen atom. _R13 is preferably a hydrogen atom or a methyl group. Also, from the viewpoint of photosensitive properties, q is preferably an integer of 2 or more and 10 or less, more preferably an integer of 2 or more and 4 or less.

In the above general formula (R1), the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably
Either a tetravalent aromatic group, in which one of the -COOR ₄ group and the -CONH- group is bonded to the same aromatic ring and both are in the ortho position relative to each other, and the other of the -COOR ₅ group and the -CONH- group is bonded to the same aromatic ring and both are in the ortho position relative to each other, or a tetravalent alicyclic aliphatic group. In the former case, the aromatic ring to which the -COOR ₄ group is bonded and
The aromatic ring to which the -COOR ₅ group is attached may be the same or different aromatic ring, preferably a benzene ring in this context.
The tetravalent organic group represented by _X1 is more preferably a group represented by the following formula:

Examples of the structure represented by each of the following formulas are included, but are not limited thereto. The structure of _X1 may be one type or a combination of two or more types. _X1 groups having these structures are preferred in that they have both heat resistance and photosensitive properties.
In the above general formula (R1), the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula:

{In the above formula, each 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 ).}, but is not limited thereto. The structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having the structure represented by the above formula is preferred in that it has both heat resistance and photosensitive properties.

In the above general formula (R1), examples of the saturated aliphatic group having 1 to 4 carbon atoms for R ₄ and R ₅ include primary hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, and a butyl group;
Secondary hydrocarbon groups such as an isobutyl group, an isopentyl group, etc.;
Examples of the aliphatic groups having 5 to 30 carbon atoms which may have a heteroatom as _R4 and _R5 include butoxymethyl, butylsulfidemethylene, butylaminomethylene, and the like; and aliphatic groups containing an oxygen atom, nitrogen atom, sulfur atom, or phosphorus atom as a heteroatom. Examples of the aromatic groups having 6 to 30 carbon atoms as _R4 and _R5 include phenyl, benzyl, and naphthyl groups.

In the above general formula (A1), R ₄ and R ₅ each independently represent
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 heteroatom, or an aromatic group having 6 to 30 carbon atoms, and the total ratio 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 heteroatom, and the aromatic group having 6 to 30 carbon atoms to all of R ₄ and R ₅ 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 %; 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,
Both R ₄ and R ₅ are not hydrogen atoms at the same time.
Such a resin (A) functions favorably as a polyimide precursor that is cyclized and converted to a polyimide by, for example, a heat treatment at 200° C. or higher.

When polymer (A1) is used as resin (A), methods for imparting radically polymerizable monovalent organic groups to polymer (A1) include ester bond type and ionic bond type. The former is a method for introducing radically polymerizable monovalent organic groups to the side chain of a polyimide precursor via ester bond. The latter is a method for introducing radically polymerizable monovalent organic groups to the side chain of a polyimide precursor via ionic bond between a carboxyl group and an amino group by reacting a polymer having a carboxyl group with a radically polymerizable compound having an amino group (e.g., a (meth)acrylate compound having an amino group). Of these, the ester bond type is preferred.

[Method for preparing ester bond type polymer (A1)]
The above-mentioned ester bond-type polymer (A1) can be prepared, for example, by first reacting a tetracarboxylic dianhydride having a desired tetravalent organic group _X1 with an alcohol having a radically polymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester body), and then subjecting this to amide polycondensation with a diamine having a divalent organic group _Y1 . Saturated aliphatic alcohols may be used in combination with the above-mentioned alcohol having a radically polymerizable group (e.g., an unsaturated double bond).

(Preparation of Acid/Ester Forms)
In this embodiment, examples of tetracarboxylic dianhydrides having a tetravalent organic group _X1 that are preferably used to prepare an ester bond-type polymer (A1) include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. In addition, these can be used alone, and two or more types can be mixed and used.

In the present invention, examples of alcohols having a radical polymerizable group that are preferably used to prepare the ester bond type polymer (A1) include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples of such acrylates include 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

The saturated aliphatic alcohols that can be optionally used together with the alcohols having a radical polymerizable group are preferably saturated aliphatic alcohols having 1 to 4 carbon atoms. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol. The amount of these saturated aliphatic alcohols used is preferably 80 mol % or less, and more preferably 50 mol % or less, based on the total amount of the alcohols having a radical polymerizable group and the saturated aliphatic alcohols.
The amount of alcohols used is preferably 10 to 500 mol %, more preferably 100 to 300 mol %, in terms of the total amount of alcohols used relative to 1 mol of the tetracarboxylic dianhydride having a tetravalent organic group _X1 .

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

The reaction solvent is preferably one which completely dissolves the raw material tetracarboxylic dianhydride and alcohols, as well as the product acid/ester. More preferably, the reaction solvent is one which completely dissolves the polymer (A1), which is the amide polycondensation product of the acid/ester and diamine. Examples of the reaction solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. Specific examples of these include:
Ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.;
Esters, for example, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, etc.;
Lactones include, for example, γ-butyrolactone;
Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran;
Halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, etc.;
Examples of hydrocarbons include hexane, heptane, benzene, toluene, and xylene.
These may be used alone or in combination of two or more kinds, as required.

(Preparation of Polymer (A1))
The acid/ester body (typically in a solution state dissolved in the reaction solvent) is mixed with a suitable dehydration condensation agent, preferably under ice cooling, to convert the acid/ester body into a polyacid anhydride. Next, a diamine having a divalent organic group _Y1 , which is preferably used in this embodiment, dissolved or dispersed in a separate solvent is added dropwise to the acid/ester body, and the two are subjected to amide polycondensation to obtain the target polymer (A1). Diaminosiloxanes may be used in combination with the diamine having a divalent organic group _Y1 .
Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. The amount of the dehydration condensation agent used is preferably 0.1 to 10 mol, more preferably 1 to 5 mol, per mol of the acid/ester.
The reaction of the acid/ester with the dehydration condensing agent is carried out, for example, at −50 to 50° C., preferably −20 to 30° C., for example, 1 minute to 24 hours, preferably 5 minutes to 18 hours.
In this manner, a polyanhydride intermediate is obtained.

In this embodiment, examples of diamines containing a divalent organic group _Y1 that are preferably used in the reaction with a polyacid anhydride include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, and 3,4'-diaminobiphenyl. , 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone,

4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidinesulfone, 9,9-bis(4-aminophenyl)fluorene, etc.;

and those in which a portion of the hydrogen atoms on the benzene ring is substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen atom, or the like;
and mixtures thereof. Specific examples of the substitution products include 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. The diamines are not limited to the above examples.

