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

Abstract

Provided is a negative photosensitive resin composition that has excellent copper adhesion and can suppress a decrease in elongation in a uHAST test. A negative photosensitive resin composition according to one embodiment of the present invention comprises a polyimide (A), a photopolymerization initiator (B), a trifunctional or higher (meth)acrylate (C) having the structure represented by general formula (1) or general formula (2), and an acid (D), wherein the acid (D) is a compound selected from the group consisting of carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids, and squaric acids. Formula (1) (wherein, * represents a bonding site.)　Formula (2) (wherein, * represent a bonding site.)

Description

Negative-type photosensitive resin composition, and method for producing a cured relief pattern using the same.

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

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like have been used as insulating materials for electronic components, and as passivation films, surface protective films, and interlayer insulating films for semiconductor devices, possessing excellent heat resistance, electrical properties, and mechanical properties. Among these resins, those provided in the form of photosensitive resin compositions allow for the easy formation of heat-resistant relief pattern films through thermal imidization treatment by coating, exposure, development, and curing of the composition. Such photosensitive resin compositions have the advantage of significantly shortening the process compared to conventional non-photosensitive materials.

[0003] On the other hand, in recent years, the mounting methods (packaging structures) for semiconductor devices on printed circuit boards have also changed from the viewpoint of improving integration density and computing power, as well as miniaturizing chip size. From conventional mounting methods using metal pins and lead-tin eutectic solder, structures in which a polyimide coating directly contacts the solder bumps are now being used, such as BGA (Ball Grid Array) and CSP (Chip Size Packaging), which enable higher density mounting. Furthermore, structures such as FO (Fan Out), which have multiple redistribution layers on the surface of the semiconductor chip with an area larger than the semiconductor chip itself, have also been proposed (see Patent Documents 1 and 2).

[0004] In FO (Focused Orientation), a problem exists where devices are prone to degradation if the elongation of the cured film of a photosensitive resin composition is poor after the high-temperature, high-humidity durability test (uHAST test). Therefore, the reliability of elongation under high temperature and high humidity conditions is a particular concern.

[0005] It is known that forming a dense crosslinked structure within the photosensitive resin composition film and improving hydrolysis resistance are important in order to suppress the decrease in elongation of a cured film after the uHAST test. For example, Patent Documents 3 and 4 disclose a technique that can suppress the hydrolysis of polyimide and the decrease in elongation of a cured film after the uHAST test by selecting a skeleton in which the positive charge of the carbonyl carbon of the imide ring is within a predetermined range, based on the discovery that the strong electron-withdrawing properties of fluorine atoms lead to the hydrolysis of polyimide.

[0006] U.S. Patent Application Publication No. 2018 / 061669, Japanese Patent Publication No. 2012-194520, International Publication No. 2022 / 270544, International Publication No. 2022 / 270546

[0007] In order to improve the performance, functionality, power consumption, and cost of semiconductor devices, the demand for miniaturization of wiring widths in semiconductor elements and circuits is increasing year by year. As wiring miniaturization progresses, higher resolution is also considered important for interlayer insulating films, and the wiring width becomes smaller. In this case, if the elongation (stretchability) of the resin layer (interlayer insulating film) is insufficient, it may break within the device, resulting in a deterioration of performance.

[0008] Conventional interlayer insulating films using polyimide suffer from reduced elongation in uHAST tests. When fracture occurs due to reduced elongation, the insulating film may not perform adequately, especially in semiconductor devices with fine wiring. Furthermore, conventional photosensitive polyimide resin compositions sometimes exhibited poor adhesion at the interface between the copper wiring and the polyimide resin layer.

[0009] The present disclosure aims to provide a negative-type photosensitive resin composition that can suppress the decrease in elongation in the uHAST test required for interlayer insulating films of FO and also exhibits excellent copper adhesion, as well as a method for manufacturing a polyimide cured film and a cured relief pattern using the same, and a semiconductor device.

[0010] Examples of embodiments of the present disclosure are listed in the following sections [1] to

[16] . [1] (A) Polyimide, (B) Photopolymerization initiator, (C) General formula (1) or General formula (2): A negative-type photosensitive resin composition comprising a trifunctional or more (meth)acrylate having a structure represented by the following formula (3): and an acid (D), wherein the acid (D) is a compound selected from the group consisting of carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids, and squalic acids. [2] The component (A) is the following general formula (3): [3] The negative-type photosensitive resin composition according to item 1, which is a polyimide having a structural unit represented by (wherein X1 is a tetravalent organic group having 4 to 32 carbon atoms, Y1 is a divalent organic group having 4 to 40 carbon atoms, and n is a positive integer). [4] The negative-type photosensitive resin composition according to item 1 or 2, wherein the content of component (C) is 1 to 60 parts by mass per 100 parts by mass of component (A). [5] The negative-type photosensitive resin composition according to any one of items 1 to 3, wherein component (C) contains a trifunctional or more (meth)acrylate having the structure represented by general formula (1) and the structure represented by general formula (2) in one molecule. [6] The negative-type photosensitive resin composition according to any one of items 1 to 5, wherein the (C) component comprises a compound containing a total of six or more structures represented by the general formula (1) in one molecule. [7] The negative-type photosensitive resin composition according to any one of items 1 to 6, wherein the acid dissociation constant (pKa) of the (D) component is in the range of 2.2 to 5.0. [8] The negative-type photosensitive resin composition according to any one of items 1 to 7, wherein the (D) component is a compound having 1 to 50 carbon atoms. [9] The negative-type photosensitive resin composition according to any one of items 1 to 8, wherein the (D) component is a carboxylic acid.

[10] The negative-type photosensitive resin composition according to any one of items 1 to 9, further comprising a monomer having a polymerizable functional group (E) other than the (C) component.

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

[12] The negative-type photosensitive resin composition according to item 11, wherein the (F) component is at least one selected from bismaleimide and compounds having an alkoxymethyl group.

[13] The negative-type photosensitive resin composition according to any one of items 1 to 12, further comprising (G) a nitrogen-containing heterocyclic compound.

[14] The negative-type photosensitive resin composition further comprising (K) a solvent, wherein the solvent has an HSP value of 22.5 (J / cm²). 3 ) 0.5 Above, 28.0 (J / cm 3 ) 0.5 Solvents with a KA of less than 22.5 (J / cm²) and / or an HSP value of 22.5 (J / cm²)3 ) 0.5 less than or 28.0 (J / cm 3 ) 0.5 or more and has a boiling point of 35°C or higher (KB), and when the negative photosensitive resin composition contains said solvent (KB), the content of said solvent (KB) relative to the total mass of the photosensitive resin composition is 20% by mass or less, the negative photosensitive resin composition according to any one of items 1 to 13.

[15] A cured film obtained by curing the negative photosensitive resin composition according to any one of items 1 to 14.

[16] The cured film according to item 15, which is an interlayer insulating film.

[17] A method for producing a cured relief pattern, comprising the following steps: (1) a step of applying the negative photosensitive resin composition according to any one of items 1 to 14 onto a substrate to form a photosensitive resin layer on said substrate; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) a step of heat-treating the relief pattern to form a cured relief pattern.

[0011] According to the present disclosure, there can be provided a negative photosensitive resin composition capable of suppressing a decrease in elongation in a uHAST test and having excellent copper adhesion, as well as a method for producing a cured polyimide film, a cured relief pattern using the same, and a semiconductor device.

[0012] Hereinafter, embodiments of the present disclosure will be described in detail. Throughout the present disclosure, when a plurality of structures represented by the same reference sign in a general formula are present in a molecule, they are each independently selected unless otherwise specified, and may be the same or different from each other. In addition, structures represented by common reference signs in different general formulas are also each independently selected unless otherwise specified, and may be the same or different from each other.

[0013] In the following description, the upper or lower limit of a numerically defined range described in stages may be replaced with the upper or lower limit of another numerically defined range described in stages. Also, in the following description, the upper or lower limit of a certain numerically defined range may be replaced with a value described in the examples. Furthermore, regarding the term "step" in the following description, this term includes not only an independent step, but also a case that cannot be clearly distinguished from other steps, as long as the function of the "step" is achieved.

[0014] <Negative Photosensitive Resin Composition> The negative photosensitive resin composition of the present disclosure (hereinafter sometimes referred to as "photosensitive resin composition") contains (A) a polyimide, (B) a photopolymerization initiator, (C) a tri- or higher functional (meth)acrylate having a structure represented by general formula (1) or general formula (2) of the present disclosure, and (D) an acid. If desired, the negative photosensitive resin composition of the present disclosure may further contain one or more selected from among a monomer having a polymerizable functional group other than component (E)(C), (F) a thermal crosslinking agent, (G) a nitrogen-containing heterocyclic compound, and other components, in addition to the above components. By including a polyfunctional (meth)acrylate having a specific structure and an acid in the photosensitive resin composition containing polyimide, the decrease in elongation after uHAST is suppressed in a cured film obtained from the photosensitive resin composition, and the cured film has excellent adhesion. Hereinafter, each component is described in detail.

[0015] (A) Polyimide The (A) polyimide according to the present embodiment is a resin component contained in the negative photosensitive resin composition. Since no resin-derived leaving component is generated during heat curing, the cure shrinkage of the photosensitive resin composition is low. Therefore, compared with a case where a polyimide precursor is used, a pattern having high flatness after curing can be obtained.

[0016] (A) The polyimide may have a polymerizable group at a terminal or a side chain, but it is preferable not to have a polymerizable group at a side chain from the viewpoint of elongation of the cured film and storage stability. It is preferable that the polyimide substantially does not contain a polyamic acid or polyamic acid ester structure. In the present disclosure, "substantially does not contain" means, for example, that the imidization ratio of the polyimide is 90% or more, preferably 95% or more.

[0017] The imidization ratio of polyimide can be measured by known methods. In the present disclosure, the imidization ratio is calculated by the following method. First, the infrared absorption spectrum of the polyimide is measured, and the absorption peak of the imide structure (1780 cm -1 -1 near, 1377 cm -1 near) is confirmed. Next, the polyimide is heat-treated at 350° C. for 1 hour, the infrared absorption spectrum after the heat treatment is measured, and the imidization ratio of the polyimide is calculated by comparing the peak intensity near 1377 cm -1 with the peak intensity before the heat treatment.

[0018] (A) Polyimide preferably has a structure represented by general formula (3) from the viewpoints of solubility in solvents, film elongation, heat resistance, and copper adhesion: (wherein, X1 is a tetravalent organic group having 4 to 32 carbon atoms, Y1 is a divalent organic group having 4 to 40 carbon atoms, and n is a positive integer.) It is preferable that the structure represented by the above formula is included. In the present disclosure, the term "organic group" intends a group containing one or more carbon atoms. The structure represented by the above general formula (3) is particularly suitable for solvent-developable photosensitive resin compositions.

