JPH10260531A - Polyimide type resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide type resin composition superior in an antirust effect and a film remaining preventive effect and a film adhesion effect to copper and copper alloys and to provide the method for manufacturing a terminally modified polyimide type resin composition by incorporating the polyimide type resin with a tetrazole group introduced into the terminal of each unit and a solvent as essential components. SOLUTION: This polyimide type resin composition is composed essentially of the polyimide having the tetrazole group introduced into the terminal of each unit and the solvent. The polyimide resin is a polyamide acid represented by formula I in which R<1> is a tetravalent organic group; R<2> is a divalent organic group; (k) is an integer of 5-10,000; W<1> is T<1> or a hydroxy or chemical sensitive group; and T<1> is an atomic group having a tetrazole group represented by formula II in which P<1> is a -NH-, -NR-, (R is a 1-3C alkyl group), -SO2 -, or -Ogroup or the like; Q is a simple bond or a divalent organic group; and R<1> is an H atom or a 1-10C alkyl or 2-10C alkenyl or 3-10C aryl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin composition for electronic materials having excellent rust-preventing effect, residual film-preventing effect, and film-adhering effect on copper and copper alloys.
The polyimide resin composition of the present invention is a semiconductor device, a printed wiring board, on a substrate such as various high-performance substrates, for example,
It can be suitably used as a resin material for forming an interlayer insulating film, a passivation film, a protective film, and the like.
The present invention also relates to a method for producing a terminal-modified polyamic acid having a tetrazole group introduced at a terminal. In the present invention, the polyimide-based resin means not only polyimide but also polyamic acid which is a precursor of polyimide. Further, the tetrazole group is an unsubstituted compound (1
Not only an H-tetrazole group) but also a substituent (1-substituted-tetrazole group) is included.

[0002]

2. Description of the Related Art Polyimide resins are excellent in heat resistance, chemical resistance, electrical properties, film forming properties, and the like. Therefore, in semiconductor devices and various high-performance substrates, interlayer insulating films, passivation films, junction coatings, etc. It is used as a protective film and the like. In these fields, heat-resistant substrates made of inorganic materials such as silicon wafers and ceramics are used, and a polyimide resin film is coated on metal wiring provided on the substrate. As a conductor for forming a metal wiring, a sputter-deposited film, a metal foil, or the like is used, and as a metal material, copper is used in many cases. In addition, in order to form various wiring patterns of conductors on a substrate, or to selectively form a resin coating layer on a fine part on the substrate, a photosensitive layer is formed on the metal wiring or metal layer provided on the substrate. Form a coating layer of a polyimide resin, then irradiate the pattern shape with actinic rays from above the coating layer, and then, utilizing the difference in solubility between the irradiated and unirradiated parts to the developer, the irradiated part Alternatively, a pattern forming method of dissolving and removing an unirradiated portion with a developer is adopted.

As the polyimide resin, a polyamic acid (polyamic acid), which is a polyimide precursor, is usually used, and a solvent solution (polyimide varnish) is coated on a substrate to form a coating film. The acid is dehydrated to form an imide. Examples of the photosensitive polyimide resin include a composition obtained by adding a photocrosslinking agent to a polyamic acid, and a precursor obtained by introducing an acryloyl group into a polyamic acid (JP-B-55-30207, JP-B-55-414).
No. 22), a precursor obtained by introducing an acrylolyl group into a polyamic acid in the form of a salt (JP-B-59-52822),
Polyamic acids having actinic ray functional groups introduced at both ends (JP-A-4-70661, JP-A-4-77741,
JP-A-8-95247, JP-A-8-286374
Publication). Also, by using an asymmetric diamine as the diamine component of the monomer,
It has been proposed to obtain a solvent-soluble polyimide or to obtain a polyimide soluble in a solvent and having photosensitivity from benzophenonetetracarboxylic anhydride and an aromatic diamine.

As described above, polyimide-based resins are widely used in the field of semiconductor devices and the like, but conventional polyimide-based resins corrode metals commonly used as conductor materials such as copper and copper alloys. It has the problem of exhibiting properties. The cause is that the polyamic acid of the polyimide precursor contains a carboxyl group. Carboxyl groups react with copper and copper alloys and corrode them. Moreover, the resin having a carboxyl group has a hygroscopic property and promotes a corrosive action. Even after the polyamic acid is imidized, a carboxyl group often remains.

Therefore, using a polyimide varnish,
When forming an interlayer insulating film for a multilayer wiring board, after a heat curing (imidization) step or curing, corrosion action and copper ions occur on copper or copper alloy in contact with the coating film, resulting in poor insulation, disconnection, short circuit, It causes various problems such as rust on the metal part, decrease in adhesion of the film, and deterioration of physical properties of the film. If the adhesion of the polyimide film to the metal wiring or metal layer is not sufficient, in the processing steps at high temperatures such as tin plating, solder plating, gold plating, solder diving, and solder reflow, the metal wiring or metal layer and the polyimide film may There is a problem that the processing liquid enters from the boundary surface. Also in the manufacturing process of the printed wiring board using the photosensitive polyimide resin, after forming the resist pattern, when performing copper electroplating or electric solder plating, when the seepage of the plating solution occurs between the cured resist and the copper surface, Solder plating is applied to portions other than the circuit portion, which causes problems such as a short circuit between copper wires, an increase in the width of the copper wire, and a disturbance in the peripheral portion of the copper wire. It is presumed that the insufficient heat-resistant adhesion of the polyimide film is caused by the above-mentioned corrosion action and generation of copper ions.

When a resist film is formed on a substrate on which metal wiring or a metal layer is formed by using a photosensitive polyimide resin, the resist film is developed due to a reaction between a carboxyl group of the resin and copper or a copper alloy. Sometimes a residual film occurs in the unexposed area,
There is a problem that it is difficult to form a clean pattern. That is, when a carboxyl group reacts with copper, carboxyl copper (copper salt) is generated. The polyamic acid produced by the carboxyl copper has reduced solubility in its own solvent, and causes a residual film to be formed in an unexposed portion when developing with a solvent after the exposure step. Carboxylic copper is oxidized by dissolved oxygen to generate divalent copper ions. Copper ions not only reduce electrical insulation,
This may cause a decrease in the molecular weight of the polyimide, a decrease in physical properties of the film, a decrease in adhesion, and the like. It is known that divalent copper ions undergo electron transfer (migration) when combined with an acrylic monomer and undergo radical polymerization. Among the photosensitive polyimide-based resins, those having an acrylolyl group as a photosensitive group are liable to cause a residual film in an unexposed portion during development, particularly under the influence of copper ions.

