Negative photosensitive resin composition and method for manufacturing cured relief pattern using the same

Abstract

To provide: a negative photosensitive resin composition which makes it possible to carry out thermal curing at a relatively low temperature, and which offers good chemical resistance and is less likely to cause cloudiness during application; and a method for manufacturing a cured relief pattern using the negative photosensitive resin composition.SOLUTION: A negative photosensitive resin composition includes 100 pts.mass of a polyimide precursor and / or polyimide, 20-150 pts.mass of a radical polymerizable compound, 0.001-1 pt.mass of a surfactant, and 0.1-10 pts.mass of a photoinitiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a negative-type photosensitive resin composition and a method for producing a cured relief pattern using the same. [Background technology]

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which combine excellent heat resistance and electrical and mechanical properties, have been used as insulating materials for electronic components, and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these resins, those provided in the form of photosensitive resin compositions can easily form heat-resistant relief pattern films by applying the composition, exposing it to light, developing it, and subjecting it to a thermal imidization treatment through curing. Such photosensitive resin compositions have the advantage of enabling significant process reduction compared to conventional non-photosensitive materials.

[0003] On the other hand, in recent years, the mounting method (packaging structure) of semiconductor devices on printed wiring boards has also changed in view of improvements in integration density and computing functionality, as well as the miniaturization of chip sizes. Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which a polyimide coating directly contacts solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher-density mounting. Furthermore, structures such as FO (fan-out) have been proposed, in which the surface of a semiconductor chip has multiple redistribution layers with an area larger than the area of ​​the semiconductor chip.

[0004] Thermally cyclizable resins, such as polyimide precursor resins, can be cyclized by heat to form cured films with excellent physical and chemical properties. However, these cyclization reactions require heat treatment at high temperatures (e.g., 350°C). However, when the area of ​​a packaging structure is large, such as the above-mentioned FO, the thermal expansion caused by heat treatment at high temperatures can lead to warping of the support, disconnection of the metal rewiring layer, or destruction of the insulating layer. Therefore, there is a demand for lowering the treatment temperature. However, lowering the treatment temperature can lead to a problem of reduced chemical resistance of the cured relief pattern.

[0005] Patent Document 1 describes adding 35 parts by mass of a radical polymerizable compound to 100 parts by mass of a polymer in order to improve the chemical resistance of a cured relief pattern. According to this document, by adding a total of 35 parts by mass of two specific radical polymerizable compounds, a cured relief pattern exhibiting good chemical resistance can be obtained even when cured at a low temperature of 225°C. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2018 / 155639 [Patent Document 2] U.S. Patent No. 5,502,143 Summary of the Invention [Problem to be solved by the invention]

[0007] However, as described in Patent Document 1, photosensitive resin compositions containing a large amount of radically polymerizable compounds have the problem of easily becoming cloudy when applied to a substrate. Therefore, an object of the present disclosure is to provide a negative-tone photosensitive resin composition that can be thermally cured at a relatively low temperature, exhibits good chemical resistance, and is less likely to become cloudy when applied, and a method for producing a cured relief pattern using the same. [Means for solving the problem]

[0008] The present inventors have found that the above-mentioned problems can be solved by combining a polyimide precursor and / or a polyimide with a radical polymerizable compound, a surfactant, and a photopolymerization initiator in specific amounts. The embodiments of the present invention are exemplified in the following items [1] to

[19] . [1] 100 parts by mass of a polyimide precursor and / or a polyimide; 20 to 150 parts by mass of a radical polymerizable compound; 0.001 to 1 parts by mass of a surfactant; 0.1 to 10 parts by mass of a photopolymerization initiator; A negative photosensitive resin composition comprising: [2] 2. The negative photosensitive resin composition according to item 1, wherein the negative photosensitive resin composition contains the polyimide precursor but does not contain the polyimide. [3] 3. The negative photosensitive resin composition according to item 1 or 2, wherein the surfactant is at least one selected from the group consisting of a fluorine-based surfactant and a silicone-based surfactant. [4] 4. The negative photosensitive resin composition according to any one of items 1 to 3, wherein the surfactant is a fluorine-containing surfactant. [5] 5. The negative photosensitive resin composition according to any one of items 1 to 4, wherein at least one of the radical polymerizable compounds is a radical polymerizable compound having at least one group selected from the group consisting of a hydroxyl group and a urea group. [6] 6. The negative photosensitive resin composition according to any one of items 1 to 5, wherein the radical polymerizable compound comprises a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound. [7] 6. The negative photosensitive resin composition according to any one of items 1 to 5, wherein the radical polymerizable compound comprises a nitrogen atom-containing radical polymerizable compound and a nitrogen atom-free radical polymerizable compound. [8] The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (1): [ka] {In formula (1), X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group.} 8. The negative photosensitive resin composition according to any one of items 1 to 7, comprising a polyimide precursor having a structural unit represented by the following formula: [9] In the above general formula (1), at least one of R1 and R2 is represented by the following general formula (2): [ka] {In formula (2), L1, L2, and L3 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.} Item 9. The negative photosensitive resin composition according to item 8, having a structural unit represented by the following formula:

[10] The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (3): [ka] {In formula (3), n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group.} 10. The negative photosensitive resin composition according to any one of items 1 to 9, comprising a polyimide precursor having a structural unit represented by the following formula:

[11] The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (4): [ka] {In formula (4), n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group.} 11. The negative photosensitive resin composition according to any one of items 1 to 10, comprising a polyimide precursor having a structural unit represented by the following formula:

[12] The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (5): [ka] {In formula (5), n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group.} 12. The negative photosensitive resin composition according to any one of items 1 to 11, comprising a polyimide precursor having a structural unit represented by the following formula:

[13] The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (6): [ka] {In formula (6), n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group.} 13. The negative photosensitive resin composition according to any one of items 1 to 12, comprising a polyimide precursor having a structural unit represented by the following formula:

[14] 14. The negative photosensitive resin composition according to any one of items 1 to 13, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an insulating member.

[15] 15. The negative photosensitive resin composition according to any one of items 1 to 14, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film.

[16] (1) A step of applying the negative photosensitive resin composition according to any one of items 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; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising:

[17] Item 17. The method for producing a cured relief pattern according to Item 16, wherein the heat treatment in step (4) is a heat treatment at 200°C or lower.

[18] Item 17. The method for producing a cured relief pattern according to Item 16, wherein the heat treatment in step (4) is a heat treatment at 170°C or lower.

[19] 16. A method for producing a polyimide, comprising curing the negative photosensitive resin composition according to any one of items 1 to 15. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a negative-type photosensitive resin composition that can be thermally cured at a relatively low temperature, exhibits good chemical resistance, and is less likely to become cloudy upon application, and a method for producing a cured relief pattern using the same. DETAILED DESCRIPTION OF THE INVENTION

[0010] <Negative Photosensitive Resin Composition> The negative photosensitive resin composition of the present disclosure comprises: 100 parts by mass of (A1) a polyimide precursor and / or (A2) a polyimide; 20 to 150 parts by mass of a radical polymerizable compound (B); 0.001 to 1 parts by mass of a surfactant (C); 0.1 to 10 parts by mass of (D) a photopolymerization initiator; The (A1) polyimide precursor and / or the (A2) polyimide may be used either alone or in combination, but is preferably used alone. The negative photosensitive resin composition more preferably contains a polyimide precursor, and even more preferably contains a polyimide precursor and does not contain a polyimide.

[0011] (A1) Polyimide precursor The (A1) polyimide precursor is a resin component contained in the negative-tone photosensitive resin composition, and is converted into a polyimide by a thermal cyclization treatment. The structure of the (A1) polyimide precursor is not limited as long as it is a resin that can be used in the negative-tone photosensitive resin composition, but it is preferable that the polyimide precursor is not alkali-soluble. Since the polyimide precursor is not alkali-soluble, high chemical resistance can be obtained.