[0019] (A) Polyimide is preferably not alkali-soluble. It is also preferable that X1 and / or Y1 do not have an acidic group such as a carboxy group or a phenolic hydroxyl group. In one embodiment, neither X1 nor Y1 has any of a carboxy group or a phenolic hydroxyl group. It is also preferable that (A) polyimide does not have a fluorine atom. In these cases, a decrease in elongation due to hydrolysis of the polyimide main chain can be suppressed.

[0020] n in general formula (3) is preferably an integer of 2 to 150, more preferably an integer of 3 to 100, and still more preferably an integer of 5 to 70. n is preferably an integer that satisfies the weight average molecular weight of (A) polyimide described later.

[0021] In general formula (3), X1 is a tetravalent organic group and is not particularly limited to structures derived from known tetracarboxylic dianhydrides. However, from the viewpoint of suppressing the decrease in elongation after the uHAST test of the cured film, and having excellent elongation, heat resistance, copper adhesion, and solubility in the solvent, a structure having one or more aromatic rings and / or alicyclic rings (for example, alicyclic rings having 4 to 6 carbon atoms or bicyclo structures containing them) linked or condensed together is preferred, and it is particularly preferred to have at least one structure represented by the following formulas (4) to (13).

[0022] From the viewpoint of the elongation of the cured film obtained from the photosensitive resin composition of this disclosure and suppression of the decrease in elongation after the uHAST test, it is more preferable that X1 has at least one structure represented by formulas (4) to (12). Furthermore, from the viewpoint of the heat resistance of the cured film obtained from the photosensitive resin composition of this disclosure, it is even more preferable that X1 has at least one structure represented by formulas (4) to (6) and (8) to (12). In addition, since the heat resistance and elongation of the cured film of the photosensitive resin composition of this disclosure are particularly excellent, it is especially preferable that X1 has at least one structure represented by formulas (4) and (11) to (12).

[0023] In general formula (3), Y1 is a divalent organic group and is not particularly limited to structures derived from known diamines. However, from the viewpoint of elongation of the cured film, suppression of elongation reduction after the uHAST test, and heat resistance, copper adhesion, and solubility of the photosensitive resin composition in the solvent, a structure having an aromatic ring (for example, a structure having 2 to 6 aromatic rings linked to each other) is preferred, and among these, it is preferable to have at least one of the structures represented by the following formulas (14) to (23).

[0024] Furthermore, Y1 is more preferably having at least one structure represented by formulas (14) to (21) from the viewpoint of excellent elongation of the cured film obtained from the photosensitive resin composition of this disclosure, suppression of elongation decrease after uHAST testing, and copper adhesion, as well as the solubility of the photosensitive resin composition in the solvent. Moreover, Y1 is even more preferably having at least one structure represented by formulas (16) to (21) from the viewpoint of elongation and heat resistance of the cured film obtained from the photosensitive resin composition of this disclosure. In addition, Y1 is particularly preferably having at least one structure represented by formulas (17) to (21) because the coating film uniformity and cured film elongation of the negative-type photosensitive resin composition of this disclosure are particularly excellent. The excellent solubility of the structures represented by formulas (17) to (21) in the solvent is due to the fact that these structures have substituted alkyl chain structures and pendant phenyl structures.

[0025] From the viewpoint of solubility in solvents, it is preferable that the terminal end of polyimide (A), preferably the main chain terminal end of polyimide (A), has at least one structure selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, and the following general formulas (24) to (26). {In the formula, R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, R3 is an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, which may contain a heteroatom (in one embodiment, oxygen, nitrogen, etc.), k is an integer from 1 to 2, R4 is a hydrogen atom or an organic group having 1 to 4 carbon atoms, and * indicates the bonding site with the end of (A) polyimide.} {In the formula, R5 and R6 are independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and * indicates the bonding site to the end of (A) polyimide.} {In the formula, R7, R8, and R9 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, j is an integer from 2 to 10, and * indicates the bonding site with the end of (A) polyimide.}

[0026] In general formulas (24) to (26), the organic group is, in one embodiment, a hydrocarbon group, preferably a methyl group.

[0027] Preferably, the acid anhydride group is derived from the starting material tetracarboxylic anhydride, the carboxyl group is obtained by ring-opening the aforementioned acid anhydride group, and the amino group is derived from the starting material diamine. (A) More detailed specific examples when the terminal end of the polyimide is a structure represented by general formula (24) include the structures represented by the following formulas (27) to (30). {In the formula, * indicates the binding site with the end of (A) polyimide.}

[0028] More detailed specific examples of the structure represented by general formula (25) include the structures represented by the following formulas (31) and (32). {In the formula, * indicates the binding site with the end of (A) polyimide.}

[0029] More detailed specific examples of the structure represented by general formula (26) include the structures represented by the following formulas (33) to (36). {In the formula, * indicates the binding site with the end of (A) polyimide.}

[0030] From the viewpoint of suppressing the decrease in elongation after the uHAST test of the cured film, having excellent elongation and copper adhesion, and having good solubility in the solvent, it is preferable that X1 of general formula (3) is one of the structures represented by general formulas (4) to (13), and Y1 of general formula (3) is one of the structures represented by general formulas (14) to (23).

[0031] (A) The weight-average molecular weight (Mw) of polyimide is not particularly limited as long as it is soluble in the solvent. From the viewpoint of film properties of the cured film and copper adhesion, the weight-average molecular weight of polyimide (A) is preferably 5,000 or more and 100,000 or less. From the viewpoint of elongation and Tg, the lower limit of the weight-average molecular weight of polyimide (A) is more preferably 6,000 or more, and even more preferably 8,000 or more. Furthermore, from the viewpoint of solubility in the solvent, the upper limit of the weight-average molecular weight of polyimide (A) is more preferably 50,000 or less, and particularly preferably 30,000 or less.

[0032] (A) The molecular weight distribution (Mw / Mn) of polyimide is preferably 1.0 or more and 2.0 or less. From the viewpoint of manufacturing efficiency, the lower limit of the molecular weight distribution of polyimide is more preferably 1.15 or more, and even more preferably 1.25 or more. From the viewpoint of resolution, the upper limit of the molecular weight distribution of polyimide is more preferably 1.8 or less, and even more preferably 1.6 or less. Mw and Mn are values ​​measured by the method described in the [Examples] section of this disclosure.

[0033] (A) The polyimide is preferably present in an amount of 10% to 70% by mass, more preferably 20% to 65% by mass, based on the total mass of the photosensitive resin composition containing the solvent.

[0034] (A) Method for preparing polyimide (A) Polyimide is obtained by reacting a tetracarboxylic dianhydride with a diamine to obtain a polyamic acid, which is then dehydrated and cyclized to form an imidate.

[0035] The method for dehydrating and cyclizing polyamic acid is not limited to this method, but examples include the thermal imidation method, in which polyamic acid is heated at a high temperature to dehydrate and cyclize, and the chemical imidation method, in which acetic anhydride and a tertiary amine, which are dehydrating reducing agents, are added to dehydrate and cyclize.

[0036] The temperature in the heating imidation method is not particularly limited, but from the viewpoint of promoting the ring-closing reaction, the lower limit is preferably 150°C or higher, and more preferably 160°C or higher. On the other hand, from the viewpoint of suppressing side reactions, the upper limit is preferably 200°C or lower, and more preferably 180°C or lower.

[0037] While there are no particular limitations on tetracarboxylic dianhydrides, specific examples include pyromellitic anhydride (PMDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,4'-oxydiphthalic anhydride, 4,4'-biphthalic dianhydride (BPDA), 3,4'-biphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BP Examples of dianhydrides include AF), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride (CpODA), bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride (6FDA). Among these, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CBDA), pyromellitic acid anhydride (PMDA), and 4,4'-oxydiphthalic acid anhydride (ODPA).

[0038] While not specifically limited to diamines, concrete examples include 4,4'-diaminodiphenyl ether (DADPE), 3,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene (APB), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 2-phenoxybenzene-1,4-diamine (PND), 9,9-bis(4-aminophenyl)fluorene (BAFL), 6-(4-aminophenoxy)biphenyl-3-amine (PDPE), and 3,3'-diphenyl-4,4' Examples include -bis(4-aminophenoxy)biphenyl (APBP-DP), 2,2-bis[3-phenyl-4-(4-aminophenoxy)phenyl]propane (DAOPPA), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAAPP), and 2-(methacryloyloxy)ethyl-3,5-diaminobenzoate (MAEDAB), m-trilysine (m-TB). Among these, preferred diamines include 6-(4-aminophenoxy)biphenyl-3-amine (PDPE), 9,9'-bis(4-aminophenyl)fluorene (BAFL), and m-trilysine (m-TB).

[0039] (A) When the terminals of polyimide are an acid anhydride group, a carboxyl group, and an amino group, polyimide (A) is a polyimide obtained by dehydrating and cyclizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine to form an imidate. The terminals of polyimide (A) may be reacted with a predetermined compound to form a structure represented by the above general formulas (24) to (26).

[0040] Polyimides (A) having a structure represented by general formula (24) at the end can be obtained, for example, by reacting the amino group at the polyimide terminus with an isocyanate compound. Specific examples of isocyanate compounds include 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate: MOI), 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate. The method for reacting the isocyanate compound is not particularly limited, but it can be reacted with the amino group of the dehydrated and cyclized polyimide by adding the isocyanate compound to a dehydrated and cyclized polyimide solution and stirring at room temperature.

[0041] Polyimide (A), whose terminal structure is represented by general formula (25), can be obtained, for example, by reacting the amino group at the polyimide terminal with a (meth)acryloyl chloride compound or (meth)acrylic anhydride. Examples of (meth)acryloyl chloride compounds include acryloyl chloride and methachloroyl chloride. There are no particular limitations on the method of reacting with the (meth)acryloyl chloride compound, but it can be reacted with the amino group of the dehydrated and cyclized polyimide by cooling the dehydrated and cyclized polyimide solution with ice and adding the (meth)acryloyl chloride compound dropwise. Examples of (meth)acrylic anhydride include methacrylic anhydride and acrylic anhydride. There are no particular limitations on the method of reacting with the (meth)acrylic anhydride, but it can be reacted with the amino group of the dehydrated and cyclized polyimide by adding the (meth)acrylic anhydride dropwise to a polyimide solution dehydrated and cyclized at room temperature, then adding a catalyst such as triethylamine dropwise at room temperature, and then heating.

[0042] Polyimide (A), whose terminal structure is represented by general formula (26), can be obtained, for example, by reacting the acid anhydride group and carboxyl group at the polyimide terminal with an alcohol compound. Examples of alcohol compounds include 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate: HEMA), 2-hydroxyethyl acrylate, 4-hydroxyethyl methacrylate, and 4-hydroxyethyl acrylate. There are no particular limitations on the method of reacting with the alcohol compound, but the acid anhydride group and carboxyl group of the dehydrated and cyclized polyimide can be reacted with the alcohol compound using a condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC) or 4-dimethylaminopyridine (DMAP), or an esterification catalyst such as p-toluenesulfonic acid.

