Photosensitive resin composition and method for producing cured film

Abstract

To provide a photosensitive resin composition that does not change in color tone of a varnish by identifying a substance capable of changing the color tone of the varnish over time, and a manufacturing method of a cured film for forming a pattern with the photosensitive resin composition.SOLUTION: A negative type photosensitive resin composition comprising the following components: (A) at least one kind of resin selected from the group consisting of polyamide acid that is a polyimide precursor, polyamide acid ester, polyamide, polyamide-imide, and polyimide: 100 pts.mass, (B) a compound represented by a chemical formula (b1), (C) a photosensitive agent: 0.5 to 30 pts.mass, and (D) a solvent, in which a total of compounds of n=1 to 5 of the compound expressed by (B) a chemical formula (b1) is smaller than 0.01 pt.mass. (In the formula, each of R1s represents independently a hydrogen atom or a monovalent organic group of an alkyl group of 1 to 12 carbon atoms, and an integer of n=1 to 5).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to, for example, an insulating material for electronic components, and a photosensitive resin composition used for forming relief patterns such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, and a method for manufacturing a cured film using the same.

Background Art

[0002] Conventionally, polyimide resins having excellent heat resistance, electrical properties, and mechanical properties have been used for insulating materials for electronic components, passivation films, surface protection films, interlayer insulating films, etc. of semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor can easily form a heat-resistant relief pattern film by coating, exposing, developing, and heat imidization treatment of the precursor. Such a photosensitive polyimide precursor has a feature of enabling a significant reduction in the number of processes compared with conventional non-photosensitive polyimides.

[0003] Such a photosensitive polyimide is provided as a varnish-like resin composition in which a resin, a photosensitizer, and other additives are dissolved in a solvent, and is applied to a substrate by a spin coating method (Patent Document 1) or a slit coating method (Patent Document 2). The color tone of this varnish shows a unique color tone from light yellow to red after the preparation of the varnish due to the light absorption of the resin.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] In a varnish with a specific composition, there was a phenomenon where the color tone of the varnish changed over time, and the color tone of the coating film also changed. Due to the change in color tone, there was a problem of misrecognition of the pattern image during the management of the relief pattern by image recognition. The present invention aims to identify a substance that can change the color tone of the varnish over time, and to provide a photosensitive resin composition in which the color tone of the varnish does not change, and a method for producing a cured film forming a pattern using the photosensitive resin composition.

Means for Solving the Problems

[0006] The present inventors have found that a specific compound in the photosensitive resin composition decomposes over time and leads to a change in the color tone of the varnish, and by reducing the remaining amount of the compound, a photosensitive resin composition in which the color tone of the varnish does not change over time can be obtained, and the present invention has been completed. That is, the present invention is as follows.

[0007] [1] The following components: (A) At least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which is a polyimide precursor: 100 parts by mass, (B) Chemical formula (b1):

Chemical formula

Chemical formula

[0008] According to the present invention, by reducing a specific compound in the photosensitive resin composition to a certain amount, a photosensitive resin composition with few voids on the film surface can be obtained, and further, a method for producing a cured film for forming a pattern using the photosensitive resin composition can be provided. [Embodiments for Carrying Out the Invention]

[0009] The present invention will be specifically described below. Throughout this specification, structures represented by the same reference numerals in the general formula may be the same as or different from each other when there are a plurality of them in the molecule.

[0010] [Photosensitive Resin Composition] The negative photosensitive resin composition of the present invention contains: (A) at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which are polyimide precursors: 100 parts by mass; (B) a compound represented by chemical formula (b1); (C) a photosensitizer: 0.5 to 30 parts by mass; and (D) a solvent. [Chemical formula] (In the formula, each R1 independently represents a monovalent organic group of a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n takes an integer of 1 to 10.). And the negative photosensitive resin composition of the present invention is characterized in that, in the compound represented by chemical formula (b1) of (B), the total of the compounds where n = 1 to 5 is less than 0.01 part by mass. In the present invention, by reducing the compound represented by chemical formula (b1) of (B) to less than 0.01 part by mass, a photosensitive resin composition with few voids on the film surface can be obtained.

[0011] (A) Resin The (A) resin used in the present invention will be described. The (A) resin of the present invention is mainly composed of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which are polyimide precursors. Here, the main component means containing 60% by mass or more of these resins in all resins, and preferably 80% by mass or more. Also, other resins may be included as necessary.

[0012] From the viewpoints of heat resistance and mechanical properties after heat treatment, the weight average molecular weight of these resins is preferably 1,000 or more, more preferably 5,000 or more, in terms of polystyrene conversion by gel permeation chromatography. The upper limit is preferably 100,000 or less, and more preferably 50,000 or less from the viewpoint of solubility in the developer when forming a photosensitive resin composition.

[0013] In the present invention, (A) the resin is preferably a photosensitive resin in order to form a relief pattern. The photosensitive resin is a resin that, when used together with a (C) photosensitizer described later, forms a photosensitive resin composition and causes a dissolution or non-dissolution phenomenon in the subsequent development process.

[0014] Examples of the photosensitive resin include polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which are polyimide precursors. Among them, since the resin after heat treatment has excellent heat resistance and mechanical properties, polyimide precursors, polyamides, and polyimides are preferably used. These photosensitive resins can be selected according to the desired application, such as preparing a negative-type photosensitive resin composition together with the (C) photosensitizer described later.

[0015] [Polyimide precursor] In the photosensitive resin composition of the present invention, one example of the most preferred (A) resin from the viewpoints of heat resistance and photosensitive properties is the general formula (1): [Chemical formula] {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group represented by the general formula (2): [Chemical formula] (In the formula, R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.) or a saturated aliphatic group having 1 to 4 carbon atoms.} It is a polyimide precursor having a structure represented by. The polyimide precursor is converted into polyimide by performing a heating (for example, 200 °C or higher) cyclization treatment. The polyimide precursor is suitable for use in a negative-type photosensitive resin composition.

[0016] In the above general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties. More preferably, it is an aromatic group or an alicyclic aliphatic group in which a -COOR1 group, a -COOR2 group, and a -CONH- group are ortho to each other. As the tetravalent organic group represented by X1, an organic group having 6 to 40 carbon atoms containing an aromatic ring is preferable. More preferably, it is the following formula (14):

Chemical formula

[0017] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties. For example, the following formula (15):

Chemical formula

Chemical formula

[0018] Regarding R1 and R2, R3 in the general formula (2) is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitive properties. Further, m1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive properties.