[0012] The polyimide precursor is preferably a polyamide having a structure represented by the following general formula (1). [ka] {In formula (1), X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group.}

[0013] In the general formula (1), at least one of R1 and R2 is represented by the following general formula (2): [ka] {In formula (2), L1, L2, and L3 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.} It is preferable that the compound has a structural unit represented by the following formula:

[0014] The proportion of hydrogen atoms in R1 and R2 in general formula (1) is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less, based on the total number of moles of R1 and R2. The proportion of monovalent organic groups represented by general formula (2) in R1 and R2 in general formula (1) is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, based on the total number of moles of R1 and R2. It is preferable that the proportion of hydrogen atoms and the proportion of organic groups of general formula (2) be within the above ranges from the viewpoints of photosensitive properties and storage stability.

[0015] In general formula (1), n1 is not limited as long as it is an integer of 2 to 150, but from the viewpoint of the photosensitivity and mechanical properties of the negative photosensitive resin composition, it is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

[0016] In general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the -COOR1 group, the -COOR2 group, and the -CONH- group are located at the ortho positions relative to each other, or an alicyclic aliphatic group. Specific examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, such as those represented by the following general formula (20): [ka] {wherein R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent hydrocarbon group, and a C1-C10 monovalent fluorine-containing hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.} However, the examples are not limited to these. The structure of X1 may be one type or a combination of two or more types. The X1 group having the structure represented by the above formula (20) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitivity.

[0017] As the X1 group, among the structures represented by the above formula (20), particularly, those represented by the following formula: [ka] A tetravalent organic group represented by the formula: {wherein R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and m is an integer selected from 0 to 3} is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

[0018] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (21): [ka] {wherein R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent hydrocarbon group, and a C1-C10 monovalent fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.} However, the examples are not limited to these. The structure of Y1 may be one type or a combination of two or more types. The Y1 group having the structure represented by the above formula (21) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0019] As the Y1 group, among the structures represented by the above formula (21), particularly, those represented by the following formula: [ka] A divalent group represented by the formula: {wherein R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4} is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

[0020] In the general formula (2), L1 is preferably a hydrogen atom or a methyl group, and L2 and L3 are preferably hydrogen atoms from the viewpoint of photosensitivity. m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitivity.

[0021] In one embodiment, the polyimide precursor (A1) is represented by the following general formula (3): [ka] {wherein R1, R2, and n1 are as defined above.} It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0022] In general formula (3), at least one of R1 and R2 is more preferably a monovalent organic group represented by general formula (2). When the polyimide precursor (A1) contains a polyimide precursor represented by general formula (3), chemical resistance is particularly enhanced.

[0023] In one embodiment, the polyimide precursor (A1) is represented by the following general formula (4): [ka] {wherein R1, R2, and n1 are as defined above.} From the viewpoint of thermal properties, it is preferable that the polyimide precursor has a structural unit represented by the following formula: In general formula (4), at least one of R1 and R2 is more preferably a monovalent organic group represented by the above general formula (2).

[0024] The polyimide precursor (A1) tends to have particularly high resolution when it contains both the structural unit represented by general formula (3) and the structural unit represented by general formula (4). For example, the polyimide precursor (A1) may contain a copolymer of the structural unit represented by general formula (3) and the structural unit represented by general formula (4), or may be a mixture of the polyimide precursor represented by general formula (3) and the polyimide precursor represented by general formula (4).

[0025] In one embodiment, the polyimide precursor (A1) is represented by the following general formula (5): [ka] {wherein R1, R2, and n1 are as defined above.} In general formula (5), at least one of R1 and R2 is more preferably a monovalent organic group represented by general formula (2). When the polyimide precursor contains the polyimide precursor represented by general formula (5), chemical resistance is particularly enhanced.

[0026] In one embodiment, the polyimide precursor (A1) is represented by the following general formula (6): [ka] {wherein R1, R2, and n1 are as defined above.} In general formula (6), at least one of R1 and R2 is more preferably a monovalent organic group represented by general formula (2). When the polyimide precursor (A1) contains the polyimide precursor represented by general formula (6), chemical resistance is particularly enhanced.

[0027] (A1) Method for preparing polyimide precursor The polyimide precursor (A1) is prepared by first reacting a tetracarboxylic acid dianhydride containing the aforementioned tetravalent organic group X1 with a photopolymerizable alcohol having an unsaturated double bond and, optionally, an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester), and then subjecting the partially esterified tetracarboxylic acid to amide polycondensation with a diamine containing the aforementioned divalent organic group Y1.

[0028] Preparation of Acid / Ester Forms (A1) Examples of tetracarboxylic acid dianhydrides containing a tetravalent organic group X1 that are suitably used for preparing the polyimide precursor include the tetracarboxylic acid dianhydride represented by the above general formula (20), as well as, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride, diphenyl Examples of suitable dianhydrides include diethylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited to these. These may be used alone or in combination of two or more.

[0029] (A1) Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing the polyimide precursor include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclopropyl acrylate, 2-hydroxy-3-methyl ... Examples of the methacryloyloxypropyl acrylate include 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0030] The above-mentioned photopolymerizable alcohols having an unsaturated double bond may be partially mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

[0031] As the polyimide precursor, a non-photosensitive polyimide precursor prepared only from the above-mentioned alcohols having no unsaturated double bonds may be used in combination with a photosensitive polyimide precursor. From the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0032] The tetracarboxylic dianhydride and the alcohol are stirred, dissolved, and mixed in a solvent as described below in the presence of a basic catalyst such as pyridine, whereby the esterification reaction of the acid anhydride proceeds to give the desired acid / ester. The stirring, dissolution, and mixing can be carried out, for example, at a temperature of 20 to 50°C for 4 to 24 hours.

[0033] Preparation of polyimide precursor The acid / ester compound (typically a solution in a solvent as described below) is mixed with an appropriate dehydration condensation agent under ice cooling to convert the acid / ester compound into a polyanhydride, and then a diamine containing a divalent organic group Y1 dissolved or dispersed in a separate solvent is added dropwise to the resulting mixture to carry out amide polycondensation, thereby obtaining the desired polyimide precursor. Examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. Alternatively, the acid moiety of the acid / ester compound can be converted into an acid chloride using thionyl chloride or the like, followed by reaction with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

[0034] Diamines containing a divalent organic group Y1 include diamines having a structure represented by the above general formula (21), as well as, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, and 3,3'-diaminodiphenyl sulfone. , 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[ 4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and compounds in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,Examples of the diaminodiphenylmethane include, but are not limited to, 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.

[0035] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution can be filtered off as needed. A poor solvent, such as water, aliphatic lower alcohol, or a mixture thereof, can then be added to the resulting polymer component to precipitate the polymer component. The polymer can then be purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution can be passed through a column packed with anion and / or cation exchange resins 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. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrenes. 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.

[0037] (A2) Polyimide The (A2) polyimide is an organic solvent-soluble polyimide, and is composed of a polycondensation product of a tetracarboxylic acid component and an organic diamine component.

[0038] The organic diamine component is not particularly limited, but examples thereof include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6 ... nyl)-1,3,3-trimethylindane, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5' -dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)-biphenyl, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenoxy) aromatic diamines such as 4,4'-(p-phenyleneisopropylidene)bisaniline, 4,4'-(m-phenyleneisopropylidene)bisaniline, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, and 4,4'-bis[4-(4-amino-2-trifluoromethyl)phenoxy]octafluorobiphenyl; aromatic diamines having two amino groups bonded to an aromatic ring and a heteroatom other than the nitrogen atom of the amino groups, such as diaminotetraphenylthiophene;Aliphatic and alicyclic diamines such as 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenediamine, and 4,4'-methylenebis(cyclohexylamine) can be used alone or in combination. Particularly preferred are 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, and 1,3-bis(3-aminophenoxy)benzene.

[0039] The organic diamine component may further contain an organic diamine having a siloxane bond. The siloxane bond-containing diamine may be a commercially available product, such as one sold by Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Co., Ltd., or Chisso Corporation. Specific examples include KF-8010 (amino group equivalent: approximately 450) and X-22-161A (amino group equivalent: approximately 840) manufactured by Shin-Etsu Chemical Co., Ltd.

