Photosensitive resin composition, cured relief pattern and method for producing same

Abstract

To provide a photosensitive resin composition, a cured relief pattern and a method for producing the same that can improve in-plane uniformity of a cured relief pattern.SOLUTION: A photosensitive resin composition contains (A) at least one resin selected from the group consisting of a polyimide and a polyimide precursor, (B) a photosensitizer, and (C) a urea compound. When a cured film obtained by heating the photosensitive resin composition at 170°C for 2 hours is brought into contact with a dimethyl sulfoxide (DMSO) solution of tetramethylammonium hydroxide pentahydrate (TMAH) at a temperature of 50°C and a concentration of 2.38 mass% for 10 minutes, before and after the contact, IR peak intensities around 1778 cm-1 of the cured film when standardized by an IR peak intensity at 1500 cm-1 satisfy the following formula (1): 0.1≤(peak intensity after contact / peak intensity before contact)≤0.8 (1).SELECTED DRAWING: None

Description

[Technical field]

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

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

[0003] Meanwhile, in recent years, the mounting method (packaging structure) of semiconductor devices on printed wiring boards has also changed from the viewpoint of improving integration and computing functions, as well as miniaturizing chip size. Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which polyimide coatings are in direct contact with solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher density mounting. Furthermore, a structure has been proposed in which the surface of a semiconductor chip has multiple redistribution layers with an area larger than that of the semiconductor chip, such as FO (fan-out).

[0004] In a packaging structure that requires the formation of a multilayer film such as the above-mentioned FO, a photosensitive resin composition is further applied onto the interlayer insulating resin and the Cu wiring. Patent Document 1 discloses that a laminate having excellent adhesion between resins can be obtained by forming a multilayer film using a resin layer having specific physical properties. Patent Document 2 discloses a photosensitive resin composition containing a polyimide precursor for use in an interlayer insulating film, a photopolymerization initiator, and a low molecular weight compound having a specific structure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2017 / 146152 [Patent Document 2] JP 2019-185031 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, it has been found that when a cured relief pattern is formed in two or more layers using a conventional photosensitive resin composition as described in Patent Document 2, the cured relief pattern of the photosensitive resin composition has low wettability, and therefore when a further photosensitive resin composition is applied onto the cured relief pattern, the in-plane uniformity is insufficient.

[0007] An object of the present invention is to provide a photosensitive resin composition, a cured relief pattern, and a method for producing the same, which are capable of improving the in-plane uniformity of a cured relief pattern. [Means for solving the problem]

[0008] The present inventors have found that the above-mentioned problems can be solved by controlling the intensity ratio of the IR peak of the cured film before and after contacting the cured film of the photosensitive resin composition containing a urea compound with a DMSO solution of TMAH under specific conditions within a specific range, and have completed the present invention. Hereinafter, examples of the embodiments of the present invention will be listed. [1] (A) at least one resin selected from the group consisting of polyimides and polyimide precursors; (B) a photosensitizer; (C) Urea compounds and A photosensitive resin composition comprising: The photosensitive resin composition was heated at 170° C. for 2 hours to cure the cured film, which was then contacted with a dimethyl sulfoxide (DMSO) solution of tetramethylammonium hydroxide pentahydrate (TMAH) having a concentration of 2.38% by mass at a temperature of 50° C. for 10 minutes. The 1500 cm of the cured film before and after contact -1 When normalized by the IR peak intensity of -1 The IR peak intensity in the vicinity is expressed by the following formula (1): 0.1≦(peak intensity after contact / peak intensity before contact)≦0.8 (1) The photosensitive resin composition satisfies the above requirements. [2] 2. The photosensitive resin composition according to item 1, wherein the change in thickness of the cured film before and after contact is 1 nm or more and 1000 nm or less. [3] 3. The photosensitive resin composition according to item 1 or 2, wherein the imidization rate of the cured film before contact is 70% or more and 100% or less. [4] 4. The photosensitive resin composition according to any one of items 1 to 3, wherein the photosensitive resin composition is a photosensitive resin composition for forming an insulating member. [5] 5. The photosensitive resin composition according to any one of items 1 to 4, which is a photosensitive resin composition for forming an interlayer insulating film. [6] 6. The photosensitive resin composition according to any one of items 1 to 5, which is a photosensitive resin composition for forming an interlayer insulating film having two or more layers. [7] (1) A step of applying the photosensitive resin composition according to any one of items 1 to 6 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; (5) contacting the cured relief pattern with an alkaline solution; (6) heat treating the cured relief pattern that has been contacted with the alkaline solution; 2. A method for producing a cured relief pattern comprising: [8] 8. The method for producing a cured relief pattern according to Item 7, wherein the heat treatment is a heat treatment at 170° C. or lower. [9] The cured relief pattern obtained in the step (4) and the cured relief pattern obtained in the step (6) have a resolution of 1500 cm -1 When normalized by the IR peak intensity of -1 The IR peak intensity around 1778 cm of the cured relief pattern obtained in step (5) above -1 9. The method for producing a cured relief pattern according to item 7 or 8, wherein the IR peak intensity is higher than that of a vicinity of the IR peak intensity.

[10] 10. The method for producing a cured relief pattern according to any one of items 7 to 9, wherein the step (5) of contacting the cured relief pattern with the alkaline solution is a photoresist stripping step.

[11] When the cured film was contacted with a DMSO solution of TMAH having a concentration of 2.38 mass% at a temperature of 50°C for 10 minutes, the 1500 cm -1 When normalized by the IR peak intensity of -1 The IR peak intensity in the vicinity is expressed by the following formula (1): 0.1≦(peak intensity after contact / peak intensity before contact)≦0.8 (1) Meet the hardening film.

[12] Item 12. The cured film according to item 11, wherein the change in thickness of the cured film before and after contact is 1 nm or more and 1000 nm or less.