Hitherto, several proposals have been made to improve the adhesion between the substrate and the polyimide film. For example, a method of improving the adhesion to a polyimide film by providing a silane coupling agent layer on the surface of a copper layer (Japanese Patent Application Laid-Open No. 1-174439).
A method for suppressing the corrosiveness of polyamic acid by adding at least one compound selected from benzotriazole, 1,2,4-triazole and derivatives thereof (Japanese Patent Application Laid-Open No. 228359/1990); By adding a silane coupling agent to
A method for improving the adhesion of a polyimide film to a substrate (Japanese Patent Laid-Open No. 60-157286) has been proposed. However, varnishes containing these compounds have a problem that storage stability is reduced. Especially,
A polyamic acid varnish to which a silane coupling agent has been added has significantly reduced storage stability.

In the field of printed wiring boards, an imidazole compound is brought into contact with and adhered to a metal wiring or a metal foil formed on a heat-resistant insulating substrate to modify the surface of the metal wiring or the metal foil, A coating method for forming an overcoat layer having excellent heat resistance adhesion (plating resistance) and flexibility by further applying a polyimide siloxane solution composition on the imidazole compound adhesion layer and drying to form a coating layer. Has been proposed. However, the imidazole compound has an insufficient effect of suppressing copper ion generation and migration into the resin coating layer. Further, the imidazole compound has an insufficient effect of suppressing the remaining film in the unexposed portion in the pattern forming method using a photoresist.

In the process of manufacturing a printed wiring board using a photosensitive resin, a poly (meth) acrylate polymer, a cross-linkable monomer, And a method of adding tetrazole or a derivative thereof to a photopolymerizable resin composition containing a photopolymerization initiator (JP-A-59-1257).
26, JP-A-61-186952 and JP-A-2-2083439. Recently, the present inventors have found that a resin composition exhibiting an excellent rust-preventing effect on copper and copper alloy can be obtained by adding 1H-tetrazole to a polyimide resin (Japanese Unexamined Patent Publication (Kokai) No. Heisei (Kokai) No. H10-260, 1988). 8-
286374). However, these methods only add a tetrazole, and do not aim at modifying the resin itself.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyimide resin composition having excellent rust-preventing effect, residual film-preventing effect, and film-adhering effect on copper and copper alloys. . More specifically, an object of the present invention is to provide a polyimide resin composition capable of exhibiting a stable rust prevention effect, a residual film prevention effect, and a film adhesion effect by using a modified polyimide resin. Is to do. Further, an object of the present invention is to provide a method for producing a terminal-modified polyimide resin that can exhibit a stable rust-preventing effect, a residual film-preventing effect, and a film adhesion effect.

The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result, have found that a terminal modified polyimide resin having a structure in which a tetrazole group is introduced at one or both ends of the polyimide resin is used. As a result, a stable rust-preventing effect, a remaining film-preventing effect, and a film adhesion effect can be obtained. Such a terminal-modified polyimide resin is obtained by reacting a polyimide resin having an amino group or a carboxyl group at a terminal with a compound having a functional group capable of reacting with an amino group or a carboxyl group and a tetrazole group. be able to. Further, this terminal-modified polyimide resin is a functional group capable of reacting with an amino group or a carboxyl group when producing a polyamic acid by reacting a diamine compound with a tetracarboxylic acid or an acid anhydride thereof in a polar organic solvent. It can be synthesized by the presence of a compound having a group and a tetrazole group. Furthermore, when synthesizing such a polyamic acid, if an actinic radiation functional group is also introduced at the end,
A polyamic acid having excellent rust prevention and photosensitivity can be obtained. The present invention has been completed based on these findings.

[0012]

According to the present invention, there is provided a polyimide resin composition comprising, as essential components, a polyimide resin (A) having at least one terminal into which a tetrazole group is introduced and a solvent (B). Is done. Further, according to the present invention, in a method for producing a polyamic acid by reacting a diamine compound with a tetracarboxylic acid or an acid anhydride thereof in a polar organic solvent, the reaction system comprises a diamine compound and a tetracarboxylic acid or an acid thereof. By the presence of a compound (a) having a functional group capable of reacting with an amino group or a carboxyl group and a tetrazole group together with an anhydride,
There is provided a method for producing a terminal-modified polyimide resin, which comprises producing a polyamic acid having a tetrazole group introduced into at least one terminal. Further, according to the present invention, a polyimide resin having an amino group or a carboxyl group at at least one terminal is reacted with a compound (a) having a functional group capable of reacting with an amino group or a carboxyl group and a tetrazole group. By doing
There is provided a method for producing a terminal-modified polyimide resin, which comprises producing a polyimide resin having a tetrazole group introduced into at least one terminal.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Polyimide Resin In the present invention, the polyimide resin to be introduced with a tetrazole group at at least one end includes polyamic acid, solvent-soluble polyimide, photosensitive polyamic acid, photosensitive polyamic acid ester, photosensitive polyamide acid ester, Polyimide. Polyamic acid is generally polycondensed at 0 to 100 ° C. in a polar organic solvent under anhydrous conditions using tetracarboxylic acid or an acid anhydride thereof as an acid component and a diamine compound as an amine component. Are synthesized by The photosensitive polyamic acid or photosensitive polyamic acid ester can be obtained by a method of introducing a photopolymerizable acryloyl group into a polyamic acid or a polyamic acid ester, a method of introducing an actinic radiation functional group into a terminal, or the like. The photosensitive polyamic acid or photosensitive polyamic acid ester may contain a photopolymerization initiator, a photosensitizer, a photosensitive auxiliary (crosslinking auxiliary), and the like, if necessary. As the solvent-soluble polyimide and the photosensitive polyimide, known polyimides can be used.

A polyimide resin having an amino group or a carboxyl group at at least one end is synthesized, and this resin is reacted with a compound (a) having a tetrazole group and a functional group capable of reacting with an amino group or a carboxyl group. By doing so, it is possible to synthesize a polyimide resin having a tetrazole group at the end, at the time of synthesis of polyamic acid, a compound having a functional group capable of reacting with an amino group, a carboxyl group or an acid anhydride group and a tetrazole group It is preferable to employ a method of synthesizing by the presence of (a) in order to surely modify the terminal.

