JP7809168B2 - Negative photosensitive resin composition, cured film and compound - Google Patents

Description

The present invention relates to a negative-type photosensitive resin composition used, for example, in forming relief patterns for insulating materials for electronic components, passivation films, buffer coat films, interlayer insulating films, and the like in semiconductor devices, as well as to a cured film and compound using the same.

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

In addition to photosensitive polyimides, polybenzoxazole (hereinafter also referred to as "PBO") is known as a resin used for similar purposes, as it becomes a heat-resistant resin after curing. Patent Document 1, for example, discloses a method in which a PBO precursor resin and a photoacid generator such as a photosensitive diazoquinone compound are mixed in a solvent such as gamma-butyrolactone (hereinafter referred to as GBL) to create a varnish of the PBO precursor composition, which is then used as a positive-tone photosensitive resin composition.

Patent Document 2 discloses a method of adding a phenolic compound to a positive-tone photosensitive resin composition of a PBO precursor composition to improve its solubility in alkaline aqueous developer and shorten the development time. Patent Document 3 also discloses a similar shortening of development time achieved by adding an N-hydroxyimide compound.

Japanese Unexamined Patent Publication No. 63-096162 Japanese Patent Application Publication No. 9-302221 Japanese Patent Application Laid-Open No. 2009-3202

On the other hand, in the case of negative photosensitive resin compositions using polyimide precursor resins or the like and developed with organic solvents, there has been little research into shortening the development time.
Therefore, an object of the present invention is to provide a negative-tone photosensitive resin composition that can be developed in an organic solvent and has excellent lithography performance with a short development time, a cured film in which a pattern is formed using the negative-tone photosensitive resin composition, and a compound.

The inventors discovered that by incorporating a specific compound into a photosensitive resin composition, a negative-tone photosensitive resin composition with excellent lithography performance can be obtained in a short development time, leading to the completion of the present invention. Specifically, the present invention is as follows:

[1]
The following ingredients:
(A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which is a polyimide precursor;
(B) Chemical formula (b1):
(wherein R1 represents a hydrogen atom or a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 10), and 0.01 to 10 parts by mass of at least one compound selected from n=1 to 10; and
(C) a photosensitizer: 0.5 to 30 parts by mass.
[2]
The resin (A) is a resin represented by the following general formula (1):
In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a group represented by the following general formula (2):
(wherein R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms.)}; or
The following general formula (3):
(In the formula, X2 is a trivalent organic group having 6 to 15 carbon atoms, Y2 is a divalent organic group having 6 to 35 carbon atoms and may have the same structure or multiple structures, R6 is an organic group having 3 to 20 carbon atoms and having at least one radically polymerizable unsaturated bond group, and n2 is an integer of 1 to 1,000.)
and a polyamide having a structure represented by the following formula (1):
[3]
(B) The negative photosensitive resin composition according to [1] or [2], wherein R1 in the compound represented by chemical formula (b1) is a monovalent organic group of an alkyl group having 1 to 12 carbon atoms.
[4]
The negative photosensitive resin composition according to any one of [1] to [3], comprising 0.05 to 5 parts by mass of the compound (B) represented by chemical formula (b1) based on 100 parts by mass of the resin (A).
[5]
The negative photosensitive resin composition according to any one of [1] to [4], further comprising a solvent (D), wherein the solvent (D) comprises at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.
[6]
The negative photosensitive resin composition according to [5], wherein the solvent (D) contains an alcohol compound having 1 to 12 carbon atoms.
[7]
(1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of [1] to [6] onto the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A cured film obtained by subjecting the relief pattern to a heat treatment to form a cured relief pattern.
[8]
(B) Chemical formula (b1):
(wherein R1 represents a hydrogen atom or a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 10).
[9]
The compound according to [8], wherein in the chemical formula (b1), R1 is one selected from the group consisting of a methyl group, an ethyl group, and an isopropyl group.
[10]
The compound according to [8] or [9], wherein in the chemical formula (b1), n=2 to 5.
[11]
A composition comprising all of the compounds represented by the chemical formula (b1) according to any one of [8] to [10], wherein n=2 to 5.

According to the present invention, by incorporating a specific compound into a photosensitive resin composition, it is possible to obtain a negative-tone photosensitive resin composition with excellent lithography performance in a short development time, and further to provide a cured film and compound in which a pattern is formed using this negative-tone photosensitive resin composition.

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

<Photosensitive resin composition>
The negative-type photosensitive resin composition of the present invention is characterized by comprising the following components: (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which is a polyimide precursor; (B) 0.01 to 10 parts by mass of at least one compound represented by chemical formula (b1) where n = 1 to 10; and (C) 0.5 to 30 parts by mass of a photosensitizer.
(wherein R1's each independently represent a hydrogen atom or a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 10) are essential components.

Resin (A) The resin (A) used in the present invention will now be described. The resin (A) of the present invention is primarily composed of at least one resin selected from the group consisting of polyimide precursors, such as polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide. Here, "primary component" means that the resin contains 60% by mass or more of the total resin, preferably 80% by mass or more. Furthermore, other resins may be contained as necessary.

From the viewpoint of heat resistance and mechanical properties after heat treatment, the weight-average molecular weight of these resins, as calculated using polystyrene standards by gel permeation chromatography, is preferably 1,000 or more, and more preferably 5,000 or more. The upper limit is preferably 100,000 or less, and when used as a photosensitive resin composition, from the viewpoint of solubility in the developer, it is more preferably 50,000 or less.

In the present invention, the (A) resin is preferably a photosensitive resin in order to form a relief pattern. The photosensitive resin is used together with the (C) photosensitizer described below to form a photosensitive resin composition, and is a resin that will dissolve or remain undissolved in the subsequent development process.

As photosensitive resins, polyimide precursors such as polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide are preferred, as the resins obtained after heat treatment have excellent heat resistance and mechanical properties. Furthermore, these photosensitive resins can be selected according to the desired application, such as whether to prepare a negative-tone photosensitive resin composition together with the (C) photosensitizer described below.

[Polyimide precursor]
In the photosensitive resin composition of the present invention, one example of the most preferable (A) resin from the viewpoint of heat resistance and photosensitive properties is a resin represented by the following general formula (1):
In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a group represented by the following general formula (2):
(wherein R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms.)
The polyimide precursor is a polyimide precursor having a structure represented by the following formula: The polyimide precursor is converted into a polyimide by heating (for example, at 200°C or higher) for cyclization. The polyimide precursor is suitable for use in a negative-type photosensitive resin composition.