[0040] In addition to the above, the organic diamine component may also include diamines having a hydroxyl group and / or a carboxyl group. The organic diamine having a hydroxyl group and / or a carboxyl group is not particularly limited as long as it has a hydroxyl group and / or a carboxyl group. Preferred examples include diaminophenols such as 2,4-diaminophenol; hydroxybiphenyl compounds such as 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, and 4,4'-diamino-2,2',5,5'-tetrahydroxybiphenyl; 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 4,4'-diamino Hydroxydiphenylmethanes such as hydroxydiphenylmethane, 3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 4,4'-diamino-2,2',5,5'-tetrahydroxydiphenylmethane Leucanes; hydroxydiphenyl ether compounds such as 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, and 4,4'-diamino-2,2',5,5'-tetrahydroxydiphenyl ether; 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether diphenyl sulfone compounds such as 4,4'-diamino-2,2'-dihydroxydiphenyl sulfone, 4,4'-diamino-2,2',5,5'-tetrahydroxydiphenyl sulfone; bis[(hydroxyphenyl)phenyl]alkane compounds such as 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]propane; bis(hydroxyphenoxy)biphenyl compounds such as 4,4'-bis(4-amino-3-hydroxyphenoxy)biphenyl;Bis[(hydroxyphenoxy)phenyl]sulfone compounds such as 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]sulfone; diaminobenzoic acids such as 3,5-diaminobenzoic acid; carboxybiphenyl compounds such as 3,3'-diamino-4,4'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, and 4,4'-diamino-2,2',5,5'-tetracarboxybiphenyl; 3 ,3'-diamino-4,4'-dicarboxydiphenylmethane, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, 4,4'-diamino-2,2'-dicarboxydiphenylmethane, 2,2-bis[3-amino-4-carboxyphenyl]propane, 2,2-bis[4-amino-3-carboxyphenyl]propane, 2,2-bis[3-amino-4-carboxyphenyl]hexafluoropropane, 4,4'-diamino-2,2',5,5'-tetracarboxydiphenylmethane, and other carbodiphenylsulfonates. Carboxydiphenylalkanes such as 4,4'-diphenylmethane; carboxydiphenyl ether compounds such as 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, and 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl ether; 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-dicarboxydiphenyl ether; Diphenyl sulfone compounds such as carboxydiphenyl sulfone, 4,4'-diamino-2,2'-dicarboxydiphenyl sulfone, and 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl sulfone; bis[(carboxyphenoxy)phenyl]alkane compounds such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane; bis(carboxyphenoxy)biphenyl compounds such as 4,4'-bis(4-amino-3-carboxyphenoxy)biphenyl;Examples of suitable organic diamines include bis[(carboxyphenoxy)phenyl]sulfone compounds such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone. These may be used alone or in combination of two or more. Other organic diamines having a hydroxyl group and / or a carboxyl group include 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1-hydroxy-2,4-diaminobenzene, 3,3'-dihydroxybenzidine, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 1,4-bis-(3-hydroxy-4-aminophenoxy)benzene, 2,2-bis(4-amino-3-hydroxyphenyl)propane, and bis[(carboxyphenoxy)phenyl]sulfone. Examples of suitable bis(3-amino-4-hydroxyphenyl)propane include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfide, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,3-diamino-4-carboxybenzene, 1,3-diamino-5-carboxybenzene, and 1,4-diamino-2-carboxybenzene.

[0041] The tetracarboxylic acid component used in the present invention is not particularly limited as long as it is a tetracarboxylic acid component. For example, butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 5-(2,5-dioxytetrahydrofuryl)-3-methyl-3-cyclohexene-1, Aliphatic or alicyclic tetracarboxylic dianhydrides such as 2-dicarboxylic dianhydride and bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3',4,4'-diphenylethertetracarboxylic dianhydride; 3,3',4,4'-Dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-Furanetetracarboxylic dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-Perfluoroisopropylidenediphthalic acid dianhydrides, aromatic tetracarboxylic acid dianhydrides such as 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene bis(trimellitic acid monoester acid anhydride), ethylene glycol bis(trimellitic acid monoester acid anhydride), m-phenylene bis(trimellitic acid monoester acid anhydride), bis(triphenylphthalic acid)-4,4'-diphenyl ether acid dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane acid dianhydride;1,3,3a,4,5,9b-Hexahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-Hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl) Examples of suitable tetracarboxylic dianhydrides include 3,3',4,4'-naphtho[1,2-c]furan-1,3-dione, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, p-phenylene bis(trimellitic acid monoester anhydride), ethylene glycol bis(trimellitic acid monoester anhydride), and bicyclo[2,2,2]-oct-7-ene tetracarboxylic dianhydride. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

[0042] (A2) Method for producing polyimide The polyimide in the negative-type photosensitive resin composition of the present disclosure can be synthesized by mixing and heating a tetracarboxylic dianhydride and a diamine in an organic solvent in the presence of an acid catalyst. The water produced can be removed from the reaction system by azeotropy with toluene, xylene, decalin, or the like mixed in the solvent.

[0043] Polyimides can be produced by a method using a catalytic system that utilizes the equilibrium reaction of lactone, base, and water as an acid catalyst. For example, a polyimide solution can be obtained by heating to 140°C to 180°C using the [acid group] + [base] formed in the equilibrium reaction of [lactone] + [base] + [water] = [acid group] + [base] as a catalyst. The water produced can be removed from the reaction system by azeotroping with toluene or the like. Upon completion of the imidization reaction, the [acid group] + [base] returns to lactone, base, and water, losing its catalytic activity and can be removed from the reaction system together with toluene or the like. The polyimide solution produced by this method is industrially usable as a high-purity polyimide solution without the above-mentioned catalytic substance being present in the polyimide solution after the reaction.

[0044] In addition to toluene, polar organic solvents can be used as the reaction solvent for the imidization reaction. Examples of such organic solvents include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, tetramethylurea, and γ-butyrolactone. These solvents can be used alone or in the form of a mixture. An appropriate amount of an aliphatic alcohol, such as isopropyl alcohol, can be mixed with these solvents.

[0045] In addition to the above reaction solvents, examples of diluents include ketone-based solvents such as acetone, cyclohexane, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve-based solvents such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and butyl cellosolve acetate; ester-based solvents such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, and methyl 3-methoxypropionate; and cyclic ether compounds such as dioxane and dioxolane.

[0046] The lactone is preferably γ-valerolactone, and the base is preferably pyridine and / or methylmorpholine. A known method for producing polyimide using a two-component catalyst containing a lactone and a base is described in, for example, U.S. Pat. No. 5,502,143.

[0047] The mixing ratio (tetracarboxylic dianhydride / diamine) between the tetracarboxylic dianhydride and diamine used in the imidization reaction is preferably 0.8 to 1.3, more preferably 0.95 to 1.05, in molar ratio. The concentration of the acid dianhydride in the entire reaction mixture at the start of the reaction is preferably about 4 to 16% by mass. When a lactone is added as a catalyst, the lactone concentration is preferably about 0.2 to 0.6% by mass. The concentration of the base is preferably about 0.3 to 0.9% by mass. The concentration of the azeotropic solvent, such as toluene, is preferably about 6 to 15% by mass. The heating temperature is preferably 140°C to 200°C, more preferably 150°C to 180°C. The reaction time is not particularly limited and varies depending on the molecular weight of the polyimide to be produced, but is usually about 2 to 10 hours. The reaction is preferably carried out with stirring.

[0048] The polyimide may be composed of one type of tetracarboxylic dianhydride and one type of organic diamine, or may be a copolymer of three or more components, with at least two or more types of tetracarboxylic dianhydride and / or organic diamine. This makes it possible to impart desired properties, such as optical transparency, high resolution, and adhesion to the substrate. Block copolymers are preferred to random copolymers in terms of copolymer structure, as this makes it easier to control the properties of the produced polyimide as desired, and therefore makes it easier to modify the polyimide.

