TW202348728A - Photosensitive resin composition and method for manufacturing cured relief pattern capable of obtaining high copper adhesion and suppressing generation of pores at an interface between a copper layer and a resin layer after a high-temperature storage test - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition capable of obtaining high copper adhesion and suppressing generation of pores at an interface between a copper layer and a resin layer after a high-temperature storage test. The negative photosensitive resin composition of the present invention is characterized in comprising the following components: (A) at least one resin selected from the group consisting of (A1) polyimide precursor and (A2) polyimide, (B) flavonoids represented by the following general formula (1), (C) a photopolymerization initiator, and (D) a solvent. (In the formula, R1 is an aromatic group having at least one hydroxyl group and may further have other substituents, R2 is a hydrogen atom or a hydroxyl group, R3 to R6 are groups selected from a hydrogen atom, a hydroxyl group, or a methoxy group, and at least one of R3 to R6 is a hydroxyl group.).

Description

Photosensitive resin composition and method for manufacturing hardened relief pattern

The present invention relates to a photosensitive resin composition and a method for manufacturing a hardened relief pattern.

Previously, polyimide resins and polybenzoconazole resins, which have excellent heat resistance, electrical properties, and mechanical properties, were used as insulating materials for electronic components and passivation films, surface protective films, and interlayer insulating films of semiconductor devices. , phenolic resin, etc. Among these resins, those provided in the form of photosensitive resin compositions can easily form heat-resistant relief patterns through coating, exposure, development, and thermal imidization treatment by curing of the compositions. membrane. This photosensitive resin composition has the characteristic of significantly shortening the steps compared to conventional non-photosensitive materials.

On the other hand, in recent years, the mounting method (packaging structure) of semiconductor devices on printed wiring boards has also changed from the viewpoint of improvements in integration and computing functions, and reduction in chip size. From previous installation methods that used metal pins and lead-tin eutectic soldering to BGA (Ball Grid Array), CSP (Chip Scale Package), etc. that can achieve higher density installation, polyimide coating has been used to directly Structure that contacts solder bumps. Furthermore, a structure including a plurality of rewiring layers having an area larger than the area of the semiconductor wafer has been proposed such as FO (fan-out) on the surface of the semiconductor wafer (for example, see Patent Document 1).

Copper is often used for wiring in semiconductor devices. However, in package structures with large areas, the stress caused by the difference in thermal expansion coefficients of dissimilar materials leads to a decrease in electrical characteristics due to peeling of copper and interlayer insulating materials. problem. Therefore, materials used as interlayer insulating films are required to have high adhesion to copper.

Furthermore, in recent years, the application of semiconductor devices in automobile applications and mobile phone applications has been extremely prominent. Semiconductor devices in this field are required to have high reliability, and reliability tests in high-temperature environments are performed. [Prior technical literature] [Patent Document]

[Patent Document 1] U.S. Patent No. 10658199 Specification

[Problem to be solved by the invention]

However, when the high-temperature storage test was performed in the above-mentioned reliability test, there was the following problem: after the test, voids were generated at the interface between the rewired copper layer and the resin layer. If pores are generated at the interface between the copper layer and the resin layer, the adhesion between the two will be reduced.

The present invention was conceived in view of such previous actual situation, and one of its objects is to provide a negative photosensitive resin composition (hereinafter, also referred to as "photosensitive resin composition" in the specification of this case), which can obtain It has high copper adhesion and can inhibit the generation of pores at the interface between the copper layer and the resin layer after high temperature storage testing. Furthermore, another object of the present invention is to provide a method for forming a hardened relief pattern using the negative photosensitive resin composition of the present invention. [Technical means to solve problems]

The present inventors discovered that the above-mentioned problems can be solved by adding specific flavonoids to a photosensitive resin composition, and completed the present invention. That is, the present invention is as follows. [1] A negative photosensitive resin composition characterized by containing the following components: (A) at least one resin selected from the group consisting of (A1) polyimide precursor and (A2) polyimide, (B) At least one flavonoid represented by the following general formula (1) or (1-2), [Chemical 1] [Chemicalization 2] (In the formula, R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents, R ₂ is a hydrogen atom or a hydroxyl group, and R ₃ to R ₆ are selected from a hydrogen atom, a hydroxyl group, or a methoxy group. group in the group, and at least one of R ₃ to R ₆ is a hydroxyl group) (C) photopolymerization initiator, and (D) solvent. [2] The negative photosensitive resin composition according to [1], wherein the flavonoid (B) is a compound represented by the following general formula (2). [Chemical 3] (In the formula, n ₁ is an integer from 1 to 3, n ₂ is 0 or 1, and n ₃ is an integer from 1 to 2) [3] The negative photosensitive resin composition as described in [2], wherein the above (B) Flavonoids are compounds represented by the following general formula (3). [Chemical 4] (In the formula, n ₄ is 2 or 3, and n ₅ is 1 or 2) [4] The negative photosensitive resin composition as described in [2], wherein the flavonoid (B) is the following general formula ( 4) The compound represented. [Chemistry 5] (In the formula, n ₄ is 2 or 3) [5] The negative photosensitive resin composition as described in [1], wherein the flavonoids (B) are represented by the following general formula (2-2) compound. [Chemical 6] (In the formula, n ₂ is 0 or 1, and R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents) [6] The negative photosensitive resin composition as described in [5], Among them, the above-mentioned (B) flavonoids are compounds represented by the following general formula (3-2). [Chemical 7] (In the formula, R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents) [7] The negative photosensitive resin composition according to any one of [1] to [6], The above-mentioned (A1) polyimide precursor contains a polyimide precursor having a structural unit represented by the following general formula (5): [Chemical 8] {In formula (5), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁₁ and R ₁₂ are independently hydrogen atoms or monovalent The organic base}. [8] The negative photosensitive resin composition as described in [7], wherein in the above general formula (4), at least one of R ₁ and R ₂ has a structural unit represented by the following general formula (6): [Chemical 9] {In formula (6), L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer from 2 to 10}. [9] The negative photosensitive resin composition according to any one of [1] to [8], wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film. [10] A method for manufacturing a hardened relief pattern, which includes the following steps: (1) Coating the negative photosensitive resin composition as described in any one of [1] to [9] on the substrate, and A photosensitive resin layer is formed on the substrate; (2) Exposing the above-mentioned photosensitive resin layer; (3) Developing the above-mentioned exposed photosensitive resin layer to form a relief pattern; (4) Performing the above-mentioned relief pattern Heat treatment to form a hardened relief pattern. [11] The method for manufacturing a hardened relief pattern as described in [10], wherein the heat treatment in the above step (4) is a heat treatment below 230°C. [12] A method for producing polyimide, which includes the step of hardening the negative photosensitive resin composition according to any one of [1] to [9]. [Effects of the invention]

According to the present invention, a negative photosensitive resin composition can be provided that can obtain high copper adhesion and suppress the generation of pores at the interface between the copper layer and the resin layer after a high temperature storage test. , and a method for forming a hardened relief pattern using the negative photosensitive resin composition can be provided.

Hereinafter, a mode for implementing the present invention (hereinafter, simply referred to as “this embodiment”) will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the spirit. Furthermore, throughout this specification, the structures represented by the same symbol in the general formula may be the same as each other or different from each other when there are plural structures in the molecule.

<Negative photosensitive resin composition> The negative photosensitive resin composition of this embodiment contains the following components: (A) Selected from (A1) polyimide precursor and (A2) polyimide At least one kind of resin, (B) At least one kind of flavonoid represented by the following general formula (1) or (1-2), [Chemical 10] [Chemical 11] (In the formula, R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents, R ₂ is a hydrogen atom or a hydroxyl group, and R ₃ to R ₆ are selected from a hydrogen atom, a hydroxyl group, or a methoxy group. group in the group, and at least one of R ₃ to R ₆ is a hydroxyl group) (C) photopolymerization initiator, and (D) solvent.

(A)Resin (A1) Polyimide precursor The (A1) polyimide precursor in this embodiment is a resin component contained in a negative photosensitive resin composition, and is converted into a polyimide by performing a heating cyclization treatment. (A1) The structure of the polyimide precursor is not limited as long as it is a resin that can be used in a negative photosensitive resin composition, but it is preferably not alkali-soluble. By making the polyimide precursor not alkali soluble, higher chemical resistance can be achieved.

The polyimide precursor is preferably a polyimide having a structure represented by the following general formula (5). [Chemical 12] {In formula (5), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁₁ and R ₁₂ are independently hydrogen atoms or monovalent of organic base}

Preferably, in the general formula (5), at least one of R ₁₁ and R ₁₂ has a structural unit represented by the following general formula (6): [Chemical 13] {In formula (6), L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer from 2 to 10}.

