Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device

Abstract

To provide a photosensitive resin composition that exhibits excellent adhesion to copper and ensures excellent adhesion between copper or a copper alloy and a cured film even after long-term low-temperature storage of a varnish.SOLUTION: The photosensitive resin composition of the present disclosure comprises: (A) at least one resin selected from the group consisting of a polyamide, a polyimide, and polyimide precursors which are polyamic acid, polyamic acid ester, and polyamic acid salt; (B) a photosensitizer; and (C) a nitrogen-containing compound having a structure represented by the following general formula (15) {where R1 is a monovalent organic group having 1-10 carbon atoms}.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a method for producing a cured relief pattern using the same, and a semiconductor device. [Background technology]

[0002] Polyimide resins have excellent heat resistance, electrical properties, and chemical resistance, and are therefore used as insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films, etc. Photosensitive polyimides, which are polyimide resins imparted with photosensitivity, are provided in the form of a varnish consisting of a polyimide precursor and a photosensitizer. Polyimide relief patterns can be formed by applying the varnish, exposing it to light, developing it, and subjecting it to a thermal imidization process involving curing. While relief pattern formation with non-photosensitive polyimides requires the application and removal of a resist material, such photosensitive polyimide precursors have the advantage of enabling significant process reductions.

[0003] In recent years, with the advancement of miniaturization of semiconductor devices, the wiring resistance of semiconductor devices has become non-negligible. Therefore, the gold or aluminum wiring that has been used until now has been replaced with copper or copper alloy wiring, which has lower resistance. However, conventional photosensitive resin compositions have had the problem of discoloration of copper or copper alloys because the compounds in the composition are prone to react with copper or copper alloys.

[0004] As a means for solving the above problems, a method has been disclosed in which tetrazole is added to a composition containing a polyimide precursor to suppress discoloration and corrosion that occurs in copper or copper alloys (see Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-99661 Summary of the Invention [Problem to be solved by the invention]

[0006] However, conventional compositions using nitrogen-containing compounds that have excellent copper adhesion have the problem that the adhesion between copper or copper alloy and the cured film decreases when stored at low temperatures for a long period of time.

[0007] An object of the present invention is to provide a photosensitive resin composition that has excellent adhesion to copper and also has excellent adhesion between copper or a copper alloy and a cured film even when the varnish is stored at low temperature for a long period of time; and to further provide a method for producing a cured relief pattern in which a pattern is formed using the photosensitive resin composition, and a semiconductor device. [Means for solving the problem]

[0008] The present inventors have found that by adding a nitrogen-containing compound having a specific structure, a photosensitive resin composition can be obtained which has excellent adhesion to copper and excellent adhesion between copper or a copper alloy and a cured film even when the varnish is stored at low temperature for a long period of time, and have completed the present invention. [1] (A) at least one resin selected from the group consisting of polyamides, polyimides, or polyimide precursors, such as polyamic acids, polyamic acid esters, and polyamic acid salts; (B) a photosensitizer, and (C) the following general formula (15): [ka] {In the formula, R1 is a monovalent organic group having 1 to 10 carbon atoms.} A nitrogen-containing compound having a structure represented by A photosensitive resin composition comprising: [2] In the above general formula (15), R1 is an aliphatic group having 1 to 10 carbon atoms, or R1 is a group represented by the following general formula (16): [ka] {In the formula, R2 is an aliphatic group having 1 to 10 carbon atoms, R3 is an aliphatic group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.} The photosensitive resin composition according to [1], wherein the group is represented by the formula: [3] The resin (A) is a resin represented by the following general formula (1): [ka] 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 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 10 carbon atoms, or a group represented by the following general formula (2): [ka] (wherein R3, R4, and R5 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10), or a monovalent organic group represented by the following general formula (3): [ka] (wherein R6, R7, and R8 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m2 represents an integer of 2 to 10)}, and The following general formula (4): [ka] {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, R 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 photosensitive resin composition according to [1] or [2], wherein the resin is at least one resin selected from the group consisting of polyamides having a structure represented by the following formula: [4] The photosensitive resin composition according to any one of [1] to [3], wherein in the general formula (15), R1 is a saturated aliphatic group having 1 to 5 carbon atoms. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of the nitrogen-containing compound (C) is 0.01 to 10 parts by mass relative to 100 parts by mass of the resin (A). [6] The photosensitive resin composition according to any one of [1] to [5], further comprising (D) a thermal crosslinking agent. [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) forming a hardened relief pattern by heat-treating the relief pattern; 1. A method for producing a cured relief pattern, comprising: [8] The method according to [7], wherein copper or a copper alloy is formed on the substrate. [9] A semiconductor device comprising a cured relief pattern formed from a cured product of the photosensitive resin composition according to any one of [1] to [6]. [Effects of the Invention]

[0009] According to the present invention, by adding a nitrogen-containing compound having a specific structure, a photosensitive resin composition can be obtained which has excellent adhesion to copper and excellent adhesion between copper or a copper alloy and a cured film even when the varnish is stored at low temperature for an extended period of time. Furthermore, the present invention can provide a method for producing a cured relief pattern in which a pattern is formed using the photosensitive resin composition, and a semiconductor device. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, exemplary embodiments for carrying out the present invention (hereinafter abbreviated as "embodiments") will be described in detail. Note that the present invention is not limited to the following embodiments, and can be practiced with various modifications within the scope of the gist. Furthermore, when a plurality of structures represented by the same symbol in a general formula are present in a molecule, they may be the same or different from each other.

