Method for manufacturing negative photosensitive resin composition and hardened embossed pattern

Abstract

The present invention provides a negative photosensitive resin composition comprising: (A) a polyimide precursor or polyimide; (B) a monofunctional (meth)acrylate compound represented by the following general formula (3): {wherein R6 to R7 as defined in the specification}; and (C) a terminally capped polyalkylene glycol compound represented by the following general formula (4): {wherein R8 to R10 and n2 as defined in the specification}.

Description

[Technical Field]

[0001] This invention relates to a negative photosensitive resin composition and a method for manufacturing a hardened embossed pattern. [Previous Technology]

[0002] Previously, polyimide resins, which possess excellent heat resistance, electrical properties, and mechanical properties, were used in insulating materials for electronic components and in passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Polyimide resins in the form of photosensitive polyimide precursors can easily form heat-resistant embossed pattern coatings through thermal imidization treatment of the precursor by coating, exposure, development, and curing. Compared with previous non-photosensitive polyimides, this type of photosensitive polyimide precursor has the advantage of significantly reduced processing steps.

[0003] However, semiconductor devices (hereinafter also referred to as "components") are mounted on printed circuit boards using various methods depending on their purpose. Previously, components were typically manufactured using wire bonding, where fine wires connect the external terminals (pads) of the component to the lead frame. However, with the continuous increase in component speed, operating frequencies have now reached GHz, to the point that differences in the length of the wiring at each terminal during the mounting process can affect the operation of the component. Therefore, when mounting components for high-end applications, it is necessary to accurately control the length of the mounting wiring, but this requirement is difficult to meet in the case of wire bonding.

[0004] Therefore, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor wafer, and bumps (electrodes) are formed on it. The wafer is then flipped and directly mounted onto a printed circuit board. This flip-chip mounting has a wide range of applications and the demand is increasing rapidly. For example, it can be used for high-end components that process high-speed signals because it can accurately control the wiring distance, or it can be used in mobile phones because of its small mounting size. Furthermore, a semiconductor wafer mounting technology called fan-out wafer-level packaging (FOWLP) has recently been proposed (e.g., Patent Document 1). In this technology, a wafer that has completed the previous steps is diced to produce a single wafer, the single wafer is then reconstructed on a support and sealed with molding resin, and then the support is peeled off to form a rewiring layer. Since FOWLP forms the rewiring layer with a thinner film thickness, it has the advantages of not only enabling highly thin packages, but also achieving high-speed transmission and low cost. Patent Document 1 discloses, for example, a photosensitive resin composition for such a rewiring layer. [Previous Technical Documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2019 / 163860 [Summary of the Invention]

[0006] [Problem to be solved by the invention] Patent Document 1 discloses the use of plasticizers such as epoxidized oil to suppress the formation of orange peel when a coating film is formed on a metal surface. However, the composition described in Patent Document 1 sometimes does not have sufficient adhesion or resolution to copper.

[0007] Therefore, the object of the present invention is to provide a negative photosensitive resin composition having good adhesion to copper and good resolution, and a method for manufacturing hardened embossed patterns using the photosensitive resin composition. [Technical Means for Solving the Problem]

[0008] In view of the problems of the prior art described above, the inventors have diligently researched and repeatedly experimented, and as a result discovered that by combining a monofunctional (meth)acrylate compound and a specific polyalkylene glycol compound in a negative photosensitive resin composition, the above problems can be solved, thereby completing the present invention. That is, the present invention is as follows.

[0009] [Item 1] A negative photosensitive resin composition comprising: (A) a polyimide precursor or polyimide; (B) a monofunctional (meth)acrylate compound represented by the following general formula (3): [Chemical 1] {wherein, R6 is a hydrogen atom or a methyl group, and R7 is a monovalent organic group not containing (meth)acrylic acid}; and (C) a terminal-capped polyalkylene glycol compound represented by the following general formula (4): [Chemical 2] {wherein, R8 and R9 are each independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, at least one of R8 and R9 is an alkyl group having 1 to 6 carbon atoms, R10 is an alkyl group having 2 to 4 carbon atoms, and n2 is an integer from 2 to 12}. [Item 2] The negative photosensitive resin composition as described in Item 1, wherein the polyimide precursor is represented by the following general formula (1): [Chemical 3] [wherein, X1 is a tetravalent organic group, Y1 is a divalent organic group, n is an integer from 2 to 150, and R1 and R2 are each independently hydrogen atoms, or the following general formula (2): [Chemical 4] {wherein, R3 is a hydrogen atom or an organic group with 1 to 3 carbon atoms, R4 and R5 are each independently hydrogen atoms or organic groups with 1 to 3 carbon atoms, and m is an integer from 2 to 10} representing a monovalent organic group or a saturated aliphatic group with 1 to 4 carbon atoms]. [Item 3] The negative photosensitive resin composition as described in Item 1 or 2, wherein in the above general formula (4), n2 is an integer from 3 to 12. [Item 4] A negative photosensitive resin composition as described in any one of items 1 to 3, wherein in the above general formula (3), R7 is an organic group containing polyoxyalkylene. [Item 5] A negative photosensitive resin composition as described in any one of items 1 to 4, wherein the molecular weight of component (B) is 500 or less. [Item 6] A negative photosensitive resin composition as described in any one of items 1 to 5, wherein in the above general formula (3), R7 is an organic group without a cyclic skeleton. [Item 7] A negative photosensitive resin composition as described in any one of items 1 to 6, wherein in the above general formula (3), R6 is methyl. [Item 8] A negative photosensitive resin composition as described in any one of items 1 to 7, wherein in the above general formula (4), R10 is ethylene. [Item 9] A negative photosensitive resin composition as described in any one of items 1 to 8, wherein in the above general formula (4), R8 and R9 are each independently an alkyl group having 1 to 6 carbon atoms. [Item 10] A negative photosensitive resin composition as described in any one of items 1 to 92, wherein R7 in the above general formula (3) is an organic group comprising a cyclic hydrocarbon group and a chain hydrocarbon group having 1 to 11 carbon atoms. [Item 11] A negative photosensitive resin composition as described in any one of items 1 to 10, comprising 0.1 to 10 parts by mass of the above component (B) relative to 100 parts by mass of component (A).[Item 12] The negative photosensitive resin composition described in any one of items 1 to 11 contains 0.1 to 10 parts by mass of the above-mentioned component (C) relative to 100 parts by mass of component (A). [Item 13] The negative photosensitive resin composition described in any one of items 1 to 12 further includes (D) a photopolymerization initiator. [Item 14] The negative photosensitive resin composition described in any one of items 1 to 13 includes (D) the following general formula (5): [Formula 5] (where R11 is a hydrogen atom, an alkyl ester, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 1 to 12 carbon atoms) representing a photopolymerization initiator. [Item 15] A method for manufacturing a hardened embossed pattern, comprising the following steps: forming a photosensitive resin layer on a substrate by coating a negative photosensitive resin composition as described in any one of items 1 to 14; exposing the photosensitive resin layer; developing the exposed photosensitive resin layer to form an embossed pattern; and forming a hardened embossed pattern by heat treatment of the embossed pattern. [Effects of the Invention]

[0010] According to the present invention, a negative photosensitive resin composition and a method for manufacturing a hardened embossed pattern using the photosensitive resin composition are provided. The negative photosensitive resin composition exhibits high adhesion to copper and can obtain good resolution.

Implementation Method

[0011] <Negative Photosensitive Resin Composition> The negative photosensitive resin composition of this embodiment (hereinafter referred to as the photosensitive resin composition of this embodiment) comprises the following three components (hereinafter also referred to as the "photosensitive resin composition"): (A) a polyimide precursor or polyimide, (B) a monofunctional (meth)acrylate compound represented by general formula (3), and (C) a terminal-capped polyalkylene glycol compound represented by general formula (4). Other components may also be included as needed. The components will be described in sequence below. Furthermore, in this specification, when multiple structures represented by the same symbol in the general formula exist in the molecule, they may be the same or different from each other.

