Negative photosensitive resin composition, method for producing cured relief pattern using same, and semiconductor device

Abstract

The present invention provides a photosensitive resin composition which exhibits high adhesion even on copper or a copper alloy, and has a high thermal curing residual film rate and sufficient reliability.　This negative photosensitive resin composition is characterized by comprising the following components: (A) a resin which is (A1) a polyimide precursor or (A2) a polyimide; (B) a photopolymerization initiator; (C) a radically polymerizable monomer; and (D) a compound represented by general formula (1), wherein the component (D) has a molecular weight of 250 or more and an absorbance of 0.05 or less at 365 nm at a concentration of 0.1 vol%. (In the formula, R may be the same or different and each independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and each independently represent an integer of 1 or 2; m may be the same or different and each independently represent an integer of 1 to 4; k represents an integer of 1 to 5; A represents an organic group having a valence of 1 to 5; a hydrogen atom is at at least one of the ortho position and the para position of the hydroxy group of general formula (1); and a t-butyl group is not at the ortho position.)

Description

Negative photosensitive resin composition, method for producing cured relief pattern using same, and semiconductor device

[0001] The present invention relates to a negative photosensitive resin composition used for forming relief patterns of insulating materials for electronic components, passivation films, buffer coat films, interlayer insulating films, and the like in semiconductor devices, a method for producing a cured relief pattern using the same, and a semiconductor device.

[0002] Polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have traditionally been used as insulating materials for electronic components, passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these polyimide resins, those provided in the form of polyimide precursors or polyimides that have been given photosensitive functionality can easily form heat-resistant relief pattern coatings by coating, exposing, developing, and curing the resin. Such photosensitive polyimide precursors and photosensitive polyimides have the advantage of enabling significant process reduction compared to conventional non-photosensitive polyimides.

[0003] Meanwhile, in recent years, the methods of mounting semiconductor devices on printed wiring boards have been changing in order to improve integration and functionality, as well as to reduce chip size. Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which a polyimide coating directly contacts solder bumps, such as BGA (ball gripped array) and CSP (chip size packaging), which enable higher density mounting.

[0004] Furthermore, as semiconductor devices become increasingly miniaturized, the wiring resistance of semiconductor devices is becoming 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 poor adhesion to copper, which causes peeling between the resin and the copper wiring.

[0005] Furthermore, such a metal redistribution layer is required to exhibit insulating properties even after a reliability test. Examples of the reliability test include a thermal cycle test in which a cycle of storing the layer at −65° C. for 30 minutes and then storing the layer at 150° C. for 30 minutes is repeated 1,000 times. In conventional photosensitive resin compositions, repeated expansion and contraction of the resin during the reliability test can cause defects such as cracks between the resin and the copper wiring, resulting in short circuits and disconnections in the redistribution layer.

[0006] As a means for solving the above problems, a method has been disclosed in which tetrazole or a derivative thereof is added to a composition containing a polyimide precursor to improve adhesion to copper or a copper alloy (see Patent Documents 1 and 2).

[0007] JP 2020-2281 A Patent No. 3170174 A

[0008] However, the heterocyclic compounds described in Patent Documents 1 and 2 have a problem in that they themselves have a strong cohesive property and aggregate in the varnish to become foreign matter. Furthermore, stress tends to concentrate in the film due to volatilization during thermal curing, and expansion and contraction stress applied during thermal cycle testing cannot be alleviated, resulting in a problem of insufficient reliability on copper wiring.

[0009] Therefore, an object of the present invention is to provide a photosensitive resin composition that has high adhesion even on copper or copper alloys, a high rate of thermosetting residual film, and sufficient reliability, a method for producing a cured relief pattern that forms a pattern using the photosensitive resin composition, and a semiconductor device.

[0010] In view of the problems of the above-mentioned conventional techniques, the present inventors conducted extensive research and experiments, and as a result discovered that the above problems could be solved by incorporating a specific compound represented by general formula (1) into a photosensitive resin composition, thereby completing the present invention. That is, the present invention is as follows: [1] A negative-type photosensitive resin composition comprising the following components: (A) a resin which is (A1) a polyimide precursor or (A2) a polyimide, (B) a photopolymerization initiator, (C) a radically polymerizable monomer, and (D) a compound represented by the following general formula (1), wherein component (D) has a molecular weight of 250 or more and an absorbance at 365 nm of 0.05 or less at a concentration of 0.1 vol%: [wherein, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; each n may be the same or different and independently represent an integer of 1 to 2; each m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 5; A is a monovalent to pentavalent organic group; and at least one of the ortho-positions or para-positions of the hydroxy group in general formula (1) is a hydrogen atom, and the ortho-position is not a t-butyl group.] [2] The component (A) is (A1) a polyimide precursor, and is represented by the following general formula (2): {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ [3] The negative photosensitive resin composition according to claim 1, wherein the polyimide precursor (A1) is represented by the following general formula (2): {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R２ At least one of the following general formula (3): (In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. (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 m2 is an integer of 2 to 10. １ , and R ２ at least one of which is a group represented by the above general formula (3) or (4). {4] The negative photosensitive resin composition according to [1] or [2], wherein the component (D) is represented by the following general formula (6): [In the formula, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group, each n may be the same or different and independently represent an integer of 1 to 2, each m may be the same or different and independently represent an integer of 1 to 4, k is an integer of 1 to 4, A is a divalent to pentavalent organic group, and at least one of the ortho-positions or para-positions of the hydroxy group in general formula (6) is a hydrogen atom.] [5] The negative photosensitive resin composition according to [1] or [2], wherein the component (D) is represented by the following general formula (7): [In the formula, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group, each n may be the same or different and independently represent an integer of 1 to 2, each m may be the same or different and independently represent an integer of 1 to 4, k is an integer of 1 to 3, A is a trivalent to pentavalent organic group, and at least one of the ortho-positions or para-positions of the hydroxy group in general formula (7) is a hydrogen atom.] [6] The negative photosensitive resin composition according to [1] or [2], wherein the component (D) is represented by the following general formula (8): [In the formula, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; each n may be the same or different and independently represent an integer of 1 to 2; each m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 3; A is a tetravalent or pentavalent organic group; and at least one of the ortho- or para-positions of the hydroxy group in general formula (8) is a hydrogen atom.] [7] The negative photosensitive resin composition according to [1] or [2], wherein the component (D) is represented by the following general formula (9): [In the formula, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group, each n may be the same or different and independently represent an integer of 1 to 2, each m may be the same or different and independently represent an integer of 1 to 4, k is an integer of 1 to 4, A is a monovalent to pentavalent organic group, and at least one of the ortho positions of the hydroxy group in general formula (9) is a hydrogen atom.] [8] The negative photosensitive resin composition according to [1] or [2], wherein the component (D) is represented by the following general formula (10): [In the formula, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group, each n may be the same or different and independently represent an integer of 1 to 2, each m may be the same or different and independently represent an integer of 1 to 4, k is an integer of 1 to 3, A is a monovalent to pentavalent organic group, and at least one of the ortho positions of the hydroxy group in general formula (10) is a hydrogen atom.] [9] The negative photosensitive resin composition according to [1] or [2], wherein the component (D) is represented by the following general formula (11): [In the formula, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; each n may be the same or different and independently represent an integer of 1 to 2; each m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 2; A is a monovalent to pentavalent organic group; and at least one of the ortho positions of the hydroxy group in general formula (11) is a hydrogen atom.]