[0011] <Photosensitive resin composition> The photosensitive resin composition according to the present embodiment is characterized by containing (A) at least one resin selected from the group consisting of polyamide, polyimide, or polyimide precursors, such as polyamic acid, polyamic acid ester, and polyamic acid salt; (B) a photosensitizer; and (C) a nitrogen-containing compound having a structure represented by the following general formula (15): [ka] {In the formula, R1 is a monovalent organic group having 1 to 10 carbon atoms.} This makes it possible to provide a photosensitive resin composition that has excellent adhesion to copper and that also has excellent adhesion between copper or copper alloy and a cured film even when the varnish is stored at low temperature for a long period of time. Each component constituting the photosensitive resin composition according to this embodiment will be specifically described below.

[0012] (A) Resin The resin (A) used in this embodiment will now be described. The resin (A) according to this embodiment is primarily composed of at least one resin selected from the group consisting of polyamides and polyimide precursors, such as polyamic acids, polyamic acid esters, and polyamic acid salts. Here, "primarily composed" means that the resin contains 60% by mass or more, and preferably 80% by mass or more, of the total resin. Furthermore, the resin (A) may contain other resins as needed.

[0013] From the viewpoints of heat resistance after heat treatment and mechanical properties, the weight-average molecular weight of these resins is preferably 1,000 or more, more preferably 5,000 or more, as calculated in terms of polystyrene by gel permeation chromatography. The upper limit is preferably 100,000 or less, and when used as a photosensitive resin composition, from the viewpoint of solubility in a developer, more preferably 50,000 or less.

[0014] Next, the resin (A) in this embodiment will be described in detail. [Polyimide precursor] An example of the resin (A) that can be used in the present embodiment is a resin represented by the following general formula (1): [ka] 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 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 10 carbon atoms, or a group represented by the following general formula (2): [ka] (wherein R3, R4, and R5 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10), or a monovalent organic group represented by the following general formula (3): [ka] (wherein R6, R7, and R8 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m2 represents an integer of 2 to 10)} The polyimide precursor has the following structure: The polymer has imide rings after heat treatment, which dramatically improves mechanical properties, heat resistance, and chemical resistance, resulting in a tough film.

[0015] 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 (6): [ka] Examples of suitable X1 structures include, but are not limited to, the following: In addition, the structure of X1 may be one type or a combination of two or more types. The X1 group having the structure represented by the above formula (6) is particularly preferred in that it achieves both heat resistance and photosensitive properties.

[0016] In the above 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 (7): [ka] and the structure represented by the following formula (8): [ka] {where, R 23 and R 24 each independently represents a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), or a butyl group (-C4H9). Examples include, but are not limited to, structures represented by the following formulae: Y1 may be one type or a combination of two or more types. Y1 groups having structures represented by the above formulae (7) and (8) are particularly preferred in that they provide both heat resistance and photosensitive properties.

[0017] Regarding R1 and R2, in the above general formula (1), R1 is preferably a saturated aliphatic group having 1 to 5 carbon atoms. In the above general formula (2), R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitive properties. 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 photosensitive properties. Regarding R1 and R2, a group represented by the above general formula (3) is preferred from the viewpoint of the coexistence of a polymerizable moiety and a nitrogen-containing moiety.

[0018] When a polyimide precursor is used as the (A) resin, methods for imparting photosensitivity to a photosensitive resin composition include an ester bond type and an ionic bond type. 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, while the latter is a method in which a carboxyl group of the polyimide precursor is bonded to an amino group of a (meth)acrylic compound having an amino group via an ionic bond to impart a photopolymerizable group.

[0019] The ester bond-type polyimide precursor is prepared by first reacting a tetracarboxylic acid dianhydride containing the above-mentioned tetravalent organic group X1 with an alcohol having a photopolymerizable unsaturated double bond and, optionally, a saturated aliphatic alcohol having 1 to 30 carbon atoms to prepare a partially esterified tetracarboxylic acid ester, and then polycondensing the tetracarboxylic acid ester with a diamine containing the above-mentioned divalent organic group Y1 to obtain a polyamic acid ester.

[0020] (Preparation of tetracarboxylic acid esters) In the present embodiment, examples of tetracarboxylic dianhydrides containing a tetravalent organic group X1 suitable for preparing an ester-bonded polyimide precursor include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. These may be used alone or in combination.

[0021] In the present embodiment, examples of alcohols having a photopolymerizable unsaturated double bond that are suitably used to prepare a polyamic acid ester 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 1-(2-hydroxypropyl)-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, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

[0022] The above alcohols can also be partially mixed with saturated aliphatic alcohols having 1 to 10 carbon atoms, such as 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.