The ratio of R ₁₁ and R ₁₂ in the general formula (5) to hydrogen atoms is preferably 10% or less, more preferably 5% or less, and still more preferably based on the molar number of the entire R ₁₁ and R ₁₂ is less than 1%. In addition, the ratio of R ₁₁ and R ₁₂ in the general formula (5) is a monovalent organic group represented by the above general formula (6), based on the molar number of the entire R ₁₁ and R ₁₂ , preferably: 70% or more, more preferably 80% or more, further more preferably 90% or more. From the viewpoint of photosensitive characteristics and storage stability, it is preferable that the ratio of hydrogen atoms and the ratio of organic groups of general formula (6) are within the above ranges.

n ₁ in the general formula (5) is not limited as long as it is an integer from 2 to 150. From the viewpoint of the photosensitive characteristics and mechanical properties of the negative photosensitive resin composition, it is preferably an integer from 3 to 100, and more preferably Preferably it is an integer from 5 to 70.

In the general formula (5), the _tetravalent organic group represented _by group and -COOR ₁₂ group and -CONH- group are aromatic groups or alicyclic aliphatic groups that are ortho-positioned to each other. Specific examples of the _tetravalent organic group represented by But it is not limited to the following: [Chemical 14] {In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with one valence of C1 to C10, and a fluorine-containing hydrocarbon group with one valence of C1 to C10, and l is selected from the group consisting of An integer from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4}. In addition, the structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having a structure represented by the above formula (20) is particularly preferred from the viewpoint of having both heat resistance and photosensitive properties.

As _the Better from the perspective of character: [Chemical 15]

{In the formula, R6 is at least one selected from the group consisting of a fluorine atom, a hydrocarbon group with a valence of 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group with a valence of 1 to 10 carbon atoms, and m is selected from An integer from 0 to 3}. In the above general formula (5), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of having both heat resistance and photosensitive properties. Examples thereof include The structure represented by the following formula (21), but is not limited to this: [Chemical 16] {In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with one valence of C1 to C10, and a fluorine-containing hydrocarbon group with one valence of C1 to C10, and n is a selected An integer from 0 to 4}. In addition, the structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having a structure represented by the above formula (21) is particularly preferred from the viewpoint of having both heat resistance and photosensitive properties.

As the Y ₁ group, among the structures represented by the above-mentioned formula (21), in particular, the divalent group represented by the following formula has an imidization rate when heated at low temperature, degassing property, copper adhesion, and chemical resistance. Better from a sexual perspective: [Chemical 17] {In the formula, R6 is at least one selected from the group consisting of a fluorine atom, a hydrocarbon group with a valence of 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group with a valence of 1 to 10 carbon atoms, and n is selected from An integer from 0 to 4}.

L ₁ in the general formula (6) is preferably a hydrogen atom or a methyl group, and L ₂ and L ₃ are preferably a hydrogen atom from the viewpoint of photosensitive characteristics. In addition, m ₁ is an integer of 2 to 10 and preferably 2 to 4 from the viewpoint of photosensitive characteristics.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (7): [Chemical 18] {In the formula, R ₁₁ , R ₁₂ , and n ₁ are those defined above}.

More preferably, in the general formula (7), at least one of R ₁₁ and R ₁₂ is a monovalent organic group represented by the above general formula (6). When the polyimide precursor (A1) contains the polyimide precursor represented by the general formula (7), in particular, the chemical resistance is improved.

In one embodiment, from the viewpoint of thermophysical properties, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (8): [Chemical 19] {In the formula, R ₁₁ , R ₁₂ , and n ₁ are those defined above}.

More preferably, in the general formula (8), at least one of R ₁₁ and R ₁₂ is a monovalent organic group represented by the above general formula (6).

When the polyimide precursor (A1) contains both the structural unit represented by the general formula (7) and the structural unit represented by the general formula (8), in particular, the resolution tends to be improved. For example, (A1) the polyimide precursor may include a copolymer of the structural unit represented by the general formula (7) and the structural unit represented by the general formula (8), or may also be a copolymer represented by the general formula (7) A mixture of a polyimide precursor and a polyimide precursor represented by general formula (8).

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (9): [Chemical 20] {In the formula, R ₁₁ , R ₁₂ , and n ₁ are those defined above}.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (10): [Chemical 21] {In the formula, R ₁₁ , R ₁₂ , and n ₁ are those defined above}. By making the polyimide precursor (A1) include the polyimide precursor represented by the general formula (10), in particular, chemical resistance is improved.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (11): [Chemical 22] {In the formula, R ₁₁ , R ₁₂ , and n ₁ are those defined above}. When the polyimide precursor (A1) contains the polyimide precursor represented by the general formula (11), in particular, Tg is improved.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (12): [Chemical 23] {In the formula, R ₁₁ , R ₁₂ , and n ₁ are those defined above}. When the polyimide precursor (A1) contains the polyimide precursor represented by the general formula (12), in particular, the dielectric constant becomes good.

In one embodiment, the polyimide precursor (A1) is preferably a polyimide precursor having a structural unit represented by the following general formula (13): [Chemical 24] {In the formula, R ₁₁ , R ₁₂ , and n ₁ are those defined above}. When the polyimide precursor (A1) contains the polyimide precursor represented by the general formula (13), in particular, the dielectric constant becomes good.

(A1) Preparation method of polyimide precursor (A1) The polyimide precursor can be obtained in the following manner: first, the _{tetracarboxylic} dianhydride containing the above-mentioned tetravalent organic group Polymerizable alcohols with unsaturated double bonds and any alcohols without unsaturated double bonds are reacted to prepare partially esterified tetracarboxylic acid (hereinafter, also referred to as acid/ester body). Thereafter, the partially esterified tetracarboxylic acid and the diamines containing the above-mentioned divalent organic group Y ₁ are subjected to amide polycondensation.

(Preparation of acid/ester body) In this embodiment, a tetracarboxylic dianhydride containing a _tetravalent organic group 20) The tetracarboxylic dianhydride represented is representative, for example: pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone- 3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsine-3,3',4,4'- Tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis (3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferred examples include: pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride Anhydrides, but are not limited to these. Moreover, these can of course be used individually or in mixture of 2 or more types.

In this embodiment, alcohols with photopolymerizable unsaturated double bonds that are preferably used to prepare the polyimide precursor (A1) include, for example: 2-propenyloxyethyl alcohol, 1-Acryloxy-3-propyl alcohol, 2-Acrylamide ethyl alcohol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate , 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butyl acrylate Oxypropyl ester, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethyl alcohol, 1-methacryloxy-3-propyl alcohol, 2-methyl Acrylamide ethyl alcohol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxy methacrylate Propyl ester, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-Hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

It is also possible to mix a portion of the alcohols with photopolymerizable unsaturated double bonds such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, and 2-pentanol. , 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol mono Methyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol and other alcohols that do not have unsaturated double bonds are used.

Furthermore, as the polyimide precursor, a non-photosensitive polyimide precursor prepared only from the above-mentioned alcohols having no unsaturated double bonds and a photosensitive polyimide precursor may be mixed and used. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor. In the presence of an alkaline catalyst such as pyridine, the above-mentioned preferred tetracarboxylic dianhydride and the above-mentioned alcohols are stirred and dissolved in a solvent as described below at a temperature of 20 to 50°C for 4 to 24 hours, and then mixed. The esterification reaction of acid anhydride can be carried out to obtain the required acid/ester body.

(Preparation of polyimide precursor) Under ice bath cooling, add a suitable dehydration condensation agent, such as dicyclohexyl carbon dioxide, into the above acid/ester body (typically, a solution in the following solvent). Imide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-bis-1,2,3-benzotriazole, N, After preparing the acid/ester body into a polyanhydride such as N'-dibutylene imide carbonate, the divalent organic group Y ₁ bis preferably used in this embodiment is added dropwise thereto. If amines are separately dissolved or dispersed in a solvent, the target polyimide precursor can be obtained by performing amide condensation polymerization. As an alternative method, the acid part of the above-mentioned acid/ester is chlorinated using thionite chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the target polyimide precursor.

The diamines containing the divalent organic group Y ₁ preferably used in this embodiment are represented by diamines having the structure represented by the general formula (21). For example, p-phenylenediamine can be exemplified. , m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether Phenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diamine Diphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl Benzene, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobis Phenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]benzene, bis[4- (3-Aminophenoxy)phenyl]terine, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[ 4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1 ,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis( 4-Aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine, 9,9-bis(4-aminophenyl)fluorine, and the Those in which part of the hydrogen atoms on the benzene ring is substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diamino Biphenyl, 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, mixtures thereof, etc., but are not limited thereto.