[0019] When a polyimide precursor is used as the resin (A), methods for imparting photosensitivity to the photosensitive resin composition include an ester bond type and an ionic bond type. The former is a method of introducing a photopolymerizable group, that is, a compound having an olefinic double bond, to the side chain of the polyimide precursor by an ester bond, and the latter is a method of bonding the carboxyl group of the polyimide precursor and the amino group of a (meth)acrylic compound having an amino group through an ionic bond to impart a photopolymerizable group.

[0020] The above ester bond type polyimide precursor is first obtained by reacting a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X1 with alcohols having a photopolymerizable unsaturated double bond and optionally saturated aliphatic alcohols having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester form), and then subjecting this to amide polycondensation with diamines containing the aforementioned divalent organic group Y1.

[0021] (Preparation of acid / ester form) In the present invention, examples of the tetracarboxylic dianhydride containing a tetravalent organic group X1, which is suitably used for preparing an ester-bonded polyimide precursor, include, but are not limited to, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and the like. These can be used alone, and of course, two or more of them may be mixed and used.

[0022] In the present invention, examples of the alcohols having a photopolymerizable unsaturated double bond, which are suitably used for preparing an ester bond type polyimide precursor, include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

[0023] A part of the above alcohols can be mixed and used with saturated aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.

[0024] By stirring and dissolving and mixing the above tetracarboxylic dianhydride suitable for the present invention and the above alcohols in a suitable reaction solvent in the presence of a basic catalyst such as pyridine at a temperature of 20 to 50 ° C for 4 to 10 hours, the esterification reaction of the acid anhydride proceeds, and a desired acid / ester form can be obtained.

[0025] As the reaction solvent, those that can completely dissolve the acid / ester form and the polyimide precursor which is an amide polycondensation product of this and the diamine component are preferred. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, etc. can be mentioned.

[0026] As other reaction solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons can be mentioned. And as hydrocarbons, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. can be mentioned. These may be used alone or in combination of two or more as needed.

[0027] (Preparation of Polyimide Precursor) To the above acid / ester form (typically a solution in the above reaction solvent), while ice-cooling, a suitable dehydrating condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. is added and mixed to convert the acid / ester form into a polyacid anhydride. Then, a solution or dispersion of diamines containing the divalent organic group Y1 preferably used in the present invention dissolved or dispersed in another solvent is added dropwise thereto, and amide polycondensation is carried out to obtain the target polyimide precursor.

[0028] Examples of the diamines containing the divalent organic group Y1 preferably used in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,

[0029] 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene rings are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, etc., for example, 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, etc. are included, but not limited thereto.

[0030] Also, for the purpose of improving the adhesion between the resin layer formed on the substrate by applying the photosensitive resin composition of the present invention on the substrate and various substrates, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can be copolymerized when preparing the polyimide precursor.

[0031] After completion of the amidopolycondensation reaction, the water-absorbing by-products of the dehydrating condensing agent coexisting in the reaction solution are filtered off as necessary, and then a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component. Further, the polymer is purified by repeating operations such as redissolution and reprecipitation, and vacuum drying is performed to isolate the target polyimide precursor. In order to improve the degree of purification, the solution of this polymer may be passed through a column filled with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0032] On the other hand, the ionic bond type polyimide precursor is typically obtained by reacting a tetracarboxylic dianhydride with a diamine. In this case, at least one of R1 and R2 in the general formula (11) is a hydroxyl group.

[0033] As the tetracarboxylic dianhydride, an anhydride of a tetracarboxylic acid having the structure of the above formula (14) is preferable, and as the diamine, a diamine having the structure of the above formula (15) or (16) is preferable. By adding a (meth)acrylic compound having an amino group, which will be described later, to the obtained polyamide precursor, a photopolymerizable group is imparted by an ionic bond between a carboxyl group and an amino group.

[0034] The molecular weight of the ester bond type and the ionic bond type polyimide precursors is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[0035] [Polyamide] Another example of the preferred (A) resin in the photosensitive resin composition of the present invention is represented by the following general formula (3): [Chemical formula] {In the formula, X2 is a trivalent organic group having 6 to 15 carbon atoms, Y2 is a divalent organic group having 6 to 35 carbon atoms, and they may have the same structure or may have a plurality of structures. R6 is an organic group having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n2 is an integer of 1 to 1000.} It is a polyamide having a structure represented by this. This polyamide is suitable for a negative photosensitive resin composition.

[0036] In the above general formula (3), as the group represented by R6, from the viewpoint of achieving both photosensitive properties and chemical resistance, the following general formula (17), [Chemical formula] {In the formula, R 25 is an organic group having at least one radically polymerizable unsaturated bond group having 2 to 19 carbon atoms.} is preferably a group represented by this.

[0037] In the above general formula (3), as the trivalent organic group represented by X2, it is preferably a trivalent organic group having 6 to 15 carbon atoms. For example, the following formula (18): [Chemical formula] is preferably an aromatic group selected from the groups represented by this, and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an amino group-substituted isophthalic acid structure.

[0038] In the above general formula (3), the divalent organic group represented by Y2 is preferably an organic group having 6 to 35 carbon atoms, and is more preferably a cyclic organic group having 1 to 4 aromatic rings or aliphatic rings which may be substituted, or an aliphatic group or a siloxane group having no cyclic structure. As the divalent organic group represented by Y2, the following general formula (15) and the following general formulas (19) and (20):

Chemical formula

Chemical formula

Chemical formula

[0039] As the aliphatic group or siloxane group having no cyclic structure, the following general formula (21):

Chemical formula

[0040] The polyamide resin of the present invention can be synthesized, for example, as follows. (Synthesis of phthalic acid compound capped body) First, at least one compound selected from the group consisting of a compound having a trivalent aromatic group X2, such as phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group (hereinafter referred to as "phthalic acid compound") is reacted with 1 mol of a compound that reacts with an amino group to modify and cap the amino group of the phthalic acid compound with a group containing a radical polymerizable unsaturated bond described below (hereinafter referred to as "phthalic acid compound capped body"). These may be used alone or in combination.