<Diamine Compound> Examples of the diamine compound include 2,2'-di (p-aminophenyl)-
6,6'-bisbenzoxazole, 2,2'-di (p
-Aminophenyl) -5,5'-bisbenzoxazole, m-phenylenediamine, 1-isopropyl-2,
4-phenylenediamine, p-phenylenediamine,
4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'diaminodiphenylethane, 4,
4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide,
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, benzidine, 4,4 "-diamino-p-terphenyl, 3, 3 "-diamino-p-terphenyl, bis (p
-Aminocyclohexyl) methene, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-
Methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene,
1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5
Aromatic diamines such as diamine, p-xylene-2,5-diamine, m-xylylenediamine and p-xylylenediamine; 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino Heterocyclic diamines such as -1,3,4-oxadiazole; alicyclic diamines such as 1,4-diaminocyclohexane; piperazine, methylene diamine, ethylene diamine, propylene diamine, 2,2-dimethyl propylene diamine, tetra Methylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, heptamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4 −
Dimethylheptamethylenediamine, octamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylnonamethylenediamine, decamethylenediamine, 1,10-diamino-1,10-
Dimethyldecane, 2,11-diaminododecane, 1,1
Aliphatic diamines such as 2-diaminooctadecane, 2,12-diaminooctadecane, and 2,17-diaminoicosane; and diaminosiloxane, 2,6-diamino-4-carboxylic benzene, 3,3'-diamino-4 , 4'-dicarboxylic benzidine and the like. These diamine compounds can be used alone or in combination of two or more. Among these, 2,2'-di (p-aminophenyl) -6,6'-bisbenzoxazole and 2,2'-di (p-aminophenyl) -6,6'-bisbenzoxazole
2'-di (p-aminophenyl) -5,5'-bisbenzoxazole is particularly preferable since a polymer having low thermal expansion and high heat resistance can be obtained.

<Tetracarboxylic acid or acid anhydride thereof>
Examples of the tetracarboxylic acid or an acid anhydride thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, benzene
1,2,3,4-tetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride , Naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5
-Tetracarboxylic dianhydride, naphthalene-1,2,2
5,8-tetracarboxylic dianhydride, naphthalene-1,
2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,
8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8- Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,
3,6,7-tetrachloronaphthalene-1,4,5,8
-Tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride Anhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3', 4'-diphenyltetracarboxylic dianhydride, 2,3 ", 4,4" -p
-Terphenyltetracarboxylic dianhydride, 2,2 ″,
3,3 "-p-terphenyltetracarboxylic dianhydride, 2,3,3", 4 "-p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl ) -Propane dianhydride, 2,2-bis (3,4
-Dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3 -Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,
3,8,9-tetracarboxylic dianhydride, perylene-
3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride,
Perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride , Phenanthrene-1,2,9,
Aromatic tetracarboxylic dianhydrides such as 10-tetracarboxylic dianhydride and hydrogenated products thereof; cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, Bicyclo [2,2,
2] oct-7-en-2-exo, 30 exo, 5-
Exo, 6-exotetracarboxylic acid 2,3: 5,6-
Alicyclic acid anhydrides such as dianhydride and bicyclo [2,2,1] heptane-2-exo, 3-exo, 5-exo, 6-exotetracarboxylic acid 2,3: 5,6-dianhydride Stuff;
Pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride And the like. These can be used alone or in combination of two or more. Among these, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, and combinations thereof,
It is particularly preferable to achieve good low thermal expansion, crack resistance, resolution, and the like.

In the present invention, the compound (a) having a functional group capable of reacting with an amino group or a carboxyl group and a tetrazole group is used as a modifying agent, so that at least one end of the compound has a tetrazole group. To synthesize a polyimide resin (A) into which is introduced. Such a tetrazole group-containing compound (a)
Can be represented by the following formula (III).

[0018]

Embedded image In the formula (III), the meaning of each symbol is as follows.
R ₁ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, a cyclic aliphatic group having 3 to 6 carbon atoms, a phenyl group, A substituted phenyl group represented by (2),

[0019]

Embedded image [In the formula (2), n = an integer of 1 to 3; X = an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, -NR'R "(R ', R" = each independently A hydrogen atom, a methyl group, an ethyl group, an acetyl group, or an ethylcarbonyl group; provided that both are not hydrogen atoms.), —COOCH ₃ , —NO ₂ , —SH,
Or —SCH ₃ ] or a substituted alkyl group represented by the following formula (3).

[0020]

Embedded image [In the formula (3), m = 1 to 10; Y = —NR′R ″ (R ′, R ″ = each independently a hydrogen atom, a methyl group, an ethyl group, an acetyl group, or an ethylcarbonyl group) However, unless both are hydrogen atoms), a phenyl group, or a substituted phenyl group represented by the above formula (2). ]

Among these substituents, specific examples of the preferred substituent for R ₁ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group and a t-butyl group. Butyl group, pentyl group,
3-methyl-1-butyl group, hexyl group, 4-methyl-
An alkyl group having 1 to 6 carbon atoms such as 1-pentyl group; a cycloaliphatic group having 3 to 6 carbon atoms such as cyclopropyl group, cyclopentyl group, 2-methylcyclopentyl group and cyclohexyl group; phenyl group; N) is 1 or 2 among the substituted phenyl groups represented by
6, an alkyl group, a methylamino group, an acetamido group,-
SH, for example, a substituted phenyl group such as a methylphenyl group, a dimethylphenyl group, a butylphenyl group, a t-butylphenyl group, an aminomethylphenyl group, an acetamidophenyl group, and a mercaptophenyl group; Among the substituted alkyl groups represented, m is 1 or 2, and Y is a phenyl group, a methylamino group,
Dimethylamino group, acetamido group, for example, benzyl group, aralkyl group such as phenethyl group, aminomethyl group, aminoethyl group, methylaminomethyl group, dimethylaminomethyl group, acetylaminomethyl group, etc. Methyl group; and the like.

P is a functional group capable of reacting with an amino group or a carboxyl group. Due to the presence of the functional group P, it can react with a polyimide resin having an amino residue or an acid anhydride residue (usually, a carboxyl group) at a terminal to introduce a tetrazole group at the terminal of the resin. . Alternatively, when the compound (a) is present together with the monomeric diamine compound and the tetracarboxylic acid or its acid anhydride during the synthesis of the polyamic acid due to the presence of the functional group P, the polyamic acid having a tetrazole group at the terminal Can be synthesized. As a preferable specific example of P, when reacting with an amino group or an amino residue, -COX [X = hydrogen atom, halogen atom, -OH,
Or -OR (R = alkyl group having 1 to 3 carbon atoms)],-
SO ₂ X [X = a halogen atom or -OH),], a halogen atom, -OH, -SH, and the like, for reacting with a carboxyl group or an acid anhydride group, -NH _2,
—NHR (R = alkyl group having 1 to 3 carbon atoms), —SH, and the like can be given.

Q is a single bond or a divalent organic group. When the functional group P is directly bonded to the tetrazole group, Q is a single bond. The functional group P does not necessarily need to be directly bonded to the tetrazole group, and may be bonded via a divalent organic group as a spacer. When Q is a divalent organic group, preferred examples thereof include groups represented by formulas (5), (6), and (7).