[0049] By carrying out the imidization reaction in two successive stages using different tetracarboxylic dianhydrides and / or different diamines, a block copolymer polyimide can be produced. Conventional methods for producing polyimides via polyamic acid have only been able to produce random copolymers. This method allows the production of block copolymer polyimides by selecting any acid anhydride and / or diamine component, thereby imparting the desired properties and functions as described above to the polyimide.

[0050] A preferred method for producing a block polyimide copolymer is to use an acid catalyst generated from the lactone and a base to prepare a polyimide oligomer by increasing the amount of either the diamine or the tetracarboxylic dianhydride, and then add the diamine and / or the tetracarboxylic dianhydride to carry out two-stage polycondensation. The molar ratio of the tetracarboxylic dianhydride to the diamine (tetracarboxylic dianhydride / diamine) is preferably 0.8 to 1.3.

[0051] Block copolymer polyimides containing alicyclic tetracarboxylic dianhydrides, diaminosiloxanes, and aliphatic disulfides are particularly used as photolithography materials that exhibit submicron optical resolution.

[0052] In addition to the polyimides produced from the above compositions, amorphous aliphatic or alicyclic block copolymer polyimides having strained groups, such as spirocyclic groups, may also be used, which can provide the block copolymer polyimides with high and dense resolution.

[0053] The molecular weight of the polyimide, 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. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in the developer and good resolution performance of the relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0054] In the production of polyimide, an acid anhydride such as phthalic anhydride or an aromatic amine such as aniline can be added to the reaction system as a terminal terminator.

[0055] (B) Radical polymerizable compound The negative-type photosensitive resin composition of the present disclosure contains a (B) radically polymerizable compound to improve the chemical resistance of the cured relief pattern. To obtain good chemical resistance, the composition contains 20 parts by mass or more of the (B) radically polymerizable compound per 100 parts by mass of the (A1) polyimide precursor and / or (A2) polyimide combined, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more. From the viewpoint of patterning properties, the amount of the (B) radically polymerizable compound is 150 parts by mass or less, preferably 100 parts by mass or less, and more preferably 60 parts by mass or less.

[0056] When the negative-type photosensitive resin composition contains the (A1) polyimide precursor but does not contain the (A2) polyimide, the amount of the (B) radical polymerizable compound is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more. When the negative-type photosensitive resin composition contains the (A1) polyimide precursor but does not contain the (A2) polyimide, the amount of the (B) radical polymerizable compound is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 60 parts by mass or less, from the viewpoint of patterning properties. When the negative-type photosensitive resin composition does not contain the (A1) polyimide precursor but does contain the (A2) polyimide, the amount of the (B) radical polymerizable compound is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and even more preferably 100 parts by mass or more, from the viewpoint of patterning properties. When the negative-type photosensitive resin composition does not contain the (A1) polyimide precursor and contains the (A2) polyimide, the amount of the (B) radically polymerizable compound is preferably 150 parts by mass or less, more preferably 130 parts by mass or less, and even more preferably 110 parts by mass or less, from the viewpoint of the mechanical properties of the film.

[0057] The radical polymerizable compound is not particularly limited as long as it is a compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, but is preferably a (meth)acrylic compound, for example, a compound represented by the following general formula (7): [ka] {In formula (7), X 11 is an organic group, and L 11 , L 12 and L 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. 11 is an integer from 1 to 10.

[0058] The radical polymerizable compound is particularly, but not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol; mono-, di-, or triacrylates and methacrylates of glycerol; cyclohexane diacrylate and dimethacrylate; diacrylates and dimethacrylates of 1,4-butanediol; and diacrylates and dimethacrylates of 1,6-hexanediol. acrylate, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds can be mentioned.

[0059] More specifically, the radical polymerizable compound is a compound represented by the following formula: [ka] [ka] Examples of the compound include, but are not limited to, compounds represented by the following formula:

[0060] In this specification, when the number of radical polymerizable groups in a radical polymerizable compound is one, it is referred to as monofunctional, and when it is two or more, it is referred to as x-functional group according to the number x of radical polymerizable groups. Difunctional or higher functional groups may be collectively referred to as polyfunctional. The radical polymerizable compound may be monofunctional or may be difunctional or higher. From the viewpoint of chemical resistance, the radical polymerizable compound is preferably trifunctional or higher, more preferably tetrafunctional or higher, and even more preferably hexafunctional or higher. On the other hand, from the viewpoint of breaking elongation, it is preferably decafunctional or lower.

[0061] The molecular weight of the radically polymerizable compound is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. The upper limit is preferably 1000 or less, and even more preferably 800 or less. By keeping the molecular weight within the above range, chemical resistance and patterning properties are improved.

[0062] At least one of the radically polymerizable compounds (B) is preferably a radically polymerizable compound having at least one hydroxyl group or urea group.

[0063] The radical polymerizable compound having a hydroxyl group in the molecule includes a compound represented by the following general formula (8): [ka] {In formula (8), X 11 is an organic group, and L 11 , L 12 and L 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. 11 is an integer from 1 to 10, and n 12 is an integer of 1 to 10.} is an example of a structure.

[0064] In the above formula (8), L 11 is a hydrogen atom or a methyl group, and L 12 , L 13is preferably a hydrogen atom from the viewpoint of radical reactivity. More specifically, [ka] Examples include, but are not limited to, compounds represented by the formula:

[0033] Having a hydroxyl group in the molecular structure provides particularly good chemical resistance. The number of hydroxyl groups in the molecular structure is preferably one or more, and more preferably two or more. The upper limit is preferably 10 or less, more preferably six or less, and even more preferably three or less. By keeping the number in the above range, good chemical resistance and adhesion to substrates are achieved.

[0065] The radical polymerizable compound having a urea group in the molecule is represented by the following general formula (9): [ka] {In formula (9), X 20 , X 21 , X 22 , X 23 are each independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (10), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and X 20 , X 21 , X 22 , X 23 At least one of the above is a monovalent organic group having a group represented by the following general formula (10): [ka] {In formula (10), L 11 , L 12 and L 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.} In the above formula (10), L 11 is a hydrogen atom or a methyl group, and L 12 , L 13 is preferably a hydrogen atom from the viewpoint of radical reactivity. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom.

[0066] In formula (9), X 20 , X 21 , X 22 , X 23 When X is a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, it preferably contains an oxygen atom from the viewpoint of developability. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. 20 , X 21 , X 22 , X 23 may be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. 20 , X 21 , X 22 , X 23 When X are bonded to each other to form a ring structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form a strong hydrogen bond. 20 , X 21 , X 22 , X 23 At least one of X is preferably a hydrogen atom. 20 , X 21 , X 22 , X 23 It is preferable that the number of hydrogen atoms in the formula is two or less. [ka] Examples of the compound are compounds represented by the following formula:

[0067] The radical polymerizable compound (B) preferably has at least one hydroxyl group and at least one urea group in the molecule. The radical polymerizable compound having at least one hydroxyl group and at least one urea group in the molecule is, for example, a compound represented by the following general formula (11): [ka] {In formula (11), X 30 , X 31 , X 32 , X 33are each independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (12), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and X 30 , X 31 , X 32 , X 33 At least one of the groups is a monovalent organic group having a group represented by the following general formula (12), and at least one of the groups is a hydroxyl group.} [ka] {In formula (12), L 11 , L 12 and L 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.} In the above formula (12), L 11 is a hydrogen atom or a methyl group, and L 12 , L 13 is preferably a hydrogen atom from the viewpoint of radical reactivity.

[0068] Formula (11)X 30 , X 31 , X 32 , X 33 When X is a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, it preferably contains an oxygen atom from the viewpoint of developability. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. 30 , X 31 , X 32 , X 33 may be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. 30 , X 31 , X 32 , X 33 When X are bonded to each other to form a ring structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form a strong hydrogen bond. 30 , X 31 , X 32 , X 33At least one of X is preferably a hydrogen atom. 30 , X 31 , X 32 , X 33 It is preferable that the number of hydrogen atoms in the formula is two or less. [ka] Examples of the compound are compounds represented by the following formula:

[0069] Among (B) radical polymerizable compounds, the radical polymerizable compound having a urea group can be produced by, for example, reacting an isocyanate compound having a radical polymerizable group with an amine-containing compound, although the method is not particularly limited. When the amine-containing compound contains a functional group such as a hydroxyl group that can react with isocyanate, a part of the isocyanate compound may contain a compound that has reacted with the functional group such as a hydroxyl group.