[0041] When the phthalic acid compound is capped with a group containing a radical polymerizable unsaturated bond, negative-type photosensitivity (photocurability) can be imparted to the polyamide resin.

[0042] The group containing a radical polymerizable unsaturated bond is preferably an organic group having a radical polymerizable unsaturated bond group having 3 to 20 carbon atoms, and a group containing a methacryloyl group or an acryloyl group is particularly preferred.

[0043] The above-mentioned phthalic acid compound capped body can be obtained by reacting the amino group of the phthalic acid compound with an acid chloride, isocyanate or epoxy compound having at least one radical polymerizable unsaturated bond group having 3 to 20 carbon atoms.

[0044] Suitable acid chlorides include (meth)acryloyl chloride, 2-[(meth)acryloyloxy]acetyl chloride, 3-[(meth)acryloyloxy]propionyl chloride, 2-[(meth)acryloyloxy]ethyl chloroformate, 3-[(meth)acryloyloxypropyl] chloroformate, and the like. Suitable isocyanates include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, 2-[2-(meth)acryloyloxyethoxy]ethyl isocyanate, and the like. Suitable epoxy compounds include glycidyl (meth)acrylate and the like. These may be used alone or in combination, but it is particularly preferred to use methacryloyl chloride and / or 2-(methacryloyloxy)ethyl isocyanate.

[0045] Furthermore, as these phthalic acid compound sealants, those in which the phthalic acid compound is 5-aminoisophthalic acid are preferred because they have excellent photosensitive properties and can obtain a polyamide with excellent film properties after heat curing.

[0046] The above sealing reaction can be carried out by stirring and dissolving and mixing the phthalic acid compound and the sealant in a solvent in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate.

[0047] As the reaction solvent, those that can completely dissolve the product phthalic acid compound sealant are preferred. Examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, and the like.

[0048] Examples of other reaction solvents include ketones, esters, lactones, ethers, and halogenated hydrocarbons. Examples of hydrocarbons include 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. These solvents can be used alone or in combination as needed.

[0049] Depending on the type of the blocking agent such as acid chloride, hydrogen chloride may be by-produced during the blocking reaction. In this case, for the purpose of preventing contamination in the subsequent processes, it is preferable to perform appropriate purification such as once reprecipitating with water, washing with water, drying, or removing and reducing ionic components by passing through a column filled with an ion exchange resin.

[0050] (Synthesis of polyamide) The polyamide of the present invention can be obtained by mixing the phthalic acid compound blocking agent and a diamine compound having a divalent organic group Y2 in a suitable solvent in the presence of a basic catalyst such as pyridine or triethylamine and subjecting them to amide polycondensation.

[0051] Examples of the amide polycondensation method include a method in which the phthalic acid compound blocking agent is made into a symmetric polyacid anhydride using a dehydrating condensing agent and then mixed with the diamine compound, a method in which the phthalic acid compound blocking agent is acid chlorided by a known method and then mixed with the diamine compound, and a method in which a dicarboxylic acid component and an active esterifying agent are reacted in the presence of a dehydrating condensing agent to perform active esterification and then mixed with the diamine compound.

[0052] Examples of the dehydration condensing agent include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and the like.

[0053] Examples of the chlorinating agent include thionyl chloride.

[0054] Examples of the active esterifying agent include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, ethyl 2-hydroxyimino-2-cyanoacetate, 2-hydroxyimino-2-cyanoacetamide, and the like.

[0055] The diamine compound having the organic group Y2 is preferably at least one diamine compound selected from the group consisting of aromatic diamine compounds, aromatic bisaminophenol compounds, alicyclic diamine compounds, linear aliphatic diamine compounds, and siloxane diamine compounds, and a plurality of them can be used in combination as desired.

[0056] Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,

[0057] 3,3'-Diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and diamine compounds in which some of the hydrogen atoms on these benzene rings are substituted with one or more groups selected from the group consisting of a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a halogen atom are included.

[0058] Examples of the diamine compounds in which the hydrogen atoms on this benzene ring are substituted include 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 the like.

[0059] Examples of the aromatic bisaminophenol compound include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(3-hydroxy-4-aminophenyl)hexafluoropropane, bis-(3-hydroxy-4-aminophenyl)methane, 2,2-bis-(3-hydroxy-4-aminophenyl)propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene)-bis(2-aminophenol), and the like.

[0060] Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 1,5-diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2,5-diethylcyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propylamine, menthendiamine, isophoronediamine, norbornanediamine, 1-cycloheptene-3,7-diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-bis(3-aminopropyl)piperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5,5]-undecane, and the like.

[0061] Examples of the straight-chain aliphatic diamine compound include hydrocarbon-type diamines such as 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane, or alkylene oxide-type diamines such as 2-(2-aminoethoxy)ethylamine, 2,2'-(ethylenedioxy)diethylamine, and bis[2-(2-aminoethoxy)ethyl]ether.

[0062] Examples of the siloxane diamine compound include dimethyl(poly)siloxane diamine, for example, those manufactured by Shin-Etsu Chemical Co., Ltd. and having trade names such as PAM-E, KF-8010, and X-22-161A.

[0063] As the reaction solvent, a solvent that can completely dissolve the resulting polymer is preferred. Examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and γ-butyrolactone.

[0064] In addition, depending on the case, ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may also be used as the reaction solvent. Specifically, examples include 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.

[0065] After completion of the amide polycondensation reaction, precipitates derived from the dehydrating condensing agent that have precipitated in the reaction solution are filtered off as necessary. Next, a poor solvent for the polyamide, such as water, a lower aliphatic alcohol, or a mixture thereof, is added to the reaction solution to precipitate the polyamide. Further, the precipitated polyamide is redissolved in a solvent and purified by repeating the reprecipitation operation, followed by vacuum drying to isolate the target polyamide. In addition, in order to further improve the degree of purification, this polyamide solution may be passed through a column filled with an ion exchange resin to remove ionic impurities.