After the amide polycondensation reaction is completed, if necessary, the water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are filtered and separated, and then poor solvents such as water, aliphatic lower alcohols, or their mixtures are added to the obtained polymer components. , to separate out the polymer components, and then repeatedly perform re-dissolution, reprecipitation and precipitation operations, etc., thereby purifying the polymer, vacuum drying, and isolating the target polyimide precursor. In order to improve the degree of purification, the polymer solution can also be passed through a column filled with anion and/or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

The molecular weight of the polyimide precursor (A1) is preferably from 8,000 to 150,000, more preferably from 9,000 to 9,000 when measured based on the polystyrene-reduced weight average molecular weight obtained by gel permeation chromatography. 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good. When the weight average molecular weight is 150,000 or less, the dispersibility in the developer is good and the resolution of the relief pattern is good. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight was determined based on 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 Co., Ltd.

(A2) Polyimide (A2) Polyimide used in this embodiment will be described. The resin component in the photosensitive resin composition is a polyimide resin having a structural unit represented by the following general formula (24). [Chemical 25] {In the _{formula ,}

The resin represented by the general formula (24) exhibits sufficient film characteristics and does not require chemical changes in the heat treatment step, so it is particularly suitable for processing at lower temperatures.

In general formula (24), the divalent organic group of X ₂ and/or the tetravalent organic group of Y ₂ preferably contains an aromatic ring structure from the viewpoint of heat resistance, and more preferably contains a benzene ring. structure.

From the viewpoint of solubility in organic solvents, it is preferable that at least one of X ₂ and Y ₂ be a group containing a fluorine atom, and it is also preferable that both X ₂ and Y ₂ be a group containing a fluorine atom. base.

In _the general formula (24 ₎ , the tetravalent organic group of structure. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. The alkylene group and the fluorinated alkylene group may be linear or branched.

(A2) Polyimide can be obtained by using a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic diester dichloride, etc., and a diamine, a corresponding diisocyanate compound, or trimethyl Obtained from the reaction of silylated diamines. Polyimide can usually be produced by dehydrating and ring-closing polyamide acid, which is one of the precursors of polyimide, obtained by reacting tetracarboxylic dianhydride and diamine by heating or chemical treatment with acid or alkali. obtain.

Preferable tetracarboxylic dianhydride includes: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyl Tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3 ,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride Anhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxylic acid) Phenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)tere dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride Anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)ethyl dianhydride, 9,9-bis{4-(3,4- Dicarboxyphenoxy)phenyl} anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9, 10-Perylene tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride aromatic tetracarboxylic dianhydride, or aliphatic tetracarboxylic dianhydride such as butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 3,3',4, Compounds represented by 4'-diphenyltetracarboxylic dianhydride, etc.

Among them, pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), and benzophenone-3,3',4 are preferably used. ,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenyltetracarboxylic acid Carboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2 -Bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA). These can be used individually or in combination of 2 or more types.

Preferred diamines include: 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl) )Biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diamine diphenylbenzidine, 3,3'-dimethylbenzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis(p-aminophenyl)hexafluoropropane, bis (Trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydiphenylamine (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2, 2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DFPOB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2 -Bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5- Diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminotrifluorotoluene (3 ,5-DABTF), 3,5-diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethyl Benzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)𠮿 (6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenyl𠮿 (3FCDAM), 3,6-diamino-9,9-diphenyl𠮿 The compounds represented, etc.

The usage ratio of diamine and acid dianhydride is basically 1:1 in terms of molar ratio. Among them, in order to obtain the desired terminal structure, an excessive amount of one of them may be used. Specifically, by using an excessive amount of diamine, the terminals (both terminals) of the polyimide (A2) tend to become amine groups. On the other hand, by using an excessive amount of acid dianhydride, the terminals (both terminals) of the polyimide (A2) tend to become acid anhydride groups. As described above, in this embodiment, the polyimide (A2) preferably has an acid anhydride group at its terminal. Therefore, in this embodiment, it is preferable to use an excessive amount of acid dianhydride when synthesizing the polyimide (A2).

The terminal amine group and/or acid anhydride group of the polyimide obtained by polycondensation can also be reacted with a certain reagent, so that the terminal end of the polyimide has the required functional group.

The molecular weight of the polyimide (A2) is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, especially when measured based on the polystyrene-reduced weight average molecular weight obtained by gel permeation chromatography. The best range is 10,000 to 50,000. When the weight average molecular weight is 5,000 or more, it is preferable because the mechanical properties are good. On the other hand, when the weight average molecular weight is 150,000 or less, the dispersibility in the developer and the resolution of the relief pattern are good. , so it is better. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight was determined based on 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 Co., Ltd.

(B) Flavonoids The (B) flavonoids used in this embodiment are not limited as long as they are compounds represented by the following formula (1) or (1-2). [Chemical 26] [Chemical 27] (In the formula, R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents, R ₂ is a hydrogen atom or a hydroxyl group, and R ₃ to R ₆ are selected from a hydrogen atom, a hydroxyl group, or a methoxy group. group in the group, and at least one of R ₃ to R ₆ is a hydroxyl group)

By using the flavonoid (B) as the formula (1) or formula (1-2), excellent copper adhesion, copper pore suppression effects, and storage stability can be obtained. Although not limited to theory, it is believed that by having hydroxyl groups in different aromatic groups in the structure, hydrogen bonds can be formed with both the copper layer and the resin layer to improve copper adhesion. In addition, it is thought that by having a plurality of aromatic hydroxyl groups, the oxidation reaction at the copper interface is strongly suppressed, thereby suppressing copper pores. Regarding storage stability, it is thought that the reason for this is that having aromatic hydroxyl groups in the structure captures free radicals that are unintentionally generated in the system and prevents viscosity increase or gelation associated with polymer cross-linking.

From the viewpoint of copper adhesion, (B) flavonoids are preferably compounds represented by the following general formula (2-2), [Chemical 28] (In the formula, n ₂ is 0 or 1, and R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents) More preferably, it is a compound represented by the following general formula (3-2). [Chemical 29] (In the formula, R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents)

It is thought that by having a plurality of hydroxyl groups on the same aromatic ring of the flavonoid (B), the interaction with the copper layer or the resin layer is enhanced and the copper adhesion becomes good.

From the viewpoint of copper adhesion, the flavonoid (B) is preferably a compound represented by the following general formula (2). [Chemical 30] (In the formula, n ₁ is an integer from 1 to 3, n ₂ is 0 or 1, and n ₃ is an integer from 1 to 2)

It is considered that since the flavonoid (B) does not have a group other than a hydroxyl group in addition to the flavonoid skeleton, the interaction with the copper layer is not three-dimensionally hindered and the copper adhesion becomes good.

Moreover, from the viewpoint of copper adhesion and suppression of copper pores, (B) flavonoids are preferably compounds represented by the following general formula (3). [Chemical 31] (In the formula, n ₄ is 2 or 3, n ₅ is 1 or 2)

From the viewpoint of storage stability, (B) flavonoids are preferably compounds represented by the following general formula (4). [Chemical 32] (In the formula, n ₄ is 2 or 3)

It is presumed that by including a large number of aromatic hydroxyl groups in the flavonoid (B) molecule, the hydrogen bond with the copper layer or the resin layer becomes strong. In addition, it is thought that the effect of inhibiting oxidation is also increased, and copper pores are further suppressed, and similarly, the effect of storage stability is also considered to be improved.

(B) Flavonoids include, for example, isorhamnetin, phylloxanthin, apigenin, quercetin, myricetin, xanthophyllin, daidzein, isorhamnetin, kanfeflavonol, and phylloxanthin. Isoflavones, morin, apigenin, lutein, naringenin, hesperetin, dihydromyricetin, (+)-dihydroquercetin, but are not limited to these. Among these, quercetin, myricetin, scutellarin, and morin are preferred. Furthermore, when these compounds are added to the resin composition, they may be hydrates.

The compounding amount of (B) flavonoids is preferably not less than 3 parts by mass and not more than 20 parts by mass, and more preferably not less than 10 parts by mass and not more than 20 parts by mass, based on 100 parts by mass of the resin (A). The above-mentioned compounding amount is preferably 3 parts by mass or more from the viewpoint of suppressing copper pores, and is preferably 20 parts by mass or less from the viewpoint of copper adhesion. When it is less than 3 parts by mass, the inhibitory effect of copper pores is insufficient, and when it exceeds 20 parts by mass, the copper adhesion decreases. The reason for the decrease in copper adhesion is not clear, but it is considered that when the compounding amount of (B) flavonoids is too large, a fragile layer will be formed between the copper layer and the resin layer.