In the above general formula (1), 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 an aromatic group in which the -COOR1 group, the -COOR2 group, and the -CONH- group are in the ortho position relative to each other, or an alicyclic aliphatic group. The tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, and more preferably a group represented by the following formula (14):
Examples of suitable X1 structures include, but are not limited to, those shown below. The structure of X1 may be one type or a combination of two or more types. The X1 group having the structure shown by the above formula (14) is particularly preferred in that it achieves both heat resistance and photosensitive properties.

In the general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, in order to achieve both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (15):
and a structure represented by the following formula (16):
{In the formula, R23 and R24 each independently represent 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 ).}
Examples of the structure represented by the formula (15) and (16) include, but are not limited to, the structure represented by the formula (15). The structure represented by the formula (16) and (17) is particularly preferred in that it provides both heat resistance and photosensitive properties.

With respect to R1 and R2, R3 in the above general formula (2) is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitivity characteristics. Furthermore, m1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitivity characteristics.

When a polyimide precursor is used as the (A) resin, methods for imparting photosensitivity to a photosensitive resin composition include ester bond and ionic bond methods. The former is a method in which a photopolymerizable group, i.e., a compound having an olefinic double bond, is introduced into the side chain of the polyimide precursor via an ester bond. The latter is a method in which a carboxyl group of the polyimide precursor is bonded to the amino group of a (meth)acrylic compound having an amino group via an ionic bond to impart a photopolymerizable group.

The ester-bonded polyimide precursor is obtained by first reacting a tetracarboxylic acid dianhydride containing the aforementioned tetravalent organic group X1 with an alcohol having a photopolymerizable unsaturated double bond and, optionally, a saturated aliphatic alcohol having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester), and then subjecting this to amide polycondensation with a diamine containing the aforementioned divalent organic group Y1.

(Preparation of Acid/Ester Form)
In the present invention, examples of tetracarboxylic acid dianhydrides containing a tetravalent organic group X1 that are suitable for use in preparing an ester-bonded polyimide precursor include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic acid dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. These may be used alone or in combination of two or more.

In the present invention, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare an ester-bond type polyimide precursor 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, 2-hydroxy Examples include 1-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 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 above alcohols can also be partially mixed with saturated aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

By dissolving and mixing the above-mentioned tetracarboxylic acid dianhydride suitable for the present invention and the above-mentioned alcohol in an appropriate reaction solvent in the presence of a basic catalyst such as pyridine 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 that completely dissolves the acid/ester and the polyimide precursor, which is the amide polycondensation product of this and a diamine component. Examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone.

Other reaction solvents include ketones, esters, lactones, ethers, and halogenated hydrocarbons, and hydrocarbons include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These may be used alone or in combination as needed.

(Preparation of Polyimide Precursor)
To the above acid/ester compound (typically a solution in the above reaction solvent) is added and mixed under ice cooling with an appropriate dehydration condensation agent, such as dicyclocarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, to convert the acid/ester compound into a polyacid anhydride, and then a diamine containing a divalent organic group Y1 preferably used in the present invention, dissolved or dispersed in a separate solvent, is added dropwise to the resulting mixture to carry out amide polycondensation, thereby obtaining the target polyimide precursor.

Diamines containing a divalent organic group Y1 that are suitable for use in the present invention include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-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]propane Examples of suitable benzene rings include, but are not limited to, 1,4-bis(3-aminopropyldimethylsilyl)benzene, 1,4-bis(3-phenyloxyphenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and compounds in which some of the hydrogen atoms on the benzene ring have been substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 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.

In addition, in order to improve the adhesion between various substrates and the resin layer formed on a substrate by applying the photosensitive resin composition of the present invention to the substrate, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized when preparing the polyimide precursor.

After the amide polycondensation reaction is complete, any water-absorbing by-products of the dehydrating condensing agent present in the reaction solution are filtered off as needed. A poor solvent, such as water, aliphatic lower alcohol, or a mixture thereof, is then added to the resulting polymer component to precipitate the polymer component. The polymer is then purified by repeated redissolution and reprecipitation procedures, and the polymer is then vacuum dried to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with anion and/or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

On the other hand, the ionic bond-type polyimide precursor is typically obtained by reacting a tetracarboxylic dianhydride with a diamine. In this case, at least one of R1 and R2 in the general formula (11) above is a hydroxyl group.

The tetracarboxylic dianhydride is preferably a tetracarboxylic anhydride having the structure of formula (14) above, and the diamine is preferably a diamine having the structure of formula (15) or (16) above. By adding a (meth)acrylic compound having an amino group (described below) to the obtained polyamide precursor, photopolymerizable groups are imparted via ionic bonds between the carboxyl groups and the amino groups.

The molecular weight of the ester-bonded and ionic-bonded polyimide precursors, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in the developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[polyamide]
Another example of a preferable resin (A) in the photosensitive resin composition of the present invention is a resin represented by the following general formula (3):
(In the formula, X2 is a trivalent organic group having 6 to 15 carbon atoms, Y2 is a divalent organic group having 6 to 35 carbon atoms and may have the same structure or multiple structures, R6 is an organic group having 3 to 20 carbon atoms and having at least one radically polymerizable unsaturated bond group, and n2 is an integer of 1 to 1,000.)
The polyamide has a structure represented by the following formula: This polyamide is suitable for use in a negative-type photosensitive resin composition.

In the above general formula (3), the group represented by R6 is preferably a group represented by the following general formula (17):
(In the formula, R25 is an organic group having at least one radically polymerizable unsaturated bond group having 2 to 19 carbon atoms.)
It is preferable that the group is a group represented by the following formula:

In the above general formula (3), the trivalent organic group represented by X2 is preferably a trivalent organic group having 6 to 15 carbon atoms, for example, a trivalent organic group represented by the following formula (18):
and more preferably an aromatic group obtained by removing the carboxyl group and the amino group from an amino-substituted isophthalic acid structure.