[13] Item 13. The cured film according to item 11 or 12, wherein the imidization rate of the cured film before contact is 70% or more and 100% or less. Effect of the Invention

[0009] According to the present invention, it is possible to provide a photosensitive resin composition, a cured relief pattern, and a method for producing the same, which can improve the in-plane uniformity of a cured relief pattern when two or more layers of the cured relief pattern of the photosensitive resin composition are laminated. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the embodiment for carrying out the present invention (hereinafter, abbreviated as "the present embodiment") will be described in detail. Note that the present invention is not limited to the following present embodiment, and can be carried out with various modifications within the scope of the gist. Note that throughout this specification, structures represented by the same symbols in general formulas may be the same or different when multiple structures are present in a molecule.

[0011] <Photosensitive resin composition> The photosensitive resin composition according to this embodiment is (A) at least one resin selected from the group consisting of polyimides and polyimide precursors; (B) a photosensitizer; (C) Urea compounds and Includes.

[0012] The photosensitive resin composition according to this embodiment can be heated at 170° C. for 2 hours to obtain a cured film. When this cured film is contacted with a dimethyl sulfoxide (DMSO) solution of tetramethylammonium hydroxide pentahydrate (TMAH) with a concentration of 2.38 mass% (hereinafter also referred to as a "standard TMAH solution") at a temperature of 50° C. for 10 minutes, the 1500 cm -1 When normalized by the IR peak intensity of -1 The IR peak intensity in the vicinity satisfies the following formula (1). 0.1≦(peak intensity after contact / peak intensity before contact)≦0.8 (1)

[0013] When the IR peak intensity of the cured film is within the above range, the hydrophilicity of the cured film is increased, and the cured film has wettability suitable for further coating of the photosensitive resin composition on the cured film. The value of the peak intensity after contact / peak intensity before contact is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, from the viewpoint of chemical resistance. A cured film having a peak intensity after contact / peak intensity before contact of less than 0.1 has poor chemical resistance. The value of the peak intensity after contact / peak intensity before contact is preferably 0.8 or less, more preferably 0.7 or less, and even more preferably 0.6 or less, from the viewpoint of wettability.

[0014] It should be noted that the temperature, concentration, and contact conditions of the standard TMAH solution are conditions for measuring the post-contact peak intensity / pre-contact peak intensity of the photosensitive resin composition, and do not limit the method or application of the photosensitive resin composition of the present embodiment. The photosensitive resin composition of the present embodiment tends to be able to adjust the post-contact peak intensity / pre-contact peak intensity to within the range of the above formula (1) by further combining the urea compound (C) in addition to the components (A) and (B).

[0015] The change in film thickness before and after contact with the standard TMAH solution is preferably 1 nm or more and 1000 nm or less. In the method for producing a cured relief pattern, low solubility in an alkaline solution can effectively suppress deterioration of the pattern (cracks, deformation of the pattern shape), so the change in film thickness of the cured film before and after contact with the standard TMAH solution is more preferably 600 nm or less, and even more preferably 300 nm or less. The change in film thickness of the cured film is measured by adjusting the film thickness of the cured film before contact to about 3 μm.

[0016] From the viewpoint of degassing and cure shrinkage in the process of forming a multilayer body, the cured film before contact with the standard TMAH solution preferably has an imidization rate of 70% or more and 100% or less. When the imidization rate is 70% or more, degassing and cure shrinkage can be suppressed in the process after contact with the alkaline solution. The imidization rate is more preferably 80% or more, and even more preferably 90% or more.

[0017] (A) Polyimide precursor The polyimide precursor (A) in this embodiment is a resin component contained in a photosensitive resin composition, and is converted to a polyimide by a thermal cyclization treatment. The polyimide precursor is preferably a polyamide having a structure represented by the following general formula (3). [ka] In the formula, X2 is a tetravalent organic group, Y2 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, and at least one of R1 and R2 is represented by the following general formula (4): [ka] (In the formula, L1, L2, and L3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.)

[0018] The ratio of hydrogen atoms in R1 and R2 in general formula (3) 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 ratio of monovalent organic groups represented by general formula (4) in R1 and R2 in general formula (3) 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 ratio of hydrogen atoms and the ratio of organic groups in general formula (4) are within the above ranges from the viewpoint of photosensitive properties and storage stability.

[0019] In general formula (3), n1 is not limited as long as it is an integer from 2 to 150, but is preferably an integer from 3 to 100, and more preferably an integer from 5 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition.

[0020] In the general formula (3), 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 and the -COOR2 group are at the ortho position relative to the -CONH- group, or an alicyclic aliphatic group. Specific examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms containing an aromatic ring, such as the following general formula (20): [ka] In the formula, R6 is a hydrogen atom, a fluorine atom, or a C 10 Hydrocarbon groups of C1 to C 10 where 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.}, but is not limited thereto. 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 in that it achieves both heat resistance and photosensitive properties.

[0021] As the X1 group, among the structures represented by the above formula (20), the following formula is particularly preferred: [ka] wherein R6 is a fluorine atom, C1 to C 10 Hydrocarbon groups of C1 to C 10 and m is an integer selected from 0 to 3. The structure represented by the formula { is preferable from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0022] In the above general formula (3), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms in order to achieve both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (21): [ka] In the formula, R6 is a hydrogen atom, a fluorine atom, or a C 10 Hydrocarbon groups of C1 to C 10 and n is an integer selected from 0 to 4.}, but is not limited thereto. 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 in that it has both heat resistance and photosensitive properties.

[0023] As the Y1 group, among the structures represented by the above formula (21), the following formula is particularly preferred: [ka] wherein R6 is a fluorine atom, C1 to C 10 Hydrocarbon groups of C1 to C 10 and n is an integer selected from 0 to 4. The structure represented by the formula { is preferable from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0024] In the above general formula (4), L1 is preferably a hydrogen atom or a methyl group, and L2 and L3 are preferably hydrogen atoms from the viewpoint of photosensitive properties. Also, m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

[0025] In one embodiment, the polyimide precursor (A) is represented by the following general formula (5): [ka] {wherein R1, R2, and n1 are defined above.} It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0026] In the general formula (5), it is more preferable that at least one of R1 and R2 is a monovalent organic group represented by the above general formula (4). When the (A) polyimide precursor contains the polyimide precursor represented by the general formula (5), the chemical resistance is particularly enhanced. [ka] {wherein R1, R2, and n1 are defined above.} It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0027] In the general formula (6), at least one of R1 and R2 is more preferably a monovalent organic group represented by the above general formula (4). The polyimide precursor (A) tends to have particularly high resolution by containing both the structural unit represented by the general formula (5) and the structural unit represented by the general formula (6). For example, the polyimide precursor (A) may contain a copolymer of the structural unit represented by the general formula (5) and the structural unit represented by the general formula (6), or may be a mixture of the polyimide precursor represented by the general formula (5) and the polyimide precursor represented by the general formula (6).