[0024]

Embedded image (Where p is an integer of 1 to 5; R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, 1 carbon atom
Alkoxy group, alkenyl group having 2 to 4 carbon atoms)

[0025]

Embedded image (Wherein, r is an integer of 0 to 2; R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, 1 carbon atom
Alkoxy group, alkenyl group having 2 to 4 carbon atoms)

[0026]

Embedded image (Wherein, R ₆ and R ₇ = each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyl group having 2 to 4 carbon atoms)

Preferred examples of the compound (a) include, for example, 5-amino-1H-tetrazole, 5-amino-1
-Methyl-1H-tetrazole, 5-amino-1-phenyl-1H-tetrazole, 5-carboxy-1H-tetrazole, 5-carboxy-1-methyl-1H-tetrazole, 5-carboxy-1-phenyl-1H-tetrazole , 5-chloro-1H-tetrazole, 5-hydroxy-1H-tetrazole, 5-nitro-1H-tetrazole and the like. Among these tetrazole group-containing compounds (a), the compound containing a 1H-tetrazole group in which R ₁ = H is excellent in the effect of preventing migration of copper ions and the effect of preventing the unexposed portion from remaining film. Particularly preferred.

The terminal-modified polyimide resin having a structure in which a tetrazole group is introduced into at least one terminal of the terminal-modified polyimide resin is obtained by reacting a diamine compound with a tetracarboxylic acid or an acid anhydride thereof in a polar organic solvent. In the method for producing polyamic acid,
In the reaction system, a compound (a) having a functional group capable of reacting with an amino group or a carboxyl group and a tetrazole group is present together with a diamine compound and a tetracarboxylic acid or an acid anhydride thereof, so that at least one end of the tetrazole compound It can be obtained by a production method for producing a polyamic acid into which a group has been introduced. The production conditions in this case are the same as the ordinary production conditions for polyamic acid except that the compound (a) is present, and the diamine compound and the tetracarboxylic acid or the acid anhydride and the compound (a) are used.
Is subjected to polycondensation in a polar organic solvent at 0 to 100 ° C. under anhydrous conditions to obtain a polyamic acid having a terminal tetrazole group. Compound (a) is
It is used in an amount of usually about 0.5 to 15 mol%, preferably about 1 to 10 mol%, per 1 mol of the diamine compound or tetracarboxylic acid or its acid anhydride.

The terminal-modified polyimide resin having a structure in which a tetrazole group is introduced into at least one terminal is obtained by reacting a polyimide resin having an amino group or a carboxyl group in at least one terminal with an amino group or a carboxyl group. It can be obtained by reacting a compound (a) having a functional group and a tetrazole group. Also in this case, the reaction is usually performed at 0 to 100 ° C. in a polar organic solvent under anhydrous conditions. Compound (a), the functional group P is, -NH _2, -NHR, -NO _2, or -
In the case of SH, these functional groups react with a carboxyl group or an acid anhydride group to form an atomic group (T ¹ ) containing a tetrazole group represented by the formula (1).

[0030]

Embedded image [In formula (1), P ¹ = —NH—, —NR— (R = alkyl group having 1 to 3 carbon atoms), —SO ₂ —, —SO ₂ O—, —O—, or —S
-; Q = single bond, or a divalent organic group; R ₁ = hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms,
A cyclic aliphatic group having 3 to 6 carbon atoms, a phenyl group, a substituted phenyl group represented by the formula (2), or the formula (3);
A substituted alkyl group represented by When a compound (a) having a functional group capable of reacting with a carboxyl group (or an acid anhydride group) and a tetrazole group is present at the time of synthesizing a polyamic acid, as shown in the formula (8), A polyamic acid (terminal-modified polyimide resin) to which T ¹ is bonded can be obtained.

[0031]

Embedded image [In the formula (8), R ¹ = tetravalent organic group; R ² = divalent organic group; k = integer of 5 to 10,000; T ¹ = atom containing tetrazole group represented by formula (1) Corps. On the other hand, the functional group P of the compound (a) is -COX, -SO ₂
X, a halogen atom, —OH, or —SH;
Since these functional groups react with an amino group or an amino residue, an atomic group (T ² ) containing a tetrazole group represented by the formula (4) is formed.

[0032]

Embedded image Wherein (4), P ² = single bond, -CO -, - COO -, - SO 2 -, or -SO ₂ O-; Q = single bond, or a divalent organic group; R ₁ = hydrogen An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms,
A cyclic aliphatic group having 3 to 6 carbon atoms, a phenyl group, a substituted phenyl group represented by the formula (2), or the formula (3);
A substituted alkyl group represented by In this case, when a compound (a) having a functional group capable of reacting with an amino group and a tetrazole group is present during the synthesis of the polyamic acid, as shown in the formula (9), T
A polyamic acid (terminal-modified polyimide resin) to which ² is bonded can be obtained.

[0033]

Embedded image [In the formula (9), R ¹ = tetravalent organic group; R ² = divalent organic group; k = integer of 5 to 10,000; T ² = atom containing tetrazole group represented by formula (4) Corps. ]

<Introduction of Actinic Radiation Functional Group> In the present invention, various photosensitive polyamic acids and photosensitive polyamic acid esters can be used as the polyimide resin. Polyamic acid having a functional group introduced is preferred. Specific examples thereof include trimellitic acid derivatives (b) such as trimellitic anhydride [tris (acryloyl) pentaerythritol] ester and trimellitic anhydride [tris (methacryloyl) pentaerythritol] ester during the synthesis of polyamic acid. ) (JP-A-8-95247); aminobenzenes (c) such as p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester (JP-A-8-82931); A polyamic acid having an actinic radiation functional group having a (meth) acryloyl group or the like at its terminal can be obtained.

The polyamic acid having such an actinic radiation functional group is obtained by adding a trimellitic acid derivative (b) and a tetracarboxylic acid or an acid anhydride thereof to a diamine compound.
A method of performing a condensation reaction by a conventional method, a method of adding a tetracarboxylic acid or an acid anhydride thereof to a mixture of a diamine compound and a trimellitic acid derivative (b), and performing a condensation reaction by a conventional method; )
Can be synthesized by a method of adding a tetracarboxylic acid or an acid anhydride thereof to a mixture and subjecting the mixture to a condensation reaction by a conventional method.