[0012] [(A) Component; Polyimide precursor or polyimide] Component (A) is a polyimide precursor or polyimide. In one form, the polyimide precursor may be polyamide or polyamide ester. The polyimide may be formed by cyclizing the polyimide precursor by heating it (e.g., above 200°C). The above-mentioned polyimide precursor can be represented by the following general formula (1): [Chemical 6] [wherein, X1 is a tetravalent organic group, Y1 is a divalent organic group, n is an integer from 2 to 150, and R1 and R2 are each independently hydrogen atoms, or the following general formula (2): [Chemical 7] {wherein, R3 is a hydrogen atom or an organic group with 1 to 3 carbon atoms, R4 and R5 are each independently hydrogen atoms or organic groups with 1 to 3 carbon atoms, and m is an integer from 2 to 10} representing a monovalent organic group, or a saturated aliphatic group with 1 to 4 carbon atoms] representing polyamide or polyamide ester.

[0013] In the above general formula (1), the tetravalent organogroup represented by X1 is preferably an organogroup with 6 to 40 carbon atoms, more preferably a -COOR1 group and a -COOR2 group, or a group that is adjacent to the -CONH- group (especially an aromatic group or an alicyclic aliphatic group). It is even more preferably selected from at least one group of the group consisting of the structures represented by the following formula (*): [Chemical 8].

[0014] From the viewpoint of balancing mechanical and photosensitive properties, the tetravalent organic group represented by X1 is preferably a structure selected from at least one of 4,4'-oxophthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride (BPADA). The structure of X1 may be one or a combination of two or more, and from the viewpoint of improving resolution, a combination of two or more is preferred. Here, when 4,4'-oxophthalic anhydride (ODPA) is selected as the anhydride to which X1 is given, X1 is the structure represented by the following general formula (6): [Chemical 9] Furthermore, when pyromellitic dianhydride (PMDA) is chosen as the anhydride to which X1 is given, X1 is the structure represented by the following general formula (7): [Chemical 10]. From the viewpoint of balancing heat resistance and photosensitivity, the above-mentioned X1 is preferably selected from at least one structure of the group consisting of the above general formulas (6) and (7).

[0015] In the above formula (1), from the viewpoint of taking into account both mechanical and photosensitive properties, the divalent organic group represented by Y1 is preferably an aromatic group with 6 to 40 carbon atoms. For example, at least one structure selected from the group represented by the following formula (**): [Chemical 11]. However, it is not limited to these. The structure of Y1 may be one type or a combination of two or more types.

[0016] In the above formula (1), the divalent organic group represented by Y1 (i.e., the diamine given to Y1) is preferably selected from at least one of diaminodiphenyl ether (DADPE), p-phenylenediamine (pPD), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB: meta-toluidine). From the viewpoint of balancing heat resistance and photosensitivity, it is particularly preferred to select from at least one of diaminodiphenyl ether (DADPE) and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB). Here, when 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) is selected as the diamine given to Y1, Y1 has the structure represented by the following general formula (8): [Chemical 12]. From the perspective of balancing heat resistance and photosensitivity, the Y1 mentioned above is preferably the structure represented by the general formula (8) above.

[0017] (A) The composition is preferably represented by the above formula (1), and at least one of R1 and R2 contains the base represented by the above formula (2). It is particularly preferred that the ends of R1 and R2 containing the base represented by the above formula (2) have double bonds, that is, R4 and R5 in formula (2) are both hydrogen atoms.

[0018] [Preparation method of polyimide precursor] The polyimide precursor represented by the above general formula (1) in this embodiment is obtained, for example, by reacting a tetracarboxylic acid dianhydride containing the above-mentioned tetravalent organic group X1 with carbon number 6 to 40 with an alcohol formed by the bonding of a monovalent organic group and a hydroxyl group represented by (a) the above general formula (2) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as acid / ester body or (a) component), and then performing polycondensation of the partially esterified tetracarboxylic acid with a diamine containing the above-mentioned divalent organic group Y1 with carbon number 6 to 40.

[0019] (Preparation of acid / ester body) In this embodiment, examples of tetracarboxylic dianhydrides containing a tetravalent organic group X1 with 6 to 40 carbon atoms include: pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylmonium-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. Furthermore, these can be used alone or in combination of two or more.

[0020] In this invention, examples of alcohols with photopolymerizable groups that are well-suited for preparing ester-bonded polyimide precursors include: 2-hydroxyethyl methacrylate, 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acryloylamine ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxyethyl methacrylate. 2-Hydroxy-3-triteryl butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethanol, 1-methacryloxy-3-propanol, 2-methacrylamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-triteryl butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

[0021] The saturated aliphatic alcohol that can be used in conjunction with the above-mentioned alcohols having photopolymerizable groups is preferably a saturated aliphatic alcohol having 1 to 4 carbon atoms. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, terbutanol, etc.

[0022] The content of component (a) in the negative photosensitive resin composition relative to the total content of R1 and R2 is preferably more than 80 mol%. If the content of component (a) is more than 80 mol%, the desired photosensitivity can be obtained, which is preferred. The content of component (a) in the negative photosensitive resin composition relative to the total content of R1 and R2 is preferably more than 85 mol%, more preferably more than 90 mol%, and more preferably more than 95 mol%.

[0023] The above-mentioned tetracarboxylic acid dianhydride and the above-mentioned alcohol can be stirred, dissolved and mixed in a reaction solvent at a reaction temperature of 20-50°C for 4 to 10 hours in the presence of an alkaline catalyst such as pyridine, so that the dianhydride can undergo a half-esterification reaction, thereby obtaining the desired acid / ester body.

[0024] Preferably, the solvent used in the above reaction is capable of dissolving the acid / ester body and the polycondensation product of the acid / ester body and diamines, i.e., the polyimide precursor. Examples include: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene, etc. These can be used alone or in combination as needed.

[0025] (Preparation of polyimide precursor) The polyimide precursor that can be used in the embodiments can be obtained by adding a mixture of known dehydrating condensing agents, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc., to the acid / ester body (typically a solution in the reaction solvent) under ice bath cooling to form a polyanhydride. Then, a diamine containing a divalent organic group Y1 with 6 to 40 carbon atoms in general formula (1) is added dropwise to the polyanhydride to dissolve or disperse in the solvent, so that the polyanhydride undergoes polycondensation.

[0026] As diamines containing a divalent organic group Y1 that are readily usable in this invention, for example, the following can be used: p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-Diaminobenzophenone, 3,4'-Diaminobenzophenone, 3,3'-Diaminobenzophenone, 4,4'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl] ion, bis[4-(3-aminophenoxy)phenyl] ion, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy) Biphenyl, bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluene Amines, 9,9-bis(4-aminophenyl)benzene, and those in which a portion of the hydrogen atoms on the benzene ring are replaced by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

[0027] Preferably, 4,4'-diaminodiphenyl ether, p-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are used, and even more preferably, 4,4'-diaminodiphenyl ether, p-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are used.

[0028] Alternatively, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane and other diaminosiloxanes can be copolymerized to improve adhesion to various substrates.

[0029] After the reaction is complete, the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution are filtered and separated as needed. Subsequently, water, aliphatic lower alcohols, or mixtures thereof are added to the obtained polymer components to precipitate the polymer components. Then, the polymer is purified by repeating the redissolution and reprecipitation operations, and vacuum drying is performed to isolate the target polyimide precursor. To improve the purification degree, the polymer solution can also be passed through a column filled with anion exchange resin and / or cation exchange resin swelled with a suitable organic solvent to remove ionic impurities.