Diaminosiloxanes are used in combination with the diamines containing the divalent organic group _Y1 when preparing the polymer (A1) for the purpose of improving adhesion between the coating film formed from the resin composition of this embodiment and various substrates. Specific examples of such diaminosiloxanes include 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane. The amount of these diaminosiloxanes used is preferably 80 mol % or less, more preferably 50 mol % or less, based on the total amount of the diamines containing the divalent organic group _Y1 and the diaminosiloxanes.

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

After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as necessary, and then a suitable poor solvent (e.g., water, aliphatic lower alcohol, a mixture thereof, etc.) is added to the solution containing the polymer component to precipitate the polymer component, and the polymer is purified by repeating operations such as redissolution and reprecipitation as necessary, and then vacuum drying is performed to isolate the target polymer (A1). In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and/or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

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

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

The polymer (A2) is, for example, a compound obtained by reacting a dicarboxylic acid having the structure R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ with
and a diamine having a structure of R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g . In these formulas, R ₁₆ to R ₂₁ and d to g each have the same meaning as in the above general formula (A2).
First, a diamine having a R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure will be described.

For example, examples of diamines in which R ₁₉ is a hydrogen atom and e is 2 include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, and others:
R ₁₇ in R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g is a group represented by the following formula:

wherein R19, R21, e, and g in the formula are each the same as in the formula (A2).
Among these bisaminophenol compounds, from the viewpoints of solubility in an alkaline developer and heat resistance, particularly preferred are compounds in which R ₁₇ is a tetravalent organic group selected from the above formula group.
In bis(aminophenols) (for example, those in which _R17 in the R17( _NH2 ) ₂ ( _OR19 ) _{e ( COOR21} ) _g structure is selected from the above formula group), the bond connecting the benzene rings may have either an amino group at the meta position and a hydroxyl group at the para position, or a hydroxyl group at the meta position and an amino group at the para position; however, from the viewpoint of solubility in a solvent, an amino group at the meta position and a hydroxyl group at the para position are preferred.
In addition, examples of diamines having an R ₁₇ (NH ₂ ) ₂ (OR ₁₉ ) _e (COOR ₂₁ ) _g structure include those having the following structure:

{wherein X ₅₂ is a tetravalent organic group having 2 to 60 carbon atoms.} can also be used.
_X52 is not limited as long as it is a tetravalent organic group having 2 to 60 carbon atoms, but from the viewpoint of solubility in an alkaline developer and heat resistance, it is preferable that it has a structure exemplified as a preferred organic group represented by _R17 described above. When _X52 is an aromatic group, the amide bond and the phenolic hydroxyl group bonded to the same aromatic ring are preferably in the ortho position relative to each other. Such a diamine is hereinafter referred to as a "diamine having a PBO precursor structure in the molecule".
More specifically, preferred structures of diamines having a PBO precursor structure in the molecule include the following structures:

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

It is also possible to use a diamine represented by the following formula: {wherein _Y7 is a divalent organic group having 2 to 60 carbon atoms.} In the above formula, _Y7 is not limited as long as it is a divalent organic group having 2 to 60 carbon atoms, but from the viewpoint of solubility in an alkaline developer and heat resistance, it is preferable that Y7 is at least one of the organic groups listed below as examples of the organic group represented by _R16 .
Specific preferred examples of such compounds include those in the following structural group:

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, as a diamine having the _R17 ( _NH2 ) ₂ ( _OR19 ) _e ( _COOR21 ) _g structure, a compound having two sets of polyimide precursor structures in the molecule (hereinafter referred to as "bisaminophenol having a PI precursor structure in the molecule") can also be used. Examples of such compounds include those having the following structure:

In the formula, _Y8 is a tetravalent organic group having 4 to 60 carbon atoms, and each _R22 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. } More specific examples of such compounds include those represented by the following structural group:

{In the formula, R ₂₂ is hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms.}
Examples of methods for producing bisaminophenol having a PI precursor structure in the molecule include
a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol, a monoamine, or the like;
An example of such a method is condensation of two molecules of an aniline derivative having a hydroxyl group and a nitro group at the ortho-position to each other, followed by reduction of the nitro group.

Next, as a diamine having the structure _R17 ( _NH2 ) ₂ ( _OR19 ) _e ( _COOR21 ) _g as a raw material, a diamine in which e and g are both 0 will be described. Such diamines can be advantageously used to adjust the solubility in an alkaline developer. Examples of these diamines include aromatic diamines. Aromatic diamines are advantageous in terms of heat resistance.

Examples of the aromatic diamines include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4-methyl-2,4-bis(4-aminophenyl)-1-pentene, 4-methyl-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-aminobenzyl)benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene,

4-methyl-2,4-bis(4-aminophenyl)pentane, 5(or 6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindane, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]benzophenone, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]benzophenone, 4,4'-bis[4-(α, α-dimethyl-4-aminobenzyl)phenoxy]diphenyl sulfone, 4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfide, 1,4-(4-aminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-di-(3-aminophenoxy)diphenyl sulfone, and 4,4'-diaminobenzanilide, etc.;
Examples of the aromatic diamines include diamines in which the hydrogen atoms of the aromatic nuclei of these aromatic diamines are substituted with chlorine atoms, fluorine atoms, bromine atoms, methyl groups, methoxy groups, cyano groups, phenyl groups, and the like.

Next, a dicarboxylic acid having the structure R ₁₆ (OR ₁₈ ) _d (COOR ₂₀ ) _f (COOH) ₂ will be described.
In _R16 ( _OR18 ) _d ( _COOR20 ) _f (COOH) ₂ , d=f=0, d=0 and f=2, d=1 or 2 and f=2, etc.
Such dicarboxylic acids can be advantageously used in adjusting the solubility in an alkaline developer.
When d=f=0, R ₁₆ may be, for example, any of the structures shown below.

In the formula, A ₁ is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C(CF ₃ ) ₂ —, and a single bond;
Each of the k L _1s bonded to a ring carbon atom is independently a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an amide group, a urea group, an imide group, and a urethane group, and k=4. }, -(CH ₂ ) _n10 - (wherein n ₁₀ is an integer of 1 to 12), and

{In the formula, L ₂ , L ₃ and L ₄ each independently represents a hydrogen atom or a methyl group.}
Among the above, a representative compound as a dicarboxylic acid having a tricyclodecane skeleton is bis(carboxy)tricyclo[5.2.1.0 ^2,6 ]decane, etc. As a method for producing this compound, for example, the synthesis example described in the pamphlet of International Publication No. 2009/081950 can be exemplified.
In _R16 ( _OR18 ) _d ( _COOR20 ) _f (COOH) ₂ , when d=0 and f=2, the dicarboxylic acid may be, for example, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol, a monoamine, or the like. Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol, and the like. Examples of the monoamine include butylamine, aniline, and the like.
Examples of the tetracarboxylic dianhydride include compounds represented by the following chemical formulae.