[10] The negative photosensitive resin composition according to any one of [1] to [9], further comprising (F) a thermal crosslinking agent.

[11] The negative photosensitive resin composition according to

[10] , wherein the (F) thermal crosslinking agent has a methylol group.

[12] The negative photosensitive resin composition according to any one of [1] to

[11] , further comprising (G) an acidic compound having a pKa of 1 to 10.

[13] The negative photosensitive resin composition according to any one of [1] to

[11] , further comprising (G) an acidic compound having a pKa of 1 to 10. １ and Y ２ The negative photosensitive resin composition according to [2], wherein the compound is represented by at least one structure selected from the group consisting of the following general formulas (12) and (13): (In the formula, R １１ , R １２ , R １３ and R １４ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different. (In the formula, R １５ ~R ２２are hydrogen atoms, halogen atoms, monovalent organic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be different from each other or the same.)

[14] A negative-type photosensitive resin composition comprising the following components: (A) a polyimide precursor, (B) a photopolymerization initiator, (C) a radically polymerizable monomer, and (D) a compound having a molecular weight of 250 or more, (F) a thermal crosslinking agent, and (G) a compound that exhibits an exothermic peak of +3 μV or more in the range of 170 to 290° C. in a thermal change DTA when differential thermal analysis is performed at a heating rate of 10° C. / min in the presence of an acidic compound having a pKa of 1 to 10.

[15] The negative-type photosensitive resin composition according to any of [1] to

[14] , which is used for forming a passivation film, a buffer coat film, or an interlayer insulating film in a semiconductor device.

[16] (1) A method for producing a cured relief pattern, comprising the steps of: applying the negative photosensitive resin composition according to any one of [1] to

[15] 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.

[17] A semiconductor device comprising a cured relief pattern obtained from the negative photosensitive resin composition according to any one of [1] to

[16] .

[0011] According to the present invention, by incorporating a specific compound represented by general formula (1) into a photosensitive resin composition, it is possible to provide a photosensitive resin composition that has high adhesion even on copper or a copper alloy, a high rate of thermosetting residual film, and sufficient reliability, a method for producing a cured relief pattern in which a pattern is formed using the photosensitive resin composition, and a semiconductor device.

[0012] Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as "embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist thereof.

[0013] In this embodiment, the photosensitive resin composition is a negative-type photosensitive resin composition (hereinafter also simply referred to as "photosensitive resin composition") containing (A) a polyimide precursor or polyimide, (B) a photopolymerization initiator, (C) a radically polymerizable monomer, and (D) a compound having a molecular weight of 250 or more and represented by general formula (1). Other components may be included as desired. Each component will be described below in order. Throughout this specification, 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.

[0014] (A) Polyimide Precursor or Polyimide (A1) Polyimide Precursor The polyimide precursor (A1) used in the present invention will be described. The resin component in the photosensitive resin composition of the present invention is a polyamide having a structural unit represented by the following general formula (2). The polyimide precursor (A1) is converted into a polyimide by heating (for example, at 200°C or higher) for cyclization treatment. {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n 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 4 carbon atoms, or a group represented by the following general formula (3): (In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. (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 m2 is an integer of 2 to 10. １ , and R ２At least one of the groups is preferably a radical reactive group, more preferably a group represented by the general formula (3) or (4). The polyimide precursor is preferably not an alkali-soluble resin, and more preferably not a resin having a phenolic hydroxyl group. This makes it easier to obtain a photosensitive resin composition that has high adhesion even on copper or a copper alloy and a high thermosetting residual film rate.

[0015] In the above general formula (2), X １ is a tetravalent organic group having 6 to 40 carbon atoms, and more preferably, -COOR １ group and -COOR ２ The group and the —CONH— group are aromatic groups or alicyclic aliphatic groups located in the ortho positions relative to each other.

[0016] In one embodiment, X in general formula (1) １ is preferably represented by the following formula (20): The compound is one or more selected from the group represented by the following formula:

[0017] In the above general formula (2), X １ It is more preferable that the tetravalent organic group represented by the formula (I) is selected from at least one of 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA).

[0018] Also, X １ The structure of may be one type or a combination of two or more types, but from the viewpoint of improving resolution, a combination of two or more types is more preferable.

[0019] In the above general formula (2), Y １ The divalent organic group represented by the formula (15) below is preferably an aromatic group having 6 to 40 carbon atoms, in order to achieve both heat resistance and photosensitive properties. and a structure represented by the following formula (16): {In the formula, R ２３ and R ２４ are each independently a methyl group (—CH ３), ethyl group (-C ２ H ５ ), propyl group (-C ３ H ７ ) or a butyl group (—C ４ H ９ ) represents a structure represented by the formula:}, but is not limited to these.

[0020] In the general formula (2), Y １ are represented by the following general formulas (12) to (13): (In the formula, R １１ , R １２ , R １３ and R １４ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different. (In the formula, R １５ ~R ２２ are preferably one or more organic groups selected from:

[0021] Also, Y １ The structure may be one type or a combination of two or more types.

[0022] In the above general formula (2), Y １ The divalent organic group represented by the formula (I) is particularly preferably selected from at least one of diaminodiphenyl ether (DADPE), p-phenylenediamine (pPD), 4,4'-diamino-2,2'-dimethylbiphenyl (mTB), and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) in terms of achieving both heat resistance and photosensitive properties.

[0023] Furthermore, the polyimide precursor (A1) is represented by the general formula (2) and R １ and R ２ At least one of the above contains a group represented by the general formula (3) or (4), and R １ and R ２ It is preferable to include a precursor having a double bond at the end of the

[0024] [(A1) Method for Preparing Polyimide Precursor] The polyimide precursor represented by the general formula (2) in this embodiment can be prepared by, for example, preparing a polyimide precursor containing the above-mentioned tetravalent organic group X having 6 to 40 carbon atoms. １ and (a) an alcohol formed by bonding a monovalent organic group represented by the general formula (3) or (4) to a hydroxyl group, to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester). １ and diamines containing the same.

