TW201944175A - Negative photosensitive resin composition and method for producing cured relief pattern capable of obtaining a relatively high imidization rate and chemical resistance in low-temperature curing - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition capable of obtaining a relatively high imidization rate and chemical resistance in low-temperature curing, exhibiting a relatively high copper adhesion, and releasing less gas in a heating step after thermal curing, and also provides a method for producing a cured relief pattern by using the negative photosensitive resin composition. The negative photosensitive resin composition of the present invention includes (A) a polyimide precursor, (B) an imide compound represented by the following general formula (1), and (C) a photo-polymerization initiator. In the formula (1), A1 is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, and an amino group, and A2 is a divalent organic group having 1 to 20 carbon atoms.

Description

Negative photosensitive resin composition and method for producing hardened relief pattern

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

Previously, polyimide resins and polybenzoxazole resins, which had excellent heat resistance, electrical properties, and mechanical properties, were used as insulating materials for electronic parts, and passivation films, surface protective films, and interlayer insulating films for semiconductor devices. , Phenolic resin, etc. Among these resins, the supplier in the form of a photosensitive resin composition can easily form a heat-resistant float by a thermally-imidized treatment using coating, exposure, development, and curing of the composition. Convex pattern film. This type of photosensitive resin composition has a feature that the number of steps can be greatly reduced compared to the conventional non-photosensitive material.

On the other hand, in recent years, from the viewpoints of increasing the integration degree and computing functions, and reducing the size of the wafer, the mounting method (package structure) of the semiconductor device on the printed wiring board has also changed. From the previous installation method using metal pins and lead-tin eutectic soldering, it has gradually changed to BGA (Ball Grid Array), CSP (Chip Size Package) For example, a structure in which a polyimide film is brought into direct contact with a solder bump is used. Furthermore, a structure such as a redistribution layer having a surface area of a semiconductor wafer having a plurality of layers larger than the area of the semiconductor wafer such as FO (fan-out) is also proposed.

Furthermore, when materials such as polyimide, polybenzoxazole, and phenol-based resin are used as the redistribution layer of the package structure, a metal wiring layer forming step is performed after the pattern of the resin layer is formed. The metal wiring layer is usually formed by plasma-etching the surface of the resin layer to roughen the surface, and then forming a metal layer as a seed layer of the plating film by sputtering to a thickness of 1 μm or less. The metal layer serves as an electrode, and a metal wiring layer is formed by electroplating. At this time, generally, titanium (Ti) is used as the metal to be the seed layer, and copper (Cu) is used as the metal of the rewiring layer formed by electroplating. However, the conventional photosensitive resin composition has a problem in that the resin and copper are separated due to insufficient adhesion between the resin and copper.

As a means to solve the above-mentioned problems, a method of providing a polyfluorene imide that exhibits good adhesion to copper by introducing an unsaturated heterocyclic group or the like to the terminal of the polyfluorene imine has been disclosed (see Patent Document 1).
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 6-106678

[Problems to be solved by the invention]

However, the polyimide described in Patent Document 1 has a problem that heat curing requires heating at 250 ° C to 400 ° C. Due to the variety of package structures, the resin used for the redistribution layer is required to be hardened at a low temperature. However, if the curing temperature is lowered, the imidization rate and chemical resistance of the polyimide precursor will be reduced, and the problem of outgassing in other heating steps after heat curing will occur.

Therefore, the object of the present invention is to provide a high-imidation ratio and chemical resistance that can be obtained in low-temperature hardening, and further have high copper adhesion, and less negative gas outgassing during the heating step after thermal hardening. Type photosensitive resin composition, and a method for producing a hardened relief pattern using the negative type photosensitive resin composition.
[Technical means to solve the problem]

The present inventors have found that the above-mentioned problems can be solved by combining a specific photosensitive resin with a fluoreneimine compound, and have completed the present invention. That is, this invention is as follows.
[1]
A negative photosensitive resin composition comprising:
(A) a polyimide precursor;
(B) a fluorene imine compound represented by the following general formula (1)
[Chemical 1]

{In formula (1), A ₁ is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, and an amine group, and A ₂ is a divalent organic group having 1 to 20 carbon atoms}; and
(C) Photopolymerization initiator.
[2]
The negative photosensitive resin composition according to item 1, wherein A ₁ of the (B) fluorene imine compound represented by the general formula (1) is any one of a hydroxyl group and an amine group.
[3]
The negative photosensitive resin composition as described in the item, where represents the above general formula (1) (B) A compound of the imine XI _is hydroxy.
[4]
The negative-type photosensitive resin composition according to any one of items 1 to 3, wherein the (B) fluorene imine compound is represented by the following general formula (2)
[Chemical 2]

{In formula (2), A ₁ is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, and an amine group, and A ₃ is a group selected from the group consisting of a nitro group, a hydroxyl group, and a monovalent organic group , B is an integer from 0 to 4, and when b is 2 or more, a plurality of A ₃ may form a ring structure together}.
[5]
The negative-type photosensitive resin composition according to any one of items 1 to 4, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (3) Thing
[Chemical 3]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ And at least one of R ₂ is a monovalent organic group represented by the following general formula (4)
[Chemical 4]

(In the formula, 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 of 2 to 10)}.
[6]
The negative-type photosensitive resin composition according to item 5, wherein the X ₁ contains a tetravalent organic group represented by the following general formula
[Chemical 5]

{In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ value of 1 in the group, m is an integer selected from 0 to 3 of}.
[7]
The negative-type photosensitive resin composition according to item 5, wherein the X ₁ contains a tetravalent organic group represented by the following general formula
[Chemical 6]

{In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ value of 1 in the group, m is an integer selected from 0 to 3 of}.
[8]
The negative-type photosensitive resin composition according to item 5, wherein the Y ₁ contains a divalent organic group represented by the following general formula
[Chemical 7]

{In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ of the monovalent group of 1, and n is an integer selected from 0 to 4} of .
[9]
The negative-type photosensitive resin composition according to item 5, wherein the Y ₁ contains a divalent organic group represented by the following general formula
[Chemical 8]

{In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ of the monovalent group of 1, and n is an integer selected from 0 to 4} of .
[10]
The negative photosensitive resin composition according to any one of items 1 to 9, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5) Thing
[Chemical 9]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[11]
The negative-type photosensitive resin composition according to any one of items 1 to 10, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (6) Thing
[Chemical 10]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[12]
The negative-type photosensitive resin composition according to any one of items 1 to 11, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (7) Thing
[Chemical 11]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[13]
The negative photosensitive resin composition according to any one of items 1 to 12, wherein the (A) polyimide precursor comprises:
[Chemical 12]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}
Represented by the structural unit; and the following general formula (6):
[Chemical 13]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above; wherein R ₁ , R ₂ , and n ₁ in formula (5) and R ₁ , R ₂ , and n ₁ are independently selected}
The structural unit represented.
[14]
The negative photosensitive resin composition according to any one of items 1 to 13, comprising:
100 parts by mass of the above (A) polyimide precursor;
0.1 to 30 parts by mass of the above (B) fluorenimide compound based on 100 parts by mass of the (A) polyfluorenimide precursor; and 100 parts by mass of the (A) polyimide precursor 0.1 to 20 parts by mass of the (C) photopolymerization initiator.
[15]
The negative photosensitive resin composition according to any one of items 1 to 14, further comprising 0.1 to 30 parts by mass of (D) hot alkali based on 100 parts by mass of (A) a polyimide precursor. Generating agent.
[16]
The negative photosensitive resin composition according to any one of items 1 to 15, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an insulating member.
[17]
The negative photosensitive resin composition according to any one of items 1 to 16, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film.
[18]
A method for manufacturing a hardened relief pattern includes the following steps:
(1) applying the negative photosensitive resin composition according to any one of items 1 to 17 to a substrate, and forming a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after exposure to form a relief pattern; and
(4) A heat treatment is performed on the embossed pattern to form a hardened embossed pattern.
[19]
The method for producing a hardened relief pattern according to item 18, wherein the heat treatment is a heat treatment at 200 ° C or lower.
[20]
The method for producing a hardened relief pattern according to item 19, wherein the heat treatment is a heat treatment of 180 ° C or lower.
[twenty one]
A method for producing polyimide, comprising curing the negative photosensitive resin composition according to any one of items 1 to 17.
[Effect of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition capable of obtaining a high sulfonium imidization rate and chemical resistance, further improving copper adhesion, and having less outgassing in a heating step after heat curing, And a method for producing a hardened relief pattern using the photosensitive resin composition.

Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof.
In addition, in the case where a plurality of structures represented by the same symbol in the general formula are present in the molecule throughout the specification, they may be the same as or different from each other.

<Negative photosensitive resin composition>
The negative photosensitive resin composition of this embodiment includes:
(A) a polyimide precursor;
(B) a fluorene imine compound represented by the following general formula (1)
[Chemical 14]

{In formula (1), A ₁ is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, and an amine group, and A ₂ is a divalent organic group having 1 to 20 carbon atoms};
(C) Photopolymerization initiator.

From the viewpoint of obtaining higher chemical resistance, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor and 100 parts by mass of (A) polyimide precursor. 0.1 to 30 parts by mass of the (B) fluorene imine compound and 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyamidine precursor.

(A) Polyimide precursor The resin component contained in (A) polyimide precursor based negative photosensitive resin composition in this embodiment is converted into polyimide by performing thermal cyclization treatment. amine. (A) The polyimide precursor is not limited in structure as long as it is a resin that can be used in a negative-type photosensitive resin composition, and is preferably non-alkali soluble. By making the polyimide precursor non-alkali soluble, higher chemical resistance can be obtained. The so-called polyfluorene imide precursor is non-alkali soluble and can be defined as follows. Using a coating and developing machine (D-Spin60A type, manufactured by SOKUDO), a solution prepared by dissolving 30% by mass of a polyimide precursor in γ-butyrolactone was spin-coated on a wafer, and a hot plate Pre-bake at 110 ° C for 180 seconds to form a coating film with a thickness of about 5 μm. This coating film was subjected to immersion development for 60 seconds by using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution, and washed with water for 10 seconds to measure the film thickness of the coating film. Based on the film thickness of the coating film before and after development, the film thickness reduction rate (1 nm / second) in the above development step was calculated. If the reduction rate of the film thickness is 1 nm / second or less, the polyimide precursor can be said to be non-alkali soluble.

The polyimide precursor is preferably a polyimide having a structure represented by the following general formula (3).
[Chemical 15]

{Wherein X ₂ is a tetravalent organic group, Y ₂ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, R ₁ And at least one of R ₂ is a monovalent organic group represented by the following general formula (4)
[Chemical 16]

(In the formula, 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 of 2 to 10)}
The ratio of R ₁ and R ₂ to a hydrogen atom in the general formula (3) is preferably 10% or less, more preferably 5% or less, and even more preferably 1% based on the entire mole numbers of R ₁ and R ₂ . the following. The ratio of R ₁ and R ₂ in the general formula (3) to the monovalent organic group represented by the general formula (4) is preferably 70% or more based on the molar number of the entire R ₁ and R ₂ . It is more preferably 80% or more, and still more preferably 90% or more. From the viewpoints of light-sensitive properties and storage stability, the ratio of the hydrogen atom and the ratio of the organic group of the general formula (4) are preferably in the above ranges.

N ₁ in the general formula (3) is not limited as long as it is an integer of 2 to 150. In terms of the photosensitive characteristics and mechanical characteristics of the negative photosensitive resin composition, it is preferably an integer of 3 to 100, and more It is preferably an integer from 5 to 70.

In terms of both heat resistance and photosensitivity, in the general formula (3), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably a -COOR ₁ group and- The COOR ₂ group and the -CONH- group are ortho aromatic groups or alicyclic aliphatic groups. Specific examples of the tetravalent organic group represented by X ₁ include an organic group having 6 to 40 carbon atoms including an aromatic ring, and a group having a structure represented by the following general formula (20), for example.
[Chemical 17]

{In the formula, R6 is selected from the group consisting of a hydrogen atom, the group consisting of a fluorine atom, C ₁ ~ C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ of the monovalent group of 1, l is selected from 0 to 2 of Integer, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4}, but is not limited thereto. The structure of X ₁ may be one type or a combination of two or more types. In terms of having both heat resistance and light-sensitive properties, an X ₁ group having a structure represented by the formula (20) is particularly preferred.

As the X ₁ group, the following formula is particularly preferred among the structures represented by the above formula (20) from the viewpoints of the fluorene imidization rate, outgassing property, copper adhesion, and chemical resistance during low-temperature heating. Structure of representation
[Chemical 18]

{In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ value of 1 in the group, m is an integer selected from 0 to 3 of}.

In terms of both heat resistance and photosensitivity, in the general formula (3), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms. Examples thereof include the following formula (21) Structure of representation
[Chemical 19]

{In the formula, R6 is selected from the group consisting of a monovalent group consisting of a hydrogen atom, a fluorine atom, C ₁ ~ C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ of the middle, and n is selected from 0 to 4, An integer}, but it is not limited to them. The structure of Y ₁ may be one type or a combination of two or more types. In terms of having both heat resistance and light-sensitive properties, a Y ₁ group having a structure represented by the formula (21) is particularly preferred.

As the Y ₁ group, the following formula is particularly preferred among the structures represented by the above formula (21) from the viewpoints of sulfonium imidization rate, outgassing property, copper adhesion, and chemical resistance during low-temperature heating. Structure of representation
[Chemical 20]

{In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ of the monovalent group of 1, and n is an integer selected from 0 to 4} of .

In the general formula (4), L _{1 is} preferably a hydrogen atom or a methyl group, and from the viewpoint of photosensitivity, L ₂ and L _{3 are} preferably a hydrogen atom. Moreover, m ₁ is an integer of 2 or more and 10 or less from a viewpoint of a photosensitive characteristic, Preferably it is an integer of 2 or more and 4 or less.

In one embodiment, the (A) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (5).
[Chemical 21]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

In the general formula (5), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the general formula (4). (A) Polyfluorene imide precursor By including a polyfluorene imide precursor represented by the general formula (5), chemical resistance becomes particularly high. Moreover, it is also preferable from a viewpoint of the imidation ratio, gas release property, and copper adhesiveness at the time of low temperature heating.

In one embodiment, the (A) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (6).
[Chemical 22]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

In the general formula (6), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the general formula (4). (A) The polyimide precursor has a structural unit represented by the general formula (5) and a structural unit represented by the general formula (6), and thus has a particularly high chemical resistance. For example, (A) the polyfluorene imide precursor may include a copolymer of a structural unit represented by the general formula (5) and a structural unit represented by the general formula (6), or may be a copolymer represented by the general formula (5) A mixture of a polyimide precursor and a polyimide precursor represented by the general formula (6). Moreover, it is also preferable from a viewpoint of the imidation ratio, gas release property, and copper adhesiveness at the time of low temperature heating.