(C) Photopolymerization initiator The (C) photopolymerization initiator used in this embodiment will be described. As the photopolymerization initiator, a photoradical polymerization initiator is preferred, and preferred examples include benzophenone, o-benzoylbenzoic acid methyl ester, and 4-benzoyl-4'- Methyl benzophenone derivatives such as methyl benzophenone, dibenzyl ketone, and fentanone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclic Acetophenone derivatives such as hexyl phenyl ketone, 9-oxosulfide𠮿 , 2-Methyl-9-oxosulfide𠮿 , 2-isopropyl-9-oxosulfide𠮿 , diethyl-9-oxosulfide𠮿 Etc. 9-oxysulfur𠮿 Derivatives, benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal, benzoyl-β-methoxyethyl acetal, benzoin, benzoin methyl ether and other benzoin derivatives, 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-diphenylpropane Triketone-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxyglycerol-2-(o-benzoyl)oxime and other oximes, N-phenylglycine, etc. N-arylglycines, peroxides such as benzyl perchloride, aromatic biimidazoles, titanocenes, α-(n-octane sulfonyloxyimino)-4-methoxy Photoacid generators such as phenylacetonitrile, etc., but are not limited to these. Among the above-mentioned photopolymerization initiators, oximes are more preferred in terms of photosensitivity.

The compounding amount of (C) the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 8 parts by mass, and still more preferably 1 part by mass relative to 100 parts by mass of the resin (A) More than 5 parts by mass and less than 5 parts by mass. The compounding amount is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or patternability, and is preferably 0.1 parts by mass or more from the viewpoint of the physical properties of the cured photosensitive resin layer of the negative photosensitive resin composition. It is 20 parts by mass or less.

(D)Solvent The solvent (D) used in this embodiment will be described. Examples of solvents include amides, tyrosines, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl can be used -2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylstyrene, tetramethylurea, acetone, methylethylketone, methyl Isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol mono Methyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, hydroxyline, methylene chloride, 1,2 -Dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. Among them, from the viewpoint of the solubility of the resin, the stability of the resin composition, and the adhesion to the substrate, N-methyl-2-pyrrolidinone, dimethylsulfoxide, and tetramethylurea are preferred. , butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenylglycol, 3-methoxy- N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and tetrahydrofurfuryl alcohol.

Among such solvents, those that completely dissolve the polyimide precursor or the polyimide are particularly preferred. Examples include: N-methyl-2-pyrrolidone, N,N-dimethylacetyl Amine, N,N-dimethylformamide, dimethyltrisoxide, tetramethylurea, γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, 3-butyrate Oxy-N,N-dimethylpropylamine, etc. In particular, from the viewpoint of in-plane uniformity when the photosensitive resin composition is applied to a substrate, γ-butyrolactone and 3-methoxy-N,N-dimethylpropylamine are preferred.

One type of solvent may be used, or two or more types of solvents may be mixed and used. From the viewpoint of appropriately adjusting the stability of the resin composition, two or more types of solvents are preferred. When two or more solvents are included, from the viewpoint of in-plane uniformity, it is preferred that at least 50% by weight of the solvent be γ-butyrolactone or 3-methoxy-N,N-dimethyl. Any of propamides, more preferably γ-butyrolactone.

In the photosensitive resin composition of this embodiment, the usage amount of the solvent is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and further preferably 125 to 500 parts by mass based on 100 parts by mass of the resin (A). Range of parts by mass.

The negative photosensitive resin composition of this embodiment may further contain components other than the above-mentioned (A) to (D) components. The components other than components (A) to (D) are not limited, and examples thereof include heterocyclic compounds, radically polymerizable compounds, thermal base generators, hindered phenol compounds, organic titanium compounds, adhesion assistants, and sensitizers. agents, polymerization inhibitors, etc.

The negative photosensitive resin composition of this embodiment may contain a heterocyclic compound. Examples of heterocyclic compounds include azole compounds, purine derivatives, and the like. Examples of the azole compound include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-benzene Base-1H-triazole, 4-tert-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-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl) methyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'- Hydroxy-5'-tertiary octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole Triazole, 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, etc.

Among them, preferred examples include: 5-amino-1H-tetrazole, tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole.

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-ethyl Adenine, 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- Azoxanthine, etc. and their derivatives.

Moreover, these heterocyclic compounds may be used 1 type or in the form of a mixture of 2 or more types.

When the photosensitive resin composition contains a heterocyclic compound, the compounding amount is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the resin (A), and from the viewpoint of copper adhesion, the amount is more preferably 0.5 to 5 parts by mass. share. When the compounding amount of the (E) heterocyclic compound relative to 100 parts by mass of the (A) resin is 0.1 parts by mass or more, the discoloration of copper is suppressed when the photosensitive resin composition of the present embodiment is formed on copper. , On the other hand, when the compounding amount of the (E) heterocyclic compound relative to 100 parts by mass of the (A) resin is 10 parts by mass or less, the copper adhesion is excellent.

free radical polymerizable compound The negative photosensitive resin composition in this embodiment may also include a radical polymerizable compound to improve the chemical resistance of the hardened relief pattern. In order to obtain good chemical resistance, the radical polymerizable compound is preferably contained at least 5 parts by mass, more preferably at least 10 parts by mass, and more preferably at least 30 parts by mass based on 100 parts by mass of the resin (A). , and more preferably contains 40 parts by mass or more. From the viewpoint of patterning properties, the radically polymerizable compound is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 80 parts by mass or less.

The radically polymerizable compound in this embodiment is not particularly limited as long as it is a compound that undergoes a radical polymerization reaction using a photopolymerization initiator. Preferably it is a (meth)acrylic compound, for example, as follows: The general formula (14) represents: [Chemical 33] {In formula (14), X ₁₁ is an organic group, and L ₁₁ , L ₁₂ and L ₁₃ are each independently a hydrogen atom or an organic group having a valence of 1 to 3 carbon atoms. n ₁₁ is an integer from 1 to 10}.

Examples of radically polymerizable compounds include mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; propylene glycol Or mono- or diacrylates and methacrylates of polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol Diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono- or dimethacrylate of bisphenol A Diacrylate and methacrylate, benzene trimethacrylate, isopropyl acrylate and isopropyl methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylol Propane triacrylate and methacrylate, glycerol di- or triacrylate and methacrylate, pentaerythritol di-, tri-, or tetraacrylate and methacrylate, and ethylene oxide or cyclic esters of these compounds Oxypropane adducts and other compounds, but are not particularly limited to the above. More specifically, compounds represented by the following formulas can be exemplified, but are not limited to the following: [Chemical 34-1] [Chemical 34-2] .

In this specification, when the number of radically polymerizable groups in a radically polymerizable compound is one, it is called monofunctional, and when the number of radically polymerizable groups in a radically polymerizable compound is two or more, it is called monofunctional. , is called x functional group according to the number x of radically polymerizable groups, and sometimes two or more functional groups are collectively called polyfunctional. The radically polymerizable compound may be monofunctional or bifunctional or more. From the viewpoint of chemical resistance, the radically polymerizable compound is preferably three or more functional, more preferably four or more functional, and more preferably six or more functional. On the other hand, from the viewpoint of elongation at break, it is preferably decafunctional or less.

The molecular weight of the radically polymerizable compound is preferably 100 or more, more preferably 200 or more, and more preferably 300 or more. As an upper limit value, 1000 or less is preferable, and 800 or less is further more preferable. By setting it within the above range, chemical resistance and patterning characteristics are improved.

It is preferable that at least one kind of the radically polymerizable compound used in this embodiment is a radically polymerizable compound having at least one radical of a hydroxyl group or a urea group.

Examples of the radically polymerizable compound having a hydroxyl group in the molecule include a structure represented by the following general formula (15): [Chemical 35] {In formula (15), X ₁₁ is an organic group, and L ₁₁ , L ₁₂ and L ₁₃ are each independently a hydrogen atom or an organic group having a valence of 1 to 3 carbon atoms. n ₁₁ is an integer from 1 to 10, n ₁₂ is an integer from 1 to 10}. From the viewpoint of radical reactivity, in the above formula (15), it is preferable that L ₁₁ is a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ are hydrogen atoms. More specifically, compounds represented by the following formulas can be exemplified, but are not limited to the following: [Chemical 36] . By having hydroxyl groups in the molecular structure, chemical resistance becomes particularly good. The number of hydroxyl groups in the molecular structure is preferably 1 or more, and more preferably 2 or more. The upper limit is preferably 10 or less, more preferably 6 or less, still more preferably 3 or less. By setting it within the above range, chemical resistance and adhesion to the substrate become good.