[0023] The tetracarboxylic acid dianhydride suitable for the present embodiment and the alcohol are stirred, dissolved, and mixed in an appropriate reaction solvent at a temperature of 20 to 50°C for 4 to 10 hours in the presence of a basic catalyst such as pyridine, whereby the esterification reaction of the acid anhydride proceeds, and a desired tetracarboxylic acid ester can be obtained.

[0024] The reaction solvent is preferably one that can completely dissolve the tetracarboxylic acid ester and the polyamic acid ester, which is a polycondensation product of the tetracarboxylic acid ester and the diamine component, and examples thereof 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, xylene, etc. These may be used alone or in combination of two or more, as necessary.

[0025] (Preparation of Polyimide Precursor) A suitable 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, is added to and mixed with the tetracarboxylic acid ester (typically a solution in the reaction solvent) under ice cooling to convert the tetracarboxylic acid ester into a polyacid anhydride, and then a diamine containing a divalent organic group Y1, which is preferably used in the present embodiment, dissolved or dispersed in a separate solvent is added dropwise to the polyamine to cause polycondensation, thereby obtaining the desired polyamic acid ester.

[0026] Examples of diamines containing a divalent organic group Y1 that are preferably used in the present embodiment 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, and 4,4'-diaminobiphenyl. nyl, 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-amino 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 compounds in which some of the hydrogen atoms on the benzene ring are 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,Examples of the diaminodiphenylmethane include, but are not limited to, 4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0027] Furthermore, in order to improve the adhesion between various substrates and the resin layer formed on a substrate by applying the photosensitive resin composition according to this embodiment onto 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 polyamic acid ester.

[0028] After the polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as needed, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the target polyamic acid ester. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0029] On the other hand, the polyamic acid salt, which is the ionic bond type polyimide precursor, is first obtained by reacting a tetracarboxylic dianhydride with a diamine to obtain a polyamic acid, which is the polyimide precursor. In this case, at least one of R1 and R2 in the general formula (1) is a hydroxyl group.

[0030] The tetracarboxylic dianhydride is preferably a tetracarboxylic anhydride having the structure of the above formula (6), and the diamine is preferably a diamine having the structure of the above formula (7) or (8). By adding a (meth)acrylic compound having an amino group, which will be described later, to the obtained polyamic acid, the carboxyl group of the polyamic acid and the amino group of the (meth)acrylic compound having an amino group form a salt through an ionic bond, thereby producing a polyamic acid salt having a photopolymerizable group.

[0031] Preferred examples of the (meth)acrylic compound having an amino group include dialkylaminoalkyl acrylates or methacrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, and diethylaminobutyl methacrylate. Among these, from the viewpoint of photosensitive properties, dialkylaminoalkyl acrylates or methacrylates in which the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain has 1 to 10 carbon atoms are preferred.

[0032] The content of these (meth)acrylic compounds having an amino group is 1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity, it is preferably 2 to 15 parts by mass. By blending 1 part by mass or more of the (meth)acrylic compound having an amino group relative to 100 parts by mass of the (A) resin, excellent photosensitivity is achieved, and by blending 20 parts by mass or less, excellent thick-film curing properties are achieved.

[0033] The molecular weight of the ester-bonded and ionic-bonded polyimide precursors is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene equivalent weight average molecular weight. A weight average molecular weight of 8,000 or higher provides good mechanical properties, while a weight average molecular weight of 150,000 or lower provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for GPC. 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-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0034] [polyamide] Another example of a preferable (A) resin in the photosensitive resin composition according to the present embodiment is a compound represented by the following general formula (4): [ka] {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, R 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.

[0035] In the above general formula (4), the group represented by R is preferably a group represented by the following general formula (9): [ka] {where, R 25 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:

[0036] In the above general formula (4), 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 (10): [ka] and more preferably an aromatic group obtained by removing the carboxyl group and the amino group from an amino-substituted isophthalic acid structure.

[0037] In the above general formula (4), 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 (11) and the following general formulas (12) and (13): [ka] [ka] {where, R 26 and R 27 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), or a butyl group (-C4H9), and the propyl group and the butyl group include various isomers. [ka] In the formula, m4 represents an integer of 0 to 8, m5 and m6 each independently represent an integer of 0 to 3, m7 and m8 each independently represent an integer of 0 to 10, and R 28 and R 29 is a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), a butyl group (-C4H9), or an isomer thereof.

[0038] The aliphatic group or siloxane group having no cyclic structure includes a group represented by the following general formula (14): [ka] In the formula, m9 is an integer of 2 to 12, and m 10 is an integer from 1 to 3, and m 11 is an integer from 1 to 20, and R 30 , R 31 , R 32 and R 33 are each independently an alkyl group having 1 to 3 carbon atoms or an optionally substituted phenyl group.} is mentioned as a preferred example.

[0039] The polyamide resin according to the present embodiment can be synthesized, for example, as follows. (Synthesis of phthalic acid compound-capped compounds) First, one 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 one 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.