In one embodiment, the (A) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (7).
[Chemical 23]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

In the general formula (7), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the general formula (4). (A) The polyimide precursor includes a structural unit represented by the general formula (5) and a structural unit represented by the general formula (7), and the effect of having particularly high resolvability is further enhanced. tendency. For example, (A) the polyfluorene imide precursor may include a copolymer of a structural unit represented by the general formula (5) and a structural unit represented by the general formula (7), or may be a copolymer represented by the general formula (5) A mixture of a polyimide precursor and a polyimide precursor represented by the general formula (7). Moreover, it is also preferable from a viewpoint of the imidation ratio, gas release property, copper adhesion, and chemical resistance at the time of low temperature heating.

(A) Preparation method of polyimide precursor
(A) The polyfluorene imide precursor system first comprises a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group X ₁ and an alcohol having an unsaturated double bond having photopolymerization, and any one having no unsaturated double bond. The alcohol reacts to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester body). Thereafter, the partially esterified tetracarboxylic acid and the diamines including the divalent organic group Y _{1 are} subjected to fluorene polycondensation to obtain (A) a polyfluorene imide precursor.

(Preparation of acid / ester)
In this embodiment, as a tetracarboxylic dianhydride containing a tetravalent organic group X _{1 which} is preferably used for the preparation of (A) a polyimide precursor, in addition to the tetracarboxylic dianhydride represented by the general formula (20), Examples of the carboxylic dianhydride include pyromellitic dianhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, and benzophenone-3,3', 4,4 '-Tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride, diphenylfluorene-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl Methane-3,3 ', 4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic acid) Formic anhydride) -1,1,1,3,3,3-hexafluoropropane and the like, preferably pyromellitic dianhydride and diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride , Benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride, but it is not limited to these. These can be used alone or in combination of two or more kinds.

In the present embodiment, as the alcohol having a photopolymerizable unsaturated double bond which is preferably used for preparing the (A) polyfluorene imide precursor, for example, 2-propenyloxyethanol and 1-propene Ethoxy-3-propanol, 2-propenylamine ethanol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-acrylate 3-butoxypropyl, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-third butoxypropyl acrylate, acrylic acid 2-hydroxy-3-cyclohexyloxypropyl ester, 2-methacrylic acid ethoxyethanol, 1-methacrylic acid oxy-3-propanol, 2-methacrylic acid amine ethanol, methylol ethylene Ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3 methacrylate -Phenoxypropyl, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-third butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyl methacrylate Oxypropyl esters, etc.

It is also possible to mix a part of the alcohol having photopolymerizable unsaturated double bonds such as methanol, ethanol, n-propanol, isopropanol, n-butanol, third butanol, 1-pentanol, 2-pentyl Alcohol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol and the like do not have unsaturated double bonds.

In addition, a non-photosensitive polyfluorene imide precursor prepared using only the above-mentioned alcohol having no unsaturated double bond and a photosensitive polyfluorene imide precursor may be mixed and used as the polyfluorene imide precursor. From the viewpoint of resolvability, the non-photosensitive polyfluorene imide precursor is based on 100 parts by mass of the photosensitive polyfluorene imide precursor, and is preferably 200 parts by mass or less.

The above-mentioned preferred tetracarboxylic dianhydride and the above-mentioned alcohols are mixed and dissolved in a solvent such as pyridine in a solvent described later at a temperature of 20 to 50 ° C. for 4 to 10 hours to be mixed and mixed, thereby performing the mixing. The esterification reaction of acid anhydride can obtain the desired acid / ester.

(Preparation of polyimide precursor)
Under ice-cooling, add an appropriate dehydrating condensing agent to the above-mentioned acid / ester (typically a solution in a solvent described later), such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2- Ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxybis (1,2,3-benzotriazole), N, N'-bissuccinimide imide carbonate, etc. After mixing, the acid / ester is made into a polyanhydride, and a solution obtained by dissolving or dispersing a diamine containing a divalent organic group Y ₁ which is preferably used in this embodiment is added dropwise thereto. The polyamidine polycondensation is performed to obtain the target polyamidine precursor. Alternatively, the acid / ester body is chlorinated with sulfinyl chloride, etc., and then reacted with a diamine compound in the presence of a base such as pyridine, thereby obtaining a target polyfluorene imine precursor. Thing.

Examples of the diamines containing the divalent organic group Y ₁ that are preferably used in this embodiment include diamines having a structure represented by the general formula (21), and examples thereof include p-phenylenediamine, M-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Sulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylphosphonium, 3,4'-diamine Diphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl , 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone Methane, 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] fluorene, bis [4- ( 3-aminophenoxy) phenyl] fluorene, 4,4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4 -(4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) Group] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2 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, biphenylmethyl Aniline, 9,9-bis (4-aminophenyl) fluorene, and a part of hydrogen atoms on the benzene ring are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc. Or, for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl -4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4 The '-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof are not limited thereto.

After the ammonium polycondensation reaction is completed, if necessary, the water absorption by-product of the dehydration condensation agent coexisting in the reaction solution is filtered and separated, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component The polymer is separated out, and then re-dissolved, re-precipitated, and the like are repeatedly performed, thereby purifying the polymer, vacuum-drying, and isolating the target polyimide precursor. In order to improve the precision system, the solution of the polymer can also be passed through a column packed with an anion and / or cation exchange resin swelling with an organic solvent, thereby removing ionic impurities.

When the polystyrene-equivalent weight-average molecular weight is measured by gel permeation chromatography, the molecular weight of the (A) polyimide precursor is preferably 8,000 to 150,000, and more preferably 9,000 to 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 developing solution is good, and the relief performance of the relief pattern is good. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight average molecular weight was determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent series standard sample STANDARD SM-105 manufactured by Showa Denko Corporation.

(B) fluorene imine compound (B) fluorene imine in this embodiment is a fluorene imine compound represented by the following general formula (1)
[Chemical 24]

{In formula (1), A ₁ is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, and an amine group, and A ₂ is a divalent organic group having 1 to 20 carbon atoms}.

Examples of the fluorene imine compound include compounds having a structure represented by the following general formula (22)
[Chemical 25]

{In formula (22), A ₁ is as defined above}.

Specific examples of the fluorene imine compound include N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy-1,8-naphthalenedimine, N, N '-Dihydroxy pyromellitic acid imine, N-hydroxy-4-nitrophthalimide, N-amino phthalimide, phthalimide, N, N '-Dihydroxy-1,2,3,4-cyclobutanetetramethylenediimide, glutarimide, 3-ethyl-3-methylpentamidineimine, hexahydrophthalimide Fluorene imine, maleimide, 1,4,5,8-naphthalenetetramethylene diimide, 1,8-naphthalene dimethyimine, 3-nitrophthalimide, 5 -Norbornene-2,3-dicarboxyfluorenimine, pyromellitic acid difluorenimine, 3,3-tetramethylene glutarimide, cis 1,2,3,6-tetrahydroo Xylylenediamine, N, N'-dihydroxy-1,2,3,4-cyclobutanetetramethylenediimide, N-hydroxy-5-norene-2,3-dicarboximidine Amine and the like are not limited thereto.