[0066] The polystyrene-reduced weight average molecular weight of the polyamide by gel permeation chromatography (hereinafter referred to as "GPC") is preferably from 7,000 to 70,000, and more preferably from 10,000 to 50,000. If the polystyrene-reduced weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are ensured. Also, if the polystyrene-reduced weight average molecular weight is 70,000 or less, the developing solubility during formation of the relief pattern is ensured.

[0067] As the eluent for GPC, tetrahydrofuran or N-methyl-2-pyrrolidone is recommended. Also, the weight average molecular weight value is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko.

[0068] (B) A compound represented by the chemical formula (b1)

Chemical formula

[0069] (B) The compound represented by Chemical Formula (b1) will be described. (B) It is considered that the compound represented by Chemical Formula (b1) is produced by the ring-opening reaction of γ-butyrolactone activated by an acid catalyst with an alkyl alcohol. For the compound represented by Chemical Formula (b1) where n ≧ 2, it is produced by the reaction of the alkyl alcohol moiety of the compound represented by Chemical Formula (b1) with γ-butyrolactone. On the other hand, it is considered that the compound represented by Chemical Formula (b1) undergoes a ring-closure reaction due to its own thermal vibration under the condition of no acid catalyst or when it is sufficiently diluted, and it is speculated that γ-butyrolactone is produced.

[0070] Although the mechanism by which the color tone of the varnish changes with the passage of time is beyond speculation, when the compound represented by Chemical Formula (b1) is present in the varnish of the photosensitive resin composition, there is a resin that interacts with the compound represented by Chemical Formula (b1) and shows a certain color tone (for example, red). As time passes for the varnish, the compound represented by Chemical Formula (b1) decomposes into γ-butyrolactone, and the interaction between the compound represented by Chemical Formula (b1) and the resin is eliminated, so it is considered that the color tone changes.

[0071] Specific examples of the compound represented by Chemical Formula (b1) include 4-hydroxybutyric acid, methyl 4-hydroxybutyrate, ethyl 4-hydroxybutyrate, propyl 4-hydroxybutyrate, isopropyl 4-hydroxybutyrate, butyl 4-hydroxybutyrate, pentyl 4-hydroxybutyrate, hexyl 4-hydroxybutyrate, heptyl 4-hydroxybutyrate, octyl 4-hydroxybutyrate, nonyl 4-hydroxybutyrate, decyl 4-hydroxybutyrate, and their derivatives.

[0072] Also, when water or an alkyl alcohol and γ-butyrolactone are subjected to a ring-opening reaction under an acid catalyst, a compound represented by Chemical Formula (b1) where n ≧ 2 can be obtained.

[0073] Examples of the alkyl alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, etc. From the viewpoint of compatibility with the resin, methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol are preferable.

[0074] Examples of the acid catalyst include hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, benzenesulfonic acid, para-toluenesulfonic acid, oxalic acid, malonic acid, etc. The higher the acidity of the acid catalyst, the higher the reaction rate, and the more easily the compound represented by the chemical formula (b1) is formed.

[0075] When the compound represented by the chemical formula (b1) is less than 0.01 part by mass with respect to 100 parts by mass of the resin (A), the change in the color tone of the varnish over time decreases, and preferably, when it is less than 0.005 part by mass, the change in the color tone further decreases.

[0076] (C) Photosensitizer The (C) photosensitizer used in the present invention will be described. Examples of the photosensitive agent include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether; 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-aryl glycines such as N-phenylglycine; peroxides such as benzoyl perchloride; and aromatic biimidazoles. However, the photosensitive agent is not limited thereto. Further, in using these, they may be used alone or as a mixture of two or more kinds.

[0077] Among the above photosensitive agents, the following general formula (29):

Chemical formula

[0078] Among them, particularly preferably, the following formula (63): [Chemistry] , formula (64): [Chemistry] , formula (65): [Chemistry] , or formula (66): [Chemistry] It is a compound represented by these, or a mixture thereof. Formula (63) is TR-PBG-305 manufactured by Changzhou Qiangli New Electronic Materials Co., Ltd., formula (64) is TR-PBG-3057 manufactured by Changzhou Qiangli New Electronic Materials Co., Ltd., and formula (65) is commercially available as Irgacure OXE-01 from BASF.

[0079] (C) The compounding amount of the photosensitizer in the resin composition is 0.5 to 30 parts by mass with respect to 100 parts by mass of the (A) resin. Preferably it is 1 to 20 parts by mass, more preferably 2 to 10 parts by mass. If this compounding amount is 0.5 parts by mass or more, the resolution of the relief pattern is excellent, and if it is 30 parts by mass or less, there is little residue in the pattern opening.

[0080] (D) Solvent The photosensitive resin composition of the present invention is used as a resin composition in which any components to be used are dissolved in a solvent to form a varnish. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in (A) the resin. Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, γ-valerolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, etc. may be mentioned, and these can be used alone or in combination of two or more. In particular, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide are presumed to have appropriate solubility in both (A) the resin and the compound represented by the chemical formula (b1), and are excellent in improving the solubility of the coating film in the developer.

[0081] The above solvent can be used in the range of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, based on 100 parts by mass of the (A) resin, according to the desired coating film thickness and viscosity of the photosensitive resin composition.

[0082] Furthermore, from the viewpoint of improving the storage stability of the photosensitive resin composition, solvents containing alcohols, particularly alcohols having 1 to 12 carbon atoms, are preferred. Alcohols that can be preferably used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, etc., lactate esters such as ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, propylene glycol-2-(n-propyl) ether, etc., propylene glycol monoalkyl ethers, monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, etc., 2-hydroxyisobutyrate esters, dialcohols such as ethylene glycol, and propylene glycol. Among these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, and particularly ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are more preferred.

[0083] When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the above content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the resin composition is good, and when it is 50% by mass or less, (A) the solubility of the resin is good.

[0084] (E) Photopolymerizable compound The (E) photopolymerizable compound used in the present invention will be described. A photopolymerizable compound is a monomer having a photopolymerizable unsaturated bond. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction by a photopolymerization initiator is preferable. Although not particularly limited to the following, mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or tri-acrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono- or di-acrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or tri-acrylates and methacrylates of glycerol, di-, tri- or tetra-acrylates and methacrylates of pentaerythritol, and compounds such as ethylene oxide or propylene oxide adducts of these compounds can be mentioned.