[0030] When the molecular weight of the polyimide precursor is determined by gel permeation chromatography using a weight-average molecular weight converted from that of polystyrene, it is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and even more preferably 20,000 to 40,000. A weight-average molecular weight of 8,000 or higher results in good mechanical properties, which is preferable. On the other hand, a weight-average molecular weight of 150,000 or lower results in good dispersibility in the developer and good resolution of the raised pattern, which is also preferable.

[0031] Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Furthermore, the molecular weights of the components used in the examples and comparative examples were determined based on calibration curves prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the standard sample STANDARD SM-105 organic solvent manufactured by Showa Denko Corporation.

[0032] <Polyimine> The polyimine used in this embodiment will be described. The resin component in the photosensitive resin composition is preferably a polyimine resin having the structural unit represented by the following general formula (9). [Chemical 13] {wherein, X2 is a tetravalent organic group, Y2 is a divalent organic group, and n is an integer from 2 to 150} The resin represented by general formula (9) does not require a heat treatment step to chemically change in order to exhibit sufficient film properties, and is therefore suitable for processing at lower temperatures, which is particularly advantageous.

[0033] In general formula (9), the divalent organic group of X2 and / or the tetravalent organic group of Y2 are preferably aromatic ring structures from the viewpoint of heat resistance, more preferably having 6 to 40 carbons respectively, and even more preferably containing benzene ring structures.

[0034] In general formula (9), the tetravalent organogroup of X2 and / or the divalent organogroup of Y2 preferably have a structure having 2 to 6 benzene rings bonded by single bonds or divalent linkages. Examples of divalent linkages here include: alkylene groups, fluorinated alkylene groups, and ether groups. alkylene groups and fluorinated alkylene groups can be linear or branched.

[0035] Polyimide can be obtained by reacting a tetracarboxylic acid, its corresponding tetracarboxylic dianhydride, a tetracarboxylic acid diester dichlorodimethyl chloride, etc., with a diamine, its corresponding diisocyanate compound, trimethylsilyl diamine, etc. Polyimide can usually be obtained by dehydrating and ring-closing polyamide, which is a polyimide precursor obtained by reacting a tetracarboxylic dianhydride with a diamine, through heating or chemical treatment with an acid or alkali.

[0036] Preferred tetracarboxylic acid dianhydrides include: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4 ... Compounds including (3,4-dicarboxyphenyl) dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl) pyridine dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl} pyridine dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and other aromatic tetracarboxylic acid dianhydrides, or butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride and other aliphatic tetracarboxylic acid dianhydrides, and 3,3',4,4'-diphenyltetracarboxylic acid dianhydride.

[0037] Preferably, the following are used: pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenyltrimethyltetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA). These can be used alone or in combination of two or more.

[0038] Preferred diamines include: 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,3'-dimethylbenzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis(para-diphenyl ether) (Aminophenyl)hexafluoropropane, bis(trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxodiphenylamine (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DF) POB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminotrifluorotoluene (3,5-DABTF), 3,5- Compounds represented by diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethylbenzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl) α (6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenyl α (3FCDAM), and 3,6-diamino-9,9-diphenyl α, etc.

[0039] The ratio of diamine to dianhydride used is approximately 1:1 in moles. However, to obtain the desired terminal structure, one may be used in excess. Specifically, by using an excess of diamine, the ends (both ends) of the polyimide are easily converted to amino groups. On the other hand, by using an excess of dianhydride, the ends (both ends) of the polyimide are easily converted to anhydride groups. As described above, in this embodiment, the polyimide preferably has anhydride groups at its ends. Therefore, in this embodiment, it is preferable to use an excess of dianhydride when synthesizing polyimide.

[0040] Certain reagents may also be reacted with the amine and / or anhydride groups at the ends of the polyimide obtained by polycondensation to give the polyimide the desired functional groups at the ends.

[0041] When the molecular weight of polyimide is determined by gel permeation chromatography to be converted from the weight average molecular weight of polystyrene, it is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, and even more preferably 10,000 to 50,000. When the weight average molecular weight is 5,000 or higher, the mechanical properties are good, which is preferable. On the other hand, when the weight average molecular weight is 150,000 or lower, the dispersibility in the developer and the resolution of the raised pattern are good, which is also preferable.

[0042] Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Furthermore, the molecular weights of the components used in the examples and comparative examples were determined based on calibration curves prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the standard sample STANDARD SM-105 organic solvent manufactured by Showa Denko Corporation.

[0043] [(B) component; monofunctional (meth)acrylate compound; polymerizable compound] (B) component is a monofunctional (meth)acrylate compound represented by the following general formula (3): [Chemical 14] {wherein, R6 is a hydrogen atom or a methyl group, and R7 is a monovalent organic group that does not contain a (meth)acrylic acid group}. From the viewpoint of resolution, R6 is preferably a methyl group.

[0044] The reason why the effects of the present invention can be achieved by using this component (B) is not yet clear, but the inventors believe the reason is as follows. The inventors believe that in order for the cured film obtained by curing the photosensitive resin composition to exhibit excellent adhesion to copper, it is generally required that there be less residue in the cured film other than the polyimide component. Generally, in the thermosetting step of the photosensitive resin composition, the volatilization of polymeric compounds such as (meth)acrylate compounds competes with their thermal polymerization reaction, so a considerable amount of polymeric compounds remain in the cured film. Here, by using the monofunctional (meth)acrylate compound represented by the above general formula (3) with fewer reaction sites, the increase in the molecular weight of the polymer can be suppressed. As a result, the polymeric compounds in the thermosetting step volatilize preferentially compared with the thermal polymerization reaction, thereby reducing the amount of polymer residue in the cured film.

[0045] Therefore, from the viewpoint of the volatility of polymeric compounds, the molecular weight of component (B) is preferably 1000 or less, more preferably 500 or less, and even more preferably 400 or less, and especially preferably 300 or less.

[0046] (B) The molecular weight of the component was determined by gel permeation chromatography using the weight-average molecular weight of polystyrene.

[0047] Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Furthermore, the molecular weights of the components used in the examples and comparative examples were determined based on calibration curves prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the standard sample STANDARD SM-105 organic solvent manufactured by Showa Denko Corporation.

[0048] R7 in formula (3) is a monovalent organic group that does not contain (meth)acrylyl, and preferably does not contain thermopolymerizable groups such as vinyl or allyl groups other than (meth)acrylyl. The structure of R7 is not particularly limited, and may contain heteroatoms or cyclic structures, be linear or branched, and be saturated or unsaturated hydrocarbon groups. Examples include alkyl groups or organic groups containing polyoxyalkylene groups. Among them, R7 is preferably an organic group that does not contain cyclic structures, more preferably a linear or branched hydrocarbon group with 1 to 50 carbon atoms, or an organic group containing polyoxyalkylene groups, and even more preferably an organic group containing polyoxyalkylene groups with 1 to 50 carbon atoms, and especially preferably an organic group containing polyoxyethylene groups with 1 to 50 carbon atoms. Therefore, R7 is preferably a structure represented by the following general formula (10): [Chemical 15] (Ra represents an alkylene group, and n represents an integer from 1 to 30).

[0049] In general formula (10), Ra is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 2 to 4 carbon atoms. Also, n is preferably 2 to 20, and even more preferably 3 to 15.

[0050] Furthermore, R7 may also contain one or more functional groups or substituents other than (meth)acrylic acid. Examples include: hydroxyl, carboxyl, carbonyl, alkoxy, phenoxy, phenyl, naphthyl, cyano, amino, and groups formed by combining these. Also, R7 may contain one or more arbitrary bonds. Examples include: ether bonds, ester bonds, amide bonds, and carbamate bonds.