By containing the fluorene imine compound, the negative photosensitive resin composition of this embodiment improves the fluorene imidization rate, chemical resistance, and copper adhesion, and further, it is difficult to generate outgassing. The reason for considering the improvement of the fluorene imine rate is that: by making fluorene imine compounds around the fluorene imine precursor, the cyclic fluorene imine ring interacts with each other to become stable, so that the cyclization reaction The activation energy is reduced, but is not limited by this theory. In addition, the reason for obtaining good chemical resistance is that by arranging a low-molecular amidine compound at a position where polyimide molecules do not sufficiently interact with each other, an interaction between the amidine rings is generated, Thereby inhibiting the penetration of the medicinal solution. The same is true for copper adhesion. It is believed that the low molecular weight imine compounds enter the micro voids where the polyimide molecules fail to interact with copper, and promote the interaction between copper and polyimide. As a result, the copper of the resin Improved tightness. The reason for the decrease in outgassing property after heat curing is not clear. The main reason for consideration is that by promoting the cyclization of the polyimide precursor, the detached component accompanying the cyclization is volatilized during the heat curing process.

As for the fluorene imine compound, A _{1 in} the general formula (1) is preferably any one of a hydroxyl group and an amine group, and more preferably a hydroxyl group. A negative photosensitive resin composition to which a fluorene imine compound in which A ₁ is a hydroxyl group is added exhibits better chemical resistance.

From the viewpoints of chemical resistance and copper adhesion, the fluorene imine compound is preferably a fluorene imine compound represented by the following general formula (2):
[Chemical 26]

{In formula (2), A ₁ is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, and an amine group, and A ₃ is a group selected from the group consisting of a nitro group, a hydroxyl group, and a monovalent organic group , B is an integer from 0 to 4, and when b is 2 or more, a plurality of A ₃ may form a ring structure together}.

It is considered that the fluorene imine compound has a structure of the general formula (2), and the interaction with the fluorene imine is further enhanced, and chemical resistance and copper adhesion are further improved. When the fluorene imine compound represented by the general formula (2) has a monovalent organic group in A ₃ , the monovalent organic group is preferably from 1 to 10 in terms of solubility in a solvent. On the other hand, from the viewpoint of chemical resistance, b of the fluorene imine compound represented by the general formula (2) is preferably 0. Also from the viewpoint of chemical resistance, A _{1 is} preferably a hydroxyl group. The above fluorene imine compound may be a single molecule or a combination of a plurality of compounds.

The fluorene imine compound is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass based on 100 parts by mass of the polyamidoimide precursor (A). By setting the fluorene imine compound to 0.1 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the polyamidoimide precursor (A), it is possible to obtain a high hydrazone imidization rate and chemical resistance in low temperature curing Negative photosensitive resin composition having high copper adhesion and high outgassing in the heating step after heat curing.

(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 benzophenone, methyl o-benzoylbenzoate, 4-benzyl-4'-methyl Dibenzophenone derivatives such as diphenyl ketone, dibenzyl ketone, and fluorenone; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylbenzene Derivatives such as acetophenone; 9-oxosulfur 2-methyl-9-oxysulfur , 2-isopropyl-9-oxysulfur Diethyl-9-oxysulfur 9-oxysulfur Derivatives; Benzophenone derivatives such as benzoin, benzophenone dimethyl ketal, benzoin-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether; 1-phenyl -1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1 2,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoylfluorenyl) oxime, 1,3-diphenylpropane Oximes such as triketone-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzylidene) oxime; N-phenylglycine N-arylglycines; peroxides such as benzamidine peroxide; aromatic biimidazoles; titanocene; α- (n-octylsulfonyloxyimino) -4-methoxybenzene Photoacid generators such as acetonitrile, and the like are not limited thereto. Among the above-mentioned photopolymerization initiators, particularly in terms of sensitivity, oximes are more preferred.

The amount of the (C) photopolymerization initiator is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less based on 100 parts by mass of the polyamidoimide precursor (A). The blending amount is preferably 0.1 parts by mass or more from the viewpoint of sensitivity or patternability, and 20 parts by mass or less from the viewpoint of physical properties of the photosensitive resin layer after the negative photosensitive resin composition is cured. .

(D) Hot alkali generator The negative photosensitive resin composition of this embodiment may contain (D) an alkali generator. The alkali generator refers to a compound that generates a base by heating. By containing a hot alkali generator, the imidization of the photosensitive resin composition can be further promoted.

There is no particular limitation on the type of the hot alkali generator, and examples thereof include an amine compound protected by a third butoxycarbonyl group, or the hot alkali generator disclosed in International Publication No. 2017/038598. However, it is not limited to these, and other well-known hot-alkali generators can also be used.

Examples of the amine compound protected by the third butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, and 4-amine 1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino- 2-methyl-1-butanol, valine alcohol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, benzoylamine, 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-pyrrolidine methanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4- (3-hydroxyphenyl) piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2- (4-piperidyl)- 2-propanol, 1,4-butanol bis (3-aminopropyl) ether, 1,2-bis (2-aminoethoxy) ethane, 2,2'-oxybis (ethylamine) , 1,14-diamino-3,6,9,12-tetraoxy Heptadecane, 1-aza-15-crown 5-ether, diethylene glycol bis (3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxadeca Monoalkane, or a compound in which the amino group of the amino acid and its derivative is protected by a third butoxycarbonyl group is not limited thereto.

The blending amount of the (D) hot alkali generator is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyamidoimide precursor (A). The blending amount is preferably 0.1 parts by mass or more from the viewpoint of the effect of promoting the imidization, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after the negative photosensitive resin composition is cured. .

The negative-type photosensitive resin composition according to this embodiment may further contain components other than the components (A) to (D). The components other than the components (A) to (D) are not limited, and examples thereof include solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesives, sensitizers, and photopolymerizable unsaturated monomers. , Thermal polymerization inhibitors, etc.

As the solvent, amines, fluorenes, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. can be mentioned. For example, N-methyl-2 can be used. -Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfine, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, phthaloline, dichloromethane, 1,2-dichloro Ethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene and the like. Among these, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesiveness to the substrate, N-methyl-2-pyrrolidone, dimethylsulfinium, 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, phenyl ethylene glycol, and tetrahydrofurfuryl alcohol.

Among such solvents, those which completely dissolve the produced polymer are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide. Ammonium amine, dimethyl sulfene, tetramethylurea, γ-butyrolactone, etc.

In the photosensitive resin composition of this embodiment, the amount of the solvent to be used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, with respect to 100 parts by mass of the polyimide precursor (A). The range of 125 to 500 parts by mass is preferred.

In the case where a nitrogen-containing heterocyclic compound is used to form a cured film on a substrate containing copper or a copper alloy using the photosensitive resin composition of this embodiment, in order to suppress discoloration on copper, the negative photosensitive resin composition may be arbitrarily contained Nitrogen-containing heterocyclic compounds. Examples of the nitrogen-containing heterocyclic compound include azole compounds and purine derivatives.

Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-phenyl- 1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-benzene -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-di Methylbenzyl) phenyl] -benzotriazole, 2- (3,5-di-third-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-third-butyl-5- Methyl-2-hydroxyphenyl) -benzotriazole, 2- (3,5-di-third-pentyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- Third octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolutriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4 -Carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino -1H-tetrazole, 1-methyl-1H-tetrazole and the like.

Particularly preferred examples include toluenetriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used singly or as a mixture of two or more.

Specific examples of the purine derivative include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyl Adenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2 -Hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-amino adenine, 6-amino-8-phenyl-9H-purine, 1-ethyl adenine Purine, 6-ethylaminopurine, 1-benzyl adenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) guanine, N- (3-ethylphenyl) guanine, 2-azine, 5-azine, 8-azine, 8-azine, 8-azine, 8-azine, 8-azine Xanthines and their derivatives.

When the photosensitive resin composition contains the above-mentioned azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A). From a viewpoint, it is more preferable that it is 0.5-5 mass parts. When the compounding amount of the azole compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy , Can suppress the discoloration of the surface of copper or copper alloy, on the other hand, in the case of 20 parts by mass or less, the sensitivity is excellent.