[0043] (A) In the production of polyimide, a reaction solvent may be used to carry out the reaction efficiently in a homogeneous system. The reaction solvent is not particularly limited as long as it can uniformly dissolve or suspend tetracarboxylic dianhydrides, diamines, and compounds having polymerizable functional groups at their terminal ends. Examples of reaction solvents include γ-butyrolactone (GBL), dimethyl sulfoxide, N,N-dimethylacetacetamide, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide.

[0044] (A) When using the heat imidation method in the production of polyimide, an azeotropic solvent may be used to accelerate the imidation reaction. The azeotropic solvent is not particularly limited as long as it is a solvent that forms an azeotrope with water, but examples include toluene, ethyl acetate, N-dichlorohexylpyrrolidone, orthodichlorobenzene, xylene, and benzene.

[0045] (A) Polyimide may be purified by methods described in Patent Document 2 (Japanese Patent Publication No. 2012-194520) or the like. For example, purification methods include removing unreacted substances by dropping the (A) polyimide solution into water and reprecipitation, removing condensing agents and the like that are insoluble in the reaction solvent by filtration, and removing the catalyst with an ion exchange resin. After these purification methods, (A) polyimide may be dried by known methods and isolated in powder form.

[0046] (B) Photopolymerization initiators (B) As photopolymerization initiators, photoradical polymerization initiators are preferred, including benzophenone, benzophenone derivatives such as o-benzoylmethyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal, and benzyl-β-methoxyethyl acetal; and benzoin, benzoin methyl ether, and other benzoin derivatives. Preferred photopolymerization initiators include, but are not limited to, oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines such as N-phenylglycine, and peroxides such as benzoyl perchloride. Among the above photopolymerization initiators, oximes are particularly preferred in terms of photosensitivity.

[0047] (B) The amount of photopolymerization initiator is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 8 parts by mass, and even more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of (A) polyimide. The above amount is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or patternability, and 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. In addition, one type of photopolymerization initiator may be used alone, or two or more types may be used in mixture.

[0048] (C) Trifunctional or more (meth)acrylate having a structure represented by general formula (1) or general formula (2) The photosensitive resin composition of this embodiment contains a compound having three or more functional groups of (meth)acrylate in one molecule and a structure represented by general formula (1) or (2). Component (C) contains a compound having the structure represented by general formula (1), the structure represented by general formula (2), or both. This strengthens the crosslinking network and molecular chain entanglement, suppresses the decrease in elongation of the cured film after uHAST, and improves the adhesion between the cured film and the copper substrate.

[0049] Examples of trifunctional or more (meth)acrylates having a structure represented by general formula (1) or (2) include: compounds obtained by (meth)acrylateing polyfunctional alcohols such as glycerin, diglycerin, trimethylolethane, and pentaerythritol, for example, glycerol triacrylate, pentaerythritol tetraallyl ether, etc.; compounds obtained by adding ethylene oxide and / or propylene oxide to the above polyfunctional alcohols and then (meth)acrylateing them; epoxy acrylates; and the like, but are not limited to these. Furthermore, specific examples of commercially available (meth)acrylates with three or more functionalities include, but are not limited to, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, ATM-4E, ATM-35E, A-DPH-12E (all trade names, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), M-310, M-321, M-350, M-360, M-460, M-930, and M-926 (all trade names, manufactured by Toagosei Co., Ltd.).

[0050] A more specific example of a (meth)acrylate having a structure represented by general formula (1) or (2) is the following formula (37): Examples of compounds represented by the formula (wherein a1 to a13 are each independent integers from 1 to 10, a1 + a2 + a3 are integers from 3 to 20, a4 + a5 + a6 + a7 are integers from 4 to 35, a8 + a9 + a10 are integers from 3 to 20, and a11 + a12 + a13 are integers from 3 to 20) can be given.

[0051] Although not bound by theory, the greater the number of structures of general formula (1) or general formula (2) in component (C), the higher the molecular chain entanglement effect, which further suppresses the decrease in elongation after uHAST testing. In addition, the density of radical polymerizable functional groups per molecule decreases, and the number of oxygen atoms increases, thus further improving copper adhesion. In component (C), the number of structures of general formula (1) in one molecule is preferably 3 to 35, more preferably 3 to 20, even more preferably 4 to 20, and particularly preferably 6 to 20. The above number of structures is preferably 3 or more from the viewpoint of elongation of the cured film and suppression of the decrease in elongation after the uHAST test, and preferably 35 or less from the viewpoint of heat resistance of the cured film. Furthermore, it is preferable for component (C) to have both structures of general formula (1) and general formula (2) in one molecule from the viewpoint of suppressing the decrease in elongation after uHAST testing. In this disclosure, the number of structures of general formula (1) means the number of -C-C- structures sandwiched between a pair of *-O- structures. However, the -C-C(-X)- structure sandwiched between the pair of *-O- structures in general formula (2) also contains a -C-C- structure. Therefore, the "number of structures in general formula (1)" in this disclosure is the number of -C-C- structures sandwiched between the pair of *-O- structures (including those contained within the -C-C(-X)- structure of general formula (2)). The "number of structures in general formula (2)" in this disclosure is the number of -C-C(-X)- structures sandwiched between the pair of *-O- structures. For example, if component (C) has an -O-CC-O-CC-O-CC-O- structure, the number of structures in general formula (1) is 3.

[0052] The number of functional groups per molecule in component (C) is preferably 3 to 10, more preferably 3 to 6, and even more preferably 3 to 4. The number of functional groups is preferably 3 or more from the viewpoint of suppressing the decrease in elongation after the uHAST test, and preferably 6 or less from the viewpoint of copper adhesion.

[0053] The amount of component (C) is preferably 0.1 parts by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 65 parts by mass or less, more preferably 5 parts by mass or more and 60 parts by mass or less, even more preferably 5 parts by mass or more and 35 parts by mass or less, and particularly preferably 5 parts by mass or more and 30 parts by mass or less, with respect to 100 parts by mass or less, particularly preferably 60 parts by mass or less, and particularly preferably 30 parts by mass or less, with respect to the physical properties of the photosensitive resin composition after curing. In addition, component (C) may be used alone, or two or more types may be mixed and used.

[0054] (D) Acid is included in the photosensitive resin composition. By including (D) acid in the (D) acid, the (D) acid removes the copper oxide layer on the copper surface, and the copper surface in close contact with the cured film is not exposed to air, making it less susceptible to re-oxidation and improving the adhesion between copper and the cured film. (D) acid is a compound selected from the group consisting of carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids, and squalic acids. If the carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid, or squalic acid has multiple acid groups, some of the acid groups may be esterified. Among these, from the viewpoint of further improving the adhesion between copper and the cured film, the acid is preferably a carboxylic acid.

[0055] (D) The acid may be an organic acid. The number of carbon atoms in (D) the acid may be 1 to 50 or 1 to 30 in one embodiment. The above number of carbon atoms does not include the carbon atoms in the acid group (which may be of the acid type or ester type).

[0056] (D) The number of acid groups in one molecule of the acid may be 1 to 10 or 1 to 5 in one embodiment.

[0057] (D) The molecular weight of the acid may, in one embodiment, be 40 to 1000 or 40 to 500.

[0058] (D) Acids have one of the following structural formulas: The compound may also be represented by the formula above. In the above formula, R is a monovalent group selected from an aliphatic hydrocarbon group, an aromatic group, a carboxyl group, a hydroxyl group, and an alkoxy group. In addition, R may contain one or more chlorine atoms, fluorine atoms, or iodine atoms. In the above formula, if there are multiple R groups, R may be independent functional groups or may be bonded to each other to form a ring structure.

[0059] Examples of carboxylic acids include acetic acid, α-methoxyphenylacetic acid, trifluoroacetic acid, benzoic acid, malonic acid, trimethylbenzoic acid, pentafluorobenzoic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, mandelic acid, acetylmandelic acid, O-acetylmandelic acid, 4-hydroxymandelic acid, 4-hydroxymandelic acid monohydrate, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2-(1-naphthyl)propionic acid, atrolactinic acid, and 2-methoxy-2-(1-naphthyl)propionic acid. In addition, other substances include tartaric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, 2-hydroxy-2-methylmalonic acid, desoxalic acid, benzyltartaronic acid, sodium isomalate, 2-hydroxy-2-(2β,3α,5β-trihydroxy-5α-carboxycyclohexane-1α-yl)malonic acid, α-hydroxy-α-(3-indolylmethyl)malonic acid, 2-[(3-nitro-6-chloroimidazo[1,2-b]pyridazin-2-yl)methyl]-2-hydroxymalonic acid, 2-[(3-nitro-6-chloroimidazo[1,2-a]pyrididine-2-yl)methyl] -2-hydroxymalonic acid, 2-[(3-nitro-6-bromoimidazo[1,2-a]pyridine-2-yl)methyl]-2-hydroxymalonic acid, 2-[(5-nitroimidazo[2,1-b]thiazole-6-yl)methyl]-2-hydroxymalonic acid, dihydroxytartaric acid, desoxalic acid, facelic acid, fuchsic acid, eucomic acid, pisidic acid, caperatic acid, 2-hydroxy-2-(2-ethylhexyloxycarbonylmethyl)succinic acid, 2-hydroxy-2-(butoxycarbonylmethyl)succinic acid, 2-hydroxy-2-(2-hydroxyethylaminocarbonylmethyl)succinic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid dihydrogen 1-isopropyl, 2-hydroxy-1,23-Propanetricarboxylic acid dihydrogen 2-isopropyl, oxalomalic acid, α-benzylmalic acid, 2-hydroxy-3-methylbutanediic acid, meso-tartaric acid, D-threo-β-hydroxyaspartic acid, L-threo-β-hydroxyaspartic acid, 2-(1,2-dicarboxyethoxy)-3-hydroxybutanediic acid, (2R)-2-amino-3-hydroxybutanediic acid, 3-hydroxy-L-aspartic acid, 2-hydroxy-2-isopropylsuccinic acid, 2-methylcitric acid, L-itatartaric acid, (R)-1-isopropyl citrate, (S)-1-isopropyl citrate, culatic acid, chicory acid, 4-hydroxy-5-methoxyisophthalic acid, 3,6-dihydroxyphthalic acid, β-coccic acid, 4-hydroxyphthalic acid, 3,4-dihydroxyphthalic acid, 3 Examples include, but are not limited to, -(2-furyl)-5-hydroxyphthalic acid, 3-(2-thienyl)-5-hydroxyphthalic acid, 3,4,6-trifluoro-5-hydroxyphthalic acid, 5-hydroxy-1,2,4-benzenetricarboxylic acid, 4,8-dimethoxy-7-hydroxy-2-oxo-2H-1-benzopyran-5,6-dicarboxylic acid, 6-hydroxy-1,2,3,4,5-benzenepentacarboxylic acid, 2-methyl 3-methyl-5-(2,3-dihydroxy-5-methylphenoxy)phthalate, 3-methyl-5-(2,3-dihydroxy-5-methylphenoxy)phthalic acid, 3,3'-oxybis(4,5-dihydroxy-1,2-benzenedicarboxylic acid, 3,5-dihydroxy-1,2-benzenedicarboxylic acid, 5-norbornene-2-carboxylic acid.