[0070] (B) The radical polymerizable compound may be used alone, but it is preferable to use two or more types in combination. Using two or more types of radical polymerizable compounds in combination improves chemical resistance and in-plane film thickness uniformity. The reason for the improved in-plane film thickness uniformity is unclear and is not limited by theory, but it is thought that when a large amount of only one type of radical polymerizable compound is added, microphase separation occurs with the polyimide precursor component in the varnish, whereas using two or more types in combination suppresses microphase separation. For the above reasons, when a radical polymerizable compound is used alone, it is preferably used in an amount of 60 parts by mass or less, more preferably 40 parts by mass or less, per 100 parts by mass of the polyimide precursor.

[0071] When two or more types of radical polymerizable compounds are used in combination, the number of types is preferably six or less, and more preferably four or less, from the viewpoint of controlling the crosslink density.

[0072] When a mixture of multiple radical polymerizable compounds is used, it is preferable that at least one of the multiple radical polymerizable compounds has a different number of functional groups. From the viewpoints of chemical resistance and in-plane film thickness uniformity, it is more preferable that the radical polymerizable compound contains at least one monofunctional radical polymerizable compound and one polyfunctional radical polymerizable compound. When three or more radical polymerizable compounds are used, it is sufficient that at least one of them has a different number of functional groups, but it is preferable that all of the radical polymerizable compounds have different numbers of functional groups. When a mixture of multiple radical polymerizable compounds is used, it is preferable that at least one monofunctional radical polymerizable compound is contained from the viewpoint of breaking elongation.

[0073] When two or more types of radical polymerizable compounds are used in combination, it is preferable to contain at least one nitrogen atom-containing radical polymerizable compound and one nitrogen atom-free radical polymerizable compound. The nitrogen atom-containing radical polymerizable compound is preferably a urea group-containing radical polymerizable compound. Nitrogen atom-containing radical polymerizable compounds are capable of forming strong hydrogen bonds and therefore have excellent chemical resistance. From the viewpoint of simplifying the hydrogen bond network and improving solubility, it is preferable to use only one type of nitrogen atom-containing radical polymerizable compound when added.

[0074] (C) Surfactant The negative-type photosensitive resin composition of the present disclosure contains a surfactant (C) to prevent clouding during application. To achieve a sufficient clouding prevention effect, the surfactant (C) is contained in an amount of 0.001 part by mass or more, preferably 0.005 part by mass or more, and more preferably 0.01 part by mass or more, per 100 parts by mass of the polyimide precursor (A1) and / or the polyimide (A2). On the other hand, if an excessive amount of surfactant is contained, the in-plane film thickness uniformity after application deteriorates. Therefore, the amount of surfactant (C) is 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, and even more preferably 0.05 parts by mass or less.

[0075] The reason why a surfactant suppresses cloudiness is unclear, but the present inventors believe it to be as follows. That is, in one embodiment, a photosensitive resin composition containing a large amount of a radically polymerizable compound is more likely to absorb moisture from the air during spin coating, and this moisture absorption causes the polyimide precursor to become insoluble in the solvent and precipitate. It is believed that the inclusion of a surfactant at this time leads to the formation of a surfactant-derived layer on the upper surface of the film, thereby suppressing moisture absorption and, ultimately, cloudiness. Alternatively, in one embodiment, a photosensitive resin composition containing a large amount of a radically polymerizable compound is likely to undergo phase separation between the polyimide precursor and the radically polymerizable compound during spin coating due to solvent volatilization or differences in compatibility, resulting in cloudiness. It is believed that the inclusion of a surfactant at this time leads to the formation of a surfactant-derived layer on the upper surface of the film, suppressing solvent volatilization or improving compatibility, thereby suppressing cloudiness.

[0076] Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant.

[0077] The fluorosurfactant is not particularly limited as long as it contains a fluorine atom in the molecule. Examples of the fluorosurfactant include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl alcohols, perfluoroalkyl alkylene oxide adducts, and perfluoroalkyl phosphates. More specifically, Megafac F-114, Megafac F-251, Megafac F-253, Megafac F-281, Megafac F-410, Megafac F-430, Megafac F-477, Megafac F-510, Megafac F-551, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-557, Megafac F-558, Megafac F-559, Megafac F-560, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-564, Megafac F-565, Megafac F-566, Megafac F-567, Megafac F-568, Megafac F-56 ...9, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-564, Megafac F-565, Megafac F-565, Megafac F-566, Megafac F-567, Megafac F-568, Megafac F-569, Megafac F Megafac F-558, Megafac F-559, Megafac F-560, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-565, Megafac F-568, Megafac F-569, Megafac F-570, Megafac F-572, Megafac F-574, Megafac F-575, Megafac F-576, Megafac R-40, Megafac R-40-LM, Megafac R-41, Megafac R-94, Megafac RS-56, Megafac RS-72-K, Megafac RS-75, Megafac RS-76-E, Megafac RS-76-NS, Megafac RS-78, Megafac RS-90, Megafac DS-21 (all manufactured by DIC), FC-4430, FC-4432 (all manufactured by 3M Japan), Surflon S-211, Surflon S-221, Surflon S-231, Surflon S-232, Examples include Surflon S-233, Surflon S-241, Surflon S-242, Surflon S-243, Surflon S-420, Surflon S-431, Surflon S-386, Surflon S-611, Surflon S-647, Surflon S-651, Surflon S-653, Surflon S-656, Surflon S-658, Surflon S-693, Surflon S-CFJ, and Surflon FPE-50 (all manufactured by AGC Seimi Chemical Co., Ltd.).

[0078] The silicone surfactant is not particularly limited as long as it has a disiloxane structure as a non-polar moiety. Examples of the silicone surfactant include polyether-modified silicones, such as linear polyether-modified silicones, linear alkyl-co-modified polyether-modified silicones, branched polyether-modified silicones, and branched alkyl-co-modified polyether-modified silicones. More specifically, the product names are KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP-341, and KP-10 4. KP-110, KP-112 (all manufactured by Shin-Etsu Chemical Co., Ltd.); DBE-224, DBE-621, DBE-712, DBE-814, DBE-821, DBE-921, DBP-732, YAD-122, YBD-125, YMS-T31, CMS-626, CMS-222, DBP-534, CMS-832, DBP-C22, QMS-435, ABP-263, DMS-R05, DMS-R11, DMS-R18, DMS-R22, DMS-R31 (all manufactured by Gelest);BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315 N, BYK-320, BYK-322, BYK-323, BYK-325 N, BYK-326, BYK-327, BYK-330, BYK-331, BYK-332, BYK-333, BYK-342, BYK-345, BYK-34 6, BYK-347, BYK-348, BYK-349, BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358 N, BYK-359, BYK-360 P, BYK-361 N, BYK-364 P, BYK-366 P, BYK-368 P, BYK-370, BYK-375, BYK-377, BYK-378, BYK-381, BYK-390, BYK-392, BYK-394, BYK-399, BYK-UV 3500, BYK-UV 3505, BYK-UV 3510, BYK-UV 3530, BYK-UV 3535, BYK-UV 3570, BYK-UV 3575, BYK-UV 3576 (all manufactured by BYK Japan); Newcol 2302, Newcol 2303, Newcol 2305, Newcol 2307, Newcol 2308, Newcol 2308-HEN, Newcol 2310, Newcol 2312, Newcol 2314, Newcol 2318, Newcol 2320, Newcol 2327(20), Newcol 2330, Newcol 2344, Newcol Examples of such silicone oils include Nycol 2360, Newcol 2399-S, and Newcol 2399-S (25) (all manufactured by Nippon Nyukazai Co., Ltd.); DMC6038, OW1500, SPG128VP, L03, L033, L053, and L066 (all manufactured by Wacker Asahi Kasei Silicone Co., Ltd.); and SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 (all manufactured by Dow Corning Toray Co., Ltd.).