In the above general formula (3), the divalent organic group represented by Y2 is preferably an organic group having 6 to 35 carbon atoms, and more preferably a cyclic organic group having 1 to 4 aromatic or aliphatic rings which may be substituted, or an aliphatic group or siloxane group which does not have a cyclic structure. Examples of the divalent organic group represented by Y2 include those represented by the following general formula (15) and the following general formulas (19) and (20):
(In the formula, R26 and R27 are each independently one group selected from _the group _consisting of a hydroxyl group, a methyl group ( _-CH3 ), an ethyl group ( _-C2H5 ), a propyl _group ( _-C3H7 ), and a butyl group ( _-C4H9 ), and the propyl group and the butyl group include various isomers.)
{wherein m4 is an integer of 0 to 8, m5 and m6 are each independently an integer of 0 to 3, m7 and m8 are each independently an integer of 0 to 10, and R28 and R29 are a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a propyl group (—C ₃ H ₇ ), a butyl group (—C ₄ H ₉ ), or an isomer thereof.}

The aliphatic group or siloxane group having no cyclic structure may be a group represented by the following general formula (21):
{In the formula, m9 is an integer of 2 to 12, m10 is an integer of 1 to 3, m11 is an integer of 1 to 20, and R30, R31, R32, and R33 each independently represent an alkyl group having 1 to 3 carbon atoms or an optionally substituted phenyl group.} is a preferred example.

The polyamide resin of the present invention can be synthesized, for example, as follows.
(Synthesis of phthalic acid compound-capped product)
First, 1 mole of a compound having a trivalent aromatic group X2, such as at least one compound selected from the group consisting of phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group (hereinafter referred to as a "phthalic acid compound"), is reacted with 1 mole of a compound that reacts with an amino group to synthesize a compound in which the amino group of the phthalic acid compound is modified and capped with a group containing a radically polymerizable unsaturated bond (described below) (hereinafter referred to as a "capped phthalic acid compound"). These compounds may be used alone or in combination.

By capping a phthalic acid compound with a group containing the above-mentioned radically polymerizable unsaturated bond, it is possible to impart negative photosensitivity (photocurability) to the polyamide resin.

The group containing a radically polymerizable unsaturated bond is preferably an organic group containing a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and groups containing a methacryloyl group or an acryloyl group are particularly preferred.

The above-mentioned phthalic acid compound-capped product can be obtained by reacting the amino group of the phthalic acid compound with an acid chloride, isocyanate, epoxy compound, or the like having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms.

Suitable acid chlorides include (meth)acryloyl chloride, 2-[(meth)acryloyloxy]acetyl chloride, 3-[(meth)acryloyloxy]propionyl chloride, 2-[(meth)acryloyloxy]ethyl chloroformate, and 3-[(meth)acryloyloxypropyl]chloroformate. Suitable isocyanates include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, and 2-[2-(meth)acryloyloxyethoxy]ethyl isocyanate. Suitable epoxy compounds include glycidyl (meth)acrylate. These may be used alone or in combination, but it is particularly preferred to use methacryloyl chloride and/or 2-(methacryloyloxy)ethyl isocyanate.

Furthermore, among these phthalic acid compound-blocked products, those in which the phthalic acid compound is 5-aminoisophthalic acid are preferred, as they have excellent photosensitive properties and can produce polyamides with excellent film properties after heat curing.

The above-mentioned sealing reaction can be carried out by stirring, dissolving, and mixing the phthalic acid compound and sealing agent in a solvent in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate.

Preferably, the reaction solvent will completely dissolve the product, the phthalic acid compound-capped product, and examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone.

Other reaction solvents include ketones, esters, lactones, ethers, and halogenated hydrocarbons, and hydrocarbons include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These solvents can be used alone or in combination as needed.

Depending on the type of capping agent, such as acid chloride, hydrogen chloride may be produced as a by-product during the capping reaction. In this case, in order to prevent contamination of subsequent processes, it is preferable to purify the product appropriately, such as by re-precipitating it in water, rinsing it with water, and drying it, or by passing it through a column filled with ion exchange resin to remove and reduce ionic components.

(Synthesis of Polyamide)
The polyamide of the present invention can be obtained by mixing the above-mentioned phthalic acid compound-blocked product and a diamine compound having a divalent organic group Y2 in a suitable solvent in the presence of a basic catalyst such as pyridine or triethylamine, and then carrying out amide polycondensation.

Examples of amide polycondensation methods include converting a phthalic acid compound-terminated product into a symmetrical polyanhydride using a dehydrating condensing agent and then mixing it with a diamine compound; converting a phthalic acid compound-terminated product into an acid chloride by a known method and then mixing it with a diamine compound; and reacting a dicarboxylic acid component with an active esterifying agent in the presence of a dehydrating condensing agent to form an active ester and then mixing it with a diamine compound.

Preferred examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

Chlorinating agents include thionyl chloride.

Activated esterifying agents include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2-cyanoethyl acetate, and 2-hydroxyimino-2-cyanoacetic acid amide.

The diamine compound having the organic group Y2 is preferably at least one diamine compound selected from the group consisting of aromatic diamine compounds, aromatic bisaminophenol compounds, alicyclic diamine compounds, linear aliphatic diamine compounds, and siloxane diamine compounds, and multiple compounds can be used in combination if desired.

Aromatic diamine compounds 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, 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- Examples of such diamine compounds include 2,2-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and diamine compounds in which some of the hydrogen atoms on the benzene rings of these compounds have been substituted with one or more groups selected from the group consisting of methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, and halogen atoms.

Examples of diamine compounds in which the hydrogen atoms on the benzene ring have been substituted 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, and 3,3'-dichloro-4,4'-diaminobiphenyl.

Aromatic bisaminophenol compounds include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl 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-(3-hydroxy-4-aminophenyl)hexafluoropropane, bis-(3-hydroxy-4-aminophenyl)hexafluoropropane, (aminophenyl)methane, 2,2-bis-(3-hydroxy-4-aminophenyl)propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene)-bis(2-aminophenol), etc.

Alicyclic diamine compounds include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 1,5-diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2,5-diethylcyclohexane, and 1,3-bis(aminomethyl)cyclohexyl. Examples include cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propylamine, menthene diamine, isophorone diamine, norbornane diamine, 1-cycloheptene-3,7-diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-bis(3-aminopropyl)piperazine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5,5]-undecane.

Straight-chain aliphatic diamine compounds include hydrocarbon-type diamines such as 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane, and alkylene oxide-type diamines such as 2-(2-aminoethoxy)ethylamine, 2,2'-(ethylenedioxy)diethylamine, and bis[2-(2-aminoethoxy)ethyl]ether.

Examples of siloxane diamine compounds include dimethyl (poly)siloxane diamine, such as PAM-E, KF-8010, and X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd.

Preferred reaction solvents are those that completely dissolve the resulting polymer, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone.

In some cases, ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may also be used as reaction solvents. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene.