In the present invention, it is necessary to introduce a tetrazole group into at least one terminal of the polyamic acid.
When synthesizing the polyamic acid, the compound (a) is preferably used in combination with the trimellitic acid derivative (b) or aminobenzenes (c) for introducing an actinic radiation functional group. Of course, a polyamic acid having a tetrazole group introduced at a terminal and a polyamic acid having an actinic ray functional group introduced at a terminal can be blended and used. The trimellitic acid derivative (b) or the aminobenzenes (c) is used in an amount of usually 0.5 to 15 mol%, preferably 1 to 5 mol per mol of a diamine compound or tetracarboxylic acid or an acid anhydride thereof.
It is used in a proportion of 10 to 10 mol%. Examples of the polyamic acid having an actinic ray functional group introduced at a terminal include a group Z ¹ represented by the formula (10),

[0037]

Embedded image [In the formula (10), X is a single bond, -O-, -CO-, -COO-, -OCO
-, - OCOO -, - COCH 2 O -, - S -, - SO
—, —SO ₂ —, or —SO ₂ O—; R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ = substituents having a photopolymerizable carbon-carbon double bond; m = 0 or 1 N = an integer from 1 to 3; And a group Z ² represented by the formula (11)

[0038]

Embedded image [In the formula (11), R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ = a substituent having a photopolymerizable carbon-carbon double bond; m = 0 or 1. Polyamic acid having at least one actinic radiation functional group selected from the group consisting of A polyamic acid having an actinic radiation functional group Z ¹ represented by the formula (10) at both ends is represented by the formula (1)
It is represented by 2).

[0039]

Embedded image [In the formula (12), R ¹ = tetravalent organic group; R ² = divalent organic group; k = integer of 5 to 10,000; Z ¹ = actinic radiation functional group represented by the above formula (10). The polyamic acid has an actinic radiation functional group Z represented by the formula (11)
^The polyamic acid having ² at both ends is represented by the formula (13).

[0040]

Embedded image [In the formula (13), R ¹ = tetravalent organic group; R ² = divalent organic group; k = integer of 5 to 10,000; Z ² = actinic radiation functional group represented by the above formula (11). As aminobenzenes used for introducing the actinic radiation functional group Z ¹ represented by the formula (10), the following formula (14)
Can be mentioned.

[0041]

Embedded image [In the formula (14), X = a single bond, -O-, -CO-, -COO-, -OCO
-, - OCOO -, - COCH 2 O -, - S -, - SO
—, —SO ₂ —, or —SO ₂ O—; R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ = substituents having a photopolymerizable carbon-carbon double bond; m = 0 or 1 N = an integer from 1 to 3; ]

Representative examples of the photopolymerizable substituent having a carbon-carbon double bond include an acryloyloxymethylene group and a methacryloyloxymethylene group, and in addition, a vinyl group, a propenyl group, and an isopropenyl group. , Butenyl, pentynyl, hexynyl, 2
An alkenyl group having 2 to 6 carbon atoms such as -ethylbutenyl group or a substituted product thereof. Specific examples of the substituent capable of bonding to an alkenyl group having 2 to 6 carbon atoms include a halogen atom, a phenyl group, an alkenyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. As the aminobenzenes, an aminobenzenecarboxylic acid ester represented by the following formula (15) is preferable.

[0043]

Embedded image The trimellitic acid derivative used to introduce the actinic radiation functional group Z ² represented by the formula (11) is represented by the formula (16)
Can be mentioned.

[0044]

Embedded image [In the formula (16), R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ = a substituent having a photopolymerizable carbon-carbon double bond; m = 0 or 1. ]

Representative examples of the photopolymerizable substituent having a carbon-carbon double bond include an acryloyloxymethylene group and a methacryloyloxymethylene group, and in addition, a vinyl group, a propenyl group, and an isopropenyl group. , Butenyl, pentynyl, hexynyl, 2
An alkenyl group having 2 to 6 carbon atoms such as -ethylbutenyl group or a substituted product thereof. Specific examples of the substituent capable of bonding to an alkenyl group having 2 to 6 carbon atoms include a halogen atom, a phenyl group, an alkenyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. When such an actinic ray functional group and a tetrazole group are introduced during the synthesis of the polyamic acid, theoretically, a polyamic acid having T ¹ introduced at both terminals represented by the formula (8) and a polyamic acid represented by the formula (12) It is estimated that a mixture of a polyamic acid having actinic radiation functional groups Z ¹ introduced at both ends and a polyamic acid having T ¹ and Z ¹ introduced at both ends represented by the formula (17) are obtained. You.

[0046]

Embedded image Therefore, the polyamic acid of the present invention having a tetrazole group introduced into at least one terminal can be represented by the formula (I).

[0047]

Embedded image [In formula (I), R ¹ = tetravalent organic group; R ² = divalent organic group; k = integer of 5 to 10,000; W ¹ = T ¹ , —OH, or actinic radiation functional group; T ¹ = Atomic group containing a tetrazole group represented by the formula (1). Here, when W ¹ is an actinic radiation functional group, it is preferably Z ¹ . When such an actinic ray functional group and a tetrazole group are introduced during the synthesis of polyamic acid,
Theoretically, polyamic acid having T ² introduced at both ends represented by formula (9), polyamic acid having actinic radiation functional group Z ² introduced at both ends represented by formula (13), and formula (18)
It is estimated that a mixture of polyamic acids having T ² and Z ² introduced at both ends represented by the following formulas is obtained.

[0048]

Embedded image Therefore, the polyamic acid of the present invention having a tetrazole group introduced into at least one terminal can be represented by the formula (II).

[0049]

Embedded image [In the formula (II), R ¹ = tetravalent organic group; R ² = divalent organic group; k = integer of 5 to 10,000; W ² = T ² , —OH, or actinic radiation functional group; T ² = Atomic group containing a tetrazole group represented by the formula (4). Here, when W ² is an actinic radiation functional group, it is preferably Z ² .

Polyimide Resin Composition The polyimide resin composition of the present invention is a composition containing, as essential components, a polyimide resin (A) having at least one terminal into which a tetrazole group is introduced and a solvent (B). is there. The polyimide resin is used by dissolving it in at least an amount of a solvent sufficient to uniformly dissolve the resin. In the polyimide resin composition of the present invention, if necessary, other polyimide resin (C), a photopolymerization initiator (D), a photosensitizer having a photopolymerizable functional group (E) and the like are mixed. be able to. Examples of other polyimide resins (C) include polyamic acid, solvent-soluble polyimide, photosensitive polyamic acid, photosensitive polyamic acid ester, and photosensitive polyimide. These can be used alone or in combination of two or more. In addition, the polyimide-based resin composition of the present invention may be mixed with a polyvinylphenol-based compound, a polyacrylate-based resin, or the like, depending on the application.