[0040] When a phthalic acid compound is capped with a group containing the radically polymerizable unsaturated bond, negative photosensitivity (photocurability) can be imparted to the polyamide resin.

[0041] 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 particularly preferably a group containing a methacryloyl group or an acryloyl group.

[0042] The above-mentioned phthalic acid compound-terminated 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.

[0043] Suitable acid chlorides include (meth)acryloyl chloride, 2-[(meth)acryloyloxy]acetyl chloride, 3-[(meth)acryloyloxy]propionyl chloride, 2-[(meth)acryloyloxy]ethyl chloroformate, 3-[(meth)acryloyloxypropyl]chloroformate, etc. Suitable isocyanates include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, 2-[2-(meth)acryloyloxyethoxy]ethyl isocyanate, etc. Suitable epoxy compounds include glycidyl (meth)acrylate, etc. 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, since they have excellent photosensitive properties and can provide polyamides with excellent film properties after heat curing.

[0044] The above-mentioned capping reaction can be carried out by stirring, dissolving and mixing the phthalic acid compound and the capping 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.

[0045] The reaction solvent is preferably one that can completely dissolve the product, the phthalic acid compound-blocked product, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone.

[0046] 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.

[0047] Some types of capping agents, such as acid chlorides, produce hydrogen chloride as a by-product during the capping reaction. In this case, in order to prevent contamination of subsequent steps, it is preferable to purify the product appropriately by, for example, reprecipitation with water, washing with water, and drying, or by passing the product through a column filled with an ion exchange resin to remove or reduce ionic components.

[0048] (Polyamide synthesis) The polyamide according to the present embodiment can be obtained by mixing the above-mentioned phthalic acid compound-blocked product and a diamine compound having a divalent organic group Y2 in an appropriate solvent in the presence of a basic catalyst such as pyridine or triethylamine and polycondensing the mixture.

[0049] Examples of the polycondensation method include a method in which a phthalic acid compound-terminated product is converted into a symmetrical polyacid anhydride using a dehydrating condensing agent and then mixed with a diamine compound; a method in which a phthalic acid compound-terminated product is converted into an acid chloride by a known method and then mixed with a diamine compound; and a method in which a dicarboxylic acid component is reacted with an active esterifying agent in the presence of a dehydrating condensing agent to form an active ester and then mixed with a diamine compound.

[0050] Preferred examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. The chlorinating agent includes thionyl chloride. Examples of the active esterifying agent 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.

[0051] 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 as desired.

[0052] Examples of 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 the 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 a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a halogen atom.

[0053] Examples of diamine compounds in which the hydrogen atoms on the benzene ring are 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.

[0054] Examples of 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, and bis-(3-hydroxy-4-aminophenyl)methane. 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), and the like.

[0055] Examples of 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 of suitable amines include 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propylamine, menthenediamine, isophoronediamine, norbornanediamine, 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.

[0056] Examples of the linear aliphatic diamine compound 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.

[0057] Examples of the siloxane diamine compound include dimethyl(poly)siloxane diamine, such as PAM-E, KF-8010, and X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd.

[0058] The reaction solvent is preferably a solvent that completely dissolves the polymer produced, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma-butyrolactone.

[0059] In some cases, ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may also be used as reaction solvents, specifically, 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.

[0060] After the amide polycondensation reaction is completed, 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, aliphatic lower 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 procedure, 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 filled with an ion exchange resin to remove ionic impurities.

[0061] The polyamide preferably has a weight-average molecular weight of 7,000 to 70,000, more preferably 10,000 to 50,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene. A weight-average molecular weight of 7,000 or more in terms of polystyrene ensures the basic physical properties of the cured relief pattern. Furthermore, a weight-average molecular weight of 70,000 or less in terms of polystyrene ensures the development solubility required for forming the relief pattern.

[0062] Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. The weight-average molecular weight can be determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select the standard monodisperse polystyrene from Showa Denko's organic solvent-based standard sample, STANDARD SM-105.

[0063] (B) Photosensitizer The photosensitizer (B) used in this embodiment will be described. As the photosensitizer (B), a photopolymerization initiator and / or a photoacid generator that generates radicals by absorbing and decomposing light of a specific wavelength is used.

[0064] The content of the (B) photosensitizer in the photosensitive resin composition is preferably 1 to 50 parts by mass relative to 100 parts by mass of the (A) resin. When the content is 1 part by mass or more, photosensitivity or patterning ability is exhibited, and when the content is 50 parts by mass or less, the physical properties of the photosensitive resin layer after curing are improved. In the case of a photopolymerization initiator, the generated radicals undergo a chain transfer reaction with the main chain skeleton of the (A) resin, or, if a photopolymerizable group is introduced into the (A) resin, undergo a radical polymerization reaction with the photopolymerizable group, thereby curing the (A) resin.