[0085] When the photosensitive resin composition contains the above monomer having a photopolymerizable unsaturated bond, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the (A) resin. If the blending amount is 1 part by mass or more, the curability of the film in the exposed area is improved and the resolution is excellent. If it is 50 parts by mass or less, the in-plane uniformity of the coating film is excellent.

[0086] (F) Organic titanium compound The resin composition of the present invention may contain (F) an organic titanium compound. By containing (F) an organic titanium compound, a photosensitive resin layer excellent in chemical resistance can be formed even when cured at a low temperature of about 250°C or lower.

[0087] Examples of the organic titanium compound that can be used as the (F) organic titanium compound include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

[0088] Specific examples of the (F) organic titanium compound are shown in the following I) to VII): I) Titanium chelate compounds: Among them, titanium chelates having two or more alkoxy groups are more preferable because of the storage stability of the resin composition and the ability to obtain good patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), and the like.

[0089] II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like.

[0090] III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5-2,4-Cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

[0091] IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.

[0092] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.

[0093] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, and the like.

[0094] VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate, and the like.

[0095] Among them, it is preferable that the (F) organic titanium compound is at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferable.

[0096] (F) When compounding an organotitanium compound, the compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the (A) resin. When the compounding 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.

[0097] (G) Other components The resin composition of the present invention may further contain components other than the above (A) to (F) components.

[0098] The resin composition of the present invention may contain a crosslinking agent. The crosslinking agent can be a crosslinking agent that can crosslink the (A) resin or the crosslinking agent itself can form a crosslinked network when the resin composition of the present invention is heat-cured. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the resin composition.

[0099] Examples of the crosslinking agent include those having one heat-crosslinkable group such as ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (above, trade names, manufactured by Honshu Chemical Industry Co., Ltd.), P-a type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc., and those having two such as DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (above, trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (above, trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.),

[0100] B-a type benzoxazine, B-m type benzoxazine (above are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. Those having three of them include TriML-P, TriML-35XL, TriML-TrisCR-HAP (above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), etc. Those having four of them include TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (above are trade names, manufactured by Sanwa Chemical Co., Ltd.), etc. Those having six of them include HML-TPPHBA, HML-TPHAP (above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MW-390, Nikalac MW-100LM (above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0101] Among these, those containing at least two heat-crosslinkable groups are preferred in the present invention. Particularly preferred are 46DMOC, 46DMOEP (above are trade names, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), B-a type benzoxazine, B-m type benzoxazine (above are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc., TriML-P, TriML-35XL (above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), etc., TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (above are trade names, manufactured by Sanwa Chemical Co., Ltd.), etc., HML-TPPHBA, HML-TPHAP (above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), etc. Further preferably, Nikalac MX-290, Nikalac MX-280, Nikalac MX-270 (above are trade names, manufactured by Sanwa Chemical Co., Ltd.), B-a type benzoxazine, B-m type benzoxazine (above are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Nikalac MW-390, Nikalac MW-100LM (above are trade names, manufactured by Sanwa Chemical Co., Ltd.), etc.

[0102] In consideration of the balance with various properties other than heat resistance and chemical resistance, when the resin composition contains a crosslinking agent, the blending amount is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, based on 100 parts by mass of the resin (A). When the blending amount is 0.5 part by mass or more, good heat resistance and chemical resistance are exhibited. On the other hand, when it is 20 parts by mass or less, excellent storage stability is obtained.

[0103] In the resin composition of the present invention, a nitrogen-containing heterocyclic compound such as an azole compound purine derivative can be optionally blended to suppress discoloration on copper. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferably, it is one or more selected from tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or as a mixture of two or more.

[0104] 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-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, etc. and their derivatives.

[0105] When the resin composition contains the above azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the resin (A). When the blending amount of the azole compound with respect to 100 parts by mass of the resin (A) is 0.1 part by mass or more, when the resin composition of the present invention is formed on copper or a copper alloy, discoloration of the copper or copper alloy surface is suppressed. On the other hand, when it is 20 parts by mass or less, the storage stability of the resin composition is excellent.

[0106] Particularly preferred examples include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Also, these azole compounds may be used alone or as a mixture of two or more.

[0107] In addition, a hindered phenol compound can be optionally blended to suppress discoloration on the copper surface. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol),

[0108] Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-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

[0109] 1,3,5-Tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione

[0110] Examples include, but are not limited to, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like are particularly preferred.

[0111] The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass from the viewpoint of the degree of polymerization of the compound having an unsaturated bond, based on 100 parts by mass of the (A) resin. When the compounding amount of the hindered phenol compound with respect to 100 parts by mass of the (A) resin is 0.1 part by mass or more, for example, when the resin composition of the present invention is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, when it is 20 parts by mass or less, the degree of polymerization of the compound having an unsaturated bond is excellent.

[0112] A sensitizer can be optionally incorporated into the resin composition of the present invention. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-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-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combinations of, for example, 2 to 5 types.

[0113] When the resin composition contains a sensitizer, the blending amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the resin (A).

[0114] In addition, an adhesion promoter can be optionally blended to improve the adhesion between the film formed using the resin composition of the present invention and the substrate. Examples of the adhesion promoter include silane coupling agents such as γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, etc., and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, etc.

[0115] Among these adhesion promoters, it is more preferable to use a silane coupling agent from the viewpoint of adhesion strength. When the resin composition contains an adhesion promoter, the blending amount of the adhesion promoter is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the resin (A).

[0116] In addition, in order to improve the viscosity stability of the resin composition particularly during storage in the state of a solution containing a solvent, a thermal polymerization inhibitor can be optionally blended. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like.

[0117] When blending the thermal polymerization inhibitor in the resin composition, the blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 to 12 parts by mass with respect to 100 parts by mass of the resin (A).

[0118] <Method for producing cured relief pattern and semiconductor device> The present invention also provides a method for producing a cured relief pattern, including: (1) a step of forming a resin layer on a substrate by coating the photosensitive resin composition of the present invention described above on the substrate; (2) a step of exposing the resin layer; (3) a step of developing the resin layer after the exposure to form a relief pattern; and (4) a step of forming a cured relief pattern by heat-treating the relief pattern. Hereinafter, typical embodiments of each step will be described.