The polyimide-based resin composition of the present invention has a polyimide-based resin composition in such a proportion that the weight ratio of the tetrazole group is within the range of 0.1 to 10 parts by weight based on 100 parts by weight of the resin component (all resin components). It is preferable to contain (A). Here, the weight ratio of the tetrazole group is represented by the formula (II)
In the compound (a) represented by I), it means the weight ratio in the resin component based on the tetrazole residue excluding the functional group P and the linking group Q. If this ratio is too small, the rust-preventing effect, residual film-preventing effect, film-adhering effect, etc. will be insufficient. If it is too large, it is not economical and may adversely affect physical properties. This ratio is preferably 0.1
To 5 parts by weight, more preferably 0.3 to 3 parts by weight.
Within these preferred ranges, the residual film ratio can be further reduced.

<Solvent> The solvent used for dissolving the polyimide resin in the present invention includes, for example, N-
Examples include polar organic solvents such as methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, and γ-butyrolactone. In addition to these polar organic solvents, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, and diethyl malonate; diethyl ether, ethylene glycol dimethyl ether , Diethylene glycol dimethyl ether, ethers such as tetrahydrofuran; dichloromethane, 1,
Halogenated hydrocarbons such as 2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene; hydrocarbons such as hexane, heptane, octane, benzene, toluene, xylene, etc. Can be. These solvents can be used alone or in combination of two or more. Among these, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferred.
The amount of the solvent used is an amount sufficient to uniformly dissolve the polyimide resin and other solid components.

<Photosensitive Aid> Typical examples of the photosensitive aid include (meth) acrylic acid compounds such as pentaerythritol triacrylate. As the acrylic acid-based compound, for example, acrylic acid, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carbitol acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butylene Glycol monoacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol monoacrylate, trimethylolpropane monoacrylate, allyl acrylate, 1,3-propylene glycol di Acrylate, 1 4- butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, 2,2-bis - (4-
Acryloxydiethoxyphenyl) propane, 2,2-
Bis- (4-acryloxypropyloxyphenyl) propane, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylformal, tetramethylolmethanetetraacrylate, tris (2-hydroxy Ethyl) acrylate of isocyanuric acid, formula (19)
A compound of

[0054]

Embedded image [In the formula (19), b = 1 to 30. A compound of the formula (20),

[0055]

Embedded image [In the formula (20), c and d = c + d = an integer of 2 to 30] A compound of the formula (21):

[0056]

Embedded image A compound of formula (22),

[0057]

Embedded image And the like.

Examples of the methacrylic acid compound include, for example,
Methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, ethylhexyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate, hydroxyethyl methacrylate, hydroxy Propyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacryloxypropyl tri Toxisilane, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, 2,2-bis- (4-methacrylic Roxydiethoxyphenyl) propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethanetetramethacrylate, methacrylic acid ester of tris (2-hydroxyethyl) isocyanuric acid,
A compound of formula (23),

[0059]

Embedded image [In the formula (23), e = 1 to 30. A compound of the formula (24),

[0060]

Embedded image [In the formula (24), f and g = f + g = 1 to 30 as integers. A compound of the formula (25),

[0061]

Embedded image Compound of Formula (26)

[0062]

Embedded image And the like.

These compounds can be used alone or in combination of two or more. Among these, pentaerythritol triacrylate and the compound of the formula (19) (b = 3) are particularly preferable, and commercially available products include 3EG-A (manufactured by Kyoeisha) and Biscoat 300 (manufactured by Osaka Organic Chemical Company). There is. The photosensitive assistant is usually added in an amount of 1 to 100 parts by weight of the polyimide resin.
It is desirable to use 0 to 40 parts by weight, preferably 15 to 35 parts by weight, more preferably 20 to 30 parts by weight.

<Photopolymerization initiator> As the photopolymerization initiator,
For example, Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone,
1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis- (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene,
2,2-dimethoxy-2-phenylacetophenone, 1
-Hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, diphenyldisulfide, anthracene, phenanthrenequinone, riboflavin tetra Butyrate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis (p-diethylaminobenzylidene) -4-methyl-4-azacyclohexanone, 6-bis (p-dimethylaminobenzylidene)
-Cyclopentanone, 2,6-bis (p-diethylaminobenzylidene) -4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compound, biscoumarin compound, N-phenylglycine, N-phenyldiethanolamine, 3,3 ', 4,4'-tetra (t-
(Butylperoxycarbonyl) benzophenone and the like. The photopolymerization initiator is used in an amount of usually 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the polyimide resin.

<Other Additives> Various additives such as an adhesion aid, a leveling agent, and a polymerization inhibitor can be used as necessary for the polyimide resin. Further, a tetrazole compound such as 1H tetrazole is used in an amount of usually 0.05 to 20 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the resin. It may be added. When a tetrazole compound is added, a more reliable effect can be obtained in combination with the action of the polyimide resin (A).

Use The terminal-modified polyimide resin of the present invention and the polyimide resin composition containing the resin are particularly useful for applications such as surface protection films and interlayer insulating films of semiconductor devices. Further, the photosensitive polyimide resin composition of the present invention is useful for applications such as interlayer insulating films for multilayer circuits, cover coats for flexible printed copper clad boards, solder resist films, and liquid crystal alignment films. The method for coating the polyimide resin composition is as follows. First, a solution containing a resin component and various additive components is used, for example, a silicon wafer, a glass substrate of a display device such as an LCD, a reticle or a mask used in a semiconductor process, a ceramic, a heat-resistant material. It is applied on a substrate such as a film. Generally, a metal wiring and a metal layer are formed on the application surface of the substrate. The application method includes spin coating using a spinner, spray coating using a spray coater,
There are methods such as dipping, printing, and roll coating.

In the case of a photosensitive polyimide resin, the coated film is dried by prebaking at a relatively low temperature, and then irradiated with actinic rays (actinic rays) in a desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used. Next, a relief pattern is usually obtained by dissolving and removing the unirradiated portion with a developer. Examples of the developing solution include polar organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, methanol, isopropyl alcohol, and water. Mix and use. In the case of an alkali-soluble polyimide resin,
An alkali developer or an aqueous alkali solution may be used.
Various methods such as spraying, paddle, immersion, and ultrasonic wave can be adopted as the developing method. The relief pattern formed by development is rinsed. Examples of the rinsing liquid include methanol, ethanol, isopropyl alcohol, and butyl acetate. Next, a heat treatment is performed to form an imide ring, and the polyamic acid is converted to a polyimide to obtain a final pattern having high heat resistance. For those already imidized, such as soluble polyimides, the imidization step is omitted.