The radically polymerizable compound having a urea group in the molecule can be represented by the following general formula (16): [Chemical 37] {In formula (16), _{X 20} , X ₂₁ , X _{22 ,} and A monovalent organic group having numbers 1 to 20, and at least one of X ₂₀ , X ₂₁ , X ₂₂ , and X ₂₃ is a monovalent organic group having a group represented by the following general formula (17)} [Chemical 38] {In formula (17), L ₁₁ , L ₁₂ and L ₁₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms}. From the viewpoint of radical reactivity, it is preferable that in the above formula (17), L ₁₁ is a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ are hydrogen atoms.

Examples of heteroatoms in this embodiment include oxygen atoms, nitrogen atoms, phosphorus atoms, and sulfur atoms.

In the formula (16), when X ₂₀ , X ₂₁ , _{X 22 ,} and Oxygen atom. The number of carbon atoms is not limited as long as it is 1 to 20. From the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. _X20 , _X21 , _{X22 ,} and By bonding _X20 , _X21 , _{X22 ,} and From the viewpoint of forming hydrogen bonds with other molecules, it is preferred that at least one of X ₂₀ , X ₂₁ , X ₂₂ and X ₂₃ be a hydrogen atom. On the other hand, from the viewpoint of solubility, the number of hydrogen atoms in X ₂₀ , X ₂₁ , X ₂₂ and X ₂₃ is preferably 2 or less. Specifically, compounds represented by the following formula can be exemplified: [Chemical 39] .

In this embodiment, the radically polymerizable compound preferably has at least one hydroxyl group and at least one urea group in the molecule. The radically polymerizable compound having at least one hydroxyl group and at least one urea group in the molecule can be represented by the following general formula (18), for example: [Chemical 40] {In formula (18), X ₃₀ , X ₃₁ , X _{32 ,} and Monovalent organic groups having numbers 1 to 20, at least one of X ₃₀ , X ₃₁ , X ₃₂ , and X ₃₃ is a monovalent organic group having a group represented by the following general formula (19), and at least one is Hydroxy}[Chemical 41] {In formula (19), L ₁₁ , L ₁₂ and L ₁₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms}. From the viewpoint of radical reactivity, it is preferable that in the above formula (19), L ₁₁ is a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ are hydrogen atoms.

In the formula (18), when X ₃₀ , X ₃₁ , _{X 32 ,} and Oxygen atom. The number of carbon atoms is not limited as long as it is 1 to 20. From the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. _X30 , _X31 , _{X32 ,} and By bonding _X30 , _X31 , _{X32 ,} and From the viewpoint of forming hydrogen bonds with other molecules, it is preferred that at least one of X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ be a hydrogen atom. On the other hand, from the viewpoint of solubility, the number of hydrogen atoms in X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ is preferably 2 or less. Specifically, compounds represented by the following formula can be exemplified: [Chemical 42] .

Among the radically polymerizable compounds in this embodiment, the method for producing the radically polymerizable compound having a urea group is not particularly limited. For example, it can be produced by reacting an isocyanate compound having a radically polymerizable group with an amine-containing compound. And get. When the above-mentioned amine-containing compound contains a functional group such as a hydroxyl group that can react with isocyanate, it may also include a compound in which a part of the above-mentioned isocyanate compound reacts with a functional group such as a hydroxyl group.

The radical polymerizable compound in this embodiment can be used individually by 1 type, and is preferably used in mixture of 2 or more types. By mixing and using two or more types, chemical resistance and in-plane uniformity become better. The reason why the in-plane uniformity becomes good is conjecture, but it is considered that when a large amount of only one radically polymerizable compound is added, microphase separation occurs with the resin component in the varnish. For the above reasons, when the radically polymerizable compound is used alone, the amount is preferably 60 parts by mass or less, and more preferably 40 parts by mass or less based on 100 parts by mass of the resin.

When two or more radically polymerizable compounds are used in a mixture, from the viewpoint of controlling the crosslinking density, the number is preferably 6 or less, and more preferably 4 or less.

When a plurality of radically polymerizable compounds are mixed and used, it is preferable that at least one radically polymerizable compound among the plurality of radically polymerizable compounds has a different number of functional groups. When three or more radically polymerizable compounds are used, it suffices that at least one of them has a different number of functional groups, and preferably all the radically polymerizable compounds have different numbers of functional groups. When a plurality of radically polymerizable compounds are used, from the viewpoint of elongation at break, it is preferred to include at least one monofunctional radically polymerizable compound.

When two or more radically polymerizable compounds are used in a mixture, it is preferable to contain at least one type each of a radically polymerizable compound containing a nitrogen atom and a radically polymerizable compound not containing a nitrogen atom. The radically polymerizable compound containing a nitrogen atom is preferably a radically polymerizable compound containing a urea group. Radically polymerizable compounds containing nitrogen atoms can form strong hydrogen bonds and therefore have excellent chemical resistance. However, if multiple types of radically polymerizable compounds containing nitrogen atoms are added, a complex hydrogen bond network structure will be formed. Solubility becomes insufficient.

Thermal base generator The negative photosensitive resin composition of this embodiment may contain a base generator. The base generator refers to a compound that generates a base by heating. By containing a thermal base generator, the imidization of the photosensitive resin composition can be further accelerated.

The type of the thermal base generator is not particularly limited, but examples thereof include an amine compound protected by a third butoxycarbonyl group, the thermal base generator disclosed in International Publication No. 2017/038598, and the like. However, it is not limited to these, and in addition, a well-known thermal base generator can also be used.

Examples of the amine compound protected by a third butoxycarbonyl group include, but are not limited to, compounds in which the amine group of the following compounds is protected by a third butoxycarbonyl group: ethanolamine, 3- Amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1- Amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino- 1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4 -Aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidine Methanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12- Tetraxatetradecane, 1-aza-15-crown ether-5, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxy Heteroundecane, or amino acids and their derivatives.

The compounding amount of the thermal base generator is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass based on 100 parts by mass of the resin (A). The above-mentioned compounding amount is preferably 0.1 parts by mass or more from the viewpoint of the imidization acceleration effect, and is preferably 0.1 parts by mass or more from the viewpoint of the physical properties of the cured photosensitive resin layer of the negative photosensitive resin composition. It is 20 parts by mass or less.

Hindered phenol compounds In order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. The hindered phenol compound is not limited, and examples thereof include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 3-( 3,5-Di-tert-butyl-4-hydroxyphenyl)octadecylpropionate, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)isooctylpropionate , 4,4'-methylene bis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4, 4'-Butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene glycol Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-tert-butyl- 4-Hydroxy-phenylpropylamine), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl -6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-diisocyanurate -Tertibutyl-4-hydroxybenzyl) ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene wait. Furthermore, examples of the hindered phenol compound include: 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris- 2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3 ,5-Tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-second-butyl-3-hydroxy-2,6-dimethylbenzyl Triketone, 1,3,5-tris[4-(1-ethylpropyl)-3- Hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-trione Ethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3, 5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris-2,4,6-(1H, 3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-Tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy -2,5-Dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-trione Butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tritrione-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-tris Ketone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H, 3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2 , 4,6-(1H,3H,5H)-trione, etc., but are not limited thereto.

Among these, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 is particularly preferred ,6-(1H,3H,5H)-triketone, etc.

The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the resin (A). From the viewpoint of light sensitivity characteristics, it is more preferably 0.5 to 10 parts by mass. When the compounding amount of the hindered phenol compound is 0.1 parts by mass or more relative to 100 parts by mass of the resin (A), for example, when the photosensitive resin composition of this embodiment is formed on copper or a copper alloy, copper or copper can be prevented from being Discoloration and corrosion of the alloy. On the other hand, when the compounding amount of the hindered phenol compound is 20 parts by mass or less with respect to 100 parts by mass of the resin (A), the light sensitivity is excellent.

Organotitanium compounds The negative photosensitive resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound, a photosensitive resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

Examples of organic titanium compounds that can be used include organic chemical substances bonded to titanium atoms via covalent bonds or ionic bonds.

Specific examples of organic titanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, in terms of storage stability of the negative photosensitive resin composition and obtaining a good pattern, a titanium chelate compound having two or more alkoxy groups is more preferred. Specific examples are: bis(triethanolamine)titanium diisopropoxide, bis(2,4-glutaric acid)titanium di-n-butoxide, bis(2,4-glutaric acid)titanium diisopropoxide, bis(2,4-glutaric acid)titanium diisopropoxide, Tetramethyl pimelic acid) titanium diisopropoxide, bis(acetyl ethyl acetate) titanium diisopropoxide, etc.