[0065] (B) The photopolymerization initiator as a photosensitizer is preferably a photoradical polymerization initiator, and examples thereof include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl 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; and 1-hydroxybenzoyl methyl ether derivatives such as benzoin, benzoin methyl ether, and benzoin methyl ether. Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; and titanocenes. Of the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

[0066] When a photoacid generator is used as the (B) photosensitizer in a negative-tone photosensitive resin composition, it exhibits acidity upon exposure to actinic rays such as ultraviolet light, and its action crosslinks the (D) crosslinking agent with the (A) resin, or polymerizes crosslinking agents themselves. Examples of such photoacid generators include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonates, nitrobenzyl esters, oximesulfonates, aromatic N-oxyimidosulfonates, aromatic sulfamides, haloalkyl-containing hydrocarbon compounds, haloalkyl-containing heterocyclic compounds, and naphthoquinone diazide-4-sulfonates. Two or more of these compounds can be used in combination, or in combination with other sensitizers, as needed. Among the above photoacid generators, aromatic oximesulfonates and aromatic N-oxyimidosulfonates are more preferred, particularly in terms of photosensitivity.

[0067] (C) Nitrogen-containing compounds with specific structures The nitrogen-containing compound (C) having a specific structure used in this embodiment will be described below: The nitrogen-containing compound (C) having a specific structure is a compound having a structure represented by the following general formula (15). [ka] {In the formula, R1 is a monovalent organic group having 1 to 10 carbon atoms.}

[0068] The use of nitrogen-containing compounds with the above structure reduces the adhesiveness to copper or copper alloys even after long-term storage at low temperatures. While the chemical mechanism is unclear, it is believed that nitrogen-containing compounds with a purine derivative structure, which has high electron density and interacts readily with copper, and substituents such as hydroxyl groups or amino groups (-NH2 groups) with high hydrogen bonding properties, exhibit high cohesion between the nitrogen-containing compounds, resulting in non-uniform distribution throughout the composition (varnish) after long-term storage at low temperatures, resulting in reduced copper adhesion. On the other hand, nitrogen-containing compounds with specific structures possess alkoxy groups with moderately reduced hydrogen bonding strength, which reduces cohesion between the nitrogen-containing compounds and allows them to be uniformly distributed throughout the composition even at low storage temperatures, thereby maintaining copper adhesion. Furthermore, high cohesion between nitrogen-containing compounds can lead to interactions between the nitrogen-containing compounds, weakening their interactions with resins such as polyimides and polyimide precursors and preventing the Tg-enhancing effect. However, as mentioned above, nitrogen-containing compounds with specific structures exhibit reduced cohesion, allowing them to interact with resins, thereby suppressing resin movement and improving Tg.

[0069] R1 is not particularly limited as long as it is a monovalent organic group having 1 to 10 carbon atoms, but is preferably an aliphatic group having 1 to 10 carbon atoms, more preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and even more preferably a saturated aliphatic group having 1 to 5 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a cyclopentanyl group, and a cyclohexyl group. Furthermore, the above R1 is also preferably a group represented by the following general formula (16): [ka] (In the formula, R2 is an aliphatic group having 1 to 10 carbon atoms, R3 is an aliphatic group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.)

[0070] From the viewpoints of copper adhesion after long-term storage at low temperatures and the glass transition temperature of the cured film, R2 and R3 are preferably alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 8 carbon atoms, and even more preferably alkyl groups having 1 to 4 carbon atoms. n is preferably an integer of 1 to 5. Specific examples of general formula (16) include alkoxy groups such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, and tetraethylene glycol monoethyl ether.

[0071] Specific examples of the nitrogen-containing compound (C) include 6-methoxypurine, 6-ethoxypurine, 6-n-propoxypurine, 6-iso-propoxypurine, 6-n-butoxypurine, 6-tert-butoxypurine, 6-n-butoxypurine, 6-n-octoxypurine, 6-decyloxypurine, and 6-(2-ethoxyethoxy)-purine.

[0072] The content of the (C) nitrogen-containing compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the (A) resin. When the content is 0.01 part by mass or more, the adhesiveness to copper or copper alloys after long-term storage at high and low temperatures tends to be excellent, while when the content is 10 parts by mass or less, the glass transition temperature of the cured film tends to be high.

[0073] (D) Crosslinking agent The photosensitive resin composition according to this embodiment may contain a (D) crosslinking agent. The crosslinking agent may be capable of crosslinking the (A) resin or of forming a crosslinked network by itself when the relief pattern formed using the photosensitive resin composition according to this embodiment is heat-cured. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the photosensitive resin composition.

[0074] Examples of crosslinking agents include those having 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 Pa-type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), and those having 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 (product name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (product name, manufactured by Sanwa Chemical Co., Ltd.),

[0075] Ba-type benzoxazine, Bm-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 having three of these compounds, such as TriML-P, TriML-35XL, TriML-TrisCR-HAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.); and those having four of these compounds, such as TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.). Examples of polyisoprene 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 of the four 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.).

[0076] Among these, in the present embodiment, those containing at least two thermally crosslinkable groups are preferred, 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.), Ba-type benzoxazine, Bm-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), and the like. 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 Industry 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 Bm-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.).