[0079] The surfactant may have a crosslinkable group in the molecule. Examples of such surfactants include silicone surfactants having a crosslinkable group in the molecule and fluorine surfactants having a crosslinkable group in the molecule. Examples of crosslinkable groups include thermally crosslinkable groups such as epoxy groups, N-methylolamide groups, oxazoline groups, and allyl groups, as well as ultraviolet (UV) crosslinkable groups such as vinyl groups, (meth)acryloyl groups, and epoxy groups. Specific examples of surfactants having a crosslinkable group in the molecule include Megafac RS-75-A, Megafac RS-72-K, Megafac RS-75-NS, Megafac RS-78, Megafac RS-90, and Megafac RS-56 (all manufactured by DIC Corporation); and BYK-UV3500, BYK-UV3505, BYK-UV3530, BYK-UV3570, BYK-UV3575, and BYK-UV3576 (all manufactured by BYK-Chemie).

[0080] The surfactant may be one in which the fluorine-containing group is eliminated by heat treatment, such as Megafac DS-21 (manufactured by DIC Corporation).

[0081] From the viewpoint of compatibility with the varnish, the surfactant (C) is preferably at least one selected from the group consisting of fluorine-based surfactants and silicone-based surfactants, and from the viewpoint of preventing clouding during application and electrical insulation, a fluorine-based surfactant is more preferable.

[0082] (D) Photopolymerization initiator The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples thereof include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; and 1-phenyl-1,2-butanedione-2-(o-methoxyphenyl)-2-methylpropiophenone. Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

[0083] The blending amount of the (D) photopolymerization initiator is 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the total of the (A1) polyimide precursor and / or the (A2) polyimide. The blending amount is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning ability, and 10 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

[0084] The negative photosensitive resin composition may further contain components other than the above components (A1) to (D). Examples of components other than components (A1) to (D) include, but are not limited to, a thermal base generator, a solvent, a nitrogen-containing heterocyclic compound, a hindered phenol compound, an organic titanium compound, an adhesion promoter, a sensitizer, a photopolymerizable unsaturated monomer, and a polymerization inhibitor.

[0085] Thermal base generator The negative photosensitive resin composition may contain a thermal base generator. A thermal base generator is a compound that generates a base upon heating. By containing the thermal base generator, imidization of the photosensitive resin composition can be further promoted.

[0086] Examples of the thermal base generator include, but are not limited to, an amine compound protected by a tert-butoxycarbonyl group, or the thermal base generators disclosed in WO 2017 / 038598. However, the thermal base generator is not limited to these, and other known thermal base generators can also be used.

[0087] Examples of amine compounds protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine Aminoamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ether Examples of the tert-butoxycarbonyl protecting agent include, but are not limited to, tert-butoxycarbonyl ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a tert-butoxycarbonyl group.

[0088] The amount of the thermal base generator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the (A1) polyimide precursor and / or the (A2) polyimide. The amount is preferably 0.1 part by mass or more from the viewpoint of the imidization-accelerating effect, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative-type photosensitive resin composition.

[0089] solvent Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, and γ-butyronitrile. Lactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. Among these, from the viewpoints of resin solubility, resin composition stability, and substrate adhesion, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

[0090] Among these solvents, those that completely dissolve the produced polymer are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone, etc. One type of solvent may be used, or two or more types of solvents may be mixed and used.

[0091] The amount of the solvent used in the negative photosensitive resin composition is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of the total of the polyimide precursor (A1) and / or the polyimide (A2).

[0092] Nitrogen-containing heterocyclic compound When a cured film is formed on a copper or copper alloy substrate using a negative photosensitive resin composition, the negative photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound to suppress discoloration on the copper. Examples of the nitrogen-containing heterocyclic compound include an azole compound and a purine derivative.

[0093] Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and 2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole. benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like.

[0094] Among these, tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole are preferable. These azole compounds may be used singly or in combination of two or more.

[0095] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 2-hydroxy ... 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

[0096] When the negative-tone photosensitive resin composition contains an azole compound or a purine derivative, the blending amount is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total of the (A1) polyimide precursor and / or the (A2) polyimide. When the blending amount of the azole compound is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the negative-tone photosensitive resin composition is formed on copper or a copper alloy. On the other hand, when the blending amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0097] Hindered phenol compounds To inhibit discoloration on copper surfaces, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and the like.

[0098] Examples of the hindered phenol compound include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3, 5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydro 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-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-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,Examples of suitable hydroxybenzoates include, but are not limited to, 6-(1H,3H,5H)-trione and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0099] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total of the (A1) polyimide precursor and / or the (A2) polyimide. When the amount of the hindered phenol compound is 0.1 part by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0100] Organotitanium Compounds The negative photosensitive resin composition may contain an organotitanium compound. By containing the organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at low temperatures. Usable organotitanium compounds include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

[0101] Specific examples of the organic titanium compound are shown below in I) to VII). I) As the titanium chelate compound, a titanium chelate having two or more alkoxy groups is more preferred because it improves the storage stability of the negative photosensitive resin composition and allows for the formation of good patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc. II) Examples of tetraalkoxytitanium compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, and titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}]. III) Examples of titanocene compounds include pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium. IV) Examples of monoalkoxytitanium compounds include titanium tris(dioctylphosphate) isopropoxide and titanium tris(dodecylbenzenesulfonate) isopropoxide. V) Examples of titanium oxide compounds include titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), and phthalocyanine titanium oxide. VI) Examples of titanium tetraacetylacetonate compounds include titanium tetraacetylacetonate. VII) Titanate coupling agents include, for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0102] Among these, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0103] When an organotitanium compound is added, the amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total of (A1) polyimide precursor and / or (A2) polyimide. When the amount is 0.05 part by mass or more, good heat resistance and chemical resistance are exhibited, while when the amount is 10 parts by mass or less, excellent storage stability is achieved.

[0104] Adhesion aid In order to improve the adhesion between a film formed using the negative photosensitive resin composition and a substrate, the negative photosensitive resin composition may optionally contain an adhesion promoter. Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl ]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and the like; and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate, and the like.

[0105] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains an adhesion aid, the amount of the adhesion aid blended is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the total of the (A1) polyimide precursor and / or the (A1) polyimide.

[0106] Examples of silane coupling agents include, but are not limited to, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxy Examples thereof include 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, and 4-mercaptobutyltrippropoxysilane.

[0107] Examples of silane coupling agents include, but are not limited to, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, and N-(3-ethoxydimethoxysilylethyl) Examples thereof include urea, N-(3-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2).

[0108] Examples of silane coupling agents include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methacryloylsilane), bis(triethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[ 3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenyl silanetriol, methyl phenyl silanediol, ethyl phenyl silanediol, n-propyl phenyl silanediol, isopropyl phenyl silanediol, n-butyldiphenyl silanediol, isobutylphenyl silanediol, tert-butylphenyl silanediol, diphenyl silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butylmethyl phenyl silanol, isobutylmethyl phenyl silanol, tert-butylmethyl phenyl silanol, ethyl n-propyl phenyl silanol, ethyl isopropyl phenyl silanol, n-butylethyl phenyl silanol, isobutylethyl phenyl silanol, tert-butylethyl phenyl silanol,Examples of the silanol include, but are not limited to, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

[0109] The silane coupling agents listed above may be used alone or in combination. Among the silane coupling agents listed above, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the silane coupling agents represented by the following formula: [ka] A silane coupling agent having a structure represented by the following formula is preferred.

[0110] When a silane coupling agent is used, the amount added is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total of the (A1) polyimide precursor and / or the (A2) polyimide.

[0111] sensitizer 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-dimethylaminocinnamylidene indole. Non, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 types.

[0112] When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the total of the (A1) polyimide precursor and / or the (A2) polyimide.