{In the formula, B is a divalent group selected from the group consisting of --CH ₂ --, --O--, --S--, --SO ₂ --, --CO--, --NHCO--, --C(CF ₃ ) ₂ --, and --COO--.}
Alternatively, the dicarboxylic acid where d=0 and f=2 in _R16 ( _OR18 ) _d ( _COOR20 ) _f (COOH) ₂ can be synthesized by reacting a tetracarboxylic dianhydride with a bisaminophenol or a diamine to produce a carboxylic acid residue, which can then be esterified or amidated with a monoalcohol or a monoamine.
In the dicarboxylic acid _R16 ( _OR18 ) _d ( _COOR20 ) _f (COOH) ₂ , where d=1 or 2 and f=2, _R18 can be, for example, hydrogen. Examples of such dicarboxylic acids include dicarboxylic acids having two pairs of amide bonds and phenolic hydroxyl groups in the ortho position in the molecule. Examples of such dicarboxylic acids include compounds represented by the following formula:

In the formula, _X53 is a trivalent or tetravalent organic group having at least 2 carbon atoms, _R23 is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and _n11 is an integer of 1 or 2.

An example of a method for producing the compound represented by the above formula is a method in which a bis(aminophenol) having the structure _R17 ( _NH2 ) ₂ (OH) ₂ or a diaminophenol having the structure _R17 ( _NH2 ) ₂ (OH) is reacted with two molecules of trimellitic acid chloride, and then the resulting mixture is reacted with an acid anhydride and an alcohol.

The polyhydroxyamide polymer (A3) can be synthesized, for example, by polycondensation of a dicarboxylic acid and a bisaminophenol compound (diamine). Typical methods include, for example, a method in which a diacid chloride is obtained using a dicarboxylic acid and thionyl chloride, and then the diacid chloride is reacted with a bisaminophenol (diamine), or a method in which a dicarboxylic acid and a bisaminophenol (diamine) are polycondensed with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenzotriazole can also be reacted at the same time.

In this embodiment, the (A) resin preferably contains at least one resin selected from the group consisting of polyamic acid (polyamic acid), polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polyoxazole, polyoxazole precursor, polybenzoxazole, polybenzimidazole, polybenzthiazole, phenolic resin, epoxy resin, siloxane resin, and acrylic resin in an amount of at least 60 mass%, more preferably at least 80 mass%, based on the total amount of the (A) resin. Even more preferably, the (A) resin contains at least one resin selected from the group consisting of the above polymer (A1) and polymer (A2), preferably at least 60 mass%, more preferably at least 80 mass%.

<(B) Amide Compound>
The amide compound (B) used in the resin composition of this embodiment will be described.
(B) The amide compound is represented by the following general formula (B1):

In the formula, R ₁ is an alkyl group having 1 to 5 carbon atoms;
R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have an ether bond, with the proviso that R ₂ and R ₃ may be the same or different and may be bonded to each other to form a ring structure.
By using such an amide compound (B), the resin composition of the present embodiment can be made into a resin composition capable of forming a thick-film relief pattern having excellent film thickness uniformity and excellent adhesion to a substrate.
When forming a relief pattern, Benard convection is likely to occur in the heating step (at about 100° C.) for removing the solvent. If this occurs, traces of the convection remain even after the solvent has been sufficiently removed, which tends to deteriorate the film thickness uniformity of the coating film. In particular, when forming a thick relief pattern, the unevenness of the coating film caused by the Benard convection becomes more severe, which tends to further deteriorate the film thickness uniformity.

In general, the ease of forming a Benard cell can be expressed by the Marangoni number. It is known that the thicker the film, the larger the Marangoni number, making it easier for convection to occur. Also, the higher the viscosity, the smaller the Marangoni number, making it harder for convection to occur.
In the heating step for removing the solvent when forming a relief pattern, the heating temperature is desirably set to 140° C. or less 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. The boiling point of N-methyl-2-pyrrolidone or the like used as the main solvent for polyimide precursors or the like is higher than the heating temperature during solvent removal, and the solvent is likely to remain in the coating film. Therefore, the viscosity during film curing is lowered, and Benard convection tends to occur easily. And, since the exposure and development steps are performed with the solvent remaining in the coating film, the resin is likely to dissolve in the developer during development, and therefore the formed relief pattern tends to peel off easily from its end face.

The amide compound (B) used in this embodiment tends to have a higher boiling point than N-methyl-2-pyrrolidone. Therefore, if the same heating temperature is used for removing the solvent during the formation of the relief pattern, the amount of solvent remaining in the coating film will be large. However, a resin composition using the amide compound (B) has a better coating film thickness uniformity than a resin composition using N-methyl-2-pyrrolidone, and peeling after development of the relief pattern is suppressed.
The mechanism by which the (B) amide compound contributes to the uniformity of the coating thickness is unclear, but it is presumed that the interaction between the (A) resin and the (B) amide compound increases the viscosity when the solvent evaporates, suppressing Benard convection. Also, the mechanism by which the relief pattern has excellent adhesion after development is unclear, but it is presumed that the interaction between the (A) resin and the (B) amide compound suppresses the dissolution of the resin due to solvation in the developer, suppressing swelling of the relief pattern, and as a result, reducing the stress applied to the interface between the substrate and the relief pattern.

(B) Specific examples of amide compounds include, for example, 3-methoxy-propionamide, 3-ethoxy-propionamide, 3-propoxy-propionamide, 3-butoxy-propionamide, 3-(2-methylpropoxy)-propionamide, 3-pentyloxy-propionamide, 3-methoxy-N-methylpropionamide, 3-ethoxy-N-methylpropionamide, 3-propoxy-N-methylpropionamide, 3-butoxy-N-methylpropionamide, 3-(2-methylpropoxy)-N-methylpropionamide, 3-pentyloxy-N-methylpropionamide, 3-methoxy-N-ethylpropionamide, 3-ethoxy-N-ethylpropionamide, Amides, 3-propoxy-N-ethylpropionamide, 3-butoxy-N-ethylpropionamide, 3-(2-methylpropoxy)-N-ethylpropionamide, 3-pentyloxy-N-ethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-propoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 3-(2-methylpropoxy)-N,N-dimethylpropionamide, 3-pentyloxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-diethylpropionamide,

3-propoxy-N,N-diethylpropionamide, 3-butoxy-N,N-diethylpropionamide, 3-(2-methylpropoxy)-N,N-diethylpropionamide, 3-pentyloxy-N,N-diethylpropionamide, 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- Examples of the alkoxy groups include, but are not limited to, (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, and 3-butoxy-1-(4-morpholinyl)propanone. These may be used alone or in a mixture of two or more.