[0060] Examples of sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids, squalanesulfonic acid, or their esterified products include, but are not limited to, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, isopropyl p-toluenesulfonate, cyclohexyl p-toluenesulfonate, propyl p-toluenesulfonate, 2-naphthyl p-toluenesulfonate, trifluoromethanesulfonic acid, xylenesulfonic acid, dodecylphosphonic acid, benzylphosphonic acid, dodecylphosphinic acid, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, 2-butoxyethyl phosphate, mono-2-ethylhexyl (2-ethylhexyl)phosphonic acid, squalanesulfonic acid, etc.

[0061] (D) Acid may be in the form of an acid, a metal salt, or a hydrate. From the viewpoint of further improving the adhesion between copper and the hardened film, the acid dissociation constant (pKa) of (D) acid (for acids having multiple pKa values, the minimum pKa) is preferably -3.0 to 7.0, more preferably 2.0 to 6.0, even more preferably 2.2 to 5.5, and particularly preferably 2.2 to 5.0. The pKa values ​​of each compound that is (D) acid are well known to those skilled in the art and are described, for example, in CAS SciFinder (registered trademark).

[0062] (D) The amount of acid to be added is preferably 0.01 parts by mass or more and 20 parts by mass or less per 100 parts by mass of polyimide, more preferably 0.01 parts by mass or more and 10 parts by mass or less, even more preferably 0.05 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 5 parts by mass or less. When the amount is 0.01 parts by mass or more, a good improvement in the redness of the copper substrate surface after development is obtained, and when it is 20 parts by mass or less, and particularly 10 parts by mass or less, excellent adhesion to copper is obtained. In addition, one type of acid (D) may be used alone, or two or more types may be used in mixture form.

[0063] (E) Monomer having a polymerizable functional group The photosensitive resin composition of this embodiment may optionally contain monomers having a polymerizable functional group (E) other than component (C). The monomer having a polymerizable functional group (E) is not particularly limited as long as it is a compound other than component (C) that undergoes radical polymerization reaction with a photopolymerization initiator or a thermal polymerization initiator, but the following general formula (38): It is preferable that the (meth)acrylic compound has a structure represented by the formula {wherein Z is an organic group, L1, L2, and L3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and n2 is an integer from 1 to 10}. When a monomer having a polymerizable functional group is used, the crosslinking of the photosensitive resin composition progresses, resulting in good mechanical properties including elongation and Tg.

[0064] In this disclosure, a monomer having a polymerizable functional group is referred to as monofunctional when it has one radical polymerizable group, and thereafter will be referred to as x-functional according to the number x of radical polymerizable groups. Furthermore, monomers with two or more functional groups will be collectively referred to as polyfunctional. A monomer having a polymerizable functional group may be monofunctional or polyfunctional. From the viewpoint of suppressing the decrease in elongation after uHAST, the radical polymerizable compound is preferably two or more functional, and more preferably three or more functional. On the other hand, from the viewpoint of elongation and copper adhesion, it is preferable to have six or fewer functional groups.

[0065] Monomers having polymerizable functional groups are not limited to the following, but examples of monofunctional or difunctional (meth)acrylates include 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- or diacrylates and methacrylates of glycerol; cyclohexane diacrylate and dimethacrylate; diacrylate and dimethacrylate of 1,4-butanediol; and 1,6-hexanediol. Examples of compounds include diacrylates and dimethacrylates of bisphenol A, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, isobornyl acrylates and methacrylates, acrylamide and its derivatives, methacrylamide and its derivatives, diacrylates and methacrylates of glycerol, diacrylates and methacrylates of pentaerythritol, diacrylates and methacrylates of diphenylfluorene, and ethylene oxide or propylene oxide adducts of these compounds, bis(2-acryloxyethyl) isocyanurate, etc. Furthermore, monomers having polymerizable functional groups may contain hydroxyl groups or urea groups. More specifically, see formulas (39) to (40) below: Examples of compounds represented by [the formula shown] are given.

[0066] Examples of trifunctional or more (meth)acrylates include, but are not limited to, compounds obtained by adding (meth)acrylate to polyfunctional alcohols such as trimethylolethane and pentaerythritol, urethane (meth)acrylates, (meth)acrylates containing urea bonds, meta(acryl)amides, polyester acrylates, tris-(2-acryloxyethyl) isocyanurate, and others. Furthermore, specific examples of (meth)acrylates with three or more functionalities include, but are not limited to, A-TMPT, A-TMMT, A-TMM-3, AD-TMP, A-DPH, A-9550, A-9300, A-9200YN (all trade names, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 1,3,5-triacryloylhexahydro-1,3,5-triazine, N-[tris(3-acryloylamidepropoxymethyl)methyl]acrylamide, N,N-bis(2-acrylamideethyl)acrylamide, and N,N-1,2-ethanediylbis{N-[2-(acryloylamino)ethyl]acrylamide}.

[0067] More specifically, see formula (41) below: Examples of compounds represented by [the formula shown] are given.

[0068] The photosensitive resin composition preferably contains (A) polyimide in an amount of (E) monomer having polymerizable functional groups of 5 to 120 parts by mass per 100 parts by mass of polyimide. To obtain good thermomechanical properties and resolution, the photosensitive resin composition preferably contains (E) monomer having polymerizable functional groups of 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. The upper limit, which can be arbitrarily combined with the lower limit above, is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 80 parts by mass or less, from the viewpoint of copper adhesion.

[0069] (E) A monomer having a polymerizable functional group may be used alone or in a mixture of two or more. When a mixture of multiple monomers having polymerizable functional groups is used, it is preferable that the number of functional groups of at least one monomer having a polymerizable functional group is different from that of the other monomers having polymerizable functional groups. When three or more monomers having polymerizable functional groups are used, it is sufficient that the number of functional groups of at least one of them is different from that of the other monomers, but it is preferable that the number of functional groups of all monomers having polymerizable functional groups is different from that of the others. When multiple monomers having polymerizable functional groups are used, it is preferable to include at least one monofunctional monomer having a polymerizable functional group from the viewpoint of elongation at break.

[0070] The molecular weight of the monomer having polymerizable functional groups is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. The upper limit is preferably 1000 or less, and even more preferably 800 or less. By keeping it within the above range, the resolution is improved and the viscosity of the composition does not increase unnecessarily.

[0071] (F) Thermal Crosslinking Agent The photosensitive resin composition of this embodiment may contain (F) a thermal crosslinking agent. Including (F) a thermal crosslinking agent has the effect of improving adhesion and / or further suppressing the decrease in elongation after uHAST. The thermal crosslinking agent is not particularly limited as long as it forms crosslinks when the relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured, but it can react with components (A), (C), (E) and / or other components to form a crosslinked body. The thermal crosslinking agent may be monofunctional or polyfunctional, but the reaction temperature is preferably 150°C or higher. Examples of (F) thermal crosslinking agents include, but are not limited to, alkoxyalkyl compounds, methylol compounds, phenol compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds. From the viewpoint of suppressing curing shrinkage, it is preferable that (F) a thermal crosslinking agent contains nitrogen atoms.

[0072] Examples of alkoxymethyl compounds, methylol compounds, and phenol compounds include monofunctional and polyfunctional compounds. Examples of commercially available alkoxymethyl compounds, methylol compounds, and phenol compounds include, but are not limited to, HMOM-TPPHBA (product name, manufactured by Honshu Chemical Industry Co., Ltd.), TML-BPA (product name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (product name, manufactured by Sanwa Chemical Co., Ltd.), Nikalac MX-270 (product name, manufactured by Sanwa Chemical Co., Ltd., 1,3,4,6-tetrakis(methoxymethyl)glycoluryl), TrisP-PA (product name, manufactured by Honshu Chemical Industry Co., Ltd.). Specifically, examples include, but are not limited to, compounds of the following formula (42).

[0073] Examples of epoxy compounds include monofunctional and polyfunctional epoxies. These include epoxy compounds containing a bisphenol A group, hydrogenated bisphenol A diglycidyl ether, compounds having epoxy and (meth)acryloyl groups in one molecule, and alicyclic epoxies. For example, commercially available epoxy compounds include Denacol EX-145 (product name, manufactured by Nagase ChemteX Corporation), EPICRON EXA-850CRP (product name, manufactured by DIC Corporation), and Ogusol. EG280 (product name, manufactured by Osaka Gas Chemical Co., Ltd.), Celoxide 2021P (product name, manufactured by Daicel Corporation), DCPD-DE (product name, manufactured by Nippon Materials Technology Co., Ltd.), 4-hydroxybutyl acrylate glycidyl ether, VG-3101L (product name, manufactured by Printec Co., Ltd.), Showfree PETG (product name, manufactured by Resonac Corporation), Showfree BATG (product name, manufactured by Resonac Corporation), HP-47 Examples include, but are not limited to, 00 (product name, manufactured by DIC Corporation), GTR-1800 (product name, manufactured by Nippon Kayaku Co., Ltd.), EPPN-502H (product name, manufactured by Nippon Kayaku Co., Ltd.), NC-7000L (product name, manufactured by Nippon Kayaku Co., Ltd.), OXT-191 (product name, manufactured by Toagosei Co., Ltd.), YX6954BH30 (product name, manufactured by Mitsubishi Chemical Corporation), and YX8100BH30 (product name, manufactured by Mitsubishi Chemical Corporation).

[0074] Examples of oxetane compounds include monofunctional oxetanes and polyfunctional oxetanes. Examples of commercially available oxetane compounds include, but are not limited to, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, bis(3-ethyl-3-oxetanylmethyl)diphenoate, and 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (product name, manufactured by Toagosei Co., Ltd.), OXT221 (product name, manufactured by Toagosei Co., Ltd.).

[0075] Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-phenylenebis( Examples include, but are not limited to, maleimide, N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane.

[0076] Allyl compounds include monofunctional, difunctional, or trifunctional allyl compounds. Examples of commercially available allyl compounds include, but are not limited to, allyl alcohol, allylanisole, allyl benzoate ester, allyl cinnamate ester, N-alyloxyphthalimide, allylphenol, allylphenylsulfone, allylurea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylic acid, triallyl trimellitate, triallyl phosphate, triallyl citrate, TRIAM-705 (product name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), L-DAIC (product name, manufactured by Shikoku Chemicals, Ltd.), and TA-G (product name, manufactured by Shikoku Chemicals, Ltd.).