[0113] Polymerization inhibitor The negative-tone photosensitive resin composition may optionally contain a polymerization inhibitor to improve the viscosity and photosensitivity stability of the negative-tone photosensitive resin composition, particularly during storage in a solvent-containing solution. Examples of polymerization inhibitors that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0114] <<Method for producing a cured relief pattern>> The method for producing a cured relief pattern includes the steps of: (1) applying the negative photosensitive resin composition of the present disclosure 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.

[0115] (1) Resin layer formation process In this step, a negative photosensitive resin composition is applied to a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0116] (2) Exposure process In this step, the resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

[0117] (3) Relief pattern formation process In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The developing method for developing the exposed (irradiated) photosensitive resin layer can be any method selected from conventionally known photoresist developing methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, as needed, for the purpose of adjusting the shape of the relief pattern, etc.

[0118] The developer used for development is preferably, for example, a good solvent for the negative-tone photosensitive resin composition, or a combination of the good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. 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-tone photosensitive resin composition. Two or more types of each solvent, for example, several types, can also be used in combination.

[0119] (4) Hardened relief pattern formation process In this step, the relief pattern obtained by the development is heat-treated to dissolve the photosensitive component and imidize the (A1) polyimide precursor, thereby converting it into a cured relief pattern composed of polyimide. Heat treatment can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. The heat treatment temperature is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower. Air or an inert gas such as nitrogen or argon can be used as the atmospheric gas during heat curing.

[0120] <Polyimide> Polyimide can be produced by curing a negative-type photosensitive resin composition. Therefore, the present disclosure also provides a method for producing polyimide, which includes curing the negative-type photosensitive resin composition described above. The imidization rate of the polyimide is preferably 80% to 100%. The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula: [ka] {In the above general formula, X1 and Y1 are the same as X1 and Y1 in general formula (1), and m is a positive integer.} For the same reason, the preferred X1 and Y1 in general formula (1) are also preferred in polyimides having a structure represented by the above general formula. In the above general formula, the number m of repeating units is not particularly limited, but may be an integer of 2 to 150.

[0121] Semiconductor Device The present disclosure also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern. Therefore, the present disclosure can also provide a semiconductor device having 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 disclosure can also be applied 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. A semiconductor device can be produced by forming the cured relief pattern formed by the 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.

[0122] 《Display device》 The present disclosure also provides a display device comprising a display element and a cured film disposed on the display element, the cured film having the above-described cured relief pattern. The cured relief pattern may be laminated directly on the display element, or may be laminated via another layer. 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.

[0123] The negative photosensitive resin composition is preferably a negative photosensitive resin composition for forming an insulating member or an interlayer insulating film. In addition to being applied to the semiconductor device described above, the negative photosensitive resin composition is also useful for applications such as an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper-clad board, a solder resist film, and a liquid crystal alignment film. [Example]

[0124] <<Measurement and Evaluation Methods>> (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Showa Denko Shodex KD-806M, two in series, or Showa Denko Shodex 805M / 806M series Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko K.K. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min.

[0125] (2) Fabrication of hardened relief patterns on Cu A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) in that order using a sputtering device (L-440S-FHL model, Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto the wafer using a coater developer (D-Spin60A model, SOKUDO Co., Ltd.), and prebaked on a hot plate at 110°C for 180 seconds to form a coating film approximately 7.5 μm thick. Using a test pattern mask, this coating film was irradiated with i-line light at 50 to 650 mJ / cm using a Prisma GHI (Ultratech Co., Ltd.). 2The coating was then spray-developed using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) using cyclopentanone as the developer for a time equal to 1.4 times the time required for the unexposed areas to completely dissolve and disappear, followed by a 10-second rotational spray rinse with propylene glycol methyl ether acetate, yielding a relief pattern on Cu. The wafer with the relief pattern formed on Cu was then heat-treated in a temperature-programmable curing furnace (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) for 2 hours under a nitrogen atmosphere at the temperatures listed in Table 1, yielding a cured relief pattern of resin approximately 4 to 7 μm thick on Cu.

[0126] (3) Chemical resistance evaluation The relief pattern prepared by the method (2) above was mixed with the following weight ratio: Dimethyl sulfoxide: 98% by weight Tetramethylammonium hydroxide pentahydrate: 2% by weight The film was immersed in the chemical solution mixed in step 1 heated to 50°C for 10 minutes, washed with running water for 30 minutes, and air-dried. The film surface was then visually observed with an optical microscope to evaluate chemical resistance based on the presence or absence of damage caused by the chemical solution, such as cracks, and / or the rate of change in film thickness before and after chemical treatment. Chemical resistance was evaluated based on the following criteria. A: No cracks or other issues occur and the film thickness change rate is less than 5% B: No cracks or the like occur, and the film thickness change rate is 5% or more but less than 10% C: No cracks or the like occur, and the film thickness change rate is 10% or more but less than 15% D: Cracks or other problems have occurred, or the film thickness change rate is 15% or more.

[0127] (4) Evaluation of opacity upon application The film immediately after spin coating using the method (2) above was visually inspected and evaluated for degree of cloudiness. The evaluation criteria are as follows: A: No cloudiness was observed. B: Slight cloudiness was observed only on the outer periphery within 4 cm from the wafer edge, which was not visible when viewing the wafer from directly above (90°) and was visible only when viewing from an angle of approximately 20° to 60°. C: White turbidity was observed only on the outer periphery within 4 cm from the wafer edge, which was visible when the wafer was viewed from directly above (90°). D: White turbidity was observed in areas other than the outer periphery within 4 cm from the wafer edge.

[0128] (5) Film thickness uniformity evaluation The coating film obtained after spin coating and pre-baking using the method described in (2) above was evaluated for in-plane thickness uniformity. The film thickness was measured using a VM-2110 manufactured by Dai-Nippon Screen Mfg. Co., Ltd. Measurements were taken at 88 points in total, at the center of the wafer and at 1.5 mm intervals of 66 mm each on both sides of the center, and the difference between the maximum and minimum values ​​was taken as the in-plane film thickness uniformity, and evaluation was performed according to the following criteria. A: Less than 0.1 B: 0.1 or more and less than 0.5 C: 0.5 or more and less than 1.0 D:1.0 or more

[0129] <Production Examples of Polyimide Precursors and Polyimides> Production Example 1: (A1) Synthesis of Polyimide Precursor A1-1 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, followed by 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone. The mixture was stirred at room temperature, and 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the reaction ceased to generate heat, the reaction mixture was allowed to cool to room temperature and left for 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 20 minutes with stirring, followed by a suspension of 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone over 30 minutes with stirring. After stirring for another 4 hours at room temperature, 30 mL of ethyl alcohol was added and the mixture was stirred for 1 hour. 400 mL of γ-butyrolactone was then added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polyimide Precursor A1-1). The molecular weight of Polyimide Precursor A1-1 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 21,000.

[0130] Production Example 2: (A1) Synthesis of Polyimide Precursor A1-2 A polymer (Polyimide Precursor A1-2) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The molecular weight of Polyimide Precursor A1-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

[0131] Production Example 3: (A1) Synthesis of Polyimide Precursor A1-3 A polymer (Polyimide Precursor A1-3) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 50.2 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The molecular weight of Polyimide Precursor A1-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000.

[0132] Production Example 4: (A1) Synthesis of Polyimide Precursor A1-4 A polymer (Polyimide Precursor A1-4) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The molecular weight of Polyimide Precursor A1-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0133] Production Example 5: (A1) Synthesis of Polyimide Precursor A1-5 A polymer (Polyimide Precursor A1-5) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 124.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 29.4 g of BPDA were used instead of the 155.1 g of ODPA used in Production Example 1. The molecular weight of Polyimide Precursor A1-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

[0134] Production Example 6: (A2) Synthesis of Polyimide A2-1 31.0 g of 4,4'-oxydiphthalic dianhydride (ODPA), 11.2 g of 4,4'-diaminodiphenyl sulfone, and 11.2 g of 3,3'-diaminodiphenyl sulfone were placed in a 1 L separable flask, and 125 g of γ-butyrolactone was added. 17 g of toluene was added dropwise with stirring. The mixture was then heated to 185°C under a nitrogen atmosphere and stirred for 2 hours. During the reaction, the toluene-water azeotrope was removed, yielding a 30% polyimide solution. The weight-average molecular weight of the resulting polyimide A2-1 was 25,000.