[0025] (Preparation of Acid / Ester Form) In this embodiment, a tetravalent organic group X having 6 to 40 carbon atoms １ Examples of tetracarboxylic dianhydrides include 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, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. These may be used alone or in combination of two or more.

[0026] In the present invention, examples of alcohols having a photopolymerizable group 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, and 2-hydroxy-3-t-butoxypropyl acrylate. acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

[0027] As the saturated aliphatic alcohols that can be optionally used together with the alcohols having a photopolymerizable group, saturated aliphatic alcohols having 1 to 4 carbon atoms are preferred, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

[0028] The content of the component (a) in the negative photosensitive resin composition is R １ and R ２ It is preferable that the content of component (a) exceeds 80 mol% relative to the total content of R1 and R2. When the content of component (a) exceeds 80 mol%, it is possible to obtain desired photosensitive characteristics, which is preferable. The content of component (a) in the negative photosensitive resin composition is preferably 85 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more relative to the total content of R1 and R2.

[0029] The above-mentioned tetracarboxylic acid dianhydride and the above-mentioned alcohol are stirred, dissolved, and mixed in a reaction solvent in the presence of a basic catalyst such as pyridine at a reaction temperature of 20 to 50°C for 4 to 10 hours, whereby the half-esterification reaction of the acid dianhydride proceeds, and the desired acid / ester form can be obtained.

[0030] The reaction solvent is preferably one that dissolves the acid / ester compound and the polyimide precursor that is a polycondensation product of the acid / ester compound and a diamine, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, 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 as needed.

[0031] (Preparation of Polyimide Precursor) A known dehydration condensation agent, such as dicyclohexylcarbodiimide, 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 acid / ester compound (typically a solution in the reaction solvent) under ice cooling to convert the acid / ester compound into a polyacid anhydride. Thereafter, a divalent organic group Y having 6 to 40 carbon atoms in general formula (1) is added to the acid / ester compound, and the resulting polyacid anhydride is converted into a polyacid anhydride. １ A diamine containing the above compound is dissolved or dispersed in a solvent and added dropwise to the resulting mixture, followed by polycondensation, to obtain a polyimide precursor that can be used in the embodiment.

[0032] Divalent organic group Y preferably used in the present invention １Examples of diamines containing the above 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- bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and compounds in which some of the hydrogen atoms on the benzene ring are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, or the like, 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 can be used.

[0033] Among these, it is preferable to use 4,4'-diaminodiphenyl ether, p-phenylenediamine, 4,4-dimethyl-2,2'-diaminobiphenyl, or 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and it is more preferable to use 4,4'-diaminodiphenyl ether, p-phenylenediamine, or 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0034] Furthermore, for the purpose of improving adhesion to various substrates, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized.

[0035] After the reaction is complete, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component. The polymer is then purified by repeated redissolution and reprecipitation procedures, and 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 an anion-cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0036] The molecular weight of the polyimide precursor (A1), as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 20,000 to 40,000. A weight average molecular weight of 8,000 or more is preferred because of good mechanical properties. On the other hand, a weight average molecular weight of 150,000 or less is preferred because of good dispersibility in the developer and good resolution performance of the relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight can be determined from a calibration curve prepared using standard monodisperse polystyrenes. 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.

[0037] (A2) Polyimide The (A2) polyimide used in this embodiment will be described. The resin component in the photosensitive resin composition is preferably a polyimide resin having a structural unit represented by the following general formula (5). {In the formula, X ２ is a tetravalent organic group, and Y ２ is a divalent organic group, and n is an integer of 2 to 150.} The resin represented by general formula (5) is particularly preferred in that it does not require chemical change in the heat treatment step in order to exhibit sufficient film properties, and is therefore suitable for treatment at lower temperatures.

[0038] In general formula (5), X ２ and / or Y ２ From the viewpoint of heat resistance, the tetravalent organic group preferably contains an aromatic ring structure, more preferably contains 6 to 40 carbon atoms, and further more preferably contains a benzene ring structure.

[0039] In general formula (5), X ２ and / or Y ２The divalent organic group preferably has a structure in which 2 to 6 benzene rings are bonded via a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a fluorinated alkylene group, and an ether group. The alkylene group and the fluorinated alkylene group may be linear or branched.

[0040] (A2) Polyimide can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic diester dichloride, etc. with a diamine, a corresponding diisocyanate compound, a trimethylsilylated diamine, etc. Polyimide can be obtained by dehydrating and ring-closing a polyamic acid, which is one of polyimide precursors generally obtained by reacting a tetracarboxylic dianhydride with a diamine, by heating or chemical treatment with an acid or a base, etc.

[0041] Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenoxy)-2,2-dicarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-bis(3,4-dicarboxyphenoxy)-2,2-di ... 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride Examples of the aromatic tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, ...

[0042] Among these, it is preferable to use pyromellitic anhydride (PMDA), diphenylether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA). These may be used alone or in combination of two or more.

[0043] Suitable diamines include 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diaminodiphenyl sulfone, 3,3'dimethylbenzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis(p-aminophenyl)hexafluoropropane, and the like. Pan, bis(trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DF POB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminobenzotrifluoride (3,5-DABTF), 3,5-diamino- Examples of the compound include 5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethylbenzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)xanthene (6FCAM), 3,6-diamino-9-trifluoromethyl-9-phenylxanthene (3FCAM), and compounds represented by 3,6-diamino-9,9-diphenylxanthene.

[0044] The molar ratio of the diamine to the acid dianhydride is basically 1:1. However, to obtain a desired terminal structure, one of them may be used in excess. Specifically, by using an excess of diamine, the terminals (both terminals) of the polyimide (A2) tend to become amino groups. On the other hand, by using an excess of acid dianhydride, the terminals (both terminals) of the polyimide (A2) tend to become acid anhydride groups. As described above, in this embodiment, it is preferable that the polyimide (A2) has acid anhydride groups at its terminals. Therefore, in this embodiment, it is preferable to use an excess of acid dianhydride when synthesizing the polyimide (A2).

[0045] The amino group and / or acid anhydride group at the end of the polyimide obtained by condensation polymerization may be reacted with some kind of reagent so that the polyimide end has a desired functional group.

[0046] The molecular weight of the (A2) polyimide, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, and particularly preferably 10,000 to 50,000. A weight average molecular weight of 5,000 or more is preferred because of good mechanical properties. On the other hand, a weight average molecular weight of 150,000 or less is preferred because of good dispersibility in the developer and good resolution performance of the relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The 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.

[0047] (B) Photopolymerization Initiator The photopolymerization initiator (B) in this embodiment will be described. As the photopolymerization initiator (B), any compound that has been conventionally used as a photopolymerization initiator for UV curing can be selected.