[0119] (1) Step of forming a resin layer on a substrate by coating the photosensitive resin composition on the substrate In this step, the photosensitive resin composition of the present invention is coated on a base material and, if necessary, dried thereafter to form a resin layer. The photosensitive resin composition of the present invention is used as a resin composition in a varnish state in which optional components used are dissolved in a solvent. In particular, in the photosensitive resin composition of the present invention as described above, the color tone of the varnish is in the range corresponding to yellow to red. As coating methods, methods conventionally used for coating photosensitive resin compositions can be employed. For example, methods such as coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., or spraying and coating with a spray coater can be used.

[0120] If necessary, a coating film made of the photosensitive resin composition can be dried. As drying methods, methods such as air drying, heat drying by an oven or a hot plate, and vacuum drying are used. Specifically, when performing air drying or heat drying, drying can be carried out under the conditions of 20°C to 140°C for 1 minute to 1 hour. As described above, a resin layer can be formed on the substrate.

[0121] (2) Step of exposing the resin layer In this step, the resin layer formed above is exposed using an exposure apparatus such as a contact aligner, a mirror projection, or a stepper, through a photomask or reticle having a pattern or directly, by an ultraviolet light source or the like.

[0122] After that, for the purpose of improving photosensitivity, etc., if necessary, post-exposure bake (PEB) and / or pre-development bake may be performed in any combination of temperature and time. The range of bake conditions is preferably that the temperature is 40 to 120°C and the time is 10 seconds to 240 seconds, but it is not limited to this range as long as the various properties of the photosensitive resin composition of the present invention are not inhibited.

[0123] (3) Step of developing the exposed resin layer to form a relief pattern In this process, the exposed or unexposed part of the photosensitive resin layer after exposure is developed and removed. In the case of a negative photosensitive resin composition, the unexposed part is developed and removed, and the exposed part remains on the substrate as a relief pattern. As the developing method, any method known in the art for developing photoresists, such as the spin spray method, paddle method, dipping method with ultrasonic treatment, etc., can be selected and used arbitrarily. Further, after development, a post-development bake may be performed at an arbitrary combination of temperature and time as needed for the purpose of adjusting the shape of the relief pattern. The range of post-development bake conditions is preferably a temperature of 40 to 180 °C and a time of 10 seconds to 600 seconds, but is not limited to this range as long as the properties of the photosensitive resin composition of the present invention are not inhibited.

[0124] As the developer used for development, a good solvent for the photosensitive resin composition or a combination of the good solvent and a poor solvent is preferred. For example, in the case of a photosensitive resin composition that is insoluble in an aqueous alkali solution, preferred good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc., and preferred poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When the good solvent and the poor solvent are mixed and used, 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. Further, two or more kinds of each solvent, for example, several kinds can be combined and used.

[0125] (4) A step of forming a cured relief pattern by heat-treating the relief pattern In this process, the relief pattern obtained by the above development is converted into a cured relief pattern by heating. As the method of heat curing, various methods such as those using a hot plate, those using an oven, and those using a temperature-programmable heating oven can be selected. Heating can be performed, for example, under the conditions of 180°C to 400°C for 30 minutes to 5 hours. As the atmosphere gas during heat curing, air may be used, or inert gases such as nitrogen and argon can also be used.

[0126] <Semiconductor device> The present invention also provides a semiconductor device including the cured relief pattern obtained by the method for manufacturing the cured relief pattern of the present invention described above. The present invention also provides a semiconductor device including a base material that is a semiconductor element and a cured relief pattern of a resin formed on the base material by the method for manufacturing the cured relief pattern described above. Further, the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a base material and includes the method for manufacturing the cured relief pattern described above as part of the process. The semiconductor device of the present invention can be manufactured by forming the cured relief pattern formed by the above method for manufacturing a cured relief pattern as a surface protection film, an interlayer insulation film, a rewiring insulation film, a protection film for a flip chip device, or a protection film of a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0127] The photosensitive resin composition of the present invention is useful not only for application to the semiconductor device as described above, but also for uses such as interlayer insulation of a multilayer circuit, cover coating of a flexible copper-clad laminate, a solder resist film, and a liquid crystal alignment film.

Examples

[0128] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

[0129] (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement was the trade name "Shodex 805M / 806M series" manufactured by Showa Denko K.K., the standard monodisperse polystyrene was the trade name "Shodex STANDARD SM-105" manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector was the trade name "Shodex RI-930" manufactured by Showa Denko K.K.

[0130] (2) Color tone change of the varnish after the passage of time A photosensitive resin composition was prepared, 5 g was taken and sealed in a 10 ml glass vial, and the color tone was observed under a UV cut fluorescent lamp. The glass vial was stored in a dark place at 25 degrees for 10 days, and the color tone was observed again under a UV cut fluorescent lamp. Those with no change in color tone were considered qualified. Those with a change were considered unqualified.

[0131] <Production Example 1> (Synthesis of Polymer A-1 as a Polyimide Precursor) 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 l separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and the mixture was stirred at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After the exothermic reaction ended, the mixture was allowed to cool to room temperature and left standing for 16 hours.

[0132] Next, under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension prepared by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0133] The obtained reaction solution was added to 3 L of ethyl alcohol to form a precipitate consisting of a crude polymer. The formed crude polymer was filtered off, dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer. After the obtained precipitate was filtered off, it was dried under vacuum to obtain a powdery polymer (Polymer A-1). When the molecular weight of Polymer A-1 was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.

[0134] <Production Example 2> ((Synthesis of Polymer A-2 as a Polyimide Precursor)) The reaction was carried out in the same manner as the method described in Production Example 1 above, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1, to obtain Polymer A-2. When the molecular weight of Polymer A-2 was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 22,000.

[0135] <Production Example 3> ((Synthesis of Polymer A-3 as a Polyimide Precursor)) The reaction was carried out in the same manner as the method described in Production Example 1 above, except that 98.6 g of 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1, to obtain Polymer A-3. When the molecular weight of Polymer A-3 was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.

[0136] <Production Example 4> ((Synthesis of Polymer A-4 as a Polyimide Precursor)) Instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 3, 109.1 g of pyromellitic dianhydride (PMDA) was used, and the reaction was carried out in the same manner as the method described in Production Example 3 above to obtain Polymer A-4. When the molecular weight of Polymer A-4 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 24,000.