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

<(C) Silane Compound>
The silane compound (C) that is optionally used in this embodiment will be described.
The silane compound (C) in this 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), _X4 and _X5 are each independently a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2, and _Y4 is a monovalent organic group having 1 to 20 carbon atoms.
In the above general formula (C1), Y ₄ is preferably a group represented by the following general formula (Y ₄ -1) or (Y ₄ -2).

In formula (Y ₄ -1), X ₆ is a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₅ is a monovalent group having at least one substituent selected from the group consisting of an amino group, a hydroxyl group, a carboxyl group, an amide group, and an alkoxy group;
In formula (Y ₄ -2), X ₇ is a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₆ is a monovalent organic group having at least one substituent selected from the group consisting of an aromatic group having 1 to 20 carbon atoms, a mercapto group, a glycidyl group, a vinyl group, an acryloyl group, and a methacryloyl group.}
From the viewpoint of suppressing occurrence of defective appearance such as wrinkles and blistering that may occur on a cured relief pattern when the pattern is subjected to a sputtering treatment, and from the viewpoint of elongation of the cured film, in the general formula (C1), _Y5 is preferably at least one selected from the five groups represented by each of the following general formulae:

{In the above formula, _X8 and _X9 are each independently a monovalent organic group having 1 to 20 carbon atoms, _X10 and _X14 are each independently a divalent organic group having 1 to 10 carbon atoms, _X11 and _X12 are each independently a monovalent organic group having 1 to 10 carbon atoms, _X13 is a tetravalent organic group, and s is an integer of 0 to 2.}
From the viewpoint of suppressing appearance defects such as wrinkles and blistering that may occur on a cured relief pattern when the pattern is subjected to a sputtering treatment, it is preferable that Y ₆ in the general formula (C1) is at least one selected from the three groups represented by each of the following general formulas (Y ₆ -1):

{In the above formula, _X15 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, the multiple _X15s may be the same or different, _X16 is a hydrogen atom or a methyl group, u is an integer of 0 to 5, and when u is 2 to 5, the multiple _X16s may be the same or different, and _X17 and _X18 are each independently a divalent group having 1 to 10 carbon atoms.}
As the compound represented by general formula (Y ₄ -1) in the above Y ₄ , from the viewpoint of adhesion of the cured film to a substrate, one or more compounds selected from the group consisting of compounds represented by each of the following general formulae (C1-1) to (C1-4) are more preferable.

In formula (C1-1), X ₁₉ and X ₂₀ each independently represent a divalent organic group having 1 to 10 carbon atoms, X ₂₁ and X ₂₂ each independently represent a monovalent organic group having 1 to 10 carbon atoms, and s represents an integer of 0 to 2;
In formula (C1-2), _X25 and _X27 each independently represent a divalent organic group having 1 to 10 carbon atoms, _X26 is a tetravalent organic group, _X23 , _X24 , _X28 and _X29 each independently represent a monovalent organic group having 1 to 10 carbon atoms, and s is an integer of 0 to 2;
In formula (C1-3), X ₃₀ is a monovalent group represented by -NH-R ₃₄ or -O-R ₃₅ (wherein R ₃₄ and R ₃₅ are each independently a monovalent organic group), X ₃₁ is a divalent organic group having 1 to 10 carbon atoms, X ₃₂ and X ₃₃ are each independently a monovalent organic group having 1 to 10 carbon atoms, and s is an integer of 0 to 2;
In formula (C1-4), X ₃₆ is a divalent organic group, X ₃₇ and X ₃₈ are each independently a monovalent organic group, and s is an integer of 0 to 2.

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

Examples of the acid dianhydrides include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene- 1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenyltetracarboxylic dianhydride,

3,3",4,4"-p-terphenyl tetracarboxylic dianhydride, 2,2",3,3"-p-terphenyl tetracarboxylic dianhydride, 2,3,3",4"-p-terphenyl tetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride , 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidenediphthalic dianhydride, and the like.

Examples of the silane compound having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropyldiethylethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and 4-aminobutyldimethylmethoxysilane.
Among the alkoxysilyl group-containing silane compounds represented by the general formula (C1-1) above, compounds represented by the following structure are particularly preferred from the viewpoint of adhesion of the cured film to a substrate.

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

The alkoxysilyl group-containing silane compound represented by the general formula (C1-3) is classified into two types, urea type and urethane type. This compound can generally be obtained by reacting a silane compound having an amino group with an isocyanate compound or a carbonate 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 general formula (C1-3) is synthesized by reacting a silane compound having an amino group with an isocyanate compound or a carbonate derivative, examples of the silane compound having an amino group include the above-mentioned compounds.

Examples of the isocyanate compound include cyclohexyl isocyanate, n-hexyl isocyanate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 1-naphthyl isocyanate, n-octadecyl isocyanate, phenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, ethyl isocyanate, and benzyl isocyanate.
Examples of carbonate derivatives include chlorocarbonate compounds such as ethyl chlorocarbonate, methyl chlorocarbonate, n-butyl chlorocarbonate, isobutyl chlorocarbonate, Z-chloride, and 2-methoxyethyl chlorocarbonate; and carbonate dianhydrides such as di-t-butyl dicarbonate. Among these carbonate derivatives, di-t-butyl dicarbonate is preferred because it does not use chlorides and therefore does not require operations such as removing chloride ions after the reaction. When di-t-butyl dicarbonate is used, the resulting t-butoxycarbonyl group is completely eliminated by baking at about 200° C., and therefore excellent adhesiveness can be achieved even by baking at a lower temperature, making it preferred.

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

Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (C1-4) include N-(3-triethoxysilylpropyl)urea (e.g., product name LS3610 manufactured by Shin-Etsu Chemical Co., Ltd., product name SIU9055.0 manufactured by AZmax Corporation, etc.), N-(3-trimethoxysilylpropyl)urea (product name SIU9058.0 manufactured by AZmax Corporation), 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-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea, etc.

In the general formula (C1), examples of the compound in which Y ₄ is a group represented by (Y ₄ -2) and Y ₆ in (Y ₄ -2) is represented by any one of the general formulas (Y ₆ -1) include the compounds represented by the following general formulas (C1-5) to (C1-7).