[0077] Examples of blocked isocyanate compounds include hexamethylene diisocyanate-based blocked isocyanates (e.g., manufactured by Asahi Kasei Corporation, trade names: Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G; manufactured by Mitsui Chemicals, Inc., trade name: Takenate B-882N; manufactured by Baxenden, trade names: 7960, 7961, 7982, 7991, and 7992, etc.); tolylene diisocyanate-based blocked isocyanates (e.g., manufactured by Mitsui Chemicals, Inc., trade name: Takenate B-830, etc.); and 4,4'-diphenylmethyl Examples include, but are not limited to, tandiisocyanate-based blocked isocyanates (e.g., Takenate B-815N, manufactured by Mitsui Chemicals, Inc.; Bronate PMD-OA01, and PMD-MA01, manufactured by Daiei Sangyo Co., Ltd.); 1,3-bis(isocyanate-methyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N, manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, and 2554, manufactured by Tosoh Corporation); and isophorone diisocyanate-based blocked isocyanates (e.g., Baxenden, hereinafter referred to as 7950, 7951, and 7990, etc.).

[0078] Among these, bismaleimide and compounds having alkoxymethyl groups are preferred from the viewpoint of suppressing the decrease in elongation after uHAST and adhesion. (F) The thermal crosslinking agent may be used alone or in combination of two or more types.

[0079] The content of (F) a thermal crosslinking agent other than component (C) in the photosensitive resin composition of this disclosure is preferably 0.2 to 40 parts by mass per 100 parts by mass of (A) polyimide. The lower limit of the thermal crosslinking agent is more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, from the viewpoint of suppressing elongation after uHAST. The upper limit of the thermal crosslinking agent is more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of elongation and resolution of the photosensitive resin composition of this disclosure.

[0080] (G) Nitrogen-containing heterocyclic compound The negative-type photosensitive resin composition of this embodiment may contain (G) a nitrogen-containing heterocyclic compound, and by adding it, the adhesion of the cured film made from the photosensitive resin composition to copper can be improved. Examples of nitrogen-containing heterocyclic compounds include azole compounds and purine derivatives. Specific examples of azole compounds include, for example, 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, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]- Examples include benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0081] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8- Examples include phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 6-methoxypurine, 2-acetamido-6-methoxypurine, 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 their derivatives.

[0082] Among nitrogen-containing heterocyclic compounds, 8-azaadenine, 6-methoxypurine, and 2-acetamido-6-methoxypurine are preferred from the viewpoint of adhesion.

[0083] These nitrogen-containing heterocyclic compounds may be used individually or as a mixture of two or more. When the photosensitive resin composition contains a nitrogen-containing heterocyclic compound, the content is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of (A) polyimide. From the viewpoint of adhesion to copper, this is preferable.

[0084] The photosensitive resin composition may further contain one or more components other than the above components (A) to (G), for example, (H) organotitanium compounds, (I) silane coupling agents, (J) polymerization inhibitors, (K) solvents, (L) hindered phenol compounds, (M) sensitizers, etc.

[0085] (H) The organic titanium compound photosensitive resin composition may contain an organic titanium compound. By including an organic titanium compound, a photosensitive resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0086] Examples of usable organotitanium compounds include those in which an organic chemical substance is bonded to a titanium atom via covalent or ionic bonds.

[0087] Specific examples of organotitanium compounds 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 and a good pattern for photosensitive resin compositions. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), titanium diisopropoxidebis(ethylacetoacetate), etc.

[0088] II) Tetraalkoxy titanium 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 tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc.

[0089] III) Titanocene compounds: e.g., pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 Examples include (-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium.

[0090] IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0091] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc.

[0092] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.

[0093] VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0094] In particular, the organotitanium 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 achieving better chemical resistance. Especially titanium diisopropoxide bis(ethyl acetate), titanium tetra(n-butoxide), and bis(η 5 (-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium is preferred.

[0095] When incorporating an organotitanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of polyimide (A). When the 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 achieved.

[0096] (I) To improve the copper adhesion of the silane coupling agent cured film, the photosensitive resin composition may optionally contain (I) a silane coupling agent.

[0097] Examples of silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM-803, manufactured by Chisso Corporation: trade name Cyra Ace S810), N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM-573), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd.: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane Examples include, but are not limited to, captoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3-triethoxysilylpropyl)-t-butylcarbamate, 4,4-carbonylbis(2-(((3-triethoxysilyl)propyl)amino)carbonyl)benzoic acid, and 2-(3-triethoxysilylpropylcarbamoyl)benzoic acid.

[0098] In addition, other silane coupling agents include, for example, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: 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-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name) Examples include, but are not limited to, SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.2).

[0099] Furthermore, for example, 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: 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(methoxy) Ethoxysilane), 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) [Xysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane Dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyln-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol,Examples include, but are not limited to, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

[0100] The silane coupling agents listed above may be used individually or in combination. Among the silane coupling agents listed above, N-phenyl-3-aminopropyltrimethoxysilane, (3-triethoxysilylpropyl)-t-butylcarbamate, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred from the viewpoint of copper adhesion.

[0101] When using a silane coupling agent, the preferred amount is 0.01 to 20 parts by mass per 100 parts by mass of polyimide (A), from the viewpoint of copper adhesion.

[0102] (J) Polymerization inhibitor The photosensitive resin composition may optionally contain (J) polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, especially when stored in a solvent solution.

[0103] Polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-methoxyphenol, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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.

[0104] (K) Solvents (K) Solvents will be explained. Examples of solvents include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl-2-pyrrolidone, N-ethyl-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 The following can be used: γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholin, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. Among these, N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide are preferred from the viewpoint of resin solubility, resin composition stability, and adhesion to the substrate.

[0105] Among such solvents, those that completely dissolve polyimide are particularly preferred, and examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. In particular, from the viewpoint of in-plane uniformity when the photosensitive resin composition is coated on a substrate, γ-butyrolactone and 3-methoxy-N,N-dimethylpropanamide are preferred.

[0106] The solvent may be one type or a mixture of two or more solvents, but from the viewpoint of appropriately adjusting the stability of the resin composition, it is preferable to use two or more types. When two or more solvents are included, 50% by mass or more of the solvent is preferably one of γ-butyrolactone, N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, or N-ethyl-2-pyrrolidone, from the viewpoint of in-plane uniformity, and more preferably 3-methoxy-N,N-dimethylpropanamide or γ-butyrolactone.

[0107] In the photosensitive resin composition, the amount of solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of (A) polyimide.

[0108] Furthermore, the photosensitive resin composition of this embodiment has a solvent (K) with an HSP value of 22.5 (J / cm²). 3 ) 0.5 Above, 28.0 (J / cm 3 ) 0.5 Solvents with a KA of less than 22.5 (J / cm²) and / or an HSP value of 22.5 (J / cm²) 3 ) 0.5 Less than or 28.0 (J / cm) 3 ) 0.5 The above is true, and it may also contain a solvent (KB) with a boiling point of 35°C or higher.

[0109] Furthermore, in this disclosure, the HSP value refers to the Hansen solubility parameter, and is calculated using the following formula, with the values ​​listed in the master table included in Hansen Solubility Parameter in Practice (HSPiP) Ver. 6.1.02, or the δD, δP, and δH calculated using the Van Krevelen method in the same software: HSP value = (δD 2 +δP 2 +δH 2 ) 0.5

[0110] <Solvent (KA)> The resin composition of this embodiment has an HSP value of 22.5 (J / cm²). 3 ) 0.5Above, 28.0 (J / cm 3 ) 0.5 It may contain a solvent (KA) with a value less than 22.5 (J / cm²). The solvent (KA) is preferably an organic solvent. The HSP value of the solvent (KA) is 22.5 (J / cm²). 3 ) 0.5 Preferably, it is 23.0 (J / cm²). 3 ) 0.5 It is more preferable that it be greater than or equal to 27.5 (J / cm²). 3 ) 0.5 Preferably, it is 27.0 (J / cm²). 3 ) 0.5 The following is more preferable:

[0111] The solubility of component (A) in solvent (KA) is preferably 5 g / 100 g or more, more preferably 10 g / 100 g or more, and even more preferably 20 g / 100 g or more, per 100 g of solvent (KA) at 25°C. If the photosensitive resin composition of this embodiment contains multiple types of either component (A) or solvent (KA), or both, it is sufficient that the solubility of each individual combination of at least one type of component (A) and at least one type of solvent (KA) is within the above range.

[0112] The solvent (KA) preferably contains at least one selected from the group consisting of γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N,N-dimethylpropionamide (NDPA), 3-methoxy-N,N-dimethylpropanamide, and 1,3-dimethyl-2-imidazolidinone (DMI).

[0113] Furthermore, from the viewpoint of the elongation at break and adhesion of the resulting cured product, and the uniformity of the film thickness of the resin composition when applied to a substrate, the solvent (KA) may be a mixture of two or more solvents. Among these, the solvent (KA) preferably contains GBL, 3-methoxy-N,N-dimethylpropanamide, NEP, or NMP, and more preferably any combination shown below (KA1) to (KA10). Furthermore, from the viewpoint of the solubility of the resin composition when applied to a substrate, any combination shown below (KA1), (KA5), or (KA7) is preferred.

[0114] (KA1) Contains GBL and 3-methoxy-N,N-dimethylpropanamide (KA2) Contains DMSO and 3-methoxy-N,N-dimethylpropanamide (KA3) Contains GBL, DMSO and 3-methoxy-N,N-dimethylpropanamide (KA4) Contains DMI and 3-methoxy-N,N-dimethylpropanamide (KA5) Contains γ-valerolactone and 3-methoxy-N,N-dimethylpropanamide (KA6) Contains NDPA and 3-methoxy-N,N-dimethylpropanamide (KA7) Contains NEP and 3-methoxy-N,N-dimethylpropanamide

[0115] When the solvent (KA) is used alone or as a mixture of two or more, it is preferable that it is present in 60 to 99.9 parts by mass, and more preferably 80 to 99.9 parts by mass, based on 100 parts by mass of the total solvent.

[0116] In the above (KA1), the content of 3-methoxy-N,N-dimethylpropanamide is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, when the content of GBL is 100 parts by mass.

[0117] In the above (KA2), when the content of 3-methoxy-N,N-dimethylpropanamide is 100 parts by mass, the content of DMSO is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass.

[0118] In the above (KA3), when the GBL content is 100 parts by mass, the combined content of DMSO and 3-methoxy-N,N-dimethylpropanamide is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass.

[0119] In the above (KA4), when the DMI content is 100 parts by mass, the content of 3-methoxy-N,N-dimethylpropanamide is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass.

[0120] In the above (KA5), the content of 3-methoxy-N,N-dimethylpropanamide is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, when the content of γ-valerolactone is 100 parts by mass.

[0121] In the above (KA6), the content of 3-methoxy-N,N-dimethylpropanamide is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, when the content of NDPA is 100 parts by mass.

[0122] In the above (KA7), the content of 3-methoxy-N,N-dimethylpropanamide is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, when the content of NEP is 100 parts by mass.