After the amide polycondensation reaction is complete, any precipitates derived from the dehydration condensation agent that have precipitated in the reaction solution are filtered off as needed. Next, a poor solvent for polyamide, such as water, a lower aliphatic alcohol, or a mixture thereof, is added to the reaction solution to precipitate the polyamide. The precipitated polyamide is then purified by redissolving it in a solvent and repeating the reprecipitation process, followed by vacuum drying to isolate the desired polyamide. To further improve the degree of purification, the polyamide solution may be passed through a column packed with ion exchange resin to remove ionic impurities.

The polystyrene-equivalent weight-average molecular weight of the polyamide, as determined by gel permeation chromatography (hereinafter referred to as "GPC"), is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. A polystyrene-equivalent weight-average molecular weight of 7,000 or more ensures the basic physical properties of the cured relief pattern. Furthermore, a polystyrene-equivalent weight-average molecular weight of 70,000 or less ensures development solubility when forming the relief pattern.

Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. The weight-average molecular weight value can be determined from a calibration curve created using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from Showa Denko's organic solvent-based standard sample, STANDARD SM-105.

(B) Compound represented by chemical formula (b1)
(wherein R1 represents a hydrogen atom or a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 10), and at least one compound selected from n=1 to 10.

The compound (B) represented by chemical formula (b1) used in the present invention will now be described. By using the compound (B) represented by chemical formula (b1), a coating film formed from a negative-tone photosensitive resin composition can be rapidly dissolved in an organic solvent developer, and an excellent relief pattern can be formed. Although the mechanism is unclear, the compound (B) represented by chemical formula (b1) is thought to have high compatibility with the resin because it has a structure similar to that of general formula (2), 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, which are used in the resin of the negative-tone photosensitive resin composition. It is therefore speculated that the compound (B) represented by chemical formula (b1) is dispersed between the resin and the resin. Therefore, the organic solvent developer easily penetrates into the coating film formed from the negative-tone photosensitive resin composition, resulting in rapid dissolution and the formation of an excellent relief pattern. Furthermore, when the compound (B) represented by chemical formula (b1) is n≧2 or is a mixture of multiple n numbers, the bulkier compound (B) represented by chemical formula (b1) is inserted between the resins, which is presumably further increasing the solubility of the organic solvent in the developer.
(B) In the compound represented by chemical formula (b1), n is preferably 2 to 5. In addition, the negative photosensitive resin composition may contain any of the compounds represented by chemical formula (b1) where n is 2 to 5, or may contain all of the compounds represented by chemical formula (b1) where n is 2 to 5.

In addition, (B) compound represented by chemical formula (b1) has the effect of promoting photocuring, and combined with the effect that (B) compound represented by chemical formula (b1) easily enters between resins, it is presumed that this promotes photocuring between resins, improving adhesion and resolution during development in the lithography process.

(B) Specific examples of compounds represented by chemical formula (b1) include 4-hydroxybutyric acid, methyl 4-hydroxybutyrate, ethyl 4-hydroxybutyrate, propyl 4-hydroxybutyrate, isopropyl 4-hydroxybutyrate, butyl 4-hydroxybutyrate, pentyl 4-hydroxybutyrate, hexyl 4-hydroxybutyrate, heptyl 4-hydroxybutyrate, octyl 4-hydroxybutyrate, nonyl 4-hydroxybutyrate, decyl 4-hydroxybutyrate, and derivatives thereof.

Furthermore, when water or an alkyl alcohol and γ-butyrolactone are subjected to a ring-opening reaction in the presence of an acid catalyst, a compound represented by (B) chemical formula (b1) where n≧2 is obtained.
Examples of alkyl alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol. From the viewpoint of compatibility with the resin, however, methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol are preferred.
Examples of the acid catalyst include hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, benzenesulfonic acid, para-toluenesulfonic acid, oxalic acid, and malonic acid, and the higher the acidity of the acid catalyst, the more desirable it is from the viewpoint of the reaction rate.

The blending amount of (B) compound represented by chemical formula (b1) is 0.01 to 10 parts by mass, and preferably 0.05 to 5 parts by mass, per 100 parts by mass of (A) resin. When the blending amount is 0.01 part by mass or more, development time is shortened, while when the blending amount is 10 parts by mass or less, excellent resolution is achieved.

(C) Photosensitizer The (C) photosensitizer used in the present invention will be explained.
Examples of photosensitizers include benzophenone derivatives such as benzophenone, o-benzoylmethylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; Preferred examples of the oxime include oximes such as 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; and aromatic biimidazoles, but are not limited to these. These may be used alone or in combination of two or more.

Among the above photosensitizers, those represented by the following general formula (29):
{In formula (29), Z represents a sulfur or oxygen atom, R12a represents a methyl group, a phenyl group, or a divalent organic group, and R13a to R15a each independently represent a hydrogen atom or a monovalent organic group.}
Among them, oxime compounds represented by the following formula (63):
, formula (64):
, formula (65):
, or formula (66):
The compound represented by formula (63) is commercially available as TR-PBG-305 manufactured by Changzhou New Power Electronic Materials Co., Ltd., the compound represented by formula (64) is commercially available as TR-PBG-3057 manufactured by Changzhou New Power Electronic Materials Co., Ltd., and the compound represented by formula (65) is commercially available as Irgacure OXE-01 manufactured by BASF.

The amount of (C) photosensitizer in the resin composition is 0.5 to 30 parts by mass per 100 parts by mass of (A) resin. It is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass. A blending amount of 0.5 parts by mass or more results in excellent relief pattern resolution, while a blending amount of 30 parts by mass or less results in little residue at the pattern openings.

(D) Solvent The photosensitive resin composition of the present invention is used as a varnish-like resin composition prepared by dissolving the optional components in a solvent. From the viewpoint of solubility in the resin (A), a polar organic solvent is preferably used as the solvent. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, γ-valerolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone. These solvents can be used alone or in combination of two or more.
In particular, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide are presumed to have moderate solubility in both (A) the resin and B) the compound represented by chemical formula (b1), and are excellent at improving the solubility of the coating film in the developer.

The above solvent can be used in an amount ranging from 30 to 1,500 parts by weight, preferably from 100 to 1,000 parts by weight, per 100 parts by weight of resin (A), depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

Furthermore, from the viewpoint of improving the storage stability of the photosensitive resin composition, solvents containing alcohols are preferred, and those containing an alcohol having 1 to 12 carbon atoms are more preferred. Suitable alcohols are typically those that have an alcoholic hydroxyl group in the molecule and 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-hydroxyisobutyrate esters; and dialcohols such as ethylene glycol and propylene glycol. Of these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, with ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether being particularly preferred.