[0051] In one form, R7 is selected from: a straight-chain or branched saturated or unsaturated chain hydrocarbon group having 1 to 11 carbon atoms; a saturated or unsaturated monocyclic or polycyclic hydrocarbon group (alicyclic hydrocarbon group) having 3 to 21 carbon atoms (e.g., cyclopentyl and cyclohexyl); an aromatic monocyclic hydrocarbon group having 3 to 21 carbon atoms (e.g., phenyl and phenyl); a condensed polycyclic aromatic hydrocarbon group having 6 to 30 carbon atoms (e.g., naphthyl); a group having 1 to 5 heteroatoms selected from nitrogen and oxygen (e.g., ether bond, ester bond, and carboxyl group); a saturated or unsaturated monocyclic heterocycle having 1 to 10 heteroatoms selected from nitrogen and oxygen; a monocyclic heteroaromatic ring having 1 to 10 heteroatoms selected from nitrogen and oxygen; and a condensed polycyclic aromatic heteroaromatic ring having 1 to 15 heteroatoms selected from nitrogen and oxygen. R7 can be one of the groups or a combination of two or more groups. R7 can also be substituted. In one form, R7 can be an organogroup comprising a cyclic hydrocarbon group and a chain hydrocarbon group having 1 to 11 carbon atoms, and optionally, 1 to 5 groups having heteroatoms selected from the group consisting of nitrogen and oxygen. These groups can also be substituted. The cyclic hydrocarbon group in one form can be a saturated or unsaturated alicyclic hydrocarbon group or an aromatic hydrocarbon group. The chain hydrocarbon group can be saturated or unsaturated, and can be straight-chain or branched. The heteroatoms in one form can be a divalent group as an ether bond or an ester bond, or a carboxyl group. Examples of R7 include: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, hydroxyl, alkoxy, carboxyl, phenyl, phenoxy, naphthyl, cyano, and amino groups.

[0052] From the viewpoint of adhesion (e.g., copper adhesion), the molecular weight of R7 is preferably 15-1000, more preferably 15-450, further preferably 15-350, and even more preferably 15-240. Furthermore, the molecular weight (e.g., weight average molecular weight) of R7 can be calculated from the chemical formula of component (B).

[0053] As component (B), any (meth)acrylate represented by the above general formula (3) may be used without particular restriction. Examples include: polyalkylene glycol mono(meth)acrylate (e.g., diethylene glycol mono(meth)acrylate), mono(meth)acrylate alkyl ester, mono(meth)acrylate cycloalkyl ester (e.g., cyclohexyl methacrylate), alkoxy polyalkylene glycol mono(meth)acrylate (e.g., methoxy polyethylene glycol mono(meth)acrylate), mono(meth)acrylate hydroxyphenyl ester, (meth)acryloyloxyalkyl phthalic acid (e.g., 2-methacryloyloxyethyl phthalic acid), alkoxylated o-phenylphenol (meth)acrylate (e.g., methoxylated o-phenylphenol (meth)acrylate and ethoxylated o-phenylphenol (meth)acrylate), etc., and one of these may be used alone or two or more may be used together. Regarding the adhesion to copper, component (B) is preferably selected from at least one of the group consisting of polyalkylene glycol mono(meth)acrylate, alkoxy polyalkylene glycol mono(meth)acrylate, and (meth)acrylic oxyalkyl phthalic acid, more preferably diethylene glycol mono(meth)acrylate, methoxy polyethylene glycol mono(meth)acrylate, and 2-methacrylic oxyethyl phthalic acid. Regarding resolution, component (B) is preferably selected from at least one of the group consisting of polyalkylene glycol mono(meth)acrylate, alkoxy polyalkylene glycol mono(meth)acrylate, and (meth)acrylic oxyalkyl phthalic acid, more preferably polyalkylene glycol mono(meth)acrylate, and alkoxy polyalkylene glycol mono(meth)acrylate, and even more preferably diethylene glycol mono(meth)acrylate and methoxy polyethylene glycol mono(meth)acrylate.

[0054] In terms of the close contact with copper, the content of component (B) relative to 100 parts by mass of component (A) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 0.1 to 10 parts by mass, even more preferably 1 to 9 parts by mass, and particularly preferably 2 to 8 parts by mass.

[0055] [(C) component; terminal-capped polyalkylene glycol compound] Component (C) is a terminal-capped polyalkylene glycol compound represented by the following general formula (4): [Chemical 16]{wherein, R8 and R9 are each independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, at least one of R8 and R9 is an alkyl group having 1 to 6 carbon atoms, R10 is an alkyl group having 2 to 4 carbon atoms, and n2 is an integer from 2 to 12}. From the viewpoint of compatibility with component (A), R8 and R9 are preferably independently hydrogen atoms or alkyl groups having 1 to 11 carbon atoms, more preferably alkyl groups having 1 to 6 carbon atoms, and even more preferably alkyl groups having 1 to 3 carbon atoms. R10 is preferably an alkyl group having 2 or 3 carbon atoms, more preferably an ethyl group. n2 is preferably an integer from 3 to 12, more preferably an integer from 4 to 10.

[0056] The reason why the effects of the present invention can be achieved by using this component (C) is not yet clear, but the inventors believe that the reason is as follows. The inventors believe that when the embossed pattern formed by the photosensitive resin composition is heat-cured, the component (C) can improve the fluidity of the polyimide film by means of its plasticizing effect. In this way, the possibility of association between the reaction sites of the polyimide precursor and the polymerizable compound is increased, resulting in good resolution. This effect is particularly important for achieving high resolution in this embodiment where the component (B) with fewer reaction sites is used as the polymerizable compound. Furthermore, the component (C) is at least one end-capped. If at least one of R8 and R9 in the above general formula (4) is an alkyl group with 1 to 6 carbon atoms, the hydrogen bond with the polyimide precursor or polyimide is weakened, and the component (C) is easily volatilized by heating and is difficult to remain in the polyimide film, thereby exhibiting good adhesion. From this perspective, it is preferable to have two end-capped (C) components, that is, it is preferable that R8 and R9 in the above general formula (4) are each an alkyl group having 1 to 6 carbon atoms.

[0057] From the viewpoint of the difficulty of volatilization in the drying step at 20 to 140°C immediately after the photosensitive resin composition is coated onto the substrate, n2 is preferably 3 to 12. Furthermore, from the viewpoint of the ease of volatilization in the thermosetting step at 170°C or above, at least one of its boiling point or thermal decomposition temperature is preferably 300°C or below, more preferably 250°C or below, and even more preferably 200°C or below.

[0058] As a component (C), examples include: polyalkylene glycol monoalkyl ethers (e.g., polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether), polyalkylene glycol dialkyl ethers (e.g., polyethylene glycol dimethyl ether (in one form, triethylene glycol dimethyl ether and diethylene glycol dimethyl ether), and polypropyl dimethyl ether (in one form, tripropylene glycol dimethyl ether)), etc. However, it is not limited to these.

[0059] From the point of view of resolution, the content of component (C) relative to 100 parts by mass of component (A) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 0.1 to 10 parts by mass, even more preferably 1 to 9 parts by mass, and particularly preferably 2 to 8 parts by mass.

[0060] [(D) Component; Photopolymerization Initiator] The photosensitive resin composition of this embodiment may also contain a photopolymerization initiator to cure efficiently by exposure. As the photopolymerization initiator, any compound previously used as a photopolymerization initiator for UV curing may be selected. In one embodiment, the photopolymerization initiator is a photoradical initiator.

[0061] As a (D) photopolymerization initiator, for example, benzophenone, methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and benzophenone derivatives such as benzophenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylphenylacetone; 9-oxothiophene derivatives such as 1-hydroxycyclohexylphenyl ketone, 9-oxothiophene, 2-methyl9-oxothiophene, 2-isopropyl9-oxothiophene, and diethyl9-oxothiophene; benzoin derivatives such as benzoin dimethyl ketal and benzoin-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; 2,6-di(4'-diazidophenyl) Azides such as benzyl)-4-methylcyclohexanone and 2,6'-di(4'-diazidobenzylidene)cyclohexanone; oximes such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenyltrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxytrione-2-(O-benzoyl)oxime; N-aryl glycines such as N-phenylglycine; peroxides such as benzoyl peroxide; aromatic biimidazoles; and titanium dioxide, etc. From the perspective of light sensitivity, the aforementioned oximes are preferred.