In formula (C1-5), X ₄₀ is a divalent organic group having 1 to 10 carbon atoms, X ₃₉ , X ₄₁ and X ₄₂ each independently are a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2, and t is an integer of 0 to 5;
In formula (C1-6), _X43 is a hydrogen atom or a methyl group, _X45 is a divalent organic group, _X46 and _X47 are each independently a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2, and u is an integer of 1 to 3;
In formula (C1-7), _X49 is a divalent organic group having 1 to 10 carbon atoms, _X50 and _X51 are each independently a monovalent organic group having 1 to 10 carbon atoms, and s is an integer of 0 to 2; and _X44 in formula (C1-6) and _X48 in formula (C1-7) are each independently a group selected from the following formula group:

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

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

Specific examples of alkoxysilyl group-containing silane compounds represented by general formula (C1-6) include 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by AZMAX Corporation, product name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by AZMAX Corporation, product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by AZMAX Corporation, product name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by AZMAX Corporation, product name SLA0599.2). Among these, the compound represented by the following structure is particularly preferred from the viewpoint of adhesion of the cured film to the substrate.

Specific examples of alkoxysilyl group-containing silane compounds represented by general formula (C1-7) include 2-(trimethoxysilylethyl)pyridine (product name SIT8396.0, manufactured by AZMAX Corporation), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, and 2-(diethoxysilylmethylethyl)pyridine. Among these, the compounds represented by the following structure are particularly preferred from the viewpoint of adhesion of the cured film to the substrate.

In the formula (C1), specific examples of the compound in which Y ₄ is a group represented by the general formula (Y ₄ -2) and Y ₆ in the general formula (Y ₄ -2) has a mercapto group include 3-mercaptopropyltrimethoxysilane (e.g., product name KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., product name Sila-Ace S810 manufactured by Chisso Corporation, etc.), 3-mercaptopropyltriethoxysilane (product name SIM6475.0 manufactured by AZmax Corporation), 3-mercaptopropylmethyldimethoxysilane (e.g., product name LS1375 manufactured by Shin-Etsu Chemical Co., Ltd., product name SIM6474.0 manufactured by AZmax Corporation, etc.), mercaptomethyltrimethoxysilane (product name SIM6473.5C manufactured by AZmax Corporation), mercaptomethyltrimethoxysilane (product name SIM6473.0 manufactured by AZmax Corporation),

3-mercaptopropyl diethoxymethoxysilane, 3-mercaptopropyl ethoxydimethoxysilane, 3-mercaptopropyl tripropoxysilane, 3-mercaptopropyl diethoxypropoxysilane, 3-mercaptopropyl ethoxydipropoxysilane, 3-mercaptopropyl dimethoxypropoxysilane, 3-mercaptopropyl methoxydipropoxysilane, 2-mercaptoethyl trimethoxysilane, 2-mercaptoethyl diethoxymethoxy Silane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, etc.

In the formula (C1), specific examples of the compound in which Y ₄ is a group represented by the general formula (Y ₄ -2) and Y ₆ in the general formula (Y ₄ -2) has a glycidyl group include 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Silicones Co., Ltd., product name KBE403), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like;
Specific examples of compounds in which _Y6 has a vinyl group include vinyltrimethoxysilane (product name KBE1003, manufactured by Shin-Etsu Silicones Co., Ltd.), vinyltriethoxysilane, and diethoxymethylvinylsilane;
Examples of the compound in which _Y6 has an acryloyl group include 3-acryloxypropyltrimethoxysilane;
Examples of compounds in which _Y6 has a methacryloyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Silicones Co., Ltd., product name KBE503), and 3-(methacryloxy)propyltri(2-methoxyethoxy)silane.
Each of them can be mentioned.

Among the many silane compounds described above, the silane compounds represented by the above general formulas (C1-1) to (C1-7) are preferred from the viewpoint of suppressing the occurrence of defects in appearance such as wrinkles and blisters that may occur on a cured relief pattern when the pattern is subjected to a sputtering treatment, and the silane compounds represented by the above general formulas (C1-1) to (C1-4) are more preferred from the viewpoint of the elongation of the obtained cured film.

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

<(D) Photosensitizer>
Next, the photosensitizer (D) that is optionally used in the resin composition of this embodiment will be described.
The photosensitizer (D) in this embodiment can be selected from any compound that is conventionally used as a photopolymerization initiator for UV curing. Compounds that can be suitably used as the photosensitizer (D) include, for example, benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone;
Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone;
Thioxanthone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone;
benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal and other benzil derivatives;
Benzoin, benzoin derivatives such as benzoin methyl ether, etc.;

Oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime;
N-arylglycines such as N-phenylglycine;
Peroxides such as benzoyl perchloride;
Preferred examples of the photopolymerization initiator include, but are not limited to, aromatic biimidazoles. These may be used alone or in combination of two or more. Among the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.
The amount of the photosensitizer (D) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the resin (A), and from the viewpoint of photosensitivity characteristics, more preferably 2 to 15 parts by mass. By adding 1 part by mass or more of the photosensitizer (D) relative to 100 parts by mass of the resin (A), excellent photosensitivity is achieved, and by adding 20 parts by mass or less, excellent thick-film curing properties are achieved.

<(E) Other Components>
The resin composition in this embodiment may further contain components other than the above components (A) to (D). The resin composition in this embodiment is typically used as a varnish-like resin composition prepared by dissolving the above components and any optional components further used as necessary in a suitable solvent. Therefore, examples of the other components (E) include, in addition to solvents, sensitizers, monomers having photopolymerizable unsaturated bonds, adhesive aids, thermal polymerization inhibitors, crosslinking agents, azole compounds, hindered phenol compounds, etc.

Examples of the solvent include polar organic solvents and alcohols.
As the solvent in the resin composition of the present embodiment, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A) resin, particularly in the polyimide precursor. Specific examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, 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 an alcohol. The alcohol that can be suitably used is typically an alcohol having an alcoholic hydroxyl group in the molecule and having no olefinic double bond. Specific examples include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol;
Lactic acid esters such as ethyl lactate;
Propylene glycol monoalkyl ethers such as 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, and propylene glycol 2-(n-propyl) ether;
Monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol-n-propyl ether;
2-Hydroxyisobutyric acid esters;
Examples of the alcohol include dialcohols such as ethylene glycol and propylene glycol. Among these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, and in particular, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are more preferred.