Hindered phenol compound In order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally include a hindered phenol compound. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, and 3- (3,5-di-tert-butyl) 4-Hydroxyphenyl) octadecyl propionate, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoate isooctyl, 4,4'-methylenebis ( 2,6-di-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-third-butylphenol), 4,4'-butylene-bis (3-methyl -6-Third-butylphenol), triethylene glycol-bis [3- (3-Third-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol -Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylidene bis [3- (3,5-di-third Butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-third-butyl-4-hydroxy-phenylpropanamine), 2,2'- Methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis [ 3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], tri- (3,5-di-third-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-third-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2, 6-dimethyl-4-iso Benzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4-thirdbutyl-3-hydroxy-2 , 6-dimethylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4-second butyl- 3-hydroxy-2,6-dimethylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4- (1-ethylpropyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1 , 3,5-tri [4-triethylmethyl-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-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-third butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-tri-2, 4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-thirdbutyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)- 1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4-third-butyl-6-ethyl-3-hydroxy-2 -Methylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4-tert-butyl-6-ethyl) Methyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri ( 4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -tri Ketone, 1,3,5- (4-Third-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5 -Tris (4-third-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-third-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H , 5H) -trione and the like, but are not limited thereto. Among these, 1,3,5-tris (4-third-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-tri-2,4, is particularly preferable. 6- (1H, 3H, 5H) -trione and the like.

The compounded amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, from the viewpoint of sensitivity characteristics, relative to 100 parts by mass of the polyamidoimide precursor (A). When the compounded amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the embodiment is formed on copper or a copper alloy It can prevent discoloration and corrosion of copper or copper alloys. On the other hand, when it is 20 parts by mass or less, it has excellent sensitivity.

Organic Titanium Compound The negative photosensitive resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound, it is possible to form a photosensitive resin layer excellent in chemical resistance even when hardened at a low temperature.

Examples of usable organic titanium compounds include organic chemical substances that are bonded to titanium atoms via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in the following I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable in terms of obtaining the storage stability and good pattern of the negative photosensitive resin composition. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium bis (2,4-glutaric acid) di-n-butoxide, titanium bis (2,4-glutaric acid) diisopropoxide, and bis (tetramethyl) (Ipipimelic acid) titanium diisopropoxide, titanium bis (ethylacetoacetic acid) titanium diisopropoxide, and the like.
II) Tetraalkoxy titanium compounds: For example, titanium (n-butanol), titanium tetraethoxide, titanium (2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium tetramethoxypropoxide, titanium tetramethylphenol, titanium tetra-n-nonanol, titanium tetra-n-propanol, titanium stearate, tetra [bis {2,2- (allyloxymethyl) Group) butanol}] titanium and the like.
III) Titanocene compounds: for example, (pentamethylcyclopentadienyl) titanium methoxide, bis (η5-2,4-cyclopentadien-1-yl) bis (2,6-difluorophenyl) ) Titanium, bis (η5-2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, and the like.
IV) Titanium monoalkoxide compounds: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonic acid) isopropoxide, and the like.
V) Titanium oxide compounds: For example, bis (glutarate) oxytitanium, bis (tetramethylpimelate) oxytitanium, phthalocyanine oxytitanium, and the like.
VI) Titanium tetraacetamidine pyruvate: For example, titanium tetraacetamidine pyruvate and the like.
VII) Titanate coupling agent: for example, isopropyltris (dodecylbenzenesulfonyl) titanate and the like.

Among these, from the viewpoint of exhibiting better chemical resistance, 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) titanocene compound. At least one compound in the group. Especially preferred are titanium bis (ethylacetoacetate) diisopropoxide, titanium (n-butanol), and bis (η5-2,4-cyclopentadien-1-yl) bis (2,6- Difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium.

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

Adhesive Auxiliary In order to improve the adhesion between the film and the substrate formed using the negative photosensitive resin composition of this embodiment, the negative photosensitive resin composition may optionally include an adhesive. Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-glycidyloxy Propylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxymethoxysilane Trimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidyloxypropylmethylsilane, N- (3-diethoxymethyl Silylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] phthalimide, benzophenone-3,3'-bis (N- [3 -Triethoxysilyl] propylamidamine) -4,4'-dicarboxylic acid, benzene-1,4-bis (N- [3-triethoxysilyl] propylamidamine) -2 , 5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Silane coupling agents such as propyltriethoxysilane, 3- (trialkoxysilyl) propylsuccinic anhydride; and aluminum tris (ethylacetoacetate), aluminum aluminum (triacetate), and ethylacetate Ethyl aluminate Aluminum-based adhesives such as diisopropyl ester.

Among these adhesion promoters, a silane coupling agent is more preferably used in terms of adhesion. When the photosensitive resin composition contains a bonding aid, the blending amount of the bonding aid is preferably in the range of 0.5 to 25 parts by mass based on 100 parts by mass of the polyamidoimide precursor (A).

Examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, Chisso Co., Ltd .: trade name Sila-Ace S810), and 3-mercaptopropyl triethyl Oxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: trade name LS1375, manufactured by Azmax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropane Silane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethyl Ethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyl Dimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltrisiloxane Propoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, 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-ethoxy Dimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropyloxysilylpropyl) urea, N- ( 3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipropoxysilylpropyl) ) Urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3 -Tripropoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- ( 3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (Azmax Manufactured by a joint stock company: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd. : Trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: merchandise SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) Pyridine, aminocarboxylic acid (3-triethoxysilylpropyl) -third butyl ester, (3-glycidyloxy (Propyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, Tertiary butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxysilane) (Ethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane , Bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propane Group] dithioether, bis [3- (triethoxysilyl) propyl] tetrasulfide, second and third butoxydiethylfluorenylsilane, diisobutoxyaluminumoxytriethoxy Silane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol , Isobutylphenylsilanediol, third butylphenylsilanediol, diphenyl Silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilane Alcohol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, third butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethylisopropyl alcohol Propylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, third butylethylphenylsilanol, methyldiphenylsilanol, ethyldibenzene Silyl alcohol, n-propyl diphenyl silanol, isopropyl diphenyl silanol, n-butyl diphenyl silanol, isobutyl diphenyl silanol, third butyl diphenyl silanol, Triphenylsilanol and the like are not limited thereto. These can be used alone or in combination.

As the silane coupling agent, from the standpoint of storage stability, among the above-mentioned silane coupling agents, phenylsilane triol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, and diphenylsilane are preferred. Diol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-phenylmethylsilane, triphenylsilanol, and a silane coupling agent having a structure represented by the following formula.
[Chemical 27]

When the silane coupling agent is used, the blending amount is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the polyamidoimide precursor (A).

Sensitizer In order to increase the sensitivity, the negative-type photosensitive resin composition of the present embodiment may optionally include a sensitizer. Examples of the sensitizer include Michelin, 4,4'-bis (diethylamino) benzophenone, and 2,5-bis (4'-diethylaminobenzylidene) cyclopentane. Alkane, 2,6-bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-diethylaminobenzylidene) -4-methylcyclohexanone, 4 , 4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminoglycine dihydroindenone, p-dimethylamino Benzyl dihydroindenone, 2- (p-dimethylaminophenylphenylbenzyl) -benzothiazole, 2- (p-dimethylaminophenylphenylvinyl) benzothiazole, 2- (p-dimethylamine Phenylphenylene vinyl) isonaphthothiazole, 1,3-bis (4'-dimethylaminobenzylidene) acetone, 1,3-bis (4'-diethylaminobenzylidene) acetone, 3 , 3'-carbonyl-bis (7-diethylaminocoumarin), 3-ethylamido-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Glucosinolate, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin Beans, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-Phenyldibenzoyl , Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p- Dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d ) Thiazole, 2- (p-dimethylaminobenzyl) styrene and the like. These can be used individually or in combination of 2 to 5 types, for example.