[0048] Examples of the photopolymerization initiator (B) 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 and 2-hydroxy-2-methylpropiophenone; thioxanthone derivatives such as 1-hydroxycyclohexyl phenyl ketone, 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 methyl ether; 2,6-di(4'-diazidobenzal)-4-methylcyclohexyl Examples of compounds that can be used include azides such as 2,6'-di(4'-diazidobenzal)cyclohexanone and 2,6'-di(4'-diazidobenzal)cyclohexanone, oximes such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-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 peroxide, aromatic biimidazoles, and titanocenes. Of these, the oximes are preferred from the viewpoint of photosensitivity.

[0049] The blending amount of the (B) photopolymerization initiator is 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, 2 to 15 parts by mass is preferable. By blending 0.1 part by mass or more of the (B) photopolymerization initiator relative to 100 parts by mass of the (A) resin, the photosensitive resin composition has excellent photosensitivity. On the other hand, by blending 20 parts by mass or less, the photosensitive resin composition has excellent thick-film curing properties.

[0050] (C) Radically Polymerizable Monomer The radically polymerizable monomer (C) in this embodiment will be described. The radically polymerizable monomer (C) is a monomer having a photopolymerizable unsaturated bond that can be blended into the negative photosensitive resin composition in order to improve the resolution of the relief pattern. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator. Examples of such a monomer include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, including 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, and 1,6-hexamethylpropional. Examples of suitable compounds include diacrylates and dimethacrylates of Sandiol, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, 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.

[0051] The amount of the monomer having a photopolymerizable unsaturated bond to be blended is preferably 1 to 50 parts by mass per 100 parts by mass of the resin (A).

[0052] (D) Compounds Represented by General Formula (1) and Having a Molecular Weight of 250 or More The compounds (D) represented by general formula (1) and having a molecular weight of 250 or more in this embodiment will be described. [In the formula, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; each n may be the same or different and independently represent an integer of 1 to 2; each m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 5; A is a monovalent to pentavalent organic group; and at least one of the ortho- and para-positions of the hydroxy group in general formula (1) is a hydrogen atom, and the ortho-position is not a t-butyl group.]

[0053] Furthermore, the component (D) has an absorbance at 365 nm of 0.05 or less at a concentration of 0.1 vol %, which prevents curing from being hindered during patterning by photolithography.

[0054] (D) By using the compound represented by general formula (1), excellent adhesion to copper or copper alloys and reliability during thermal cycle tests are achieved. Although the chemical mechanism by which excellent adhesion to copper or copper alloys and reliability during thermal cycle tests are achieved is not clear, the presumed mechanism is described below.

[0055] Phenol compounds are ortho-para oriented, and the ortho or para position of the hydroxyl group is δ ― The phenolic compound has a molecular weight low enough to prevent volatilization during thermal curing, and is therefore active. Therefore, phenolic compounds with molecular weights low enough to prevent volatilization during thermal curing undergo addition polymerization at high temperatures during thermal curing, producing phenolic resins in the film. Phenolic resins have a high affinity with copper or copper alloys, which is presumably responsible for improved adhesion. While polyimide precursors or polyimides and phenolic resins are generally considered to be poorly compatible with each other, in the present invention, phenolic addition polymerization occurs within the bulk of the polyimide precursor or polyimide, allowing the phenolic resin to exist in the system without phase separation or other problems. Since component (D) undergoes a phenolic addition polymerization reaction at high temperatures during thermal curing, the heat of reaction is observed as an exothermic peak in DTA when differential thermal analysis is performed. In other words, component (D) of this embodiment preferably exhibits an exothermic peak in the range of 170 to 290°C when differential thermal analysis (DTA) is performed in the presence of components (F) and (G) at a heating rate of 10°C / min.

[0056] In addition, it is believed that the formation of a mesh network at the copper or copper alloy interface due to hydrogen bonding and coordination can alleviate stress caused by expansion and contraction during thermal cycling. Furthermore, by making the molecular weight of component (D) 250 or more, the thermal weight loss temperature of the compound itself is improved, making it more likely to remain in the film after the thermal curing process, contributing to improved adhesion and reliability.

[0057] Furthermore, the component (D) is represented by the following general formula (6): [wherein R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 4; A is a monovalent to pentavalent organic group; and at least one of the ortho- and para-positions of the hydroxy group in general formula (6) is a hydrogen atom] is preferred from the viewpoint of adhesion on copper or a copper alloy and reliability after thermal cycling.

[0058] Furthermore, the component (D) is represented by the following general formula (7): [wherein, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; each n may be the same or different and independently represent an integer of 1 to 2; each m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 3; A is a trivalent to pentavalent organic group; and at least one of the ortho- and para-positions of the hydroxy group in general formula (7) is a hydrogen atom] is preferred from the viewpoint of adhesion on copper or a copper alloy and reliability after thermal cycling.

[0059] Furthermore, the component (D) is represented by the following general formula (8): [wherein, each R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; each n may be the same or different and independently represent an integer of 1 to 2; each m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 3; A is a monovalent to pentavalent organic group; and at least one of the ortho-position or para-position of the hydroxy group in general formula (8) is a hydrogen atom] is preferred from the viewpoint of adhesion on copper or a copper alloy and reliability after thermal cycling.

[0060] Furthermore, the component (D) is represented by the following general formula (9): [wherein R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 4; A is a monovalent to pentavalent organic group; and at least one ortho-position of the hydroxy group in general formula (9) is a hydrogen atom] is preferred from the viewpoint of adhesion on copper or a copper alloy and reliability after thermal cycling.

[0061] Furthermore, the component (D) is represented by the following general formula (10): [wherein R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 3; A is a monovalent to pentavalent organic group; and at least one ortho-position of the hydroxy group in general formula (10) is a hydrogen atom] is preferred from the viewpoint of adhesion on copper or a copper alloy and reliability after thermal cycling.

[0062] Furthermore, the component (D) is represented by the following general formula (11): [R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 2; A is a monovalent to pentavalent organic group; and at least one of the ortho-positions of the hydroxy group in general formula (11) is a hydrogen atom] is preferred from the viewpoint of adhesion on copper or a copper alloy and reliability after thermal cycling.