The above-mentioned solvent can be used in an amount of, for example, 30 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass, per 100 parts by mass of the (A) resin, depending on the desired coating film thickness and viscosity of the resin composition. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the negative photosensitive resin composition is improved, and when it is 50% by mass or less, the solubility of the (A) resin is improved.
In addition, the (B) amide compound in the resin composition of this embodiment includes those that are liquid at room temperature. When the resin composition of this embodiment contains the (B) amide compound in liquid form, it may be possible to exist as a varnish-like composition without adding a solvent. In such a case, the resin composition of this embodiment does not need to contain a solvent, but a solvent may be added.

The resin composition of this embodiment can be optionally blended with a sensitizer to improve photosensitivity. Examples of such sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene. Danone, 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),

Examples of the amines include 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-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-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These may be used alone or in combination of, for example, 2 to 5 types.
When the resin composition of the present embodiment contains a sensitizer, the blending amount is preferably 0.1 to 25 parts by mass per 100 parts by mass of the resin (A).

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 examples thereof include, but are not limited to, mono- or di(meth)acrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate;
Mono- or di(meth)acrylates of propylene glycol or polypropylene glycol;
Mono-, di-, or tri(meth)acrylates of glycerol;
Cyclohexane di(meth)acrylate;
Di(meth)acrylate of 1,4-butanediol;
Di(meth)acrylate of 1,6-hexanediol;
Neopentyl glycol di(meth)acrylate;
Mono- or di(meth)acrylate of bisphenol A;

Benzene trimethacrylate;
Isobornyl (meth)acrylate;
Acrylamide and its derivatives;
Methacrylamide and its derivatives;
Trimethylolpropane tri(meth)acrylate;
Di- or tri(meth)acrylates of glycerol;
Di-, tri-, or tetra(meth)acrylates of pentaerythritol;
Also included are compounds such as ethylene oxide or propylene oxide adducts of these compounds.

When the resin composition of this embodiment contains the above-mentioned monomer having a photopolymerizable unsaturated bond to improve the resolution of the relief pattern, the blending amount is preferably 1 to 50 parts by mass per 100 parts by mass of the (A) resin.

In order to improve the adhesion between the film formed using the resin composition of the present embodiment and the substrate, an adhesive aid can be optionally blended. Examples of the adhesive 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-diethoxypropylmethylsilane), and the like. silane coupling agents such as N-[3-(triethoxysilyl)propyl]succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane;
Examples of the aluminum-based adhesion promoter include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

Among these adhesive aids, it is more preferable to use a silane coupling agent in terms of adhesive strength. When the resin composition in this embodiment contains an adhesive aid, the blending amount is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the (A) resin.

In order to improve the stability of the viscosity and photosensitivity of the resin composition of the present embodiment, particularly when the resin composition is stored in the form of a solution containing a solvent, a thermal polymerization inhibitor can be optionally blended. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.
The amount of the thermal polymerization inhibitor to be added to the resin composition of the present embodiment is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the resin (A).

A crosslinking agent can be optionally blended into the resin composition of the present embodiment.
The crosslinking agent has a function of being able to crosslink the (A) resin or to form a crosslinked network by itself when the relief pattern formed using the resin composition of the present embodiment is heat-cured, and can further enhance the heat resistance and chemical resistance of the cured film.
As such a crosslinking agent, amino resins and derivatives thereof are preferably used, and among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used. Particularly preferred are alkoxymethylated urea compounds and alkoxymethylated melamine compounds. Specific examples thereof include MX-290 (manufactured by Nippon Carbide Corporation), UFR-65 (manufactured by Nippon Cytec Corporation), and MW-390 (manufactured by Nippon Carbide Corporation).
In consideration of the balance between various properties other than heat resistance and chemical resistance, the blending amount of the crosslinking agent in the resin composition of this embodiment is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the (A) resin. When the blending amount is 0.5 part by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 20 parts by mass or less, excellent storage stability is obtained.

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 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, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyltriazole, 5-phenyl-1H-triazole, 5-phenyl-1H-triazole, 5-phenyl-1H-triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 5-phenyl-1H- ... 1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,

Hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. are included. Particularly preferred are one or more selected from tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in a mixture of two or more.

When the resin composition of this embodiment contains the azole compound, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the resin composition of this embodiment is formed on copper or a copper alloy, while when the blending amount is 10 parts by mass or less, the excellent photosensitivity of the resin composition is maintained.

In order to suppress discoloration of the copper surface, a hindered phenol compound can be optionally blended in place of or together with the azole compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butyl)propionate, and 4,4'-thio-bis(3-methyl-6-t-butyl)propionate. ethylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],

N,N'Hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-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-tri Azine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

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

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

<<Method for Producing Cured Relief Pattern>>
The present invention also provides a method for producing a cured relief pattern.
In this embodiment, to form a cured relief pattern,
It is preferable to use a resin composition that satisfies at least one of the following conditions: (A) the resin contains a polymerizable group in its side chain, and (B) the resin composition contains a crosslinking agent. Such a resin composition functions as a negative photosensitive resin composition, and makes it possible to easily and efficiently produce an effect relief pattern.
In any of the above cases, the resin composition preferably further contains (D) a photosensitizer.

The method for producing the effect relief pattern in this embodiment includes, for example, the following steps:
(1) a coating step of coating the negative photosensitive resin composition on a substrate to form a resin layer on the substrate;
(2) an exposure step of exposing the resin layer to light;
(3) a development step of developing the exposed resin layer to form a relief pattern;
(4) a heating step of heat-treating the relief pattern to form a cured relief pattern, in the order described above. When the resin composition used functions as a negative type photosensitive resin composition, the resin layer is a photosensitive resin layer.
A typical embodiment of each of the above steps will now be described.

(1) Coating Step In this step, a negative photosensitive resin composition is coated on a substrate, and then dried as necessary to form a photosensitive resin layer.
The substrate may be made of, for example, silicon, silicon nitride, silicon oxide, aluminum, nickel, titanium, copper, a copper alloy, or the like.
As the coating method, any method that has been conventionally used for coating a photosensitive resin composition can be used, such as a coating method using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a spray coating method using a spray coater.
If necessary, the photosensitive resin layer can be dried. Examples of the drying method include air drying, heat drying using an oven or a hot plate, and vacuum drying. When the resin (A) contained in the resin composition used is made of a polymer (A1), it is desirable to dry the coating film under conditions that do not cause imidization of the polymer (A1). Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the substrate.

(2) Exposure Step In this step, the photosensitive resin layer formed above is exposed to light. For example, a contact aligner, a mirror projection, a stepper, or the like is used as an exposure device. The exposure can be performed through a photomask or a reticle having a pattern, or directly. The light used for exposure is, for example, ultraviolet light, or the like.
After the exposure, post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time, as necessary, for the purpose of improving photosensitivity, etc. The range of baking conditions is preferably a temperature of 40 to 120° C. and a time of 10 to 240 seconds, but is not limited to this range as long as it does not impair the various properties of the negative photosensitive resin composition of this embodiment.