When the solvent contains an alcohol that does not have an olefinic double bond, the content of the alcohol that does not have an olefinic double bond in the total solvent is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass. When the content of the alcohol that does not have an olefinic double bond is 5% by mass or more, the storage stability of the resin composition is improved, and when it is 50% by mass or less, the solubility of the (A) resin is improved.

(E) Photopolymerizable Compound The photopolymerizable compound (E) used in the present invention will be explained. The photopolymerizable compound is a monomer having a photopolymerizable unsaturated bond, and such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, and examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates of 1,4-butanediol, and and dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds can be mentioned.

When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass per 100 parts by mass of the (A) resin. A blending amount of 1 part by mass or more improves the curing properties of the film in exposed areas and provides excellent resolution, while a blending amount of 50 parts by mass or less provides excellent in-plane uniformity of the coating film.

(F) Organotitanium Compound The resin composition of the present invention may contain (F) an organotitanium compound. By containing (F) an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 250°C or less.

(F) Examples of organotitanium compounds that can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of the organotitanium compound (F) are shown below in I) to VII):
I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide the resin composition with good storage stability and produce good patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc.

III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.

VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

Of these, it is preferable that the (F) organic titanium compound be at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, as this provides better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

When (F) an organotitanium compound is added, the amount added is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of (A) resin. When the amount added is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is achieved.

(G) Other Components The resin composition of the present invention may further contain components other than the above components (A) to (F).

The resin composition of the present invention may contain a crosslinking agent. The crosslinking agent can be one that can crosslink the (A) resin when the resin composition of the present invention is heat-cured, or one that can itself form a crosslinked network. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the resin composition.

Examples of crosslinking agents include those with one thermally crosslinkable group such as ML-26X, ML-24X, ML-236TMP, 4-methylol3M6C, ML-MC, and ML-TBC (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and P-a-type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), and those with two such groups such as DM-BI25X-F, 46DMOC, 46DMOIPP, and 46DMOEP (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, and DML-P. C, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethylol-Bis-C, Dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PF P, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.),

B-a type benzoxazine, B-m type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.; those containing three compounds, such as TriML-P, TriML-35XL, TriML-TrisCR-HAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.); and those containing four compounds, such as TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.). Examples of 1-component compounds include TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, and TMOM-BP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280 and Nikalac MX-270 (all trade names, manufactured by Sanwa Chemical Co., Ltd.), and those containing six compounds include HML-TPPHBA and HML-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MW-390, and Nikalac MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

Among these, those containing at least two thermally crosslinkable groups are preferred in the present invention, and particularly preferred are 46DMOC, 46DMOEP (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), B-a-type benzoxazine, B-m-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.) Examples of suitable phenols include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, TriML-P, TriML-35XL (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (all trade names, manufactured by Sanwa Chemical Co., Ltd.), HML-TPPHBA, HML-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and the like. More preferred examples include Nikalac MX-290, Nikalac MX-280, and Nikalac MX-270 (all trade names, manufactured by Sanwa Chemical Co., Ltd.), Ba-type benzoxazine and B-m-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), Nikalac MW-390, and Nikalac MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), etc.

When considering the balance of performance properties other than heat resistance and chemical resistance, if the resin composition contains a crosslinking agent, the amount blended is preferably 0.5 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the (A) resin. When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when the blending amount is 20 parts by mass or less, excellent storage stability is achieved.

The resin composition of the present invention can optionally contain nitrogen-containing heterocyclic compounds such as azole compounds and purine derivatives to suppress discoloration on copper. Examples of azole compounds 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-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and the like. 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. Particularly preferred is 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.

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminopurine, These include aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

When the resin composition contains the above-mentioned azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass per 100 parts by mass of the (A) resin, and more preferably 0.5 to 5 parts by mass from the viewpoint of the storage stability of the resin composition. When the blending amount of the azole compound per 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 the present invention is formed on copper or a copper alloy. On the other hand, when the blending amount is 20 parts by mass or less, the storage stability of the resin composition is excellent.

Particularly preferred are 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.

Hindered phenol compounds can also be optionally blended to suppress discoloration on the copper surface. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), and triethylene glycol-bis [3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-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-triazine-2,4,6-(1H,3H,5H)-trione,

1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

Examples include, but are not limited to, 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, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. 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 per 100 parts by mass of the (A) resin, and more preferably 0.5 to 10 parts by mass from the viewpoint of the degree of polymerization of the compound having an unsaturated bond. When the amount of the hindered phenol compound per 100 parts by mass of the (A) resin is 0.1 part by mass or more, discoloration and corrosion of the copper or copper alloy are prevented when the resin composition of the present invention is formed on copper or a copper alloy, for example. On the other hand, when the amount is 20 parts by mass or less, the degree of polymerization of the compound having an unsaturated bond is excellent.

A sensitizer can be optionally blended into the resin composition of the present invention. 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-dimethylaminocinnamylideneindaline. Non, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-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, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combinations of, for example, 2 to 5 types.

When the resin composition contains a sensitizer, the amount blended is preferably 0.1 to 25 parts by mass per 100 parts by mass of the (A) resin.

In addition, an adhesion promoter can be optionally blended to improve adhesion between the film formed using the resin composition of the present invention and the substrate. Examples of adhesion promoters include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, and benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl). Examples of suitable adhesives include silane coupling agents such as benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-(trialkoxysilyl)propyl succinic anhydride, and aluminum-based adhesion promoters such as 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 contains an adhesive aid, the amount of adhesive aid blended is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of resin (A).

In addition, a thermal polymerization inhibitor can be optionally added to improve the viscosity stability of the resin composition, especially when stored in a solvent-containing solution. Examples of thermal polymerization inhibitors that can be used 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.

When blended into a resin composition, the amount of thermal polymerization inhibitor blended is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of (A) resin.

<Method for producing cured relief pattern and semiconductor device>
The present invention also provides a method for producing a cured relief pattern, comprising the steps of: (1) applying the above-described photosensitive resin composition of the present invention onto a substrate to form a resin layer on the substrate; (2) exposing the resin layer to light; (3) developing the exposed resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern. Typical aspects of each step are described below.

(1) Step of forming a resin layer on a substrate by applying a photosensitive resin composition onto the substrate In this step, the photosensitive resin composition of the present invention is applied to a substrate, and then dried as necessary to form a resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray application using a spray coater, etc. can be used.

If necessary, the coating film made from the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or hot plate, and vacuum drying. Specifically, when air drying or heat drying is used, drying can be carried out at 20°C to 140°C for 1 minute to 1 hour. As described above, a resin layer can be formed on the substrate.