[0063] (D) Specific examples of the compound having a molecular weight of 250 or more and represented by general formula (1) include bis(4-hydroxyphenyl)sulfone, 2,2'-diallylbisphenol A, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 4,4'-{(propane-2,2-diyl)bis[1-(4-hydroxyphenyl)cyclohexane-1,4-diyl]}diphenol, 4,4',4'',4'''-[4,4'-(1-methylethane-1,1-diyl)dicyclohexane-1,1,1',1'-tetrayl]tetrakis(2-methylphenol), α,α,α'-tris(3-methyl-4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 2-[bis (4-hydroxy-2,3,5-trimethylphenyl)methyl]phenol, 1,1,1-tris(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(4-hydroxyphenyl)-4,4'-dimethylbiphenyl, 9,9-bis(4-hydroxyphenyl)fluorene, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, tris(4-hydroxyphenyl)methane, 4-tritylphenol, 4,4',4''-(1-methyl-1,3,3-propaneethynyl)tris[2-(tert-butyl)phenol], and the like.

[0064] The amount of the compound (D) having a molecular weight of 250 or more and represented by general formula (1) is 0.1 to 30 parts by mass, preferably 1 to 15 parts by mass, per 100 parts by mass of the resin (A). When the amount is 0.01 part by mass or more, adhesion to copper or copper alloys is exhibited. On the other hand, when the amount is 30 parts by mass or less, excellent storage stability is achieved.

[0065] (E) Solvent The (E) solvent in this embodiment will be described. As the (E) solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A1) polyimide precursor and the polyimide. Specific examples of the (E) solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, and N-cyclohexyl-2-pyrrolidone, which can be used alone or in combination of two or more.

[0066] The solvent can be used in an amount of, for example, 30 parts by mass to 1,500 parts by mass, preferably 100 parts by mass to 1,000 parts by mass, relative to 100 parts by mass of the (A) resin, depending on the desired coating film thickness and viscosity of the negative-type photosensitive resin composition.

[0067] Furthermore, from the viewpoint of improving the storage stability of the negative-type photosensitive resin composition, a solvent containing an alcohol is preferred. Suitable alcohols are typically alcohols 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. 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.

[0068] 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% by mass to 50% by mass, and more preferably 10% by mass to 30% by mass, based on the mass of the total solvent. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the negative photosensitive resin composition is improved. On the other hand, when the content is 50% by mass or less, the solubility of the (A) polyimide precursor is improved, which is preferable.

[0069] (F) Thermal Crosslinking Agent The negative photosensitive resin composition of the present embodiment may further contain (F) a thermal crosslinking agent. By containing (F) a thermal crosslinking agent, the film strength after thermal curing is improved, and reliability during thermal cycling is improved.

[0070] The thermal crosslinking agent contains a compound that has the function of initiating an addition reaction or a condensation polymerization reaction by heat. These reactions occur between the components (A) and (F), between the components (D) and (F), between the components (F) themselves, and between the component (F) and other components described below, and the reaction temperature is preferably 150°C or higher.

[0071] Examples of the component (F) include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds.

[0072] Examples of alkoxymethyl compounds include those of the following formula: Examples of the compound include compounds represented by the following formula:

[0073] Examples of epoxy compounds include epoxy compounds containing a bisphenol A group and hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.).

[0074] Examples of the oxetane compound include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl) ) diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicate, phenol novolac-type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei, trade name), and OXT221 (manufactured by Toagosei, trade name).

[0075] Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3- phenylene bis(maleimide), N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene bis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0076] Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allylphenylsulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0077] Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882N manufactured by Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.), ), 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (for example, Takenate B-815N manufactured by Mitsui Chemicals, Inc., and Bronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (for example, Takenate B-846N manufactured by Mitsui Chemicals, Inc., and Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (for example, 7950, 7951, and 7990 manufactured by Baxenden).

[0078] From the viewpoint of reactivity, it is preferable that component (F) has a methylol group. By having a methylol group, the thermal crosslinking reaction with component (A) or component (D) proceeds efficiently, and the amount of volatile components is reduced, thereby improving the film remaining rate upon thermal curing. Component (F) may be used alone or in combination of two or more types.

[0079] From the viewpoints of heat resistance and relief pattern development characteristics, the content of the component (F) is preferably from 0.2 to 40 mass %, and more preferably from 1 to 20 mass %, based on the total mass of the solid content of the photosensitive resin composition.

[0080] The negative photosensitive resin composition of the present embodiment may further contain (G) an acidic compound having a pKa of 1 to 10. By containing (G) an acidic compound having a pKa of 1 to 10, the storage stability of the varnish is improved.

[0081] Furthermore, in this embodiment, it is preferable to combine component (G) with a thermal crosslinking agent (F). By including (G) an acidic compound with a pKa of 1 to 10 and (F) a thermal crosslinking agent, reliability during thermal cycling can be further improved. While the reason for this is unclear, it is believed to be due to catalytic promotion of the crosslinking reaction of the thermal crosslinking agent, improving film strength after thermal curing. Furthermore, by including components (F) and (G), the reaction of component (D) is promoted, making it easier to achieve the effects of the present invention. In this embodiment, when DTA analysis of component (D) in the presence of component (G) is performed, an exothermic peak appears in the range of 170 to 290°C.

[0082] The component (G) is not particularly limited as long as it has a pKa in the range of 1 to 10, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, mandelic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, malonic acid, succinic acid, citric acid, glutaric acid, adipic acid, malic acid, ascorbic acid, tartaric acid, valeric acid, benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-nitrobenzoic acid, carbonic acid, boronic acid, phosphoric acid, phosphonic acid, and phosphinic acid.

[0083] From the viewpoints of heat resistance and relief pattern development characteristics, the content of the component (G) is preferably 0.01 to 5 mass %, and more preferably 0.1 to 2 mass %, based on the total mass of the solids content of the photosensitive resin composition.

[0084] (Other Components) In the present embodiment, the negative photosensitive resin composition may further contain components other than the components (A) to (G) described above. Examples of the other components include resin components other than the resin (A), sensitizers, adhesion promoters, polymerization inhibitors, and hindered phenol compounds.

[0085] In an embodiment, the negative-type photosensitive resin composition may further contain a resin component other than the resin (A). Examples of resin components that can be contained in the negative-type photosensitive resin composition include polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The amount of these resin components to be added is preferably in the range of 0.01 to 20 parts by mass per 100 parts by mass of the resin (A).

[0086] In the present embodiment, the negative photosensitive resin composition may optionally contain a sensitizer 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-dimethylaminocinnamylideneindane. 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 combination of two or more (for example, two to five types).

[0087] The amount of the sensitizer to be added is preferably 0.1 to 25 parts by mass per 100 parts by mass of the resin (A).

[0088] In this embodiment, in order to improve the adhesion between a film formed using the negative photosensitive resin composition and a substrate, an adhesion aid can be optionally blended into the negative photosensitive resin composition. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, and N-[3-(triethoxysilyl)propyl]phthalate. Examples of the adhesive agent include silane coupling agents such as amido acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride and N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate) and ethylacetoacetate aluminum diisopropylate.