The effect of the resin composition of the present invention is remarkable in the following cases. (1) A case in which a polyamic acid is applied in a varnish state onto a copper wiring or a copper layer, and is cured by heating (curing) to form a polyimide insulating film. (2) A case where a polyimide pattern is formed on a copper wiring or a copper layer using photosensitive polyamic acid. (3) When a polyimide film is formed on a copper wiring or a copper layer using a solvent-soluble polyimide. (4) A case where a polyimide pattern is formed on a copper wiring or a copper layer using a photosensitive polyamic acid ester. (5) A case where a photosensitive polyimide is used to form a polyimide pattern on a copper wiring or a copper layer.

When the polyimide resin composition of the present invention is used to form a flexible overcoat layer on a metal wiring or a metal layer formed on a substrate surface, high heat resistance and heat resistance (for example, tin plating) It is possible to obtain a resin-coated substrate excellent in plating resistance, which suppresses a plating solution in a treatment, a solder plating treatment, a gold plating treatment or the like from penetrating into a boundary surface between a metal wiring and a coating layer. Further, when the photosensitive polyimide-based resin composition is used, a remaining film in an unexposed portion can be suppressed, and a clear pattern can be formed. In particular, when using a photosensitive polyamic acid resin, generally,
Although the remaining film in the unexposed portion is remarkable, the use of the photosensitive polyamic acid having a tetrazole group introduced into the terminal of the present invention makes it possible to make a significant improvement and to form a clear pattern. The metal wiring or metal layer is made of copper, silver, gold, aluminum or the like. Particularly, in the case of copper and copper alloy, this effect is large.

[0070]

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to only these Examples. [Synthesis Example 1] In a reactor, 2,2'-di (p-aminophenyl) -6,6'-bisbenzoxazole 110.9 was added.
g (0.265 mol), 10.1 g of p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester as an aminobenzene for terminal modification (0.1 g).
022 mol), 552 g of dimethylacetamide, and 552 g of N-methylpyrrolidone to prepare a uniform solution. Under ice-cooling and stirring of this homogeneous solution, 44.3 g (0.138 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 30 g (0.138 mol) of pyromellitic dianhydride were obtained as acid anhydrides. ) Was added in small portions in powder form. Then, the reaction was carried out for 3 hours under ice cooling and for 20 hours at room temperature. Thus, a solution containing polyamic acid (code No. A) was obtained.

[Synthesis Example 2] 2,2'-di (p
-Aminophenyl) -6,6'-bisbenzoxazole 110.8 g (0.265 mol), p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester 5.0 g (0.011 mol), 5-amino-1H 0.94 g of tetrazole (0.011 mo
l), 540 g of dimethylacetamide and 540 g of N-methylpyrrolidone were added to prepare a homogeneous solution. Under ice-cooling and stirring, the homogeneous solution was acidified as 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride 4
A mixture of 4.3 g (0.138 mol) and 30 g (0.138 mol) of pyromellitic dianhydride was added little by little as a powder. Then, the reaction was carried out for 3 hours under ice cooling and for 20 hours at room temperature. Thus, a solution containing polyamic acid (code No. B) was obtained.

[Synthesis Example 3] A 2,2'-di (p
-Aminophenyl) -6,6'-bisbenzoxazole 110.8 g (0.265 mol), 5-amino-1
1.87 g (0.022 mol) of H-tetrazole, 529 g of dimethylacetamide, and 529 g of N-methylpyrrolidone were added to prepare a uniform solution. 3,3 ′, 4,4′- as an acid anhydride was added to the homogeneous solution under ice-cooling and stirring.
Benzophenonetetracarboxylic dianhydride 44.3 g
(0.138 mol) and pyromellitic dianhydride 30 g
(0.138 mol) was added in small portions in powder form. Then, the reaction was carried out for 3 hours under ice cooling and for 20 hours at room temperature. Thus, the polyamic acid (code N
o. A solution containing C) was obtained.

[Synthesis Example 4] 2,2'-di (p
-Aminophenyl) -6,6'-bisbenzoxazole 110.8 g (0.265 mol), p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester 10.1 g (0.022 mol), dimethylacetamide 552 g, and N-methylpyrrolidone 5
52 g was charged to prepare a homogeneous solution. To this homogeneous solution, 44.3 g (0.3%) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added as an acid anhydride under ice-cooling and stirring.
138 mol) and pyromellitic dianhydride 30 g (0.
138 mol) was added as a powder in small portions. Then, the reaction was carried out for 3 hours under ice cooling and for 20 hours at room temperature. Thus, a solution containing polyamic acid was obtained.
Next, the polyamic acid solution 66 thus obtained is obtained.
6.7 parts by weight (100 parts by weight of solid content) to 3,3 ',
4,4'-tetra (t-butylperoxycarbonyl)
2 parts by weight of benzophene, 2 parts by weight of N-phenylglycine, and 28 parts by weight of 3EG-A (manufactured by Kyoeisha Co., Ltd.) as a photosensitizer were added and dissolved at room temperature. Thus, a photosensitive polyamic acid (code No. D) was obtained.

[Synthesis Example 5] 2,2'-di (p
-Aminophenyl) -6,6'-bisbenzoxazole 110.8 g (0.265 mol), p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester 5.1 g (0.011 mol), 5-amino-1H 0.94 g of tetrazole (0.11 mol
l), 540 g of dimethylacetamide and 540 g of N-methylpyrrolidone were added to prepare a uniform solution. Under ice-cooling and stirring, the homogeneous solution was acidified as 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride 4
A mixture of 4.3 g (0.138 mol) and 30 g (0.138 mol) of pyromellitic dianhydride was added little by little as a powder. Then, the reaction was carried out for 3 hours under ice cooling and for 20 hours at room temperature. Thus, a solution containing polyamic acid was obtained. Next, 26.6 parts by weight of 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone was added to 666.7 parts by weight (100 parts by weight of solid content) of the polyamic acid solution thus obtained. , N-phenylglycine (2 parts by weight) and 28 parts by weight of a photosensitizer 3EG-A (manufactured by Kyoeisha Co., Ltd.) and dissolved at room temperature. Thus, a photosensitive polyamic acid (code No. E) was obtained.

[Synthesis Example 6] 2,2'-di (p
-Aminophenyl) -6,6'-bisbenzoxazole 98.2 g (0.235 mol), 5-amino-1H
-6.98 g (0.082 mol) of tetrazole, 508 g of dimethylacetamide, and 508 g of N-methylpyrrolidone were added to prepare a uniform solution. 44.3 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride as an acid anhydride was added to the homogeneous solution under ice-cooling and stirring.
(0.138 mol) and pyromellitic dianhydride 30 g
(0.138 mol) was added in small portions in powder form. Then, the reaction was carried out for 3 hours under ice cooling and for 20 hours at room temperature. Thus, the polyamic acid (code N
o. A solution containing F) was obtained.