[0062] From the viewpoint that the effects of the present invention can be easily achieved, (D) the photopolymerization initiator is preferably an oxime represented by the following general formula (5): [Chemical 17] (wherein, R11 is a hydrogen atom, an alkyl ester, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 1 to 12 carbon atoms).

[0063] The content of (D) photopolymerization initiator is 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), and preferably 2 to 15 parts by mass from the viewpoint of photosensitivity characteristics. By containing more than 0.1 parts by mass of (D) photopolymerization initiator relative to 100 parts by mass of component (A), the photosensitivity of the photosensitive resin composition is excellent. On the other hand, by containing less than 20 parts by mass of (D) photopolymerization initiator relative to 100 parts by mass of component (A), the curing properties of the photosensitive resin composition are excellent.

[0064] <Other Ingredients> The photosensitive resin composition of this embodiment may further include thermal crosslinking agents, photopolymerization inhibitors, sensitizers, thermal polymerization inhibitors, bonding agents, rust inhibitors, solvents, etc.

[0065] (Sensitizer) The photosensitive resin composition of this embodiment may optionally contain a sensitizer to improve photosensitivity. Examples of sensitizers include: milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylamino 2-(p-dimethylaminophenylbenzyl)-benzothiazole, 2-(p-dimethylaminophenylbenzyl)benzothiazole, 2-(p-dimethylaminophenylbenzyl)isonaphthothiazole, 1,3-bis(4'-dimethylaminophenylbenzyl)acetone, 1,3-bis(4'-diethylaminophenylbenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminophenyl)-benzyl)acetone (aminocoumarin), 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, N-p-tolyldiethanolamine, N-phenylethanolamine, 4- Phosphorylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzo[a]azole, 2-(p-dimethylaminostyryl)benzo[a]thiazole, 2-(p-dimethylaminostyryl)naphtho[(1,2-d)thiazole], 2-(p-dimethylaminobenzoyl)styrene, etc. These can be used alone or in combination of two or more. The sensitizer content is preferably 0.1 to 25 parts by weight relative to 100 parts by weight of component (A).

[0066] (Photopolymerization Inhibitor) The photosensitive resin composition of this embodiment may optionally contain a photopolymerization inhibitor to appropriately control the photoradical crosslinking reaction. Examples of photopolymerization inhibitors include: compounds containing aromatic hydroxyl groups, nitroso compounds, N-oxide compounds, quinone compounds, N-hydroxyl compounds, phenoxy compounds, and hindered phenolic compounds.

[0067] Examples of compounds containing aromatic hydroxyl groups include: 4-methoxyphenol (p-methoxyphenol), 2,6-di-tert-butyl-4-methylphenol, neopentyl tetroxide tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-dimethyl Bis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionamide], 3,3',3'',5,5',5''-hexa-tertiary butyl-a,a',a''-(symmetric tricresyl-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylbis(oxyethyl)bis[3-(5-tertiary butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate], 1,3,5-Tris(3,5-di-tertiary butyl-4-hydroxybenzyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione), 2,6-di-tertiary butyl-4-(4,6-bis(octylthio)-1,3,5-tris(2,4,5)-amino)phenol, catechol, tertiary butyl-catechol, 4,4',4''-(1-methylpropyl-3-ylidene)tris(6-tertiary butyl-m-cresol), 6,6'-di-tertiary butyl-4,4'-butylene- m-Cresol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxospiro[5,5]undecane, hydroquinone, methyl hydroquinone, tert-butylhydroquinone, di-tert-butyl-p-cresol, pyrogallol, 4,4-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), phenolic resins, and cresol resins.

[0068] Examples of nitroso compounds include: nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitroso-diphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopyrrolidone, and N-tert-butyl-N-nitrosoaniline. N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine, 4-nitrosophospholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, cerium(III) salt of N-nitrosophenylhydroxylamine, aluminum salt of N-nitrosophenylhydroxylamine, 2,4,6-tri-tertiary butyl-nitrosobenzene, and N-nitrosodiphenylamine, etc.

[0069] Examples of N-oxide compounds include: phenyl-tert-butylnitrone, 3,3,5,5-tetramethyl-1-pyrrolidone-N-oxide, 5,5-dimethyl-1-pyrrolidone N-oxide, 4-methylpyrrolidone N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, pyridinecarboxylic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide, etc.

[0070] Examples of quinone compounds include: p-benzoquinone, p-benzoquinone, methyl p-benzoquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-tri-butyl-p-benzoquinone, 2,5-di-tri-butyl-1,4-benzoquinone, 2,6-di-tri-1,4-benzoquinone, thymolinoquinone, 2,5-di-tri-pentylbenzoquinone, 2-bromo-1,4-benzoquinone, 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, 2-chloro-5-methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-Dihydroxy-1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, tetrahydroxy-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1,4-naphthoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4-naphthoquinone, 1-nitroanthraquinone, anthraquinone, 1-aminoanthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthraquinone, 2-methylanthraquinone, and 5,12-naphthoanthraquinone, etc.

[0071] Examples of N-hydroxyl groups include: 2,2,6,6-tetramethylpiperidine-1-hydroxyl, 4-cyano-2,2,6,6-tetramethylpiperidine-1-hydroxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-hydroxyl, 4-carboxyl-2,2,6,6-tetramethylpiperidine-1-hydroxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-hydroxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-hydroxyl, and 4-methacryloxy-2,2,6,6-tetramethylpiperidine-1-hydroxyl. The free radicals include 1-hydroxyl radicals of piperidine, 4-sideoxy-2,2,6,6-tetramethylpiperidine, 4-acetylamine-2,2,6,6-tetramethylpiperidine, 4-maleimine-2,2,6,6-tetramethylpiperidine, 4-phosphatoxy-2,2,6,6-tetramethylpiperidine, pyrrolidine, and 3-carboxylPROXYL radical (3-carboxyl-2,2,5,5-tetramethylpyrrolidine).

[0072] Examples of phenoxythiazoline compounds include: phenoxythiazoline, 10-methylphenoxythiazoline, 2-methylthiophenoxythiazoline, 2-chlorophenoxythiazoline, 2-ethylthiophenoxythiazoline, 2-(trifluoromethyl)phenoxythiazoline, and 2-methoxyphenoxythiazoline, etc.

[0073] Examples of hindered phenolic compounds include: 2,6-di-tri-butyl-4-methylphenol, 2,5-di-tri-butyl-hydroquinone, octadecyl 3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tri-butylphenol), 4,4'-thiobis(3-methyl-6-tri-butylphenol), 4,4'-butylenebis(3-methyl-6-tri-butylphenol), triethylene glycol-bis[3-(3-tri-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol-bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate]. [3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylbis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tri-butyl-4-hydroxy-hydrocinnamic acid), 2,2'-methylenebis(4-methyl-6-tri-butylphenol), 2,2'-methylenebis(4-ethyl-6-tri-butylphenol), neopentyltetramethyltetra[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], tri-(3,5-di-tri-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tri-butyl-4-hydroxybenzyl)benzene, 1,3,5- Tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris(3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(4-tertiary-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris( ... Tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tripropylbutyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tripropylbutyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-tripropylbutyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione), 1,3,5-tris(4-tripropylbutyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione), 1,3,5-tris(4-tripropylbutyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H))-trione Triones, 1,3,5-tris(4-tributyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tributyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-tributyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, etc.

[0074] From the viewpoint of patternability and residual film rate after development, photopolymerization inhibitors are preferably 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-methoxyphenol, and 1,3,5-tris(4-tributyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione.