In the case where the photosensitive resin composition contains a sensitizer for improving sensitivity, it is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

Photopolymerizable unsaturated monomer In order to improve the resolution of the relief pattern, the negative photosensitive resin composition may optionally include a monomer having a photopolymerizable unsaturated bond. As such a monomer, a (meth) acrylic compound which is subjected to a radical polymerization reaction by a photopolymerization initiator is not particularly limited, and examples thereof include diethylene glycol dimethacrylate, Mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol such as tetraethylene glycol dimethacrylate; mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol; Di or triacrylates and methacrylates; cyclohexane diacrylate and cyclohexane dimethacrylate; 1,4-butanediol diacrylate and dimethacrylate; 1,6-hexane Diacrylates and dimethacrylates of diols; diacrylates and dimethacrylates of neopentyl glycol; mono- or diacrylates and methacrylates of bisphenol A; benzenetrimethacrylates; Isopropyl acrylate and methacrylic acid; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; glycerol Di- or tri-acrylate and methacrylate; pentaerythritol And a compound of ethylene oxide or propylene oxide adducts of such compounds and the like; of di-, tri-, or tetra-acrylates and methacrylates.

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

The thermal polymerization inhibitor further improves the viscosity and the stability of the sensitivity of the negative photosensitive resin composition, particularly when stored in a solution containing a solvent. The negative photosensitive resin composition of this embodiment may be arbitrarily selected. Contains thermal polymerization inhibitors. As the thermal polymerization inhibitor, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothia, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2- Cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2- Naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine Salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt, and the like.

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

(1) Resin layer forming step In this step, the negative-type photosensitive resin composition of this embodiment is applied to a substrate, and if necessary, it is then dried to form a resin layer. As the coating method, a coating method used for a photosensitive resin composition from the past can be used, and for example, a spin coater, a bar coater, a blade coater, a curtain coater, and a screen can be used. A method of coating by a printer, a method of spray coating by a sprayer, and the like.

If necessary, the coating film containing the photosensitive resin composition is dried. As a drying method, methods such as air-drying, heating drying using an oven or a hot plate, and vacuum drying can be used. Specifically, in the case of air-drying or heat-drying, drying can be performed under conditions of 20 ° C to 150 ° C for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the substrate.

(2) Exposure step In this step, an exposure device such as a contact alignment machine, a mirror projection exposure machine, a stepper, etc. is used, and a patterned mask or a reduction mask is used, or an ultraviolet light source is directly used. The resin layer formed as described above is exposed.

Thereafter, for the purpose of improving light sensitivity and the like, post-exposure baking (PEB) and / or pre-development baking may be performed at any combination of temperature and time as required. The range of the baking conditions is preferably a temperature of 40 ° C. to 120 ° C. and a time of 10 seconds to 240 seconds. However, the range is not limited as long as the characteristics of the photosensitive resin composition of this embodiment are not hindered.

(3) Relief pattern forming step In this step, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), any one of previously known development methods of photoresist, such as a spin spray method, an immersion method, and an immersion method with ultrasonic treatment, can be selected. Method used. After the development, for the purpose of adjusting the shape of the embossed pattern, the post-development baking may be performed at any combination of temperature and time as required.

As a developing solution used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferred. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, and γ. -Butyrolactone, α-ethenyl-γ-butyrolactone, and the like. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Moreover, you may use each solvent in combination of 2 or more type, for example several types.

(4) Hardened relief pattern forming step In this step, the relief pattern obtained by the above development is subjected to a heat treatment to volatilize the photosensitive component, and (A) the polyfluorene imide precursor sulfonimide, This translates into a hardened relief pattern containing polyimide. As a method of the heat treatment, for example, various methods such as those using a hot plate, those using an oven, and those using a temperature-adjustable oven capable of setting a temperature control program can be selected. The heat treatment can be performed, for example, under conditions of 160 ° C to 350 ° C and 30 minutes to 5 hours. The temperature of the heat treatment is preferably 200 ° C or lower, and more preferably 180 ° C or lower. As the atmosphere gas during heating and curing, air may be used, and inert gas such as nitrogen or argon may also be used.

＜ Polyimide ＞
The polyimide of this embodiment can be manufactured by hardening a negative photosensitive resin composition. The structure of the polyimide contained in the hardened relief pattern formed from the said polyimide precursor composition is represented by following General formula (8).
[Chemical 28]

{In the general formula (8), X ¹ and Y ¹ in the general formula (3) in the same as X ¹ and Y ^1. For the same reason, preferred X ¹ and Y ¹ in the general formula (3) are also preferred in the polyfluorene imine of the general formula (8). The number of repeating units m is not particularly limited, and may be an integer of 2 to 150}.

＜ Semiconductor device ＞
In this embodiment, there is also provided a semiconductor device having a hardened relief pattern obtained by the manufacturing method of the hardened relief pattern described above. Therefore, it is possible to provide a semiconductor device including: a base material for a semiconductor element; and a hardened relief pattern of polyimide, which is formed on the base material by the above-mentioned hardened relief pattern manufacturing method. It can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the method for manufacturing a hardened relief pattern of the present embodiment as part of the steps. The semiconductor device can be formed into a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip-chip device protective film, or the like by forming a hardened embossed pattern formed using the method of manufacturing a hardened embossed pattern of this embodiment, or having A protective film or the like of a semiconductor device having a bump structure is manufactured in combination with a known method for manufacturing a semiconductor device.

＜ Display body device ＞
In this embodiment, a display device is provided, which includes a display element and a cured film provided on an upper portion of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the hardened embossed pattern may be directly connected to the display element and laminated, or may be laminated with other layers interposed therebetween. For example, examples of the cured film include surface protection films, insulating films, and planarization films of TFT (Thin-Film Transistor) thin-film transistor and color filter elements, MVA (Multi-Domain Vertical Alignment, A multi-domain vertical alignment) type projection for a liquid crystal display device and a partition wall for a cathode of an organic EL (Electroluminescence) element.

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. The negative photosensitive resin composition of this embodiment can be used in addition to the semiconductor devices described above, and can also be used for interlayer insulation films of multilayer circuits, surface coatings of flexible copper foils, solder resist films, and liquid crystal alignment films. use.
[Example]

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

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

(2) Sputtering device (L-440S-FHL, manufactured by Canon Anelva) was used to produce the hardened relief pattern on Cu. It was fabricated on a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625 ± 25 μm), sequentially sputtering Ti with 200 nm thickness and Cu with 400 nm thickness. Then, using a coating and developing machine (D-Spin60A type, manufactured by SOKUDO), the photosensitive resin composition prepared by the method described below was spin-coated on the wafer, and preheated at 110 ° C on a hot plate for 180 In 15 seconds, a coating film having a thickness of about 15 μm was formed. Using a photomask with a test pattern, the coating film was irradiated with energy of 1000 mJ / cm ² through Prisma GHI (manufactured by Ultratech). Next, cyclopentanone was used as a developing solution, and a coating and developing machine (D-Spin60A type, manufactured by SOKUDO) was used to spray-develope the coating film by the time that the unexposed portion completely dissolved and disappeared multiplied by 1.4, and propylene glycol was used. The ether acetate was subjected to spin spray washing for 10 seconds, thereby obtaining a relief pattern on Cu.
Using a temperature-programming type curing furnace (VF-2000 type, manufactured by Koyo Lindberg), a wafer having the relief pattern formed on Cu was heated under a nitrogen atmosphere at the temperature described in Table 1 for 2 hours. Processing, thereby obtaining a hardened embossed pattern containing a resin having a thickness of about 8 to 10 μm on Cu.