[0077] In consideration of the balance between various properties other than heat resistance and chemical resistance, when the photosensitive resin composition contains a crosslinking agent, the content is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the (A) resin. When the content is 0.5 part by mass or more, good heat resistance and chemical resistance are exhibited, while when the content is 20 parts by mass or less, excellent storage stability is achieved.

[0078] (E) Organotitanium compounds The photosensitive resin composition according to the present embodiment may contain (E) an organotitanium compound. By containing (E) an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 200°C.

[0079] (E) 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.

[0080] (F) Other ingredients The photosensitive resin composition according to this embodiment may further contain components other than the components (A) to (E). The photosensitive resin composition according to this embodiment is typically used as a varnish-like photosensitive resin composition prepared by dissolving the above components and any optional components in a solvent. Therefore, examples of the (F) other components include solvents. From the viewpoint of solubility in the (A) resin, polar organic solvents are preferred. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more.

[0081] The solvent can be used in an amount of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, per 100 parts by mass of the (A) resin, depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0082] Furthermore, from the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing an alcohol is preferred. Suitable usable alcohols are typically alcohols having an alcoholic hydroxyl group in the molecule and not having an olefinic double bond, and specific examples thereof include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol, lactic acid esters such as ethyl lactate, propylene glycol monoalkyl ethers such as propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, and propylene glycol-2-(n-propyl) ether, monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol-n-propyl ether, 2-hydroxyisobutyric acid esters, and dialcohols such as ethylene glycol and propylene glycol. Among these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are particularly preferred.

[0083] When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50 mass %, more preferably 10 to 30 mass %. When the content of the alcohol having no olefinic double bond is 5 mass % or more, the storage stability of the photosensitive resin composition is improved, and when it is 50 mass % or less, the solubility of the (A) resin is improved.

[0084] In addition, a hindered phenol compound can be optionally blended to suppress discoloration on the copper surface. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol bis(methyl methyl ester), and 2,5-di-t-butyl-hydroxyquinone. [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),

[0085] 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,

[0086] 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,

[0087] Examples of the hydroxybenzoates 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.

[0088] The content of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the hindered phenol compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, for example, when the photosensitive resin composition according to this embodiment is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the content is 20 parts by mass or less, excellent photosensitivity is achieved.

[0089] The photosensitive resin composition according to the present embodiment may contain components other than those described above. For example, a sensitizer may be optionally blended to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene indole. Non, p-dimethylaminobenzylideneindanone, 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, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 types.

[0090] When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the content thereof is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) resin.

[0091] In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be optionally blended. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, and includes, but is 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, diacrylate and dimethacrylate of 1,4-butanediol, 1,6-hexane Examples of such compounds include diacrylates and dimethacrylates of diols, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, di- or triacrylates and methacrylates of glycerol, di-, tri-, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0092] When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the content 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.

[0093] Furthermore, an adhesion promoter can be optionally blended to improve adhesion between a film formed using the photosensitive resin composition according to this embodiment and a substrate. Examples of the adhesion promoter 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, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)propanol, and the like. 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-phenylaminopropyltrimethoxysilane, 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.

[0094] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains an adhesion aid, the content of the adhesion aid is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the (A) resin.

[0095] Furthermore, a thermal polymerization inhibitor can be optionally blended to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, particularly during storage in a solvent-containing solution. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0096] The content of the thermal polymerization inhibitor when blended in the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the (A) resin.

[0097] <Method for producing cured relief pattern and semiconductor device> In another embodiment, there is provided a method for producing a cured relief pattern, comprising the steps of: (1) applying the above-described photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive 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.

[0098] (1) A step of forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition onto the substrate. In this step, the photosensitive resin composition is applied to a substrate, and then dried as necessary to form a photosensitive 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, or the like, or spray application using a spray coater, can be used.

[0099] In addition, copper or a copper alloy may be formed on the substrate. In particular, by using the above-mentioned photosensitive resin composition, excellent adhesion to copper can be achieved, and even when the varnish is stored at low temperature for a long period of time, excellent adhesion can be achieved between the copper or copper alloy and the cured film.

[0100] If necessary, the coating film made of the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, and vacuum drying. Specifically, when air drying or heat drying is performed, drying can be carried out at 20°C to 140°C for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on a substrate.

[0101] (2) A step of exposing the photosensitive resin layer to light In this step, the photosensitive 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.

[0102] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and / or pre-development baking may be performed as necessary using any combination of temperature and time. The baking conditions preferably range from a temperature of 40 to 130°C and a time 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 disclosure.

[0103] (3) A step of developing the exposed resin layer to form a relief pattern. In this step, exposed or unexposed portions of the photosensitive resin layer after exposure are developed and removed. In the composition of the present disclosure, which is a negative photosensitive resin composition, only unexposed portions are developed and removed. Any of the conventionally known photoresist development methods, such as the rotary spray method, the puddle method, and the immersion method accompanied by ultrasonic treatment, can be used as the development method. Furthermore, after development, post-development baking may be performed at any combination of temperature and time, as needed, for the purpose of adjusting the shape of the relief pattern, etc. The baking conditions preferably range from 40 to 180°C for a temperature of 40 to 180°C and a time of 10 to 600 seconds.