[0137] <Production Example 5> ((A) Synthesis of Polymer A-5 as a Polyimide Precursor) Instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1, 77.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 73.6 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were used, and the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain Polymer A-5. When the molecular weight of Polymer A-5 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

[0138] <Production Example 6> ((A) Synthesis of Polymer A-6 as a Polyimide Precursor) Instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 3, 77.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 54.6 g of pyromellitic dianhydride (PMDA) were used, and the reaction was carried out in the same manner as the method described in Production Example 3 above to obtain Polymer A-6. When the molecular weight of Polymer A-6 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 23,000.

[0139] <Production Example 7> ((A) Synthesis of Polymer A-7 as a Polyamide) (Synthesis of Phthalic Acid Compound Sealing Body AIPA-MO) Into a separable flask with a capacity of 5 L, 543.5 g of 5-aminoisophthalic acid {hereinafter abbreviated as AIPA}, and 1700 g of N-methyl-2-pyrrolidone were charged and mixed with stirring, and then heated to 50 °C in a water bath. To this, a solution of 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise through a dropping funnel, and the mixture was stirred at 50 °C for about 2 hours as it was.

[0140] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter abbreviated as low molecular weight GPC}, this reaction solution was poured into 15 L of ion-exchanged water, stirred, allowed to stand, waited for the crystallization precipitation of the reaction product to be filtered off, washed with water as appropriate, and then dried in vacuo at 40 °C for 48 hours to obtain AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate reacted. The low molecular weight GPC purity of the obtained AIPA-MO was about 100%.

[0141] (Synthesis of Polymer A-7) Into a separable flask with a capacity of 2 L, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were charged and mixed, and then cooled to 5 °C in an ice bath. To this, a solution of 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted with 125 g of GBL was added dropwise over about 20 minutes under ice cooling, and then a solution of 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter abbreviated as BAPB} dissolved in 168 g of NMP was added dropwise over about 20 minutes, and the mixture was stirred for 3 hours while maintaining a temperature below 5 °C in the ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0142] To the obtained reaction solution, a mixed solution of 840 g of water and 560 g of isopropanol was added dropwise, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was added dropwise to 5 l of water to precipitate the polymer. After the obtained precipitate was filtered off, it was dried under vacuum to obtain a powdery polymer (Polymer A-7). When the molecular weight of Polymer A-7 was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 34,700.

[0143] <Production Example 8> (Synthesis of Compound B-1 as the Compound Represented by Chemical Formula (b1)) 31.4 g (0.36 mol) of GBL and 67.3 g (1.46 mol) of ethanol were charged into a 100 ml one-necked flask and mixed. To this, 0.1 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 18 hours. The reaction product was confirmed by 1H NMR to obtain a reaction solution of Compound B-1 containing 27.5 wt% (27.2 g) of ethyl 4-hydroxybutyrate. The structure represented by Chemical Formula (b1) with n ≥ 2 was not observed by 1H NMR.

[0144] <Production Example 9> (Synthesis of Compound B-2 as the Compound Represented by Chemical Formula (b1)) 85.0 g (0.99 mol) of GBL and 5 g of Solmix AP-1 (a mixed solution of 85.5 mass% ethanol, 13.4 mass% isopropanol, and 1.1 mass% methanol, manufactured by Nippon Alcohol Co., Ltd.) were charged into a 100 ml one-necked flask and mixed. To this, 0.1 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 24 hours. The reaction product was confirmed by 1H NMR to obtain a reaction solution of Compound B-3 containing 9.2 wt% (8.2 g) of the compound represented by Chemical Formula (b1). From the mass fragment of LC-MS measurement, it was confirmed that R1 was a methyl group, an ethyl group, or an isopropyl group, and the compound was the one represented by Chemical Formula (b1) with n = 1 to 5.

[0145] <Example 1> Using Polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of Polymer A-1, which is a polyimide precursor, was dissolved in 100 g of GBL together with 0.03 g of a reaction solution containing B-1 (0.008 g of the B-1 component), 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (described as "PDO" in Table 1), 1.5 g of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 10 g of N-phenyldiethanolamine, 4 g of methoxymethylated urea resin (MX-290), 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N-phenyl-3-aminopropyltrimethoxysilane, and 0.05 g of 2-nitroso-1-naphthol. The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of the above mixed solvent to obtain a negative photosensitive resin composition.

[0146] As a result of evaluating the negative photosensitive resin composition according to the above-described method, the results shown in Table 1 were obtained.

[0147] <Example 2> 100 g of Polymer A-1, which is the polyimide precursor of Example 1, was changed to 100 g of Polymer A-2, which is a polyimide precursor, and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed respectively. The evaluation results are shown in Table 1.

[0148] <Example 3> 100 g of Polymer A-1, which is the polyimide precursor of Example 1, was changed to 100 g of Polymer A-3, which is a polyimide precursor, and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed respectively. The evaluation results are shown in Table 1.

[0149] <Example 4> 100 g of polymer A-1, which is the polyimide precursor of Example 1, was changed to 100 g of polymer A-4, which is the polyimide precursor, and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed respectively. The evaluation results are shown in Table 1.

[0150] <Example 5> 100 g of polymer A-1, which is the polyimide precursor of Example 1, was changed to 100 g of polymer A-5, which is the polyimide precursor, and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed respectively. The evaluation results are shown in Table 1.

[0151] <Example 6> 100 g of polymer A-1, which is the polyimide precursor of Example 1, was changed to 100 g of polymer A-6, which is the polyimide precursor, and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed respectively. The evaluation results are shown in Table 1.

[0152] <Example 7> 100 g of polymer A-1, which is the polyimide precursor of Example 1, was changed to 100 g of polymer A-7, which is a polyamide, and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed respectively. The evaluation results are shown in Table 1.

[0153] <Example 8> 0.03 g of the reaction solution containing B-1 (0.008 g of the B-1 component) in Example 8 was changed to 0.087 g of the reaction solution containing B-2 (0.008 g of the B-2 component), and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed respectively. The evaluation results are shown in Table 1.