(2) Step of exposing resin layer In this step, the resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

After this, for purposes such as improving photosensitivity, post-exposure baking (PEB) and/or pre-development baking may be performed as needed using any combination of temperature and time. The baking conditions preferably range from 40 to 120°C for a temperature of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition of the present invention.

(3) Step of Developing the Exposed Resin Layer to Form a Relief Pattern In this step, either the exposed or unexposed portions of the exposed photosensitive resin layer are developed and removed. In the case of a negative-type photosensitive resin composition, the unexposed portions are developed and removed, while the exposed portions remain on the substrate as a relief pattern. Any of the conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment, can be used as the development method. Furthermore, after development, a post-development bake may be performed at any desired temperature and time combination, as needed, for purposes such as adjusting the shape of the relief pattern. The post-development bake conditions preferably range from 40 to 180°C for a temperature of 10 to 600 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition of the present invention.

The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of such a good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that is insoluble in an alkaline aqueous solution, good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone, while poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. 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 photosensitive resin composition. It is also possible to use two or more types of each solvent, for example, a combination of several types.

(4) Step of forming a hardened relief pattern by heat treatment of the relief pattern In this step, the relief pattern obtained by the above development is heated to convert it into a hardened relief pattern. Various methods can be selected for heat curing, such as using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be carried out, for example, at 180°C to 400°C for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may also be used.

<Semiconductor Device>
The present invention also provides a semiconductor device including a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention. The present invention also provides a semiconductor device including a substrate that is a semiconductor element and a cured relief pattern of resin formed on the substrate by the above-described method for producing a cured relief pattern. The present invention is also applicable to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-described method for producing a cured relief pattern as part of its process. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-described method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

In addition to its application to semiconductor devices such as those described above, the photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

The present invention will be described in detail below using 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 resin was measured by gel permeation chromatography (standard polystyrene equivalent). The column used for the measurement was a "Shodex 805M/806M series" column manufactured by Showa Denko K.K. The standard monodisperse polystyrene was "Shodex STANDARD SM-105" manufactured by Showa Denko K.K. The developing solvent was N-methyl-2-pyrrolidone, and the detector was "Shodex RI-930" manufactured by Showa Denko K.K.

(2) Adhesion after Development The photosensitive resin composition was spin-coated onto a 6-inch silicon wafer using a spin coater (D-SPIN636 model, manufactured by Dai-Nippon Screen Mfg. Co., Ltd., Japan) and dried on a hot plate at 100°C for 240 ^seconds to form a 10 μm-thick coating film. Using a test pattern reticle, this coating film was sequentially irradiated at specific wafer positions with an i-line stepper NSR1755i7B (manufactured by Nikon Corporation) at energy levels of 100 to 700 mJ/cm². The coating film formed on the wafer was then spray-developed using cyclopentanone in a developing machine (D-SPIN636 model, manufactured by Dai-Nippon Screen Mfg. Co., Ltd.) and rinsed with propylene glycol methyl ether acetate to obtain a photosensitive resin composition pattern. The patterned wafer was heat-treated in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg, Japan) at 300°C for 2 hours in a nitrogen atmosphere to obtain a polyimide pattern approximately 6 μm thick on the silicon wafer. The pattern shape and width of the patterned portion of each obtained pattern were observed under an optical microscope to determine the post-development adhesion at an exposure of 500 mJ/ ^cm2 .
A plurality of patterns of different sizes were formed by the above method by exposure through a reticle with a test pattern, and whether the independent cylindrical patterns remained on the substrate after development was observed and evaluated based on the following criteria.
◎: Residual pattern size is 10 μm or more. ○: Residual pattern size is 14 μm or more. △: Residual pattern size is 18 μm or more. ×: Residual pattern size is 22 μm or more.

(3) Resolution: As in (2) Adhesion after development, via hole patterns having openings of different areas were formed by the above method by exposure through a test pattern reticle. If the area of the resulting pattern opening was at least half the area of the corresponding pattern mask opening, it was considered resolved, and the length of the mask opening side corresponding to the resolved opening with the smallest area was taken as the resolution. The resolution was evaluated based on the following criteria:
◎: Patterns of 12 μm or less are resolved. ○: Patterns of 13 to 16 μm are resolved. △: Patterns of 17 to 20 μm are resolved. ×: Patterns of 21 μm or more are resolved.

<Production Example 1> (A) Synthesis of Polymer A-1 as Polyimide Precursor)
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and the mixture was stirred at room temperature. 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Next, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The resulting crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (Polymer A-1). The molecular weight of Polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 20,000.

<Production Example 2> (A) Synthesis of Polymer A-2 as Polyimide Precursor)
Polymer A-2 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The molecular weight of Polymer A-2 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 22,000.

<Production Example 3> (A) Synthesis of Polymer A-3 as Polyimide Precursor)
Polymer A-3 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 98.6 g of 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1. The molecular weight of Polymer A-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

<Production Example 4> (A) Synthesis of Polymer A-4 as Polyimide Precursor)
Polymer A-4 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 3, except that 109.1 g of pyromelotic dianhydride (PMDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 3. The molecular weight of Polymer A-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

<Production Example 5> (A) Synthesis of Polymer A-5 as Polyimide Precursor)
Polymer A-5 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 77.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 73.6 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

<Production Example 6> (A) Synthesis of Polymer A-6 as Polyimide Precursor)
Polymer A-6 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 3, except that 77.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 54.6 g of pyromelotic dianhydride (PMDA) were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 3. The molecular weight of Polymer A-6 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 23,000.

<Production Example 7> ((A) Synthesis of Polymer A-7 as Polyamide)
(Synthesis of phthalic acid compound-capped compound AIPA-MO)
A 5 L separable flask was charged with 543.5 g of 5-aminoisophthalic acid (hereinafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone, which were then mixed and stirred and heated to 50°C in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise to the flask using a dropping funnel, and the mixture was stirred at 50°C for approximately 2 hours.

After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) using low-molecular-weight gel permeation chromatography (hereinafter referred to as low-molecular-weight GPC), the reaction solution was poured into 15 liters of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered, washed appropriately with water, and then vacuum-dried at 40°C for 48 hours to obtain AIPA-MO, in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low-molecular-weight GPC purity of the resulting AIPA-MO was approximately 100%.

(Synthesis of Polymer A-7)
A 2-liter separable flask was charged with 100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL, mixed, and cooled to 5°C in an ice bath. A solution of 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise to the mixture over approximately 20 minutes under ice cooling. Subsequently, a solution of 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl (hereinafter referred to as BAPB) dissolved in 168 g of NMP was added dropwise over approximately 20 minutes. The mixture was stirred for 3 hours while maintaining the temperature below 5°C in an ice bath, and then the ice bath was removed and the mixture was stirred at room temperature for 5 hours. The precipitate that formed in the reaction mixture was removed by filtration, yielding a reaction solution.