[0028] In one embodiment, the polyimide precursor (A) is represented by the following general formula (7): [ka] {wherein R1, R2, and n1 are defined above.} It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0029] In the general formula (7), at least one of R1 and R2 is more preferably a monovalent organic group represented by the above general formula (4). The polyimide precursor (A) tends to have higher resolution by containing both the structural unit represented by the general formula (5) and the structural unit represented by the general formula (7). For example, the polyimide precursor (A) may contain a copolymer of the structural unit represented by the general formula (5) and the structural unit represented by the general formula (7), or may be a mixture of the polyimide precursor represented by the general formula (5) and the polyimide precursor represented by the general formula (7).

[0030] In one embodiment, the polyimide precursor (A) is represented by the following general formula (9): [ka] {wherein R1, R2, and n1 are defined above.} It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0031] In general formula (9), at least one of R1 and R2 is more preferably a monovalent organic group represented by the above general formula (4).

[0032] In one embodiment, the polyimide precursor (A) is represented by the following general formula (10): [ka] {wherein R1, R2, and n1 are defined above.} In the general formula (10), at least one of R1 and R2 is more preferably a monovalent organic group represented by the above general formula (4). When the (A) polyimide precursor contains a polyimide precursor having a structural unit represented by the general formula (10), the resolution, imidization rate, and chemical resistance are improved, and in particular, the in-plane uniformity is improved.

[0033] (A) Method for preparing polyimide precursor (A) Polyimide precursor is obtained by first reacting the above-mentioned tetracarboxylic dianhydride containing the tetravalent organic group X1 with an alcohol having a photopolymerizable 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 body), and then subjecting the partially esterified tetracarboxylic acid to amide polycondensation with the above-mentioned diamine containing the divalent organic group Y1.

[0034] (Preparation of Acid / Ester Forms) In the present embodiment, examples of the tetracarboxylic acid dianhydride containing a tetravalent organic group X1 that is suitably used for preparing the polyimide precursor (A) include the tetracarboxylic acid dianhydride represented by the above general formula (20), as well as, for example, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic acid dianhydride, Examples of the diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride include diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably include 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 thereto. These may be used alone or in combination of two or more.

[0035] In the present embodiment, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare the polyimide precursor (A) include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy- Examples of the methacryloyloxypropyl acrylate include 3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0036] 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.

[0037] As the polyimide precursor, a non-photosensitive polyimide precursor prepared only from the alcohols having no unsaturated double bonds may be used by mixing with the photosensitive polyimide precursor. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0038] The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol are 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 obtain the desired acid / ester. The reaction conditions include, for example, stirring at a temperature of 20 to 50°C for 4 to 24 hours.

[0039] (Preparation of polyimide precursor) The acid / ester body (typically a solution in a solvent described below) is mixed with an appropriate dehydration condensation agent under ice cooling to convert the acid / ester body into a polyacid anhydride, and then a diamine containing a divalent organic group Y1 preferably used in this embodiment dissolved or dispersed in a separate solvent is added dropwise to the acid / ester body to perform amide polycondensation to obtain a target polyimide precursor. Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. Alternatively, the acid moiety of the acid / ester body is converted into an acid chloride using thionyl chloride or the like, and then the acid is reacted with a diamine compound in the presence of a base such as pyridine to obtain a target polyimide precursor.

[0040] Diamines containing a divalent organic group Y1 that are preferably used in this embodiment 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, 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)hex 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those 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 and 2,2'-dimethyl-4,Examples of the diaminobiphenyl include, but are not limited to, 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0041] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component. Furthermore, the polymer can be purified by repeating redissolution and reprecipitation operations, and then vacuum dried to isolate the desired polyimide precursor. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0042] The molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[0043] (B) Photosensitizer The photosensitizer (B) used in this embodiment will be described. The photosensitizer is preferably a photoradical polymerization initiator, and examples of the photosensitizer include benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzyl derivatives, benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(o-methoxycathionyl) ether derivatives, and the like. 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.

[0044] The blending amount of the (B) photosensitizer is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. The blending amount of the (B) photosensitizer is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning property, and is preferably 20 parts by mass or less from the viewpoint of physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0045] (C) Urea compounds The (C) urea compound used in this embodiment is not limited in structure as long as it has a urea bond in its molecular structure. From the viewpoint of chemical resistance and from the viewpoint of easily adjusting the peak intensity after contact / peak intensity before contact to the range of this embodiment, the (C) urea compound is preferably a urea compound having a structure represented by the following general formula (11) or (12). [ka] In formula (11), R7 and R8 each independently represent a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom; R9 and R 10 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.} [ka] {In formula (12), R 11 , R 12 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R 13 is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.}

[0046] Examples of the heteroatom according to this embodiment include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom.

[0047] In formula (11), R7 and R8 are not limited as long as they are monovalent organic groups having 1 to 20 carbon atoms, which may contain a heteroatom, but from the viewpoint of developability, they preferably contain an oxygen atom. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10. 10 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. 10 When these are bonded to each other to form a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form strong hydrogen bonds.

[0048] R9, R in formula (11)10 is not limited as long as it is a monovalent organic group having 1 to 20 carbon atoms which may contain a hydrogen atom or a heteroatom, but from the viewpoint of developability, it is more preferable that it contains a hydrogen atom or an oxygen atom. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it is preferably 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms.

[0049] R in formula (12) 11 , R 12 is not limited as long as it is a monovalent organic group having 1 to 20 carbon atoms, which may contain a heteroatom, but from the viewpoint of developability, it is more preferable that it contains an oxygen atom. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it is preferably 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. R in formula (12) 11 , R 12 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. 11 ,R 12 When these are bonded to each other to form a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form strong hydrogen bonds.