[0154] <Example 9> 100 g of polymer A-1, which is the polyimide precursor of Example 8, was changed to 100 g of polymer A-3, which is the polyimide precursor, and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed respectively. The evaluation results are shown in Table 1.

[0155] <Example 10> 0.03 g of the reaction solution containing B-1 in Example 1 (0.008 g of the B-1 component) was changed to 0.018 g of the reaction solution containing B-1 (0.005 g of the B-1 component), and a resin composition was prepared in the same manner as in Example 1, and the same evaluations as in Example 1 were performed. The evaluation results are shown in Table 1.

[0156] <Comparative Example 1> Using polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer A-1, which is a polyimide precursor, was dissolved in 100 g of GBL together with 0.073 g of the reaction solution containing B-1 (0.02 g of the B-1 component), 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (described as "PDO" in Table 1), 1.5 g of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 10 g of N-phenyldiethanolamine, 4 g of methoxymethylated urea resin (MX-290), 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N-phenyl-3-aminopropyltrimethoxysilane, and 0.05 g of 2-nitroso-1-naphthol. The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of the above mixed solvent to obtain a negative photosensitive resin composition. As a result of evaluating the negative photosensitive resin composition according to the above-described method, the results shown in Table 1 were obtained.

[0157] <Comparative Example 2> 100 g of polymer A-1, which is a polyimide precursor in Comparative Example 1, was changed to 100 g of polymer A-2, which is a polyimide precursor, and a resin composition was prepared in the same manner as in Comparative Example 1, and the same evaluations as in Example 1 were performed. The evaluation results are shown in Table 1.

[0158] <Comparative Example 3> 100 g of polymer A-1, which is a polyimide precursor in Comparative Example 1, was changed to 100 g of polymer A-3, which is a polyimide precursor, and a resin composition was prepared in the same manner as in Comparative Example 1, and the same evaluations as in Example 1 were performed. The evaluation results are shown in Table 1.

[0159] <Comparative Example 4> 100 g of polymer A-1, which is the polyimide precursor of Comparative Example 1, was changed to 100 g of polymer A-4, which is the polyimide precursor, and a resin composition was prepared in the same manner as in Comparative Example 1, and the same evaluations as in Example 1 were performed on each. The evaluation results are shown in Table 1.

[0160] <Comparative Example 5> 100 g of polymer A-1, which is the polyimide precursor of Comparative Example 1, was changed to 100 g of polymer A-5, which is the polyimide precursor, and a resin composition was prepared in the same manner as in Comparative Example 1, and the same evaluations as in Example 1 were performed on each. The evaluation results are shown in Table 1.

[0161] <Comparative Example 6> 100 g of polymer A-1, which is the polyimide precursor of Comparative Example 1, was changed to 100 g of polymer A-6, which is the polyimide precursor, and a resin composition was prepared in the same manner as in Comparative Example 1, and the same evaluations as in Example 1 were performed on each. The evaluation results are shown in Table 1.

[0162] <Comparative Example 7> 100 g of polymer A-1, which is the polyimide precursor of Comparative Example 1, was changed to 100 g of polymer A-7, which is the polyimide precursor, and a resin composition was prepared in the same manner as in Comparative Example 1, and the same evaluations as in Example 1 were performed on each. The evaluation results are shown in Table 1.

[0163]

Table 1

[0164] As is clear from Table 1, it can be seen that, for the comparative examples in which the compound represented by chemical formula (b1) is contained in an amount of 0.01 part by mass or more, the examples in which the amount is less than 0.01 part by mass exhibit the property of little change in the color tone of the varnish after the passage of time.

Industrial Applicability

[0165] The resin composition of the present invention can be suitably used, for example, as a surface protective film, an interlayer insulating film, and an insulating film for rewiring, a cover coat, and a solder resist film of a semiconductor device having a copper pattern, a multilayer wiring board, and the like.

Claims

1. The following components: (A) At least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which are polyimide precursors: 100 parts by mass, (B) Chemical formula (b1): 【Chemical formula 1】 (In the formula, each R1 independently represents a monovalent organic group of a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n takes an integer of 1 to 5.) A compound represented by, (C) A photosensitizer: 0.5 to 30 parts by mass, and (D) A solvent, and In the compound represented by the above (B) chemical formula (b1), the total of the compounds where n = 1 to 5 is 0.005 parts by mass or more and less than 0.01 parts by mass. A negative-type photosensitive resin composition characterized by this.

2. The above (A) resin has the following general formula (1): 【Chemical formula 2】 {In the formula, X 1 is a tetravalent organic group, Y 1 is a divalent organic group, n 1 is an integer of 2 to 150, and R 1 and R 2 are each independently a hydrogen atom, or a monovalent organic group represented by the following general formula (2): 【Chemical formula 3】 (In the formula, R 3 、R 4 and R 5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 1 is an integer of 2 to 10.) Or a saturated aliphatic group having 1 to 4 carbon atoms.} A polyimide precursor having a structure represented by, or the following general formula (3): 【Chemical formula 4】 {In the formula, X 2 is a trivalent organic group having 6 to 15 carbon atoms, Y 2is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or a plurality of structures, R 6 is an organic group having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n 2 is an integer from 1 to 1000.} The negative photosensitive resin composition according to claim 1, which is at least one resin selected from the group consisting of polyamides having a structure represented by

3. In the compound represented by the chemical formula (b1) of (B), the negative photosensitive resin composition according to claim 1 or 2, wherein R1 is a monovalent organic group which is an alkyl group having 1 to 12 carbon atoms.

4. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the (D) solvent is at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.

5. The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the (D) solvent contains an alcohol compound having 1 to 12 carbon atoms.

6. (1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of claims 1 to 5 on the substrate; (2) A step of exposing the photosensitive resin layer; (3) A step of developing the exposed photosensitive resin layer to form a relief pattern; (4) A method for producing a cured film, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.

7. (1) A step of forming a photosensitive resin layer on the substrate by applying a varnish of the photosensitive resin composition according to any one of claims 1 to 5 on the substrate; (2) A step of exposing the photosensitive resin layer; (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern; (4) A step of forming a cured relief pattern by heat-treating the relief pattern, A method for producing a cured film, wherein the color tone of the varnish of the photosensitive resin composition falls within a range corresponding to yellow to red.

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