[0089] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The amount of the adhesion aid to be blended is preferably in the range of 0.5 parts by mass to 25 parts by mass per 100 parts by mass of the (A) resin.

[0090] In this embodiment, a thermal polymerization inhibitor can be optionally blended to improve the stability of the viscosity and photosensitivity of the negative-type photosensitive resin composition, particularly when stored in a solvent-containing solution. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, 4-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.

[0091] The amount of the thermal polymerization inhibitor to be added is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the resin (A).

[0092] In this embodiment, a hindered phenol compound can be optionally blended into the negative photosensitive resin composition in order to suppress discoloration on copper.

[0093] Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydrox-phenyl)propionate] ... 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-tri Azine-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) 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione )-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and the like, but are not limited thereto.

[0094] 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.

[0095] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity, more preferably 0.5 to 10 parts by mass. When the amount of the hindered phenol compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, for example, when the negative photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, when the amount is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0096] In this embodiment, an anti-rust agent can be optionally blended to suppress copper migration. The anti-rust agent is not limited as long as it can prevent metals from rusting, but examples of the anti-rust agent include nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include azole compounds and purine derivatives.

[0097] Examples of the 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, azole, 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, and 1-methyl-1H-tetrazole.

[0098] Particularly preferred azole compounds include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0099] 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, and 8-aminoadenine. purine, 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, and 8-azahypoxanthine, as well as derivatives thereof.

[0100] When the negative-tone photosensitive resin composition contains an azole compound or a purine derivative, the blending amount thereof is preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.1 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the (A) resin is 0.05 parts by mass or more, discoloration of the copper or copper alloy surface is suppressed when the negative-tone photosensitive resin composition of this embodiment is formed on copper or a copper alloy. On the other hand, when the blending amount of the azole compound is 5 parts by mass or less, excellent photosensitivity is achieved.

[0101] <Method for Producing Cured Relief Pattern> In the present embodiment, it is possible to provide a method for producing a cured relief pattern, comprising the following steps (1) to (4): (1) a step of applying the negative photosensitive resin composition of the present embodiment onto a substrate to form a photosensitive resin layer on the substrate, (2) a step of exposing the photosensitive resin layer to light, (3) a step of developing the exposed photosensitive resin layer to form a relief pattern, and (4) a step of heat-treating the relief pattern to form a cured relief pattern.

[0102] Each step will be described below.

[0103] (1) Step of applying the negative photosensitive resin composition of the present embodiment onto a substrate to form a photosensitive resin layer on the substrate In this step, the negative photosensitive resin composition of the present embodiment is applied onto 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 can be used, such as a method of applying using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or a method of spray application using a spray coater.

[0104] If necessary, the coating film made of the negative photosensitive resin composition can be dried. Examples of drying methods include air drying, heat drying using an oven or a hot plate, and vacuum drying. It is desirable to dry the coating film under conditions that do not cause imidization of the polyimide precursor (A) in the negative photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be performed at 20°C to 140°C for 1 minute to 1 hour. A photosensitive resin layer can be formed on the substrate in this manner.

[0105] (2) Step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed in step (1) above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, a mirror projection, or a stepper, either directly or through a photomask or reticle having a pattern.

[0106] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed as necessary using any combination of temperature and time for the purpose of improving photosensitivity, etc. The baking conditions are preferably in the range of a temperature of 40°C to 120°C and a time of 10 seconds to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the negative-type photosensitive resin composition.

[0107] (3) Step of Developing the Exposed Photosensitive Resin Layer to Form a Relief Pattern. In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The development method for developing the exposed (irradiated) photosensitive resin layer can be any of the conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment. Furthermore, after development, a post-development bake may be performed at any temperature and time combination, as needed, for the purpose of adjusting the shape of the relief pattern. The developer used for development is preferably, for example, a good solvent for the negative-tone photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Examples of suitable good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition. Two or more types of each solvent, for example, several types, can also be used in combination. The negative photosensitive resin composition of this embodiment is preferably used for development with a developer containing 90% by mass or more of an organic solvent.

[0108] (4) Step of Heating the Relief Pattern to Form a Cured Relief Pattern In this step, the relief pattern obtained by the development described above is heated to dissolve the photosensitive component and imidize the (A) polyimide precursor, thereby converting it into a cured relief pattern made of polyimide. 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 200°C to 400°C for 30 minutes to 5 hours. The atmospheric gas used during heat curing may be air, or an inert gas such as nitrogen or argon.

[0109] <Semiconductor Device> This embodiment also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern. Therefore, a semiconductor device can be provided that has a substrate that is a semiconductor element and a cured relief pattern of polyimide 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.

[0110] <Display Device> In this embodiment, a display device is provided that includes a display element and a cured film provided on the display element, the cured film having the above-described cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

[0111] The negative photosensitive resin composition of the present invention is useful not only for application to the semiconductor devices described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[0112] The present embodiment will be specifically described below using examples. However, the present embodiment is not limited to the examples. In the examples, comparative examples, and production examples, the physical properties of the polymer and photosensitive resin composition were measured and evaluated according to the following methods.

[0113] (1) Evaluation of Copper Adhesion A photosensitive resin composition prepared by the method described below was applied to a 6-inch silicon wafer that had been previously sputtered with Ti and Cu, and prebaked, in the same manner as in the preparation of the cured relief pattern described above. The wafer was then heat-treated for 2 hours at 230°C in a nitrogen atmosphere using a temperature-programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured relief pattern of resin approximately 10 μm thick on the Cu. The heat-treated film was evaluated for adhesion properties between the copper substrate and the cured resin coating film according to the cross-cut method of JIS K 5600-5-6, based on the following criteria: "S": The lattice number of the cured resin coating film adhered to the substrate is 100; "A": The lattice number of the cured resin coating film adhered to the substrate is 70 to 99; "B": The lattice number of the cured resin coating film adhered to the substrate is 40 to 69; "C": The lattice number of the cured resin coating film adhered to the substrate is less than 40.

[0114] (2) Evaluation of film remaining rate upon curing The photosensitive resin composition was spin-coated onto a silicon wafer, and the silicon wafer and spin-coated film were pre-baked on a hot plate at 110°C for 240 seconds to form a coating film with a thickness of 10 µm. This coating film was exposed to light at an exposure dose of 500 mJ / cm using a stepper FPA-3030iWa (manufactured by Canon) with an exposure wavelength of i-line (365 nm) through a test patterned reticle. ２ The film was exposed by irradiating it with i-rays. After exposure, the film was developed using a developer (D-SPIN) and cured in a temperature-rising programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg) at 230°C for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern. At this time, the film thickness was measured before and after curing using a contact film thickness measuring device P-15 (manufactured by KLA Tencor Corporation), and the remaining film ratio at the time of curing was calculated.