[0050] In this embodiment, it is preferable that the (C) urea compound further has at least one functional group selected from the group consisting of a (meth)acrylic group, a hydroxyl group, and an amino group.

[0051] In this embodiment, the molecular weight of the urea compound (C) is preferably 150 g / mol or more, and more preferably 250 g / mol or more. When the molecular weight of the urea compound is 250 g / mol or more, the urea compound is less likely to volatilize during the heat curing process, and the effect of promoting imidization is further enhanced.

[0052] The number of urea groups in the molecule of the (C) urea compound is preferably 1 or 2. When the number of urea groups in the molecule is less than 3, the interaction between the urea compounds is small, the solubility is improved, and the filterability of the resin composition is improved.

[0053] The molecular weight per urea group of the (C) urea compound (MW / number of urea groups) is preferably 150 g / mol or more, more preferably 200 g / mol or more. When the molecular weight per urea group is 200 g / mol or more, the interaction between the urea compounds is small, the solubility is improved, and the filterability of the resin composition is improved.

[0054] By containing the urea compound (C) in this embodiment, the peak intensity before and after contact with the standard TMAH solution can be easily adjusted to the range of this embodiment, and as a result, the wettability after the alkaline solution treatment tends to improve. The reason is not clear, but the present inventors believe as follows. First, in one aspect, when the photosensitive resin composition containing the polyimide precursor is heated and cyclized at a low temperature of, for example, 170°C, the conversion of the polyimide precursor to a polyimide tends to be insufficient. On the other hand, the photosensitive resin composition of this embodiment contains the urea compound (C), and it is believed that a part of the urea compound (C) is thermally decomposed to generate amines, etc., and the amines etc. promote the conversion of the polyimide precursor to a polyimide. And, in a preferred aspect, the urea compound (C) further has a (meth)acrylic group, and when the photosensitive resin composition is negative type, the (meth)acrylic group of the urea (C) reacts with the side chain portion of the polyimide precursor (A) by irradiation with light using the compound (B) as an initiator, and crosslinking occurs. It is believed that this allows the urea compound (C) to be more easily present in the vicinity of the polyimide precursor (A), dramatically increasing the conversion efficiency. This suppresses the dissolution rate of the cured film when it comes into contact with an alkaline solution, allowing the cured film to remain sufficiently even after contact with the alkaline solution. It is believed that the urea compound (C) then forms strong hydrogen bonds with functional groups such as imide groups. This is believed to allow the film to remain without dissolving in the alkaline solution due to hydrogen bonds, even if some imide groups are ring-opened by the alkaline solution. This is believed to open the imide rings on the film surface, exposing highly hydrophilic functional groups, improving wettability.

[0055] In this embodiment, when the (C) urea compound further has a (meth)acrylic group, the (meth)acrylic equivalent of the (C) urea compound is preferably 150 to 400 g / mol. When the (meth)acrylic equivalent of the (C) urea compound is 150 g / mol or more, the chemical resistance of the negative photosensitive resin composition tends to be good, and when it is 400 g / mol or less, the developability tends to be good. The lower limit of the (meth)acrylic equivalent of the (C) urea compound is more preferably 200 g / mol or more, 210 g / mol or more, 220 g / mol or more, 230 g / mol or more, more preferably 240 g / mol or more, 250 g / mol or more, and the lower limit is more preferably 350 g / mol or less, 330 g / mol or less, and more preferably 300 g / mol or less. The (meth)acrylic equivalent of the (C) urea compound is even more preferably 210 to 400 g / mol, particularly preferably 220 to 400 g / mol.

[0056] The method for producing the (C) urea compound is not particularly limited, but for example, the urea compound can be obtained by reacting an isocyanate compound with an amine-containing compound. When the amine-containing compound contains a functional group such as a hydroxyl group that can react with an isocyanate, the urea compound may contain a compound in which a part of the isocyanate compound has reacted with the functional group such as a hydroxyl group.

[0057] The urea compound (C) in the present embodiment may be used alone or in combination of two or more kinds.

[0058] The amount of the urea compound (C) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the polyimide precursor (A). The amount of the urea compound is 1 part by mass or more from the viewpoint of chemical resistance, and 50 parts by mass or less from the viewpoint of film properties and photopatterning.

[0059] The photosensitive resin composition of the present embodiment may further contain components other than the above components (A), (B), and (C). The components other than the components (A), (B), and (C) are not limited, but include a thermal base generator, a solvent, a nitrogen-containing heterocyclic compound, a hindered phenol compound, an organic titanium compound, an adhesion aid, a sensitizer, a photopolymerizable unsaturated monomer, and a thermal polymerization inhibitor.

[0060] Thermal base generator The photosensitive resin composition of the present embodiment may contain a base generator. The base generator refers to a compound that generates a base when heated. By containing the thermal base generator, it is possible to further promote imidization of the photosensitive resin composition.

[0061] The thermal base generator is not particularly limited in type, but examples thereof include amine compounds protected by a tert-butoxycarbonyl group, thermal base generators disclosed in International Publication No. 2017 / 038598, etc. However, the thermal base generator is not limited thereto, and other known thermal base generators can be used.

[0062] 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, 2-amino-1,3-propanediol, 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-(isopropyl ... propylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, 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-butanol bis(3-aminopropyl)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, but these are not limited thereto.

[0063] The amount of the thermal base generator is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the polyimide precursor (A). The amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization promotion 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 photosensitive resin composition.

[0064] solvent Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Examples of the solvent include 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, γ-butyroacetone, ethyl acetate, butyl lactate ... 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. can be used. Among them, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesion to the substrate, 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.

[0065] Among these solvents, those capable of completely dissolving the produced polymer are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma-butyrolactone, etc. One type of solvent may be used, or two or more types of solvents may be mixed and used.

[0066] In the photosensitive resin composition of the present embodiment, the amount of the solvent used 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, relative to 100 parts by mass of the (A) polyimide precursor.

[0067] Nitrogen-containing heterocyclic compound When the photosensitive resin composition of the present embodiment is used to form a cured film on a substrate made of copper or a copper alloy, the photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound in order to suppress discoloration on the copper. Examples of the nitrogen-containing heterocyclic compound include an azole compound and a purine derivative.