[0104] The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that is insoluble in an alkaline aqueous solution, good solvents such as N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone are preferred, while poor solvents such as toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a good solvent and a poor solvent are used in combination, 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. Furthermore, two or more types of each solvent, for example, several types, can also be used in combination.

[0105] (4) A step of forming a hardened relief pattern by heat treating the relief pattern. In this step, the relief pattern obtained by the 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 performed, for example, at 180°C to 400°C for 30 minutes to 5 hours. The atmospheric gas used for heat curing may be air, or an inert gas such as nitrogen or argon.

[0106] <Semiconductor device> The present disclosure also provides a semiconductor device including a cured relief pattern obtained by the above-described method for producing a cured relief pattern. The present disclosure further 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 disclosure 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 disclosure 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.

[0107] The photosensitive resin composition according to the present embodiment is useful not only for application to the semiconductor device described above, but also for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. [Example]

[0108] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin compositions were measured and evaluated according to the following methods.

[0109] <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 while 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.

[0110] 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. Subsequently, 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, followed by the addition of 400 ml of γ-butyrolactone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0111] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced 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, and the resulting precipitate was filtered off and 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.

[0112] <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 found to have a weight average molecular weight (Mw) of 22,000.

[0113] <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.

[0114] <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.

[0115] <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 the 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) used 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.

[0116] <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 piromelotic 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.

[0117] <Production Example 7> (A) Synthesis of Polymer A-7 as Polyimide Precursor) Polymer A-7 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 50.2 g of 1,4-phenylenediamine (pPD) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1. The molecular weight of Polymer A-7 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 18,000.

[0118] <Production Example 8> ((A) Synthesis of Polymer A-8 as Polyamide) (Synthesis of phthalic acid compound-capped AIPA-MO) A 5-liter separable flask was charged with 543.5 g of 5-aminoisophthalic acid (hereafter 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.

[0119] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography (hereinafter referred to as low-molecular-weight GPC), the reaction solution was poured into 15 L 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%.

[0120] (Synthesis of Polymer A-8) 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 in 125 g of GBL was added dropwise 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 for 5 hours at room temperature. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0121] 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-8). The molecular weight of Polymer A-8 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 34,700.

[0122] (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 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.

[0123] (2) Copper adhesion test (number of substrate adhesion grids) The photosensitive resin composition was spin-coated onto a copper substrate and dried to form a 9 μm-thick coating film as a photosensitive resin layer, which was then heat-treated (cured) for 2 hours at 250°C in a nitrogen atmosphere using a temperature-programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg, Japan) to obtain a 5 μm-thick cured resin coating film. The adhesive properties between the copper substrate and the cured resin coating film after being kept in a high-temperature environment were evaluated according to the following criteria using the cross-cut method of JIS K 5600-5-6. "Best": The lattice number of the cured resin coating adhered to the substrate is 100. "Good": The lattice number of the cured resin coating adhered to the substrate is 80 to 99. "Fairly good": The lattice number of the cured resin coating adhered to the substrate is 50 to 79. "Slightly poor": The lattice number of the cured resin coating adhered to the substrate is 20 to 49. "Poor": The number of lattices in the cured resin coating adhered to the substrate is less than 20.

[0124] (3) Copper adhesion test after storage at low temperature (number of substrate adhesion grids) A photosensitive resin composition prepared to 100 poise was left to stand in a freezer at -20°C for 60 days, and then returned to room temperature. The photosensitive resin composition was diluted with a solvent to 35 poise and spin-coated onto a copper substrate. The substrate was dried to form a 9 μm-thick coating film as a photosensitive resin layer. The substrate was then heat-treated (cured) at 250°C for 2 hours in a nitrogen atmosphere using a temperature-programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd., Japan) to obtain a 5 μm-thick cured resin coating film. This cured film was subjected to high-temperature storage at 150°C for 500 and 1000 hours in an air atmosphere at atmospheric pressure using an unsaturated pressure cooker (Model PC-R8D, manufactured by HIRAYAMA Corporation, Japan). The adhesive properties of the cured film after storage in the high-temperature environment between the copper substrate and the cured resin coating film were evaluated according to the following criteria using the cross-cut method of JIS K 5600-5-6. "Best": The lattice number of the cured resin coating adhered to the substrate is 100. "Good": The lattice number of the cured resin coating adhered to the substrate is 80 to 99. "Fairly good": The lattice number of the cured resin coating adhered to the substrate is 50 to 79. "Slightly poor": The lattice number of the cured resin coating adhered to the substrate is 20 to 49. "Poor": The number of lattices in the cured resin coating adhered to the substrate is less than 20.