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

The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. As good solvents, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred, and as poor solvents, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferred. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more types of each solvent, for example, several types, can be used in combination.

(4) Heating Step In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component. When the resin (A) contained in the resin composition used is made of a polymer (A1), the resin can be imidized in this step to convert it into a cured relief pattern made of a polyimide.
As the heat curing method, various methods can be selected, such as using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 200°C to 400°C for 30 minutes to 5 hours. The atmospheric gas during heat curing may be air or an inert gas such as nitrogen or argon.
In this manner, an effect relief pattern can be produced.
<<Semiconductor device>>
The present invention also provides a semiconductor device comprising a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern of the present invention.
The above-mentioned semiconductor device may be a semiconductor device having a substrate which is, for example, a semiconductor element, and a cured relief pattern formed on the substrate by the above-mentioned method for producing a cured relief pattern.

The above-mentioned semiconductor device can be manufactured, for example, by using a semiconductor element as a substrate and by a method that includes the above-mentioned method for manufacturing a cured relief pattern as part of the process. The semiconductor device of this embodiment can be manufactured by forming the cured relief pattern formed by the above-mentioned method for manufacturing a cured relief pattern as, for example, a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a semiconductor device having a bump structure, etc., and combining it with a known method for manufacturing a semiconductor device.

In addition to being applied to semiconductor devices as described above, the negative-type photosensitive resin composition of this embodiment is also useful for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each photosensitive resin was measured by gel permeation chromatography (converted into standard polystyrene) under the following conditions.
Column: Shodex 805M/806M series, manufactured by Showa Denko K.K. Standard monodisperse polystyrene: Shodex STANDARD SM-105, manufactured by Showa Denko K.K.
Developing solvent: N-methyl-2-pyrrolidone Detector: Shodex RI-930 (trade name, manufactured by Showa Denko)

(2) Film Thickness Uniformity Evaluation A negative photosensitive resin composition using a polyimide precursor as the photosensitive resin was spin-coated on a 6-inch silicon wafer, and then heated at 100° C. for 5 minutes to remove the solvent, forming a coating film having the average film thickness shown in Table 1. The film thickness (T1) of this coating film was then measured at 39 points on the wafer selected according to the following criteria. The film thickness was measured using a Nanospec 5100 optical film thickness measuring instrument (manufactured by Nanometrics). The film thickness uniformity of the photosensitive resin composition was estimated from the following formula.
Film thickness uniformity [%] = (maximum film thickness at 39 film thickness points after coating - minimum film thickness at 39 film thickness points after coating) / average film thickness at 39 points. Criteria for selecting measurement points: Except for a region 10 mm from the outer periphery of the wafer, 39 points were set concentrically at equal intervals from the entire remaining region as the measurement points.

(3) Evaluation of Adhesion to Substrate A negative photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and the solvent was removed to form a coating film. This coating film was exposed to light at an energy of 300 mJ/ ^cm2 using an i-line stepper NSR2005i8A (Nikon Corporation) through a test pattern reticle. The exposed coating film was then spray-developed using cyclopentanone as a developer and a developing machine (D-SPIN636, Dai Nippon Screen Mfg. Co., Ltd., Japan). The developed coating film was then rinsed with propylene glycol methyl ether acetate to develop and remove the unexposed areas, thereby obtaining a relief pattern.
The resulting patterns were observed under an optical microscope for the shape of the 2 to 30 μm wide thin line patterns in the exposed areas. Patterns with a minimum width that did not peel off and was less than 16 μm in size were rated as having "good" adhesion, and patterns with a minimum width of 16 μm or more were rated as having "poor" adhesion.

<Production Example 1>
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, to which 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were then added, and 81.5 g of pyridine was added with stirring at room temperature to obtain a reaction mixture.
After the heat generation due to the reaction had ceased, the reaction mixture was allowed to cool to room temperature and was then allowed to stand for an additional 16 hours.

Next, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture under ice cooling over a period of 40 minutes while stirring, and then a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone was added over a period of 60 minutes while stirring. Stirring was continued for another 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour, after which 400 ml of γ-butyrolactone was added.
The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The reaction solution obtained was poured into 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and dried in vacuum to obtain a powdered polymer (1).
The molecular weight of this polymer (1) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 20,000 in weight average molecular weight (Mw).

<Production Example 2>
A reaction was carried out in the same manner as in Production Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride, to obtain polymer (2).
The molecular weight of this polymer (2) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 22,000 in weight average molecular weight (Mw).

Example 1
Using the polymer (1) and polymer (2) obtained in the above-mentioned Production Examples, photosensitive resin compositions were prepared by the following method and evaluated. (A) 50 g of polymer (1) and 50 g of polymer (2) as resins were dissolved in 200 g of 3-methoxy-N,N-dimethylpropionamide as an amide compound (B) to prepare a resin composition.
When this resin composition was applied onto a silicon wafer and dried in accordance with the above-mentioned method, the film thickness uniformity was 4.5%.

Example 2
To the resin composition of Example 1, 6 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime as a photosensitizer (D) was added to prepare a negative photosensitive resin composition.
When this resin composition was applied to a silicon wafer and dried according to the above-mentioned method, the film thickness uniformity was 4.3%. Furthermore, when the resin composition was applied to a silicon wafer and dried according to the above-mentioned method, and after exposure and development, the exposed fine lines were 12 μm or more in adhesion, and the adhesion was "good".

Example 3
1 g of N-[3-(triethoxysilyl)propyl]phthalamic acid as the silica compound (C) was added to the resin composition of Example 2 to prepare a negative photosensitive resin composition.
When this resin composition was applied to a silicon wafer and dried according to the above-mentioned method, the film thickness uniformity was 4.4%. Furthermore, when the resin composition was applied to a silicon wafer and dried according to the above-mentioned method, and after exposure and development, the exposed fine lines were 10 μm or more in adhesion, and the adhesion was "good".

Example 4
A negative type photosensitive resin composition was prepared in the same manner as in Example 3, except that in Example 3, the amount of 3-methoxy-N,N-dimethylpropionamide as the amide compound (B) was changed to 1 g, and 199 g of N-methyl-2-pyrrolidone was added as the solvent.
When this resin composition was applied to a silicon wafer and dried according to the above-mentioned method, the film thickness uniformity was 7.1%. Furthermore, when the resin composition was applied to a silicon wafer and dried according to the above-mentioned method, and after exposure and development, the exposed fine lines were 14 μm or more in adhesion, and the adhesion was "good".