[0068] Examples of the azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, triazole, 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.

[0069] Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0070] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminopurine, and the like. 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 the like, and derivatives thereof.

[0071] When the photosensitive resin composition contains the azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, discoloration of the copper or copper alloy surface is suppressed, while when the blending amount is 20 parts by mass or less, the photosensitivity is excellent.

[0072] In order to suppress discoloration on the copper surface, the photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenon), and the like. ol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol) 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6 -(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, Examples of the hydroxyl group include, but are not limited to, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred. ,

[0073] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and from the viewpoint of photosensitivity characteristics, more preferably 0.5 to 10 parts by mass. When the amount of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor (A), for example, when the photosensitive resin composition of the present embodiment 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.

[0074] Organotitanium Compounds The photosensitive resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0075] Organotitanium compounds that can be used include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond.

[0076] Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability for the photosensitive resin composition and 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) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate.

[0077] Among them, 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. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0078] When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the polyimide precursor (A). When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is obtained.

[0079] Adhesive Aid In order to improve the adhesion between the film formed using the photosensitive resin composition of the present embodiment and the substrate, the photosensitive resin composition may optionally contain an adhesion aid. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)propane, and the like. silane coupling agents such as benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0080] 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 is preferably in the range of 0.5 to 25 parts by mass based on 100 parts by mass of the (A) polyimide precursor.

[0081] Examples of silane coupling agents include 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), and 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-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethyl triethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name) LS3610, Azmax Corporation: Trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (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, N-(3-ethoxydimethoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea, 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) aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 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(methoxyethoxysilane), tetra 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, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butyl Examples of the silanol include, but are not limited to, ethyl methyl phenyl silanol, isobutyl methyl phenyl silanol, tert-butyl methyl phenyl silanol, ethyl n-propyl phenyl silanol, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol, isobutyl ethyl phenyl silanol, tert-butyl ethyl phenyl silanol, methyl diphenyl silanol, ethyl diphenyl silanol, n-propyl diphenyl silanol, isopropyl diphenyl silanol, n-butyl diphenyl silanol, isobutyl diphenyl silanol, tert-butyl diphenyl silanol, and triphenyl silanol. These may be used alone or in combination.

[0082] Among the above-mentioned silane coupling agents, from the viewpoint of storage stability, preferred silane coupling agents include phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and compounds represented by the following formula: [ka] A silane coupling agent having a structure represented by the following formula is preferred.

[0083] 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 (A) polyimide precursor.

[0084] Sensitizer The photosensitive resin composition of the present embodiment 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, p-dimethylaminocinnamylidene indane, and the like. Non, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone ethyl-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.

[0085] 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 (A) polyimide precursor.

[0086] Photopolymerizable Unsaturated Monomers The photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferred, and examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, and 1,6-hexane diacrylate and dimethacrylate. Examples of such compounds include diacrylates and dimethacrylates of diols, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylates and methacrylates of glycerol, di-, tri-, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0087] When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0088] Thermal Polymerization Inhibitor In addition, the photosensitive resin composition of the present embodiment may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage, particularly in the form of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0089] <Method for Producing Cured Relief Pattern and Semiconductor Device> The method for producing a cured relief pattern of the present embodiment includes the steps of: (1) applying the above-mentioned photosensitive resin composition of the present embodiment onto a substrate to form a resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a cured relief pattern; (5) contacting the cured relief pattern with an alkaline solution; and (6) heat-treating the cured relief pattern that has been contacted with the alkaline solution.

[0090] (1) Resin layer formation process In this step, the photosensitive resin composition of the present embodiment is applied onto a substrate, and then dried as necessary to form a resin layer. As the application method, a method that has been conventionally used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, or a method of spray application using a spray coater, can be used.

[0091] (2) Exposure process In this step, the resin layer formed above is exposed to an ultraviolet light source or the like through a photomask or reticle having a pattern, or directly, using an exposure device such as a contact aligner, mirror projection, or stepper.

[0092] (3) Relief pattern formation process In this process, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.

[0093] The developer used for development is preferably, for example, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferable. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. In addition, two or more types of each solvent, for example, several types, can be used in combination.

[0094] (4) Relief pattern heat treatment process In this step, the relief pattern obtained by the above development is heat-treated to dissolve the photosensitive component and imidize the polyimide precursor (A), thereby converting it into a cured relief pattern made of polyimide. As the method of heat treatment, various methods can be selected, such as using a hot plate, an oven, or a temperature-programmable heating oven. The heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. The temperature of the heat treatment is preferably 160°C to 200°C, more preferably 160°C to 180°C, and even more preferably 160°C to 170°C. Air may be used as the atmospheric gas during heat curing, and inert gases such as nitrogen and argon may also be used.

[0095] (5) Contacting the cured relief pattern with an alkaline solution In this step, the cured relief pattern obtained by the heat treatment step is brought into contact with an alkaline solution, thereby improving the in-plane uniformity of the cured relief pattern made of polyimide. The alkali source of the alkaline solution is not limited as long as it can improve the in-plane uniformity, and for example, tetramethylammonium hydroxide pentahydrate (TMAH) can be mentioned. For example, the solvent of the alkaline solution is dimethyl sulfoxide (DMSO). Typically, a DMSO solution of TMAH, more specifically, a DMSO solvent of 2.38 mass% TMAH can be used. The alkaline solution may contain, as other components, an amine such as monoethanolamine, or a solvent. As the alkaline solution, a stripping solution used for stripping photoresist or dry film resist may be used. The contact with the alkaline solution may be performed, for example, at room temperature to 100°C, for 5 to 120 minutes. When the solution is brought into contact with the alkaline solution, the solution may be stirred. After the contact with the alkaline solution, the cured film may be washed with an organic solvent or water, and then dried. The temperature during drying is preferably 100°C or lower. The atmospheric gas during drying may be air, or an inert gas such as nitrogen or argon.