II) Titanium tetraalkoxide compounds: for example, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tetra(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, tetramethyl Titanium oxypropoxide, titanium tetramethylphenolate, titanium tetra-n-nonoxide, titanium tetra-n-propoxide, titanium tetrastearylate, tetrakis[bis{2,2-(allyloxymethyl)butanol}] Titanium etc.

III) Titanium compounds: for example, (pentamethylcyclopentadienyl)titanium trimethoxide, bis(eta5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) ) titanium, bis(eta5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

IV) Monoalkoxy titanium compound: for example, tris(dioctylphosphate)titanium isopropoxide, tris(dodecylbenzenesulfonate)titanium isopropoxide, etc.

V) Oxytitanium compound: for example, bis(glutaric acid)oxytitanium, bis(tetramethylpymelyl)oxytitanium, phthalocyanine titanyloxy, etc.

VI) Titanium tetraacetyl acetonate compound: for example, titanium tetraacetyl acetonate.

VII) Titanate coupling agent: for example, tris(dodecylbenzenesulfonyl)isopropyl titanate, etc.

Among them, the organic titanium compound is preferably selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanium compound from the viewpoint of exhibiting better chemical resistance. At least one compound in the group. Particularly preferred are bis(ethyl acetyl acetate) titanium diisopropoxide, titanium tetra-n-butoxide, and bis(eta5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro- 3-(1H-pyrrol-1-yl)phenyl)titanium.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the resin (A). When the compounding amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited. On the other hand, when the compounding amount is 10 parts by mass or less, storage stability is excellent.

Then auxiliary In order to improve the adhesiveness between the film formed using the negative photosensitive resin composition of this embodiment, and a base material, the negative photosensitive resin composition may optionally contain an adhesive auxiliary agent. Examples of adhesion aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethoxysilane, and γ-aminopropyldimethoxysilane. Glyceroxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacrylyl Oxypropyltrimethoxysilane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-glycidyloxypropylmethylsilane, N-(3-diethoxy Methylmethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamide, benzophenone-3,3'-bis( N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide) Amine)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane , silane coupling agents such as 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and tris(acetyl ethyl acetate) aluminum, tris(acetyl acetone) Aluminum, acetyl ethyl acetate, aluminum diisopropyl and other aluminum-based adhesive additives, etc.

Among these adhesive agents, in terms of adhesive strength, a silane coupling agent is more preferred. When the photosensitive resin composition contains an adhesive agent, the compounding amount of the adhesive agent is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the resin (A).

The silane coupling agent is not limited, and examples thereof include: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace S810), 3-Mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name LS1375, Azmax Co., Ltd.: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name) Trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyl diethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane Silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane , 2-mercaptoethyl tripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane Oxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, etc.

In addition, the silane coupling agent is not limited, and examples thereof include: N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name LS3610, product of Azmax Co., Ltd.: Trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: Trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl) urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxypropyl) Silylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-Dimethoxypropoxysilylpropyl)urea, N-(3 -Methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N -(3-Tripropoxysilylethyl)urea, N-(3-Tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl )urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxy Silane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0) Co., Ltd.: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), etc.

Examples of the silane coupling agent include: 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxysilylethyl) Pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-tert-butyl hydroxycarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane , Tetrakis-n-butoxysilane, Tetrakis-isobutoxysilane, Tetrakis-tertiary-butoxysilane, Tetrakis(methoxyethoxysilane), Tetrakis(methoxy-n-propoxysilane), Tetrakis(ethoxyethoxysilane),tetrakis(methoxyethoxyethoxysilane),bis(trimethoxysilyl)ethane,bis(trimethoxysilyl)hexane,bis(trimethoxysilyl)hexane Ethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)ethane yl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-tert-butoxy diethyloxysilane, di-isobutoxyaluminumoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenyl Silane diol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethyl Oxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylsilanol phenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol , n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyl diphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, etc. , but not limited to such.

The silane coupling agents exemplified above can be used alone or in combination. Among the silane coupling agents exemplified above, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, and diphenylsilane are preferred. Diol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and silanols having a structure represented by the following formula Mixture: [Chemical 43] . When using a silane coupling agent, the compounding amount is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the resin (A).

Sensitizer The negative photosensitive resin composition of this embodiment may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michelone, 4,4'-bis(diethylamino)benzophenone, and 2,5-bis(4'-diethylaminobenzophenone). Methyl)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)- 4-Methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamonide Indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminobenzene 1,3-bis(4'-dimethylaminophenylidene)benzothiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-ethyl-7-dimethyl Aminocoumarin, 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-𠰌linylbenzophenone, isoamyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole , 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoethyl, 2-(p-dimethylaminostyryl) Benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These can be used individually or in combination of 2 to 5 types, for example.

When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the compounding amount is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the resin (A).

polymerization inhibitor In addition, the negative photosensitive resin composition of this embodiment may optionally contain a polymerization inhibitor to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition especially when it is stored in a solution containing a solvent. sex. As polymerization inhibitors, it is possible to use: hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenylnaphthylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid , 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1- Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso- N-phenylhydroxylamine ammonium salt, N-nitroso-N-(1-naphthyl)hydroxylammonium ammonium salt, etc.

＜Manufacturing method of hardened relief pattern and semiconductor device＞ The manufacturing method of the hardened relief pattern of this embodiment includes the following steps: (1) Coating the above-mentioned negative photosensitive resin composition of this embodiment on a substrate, and forming a photosensitive resin layer on the above substrate; ( 2) Expose the above-mentioned resin layer; (3) Develop the above-mentioned resin layer after exposure to form a relief pattern; (4) Heat-process the above-mentioned relief pattern to form a hardened relief pattern.

(1) Resin layer formation step In this step, the negative photosensitive resin composition of this embodiment is applied to a base material, and then dried if necessary to form a photosensitive resin layer. As the coating method, methods conventionally used for coating photosensitive resin compositions can be used, such as spin coaters, rod coaters, blade coaters, and curtain coaters. , the method of coating with a screen printing machine, the method of spray coating with a spray coater, etc.

(2)Exposure step In this step, exposure devices such as contact aligners, mirror projections, and stepper machines are used, and ultraviolet light sources are used to illuminate the above-mentioned structures through a patterned mask or a main mask (reticle) or directly. The resin layer is exposed.

(3) Embossed pattern formation step In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from conventionally known photoresist development methods, such as spin spray method, liquid coating method, immersion method accompanied by ultrasonic treatment, etc. method to use. In addition, after development, post-development baking at any combination of temperature and time may be performed as necessary for the purpose of adjusting the shape of the relief pattern.

As a developer used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of this good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ -Butyrolactone, α-acetyl-γ-butyrolactone, etc. Preferable examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent based on the solubility of the polymer in the negative photosensitive resin composition. Moreover, each solvent can also be used in combination of 2 or more types, for example, several types.

(4) Hardened relief pattern formation step In this step, the relief pattern obtained by the above-mentioned development is subjected to heat treatment to volatilize the photosensitive component, and the polyimide precursor (A1) is imidized, thereby converting it into a hardened relief containing polyimide. Convex pattern. As a heat treatment method, various methods can be selected, such as a method using a heating plate, a method using an oven, and a method using a temperature-raising oven with a settable temperature control program. The heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. The temperature of the heat treatment is preferably 230°C or lower, more preferably 200°C or lower, further preferably 180°C or lower. As the atmosphere gas during heat hardening, air can be used, and inert gases such as nitrogen and argon can also be used.

<Polyimide> The polyimide of this embodiment can be produced by curing a negative photosensitive resin composition. Moreover, another aspect of the present invention also provides a method for manufacturing a polyimide cured film, which includes the following steps: imidizing the negative photosensitive resin composition described above to form an imidization rate of 80 ~100% polyimide hardener. The structure of the polyimide contained in the hardened relief pattern formed from the above-mentioned polyimide precursor composition is represented by the following general formula. [Chemical 44] {In the above general formula, X ₁ and Y ₁ are the same as X ₁ and Y ₁ in the general formula (5), and m is a positive integer}

For the same reason, the preferred X ₁ and Y ₁ in the general formula (5) are also preferred in the polyimide having the structure represented by the above general formula. In the above general formula, the number m of repeating units is not particularly limited and may be an integer from 2 to 150.