[0123] <Solvent (KB)> The photosensitive resin composition of this embodiment may contain a solvent (KB). The solvent (KB) has an HSP value of 22.5 (J / cm²). 3 ) 0.5 Less than or 28.0 (J / cm) 3 ) 0.5 The solvent meets the above criteria and has a boiling point of 35°C or higher. The above boiling point is the value at 1 atmosphere (101,325 Pa).

[0124] The solvent (KB) is preferably selected from the group consisting of ethyl acetate, isopropyl acetate, n-propyl acetate, ethyl lactate, butyl acetate, 1,2-dichloroethane, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone, tetramethylurea, and cyclohexanone. All of these have an HSP value of 22.5 (J / cm²). 3 ) 0.5 Less than or 28.0 (J / cm) 3 ) 0.5 The solvent meets the above criteria and has a boiling point of 35°C or higher.

[0125] When the photosensitive resin composition contains a solvent (KB), the amount of solvent (KB) relative to the total mass of the photosensitive resin composition may, in one embodiment, be 20% by mass or less. From the viewpoint of elongation at break, the above content is preferably 0.0001% by mass or more, or 0.0005% by mass or more, or 0.001% by mass or more. From the viewpoint of uniformity of film thickness of the resin composition when applied to a substrate, the above content is preferably 20% by mass or less, or 19% by mass or less, or 18% by mass or less, or 17.5% by mass or less.

[0126] The HSP value of the solvent (KB) is 22.5 (J / cm²). 3 ) 0.5 Less than 28.0 (J / cm²) 3 ) 0.5 That concludes the report. The HSP value is 16.0 (J / cm²). 3 ) 0.5 More than 22.5 (J / cm 3 ) 0.5 Less than 28.0 (J / cm²) 3 ) 0.5 or more 30.0 (J / cm 3 ) 0.5 Preferably less than 17.0 (J / cm²) 3 ) 0.5 More than 22.5 (J / cm 3 ) 0.5 It is more preferable that it be less than [a certain value].

[0127] The boiling point of the solvent (KB) is 35°C or higher, preferably 60°C or higher. The upper limit of the boiling point is preferably 250°C or lower. If the boiling point is above the lower limit, for example, the volatilization of the solvent (KB) is suppressed during heating, and the aggregation of resins with low solubility to this solvent KB is promoted during curing, making it easier to obtain the effect of improving the elongation at break of the cured product. Furthermore, if the solvent (KB) content is within the above range, the elongation at break can be improved while maintaining the coatability of the photosensitive resin composition.

[0128] The solubility of component (A) in the solvent (KB) is preferably less than 20 g / 100 g, more preferably less than 10 g / 100 g, and even more preferably less than 5 g / 100 g, per 100 g of solvent (KB) at 25°C. The lower limit of the above solubility is not particularly limited, but for example, it is preferably 0.1 g / 100 g or more. If the photosensitive resin composition of this embodiment contains multiple types of either component (A) or solvent (KB), or both, it is sufficient that the solubility of the combination of at least one type of component (A) and at least one type of solvent (KB) is within the above range.

[0129] (L) Hindered phenol compound: To suppress discoloration on the copper surface, the photosensitive resin composition may optionally contain (L) hindered phenol compound.

[0130] Hindered phenol compounds are not limited to, but include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t- Examples include butyl-4-hydroxyphenyl)propionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene.

[0131] Furthermore, examples of hindered phenol compounds include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-Tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-Tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-Tris(4-t-butyl-3-H (Droxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-di Methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4Examples include, but are not limited to, 6-(1H,3H,5H)-trione and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0132] 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.

[0133] The amount of hindered phenol compound blended is preferably 0.1 to 20 parts by mass per 100 parts by mass of polyimide (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount is 0.1 parts by mass or more, for example, when a photosensitive resin layer is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when it is 20 parts by mass or less, the photosensitivity is excellent.

[0134] (M) Sensitizer The photosensitive resin composition may optionally contain (M) sensitizer in order to improve photosensitivity.

[0135] Examples of sensitizers include Michla'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-dimethylaminocinnamyrideneindanone, p-dimethylamino Minobenzylidene 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-acetyl-7-dimethylaminocoumarin, 3 -Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, p-tolyldiethanolamine, m-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid Examples include isoamyl, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and 2,2'-(phenylimino)diethanol. These can be used individually or in combinations of, for example, two to five types.

[0136] When the photosensitive resin composition contains a sensitizer, the amount added is preferably 0.1 to 25 parts by mass per 100 parts by mass of (A) polyimide.

[0137] <Method for manufacturing a cured relief pattern and semiconductor device> The method for manufacturing a cured relief pattern according to the present disclosure includes the following steps: (1) applying the above-described photosensitive resin composition of the present disclosure onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the photosensitive resin layer after exposure to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

[0138] (1) Resin layer formation process In this process, a photosensitive resin composition is applied to a substrate and then dried as necessary to form a photosensitive resin layer. As for the application method, conventional methods used for applying photosensitive resin compositions, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray application using a spray coater, etc., can be used.

[0139] (2) Exposure process In this process, the photosensitive resin layer formed above is exposed to ultraviolet light or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either through a photomask or reticle having a pattern, or directly.

[0140] (3) Relief pattern formation process In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected and used from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment. In addition, after development, if necessary, a post-development bake may be performed using any combination of temperature and time for purposes such as adjusting the shape of the relief pattern.

[0141] 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. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of the good solvent and the poor solvent, 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 can be used in combination, for example, several types.

[0142] (4) Cured Relief Pattern Formation Process In this process, the relief pattern obtained by the above development is heat-treated to dilute the photosensitive component and to promote the crosslinking reaction by component (C) and component (D), converting it into a cured relief pattern (cured film) made of polyimide. Various methods can be selected for the heat treatment, such as using a hot plate or an oven (for example, a heating oven with a temperature program that can be set). The heat treatment can be carried out, for example, at a temperature of 160°C to 350°C for 30 minutes to 5 hours. To further improve copper adhesion, the heat treatment temperature is preferably 350°C or lower, more preferably 230°C or lower, even more preferably 200°C or lower, and even more preferably 180°C or lower. To further suppress the decrease in elongation after uHAST, the temperature is preferably 170°C or higher, more preferably 250°C or higher. To achieve both copper adhesion and copper migration suppression, the temperature is preferably 170°C to 350°C, and more preferably 200°C to 280°C. Air may be used as the atmospheric gas during heat curing, or inert gases such as nitrogen or argon may be used.

[0143] <Polyimide Film> The polyimide film (cured film) of the present disclosure can be produced by curing the photosensitive resin composition of the present disclosure, and the present disclosure also provides a cured film formed from a cured product of the photosensitive resin composition of the present disclosure. For example, a photosensitive resin composition containing (A) polyimide resin of the present disclosure can be used to produce a polyimide film based on the method for producing the cured relief pattern described above. The structure of the polyimide included in the cured relief pattern formed from the above photosensitive resin composition will have a structure represented by the above-mentioned general formula (3). The number of repetitions of the polyimide included in the cured relief pattern, that is, the number corresponding to n in the above-mentioned general formula (3), may, in one embodiment, be an integer from 2 to 150.

[0144] <Semiconductor Device> A semiconductor device preferably has a cured relief pattern obtained by the method for manufacturing a cured relief pattern described above. A semiconductor device preferably has a substrate which is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the method for manufacturing a cured relief pattern described above. A semiconductor device can be manufactured using a semiconductor element as the substrate and the method for manufacturing a cured relief pattern of this disclosure as part of the process. More specifically, a semiconductor device can be manufactured by a method for manufacturing a semiconductor device, which includes forming the cured relief pattern formed by the method for manufacturing a cured relief pattern of this disclosure as a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure.

[0145] <Display Device> The display device comprises a display element and a cured film provided on the upper part of the display element, wherein the cured film is preferably the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or it may be laminated with another layer in between. For example, the cured film can be a surface protective film, insulating film, and planarization film for TFT liquid crystal display elements and color filter elements, a projection for MVA type liquid crystal display devices, and a partition wall for the cathode of an organic EL element.

[0146] The photosensitive resin composition of this disclosure is preferably a photosensitive resin composition for forming insulating members or interlayer insulating films. Furthermore, the photosensitive resin composition can be used to form surface protective films, interlayer insulating films, redistribution insulating films, protective films for flip-chip devices, or protective films for semiconductor devices having a bump structure. In addition to applications to semiconductor devices as described above, the photosensitive resin composition of this disclosure is also useful for applications such as interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[0147] The embodiments of this disclosure will be described below in detail, but the embodiments are not limited to these. In the examples, comparative examples, and manufacturing examples, the physical properties of the polyimide or photosensitive resin composition were measured and evaluated according to the following methods.

[0148] <Measurement and Evaluation Method> (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: Two Shodex KD-806M columns in series, manufactured by Resonaq Corporation, or Shodex 805M / 806M columns in series, manufactured by Resonaq Corporation Standard monodisperse polystyrene: Shodex STANDARD SM-105, manufactured by Showa Denko K.K. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL / min.

[0149] (2) Evaluation of heat resistance: Measurement method and evaluation method of Tg of cured film The negative-type photosensitive resin composition described below was rotary coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625 ± 25 μm) using a coater developer (D-Spin 60A type, manufactured by SOKUDO Corporation), and pre-baked on a hot plate at 110°C for 180 seconds to form a pre-cured film with a thickness of approximately 7 μm. The entire surface of this film was subjected to 800 mJ / cm² using Prisma GHI (manufactured by Ultratech). 2The material was irradiated with energy. Next, using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), the material was cured by post-bake curing at 230°C for 120 minutes under a nitrogen atmosphere to produce a cured film, and a test piece measuring 3 mm in width and 10 mm in length was cut out. The heat resistance of the post-bake film obtained by the above method was measured using the following method. Using a thermomechanical analyzer (manufactured by Seiko Instruments, product name: TMA / EXSTAR 6000), the obtained test piece (3 mm in width, 10 mm in length) was heated to 350°C at a heating rate of 10°C / min, and the thermal expansion coefficient of the obtained test piece was measured. Next, based on the obtained measurement results, the glass transition temperature (Tg) of the cured film was calculated from the inflection point of the thermal expansion coefficient. The unit of Tg is °C. Furthermore, the glass transition temperature (Tg) of the cured film was evaluated based on the following criteria. If the rating is △ or higher, it can be suitably used as a hardened relief pattern for semiconductors. Excellent: Glass transition temperature (°C) of 240 or higher Good: Glass transition temperature (°C) of 220 or higher and less than 240 Acceptable: Glass transition temperature (°C) of 200 or higher and less than 220 Poor: Glass transition temperature (°C) of less than 200