[0115] (3) Thermal Cycle Test (TCT) Evaluation The photosensitive resin composition was spin-coated onto a silicon wafer, and the silicon wafer and spin-coated film were pre-baked on a hot plate at 110°C for 240 seconds to form a coating film with a thickness of 10 μm. The film thickness was measured using a film thickness measuring device Lambda Ace (manufactured by Dainippon Screen Mfg. Co., Ltd.). This coating film was exposed to light at an exposure dose of 500 mJ / cm using a stepper FPA-3030iWa (manufactured by Canon) with an exposure wavelength of i-line (365 nm) through a test patterned reticle. ２ The film was exposed by irradiating it with i-rays. After exposure, the film was developed using a developer (D-SPIN) and cured in a temperature-rising programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg) in a nitrogen atmosphere at 230°C for 2 hours to obtain a cured relief pattern. The obtained relief pattern was subjected to a thermal cycle chamber TSE-11 (manufactured by Espec Corporation) at temperatures from -65°C to 150°C for 30 minutes each, for 1000 cycles, and then the film surface was observed with an optical microscope. Films with no cracks were rated A, and films with cracks were rated B.

[0116] (4) Differential thermal analysis evaluation of component (D) Component (D), MX-270 as component (F), and mandelic acid as component (G) were placed in an aluminum macrocell in a weight ratio of 1:1:0.1 to prepare a measurement sample. Thermal change DTA was measured under the following conditions using a differential thermal / thermogravimetric (TG / DTA) simultaneous measurement device (DTG-60A, Shimadzu Corporation). From the measurement results, a peak that was 3 μV or more from the baseline and convex in the positive direction was defined as an exothermic peak. Measurement atmosphere: nitrogen Gas flow rate: 50 ml / min Heating rate: 10°C / min Upper temperature rise limit: 500°C

[0117] (5) Measurement of absorbance of component (D): 0.1 g of component (D) was dissolved in 100 mL of N-methyl-2-pyrrolidone solvent to prepare a 0.1 vol% solution. The range of 800 to 200 nm was scanned using an ultraviolet-visible spectrophotometer (UV-1800, Shimadzu Corporation), and the absorbance at 365 nm was measured.

[0118] [Component (A)] <Production Example 1> (Polymer A-1) 155 g (0.5 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, and 135 g (1.04 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 79.1 g of pyridine was added with stirring, and the mixture was stirred for 16 hours.

[0119] Next, under ice cooling, a solution of 203 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 89 g (0.44 mol) of diaminodiphenyl ether (DADPE) in 280 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 4 hours, 40 ml of ethyl alcohol was added and stirred for 1 hour, and then 1 liter of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0120] The resulting reaction solution was added to 4 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 30 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdery polymer (Polymer A-1). The molecular weight of Polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 24,000.

[0121] <Production Example 2> (Polymer A-2) Except for using 94 g (0.44 mol) of 2,2'-dimethyl-4,4-diaminobiphenyl (m-TB) instead of 89 g of DADPE, a reaction was carried out in the same manner as in Production Example 1 to obtain Polymer A-2. 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 26,000.

[0122] <Production Example 3> (Polymer A-3) Except for using 46 g (0.44 mol) of p-phenylenediamine (pPD) instead of 89 g of DADPE, a reaction was carried out in the same manner as in Production Example 1 to obtain Polymer A-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 19,000.

[0123] <Production Example 4> (Polymer A-4) Except for using 176 g (0.44 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) instead of 89 g of DADPE, a reaction was carried out in the same manner as in Production Example 1 to obtain Polymer A-4. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 25,000.

[0124] <Production Example 5> (Polymer A-5) A reaction was carried out in the same manner as in Production Example 1, except that 124 g (0.4 mol) of ODPA and 29 g (0.1 mol) of BPDA were used instead of 155 g of ODPA, to obtain Polymer A-5. 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 20,000.

[0125] <Production Example 6> (Polymer A-6) Except for using 62 g (0.2 mol) of ODPA and 65 g (0.3 mol) of pyromellitic dianhydride (PMDA) instead of 155 g of ODPA, and using 94 g (0.44 mol) of m-TB instead of 89 g of DADPE, a reaction was carried out in the same manner as in Production Example 1, to obtain Polymer A-6. 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 20,000.

[0126] <Production Example 7> (Synthesis of Polymer A-7 as Resin (A)) A 3 L separable glass flask equipped with a stirrer and a stirring blade was charged with 64.1 g (0.20 mol) of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 97.7 g (0.22 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), and 500 g of DMAc, and the mixture was stirred to dissolve the TFMB and 6FDA in the DMAc. Further, stirring was continued for 12 hours at room temperature under a nitrogen stream to carry out a polymerization reaction, yielding a polyamic acid solution.

[0127] To the resulting polyamic acid solution, 16 g of pyridine was added, and then 82 g of acetic anhydride was added dropwise at room temperature. Thereafter, the liquid temperature was maintained at 20 to 100°C and stirring was continued for 24 hours to carry out the imidization reaction, thereby obtaining a polyimide solution.

[0128] The obtained polyimide solution was poured into 1,000 g of methanol in a 5 L container while stirring, to precipitate a polyimide resin. The solid polyimide resin was then filtered off using a suction filtration device. It was then washed with 1,000 g of methanol. It was then dried at 100°C for 24 hours using a vacuum dryer, and then further dried at 200°C for 3 hours. This yielded Polymer (A-7), a polyimide powder having acid anhydride groups at its terminals. 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 25,000.

[0129] The compositions of polymers A-1 to A-7 as component (A) are shown in Table 1.

[0130]

[0131] Example 1 (A) 100 g of polymer A-1, (B) 6.0 g of photopolymerization initiator B-1, (C) 8.0 g of NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.) as radical polymerizable monomer C-1, (D) 8 g of compound D-1, 0.5 g of Cyanox 1790 as a radical polymerization inhibitor, and 0.5 g of 8-azaadenine as a rust inhibitor were dissolved in (E) 160 g of solvent E-1 (γ-butyrolactone) and 40 g of solvent E-2 (dimethyl sulfoxide). The viscosity of the resulting solution was adjusted to about 4.0 Pa s by further adding a small amount of the solvent, yielding a photosensitive resin composition.

[0132] Examples 2 to 20 and Comparative Examples 1 to 3 Photosensitive resin compositions similar to those in Example 1 were prepared except that they were formulated in the blending ratios shown in Table 2, and evaluations were carried out in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0133] It was confirmed that in Examples 2 to 20, including Example 1, semiconductor devices could be fabricated using the cured relief patterns obtained from those photosensitive resin compositions as interlayer insulating films, and that these devices operated without any problems.