＜Semiconductor Device＞ This embodiment also provides a semiconductor device having a hardened relief pattern obtained by the above-described method of manufacturing a hardened relief pattern. Therefore, it is possible to provide a semiconductor device having a substrate as a semiconductor element and a hardened relief pattern of polyimide formed on the base material by the above-mentioned hardened relief pattern manufacturing method. Furthermore, it can also be applied to a manufacturing method of a semiconductor device using a semiconductor element as a base material and including the above-mentioned manufacturing method of the hardened relief pattern of this embodiment as a part of the steps. The semiconductor device can be used as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or has a bump by forming a hardened embossed pattern formed by the method of manufacturing a hardened embossed pattern of this embodiment. The protective film, etc. of a structured semiconductor device is manufactured by combining it with a known manufacturing method of a semiconductor device.

＜Display device＞ This embodiment provides a display device including a display element and a cured film provided on an upper part of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the hardened relief pattern can be directly connected to the display element and laminated on it, or can be laminated on the display element with another layer in between. Examples of the cured film include surface protective films, insulating films, and planarizing films for TFT (thin-film transistor) liquid crystal display elements and color filter elements, MVA (Multi-Domain Vertical Alignment) , protrusions for multi-domain vertical alignment) type liquid crystal display devices, and partition walls for cathodes of organic EL (Electroluminescence, electroluminescence) elements.

The negative photosensitive resin composition of this embodiment is preferably a negative photosensitive resin composition for forming an insulating member or for forming an interlayer insulating film. In addition to its application in semiconductor devices as described above, the negative photosensitive resin composition of this embodiment can also be used for interlayer insulating films of multilayer circuits, cover coatings of flexible copper foil boards, and solder resists. film, and liquid crystal alignment film. [Example]

Hereinafter, this embodiment will be specifically described using examples, but this embodiment is not limited thereto. In the Examples, Comparative Examples, and Production Examples, the physical properties of the resin or negative photosensitive resin composition were measured and evaluated according to the following method.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene conversion) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Pipe string: Shodex KD-806M made by Showa Denko Co., Ltd. 2 pieces in series, or Shodex 805M/806M made by Showa Denko Co., Ltd. in series Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd. Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL/min.

(2) The hardened relief pattern on Cu was produced using a sputtering device (L-440S-FHL type, manufactured by CANON ANELVA Co., Ltd.) on a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm), 200 nm thick titanium (Ti) and 400 nm thick copper (Cu) are sequentially sputtered. Next, a coater developer (D-Spin60A type, manufactured by SOKUDO Corporation) was used to spin-coat the photosensitive resin composition prepared by the following method on the wafer, and a heating plate was used to heat the photosensitive resin composition at 110° C. Pre-bake for 180 seconds to form a coating film about 10 μm thick. Using a mask with a test pattern, the coating film was irradiated with i-rays using Prisma GHI (manufactured by Ultratech) with an energy of 50 to 650 mJ/cm ² . Then, using cyclopentanone as a developer, the coating film was spray developed with a coating developing machine (D-Spin60A type, manufactured by SOKUDO Co., Ltd.) for 1.4 times the time until the unexposed portion was completely dissolved and disappeared. Use propylene glycol methyl ether acetate to rotate and spray wash for 10 seconds to obtain a relief pattern on Cu.

Using a programmed temperature curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.), the wafer with the relief pattern formed on Cu was heated at 230°C for 2 hours in a nitrogen atmosphere, thereby forming the wafer on Cu. A hardened relief pattern containing approximately 6 to 9 μm thick resin is obtained.

(3) High temperature storage test of hardened relief pattern on Cu and subsequent pore area evaluation

Using a programmed temperature curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.), the wafer with the hardened relief pattern formed on Cu was heated in air at 150°C for 168 hours. Then, a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.) was used to completely remove the resin layer on Cu by plasma etching. Plasma etching conditions are as follows. Output: 133 W Gas type, flow rate: _O2 : 40 mL/min＋CF ₄ : 1 mL/min Gas pressure: 50 Pa Mode: Difficult mode Etching time: 1800 seconds

The Cu surface after all the resin layer was removed was observed with FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Co., Ltd.), and the pores in the Cu layer were calculated using image analysis software (A image kun, manufactured by Asahi Kasei Co., Ltd.) The area occupied by the surface. When the total area of pores when evaluating the photosensitive resin composition described in Comparative Example 1 is 100%, the total area ratio of pores is less than 50% and is judged as "A", and the total area ratio of pores is If the ratio is 50% or more and less than 100%, it is judged as "B", and if the total area ratio of pores is 100% or more, it is judged as "C".

(3)Copper adhesion evaluation Using a sputtering device (L-440S-FHL type, manufactured by CANON ANELVA Co., Ltd.), 200 nm thick titanium was sequentially sputtered on a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm) (Ti), 400 nm thick copper (Cu). Then, the photosensitive resin composition was spin-coated on the wafer so that the film thickness after hardening became about 9 μm and dried. Then, the entire surface was exposed using a programmed temperature-increasing curing oven (VF-2000 model, Koyo Lindberg). company), heat it at 230°C for 2 hours in a nitrogen atmosphere to obtain a hardened relief pattern (thermally hardened polyimide coating). For the heat-treated film, the adhesion characteristics between the copper substrate and the cured resin coating film were evaluated based on the following criteria using the cross-cutting method of the JIS K 5600-5-6 standard. A: The number of grids of the hardened resin coating film adhered to the substrate is between 80 and 100 B: The number of grids of the hardened resin coating film adhered to the substrate is more than 40 and less than 80 C: The number of grids of the hardened resin coating adhered to the substrate does not reach 40

(4) Storage stability evaluation The photosensitive resin composition prepared by the following method was placed in a sealed container and left to stand in an incubator at 40° C. for 4 days. The smaller the viscosity change of the composition, the better the storage stability. Storage stability was evaluated based on the following criteria. A: The viscosity of the photosensitive resin composition is 35 poise or more and less than 45 poise. B: The viscosity of the photosensitive resin composition is above 45 poise or less than 35 poise. C: Photosensitive resin composition gels

Production Example 1: (A) Synthesis of polyimide precursor A1 Add 124.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) to a separable container with a capacity of 2 L In a flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone, stir at room temperature, and add 81.5 g of pyridine while stirring to obtain a reaction mixture. After the exotherm caused by the reaction ended, the reaction mixture was allowed to cool to room temperature and left for 16 hours.

Then, under cooling in an ice bath, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture while stirring for 20 minutes. While stirring for 30 minutes, 93.0 g of 4,4'-oxydiphenylamine (ODA) was suspended in 350 mL of γ-butyrolactone. Furthermore, after stirring at room temperature for 4 hours, 30 mL of ethanol was added, the mixture was stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate generated in the reaction mixture is removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The generated crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polyimide precursor A1). The molecular weight of polyimide precursor A1 was measured using gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 24,000.

Production Example 2: (A) Synthesis of polyimide precursor A2 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 124.0 g and 3,3 of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. Except for 29.4 g of ',4,4'-biphenyltetracarboxylic dianhydride (BPDA), the reaction was carried out in the same manner as described in the above-mentioned Production Example 1 to obtain a polymer (polyimide precursor). Thing A2). The molecular weight of the polyimide precursor A2 was measured using gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 24,000.

Production Example 3: (A) Synthesis of polyimide precursor A3 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was used instead of 124.0 g and 3,3',4 of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. Except for 29.4 g of 4'-biphenyltetracarboxylic dianhydride (BPDA), the reaction was carried out in the same manner as described in the above-mentioned Production Example 1 to obtain a polymer (polyimide precursor A3). The molecular weight of polyimide precursor A3 was measured using gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 21,000.

Production Example 4: (A) Synthesis of polyimide precursor A4 In addition to using 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example 3, The reaction was carried out in the same manner as described in the above-mentioned Production Example 1 to obtain polymer (A4). The molecular weight of the polymer (A4) was measured using gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 21,000.

Production Example 5: (A) Synthesis of polyimide precursor A5 The method was the same as that described in Production Example 1 except that 48.1 g of p-phenylenediamine (p-PD) was used instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example 3. react to obtain polymer (A5). The molecular weight of the polymer (A5) was measured using gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 19,000.

Production Example 6: (A) Synthesis of polyimide precursor A6 62.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 65.4 g of pyromellitic dianhydride (PMDA) were used instead of 4,4'-oxydiphthalic dianhydride (in Production Example 4). ODPA) 155.1 g, the reaction was carried out in the same manner as described in the above-mentioned Production Example 1, and polymer (A6) was obtained. The molecular weight of the polymer (A6) was measured using gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 20,000.

Production Example 7: (A) Synthesis of polyimide precursor A7 In addition to using 182.5 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example 3, The reaction was carried out in the same manner as described in the above-mentioned Production Example 1 to obtain a polymer (A7). The molecular weight of the polymer (A7) was measured using gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 25,000.