[0125] (4) Measurement of the glass transition temperature of cured polyimide coatings The photosensitive resin composition was spin-coated onto a 6-inch silicon wafer so that the film thickness after curing would be approximately 10 μm, and after pre-baking on a hot plate at 110°C for 180 seconds, the film was heated at 250°C for 2 hours in a nitrogen atmosphere using a temperature-programmable curing oven (VF-000 model, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured polyimide coating film. The film thickness was measured using a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen Co., Ltd.). The obtained polyimide coating film was cut into strips and subjected to a load of 200 g / mm. 2The measurement was performed using a thermomechanical testing device (TMA-50 manufactured by Shimadzu Corporation) at a temperature rise rate of 10°C / min in the range of 20°C to 500°C. The glass transition temperature (Tg) was determined as the intersection of the tangent lines to the thermal yield point of the polyimide film in the measurement chart, where the horizontal axis is temperature and the vertical axis is displacement.

[0126] Example 1 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 80 g of GBL and 20 g of dimethyl sulfoxide together with (B) 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 1) as a photosensitizer, (C) 1 g of 6-methoxypurine, 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 as nitrogen-containing compounds. The viscosity of the resulting solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent, to obtain a photosensitive resin composition.

[0127] <Examples 2 to 21 and Comparative Examples 1 to 7> Photosensitive resin compositions were obtained in the same manner as in Example 1, except that the types and contents of components (A) to (C) were changed as shown in Table 1.

[0128] Table 1 shows the formulation and evaluation results for the photosensitive resin compositions of the examples and comparative examples. The ingredients and names in the table are as follows: PDO: 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime OXE-1: 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime)) (trade name: IRGACURE-OXE-01, manufactured by BASF)

[0129] C-1: 6-Methoxypurine C-2: 6-ethoxypurine C-3: 6-tert-butoxypurine C-4: 6-n-octoxypurine C-5:6-n-Desyloxypurine C-6: 5-amino-1H-tetrazole C-7: Adenine C-8: 8-Azaadenine C-9:8-Azaguanine C-10: Hypoxanthine C-11: N,N-dimethyladenine

[0130] [Table 1]

[0131] As is clear from Table 1, in the examples containing the nitrogen-containing compound (C) having a structure represented by general formula (15), good results were obtained in all of copper adhesion, copper adhesion after frozen storage, and Tg, whereas in the comparative examples not containing the nitrogen-containing compound (C) having a structure represented by general formula (15), satisfactory results were not obtained in all of copper adhesion, copper adhesion after frozen storage, and Tg. [Industrial Applicability]

[0132] The photosensitive resin composition according to the present invention can be suitably used in the field of photosensitive materials useful for producing electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) at least one resin selected from the group consisting of polyamide, polyimide, or polyimide precursor polyamic acid, polyamic acid ester, and polyamic acid salt; (B) a photosensitizer, and (C) the following general formula (15): 【Chemistry 1】 {In the formula, R １ is a monovalent organic group having 1 to 10 carbon atoms. A nitrogen-containing compound having a structure represented by A photosensitive resin composition comprising:

2. In the general formula (15), the R １ is an aliphatic group having 1 to 10 carbon atoms, or is represented by the following general formula (16): 【Chemistry 2】 {In the formula, R ２ is an aliphatic group having 1 to 10 carbon atoms, and R ３ is an aliphatic group having 1 to 10 carbon atoms, and n is an integer of 1 to 10. The photosensitive resin composition according to claim 1 , wherein the aryl group is a group represented by the formula:

3. The resin (A) is a resin represented by the following general formula (1): 【Transformation 3】 {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom, a saturated aliphatic group having 1 to 10 carbon atoms, or a group represented by the following general formula (2): 【Chemistry 4】 (In the formula, R ３ , R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10, or a monovalent organic group represented by the following general formula (3): 【Transformation 5】 (In the formula, R ６ , R ７ and R ８ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ２ is an integer of 2 to 10); and The following general formula (4): 【Transformation 6】 {In the formula, X ２ is a trivalent organic group having 6 to 15 carbon atoms, and Y ２ is a divalent organic group having 6 to 35 carbon atoms and may have the same structure or a plurality of structures, R is an organic group having 3 to 20 carbon atoms and having at least one radically polymerizable unsaturated bond group, and n ２ is an integer from 1 to 1000.

3. The photosensitive resin composition according to claim 1, wherein the resin is at least one resin selected from the group consisting of polyamides having a structure represented by the following formula:

4. In the general formula (15), the R １ The photosensitive resin composition according to claim 1 or 2, wherein is a saturated aliphatic group having 1 to 5 carbon atoms.

5. 3. The photosensitive resin composition according to claim 1, wherein the content of the nitrogen-containing compound (C) is 0.01 to 10 parts by mass relative to 100 parts by mass of the resin (A).

6. The photosensitive resin composition according to claim 1 or 2, further comprising (D) a thermal crosslinking agent.

7. (1) forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to claim 1 or 2 onto the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) forming a hardened relief pattern by heat-treating the relief pattern; 1. A method for producing a cured relief pattern, comprising:

8. The method of claim 7 , wherein copper or a copper alloy is formed on the substrate.

9. A semiconductor device comprising a cured relief pattern which is a cured product of the photosensitive resin composition according to claim 1 or 2.

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