Example 5
A negative type photosensitive resin composition was prepared in the same manner as in Example 3, except that in Example 3, the amount of 3-methoxy-N,N-dimethylpropionamide as the amide compound (B) was changed to 10 g and 190 g of N-methyl-2-pyrrolidone was added as the solvent.
When this resin composition was applied to a silicon wafer and dried according to the above-mentioned method, the film thickness uniformity was 6.9%. Furthermore, when the resin composition was applied to a silicon wafer and dried according to the above-mentioned method, and after exposure and development, the exposed fine lines were 14 μm or more and had good adhesion, and the adhesion was "good".

Example 6
A negative type photosensitive resin composition was prepared in the same manner as in Example 3, except that in Example 3, the amount of 3-methoxy-N,N-dimethylpropionamide as the amide compound (B) was changed to 100 g, and 100 g of N-methyl-2-pyrrolidone was added as the solvent.
When this resin composition was applied to a silicon wafer and dried according to the above-mentioned method, the film thickness uniformity was 6.3%. Furthermore, when the resin composition was applied to a silicon wafer and dried according to the above-mentioned method, and after exposure and development, the exposed fine lines were 12 μm or more in thickness and had good adhesion, and the adhesion was "good".

Example 7
A negative photosensitive resin composition was prepared in the same manner as in Example 3, except that the amount of 3-methoxy-N,N-dimethylpropionamide used as the amide compound (B) was changed to 1,000 g.
When this resin composition was applied to a silicon wafer and dried in accordance with the above-mentioned method, the film thickness uniformity was 3.8%.

Example 8
A negative photosensitive resin composition was prepared in the same manner as in Example 3, except that the amount of 3-methoxy-N,N-dimethylpropionamide used as the amide compound (B) was changed to 10,000 g.
When this composition was applied to a silicon wafer and dried in accordance with the above-mentioned method, the film thickness uniformity was 2.1%.

<Example 9>
A negative type photosensitive resin composition was prepared in the same manner as in Example 3, except that 100 g of 3-butoxy-N,N-dimethylpropionamide was used instead of 3-methoxy-N,N-dimethylpropionamide as the amide compound (B) and 100 g of N-methyl-2-pyrrolidone was added as the solvent.
When this resin composition was applied to a silicon wafer and dried according to the above-mentioned method, the film thickness uniformity was 7.2%. Furthermore, when the resin composition was applied to a silicon wafer and dried according to the above-mentioned method, and after exposure and development, the exposed fine lines were 14 μm or more and had good adhesion, and the adhesion was "good".

<Comparative Example 1>
(A) 50 g of the polymer (1) as the resin and 50 g of the polymer (2) were dissolved in 200 g of N-methyl-2-pyrrolidone to prepare a resin composition.
When this resin composition was applied to a silicon wafer and dried in accordance with the above-mentioned method, the film thickness uniformity was 8.2%.

<Comparative Example 2>
A negative photosensitive resin composition was prepared by adding (D) 6 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime as a photosensitizer and (C) 1 g of N-[3-(triethoxysilyl)propyl]phthalamic acid as a silica compound to the resin composition of Comparative Example 1.
When this resin composition was applied to a silicon wafer and dried according to the above-mentioned method, the film thickness uniformity was 8.1%. Furthermore, after the resin composition was applied to a silicon wafer according to the above-mentioned method, dried, exposed to light, and developed, the exposed thin lines that had been in contact were 20 μm or more, and the adhesion was "poor".

The above results are summarized in the table below.

In the above table, an upward arrow indicates that the type and amount of the blended ingredient in that column are the same as those in the column above.
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 that are useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (14)

(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,
The resin (A) is a polymer having a structure represented by the following general formula (A1),
The resin composition , wherein the compound (B) is one or two selected from the group consisting of 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide .
In the formula, R ₁ is an alkyl group having 1 to 5 carbon atoms;
R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have an ether bond, provided that R ₂ and R ₃ may be the same or different and may be bonded to each other to form a ring structure.
In the general formula (A1), _X1 is a tetravalent organic group;
_Y1 is a divalent organic group;
R ₄ and R ₅ each independently represent 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 heteroatom, an aromatic group having 6 to 30 carbon atoms, or a monovalent organic group capable of radical polymerization;
At least one of _R4 and _R5 is a monovalent organic group capable of radical polymerization. The resin composition according to claim 1, wherein the (A) resin is a polymer having a weight average molecular weight of 5,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography. The resin composition according to claim 1 or 2 , wherein the amide compound (B) is 3-methoxy-N,N-dimethylpropionamide. The resin composition according to claim 1 or 2, wherein the amide compound (B) is 3-butoxy-N,N-dimethylpropionamide. The resin composition according to claim 4, wherein the content of the amide compound (B) is 1 to 1,000 parts by mass per 100 parts by mass of the resin (A). (C) The following general formula (C1):
The resin composition according to any one of claims 1 to 5, further comprising a silane compound represented by the following formula (C1): {In formula (C1), _X4 and _X5 are each independently a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2, and _Y4 is a monovalent organic group having 1 to 20 carbon atoms.} X ₁ in the general formula (A1) is the following formula:
The resin composition according to any one of claims 1 to 6, wherein the tetravalent group is selected from those represented by each of the following formulas: In the general formula (A1), Y ₁ is represented by the following formula:
The resin composition according to any one of claims 1 to 7, wherein each 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 ). X ₁ in the general formula (A1) is the following formula:
is a tetravalent group represented by
Y ₁ is a group represented by the following formula:
The resin composition according to any one of claims 1 to 8, wherein the divalent group is represented by: (D) further containing a photosensitizer,
The resin composition according to any one of claims 1 to 3, wherein the (D) photosensitizer contains an oxime. The resin composition according to claim 10, wherein the amount of the photosensitizer (D) is 0.1 to 20 parts by mass per 100 parts by mass of the resin (A). Further comprising a solvent,
The resin composition according to any one of claims 1 to 11, wherein the solvent comprises at least one selected from N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone. The following steps:
(1) a coating step of coating a substrate with the resin composition according to any one of claims 1 to 12 to form a resin layer on the substrate;
(2) an exposure step of exposing the resin layer to light;
(3) a development step of developing the exposed resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the steps of: (a) subjecting the relief pattern to a heat treatment to form a cured relief pattern; and (b) heating the relief pattern in the order described above. A semiconductor device having a cured relief pattern obtained by the manufacturing method described in claim 13.