[0096] The alkaline solution contact step may be performed immediately after the formation of the cured relief pattern, or may be performed after the formation of the cured relief pattern, followed by Ti / Cu sputtering to form a photoresist pattern and plating to form Cu wiring. In this case, the alkaline solution can peel off the photoresist and further act on the cured relief pattern by seeping in through the edge of the wafer or pinholes of the sputter. That is, the contact step with the alkaline solution may be a photoresist peeling step.

[0097] (6) Reheating the cured relief pattern after contact with the alkaline solution In this step, the cured relief pattern after contact with the alkaline solution is reheated. This step may be performed immediately after the alkaline solution contact step, or after forming an upper relief pattern on the cured relief pattern after the alkaline solution contact step. That is, the reheating step of the cured relief pattern after contact with the alkaline solution may be performed simultaneously with the heating of the upper relief pattern after forming a multilayer interlayer insulating film of two or more layers. As the method of the heating treatment, various methods can be selected, such as a method using a hot plate, a method using an oven, or a method using a temperature-elevating oven that can set a temperature program. The heating treatment can be performed, for example, under conditions of 160°C to 350°C for 30 minutes to 5 hours. The temperature of the heating treatment is preferably 160°C to 200°C, more preferably 160°C to 180°C, and even more preferably 160°C to 170°C. The atmospheric gas during the heat curing may be air, or an inert gas such as nitrogen or argon.

[0098] In the method for producing a cured relief pattern of the present embodiment, the cured relief pattern obtained in the above step (4) and the cured relief pattern obtained in the above step (6) are -1 When normalized by the IR peak intensity of -1 The IR peak intensity around 1778 cm of the cured relief pattern obtained in step (5) above -1In the above step (5), the IR peak intensity is preferably higher than the IR peak intensity in the vicinity of 1778 cm -1 By reducing the IR peak intensity in the vicinity, wettability is imparted to the cured film, resulting in a cured relief pattern with high in-plane uniformity.

[0099] <Cured film> The cured film of the present embodiment has a viscosity of 1500 cm when contacted with a 2.38 mass % DMSO solution of TMAH (hereinafter, simply referred to as a "standard TMAH solution") at a temperature of 50° C. for 10 minutes. -1 When normalized by the IR peak intensity of -1 The IR peak intensity around the contact point is in the range of the following formula (1) before and after the contact. 0.1≦(peak intensity after contact / peak intensity before contact)≦0.8 (1)

[0100] When the IR peak intensity of the cured film is within the above range, the hydrophilicity of the cured film is increased, and the cured film has wettability suitable for further coating of the photosensitive resin composition on the cured film. The value of the peak intensity after contact / peak intensity before contact is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, from the viewpoint of chemical resistance. A cured film having a peak intensity after contact / peak intensity before contact of less than 0.1 has poor chemical resistance. The value of the peak intensity after contact / peak intensity before contact is preferably 0.8 or less, more preferably 0.7 or less, and even more preferably 0.6 or less, from the viewpoint of wettability.

[0101] The change in film thickness between before and after contact is preferably 1 nm or more and 1000 nm or less. High solubility in an alkaline solution causes pattern deterioration (cracks, pattern shape deformation), so the change in film thickness of the cured film upon contact with a standard TMAH solution is more preferably 600 nm or less, and even more preferably 300 nm or less. The change in film thickness of the cured film is measured by adjusting the film thickness of the cured film before contact to about 3 μm.

[0102] From the viewpoint of degassing and cure shrinkage in the process of forming a multilayer body, the imidization rate of the cured film before contact with the standard TMAH solution is preferably 70% or more and 100% or less. If the imidization rate is less than 70%, degassing and cure shrinkage become problems in the process after contact with the chemical solution. The imidization rate is more preferably 80% or more, and even more preferably 90% or more.

[0103] <Semiconductor device> In this embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. The semiconductor device in this embodiment has a substrate which is a semiconductor element, and a cured relief pattern of polyimide formed on the substrate by the above-mentioned method for producing a cured relief pattern. Also provided is a method for producing a semiconductor device using a semiconductor element as the substrate and including the above-mentioned method for producing a cured relief pattern of this embodiment as part of the process. More specifically, the semiconductor device in this embodiment can be produced by forming the cured relief pattern formed by the method for producing a cured relief pattern in this embodiment 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 it with a known method for producing a semiconductor device.

[0104] <Display device> In this embodiment, a display device is provided that includes a display element and a cured film provided on the upper portion of the display element, the cured film being the cured relief pattern of the present embodiment described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. For example, the cured film may be a surface protective film, an insulating film, and a planarizing film for a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for a cathode of an organic EL element.

[0105] The photosensitive resin composition of the present embodiment is preferably a 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 photosensitive resin composition of the present embodiment is also useful for applications such as an interlayer insulating film for a multilayer circuit having two or more layers, a cover coat for a flexible copper-clad board, a solder resist film, and a liquid crystal alignment film. EXAMPLES

[0106] The present embodiment will be described in detail below with reference to examples, but the present embodiment is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polyimide precursor or the photosensitive resin composition were measured and evaluated according to the following methods.

[0107] <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, 2 in series, or Showa Denko Shodex 805M / 806M series Standard monodisperse polystyrene: Showa Denko Co., Ltd. Shodex STANDARD SM-105 Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min.

[0108] (2) Fabrication of hardened relief patterns on Cu A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with 200 nm thick Ti and 400 nm thick Cu in that order using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation). Next, a photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Co., Ltd.), and prebaked on a hot plate at 110°C for 180 seconds to form a coating film with a thickness of approximately 4.5 μm. Using a test pattern mask, this coating film was irradiated with 100 to 1300 mJ / cm2 of i-line using Prisma GHI (manufactured by Ultratech Co., Ltd.). 2 The coating was then spray-developed with a coater developer (D-Spin60A, manufactured by SOKUDO) using cyclopentanone as a developer for a time equal to 1.4 times the time required for the unexposed areas to completely dissolve and disappear, and then rinsed with propylene glycol methyl ether acetate for 10 seconds by rotary spray to obtain a relief pattern on Cu.

[0109] The wafer with the relief pattern formed on Cu was heat-treated in a temperature-ramp programmable curing furnace (VF-2000 type, manufactured by Koyo Lindberg) for 2 hours in a nitrogen atmosphere at the temperature shown in Table 1, thereby obtaining a cured relief pattern made of resin approximately 3 μm thick on Cu.