[0135] <<Production Example of Radically Polymerizable Compound>> Production Example 7: (B) Synthesis of radical polymerizable compound B-6 60.4 g (0.25 mol) of di-n-octylamine was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 38.8 g (0.25 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko K.K., product name: Karenz MOI) and 150 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes and stirred at room temperature for 5 hours. Then, tetrahydrofuran was distilled off using a rotary evaporator to obtain radical polymerizable compound B-7.

[0136] Production Example 8: (B) Synthesis of radical polymerizable compound B-7 26.3 g (0.25 mol) of diethanolamine was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 38.8 g (0.25 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko K.K., product name: Karenz MOI) and 150 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes and stirred at room temperature for 5 hours. Then, tetrahydrofuran was distilled off using a rotary evaporator to obtain radical polymerizable compound B-7.

[0137] Examples and Comparative Examples Example 1 A photosensitive resin composition was prepared using polyimide precursor A-1 by the following method, and the prepared composition was evaluated. 100 g of (A1) polyimide precursor A1-1, 10 g of (B) radical polymerizable compounds B-1 and B-7, 20 g of (B), 0.01 g of (C) surfactant C-1, and 3 g of (D) photopolymerization initiator D-1 were dissolved in a mixed solvent of 80 g of γ-butyrolactone (hereinafter referred to as GBL) and 20 g of dimethyl sulfoxide (hereinafter referred to as DMSO). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding the required amount of a GBL:DMSO = 80:20 solution, yielding a photosensitive resin composition. The composition was evaluated according to the aforementioned method. The results are shown in Table 1.

[0138] Examples 2 to 31 and Comparative Examples 1 to 3 Photosensitive resin compositions similar to those in Example 1 were prepared, except that they were prepared at the blending ratios shown in Tables 1 and 2, and were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[0139] The (A1) polyimide precursor, (A2) polyimide, (B) radical polymerizable compound, (C) surfactant, and (D) photopolymerization initiator listed in Tables 1 and 2 are as follows: When (A2) polyimide was used, the photosensitive resin composition was prepared taking into consideration the amount of GBL contained therein.

[0140] A1-1: Polyimide precursor described in Production Example 1 A1-2: Polyimide precursor described in Production Example 2 A1-3: Polyimide precursor described in Production Example 3 A1-4: Polyimide precursor described in Production Example 4 A1-5: Polyimide precursor described in Production Example 5 A2-1: Polyimide described in Production Example 6

[0141] B-1: NK Ester 4G (Shin-Nakamura Chemical Co., Ltd.): [ka] B-2: NK Ester A-DCP (Shin-Nakamura Chemical Co., Ltd.): [ka] B-3: NK Ester A-DPH (Shin-Nakamura Chemical Co., Ltd.): [ka] B-4: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.): [ka] B-5: NK Ester A-TMM-3L (Shin-Nakamura Chemical Co., Ltd.): (Contains approximately 55% of the following structure) [ka] B-6: Compound described in Production Example 7: [ka] B-7: Compound described in Preparation Example 8: [ka]

[0142] C-1: Megafac F-557 (DIC): Fluorine-based surfactant C-2: Megafac F-554 (DIC): Fluorine-based surfactant C-3: Megafac F-556 (DIC): Fluorine-based surfactant C-4: Megafac F-447 (DIC): Fluorine-based surfactant C-5: Megafac R-40 (DIC): Fluorine-based surfactant C-6: KP-341 (Shin-Etsu Chemical Co., Ltd.): Silicone surfactant C-7: KP-323 (Shin-Etsu Chemical Co., Ltd.): Silicone surfactant C-8: KP-110 (Shin-Etsu Chemical Co., Ltd.): Silicone surfactant

[0143] D-1:OXE-01 D-2:OXE-02 D-3:PBG-305 D-4:PBG-3057

[0144] [Table 1]

[0145] [Table 2]

[0146] As shown in Table 1, the negative photosensitive resin composition of Example 1 was rated A for chemical resistance, B for cloudiness during application, and B for in-plane film thickness uniformity. All of the photosensitive resin compositions of Examples 2 to 31 were rated C or higher for chemical resistance, cloudiness during application, and in-plane film thickness uniformity. In Comparative Example 1, a large amount of film dissolved in the chemical solution, and the chemical resistance was rated D. In Comparative Example 2, the in-plane film thickness uniformity was poor, and the evaluation was D. In Comparative Example 3, cloudiness occurred on the front surface of the film during application, and the evaluation was D. [Industrial Applicability]

[0147] By using the photosensitive resin composition of the present invention, it is possible to obtain a coating film that is less likely to become cloudy during the coating process and has excellent in-plane film thickness uniformity, and further to obtain a cured relief pattern that has excellent chemical resistance. The present invention can be suitably used in the field of photosensitive materials that are useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. 100 parts by weight of a polyimide precursor and / or a polyimide; 20 to 150 parts by mass of a radical polymerizable compound; 0.001 to 1 parts by weight of a surfactant; 0.1 to 10 parts by mass of a photopolymerization initiator; A negative photosensitive resin composition comprising:

2. The negative photosensitive resin composition according to claim 1 , wherein the negative photosensitive resin composition contains the polyimide precursor but does not contain the polyimide.

3. 3. The negative photosensitive resin composition according to claim 1, wherein the surfactant is at least one selected from the group consisting of a fluorine-based surfactant and a silicone-based surfactant.

4. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the surfactant is a fluorine-containing surfactant.

5. 5. The negative photosensitive resin composition according to claim 1, wherein at least one of the radical polymerizable compounds is a radical polymerizable compound having at least one group selected from the group consisting of a hydroxyl group and a urea group.

6. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the radical polymerizable compound comprises a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound.

7. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the radical polymerizable compound comprises a nitrogen atom-containing radical polymerizable compound and a nitrogen atom-free radical polymerizable compound.

8. The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (1): 【Chemical 1】 {In formula (1), X １ is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group. The negative photosensitive resin composition according to any one of claims 1 to 7, comprising a polyimide precursor having a structural unit represented by the formula:

9. In the general formula (1), R １ and R ２ At least one of the following general formula (2): 【Chemistry 2】 {In formula (2), L １ , L ２ and L ３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10. The negative photosensitive resin composition according to claim 8, which has a structural unit represented by the following formula:

10. The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (3): 【Chemistry 3】 {In formula (3), n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group. The negative photosensitive resin composition according to any one of claims 1 to 9, comprising a polyimide precursor having a structural unit represented by the formula:

11. The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (4): 【Chemistry 4】 {In formula (4), n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group. The negative photosensitive resin composition according to any one of claims 1 to 10, comprising a polyimide precursor having a structural unit represented by the following formula:

12. The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (5): 【Chemistry 5】 {In formula (5), n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group. The negative photosensitive resin composition according to any one of claims 1 to 11, comprising a polyimide precursor having a structural unit represented by the formula:

13. The negative photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (6): 【Chemistry 6】 {In formula (6), n １ is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group. The negative photosensitive resin composition according to any one of claims 1 to 12, comprising a polyimide precursor having a structural unit represented by the formula:

14. The negative photosensitive resin composition according to any one of claims 1 to 13, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an insulating member.

15. The negative photosensitive resin composition according to any one of claims 1 to 14, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film.

16. (1) applying the negative photosensitive resin composition according to any one of claims 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; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising:

17. The method for producing a cured relief pattern according to claim 16, wherein the heat treatment in the step (4) is a heat treatment at 200°C or less.

18. The method for producing a cured relief pattern according to claim 16, wherein the heat treatment in the step (4) is a heat treatment at 170°C or less.

19. A method for producing a polyimide, comprising curing the negative photosensitive resin composition according to any one of claims 1 to 15.

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