(3) Measurement of fluorinated imidization A Si-ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared Spectrometry) measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) was used. The hardened embossed pattern resin portion was measured, and the value obtained by dividing the peak intensity of 1380 cm ^-1 by the peak intensity of 1500 cm ^-1 was set as the fluorinated index. The value obtained by dividing the fluorene imidization index by the fluorene imidization index of a film obtained by curing the corresponding resin composition at 350 ° C. is the fluorination ratio.醯 The imidization rate was evaluated based on the following criteria.
"Excellent": 醯 imidization rate is above 80% "Good": 醯 imidization rate is above 60%-less than 80%
"Yes": the imidization rate is over 40%-less than 60%
"Impossible": the imidization rate is less than 40%

(4) Evaluation of outgassing The photosensitive resin composition prepared by the method described later was coated on a 6-inch silicon wafer previously sputtered with Al in the same manner as in the above-mentioned production of the hardened relief pattern. After baking, a heating program type curing oven (VF-2000 type, manufactured by Koyo Lindberg) was used, and a heating treatment was performed in a nitrogen atmosphere at the temperature described in Table 1 for 2 hours, thereby obtaining the inclusion of Al on Hardened relief pattern of about 10 μm thick resin. This resin film was cut to a width of 3.0 mm using a wafer dicing machine (manufactured by Disco, model name DAD-2H / 6T), immersed in a 10% aqueous hydrochloric acid solution, and peeled off from the silicon wafer to make a short film. sample. This film sample was left in an environment of 23 ° C. and 55% RH (Relative Humidity) for more than 24 hours, and then a thermogravimetry device (manufactured by Shimadzu Corporation, TGA-50) was used at room temperature at 10 ° C./min. When the temperature was raised, the temperature at which the weight of the film reached 150 ° C was taken as 100%, and the weight was reduced by 5% (5% weight reduction temperature). The outgassing was evaluated based on the following criteria.
"Excellent": 5% weight reduction temperature is above 300 ° C "Good": 5% weight reduction temperature is above 280 ° C and less than 300 ° C
"OK": 5% weight reduction temperature is above 260 ℃ and below 280 ℃
"Impossible": 5% weight reduction temperature does not reach 260 ℃

(5) Evaluation of copper adhesion In the same manner as in the production of the hardened relief pattern, a photosensitive resin composition prepared by a method described later was applied to a 6-inch silicon wafer previously sputtered with Ti and Cu. After pre-baking, a temperature-programming type curing oven (VF-2000 type, manufactured by Koyo Lindberg) was used, and a heating treatment was performed in a nitrogen atmosphere at the temperature listed in Table 1 for 2 hours, thereby obtaining Cu contains a hardened relief pattern of about 10 μm thick resin. The cross-cut method according to JIS K 5600-5-6 was used to evaluate the adhesion characteristics of the film after heat treatment between the copper substrate and the cured resin coating film based on the following criteria.
"Excellent": The grid number of the hardened resin coating film on the substrate is 100
"Good": The number of lattices of the hardened resin coating film on the substrate is 70 to 99
"OK": The number of lattices of the hardened resin coating film on the substrate is 40 to 69
"Impossible": The number of lattices of the hardened resin coating film on the substrate is less than 40

(6) Evaluation of chemical resistance The embossed pattern produced by the method described in (2) above was immersed in a resist release film {manufactured by ATMI, product name ST-44, and the main component was 2- (2-aminoethyl) (Oxy) ethanol, 1-cyclohexyl-2-pyrrolidone} were heated to 50 ° C for 5 minutes, washed with running water for 30 minutes, and air-dried. Thereafter, the surface of the film was visually observed with an optical microscope, and the chemical resistance was evaluated by the presence or absence of damage caused by a chemical solution such as cracks and the change rate of the film thickness after the chemical solution was treated. Chemical resistance was evaluated based on the following criteria.
"Excellent": no cracks, etc., and the film thickness change rate is less than 5% based on the film thickness before the liquid immersion
"Good": No cracks, etc., and the film thickness change rate is 5% or more and less than 10% based on the film thickness before the liquid immersion.
"OK": No cracks, etc., and the film thickness change rate is 10% or more and less than 15% based on the film thickness before the chemical solution is immersed
"Impossible": cracks, etc., or the film thickness change rate is 15% or more based on the film thickness before the liquid immersion

Production Example 1: (A) Synthesis of Polyfluorene Imide Precursor A-1 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask with a capacity of 2 L and placed in 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were stirred at room temperature, and 81.5 g of pyridine was added while stirring, to obtain a reaction mixture. After the exotherm caused by the reaction was completed, the reaction mixture was left to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, and then stirred It took 60 minutes to add 93.0 g of 4,4'-diaminodiphenyl ether (ODA) in 350 mL of γ-butyrolactone. After further stirring at room temperature for 2 hours, 30 mL of ethanol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate produced by the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing a crude polymer. The resulting 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 a polymer, and the obtained precipitate was separated by filtration and vacuum-dried to obtain a powdery polymer (polyimide precursor A-1) . When the molecular weight of the polyfluorene imide precursor A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000. Polyfluorene imine precursor A-1 is non-alkali soluble.

Production Example 2: (A) Synthesis of Polyfluorene Imide Precursor A-2 Using 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) 147.1 g instead of 4,4' of Production Example 1 Except for 155.1 g of oxydiphthalic dianhydride (ODPA), a reaction was performed in the same manner as in the method described in Production Example 1 above to obtain a polymer (polyimide precursor A-2). The molecular weight of the polyfluorene imide precursor A-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000. Polyimide precursor A-2 is non-alkali soluble.

Production Example 3: (A) Synthesis of Polyfluorene Imide Precursor A-3 50.2 g of p-phenylenediamine was used in place of 93.0 g of 4,4'-diaminodiphenyl ether (ODA) in Production Example 1 The polymer was reacted in the same manner as in the method described in Production Example 1 above to obtain a polymer (polyimide precursor A-3). When the molecular weight of the polyfluorene imide precursor A-3 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 19,000. Polyimide precursor A-3 is non-alkali soluble.

Production Example 4: (D) Synthesis of Hot Alkali Generator D-1 To a 1 L eggplant type flask was added diethylene glycol bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 g and 100 g of ethanol, mixed with a stirrer to make a homogeneous solution, and cooled to below 5 ° C with ice water. A solution obtained by dissolving 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 120 g of ethanol was added dropwise thereto through a dropping funnel. At this time, dropping was performed while adjusting the dropping acceleration so that the temperature of the reaction solution was kept at 50 ° C or lower. After 2 hours from the end of the dropwise addition, the reaction solution was concentrated under reduced pressure at 50 ° C for 3 hours to obtain the target compound D-1.