[0110] (3) Exposure of the cured relief pattern to a standard TMAH solution The cured relief pattern created by the method (2) above was mixed with a standard TMAH solution in the following weight ratio: Dimethyl sulfoxide (DMSO): 97.62% by mass Tetramethylammonium hydroxide pentahydrate (TMAH): 2.38% by mass The film was immersed in a heated solution of TMAH for 10 minutes, washed with running water for 30 minutes, and air-dried. The film thickness was measured before and after contact with the standard TMAH solution, and the change in film thickness (amount dissolved) was calculated.

[0111] (4) Reheating of the cured relief pattern after contact with standard TMAH solution The cured relief pattern that had been contacted with the standard TMAH solution by the method (3) above was heat-treated for 2 hours in a nitrogen atmosphere using a temperature-ramp programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.) at the same temperature as the first treatment.

[0112] (5) IR measurement The cured relief pattern resin portion was measured using an ATR-FTIR measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) with a Si prism. -1 The peak intensity at 1500cm -1 The imidization index of the cured film of each Example and Comparative Example was divided by the imidization index of the film obtained by curing the resin composition at 350° C. for 2 hours to calculate the imide ratio. -1 When normalized by the IR peak intensity of -1 The IR peak intensity around the wavelength was also calculated. The peak intensity at each wavelength was calculated 10 cm before and after the wavelength indicated. -1 The wavelength with the highest intensity was taken as the peak intensity for each wavelength. -1 The peak intensity is 1490-1510 cm -1 The most intense wavelength is 1500 cm -1 The peak intensity was determined as

[0113] (6) Measurement of in-plane uniformity The photosensitive resin composition used in (2) above was spin-coated on the cured relief pattern using a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and pre-baked on a hot plate at 110°C for 180 seconds. The rotation speed during coating was adjusted so that the thickness of the coating film formed on the resin of the cured relief pattern was about 6.0 μm. The thickness of the coating film formed on the cured relief pattern was measured using a step gauge (P-15: manufactured by KLA Tenkor Co., Ltd.) over a width of 6000 μm, centered on the boundary between the resin part formed in the lower layer and the Cu part. The in-plane uniformity was calculated using the following formula. In-plane uniformity = [(maximum thickness) - (minimum thickness) / (average thickness of measured area)] The results were evaluated according to the following criteria. A: In-plane uniformity less than 0.6 B: In-plane uniformity 0.6 or more and less than 0.8 C: In-plane uniformity 0.8 or more and less than 1.0 D: In-plane uniformity 1.0 or more

[0114] <Synthesis Example of (A) Polyimide Precursor and (C) Urea Compound> Production Example 1: (A) Synthesis of polyimide precursor A-1 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the reaction mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0115] 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 while stirring, followed by the addition of 93.0 g of 4,4'-oxydianiline (ODA) suspended in 350 mL of γ-butyrolactone over 30 minutes while stirring. After further stirring at room temperature for 4 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0116] The reaction solution obtained was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polyimide precursor A-1). The molecular weight of polyimide precursor A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 21,000.

[0117] Production Example 2: (A) Synthesis of Polyimide Precursor A-2 A polymer (polyimide precursor A-2) was obtained by carrying out a reaction in the same manner as in the above-mentioned 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 A-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

[0118] Production Example 3: (A) Synthesis of polyimide precursor A-3 A polymer (polyimide precursor A-2) was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 124.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 29.4 g of BPDA were used instead of 155.1 g of ODPA in Production Example 1. The molecular weight of polyimide precursor A-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

[0119] Production Example 4: (A) Synthesis of polyimide precursor A-4 Polymer (A-2) was obtained by carrying out a reaction in the same manner as in the above-mentioned 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 polymer (A-2) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0120] Production Example 5: (C) Synthesis of urea compound C-1 55.1 g (0.25 mol) of diethylene glycol bis(3-aminopropyl) ether was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added thereto and stirred at room temperature.

[0121] Next, under ice cooling, a solution of 77.6 g (0.50 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz MOI) and 150 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes, and the mixture was stirred at room temperature for 5 hours. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound C-1.

[0122] Production Example 6: (C) Synthesis of urea compound C-2 In the above Production Example 5, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 26.3 g (0.25 mol) of diethanolamine, and 77.6 g of 2-methacryloyloxyethyl isocyanate (product of Showa Denko K.K., product name: Karenz MOI) was replaced with 38.8 g (0.25 mol), but the synthesis was carried out in the same manner as in Production Example 5 to obtain compound C-2.

[0123] Production Example 7: (C) Synthesis of urea compound C-3 In the above Production Example 5, 55.1 g of diethylene glycol bis(3-aminopropyl) ether was replaced with 60.4 g (0.25 mol) of di-n-octylamine, and 77.6 g of 2-methacryloyloxyethyl isocyanate (product of Showa Denko K.K., product name: Karenz MOI) was replaced with 38.8 g (0.25 mol), but the synthesis was carried out in the same manner as in Production Example 5 to obtain compound C-3.

[0124] Production Example 8: (C) Synthesis of urea compound C-4 26.3 g (0.25 mol) of diethanolamine was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added thereto, followed by stirring at room temperature.

[0125] Next, under ice cooling, a solution of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz BEI) 59.8g (0.25mol) and 150mL of tetrahydrofuran was added dropwise to the flask over 30 minutes, and the mixture was stirred at room temperature for 5 hours. After that, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound C-4.

[0126] Production Example 9: (C) Synthesis of urea compound C-5 Compound C-5 was obtained by the same synthesis method as in Production Example 6, except that 38.8 g (0.25 mol) of 2-methacryloyloxyethyl isocyanate (product of Showa Denko K.K., product name: Karenz MOI) was replaced with 31.8 g (0.25 mol) of hexyl isocyanate (product of Tokyo Chemical Industry Co., Ltd.).

[0127] <Example 1> A photosensitive resin composition was prepared using polyimide precursor A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of A-1 as a polyimide precursor, (B) 2 g of B-1 as a photosensitizer, and (C) 15 g of C-1 as a urea compound were dissolved in 100 g of γ-butyrolactone (hereinafter referred to as GBL). The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of GBL to obtain a photosensitive resin composition. The composition was evaluated according to the above-mentioned method. The results are shown in Table 1.