A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The resulting crude polymer solution was added dropwise to 5 L of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer A-7). The molecular weight of Polymer A-7 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 34,700.

<Production Example 8> ((B) Synthesis of Compound B-1 as a Compound Represented by Chemical Formula (b1))
31.4 g (0.36 mol) of GBL and 67.3 g (1.46 mol) of ethanol were placed in a 100 ml single-neck flask and mixed. 0.1 g of para-toluenesulfonic acid monohydrate was added to the mixture, and the mixture was stirred at room temperature for 18 hours. The reaction product was confirmed by 1H NMR, and a reaction solution of compound B-1 containing 27.5 weight percent (27.2 g) of ethyl 4-hydroxybutyrate was obtained. The structure represented by chemical formula (b1) where n≧2 was not observed by 1H NMR.

<Production Example 9> ((B) Synthesis of Compound B-2 as a Compound Represented by Chemical Formula (b1))
A reaction was carried out in the same manner as in the above-described Production Example 8, except that 46.8 g (1.46 mol) of methanol was used instead of 46.8 g (1.46 mol) of ethanol in Production Example 8, to obtain a reaction solution of Compound B-2 containing 29.1 mass percent (22.8 g) of methyl 4-hydroxybutyrate. A structure represented by chemical formula (b1) where n≧2 was not observed by 1H NMR.

<Production Example 10> ((B) Synthesis of Compound B-3 as a Compound Represented by Chemical Formula (b1))
85.0 g (0.99 mol) of GBL and 5 g of Solmix AP-1 (manufactured by Nippon Alcohol Co., Ltd., a mixture of 85.5 mass % ethanol, 13.4 mass % isopropanol, and 1.1 mass % methanol) were placed in a 100 ml single-neck flask and mixed. 0.1 g of para-toluenesulfonic acid monohydrate was added to the mixture, and the mixture was stirred at room temperature for 24 hours. The reaction product was confirmed by 1H NMR, yielding a reaction solution of Compound B-3 containing 9.2 weight % (8.2 g) of the compound represented by chemical formula (b1). Mass fragments from LC-MS measurement confirmed that the compound was the compound represented by chemical formula (b1) where R1 is a methyl group, an ethyl group, or an isopropyl group, and n = 1 to 5.

<Production Example 11> ((B) Synthesis of Compound B-4 as a Compound Represented by Chemical Formula (b1))
85.0 g (0.99 mol) of GBL and 5 g of Solmix AP-1 (manufactured by Nippon Alcohol Co., Ltd., a mixture of 85.5 mass % ethanol, 13.4 mass % isopropanol, and 1.1 mass % methanol) were placed in a 100 mL single-neck flask and mixed. 0.1 g of para-toluenesulfonic acid monohydrate was added to the mixture, and the mixture was stirred at 40°C for 24 hours. The reaction product was confirmed by 1H NMR, yielding a reaction solution of Compound B-4 containing 12.3 weight % (11.1 g) of the compound represented by chemical formula (b1). Mass fragments from LC-MS measurement confirmed that the compound was a compound represented by chemical formula (b1) where R1 is a methyl group, an ethyl group, or an isopropyl group, and n = 4 to 10.

<Production Example 12> ((B) Synthesis of Compound B-5 as a Compound Represented by Chemical Formula (b1))
A reaction was carried out in the same manner as in the above-described Production Example 8, except that 26.3 g (1.46 mol) of water was used instead of 46.8 g (1.46 mol) of ethanol in Production Example 8, to obtain a reaction solution of compound B-5 containing 24.6 mass percent (14.2 g) of 4-hydroxybutyric acid. A structure represented by chemical formula (b1) where n≧2 was not observed by H NMR.

Example 1
Negative photosensitive resin compositions were prepared using Polymer A-1 by the following method, and the prepared photosensitive resin compositions were evaluated. 100 g of polymer A-1, a polyimide precursor, was dissolved in 100 g of GBL together with 7.3 g of a reaction solution containing B-1 (2 g of component B-1), 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 1), 1.5 g of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 10 g of N-phenyldiethanolamine, 4 g of methoxymethylated urea resin (MX-290), 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N-phenyl-3-aminopropyltrimethoxysilane, and 0.05 g of 2-nitroso-1-naphthol. The viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of the mixed solvent, to obtain a negative photosensitive resin composition.

The negative-tone photosensitive resin composition was evaluated according to the method described above, and the results are shown in Table 1.

Example 2
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-2, a polyimide precursor, was used instead of 100 g of Polymer A-1, a polyimide precursor, in Example 1, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-3, a polyimide precursor, was used instead of 100 g of Polymer A-1, a polyimide precursor, in Example 1, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1 (polyimide precursor) in Example 1 was replaced with 100 g of Polymer A-4 (polyimide precursor), and the compositions were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 5
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1 (polyimide precursor) in Example 1 was replaced with 100 g of Polymer A-5 (polyimide precursor), and the compositions were evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 6
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1 (polyimide precursor) in Example 1 was replaced with 100 g of Polymer A-6 (polyimide precursor), and the compositions were evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 7
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, the polyimide precursor in Example 1, was replaced with 100 g of Polymer A-7, a polyamide, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 8
The 7.3 g (2 g B-1 component) of the reaction liquid containing B-1 in Example 1 was changed to 6.9 g (2 g B-2 component) of the reaction liquid containing B-2, and resin compositions were prepared in the same manner as in Example 1, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Example 9
The 7.3 g reaction liquid containing B-1 (2 g of B-1 component) in Example 1 was changed to 21.7 g reaction liquid containing B-3 (2 g of B-3 component), and the amount of GBL to be dissolved was changed to 80 g, and resin compositions were prepared in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Example 10
The 7.3 g reaction solution containing B-1 (2 g of B-1 component) in Example 1 was changed to 16.3 g reaction solution containing B-4 (2 g of B-4 component), and the amount of GBL to be dissolved was changed to 90 g, and resin compositions were prepared in the same manner as in Example 1, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Example 11
Resin compositions were prepared in the same manner as in Example 1, except that 7.3 g of the reaction liquid containing B-1 (2 g of B-1 component) in Example 1 was changed to 8.1 g of the reaction liquid containing B-5 (2 g of B-5 component), and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 12
Resin compositions were prepared in the same manner as in Example 9, except that 100 g of Polymer A-1, a polyimide precursor, in Example 9 was changed to 50 g of Polymer A-1, a polyimide precursor, and 50 g of Polymer A-2, a polyimide precursor, and each was evaluated in the same manner as in Example 9. The evaluation results are shown in Table 1.