Production Example 8: (A) Synthesis of polyimide precursor A8 260.3 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic dianhydride (BPADA) was used instead of 4,4'-oxydiphthalic acid dianhydride in Production Example 4. Except for 155.1 g of anhydride (ODPA), the reaction was carried out in the same manner as described in the above-mentioned Production Example 1 to obtain a polymer (A8). The molecular weight of the polymer (A8) was measured using gel permeation chromatography (standard polystyrene conversion), and the result was that the weight average molecular weight (Mw) was 25,000.

Production Example 9: (A) Synthesis of polyimide A9 Add 64.1 g (0.20 mol), 97.7 g (0.22 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA) and 500 g of DMAc, and stir to dissolve TFMB and 6FDA in DMAc. Furthermore, under nitrogen flow, the polymerization reaction was continued at room temperature for 12 hours to obtain a polyamide solution. After adding 16 g of pyridine to the obtained polyamic acid solution, 82 g of acetic anhydride was added dropwise at room temperature. Thereafter, the liquid temperature is further maintained at 20 to 100°C, and stirring is continued for 24 hours to perform an imidization reaction to obtain a polyimide solution.

In a container with a capacity of 5 L, add the obtained polyimide solution to 1,000 g of methanol while stirring to precipitate the polyimide resin. Thereafter, a suction filtration device was used to filter and separate the solid polyimide resin, and then 1,000 g of methanol was used for washing. Then, using a vacuum dryer, drying was performed at 100°C for 24 hours, and then dried at 200°C for 3 hours. Through the above operation, a polyimide powder having an acid anhydride group at the terminal, that is, polymer (A-11) is obtained. The molecular weight of polymer A-11 was measured using gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 25,000.

<Example 1> Using the polyimide precursor A1, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. A1 as (A) resin: 100 g, B1 as (B) flavonoids: quercetin hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g, C1 as (C) photopolymerization initiator: TR - 3 g of PBG-3057 (manufactured by TRONLY Co., Ltd.) and 40 g of NK ESTER A-9300 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as a radical polymerizable compound were dissolved in γ-butyrolactone (hereinafter referred to as GBL, Mitsubishi Chemical Co., Ltd. (manufactured by Toray Fine Chemical Co., Ltd.): 80 g and dimethylstyrene (hereinafter referred to as DMSO, manufactured by Toray Fine Chemical Co., Ltd.): 20 g in a mixed solvent. The viscosity of the resulting solution was adjusted to about 40 poise by adding a necessary amount of GBL:DMSO=80:20 solution to prepare a photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

<Examples 2 to 18, Comparative Examples 1 to 4> A photosensitive resin composition similar to Example 1 was prepared except that it was prepared at the mixing ratio shown in Table 1, and the same evaluation as Example 1 was performed. The results are shown in Table 1. The (A) resins and (B) flavonoids described in Table 1 are as follows.

A1: The polyimide precursor described in Production Example 1 A2: The polyimide precursor described in Production Example 2 A3: The polyimide precursor described in Production Example 3 A4: The polyimide precursor described in Production Example 4 A5: The polyimide precursor described in Production Example 5 A6: The polyimide precursor described in Production Example 6 A7: The polyimide precursor described in Production Example 7 A8: The polyimide precursor described in Production Example 8 A9: Polyimide described in Production Example 9

B1: Quercetone hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) B2: Myricetin (manufactured by Tokyo Chemical Industry Co., Ltd.) B3: Flavonoids (manufactured by Tokyo Chemical Industry Co., Ltd.) B4: Hesperetin (manufactured by Tokyo Chemical Industry Co., Ltd.) B5: Naringenin (manufactured by Tokyo Chemical Industry Co., Ltd.) B1': 7-hydroxyflavone (manufactured by Tokyo Chemical Industry Co., Ltd.) B2': 3',4'-dihydroxyflavone (manufactured by Tokyo Chemical Industry Co., Ltd.) B3': Curcumin (manufactured by Tokyo Chemical Industry Co., Ltd.) B4': (+)-catechin hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Table 1] Table 1 (A)Resin (B) Flavonoids Evaluation results Kind parts by mass Kind parts by mass copper adhesion copper pores Storage stability Example 1 A1 100 B1 10 A A A Example 2 A1 100 B2 10 A A A Example 3 A1 100 B3 10 A B B Example 4 A1 100 B1 3 B B B Example 5 A1 100 B1 20 B A B Example 6 A2/A3 50/50 B1 10 A A A Example 7 A3 100 B1 10 A A A Example 8 A4 100 B1 10 A A A Example 9 A5 100 B1 10 A A A Example 10 A6 100 B1 10 A A A Example 11 A7 100 B1 10 A A A Example 12 A8 100 B1 10 A A A Example 13 A9 100 B1 10 B B B Example 14 A1 100 B4 10 B B B Example 15 A1 100 B5 10 B B B Comparative example 1 A1 100 C C C Comparative example 2 A1 100 B1' 10 C B C Comparative example 3 A1 100 B2' 10 C B B Comparative example 4 A1 100 B3' 10 C B B Comparative example 5 A1 100 B4' 10 C B A

As shown in Table 1, regarding the negative photosensitive resin composition of Example 1, the copper adhesiveness was A, and the copper pores were also A. The photosensitive resin compositions of Examples 2 to 15 were all evaluated as follows: copper adhesion, copper voids, and storage stability were B or higher. On the other hand, in Comparative Example 1, the copper adhesion, copper pores, and storage stability were all C, and in Comparative Examples 2 to 5, the copper adhesion was C. [Industrial availability]

By using the photosensitive resin composition of the present invention, a hardened relief pattern excellent in copper adhesion, suppression of copper pores, and storage stability can be obtained. The present invention can be preferably used in the field of photosensitive materials useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (12)

A negative photosensitive resin composition characterized by containing the following components: (A) at least one resin selected from the group consisting of (A1) polyimide precursor and (A2) polyimide, (B) At least one flavonoid represented by the following general formula (1) or (1-2), [Chemical 1] [Chemicalization 2] (In the formula, R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents, R ₂ is a hydrogen atom or a hydroxyl group, and R ₃ to R ₆ are selected from a hydrogen atom, a hydroxyl group, or a methoxy group. group in the group, and at least one of R ₃ to R ₆ is a hydroxyl group) (C) photopolymerization initiator, and (D) solvent. The negative photosensitive resin composition according to claim 1, wherein the flavonoid (B) is a compound represented by the following general formula (2), [Chemical 3] (In the formula, n ₁ is an integer from 1 to 3, n ₂ is 0 or 1, and n ₃ is an integer from 1 to 2). The negative photosensitive resin composition according to claim 2, wherein the flavonoid (B) is a compound represented by the following general formula (3), [Chemical 4] (In the formula, n ₄ is 2 or 3, n ₅ is 1 or 2). The negative photosensitive resin composition according to claim 2, wherein the flavonoid (B) is a compound represented by the following general formula (4), [Chemical 5] (In the formula, n ₄ is 2 or 3). The negative photosensitive resin composition according to claim 1, wherein the flavonoid (B) is a compound represented by the following general formula (2-2), [Chemical 6] (In the formula, n ₂ is 0 or 1, and R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents). The negative photosensitive resin composition of claim 5, wherein the flavonoid (B) is a compound represented by the following general formula (3-2), [Chemical 7] (In the formula, R ₁ is an aromatic group having at least one hydroxyl group and may further have other substituents). The negative photosensitive resin composition of claim 1, wherein the polyimide precursor (A1) contains a polyimide precursor having a structural unit represented by the following general formula (5): [Chemical 8] {In formula (5), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁₁ and R ₁₂ are independently hydrogen atoms or monovalent The organic base}. The negative photosensitive resin composition of claim 7, wherein in the above general formula (5), at least one of R ₁ and R ₂ has a structural unit represented by the following general formula (6): [Chemical 9] {In formula (6), L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer from 2 to 10}. The negative photosensitive resin composition of claim 1, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film. A method of manufacturing a hardened relief pattern, which includes the following steps: (1) Coating the negative photosensitive resin composition according to any one of claims 1 to 9 on the substrate to form a photosensitive resin layer on the substrate; (2) Expose the above-mentioned photosensitive resin layer; (3) Develop the above-mentioned exposed photosensitive resin layer to form a relief pattern; (4) Heat the above embossed pattern to form a hardened embossed pattern. As claimed in claim 10, the method for manufacturing a hardened relief pattern, wherein the heat treatment in step (4) is a heat treatment below 230°C. A method for producing polyimide, which includes hardening the negative photosensitive resin composition according to any one of claims 1 to 9.