[0075] Photopolymerization inhibitors can be used alone or in combination of two or more. The content of the photopolymerization inhibitor is preferably 0.005 to 12 parts by weight relative to 100 parts by weight of component (A).

[0076] (Rust Inhibitor) The photosensitive resin composition of this embodiment may optionally contain a rust inhibitor to inhibit copper migration. As a rust inhibitor, it is not limited to anything that can prevent metal from rusting; examples include nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include azole compounds and purine derivatives.

[0077] Examples of azole compounds include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tributyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole. Triazoles, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-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, 1H-tetrazole-5-acetic acid, and 1-methyl-1H-tetrazole, etc.

[0078] Examples of azole compounds that are particularly preferred include 5-amino-1H-tetrazole and 1H-tetrazole-5-acetic acid. Furthermore, these azole compounds can be used alone or in combination of two or more.

[0079] 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-phenyl-9H- Purines, 2-acetaminophen-9-acetaminophen-6-oxopurine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 2-acetaminophen-6-hydroxypurine, and 8-azahypoxanthine, etc.; and derivatives thereof.

[0080] When the photosensitive resin composition contains an azole compound or a purine derivative, its content is preferably 0.05 to 5 parts by weight relative to 100 parts by weight of resin (A), and more preferably 0.1 to 5 parts by weight from the viewpoint of photosensitivity characteristics. When the content of the azole compound or purine derivative relative to 100 parts by weight of resin (A) is 0.05 parts by weight or more, when the negative photosensitive resin composition of this embodiment is formed on copper or copper alloy, discoloration of the copper or copper alloy surface can be suppressed. On the other hand, when the content of the azole compound or purine derivative is 5 parts by weight or less, the photosensitivity is excellent.

[0081] (Adhesion Enhancer) The photosensitive resin composition of this embodiment may optionally contain an adhesion enhancer to improve the adhesion between the film formed using the photosensitive resin composition and the substrate. Examples of adhesion enhancers include: γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyl dimethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane, γ-mercaptopropylmethyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, and diethoxy-3-glycidoxypropylmethyl Silane coupling agents such as N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylacetamide)-4,4'-dicarboxylic acid, phenyl-1,4-bis(N-[3-triethoxysilyl]propylacetamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride; N-phenylaminopropyltrimethoxysilane and other silane coupling agents; and aluminum-based bonding aids such as tri(ethylacetate)aluminum, tri(acetylacetonate)aluminum, ethyl acetate diisopropoxide aluminum.

[0082] Of these bonding aids, from the viewpoint of bonding performance, silane coupling agents are preferred. The content of the bonding aid relative to 100 parts by weight of component (A) is preferably 0.1 to 25 parts by weight.

[0083] (Solvent) Examples of solvents include: amides, sulfides, 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-dimethylmethamide, dimethyl sulfide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate Esters, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, α-porphyrin, dichloromethane, 3-methoxy-N,N-dimethylpropionic acid, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, symmetrical trimethylbenzene, etc. From the viewpoints of resin solubility, resin composition stability, and adhesion to the substrate, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3-methoxy-N,N-dimethylpropionic acid, benzyl alcohol, phenylethylene glycol, tetrahydrofurfuryl alcohol, and 1,3-dimethyl-2-imidazolidineone are preferred.

[0084] Among such solvents, those that can completely dissolve the resulting polymer are particularly preferred, and examples include: N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 3-methoxy-N,N-dimethylpropionic acid, tetramethylurea, γ-butyrolactone, and 1,3-dimethyl-2-imidazolidineone. One solvent may be used, or two or more solvents may be mixed.

[0085] In the photosensitive resin composition of this embodiment, the amount of solvent used is preferably 100 to 1000 parts by mass relative to 100 parts by mass of component (A), more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass.

[0086] [Method for manufacturing a hardened embossed pattern] The present invention provides a method for manufacturing a hardened embossed pattern, comprising the following steps (1) to (4): (1) coating a negative photosensitive resin composition of the present embodiment onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form an embossed pattern; and (4) heat-treating the embossed pattern to form a hardened embossed pattern.

[0087] The following explains each step.

[0088] (1) In the step of coating the negative photosensitive resin composition of this embodiment onto a substrate to form a photosensitive resin layer on the substrate, the negative photosensitive resin composition of this embodiment is coated onto a substrate, and then dried as needed to form a photosensitive resin layer. As a coating method, methods previously used for coating photosensitive resin compositions can be used, such as coating methods using a spin coater, bar coater, doctor blade coater, curtain coater, screen printing machine, etc., or spray coating methods using a spray coater, etc.

[0089] The coating containing the negative photosensitive resin composition can be dried as needed, and drying methods include, for example, air drying, drying using an oven or heating plate, and vacuum drying. Ideally, the drying of the coating should be carried out under conditions where the polyimide precursor in the negative photosensitive resin composition does not undergo amide formation. Specifically, in the case of air drying or heating drying, drying can be performed at 20°C to 140°C for 1 minute to 1 hour. Through the above operations, a photosensitive resin layer can be formed on the substrate.

[0090] (2) The step of exposing the photosensitive resin layer In this step, an exposure device such as a contact alignment machine, a mirror projection exposure machine, or a step exposure machine is used to expose the photosensitive resin layer formed by the above (1) step through a patterned photomask or a marker sheet or directly using an ultraviolet light source.

[0091] Subsequently, for purposes such as improving photosensitivity, post-exposure baking (PEB) and / or pre-development baking with any combination of temperature and time may be performed as needed. As baking conditions, the temperature is preferably 40°C to 120°C and the time is preferably 10 seconds to 240 seconds, but it is not limited to this range as long as it does not impair the properties of the negative photosensitive resin composition.

[0092] (3) In the step of developing the exposed photosensitive resin layer to form a raised pattern, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from previously known photoresist developing methods, such as spin spraying, liquid coating, and immersion with ultrasonic treatment. Furthermore, after development, for the purpose of adjusting the shape of the raised pattern, a developing bake with any combination of temperature and time can be performed as needed.

[0093] The developing solution used for developing is preferably a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. The good solvent is preferably N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. The poor solvent is preferably toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Furthermore, two or more solvents, such as several different solvents, can also be combined and used.

[0094] (4) Step of heat-treating the embossed pattern to form a hardened embossed pattern: In this step, the embossed pattern obtained by the above development is heated to dilute the photosensitive components and to amide the polyimide precursor, thereby transforming it into a hardened embossed pattern containing polyimide. Various methods can be selected for heat curing, such as using a heating plate, using an oven, or using a temperature-programmable heating oven. Heating can be performed, for example, at 200°C to 400°C for 30 minutes to 5 hours. Air, or inert gases such as nitrogen or argon, can be used as the ambient gas during heat curing.

[0095] <Semiconductor Device> In this embodiment, a semiconductor device is also provided, which is formed by a hardened raised pattern obtained by the above-described method for manufacturing a hardened raised pattern. Therefore, the present invention can provide a semiconductor device comprising: a semiconductor element, i.e., a substrate, and a hardened raised pattern of polyimide formed on the substrate by the above-described method for manufacturing a hardened raised pattern. Furthermore, the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a hardened raised pattern as a step. The semiconductor device of the present invention can be manufactured by forming a hardened raised pattern formed by the above-described method as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for flip-chip devices, or a protective film for a semiconductor device having a bump structure, etc., and combining it with a known method for manufacturing a semiconductor device.

[0096] <Display Device> In this embodiment, a display device is provided, which includes a display element and a hardened film disposed on the upper part of the display element, wherein the hardened film is the aforementioned hardened raised pattern. Here, the hardened raised pattern can be directly deposited with the display element or deposited with other layers in between. Examples of such hardened films include: surface protective films, insulating films, and planarization films for TFT liquid crystal display elements and color filter elements, protrusions for MVA type liquid crystal display devices, and spacers for organic EL element cathodes.