[0128] <Examples 2 to 13 and Comparative Examples 1 to 3> A photosensitive resin composition similar to that in Example 1 was prepared and evaluated in the same manner as in Example 1, except that it was prepared in the compounding ratio shown in Table 1. The results are shown in Table 1. (B) Photosensitizers B-1 and B-2, (C) Urea compounds C-1 to C-6, (D) Photopolymerizable unsaturated monomer D-1, and (E) Thermal base generator E-1 described in Tables 1 and 2 are respectively as follows.

[0129] B-1: PBG305 (manufactured by Changzhou Powerful Company) B-2: PBG3057 (manufactured by Changzhou Powerful Co., Ltd.)

[0130] C-1: Compound described in Production Example 5 [ka]

[0131] C-2: Compound described in Production Example 6 [ka]

[0132] C-3: Compound described in Production Example 7 [ka]

[0133] C-4: Compound described in Production Example 8 [ka]

[0134] C-5: Compound described in Production Example 9 [ka]

[0135] C-6: 1,3-Dimethylurea (Tokyo Chemical Industry Co., Ltd.)

[0136] D-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.) E-1: 1-(tert-butoxycarbonyl)-4-hydroxypiperidine (Tokyo Chemical Industry Co., Ltd.)

[0137] [Table 1]

[0138] As shown in Table 1, the photosensitive resin composition of Example 1 had a peak at 1500 cm -1 When normalized by the IR peak intensity of -1 The post-contact peak intensity / pre-contact peak intensity ratio of the IR peak intensity around the area was 0.45, and the in-plane uniformity was evaluated as B. The photosensitive resin compositions of Examples 2 to 13 all had an intensity ratio within the range of 0.1 to 0.8, and the in-plane uniformity was evaluated as C or higher. The imidization rate was 70% or higher in all cases, and the peak intensity before contact with the chemical solution and the peak intensity after reheating were higher than the peak intensity after contact with the chemical solution. The film thickness change (amount of dissolution) upon contact with the chemical solution was 1000 nm or less.

[0139] In Comparative Example 1, the amount of dissolution upon contact with the chemical solution was large, and the film disappeared. In Comparative Example 2, the amount of dissolution upon contact with the chemical solution was large, exceeding 1000 nm. The peak intensity ratio was 1.20, and the in-plane uniformity was evaluated as D. In Comparative Example 3, the IR peak intensity hardly changed before and after contact with the chemical solution, and the intensity ratio exceeded 0.9, resulting in an in-plane uniformity evaluation result of D. [Industrial Applicability]

[0140] By using the photosensitive resin composition according to the present invention, a cured relief pattern with excellent in-plane uniformity can be obtained by contacting with a chemical solution. The present invention can be suitably used in the field of photosensitive materials useful for producing electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) at least one resin selected from the group consisting of polyimides and polyimide precursors; (B) a photosensitizer which is an oxime; (C) a urea compound having a (meth)acrylic group; A photosensitive resin composition comprising: The photosensitive resin composition was heated at 170° C. for 2 hours to cure the cured film, and the cured film was contacted with a dimethyl sulfoxide (DMSO) solution of tetramethylammonium hydroxide pentahydrate (TMAH) having a concentration of 2.38% by mass at a temperature of 50° C. for 10 minutes. 1500 cm of the cured film before and after contact －１ When normalized by the IR peak intensity of －１ The IR peak intensity in the vicinity of 0.1≦(peak intensity after contact / peak intensity before contact)≦0.8 (1) Fulfilling The urea compound is represented by the following general formula (11) or (12): 【Chemistry 1】 {In formula (11), R 7 and R 8 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, R 9 is a hydrogen atom, and R 10 is a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.} 【Chemistry 2】 A photosensitive resin composition, which is a urea compound having a structure represented by the following formula (12): {In formula (12), R 11 and R 12 are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R 13 is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.}. However, the (C) urea compound is a condensate of a compound having a structure represented by the following general formula (1) and a structure represented by the following general formula (2-1), and does not include a polyfunctional (meth)acrylic group-containing silane condensate having a plurality of structures of general formula (1) and a weight average molecular weight of 1,000 to 20,000. 【Chemistry 3】 In the general formula (1), R 1 represents a hydrogen atom or a methyl group, and m represents an integer within the range of 1≦m≦10. The symbol * represents a bond. 【Chemistry 4】 In the general formula (2-1), R 2 represents a methyl group or an ethyl group, and n represents an integer within the range of 1≦n≦10. The symbol * represents a bond.

2. 2. The photosensitive resin composition according to claim 1, wherein a change in thickness of the cured film before and after contact is from 1 nm to 1000 nm.

3. 3. The photosensitive resin composition according to claim 1, wherein the imidization rate of the cured film before contact is 70% or more and 100% or less.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition is a photosensitive resin composition for forming an insulating member.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the photosensitive resin composition is a photosensitive resin composition for forming an interlayer insulating film.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the photosensitive resin composition is a photosensitive resin composition for forming an interlayer insulating film having two or more layers.

7. (1) applying the photosensitive resin composition according to any one of claims 1 to 6 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; (5) contacting the cured relief pattern with an alkaline solution; (6) heat-treating the cured relief pattern that has been contacted with the alkaline solution; and 2. A method for producing a cured relief pattern comprising:

8. The method for producing a cured relief pattern according to claim 7 , wherein the heat treatment in (4) and / or (6) is a heat treatment at 170° C. or less.

9. The cured relief pattern obtained in the step (4) and the cured relief pattern obtained in the step (6) have a width of 1500 cm －１ When normalized by the IR peak intensity of －１ The IR peak intensity around 1778 cm of the cured relief pattern obtained in step (5) －１ The method for producing a cured relief pattern according to claim 7 or 8, wherein the IR peak intensity is higher than that of a neighboring IR peak intensity.

10. The method for producing a cured relief pattern according to any one of claims 7 to 9, wherein the step (5) of contacting the cured relief pattern with the alkaline solution is a photoresist stripping step.

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