[0150] (3) Method for Evaluating the Elongation of the Cured Film Using the post-baked film obtained by the method in (2) above, the elongation of the cured film was measured in the following two ways. Tensile tests were performed on the obtained test specimens using a tensile testing machine (Orientec Co., Ltd., product name: Tensilon UTM-II-20) in a 23°C atmosphere in accordance with JIS K 7161, and the tensile elongation (elongation) of the test specimens was measured. The stretching speed in the tensile test was set to 40 mm / min. The unit of elongation of the cured film is %. Furthermore, the elongation of the cured film was evaluated based on the following criteria. If the evaluation is △ or higher, it can be suitably used as a cured relief pattern for semiconductors. Excellent: Elongation (%) is 30 or higher Good: Elongation (%) is 20 or higher and less than 30 Acceptable: Elongation (%) is 10 or higher and less than 20 Poor: Elongation (%) is less than 10

[0151] (4) Method for calculating and evaluating the uHAST post-elongation and uHAST post-elongation change rate of the cured film The obtained test pieces were subjected to three cycles of 260°C for 15 minutes each in a reflow oven (manufactured by Koyo Thermo Systems Co., Ltd., product name: 810-II-5Z), followed by a uHAST test in a high-temperature constant-humidity chamber (manufactured by Hirayama Seisakusho Co., Ltd., product name: PC-422R8D) at a temperature of 130°C, humidity of 85%, and time of 168 hours. After that, the uHAST post-elongation was measured under the same conditions as in (3). The uHAST post-elongation change rate was calculated using the following formula: uHAST post-elongation change rate (%) = (uHAST post-elongation - initial elongation) ÷ initial elongation × 100 In addition, the uHAST post-elongation change rate of the cured film was evaluated based on the following criteria. If the evaluation is △ or higher, it can be suitably used as a cured relief pattern for semiconductors. Excellent: uHAST post-stretch change rate (%) is -35 or higher Good: uHAST post-stretch change rate (%) is -45 or higher and less than -35 Acceptable: uHAST post-stretch change rate (%) is -55 or higher and less than -45 Poor: uHAST post-stretch change rate (%) is less than -55

[0152] (5) Copper Adhesion (Peel Strength) Evaluation A 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625 ± 25 μm) was sputtered with 200 nm thick titanium (Ti) and 400 nm thick copper (Cu) in that order using a sputtering apparatus (SME-200E model, manufactured by ULVAC, Inc.). Subsequently, the negative-type photosensitive resin composition described later was rotary coated using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation), and pre-baked on a hot plate at 110°C for 180 seconds to form a pre-cured film with a thickness of approximately 7 μm. The entire surface of this film was treated with 800 mJ / cm using Prisma GHI (manufactured by ULVAC, Inc.). 2The sample was irradiated with the specified energy. Next, a cured film was prepared by post-bake curing at 230°C for 120 minutes under a nitrogen atmosphere using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh). Evercell OPP tape (No. 830NEV, manufactured by Sekisui Chemical Co., Ltd.) was applied to this sample, and the tape and polyimide coating were cut into 5 mm wide strips with a cutter. Then, using a Tensilon universal material tester (RTG-1210, manufactured by A&D Co., Ltd.), the tape and polyimide coating were peeled off at a speed of 50 mm / min at 180 degrees Celsius for 60 mm to separate them between copper and polyimide. The load at that time was calculated by integral averaging, and this value was evaluated as the adhesion strength. If the evaluation is △ or higher, it can be suitably used as a cured relief pattern for semiconductors. Excellent: Adhesion strength of 0.20 N / mm or higher Good: Adhesion strength of 0.17 N / mm or higher but less than 0.20 N / mm Acceptable: Adhesion strength of 0.14 N / mm or higher but less than 0.17 N / mm Poor: Adhesion strength less than 0.14 N / mm

[0153] (6) Overall Evaluation The overall evaluation of (4) change rate of elongation after uHAST and (5) copper adhesion described above was judged according to the following criteria. A is judged to be the best result and D is judged to be the worst result. If the evaluation is B or higher, it can be suitably used as a photosensitive resin composition and cured relief pattern for semiconductors. A: Both items are ○ or higher B: One item is ○ or higher and one item is △ C: Both items are △ D: One or more items are ×

[0154] <Production of Polyimide> Production Example 1: (A) Synthesis of Polyimide A-1 (Terminal MOI-modified ODPA-BAFL) A Dean-Stark extractor was attached, and 200 g of N-methyl-2-pyrrolidone (hereinafter NMP) and 41.8 g (0.12 mol) of 9,9'-bis(4-aminophenyl)fluorene (hereinafter BAFL) were added to a nitrogen-purged three-necked flask and dissolved. To this, 31.0 g (0.10 mol) of 4,4'-oxydiphthalic anhydride (hereinafter ODPA) and 50.0 g of toluene were added and heated to 180°C. After confirming that the theoretical amount of water and the added toluene had been extracted into the Dean-Stark extractor, heating was stopped and the mixture was cooled to room temperature.

[0155] Next, 15.5 g of 2-isocyanatoethyl methacrylate (hereinafter referred to as MOI) was added at room temperature and the mixture was reacted at room temperature for 12 hours. The resulting reaction solution was added dropwise to 8000 g of deionized water to precipitate the polymer, which was then filtered off and vacuum-dried at 40°C to obtain a powdered polymer (polyimide A-1). The weight-average molecular weight of polyimide A-1 was measured by gel permeation chromatography (in terms of standard polystyrene), and it was found to be Mw = 1.7 × 10⁻⁶. 4 That was the case.

[0156] Production Example 2: (A) Synthesis of Polyimide A-2 (Terminal MOI-modified ODPA-BAFL / m-TB) Polyimide A-2 was obtained in the same manner as in Production Example 1, except that 20.9 g of BAFL and 12.7 g of m-trilysine (hereinafter referred to as m-TB) were used.

[0157] Production Example 3: (A) Synthesis of Polyimide A-3 (Terminal MOI-modified ODPA-PDPE) Polyimide A-3 was obtained in the same manner as in Production Example 1, except that 33.2 g of 6-(4-aminophenoxy)biphenyl-3-amine (hereinafter referred to as PDPE) was used instead of BAFL.

[0158] Production Example 4: (A) Synthesis of Polyimide A-4 (Terminal BEI-modified ODPA-BAFL) Polyimide A-4 was obtained in the same manner as in Production Example 1, except that 23.9 g of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (hereinafter BEI) was used instead of MOI.

[0159] Production Example 5: (A) Synthesis of Polyimide A-5 (Terminal AOI-modified ODPA-BAFL) Polyimide A-5 was obtained in the same manner as in Production Example 1, except that 14.1 g of 2-acryloyloxyethyl isocyanate (hereinafter referred to as AOI) was used instead of MOI.

[0160] Manufacturing Example 6: (A) Synthesis of Polyimide A-6 (without end modification, ODPA-BAFL) A Dean-Stark extractor was attached, and 200 g of NMP and 29.0 g (0.083 mol) of BAFL were added to a nitrogen-purged three-necked flask and dissolved. To this, 31.0 g (0.10 mol) of ODPA and 50.0 g of toluene were added and heated to 180°C. After confirming that the theoretical amount of water and the added toluene had been extracted into the Dean-Stark extractor, heating was stopped and the mixture was cooled to room temperature.

[0161] Next, the resulting reaction solution was added dropwise to 8000 g of deionized water to precipitate the polymer, filtered off, and then vacuum-dried at 40°C to obtain a powdered polymer (polyimide A-6).

[0162] Production Example 7: (A) Synthesis of Polyimide A-7 (No End Modification, ODPA-BAFL, High Molecular Weight) Polyimide A-7 was obtained in the same manner as in Production Example 6, except that the amount of BAFL used was 31.4 g (0.090 mol).

[0163] Production Example 8: (A) Synthesis of Polyimide A-8 (Terminal MOI-modified PMDA-PDPE) Polyimide A-8 was obtained in the same manner as in Production Example 1, except that 21.8 g of pyromellitic anhydride (hereinafter PMDA) was used instead of ODPA and 33.2 g of PDPE was used instead of BAFL.

[0164] Production Example 9: (A) Synthesis of Polyimide A-9 (Terminal MOI-modified PMDA / CBDA (90 / 10)-PDPE) Polyimide A-9 was obtained in the same manner as in Production Example 1, except that 19.6 g of PMDA and 2.0 g of CBDA were used instead of ODPA, and 33.2 g of PDPE was used instead of BAFL.

[0165] Production Example 10: (A) Synthesis of Polyimide A-10 (Terminal MOI-modified PMDA / CBDA (10 / 90)-PDPE) Polyimide A-10 was obtained in the same manner as in Production Example 1, except that 2.2 g of PMDA and 17.6 g of CBDA were used instead of ODPA, and 33.2 g of PDPE was used instead of BAFL.

[0166] Production Example 11: (A) Synthesis of Polyimide A-11 (Terminal MOI-modified PMDA / BCD(35 / 65)-PDPE) Polyimide A-11 was obtained in the same manner as in Production Example 1, except that 7.6 g of PMDA and 16.1 g of BCD were used instead of ODPA, and 33.2 g of PDPE was used instead of BAFL.

[0167] Production Example 12: (A) Synthesis of Polyimide A-12 (Terminal MOI-modified PMDA / BCD(50 / 50)-PDPE) Polyimide A-12 was obtained in the same manner as in Production Example 1, except that 10.9 g of PMDA and 12.4 g of BCD were used instead of ODPA, and 33.2 g of PDPE was used instead of BAFL.

[0168] Production Example 13: (A) Synthesis of Polyimide A-13 (Terminal MOI-modified PMDA / BCD(65 / 35)-PDPE) Polyimide A-13 was obtained in the same manner as in Production Example 1, except that 14.2 g of PMDA and 8.7 g of BCD were used instead of ODPA, and 33.2 g of PDPE was used instead of BAFL.

[0169] Production Example 14: (A) Synthesis of Polyimide A-14 (Terminal MOI-modified BCD-PDPE) Polyimide A-14 was obtained in the same manner as in Production Example 1, except that 24.8 g of BCD was used instead of ODPA and 33.2 g of PDPE was used instead of BAFL.

[0170] Production Example 15: (A) Synthesis of Polyimide A-15 (Terminal Anhydride Modified PMDA / BCD(50 / 50)-PDPE) The process was carried out in the same manner as in Production Example 1, except that 10.9 g of PMDA and 12.4 g of BCD were used instead of ODPA, and 33.2 g of PDPE was used instead of BAFL. The mixture was then stopped heating and cooled to room temperature. Subsequently, 15.4 g of methacrylic anhydride (hereinafter referred to as anhydride MA) and 10.1 g of triethylamine were added instead of MOI, and the mixture was heated at 80°C for 1 hour, followed by reaction at room temperature for 12 hours. Polyimide A-15 was then obtained in the same manner as in Production Example 1.