[0097] In addition to its use in semiconductor devices as described above, the negative photosensitive resin composition of the present invention can also be used for interlayer insulation in multilayer circuits, surface coatings of flexible copper foils, solder resists, and liquid crystal alignment films, etc. [Examples]

[0098] Hereinafter, this embodiment will be specifically described using examples. However, this embodiment is not limited to the examples. In the examples, comparative examples, and manufacturing examples, the physical properties of the polymer and photosensitive resin composition were measured and evaluated according to the following methods.

[0099] ・Weight-average molecular weight was determined using gel permeation chromatography (converted from standard polystyrene) under the following conditions.

[0100] Pump: JASCO PU-980; Detector: JASCO RI-930; Column Oven: JASCO CO-965 40℃; Column: 2 Shodex KD-806M (manufactured by Showa Denko) in series or Shodex 805M / 806M (manufactured by Showa Denko) in series; Standard Monodisperse Polystyrene: Shodex STANDARD SM-105 (manufactured by Showa Denko); Mobile Phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP); Flow Rate: 1 mL / min.

[0101] (1) Copper adhesion evaluation was performed using a sputtering apparatus (L-440S-FHL type, manufactured by CANON ANELVA) to sequentially sputter Ti with a thickness of 200 nm and Cu with a thickness of 400 nm on a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., with a thickness of 625±25 μm). Subsequently, a photosensitive resin composition was spin-coated onto the wafer with a cured film thickness of approximately 9 μm using a coating and developing machine (D-spin60A type, manufactured by SOKUDO). After drying, the entire surface was exposed and heated at 230°C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing oven (VF-2000 type, manufactured by KOYO LINDBERG) to obtain a hardened raised pattern (a heat-cured polyimide coating). For the heat-treated film, the adhesion characteristics between the copper substrate and the hardened resin coating are evaluated according to the cross-cutting method of JIS K 5600-5-6 standard, based on the following criteria. If the evaluation is S, A, or B, it can be well used as a hardened relief pattern suitable for semiconductors. S: The number of grids in the hardened resin coating bonded to the substrate is 90 to 100. A: The number of grids in the hardened resin coating bonded to the substrate is 80 to less than 90. B: The number of grids in the hardened resin coating bonded to the substrate is 40 to less than 80. C: The number of grids in the hardened resin coating bonded to the substrate is less than 40.

[0102] (2) Resolution evaluation: Using a sputtering apparatus (L-440-FHL type, manufactured by CANON ANELVA), Ti with a thickness of 200 nm and Cu with a thickness of 400 nm were sequentially sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., with a thickness of 625±25 μm). Subsequently, using a coating and developing machine (D-spin60A type, manufactured by SOKUDO), the photosensitive resin composition prepared by the method described later was spin-coated onto the wafer with a film thickness of approximately 8 μm. The wafer was then pre-baked at 110°C for 240 seconds using a heating plate to form a coating film. Using a Prisma GHI (Ultratech) with an exposure wavelength of i-rays (365 nm), the coating was exposed to i-rays through a marker film with a test pattern, starting from 400 mJ / cm² and increasing in 50 mJ / cm² increments to 1000 mJ / cm². Subsequently, a coating and developing machine (D-Spin 60A, SOKUDO) was used at 23°C with cyclopentanone as the developer for 1.4 times the time required for the unexposed areas to completely dissolve and disappear. Next, a 10-second spin-spray cleaning with propylene glycol monomethyl ether acetate was applied to obtain an embossed pattern formed by the resin film. Finally, a temperature-programmed curing oven (VF-2000, KOYO LINDBERG) was used in a nitrogen atmosphere at 230°C for 2 hours to obtain a cured embossed pattern.

[0103] For each obtained pattern, the pattern shape or width of the pattern portion is observed under an optical microscope to determine the resolution. Regarding the resolution, a pattern with multiple openings of different areas is formed by exposing a test pattern to a caliper with the test pattern using the same method as described above. If the area of ​​the obtained pattern opening is more than 1 / 2 of the corresponding pattern mask opening area, it is considered resolved. The length of the mask opening edge corresponding to the smallest area among the resolved openings is taken as the resolution. The exposure with the best resolution among the exposures is taken as the optimal exposure, and the pattern accuracy is evaluated according to the following criteria. If the evaluation is S, A, or B, it can be well used as a hardened relief pattern suitable for semiconductors. S: No skirt-like bottom is formed in the pattern cross section, no bottom warping, swelling, or bridging occurs, and the resolution does not reach 5 μm. A: The patterned cross-section does not produce a skirt-like bottom, and there is no warping, swelling, or bridging of the bottom, and the resolution is 5 μm or higher but less than 6 μm. B: The patterned cross-section does not produce a skirt-like bottom, and there is no warping, swelling, or bridging of the bottom, and the resolution is 6 μm or higher but less than 8 μm. C: A skirt-like bottom is produced on the patterned cross-section, as well as warping, swelling, or bridging of the bottom, or the resolution is 8 μm or higher.

[0104] <Manufacturing Example 1>((A) Synthesis of Polyimide Precursor A-1) 62 g (0.2 mol) of 4,4'-oxophthalic dianhydride ODPA and 65 g (0.3 mol) of pyromellitic dianhydride (PMDA) were added to a 2-liter separable flask, along with 135 g (0.2 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone. The mixture was stirred at room temperature, and 79.1 g of pyridine was added while stirring. After stirring for 16 hours, a reaction mixture was prepared.

[0105] Subsequently, under ice bath cooling, a solution obtained by dissolving 203 g of dicyclohexylcarbodiimide (DCC) in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Then, a solution obtained by suspending 94 g (0.44 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB: meta-toluidine) in 280 ml of γ-butyrolactone was added over 60 minutes with stirring. After stirring at room temperature for 4 hours, 40 ml of ethanol was added and stirring for 1 hour, followed by the addition of 1 liter of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0106] The obtained reaction solution was added to 4 liters of ethanol to generate a precipitate containing crude polymer. The generated crude polymer was filtered and separated, and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 30 liters of water to precipitate the polymer. The obtained precipitate was filtered and separated, and then vacuum dried to obtain a powdered polymer (polymer A1). The molecular weight of polymer A1 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight average molecular weight (Mw) was 20,000.

[0107] <Manufacturing Example 2>((A) Synthesis of Polyimide Precursor A-2) 155 g (0.5 mol) of 4,4'-oxophthalic dianhydride (ODPA) was used instead of 62 g (0.2 mol) of 4,4'-oxophthalic dianhydride (ODPA) and 65 g (0.3 mol) of pyromellitic dianhydride (PMDA) in Manufacturing Example 1, and 88 g (0.44 mol) of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 94 g (0.44 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB: meta-toluidine). Otherwise, the reaction was carried out in the same manner as described in Manufacturing Example 1 above to obtain polymer A2. The molecular weight of polymer A2 was determined by gel permeation chromatography (conversion to standard polystyrene), and the weight-average molecular weight (Mw) was 24,000.

[0108] <Manufacturing Example 3> ((A) Synthesis of Polyimide Precursor A-3) 147 g (0.5 mol) of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 155 g of 4,4'-oxophthalic acid dianhydride (ODPA) in Manufacturing Example 2. Otherwise, the reaction was carried out in the same manner as described in Manufacturing Example 1 above to obtain polymer A3. The molecular weight of polymer A3 was determined by gel permeation chromatography (standard polystyrene conversion), and the weight-average molecular weight (Mw) was 20,000.

[0109] <Example 1> (Preparation of a negative photosensitive resin composition) A negative photosensitive resin composition was prepared by dissolving 100 g of (A) polyimide precursor A-1 (polymer A1), 5 g of diethylene glycol monomethacrylate (B1 component: BLEMMER PE90, manufactured by Nippon Oil Co., Ltd.), 5 g of polyethylene glycol dimethyl ether (C3 component: UNIOX MM-400, manufactured by Nippon Oil Co., Ltd.), and 10 g of 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (D component) in a mixed solvent of γ-butyrolactone and dimethyl sulfoxide in 207 g. The composition was evaluated according to the above method. The results are shown in Table 1. Unless otherwise specified, the units of the values ​​listed in the table are parts by mass.