[0134] Table 2 shows the compositions of the photosensitive resin compositions of Examples 1 to 20 and Comparative Examples 1 to 3, and Table 3 shows the evaluation results thereof.

[0135]

[0136]

[0137] The compounds of components (B) to (G) used in this example are shown below. Component (B) B-1:

[0138] (D) Component D-1: 2,2'-diallylbisphenol A (manufactured by Wako Pure Chemical Industries, Ltd.) D-2: bis(4-hydroxyphenyl)sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) D-3: TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) D-4: TrisOC-PA (manufactured by Honshu Chemical Industry Co., Ltd.) D-5: TekOC-DABP (manufactured by Honshu Chemical Industry Co., Ltd.) D-6: N-P4HBPA (manufactured by Honshu Chemical Industry Co., Ltd.) D-7: TekOC-4HBPA (manufactured by Honshu Chemical Industry Co., Ltd.) D-8: TrisP-236S (manufactured by Honshu Chemical Industry Co., Ltd.) D-9: 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) D-10: 2,6-di-tert-butyl-4-methylphenol (Tokyo Chemical Industry Co., Ltd.) D-11: naphthoquinone diazide sulfonic acid ester

[0139]

[0140] Component (F) F-1: Nikalac MX-290 (manufactured by Sanwa Chemical Co., Ltd.) F-2: Nikalac MX-270 (manufactured by Sanwa Chemical Co., Ltd.) F-3: Nikalac MW-390 (manufactured by Sanwa Chemical Co., Ltd.)

[0141] (G) Component G-1: Mandelic acid

[0142] As is clear from the table, all of the examples exhibited excellent copper adhesion and a high film remaining rate. Furthermore, good results were obtained in the thermal cycle test. In contrast, the comparative examples did not provide satisfactory results.

[0143] The photosensitive resin composition of the present invention is suitable as a photosensitive material used for forming, for example, insulating materials for electronic components, and passivation films, buffer coat films, and interlayer insulating films in semiconductor devices. The photosensitive resin composition of the present invention can also be suitably used in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. A negative type photosensitive resin composition comprising the following components: (A) a resin which is (A1) a polyimide precursor or (A2) a polyimide, (B) a photopolymerization initiator, (C) a radical polymerizable monomer, and (D) a compound represented by the following general formula (1), wherein the component (D) has a molecular weight of 250 or more and an absorbance at 365 nm of 0.05 or less at a concentration of 0.1 vol %. [In the formula, R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 5; A is a monovalent to pentavalent organic group; and at least one of the ortho-positions or para-positions of the hydroxy group in general formula (1) is a hydrogen atom, and the ortho-position is not a t-butyl group.] 2. The component (A) is (A1) a polyimide precursor having the following general formula (2): {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group; R １ and R ２ At least one of the above formula (1) contains a radical reactive group.

3. The polyimide precursor (A1) is represented by the following general formula (2): {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group; R １ and R ２ At least one of the following general formula (3): (In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. (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 m2 is an integer of 2 to 10. １ , and R ２ The negative type photosensitive resin composition according to claim 1 or 2, wherein at least one of the above is a group represented by general formula (3) or (4).

4. The negative photosensitive resin composition according to claim 1 or 2, wherein the component (D) is represented by the following general formula (6): [In the formula, R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 4; A is a divalent to pentavalent organic group; and at least one of the ortho-positions or para-positions of the hydroxy group in general formula (6) is a hydrogen atom.] 5. The negative photosensitive resin composition according to claim 1 or 2, wherein the component (D) is represented by the following general formula (7): [In the formula, R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 3; A is a trivalent to pentavalent organic group; and at least one of the ortho-position or para-position of the hydroxy group in general formula (7) is a hydrogen atom.] 6. The negative photosensitive resin composition according to claim 1 or 2, wherein the component (D) is represented by the following general formula (8): [In the formula, R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 3; A is a tetravalent or pentavalent organic group; and at least one of the ortho-position or para-position of the hydroxyl group in general formula (8) is a hydrogen atom.] 7. The negative photosensitive resin composition according to claim 1 or 2, wherein the component (D) is represented by the following general formula (9): [In the formula, R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 4; A is a monovalent to pentavalent organic group; and at least one of the ortho positions of the hydroxy group in general formula (9) is a hydrogen atom.] 8. The negative photosensitive resin composition according to claim 1 or 2, wherein the component (D) is represented by the following general formula (10): [In the formula, R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 3; A is a monovalent to pentavalent organic group; and at least one of the ortho positions of the hydroxy group in general formula (10) is a hydrogen atom.] 9. The negative photosensitive resin composition according to claim 1 or 2, wherein the component (D) is represented by the following general formula (11): [In the formula, R may be the same or different and independently represent a hydrogen atom, an alkyl group, or an alkoxy group; n may be the same or different and independently represent an integer of 1 to 2; m may be the same or different and independently represent an integer of 1 to 4; k is an integer of 1 to 2; A is a monovalent to pentavalent organic group; and at least one of the ortho positions of the hydroxy group in general formula (11) is a hydrogen atom.] 10. The negative photosensitive resin composition according to claim 1, further comprising (F) a thermal crosslinking agent.

11. The negative type photosensitive resin composition according to claim 10, wherein the thermal crosslinking agent (F) has a methylol group.

12. The negative photosensitive resin composition according to claim 1 or 10, further comprising (G) an acidic compound having a pKa value of 1 to 10.

13. Y in the general formula (2) １ and Y ２ The negative type photosensitive resin composition according to claim 2, wherein the compound is represented by at least one structure selected from the group consisting of the following general formulas (12) and (13): (In the formula, R １１ , R １２ , R １３ and R １４ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different. (In the formula, R １５ ~R ２２ are hydrogen atoms, halogen atoms, monovalent organic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be different or the same.

14. A negative type photosensitive resin composition comprising the following components: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a radical polymerizable monomer; and (D) a compound having a molecular weight of 250 or more, (F) a thermal crosslinking agent, and (G) a compound which exhibits an exothermic peak of +3 μV or more in the range of 170 to 290° C. in a thermal change DTA when differential thermal analysis is performed at a heating rate of 10° C. / min in the presence of an acidic compound having a pKa of 1 to 10.

15. The negative photosensitive resin composition according to claim 1, which is used for forming a passivation film, a buffer coat film, or an interlayer insulating film in a semiconductor device.

16. A method for producing a cured relief pattern, comprising: (1) a step of forming a photosensitive resin layer on a substrate by applying a negative photosensitive resin composition according to claim 1, 2, 14, or 15 onto the substrate; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) a step of heat-treating the relief pattern to form a cured relief pattern.

17. A semiconductor device comprising a cured relief pattern obtained from the negative photosensitive resin composition according to claim 1, 2, 14 or 15.