<Example 1>
A polyimide precursor A-1 was used to prepare a negative photosensitive resin composition by the following method, and the prepared composition was evaluated. A-1: 100 g of (A) a polyimide precursor, B-1: 5 g of a (B) imine compound, and 1-phenyl group (C) as a photopolymerization initiator -1,2-propanedione-2- (o-ethoxycarbonyl) -oxime (hereinafter referred to as PDO, equivalent to photosensitizer C-1): 3 g dissolved in γ-butyrolactone (hereinafter referred to as GBL) : 100 g. The viscosity of the solution was adjusted to about 40 poise by further adding a small amount of GBL to prepare a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

<Examples 2 to 17, Comparative Examples 1 to 3>
A negative-type photosensitive resin composition similar to that of Example 1 was prepared and prepared in the blending ratios shown in Table 1 and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. (B) fluorene imine compounds B-1 to B-7, (C) photopolymerization initiator C-1, and (D) thermal base generators D-1, D-2 described in Tables 1 and 2 They are as follows.

B-1: N-Hydroxyphthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-2: N-hydroxysuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-3: N-hydroxy-1,8-naphthalenedimethylimide (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-4: N, N'-dihydroxy pyromellitic acid imide (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-5: N-hydroxy-4-nitrophthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-6: N-Aminophthalimidine (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-7: phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-1: 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) -oxime
D-1: Compound described in Production Example 4
D-2: 1- (third butoxycarbonyl) -4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Table 1]

[Table 2]

It is clear from Tables 1 and 2 that the negative photosensitive resin composition of Example 1 was "good" in the evaluation of the imidization rate of fluorene, "excellent" in the evaluation of outgassing, and evaluated in copper adhesion. The rating is "good" and "excellent" in the chemical resistance evaluation. Similarly, all of the negative-type photosensitive resin compositions of Examples 2 to 17 were "Possible" or more in all of the fluorinated imidization rate, the outgassing evaluation, the copper adhesion evaluation, and the chemical resistance evaluation.
In particular, Example 1 using A-1 as the (A) polyfluorene imide precursor showed excellent chemical resistance. In addition, when 5 parts by mass of B-1 is added as the (B) fluorene imine compound based on 100 parts by mass of the polymer, particularly excellent chemical resistance and outgassing reduction effect can be obtained. In addition, when (D) the hot alkali generators D-1 and D-2 were added, the fluorene imidization ratio was particularly excellent.
On the other hand, Comparative Example 1 in which (B) the imine compound was not added was "impossible" in all evaluations, and Comparative Example 2 in which the hardening temperature was increased from 170 ° C to 200 ° C was also evaluated in copper adhesion. Is "impossible". In addition, Comparative Example 3 in which (B) the fluorene imine compound was not added and only (D) the hot alkali generator D-1 was added. Although the fluorene imine ratio was "good", it was evaluated for copper adhesion and chemical resistance. The evaluation was "impossible".
[Industrial availability]

By using the photosensitive resin composition of the present invention, a hardened float having a high fluorinated imidization rate and chemical resistance, high copper adhesion, and less outgassing in a heating step after thermal hardening can be obtained. Convex pattern. The present invention can be preferably used in the field of photosensitive materials used in the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (21)

A negative photosensitive resin composition comprising: (A) a polyimide precursor; (B) a fluorene imine compound represented by the following general formula (1) [Chem. 1] {In formula (1), A ₁ is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, and an amine group, and A ₂ is a divalent organic group having 1 to 20 carbon atoms}; and (C) photopolymerization Starting agent. The negative-type photosensitive resin composition according to claim 1, wherein A ₁ of the (B) fluorene imine compound represented by the general formula (1) is any one of a hydroxyl group and an amine group. The negative-type photosensitive resin composition according to claim 1, wherein A ₁ of the (B) fluorene imine compound represented by the general formula (1) is a hydroxyl group. The negative-type photosensitive resin composition according to any one of claims 1 to 3, wherein the (B) fluorene imine compound is represented by the following general formula (2) {In formula (2), A ₁ is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, and an amine group, and A ₃ is a group selected from the group consisting of a nitro group, a hydroxyl group, and a monovalent organic group, b is an integer of 0 to 4, and when b is 2 or more, a plurality of A ₃ may form a ring structure together}. The negative-type photosensitive resin composition according to any one of claims 1 to 4, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (3) [Chemical 3] {In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and R ₁ And at least one of R ₂ is a monovalent organic group represented by the following general formula (4) (In the formula, 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 of 2 to 10)}. The negative-type photosensitive resin composition according to claim 5, wherein X ₁ contains a tetravalent organic group represented by the following general formula [Chem. 5] {In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ value of 1 in the group, m is an integer selected from 0 to 3 of}. The negative-type photosensitive resin composition according to claim 5, wherein X ₁ contains a tetravalent organic group represented by the following general formula [Chem. 6] {In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ value of 1 in the group, m is an integer selected from 0 to 3 of}. The negative-type photosensitive resin composition according to claim 5, wherein said Y ₁ contains a divalent organic group represented by the following general formula [Chem. 7] {In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ of the monovalent group of 1, and n is an integer selected from 0 to 4} of . The negative-type photosensitive resin composition according to claim 5, wherein said Y ₁ contains a divalent organic group represented by the following general formula [Chem. 8] {In the formula, R6 is selected from the group consisting of a fluorine atom, the group consisting of C ₁ - C ₁₀ hydrocarbon group, the hydrocarbon group and the fluorine-containing C ₁ ~ C ₁₀ of the monovalent group of 1, and n is an integer selected from 0 to 4} of . The negative-type photosensitive resin composition according to any one of claims 1 to 9, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5) [Chemical 9] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}. The negative photosensitive resin composition according to any one of claims 1 to 10, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (6) [Chemical 10] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}. The negative-type photosensitive resin composition according to any one of claims 1 to 11, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (7) [Chemical 11] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}. The negative-type photosensitive resin composition according to any one of claims 1 to 12, wherein the (A) polyfluorene imide precursor comprises: in the following general formula (5): [化 12] {Wherein R ₁ , R ₂ , and n ₁ are those defined above}; and a structural unit represented by the following general formula (6): [化 13] {Wherein R ₁ , R ₂ , and n ₁ are as defined above; wherein R ₁ , R ₂ , and n ₁ in formula (5) and R ₁ , R ₂ , and n ₁ independently selects the structural unit represented by}. The negative photosensitive resin composition according to any one of claims 1 to 13, comprising: 100 parts by mass of the above (A) polyimide precursor; 0.1 to 30 parts by mass of the above (B) fluorene imine compound based on 100 parts by mass of the (A) polyfluorene imide precursor; and The photopolymerization initiator (C) described above is 0.1 to 20 parts by mass based on 100 parts by mass of the polyamidoimide precursor (A). The negative photosensitive resin composition according to any one of claims 1 to 14, further comprising (D) hot alkali generation of 0.1 to 30 parts by mass based on 100 parts by mass of (A) a polyimide precursor. Agent. The negative-type photosensitive resin composition according to any one of claims 1 to 15, wherein the negative-type photosensitive resin composition is a negative-type photosensitive resin composition for forming an insulating member. The negative photosensitive resin composition according to any one of claims 1 to 16, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film. A method for manufacturing a hardened relief pattern includes the following steps: (1) coating the negative photosensitive resin composition according to any one of claims 1 to 17 on a substrate, and forming a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the photosensitive resin layer after exposure to form a relief pattern; and (4) A heat treatment is performed on the embossed pattern to form a hardened embossed pattern. The method for manufacturing a hardened embossed pattern according to claim 18, wherein the heat treatment is a heat treatment of 200 ° C or lower. The method for manufacturing a hardened relief pattern according to claim 19, wherein the heat treatment is a heat treatment of 180 ° C or lower. A method for producing polyimide, comprising curing a negative photosensitive resin composition according to any one of claims 1 to 17.