[0110] <Examples 2-14, Comparative Examples 1-5> As shown in Table 1, components (A), (B), and (C) were changed, except that the negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation was performed as in Example 1. The results are shown in Table 1.

[0111] The ingredients used in the examples and comparative examples are as follows. • (B) Ingredients and other (meth)acrylate compounds: (B1) Diethylene glycol monomethacrylate (BLEMMER PE90, molecular weight: 90, manufactured by Nippon Oil Co., Ltd.) (B2) 2-Methacryloxyethyl phthalic acid (NK Ester CB-1, molecular weight: 278, manufactured by Shin-Nakamura Chemical Co., Ltd.) (B3) Methoxy polyethylene glycol monomethacrylate (BLEMMER PME-400, molecular weight: 400, manufactured by Nippon Oil Co., Ltd.) (B4) Methoxy polyethylene glycol monomethacrylate (BLEMMER AME-400, molecular weight: 400, manufactured by Nippon Oil Co., Ltd.) (B5) Methoxy polyethylene glycol monomethacrylate (BLEMMER PME-1000, molecular weight: 1000, manufactured by Nippon Oil Co., Ltd.) (B6) Cyclohexyl methacrylate (BLEMMER CHMA, molecular weight: 168, manufactured by Nippon Oil Co., Ltd.) (B7) Ingredient: Ethoxylated o-phenylphenol acrylate (NK Ester A-LEN-10, molecular weight 268, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (B8) Ingredient: Tetraethylene glycol dimethacrylate (NK Ester NK-4GT, molecular weight: 330, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • (C) Ingredients and other plasticizers (C1) Ingredient: Triethylene glycol dimethyl ether (n2≒3, molecular weight: 178, manufactured by Tokyo Chemical Industry Co., Ltd.) (C2) Tripropylene glycol dimethyl ether (n2≒3, molecular weight: 220, manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.) (C3) Polyethylene glycol dimethyl ether (n2≒7, UNIOX MM-400, molecular weight: 400, manufactured by Nippon Oil Co., Ltd.) (C4) Polyethylene glycol monomethyl ether (n2≒11, UNIOX M-550, molecular weight: 550, manufactured by Nippon Oil Co., Ltd.) (C5) Diethylene glycol dimethyl ether (n2≒2, molecular weight: 180, manufactured by Tokyo Chemical Industry Co., Ltd.) (C6) Polyethylene glycol monomethyl ether (n2≒21, UNIOX M-1000, molecular weight: 1000, manufactured by Nippon Oil Co., Ltd.) (C7) Lauryl alcohol ethoxide (ADEKA TOL LA-775, manufactured by ADEKA Co., Ltd.) ・(D) Photopolymerization initiator 1-Phenylon-1,2-propanedione-2-(O-benzoyl)oxime

[0112] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 A ingredient (A1) (A1) (A1) (A1) (A1) (A1) (A1) (A1) (A1) (A1) (A1) (A1) (A2) (A3) (A1) (A1) (A1) (A1) (A1) Quality 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Component B (B1) (B2) (B3) (B4) (B5) (B6) (B7) (B1) (B1) (B1) (B1) (B1) (B1) (B1) (B8) (B1) - (B1) (B1) Quality 5 5 5 5 5 5 5 5 5 5 5 15 5 5 10 5 - 5 5 Component C (C3) (C3) (C3) (C3) (C3) (C3) (C3) (C1) (C2) (C4) (C5) (C3) (C3) (C3) - - (C1) (C6) (C7) Quality 5 5 5 5 5 5 5 5 5 5 5 15 5 5 - - 5 5 5 Copper tightness S S S S S B A A A A B A S S C B B C C resolution S A S A A B B A B A B B S S B C C C C [Industrial Applicability]

[0113] By using the negative photosensitive resin composition of the present invention, a negative photosensitive resin composition having good adhesion to copper and resolution can be provided, as well as a method for manufacturing hardened embossed patterns using the photosensitive resin composition. The present invention can be well used in the field of photosensitive materials, such as electrical and electronic materials used in the manufacture of semiconductor devices, multilayer wiring boards, etc.

Claims

1. A negative photosensitive resin composition comprising: (A) a polyimide precursor or polyimide; (B) a monofunctional (meth)acrylate compound represented by the following general formula (3): [Chemical 1] {wherein, R6 is a hydrogen atom or a methyl group, and R7 is a monovalent organic group not containing a thermopolymerizable group}; and (C) a terminal-capped polyalkylene glycol compound represented by the following general formula (4): [Chemical 2] {wherein, R8 and R9 are each independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, at least one of R8 and R9 is an alkyl group having 1 to 6 carbon atoms, R10 is an alkyl group having 2 to 4 carbon atoms, and n2 is an integer from 2 to 12}.

2. The negative photosensitive resin composition of claim 1, wherein the polyimide precursor is represented by the following general formula (1): [Chemical 3] [wherein, X1 is a tetravalent organic group, Y1 is a divalent organic group, n is an integer from 2 to 150, and R1 and R2 are each independently hydrogen atoms, or the following general formula (2): [Chemical 4] {wherein, R3 is a hydrogen atom or an organic group with 1 to 3 carbon atoms, R4 and R5 are each independently hydrogen atoms or organic groups with 1 to 3 carbon atoms, and m is an integer from 2 to 10} representing a monovalent organic group or a saturated aliphatic group with 1 to 4 carbon atoms].

3. The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (3), the molecular weight of R7 is 1000 or less.

4. The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (4), n2 is an integer from 3 to 12.

5. The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (3), R7 is an organic group containing polyoxyalkylene.

6. The negative photosensitive resin composition of claim 1 or 2, wherein the molecular weight of component (B) is 500 or less.

7. The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (3), R7 is an organic group without a cyclic structure.

8. The negative photosensitive resin composition of claim 1 or 2, wherein R6 in the above general formula (3) is methyl.

9. The negative photosensitive resin composition of claim 1 or 2, wherein R10 in the above general formula (4) is ethylenyl.

10. The negative photosensitive resin composition of claim 1 or 2, wherein in the above general formula (4), R8 and R9 are each independently an alkyl group having 1 to 6 carbon atoms.

11. The negative photosensitive resin composition of claim 1 or 2, wherein R7 in the above general formula (3) is an organic group comprising a cyclic hydrocarbon group and a chain hydrocarbon group having 1 to 11 carbon atoms.

12. The negative photosensitive resin composition of claim 1 or 2, wherein the negative photosensitive resin composition comprises 0.1 to 10 parts by mass of the above-mentioned component (B) relative to 100 parts by mass of component (A).

13. The negative photosensitive resin composition of claim 1 or 2, wherein the negative photosensitive resin composition contains 0.1 to 10 parts by mass of the above-mentioned component (C) relative to 100 parts by mass of component (A).

14. The negative photosensitive resin composition of claim 1 or 2 further comprises (D) a photopolymerization initiator.

15. The negative photosensitive resin composition of claim 1 or 2, comprising (D) the following general formula (5): [Chemical 5] (wherein R11 is a photopolymerization initiator represented by a hydrogen atom, an alkyl ester, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 1 to 12 carbon atoms).

16. A method for manufacturing a hardened embossed pattern, comprising the following steps: The steps include: forming a photosensitive resin layer on a substrate by coating a negative photosensitive resin composition as claimed in claim 1 or 2 onto the substrate; exposing the photosensitive resin layer; developing the exposed photosensitive resin layer to form an embossed pattern; and forming a hardened embossed pattern by heat treatment of the embossed pattern.