[0171] Manufacturing Example 16: (A) Synthesis of Polyimide A-16 (Terminal HEMA-Modified ODPA / BAFL) A Dean-Stark extractor was attached, and 550 g of GBL and 87.1 g (0.25 mol) of BAFL were added to a nitrogen-purged three-necked flask and dissolved. To this, 93.1 g (0.30 mol) of ODPA and 85.0 g of toluene were added, and the mixture was heated to 180°C. After confirming that the theoretical amount of water and the added toluene had been extracted into the Dean-Stark extractor, heating was stopped and the mixture was cooled to -10 to -40°C.

[0172] Next, 20.6 g (0.10 mol) of DCC was added, followed by 130.1 g (0.22 mol) of HEMA and 12.2 g (0.10 mol) of DMAP. The mixture was then brought to room temperature over 2 hours from below -10°C and reacted at room temperature for 12 hours. The resulting reaction solution was filtered under pressure, and 714 g of Solmix AP-1 (manufactured by Nippon Alcohol Sales Co., Ltd.) was added dropwise to the filtrate to separate the supernatant from the precipitate. The obtained precipitate was dissolved in 714 g of GBL, passed through 54.4 g of ion exchange resin (15-J-WET) over 3 to 5 hours, diluted with 410 g of GBL, and then added dropwise to 8600 g of ion-exchanged water to precipitate the polymer. After filtering, the mixture was vacuum-dried at 40°C to obtain a powdered polymer (polyimide A-16).

[0173] Production Example 17: (A) Synthesis of Polyimide A-17 (Terminal HEMA-modified PMDA / BCD(50 / 50)-PDPE) Polyimide A-17 was obtained in the same manner as in Production Example 16, except that 32.7 g of PMDA and 37.2 g of BCD were used instead of ODPA, and 69.1 g of PDPE was used instead of BAFL.

[0174] Table 1 summarizes the acid anhydrides, diamines, main chain end structures, end encapsulants, and the weight-average molecular weight Mw of the synthesized polyimides used in the production of polyimides A-1 to A-17.

[0175]

[0176] <Production and Evaluation of Photosensitive Resin Compositions> [Example 1] A photosensitive resin composition was prepared using polyimide A-1 by the following method, and the prepared composition was evaluated. (A-1) Terminal MOI-modified ODPA-BAFL: 100.0 g, (B-1) TR-PBG-3057: 5.0 g, (C-1) Glycerol triacrylate: 30.0 g, (D-1) Mandelic acid: 1.0 g, (E-5) 4G: 20.0 g, (F-2) BMI-80: 3.0 g, (G-1) 2-Acetamido-6-methoxypurine: 0.5 g, (H-1) TC-750: 0.5 g, (I-1) KBM-573: 1.5 g, (J-1) p-methoxyphenol: 1.0 g were dissolved in a mixed solvent of (K-1) γ-butyrolactone: (K-2) dimethyl sulfoxide = 75:25 (mass ratio). The obtained solution was adjusted to a solid content (NV) of 31% by adding the required amount of γ-butyrolactone:dimethyl sulfoxide solution = 75:25 (mass ratio) to obtain a photosensitive resin composition (varnish). This composition was evaluated according to the method described above. The results are shown in Table 2.

[0177] [Examples 2-55, Comparative Examples 1-8] Except for the solvent, the compounds were prepared in the mixing ratios shown in Tables 2-5. For the other compounds, the photosensitive resin compositions were prepared by dissolving them in the solvent and adjusting the viscosity in the same manner as in Example 1. The storage stability of the photosensitive resin compositions shown in Tables 2-5 was evaluated, and then the Tg, elongation, copper adhesion, and change in elongation after uHAST of the cured film were evaluated. The results are shown in Tables 2-5. The compounds listed in Tables 2-5 are as follows. Also, phr and % in Tables 2-5 are based on mass.

[0178] (A) Polyimide A-1 to A-17: Polyimides described in each of the above-mentioned manufacturing examples 1 to 17

[0179] (B) Photopolymerization initiators B-1: TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) B-2: Irgacure OXE01 (manufactured by BASF Japan Ltd.) B-3: NCI-831 (manufactured by ADEKA Corporation) B-4: Diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide

[0180] (C) Trifunctional or greater (meth)acrylates having a structure represented by general formula (1) or general formula (2) C-1: Glycerol triacrylate (Number of (1) units: 2, Number of (2) units: 2) C-2: A-GLY-3E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (Number of (1) units: 5, Number of (2) units: 2) C-3: A-GLY-9E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (Number of (1) units: 11, Number of (2) units: 2) C-4: ATM-4E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (Number of (1) units: 4, Number of (2) units: 0) C-5: A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (Number of (1) units: 12, Number of (2) units: 0)

[0181] (D) Acids D-1: Mandelic acid (pKa = 3.4) Number of hydroxyl groups: 1 D-2: 4-Hydroxymandelic acid monohydrate (pKa = 3.5) Number of hydroxyl groups: 2 D-3: Benzoic acid (pKa = 4.2) Number of hydroxyl groups: 0 D-4: 2,4,6-Trimethylbenzoic acid (pKa = 3.8) Number of hydroxyl groups: 0 D-5: Acetic acid (pKa = 4.8) Number of hydroxyl groups: 0 D-6: α-Methoxyphenylacetic acid (pKa = 3.1) Number of hydroxyl groups: 0 D-7: 3-Phenyllactic acid (pKa = 3.7) Number of hydroxyl groups: 1 D-8: 4-Hydroxyphenyllactic acid (pKa = 3.8) Number of hydroxyl groups: 2 D-9: Tartronic acid (pKa = 2.0) Number of hydroxyl groups: 1 D-10: Phosphate (pKa = 2.0) D-11: Dodecyl phosphate (pKa = 1.9) D-12: p-Toluene sulfonic acid monohydrate (pKa = -0.4)

[0182] (E) Monomers having polymerizable functional groups E-1: A-9300 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E-2: Trimethylolpropane triacrylate E-3: A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E-4: A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E-5: 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E-6: PME-400 (manufactured by NOF Corporation) E-7: 9G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0183] (F) Thermal crosslinking agent F-1: Alkylated urea resin (product name Nikalac MX-290, manufactured by Sanwa Chemical Co., Ltd.) F-2: BMI-80 (manufactured by K.I. Chemicals Co., Ltd.)

[0184] (G) Nitrogen-containing heterocyclic compounds G-1: 2-acetamido-6-methoxypurine G-2: 8-azaadenine G-3: 6-methoxypurine

[0185] (H) Organotitanium compounds H-1: Diisopropoxytitanium bis(ethyl acetate) (Product name: Orgatics TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.) H-2: Diisopropoxytitanium bis(ethyl acetate) (Product name: Orgatics TC-100, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0186] (I) Silane coupling agents I-1: N-phenyl-3-aminopropyltrimethoxysilane (product name KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) I-2: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0187] (J) Polymerization inhibitor J-1: p-methoxyphenol

[0188] (K) Solvents K-1: γ-Butyrolactone (GBL) (HSP value 25.6, boiling point 204°C) K-2: Dimethyl sulfoxide (DMSO) (HSP value 26.7, boiling point 191°C) K-3: N-methyl-2-pyrrolidone (NMP) (HSP value 23.0, boiling point 202°C) K-4: N-ethyl-2-pyrrolidone (NEP) (HSP value 22.8, boiling point 211°C) K-5: 3-Methoxy-N,N-dimethylpropanamide (Product name KJCMPA®-100, manufactured by KJ Chemicals Co., Ltd.) (HSP value 24.0, boiling point 215°C) K-6: Ethyl lactate (EL) (HSP value 21.7, boiling point 77°C) K-7: Toluene (HSP value 18.2, boiling point 111°C)

[0189]

[0190]

[0191]

[0192]

[0193] By using the photosensitive resin composition according to this disclosure, it is possible to suppress the decrease in elongation after uHAST testing and obtain a cured product with good copper adhesion. The photosensitive resin composition according to this disclosure can be suitably used in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, it can be used, for example, as an insulating material for electronic components, and for forming relief patterns such as passivation films, buffer coat films, and interlayer insulating films in semiconductor devices.

Claims

1. (A) a polyimide, (B) a photopolymerization initiator, (C) the following general formula (1) or the following general formula (2): a tri- or higher functional (meth)acrylate having a structure represented by , and (D) an acid, wherein (D) the acid is a compound selected from the group consisting of carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids and squaric acids, which is a negative photosensitive resin composition.

2. The above component (A) is given by the following general formula (3): The negative-type photosensitive resin composition according to claim 1, which is a polyimide having a structural unit represented by the formula: (wherein X1 is a tetravalent organic group having 4 to 32 carbon atoms, Y1 is a divalent organic group having 4 to 40 carbon atoms, and n is a positive integer.) 3. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the content of component (C) is 1 to 60 parts by mass per 100 parts by mass of component (A).

4. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the component (C) comprises a trifunctional or more (meth)acrylate having a structure represented by general formula (1) and a structure represented by general formula (2) in one molecule.

5. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the component (C) comprises a compound containing a total of three or more structures represented by the general formula (1) in one molecule.

6. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the component (C) comprises a compound containing a total of six or more structures represented by the general formula (1) in one molecule.

7. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the acid dissociation constant (pKa) of component (D) is in the range of 2.2 to 5.

0.

8. The negative-type photosensitive resin composition according to claim 1 or 2, wherein component (D) is a compound having 1 to 50 carbon atoms.

9. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the component (D) is a carboxylic acid.

10. The negative-type photosensitive resin composition according to claim 1 or 2, further comprising a monomer having a polymerizable functional group (E) other than the component (C) mentioned above.

11. (F) The negative-type photosensitive resin composition according to claim 1 or 2, further comprising a thermal crosslinking agent.

12. The negative-type photosensitive resin composition according to claim 11, wherein component (F) is at least one selected from bismaleimide and compounds having an alkoxymethyl group.

13. (G) The negative-type photosensitive resin composition according to claim 1 or 2, further comprising a nitrogen-containing heterocyclic compound.

14. The negative-type photosensitive resin composition further comprises (K) solvent, wherein the solvent has an HSP value of 22.5 (J / cm²). 3 ) 0.5 Above, 28.0 (J / cm 3 ) 0.5 Solvents with a KA of less than 22.5 (J / cm²) and / or an HSP value of 22.5 (J / cm²) 3 ) 0.5 Less than 28.0 (J / cm²) 3 ) 0.5 The negative-type photosensitive resin composition according to claim 1 or 2, comprising a solvent (KB) having the above-mentioned properties and a boiling point of 35°C or higher, wherein, when the negative-type photosensitive resin composition contains the solvent (KB), the content of the solvent (KB) relative to the total mass of the photosensitive resin composition is 0.01% by mass or more and 20% by mass or less.

15. A cured film obtained by curing the negative-type photosensitive resin composition according to claim 1 or 2.

16. The cured film according to claim 14, which is an interlayer insulating film.

17. A method for producing a cured relief pattern, comprising the following steps: (1) applying the negative-type photosensitive resin composition described in claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the photosensitive resin layer after exposure to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

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