Example 13
Resin compositions were prepared in the same manner as in Example 9, except that 100 g of Polymer A-1, a polyimide precursor, in Example 9 was replaced with 50 g of Polymer A-3, a polyimide precursor, and 50 g of Polymer A-4, a polyimide precursor, and each composition was evaluated in the same manner as in Example 9. The evaluation results are shown in Table 1.

Example 14
Resin compositions were prepared in the same manner as in Example 9, except that 100 g of Polymer A-1 (a polyimide precursor) in Example 9 was replaced with 100 g of Polymer A-5 (a polyimide precursor), and the compositions were evaluated in the same manner as in Example 9. The evaluation results are shown in Table 1.

Example 15
Resin compositions were prepared in the same manner as in Example 9, except that 100 g of Polymer A-1, the polyimide precursor in Example 9, was replaced with 100 g of Polymer A-6, the polyimide precursor, and the compositions were evaluated in the same manner as in Example 9. The evaluation results are shown in Table 1.

Example 16
Resin compositions were prepared in the same manner as in Example 9, except that 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime, the photosensitizer (C) in Example 9, was changed to 4 g of 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime) (trade name: IRGACURE-OXE-01, manufactured by BASF, indicated as OXE-1 in Table 1), and the same evaluations as in Example 9 were carried out for each composition. The evaluation results are shown in Table 1.

Example 17
Resin compositions were prepared in the same manner as in Example 1, except that 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime, the photosensitizer (C) in Example 1, was changed to 4 g of 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime) (trade name: IRGACURE-OXE-01, manufactured by BASF, indicated as OXE-1 in Table 1), and the same evaluations as in Example 1 were carried out for each composition. The evaluation results are shown in Table 1.

Example 18
Resin compositions were prepared in the same manner as in Example 1, except that the 7.3 g of reaction liquid containing B-1 (2 g of B-1 component) in Example 1 was changed to 0.036 g of reaction liquid containing B-1 (0.01 g of B-1 component), and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 19
Resin compositions were prepared in the same manner as in Example 1, except that the 7.3 g of reaction liquid containing B-1 (2 g of B-1 component) in Example 1 was changed to 0.18 g of reaction liquid containing B-1 (0.05 g of B-1 component), and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 20
The 7.3 g (2 g B-1 component) reaction liquid containing B-1 in Example 1 was changed to 18.2 g (5 g B-1 component) reaction liquid containing B-1, and the amount of GBL was changed to 80 g, and resin compositions were prepared in the same manner as in Example 1, and each composition was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
Example 21
The 7.3 g of reaction liquid containing B-1 (2 g of B-1 component) in Example 1 was changed to 36.4 g of reaction liquid containing B-1 (10 g of B-1 component), and the amount of GBL was changed to 60 g, and resin compositions were prepared in the same manner as in Example 1, and each composition was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

<Comparative Example 1>
A negative-tone photosensitive resin composition was prepared using Polymer A-1 by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of Polymer A-1, a polyimide precursor, was dissolved in 100 g of GBL together with 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 1), 1.5 g of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 10 g of N-phenyldiethanolamine, 4 g of methoxymethylated urea resin (MX-290), 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N-phenyl-3-aminopropyltrimethoxysilane, and 0.05 g of 2-nitroso-1-naphthol. The viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of the mixed solvent, to obtain a negative photosensitive resin composition.
The negative photosensitive resin composition was evaluated according to the above-mentioned methods, and the results are shown in Table 1.

<Comparative Example 2>
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-2, a polyimide precursor, was used instead of 100 g of Polymer A-1, a polyimide precursor, in Comparative Example 1, and the compositions were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 3>
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, the polyimide precursor of Comparative Example 1, was replaced with 100 g of Polymer A-3, the polyimide precursor, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 4>
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-4, a polyimide precursor, was used instead of 100 g of Polymer A-1, a polyimide precursor, in Comparative Example 1, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 5
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, the polyimide precursor of Comparative Example 1, was replaced with 100 g of Polymer A-5, the polyimide precursor, and the compositions were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
<Comparative Example 6>

Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, the polyimide precursor in Comparative Example 1, was replaced with 100 g of Polymer A-6, the polyimide precursor, and the compositions were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 7
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, the polyimide precursor of Comparative Example 1, was replaced with 100 g of Polymer A-7, the polyimide precursor, and the compositions were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 8>
Resin compositions were prepared in the same manner as in Example 1, except that the 7.3 g of reaction liquid containing B-1 (2 g of B-1 component) in Example 1 was changed to 0.018 g of reaction liquid containing B-1 (0.005 g of B-1 component), and each composition was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

<Comparative Example 9>
The 7.3 g of reaction liquid containing B-1 (2 g of B-1 component) in Example 1 was changed to 54.5 g of reaction liquid containing B-1 (15 g of B-1 component), and the amount of GBL was changed to 50 g, and resin compositions were prepared in the same manner as in Example 1, and each composition was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

As is clear from Table 1, compared to the comparative examples that do not contain the compound (B) represented by chemical formula (b1), the examples that contain this compound exhibit shorter development times for the photosensitive resin compositions and better lithography performance.

The resin composition of the present invention can be suitably used, for example, as a surface protection film for semiconductor devices having copper patterns, multilayer wiring boards, etc., an interlayer insulating film, an insulating film for rewiring, a cover coat, or a solder resist film.

Claims (8)

(B) Chemical formula (b1):
(wherein R1 represents a methyl group or an ethyl group , and n is an integer of 2 to 10). The compound according to claim 1 , wherein in the chemical formula (b1), n=2 to 5. A composition comprising all compounds in which n=2 to 5 in the chemical formula (b1) according to claim 1 or 2 . A negative photosensitive resin composition comprising the compound according to claim 1 or 2 . The negative photosensitive resin composition according to claim 4 , further comprising a photosensitive material. (B) Chemical formula (b1):
(wherein R1 represents a hydrogen atom or a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and n is an integer from 1 to 10), a composition containing all compounds where n is 2 to 5. 7. The composition according to claim 6, wherein in the chemical formula (b1), R1 is an alkyl group having 1 to 12 carbon atoms. The composition according to claim 6 or 7, wherein in the chemical formula (b1), R1 is one selected from the group consisting of a methyl group, an ethyl group, and an isopropyl group.