[Synthesis Example 7] The photosensitive polyamic acid (D) 100 of Synthesis Example 4 which is a monomer-added photosensitive polyimide
After adding 100 g of the terminal tetrazole group-introduced polyamic acid obtained in Synthesis Example 7 to the resulting mixture under stirring at room temperature, the mixture was stirred at room temperature for 3 hours. Thus, a photosensitive polyamic acid (code No. G) was obtained.

[Synthesis Example 8] The photosensitive polyamic acid (D) 100 of Synthesis Example 4 which is a monomer-added photosensitive polyimide
After adding 36 g of the terminal tetrazole group-introduced polyamic acid (F) obtained in Synthesis Example 6 to the resulting solution under stirring at room temperature,
The mixture was stirred at room temperature for 3 hours. Thus, a photosensitive polyamic acid (code No. H) was obtained.

[Synthesis Example 9] The photosensitive polyamic acid (D) 100 of Synthesis Example 4 which is a monomer-added photosensitive polyimide
After adding 15 g of terminal tetrazole group-introduced polyamic acid (F) obtained in Synthesis Example 6 to the resulting solution under stirring at room temperature,
The mixture was stirred at room temperature for 3 hours. Thus, a photosensitive polyamic acid (code No. I) was obtained.

[Synthesis Example 10] The photosensitive polyamic acid (D) 10 of Synthesis Example 4 which is a monomer-added photosensitive polyimide
After adding 3 g of the terminal tetrazole group-introduced polyamic acid (F) obtained in Synthesis Example 6 to 0 g under stirring at room temperature,
The mixture was stirred at room temperature for 3 hours. Thus, a photosensitive polyamic acid (code No. J) was obtained.

[Examples 1 to 7, Comparative Examples 1 and 2] As shown in Table 1, the polyamic acid solution prepared in each of the above-mentioned synthesis examples was applied to a silicon wafer on which a copper sputtering film was formed by a spinner. And then the dryer 6
After drying at 0 ° C. for 30 minutes, a film having a thickness of about 10 μm was formed. Using a step tablet mask made by letterpress printing, PLA-501F (manufactured by Canon Inc.) was used to expose (300 mJ / cm ² (436n) over the wafer on which the film was formed.
m) or more], and then spray-developed with a developer composed of a mixture of N-methyl-2-pyrrolidone and isopropyl alcohol (weight ratio 70:30). Next, the film was rinsed with isopropyl alcohol to form a pattern on the polyimide precursor coating. The residual film thickness of the exposed portion and the unexposed portion of the film on which the pattern was formed was measured using a stylus type surface shape measuring device (P-10 manufactured by Tencor Corporation). The residual film ratio at the time of development was calculated from the residual film thickness of the unexposed portion. The silicon wafer on which the pattern was formed was placed in a nitrogen atmosphere at 10
1 hour at 0 ° C., 1 hour at 200 ° C., and 2 hours at 400 ° C.
The polyimide precursor was cured (polyimide) by heating for a period of time. The obtained polyimide pattern was heated at 25 ° C for 2 hours.
The mixture was treated with a volume% aqueous sulfuric acid solution for 2 minutes. The surface state of the polyimide pattern and through-hole portion was observed using a scanning electron microscope (JSM5400 manufactured by JEOL Ltd.), and the residual film thickness of the exposed portion and the unexposed portion was measured. (Residual film ratio after curing) was calculated. The surface state of the substrate on which the pattern was formed was observed using a scanning electron microscope (JSM5400 manufactured by JEOL Ltd.), and evaluated on the following four levels. <Surface state> A: No polyimide residual film is observed. ：: Very little polyimide film remained, △: Small amount of polyimide film remained, ×: Large amount of polyimide film remained,

[0081]

[Table 1] (* 1) Percentage to 100 parts by weight of resin component

Each of the polyimide film-coated silicon wafers obtained in Example 1 and Comparative Example 1 was divided and a cross section was cut out.
The cross section of the sample is coated with platinum (Pt), and the surface analysis of the interface of the Si / Cu / polyimide film is performed by the WDS beam scanning method, and the distribution (movement) of copper ions in the polyimide film is observed. Was evaluated. Table 2 shows the results. <Effect of suppressing movement of copper in the film> A: The movement of copper ions into the polyimide film is suppressed. Δ: Transfer of copper ions into the polyimide film was slightly observed from the interface. ×: Copper ions migrated strongly into the polyimide film, and there was no effect of suppressing copper migration.

[0083]

[Table 2] (* 1) Percentage to 100 parts by weight of resin component

[0084]

According to the present invention, there is provided a polyimide resin composition having excellent rust-preventing effect, residual film-preventing effect, and film-adhering effect on copper and copper alloys. The polyimide resin composition of the present invention, a semiconductor element or a printed wiring board,
In the production of resin-coated boards such as high-performance boards, it has an excellent rust prevention effect on metal wiring or metal layers on the board,
A polyimide film having high adhesion can be formed. When the photosensitive polyimide resin composition of the present invention is used, a polyimide film and a pattern excellent in the effect of preventing unexposed portions from remaining can be formed on a substrate provided with a metal wiring or a metal layer. . The polyimide resin composition of the present invention has a particularly remarkable effect when a coating layer is formed on a copper wiring or copper layer using copper or a copper alloy. Further, according to the present invention, there is provided a method for producing a terminal-modified polyimide-based resin exhibiting a stable rust prevention effect, a residual film prevention effect, and a film adhesion effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/312 B 21/312 21/30 502R (72) Inventor Kenichi Ito 1-chome, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture No.2-1 Inside the Zeon Corporation General Development Center (72) Inventor Akira Tanaka 1-1-2 Yakko, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Inside the Zeon Corporation General Development Center (72) Inventor Yoshikatsu Ishizuki Kanagawa Fujitsu, Ltd. (1-1) Kamikodanaka 4-1-1, Nakahara-ku, Kawasaki, Japan Inventor Yasuhiro Yoneda 4-1-1, Kamiodanaka, Nakahara-ku, Kawasaki, Kawasaki, Kanagawa Prefecture Fujitsu Limited (72) Inventor Takao Yokouchi Fujitsu Limited, 4-1-1 Kamikadanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture

Claims (9)

[Claims] 1. A polyimide resin composition comprising, as essential components, a polyimide resin (A) having a tetrazole group introduced into at least one terminal and a solvent (B). 2. The polyimide resin composition according to claim 1, wherein the polyimide resin (A) is a polyamic acid (A ₁ ) represented by the formula (I). Embedded image Wherein (I), R ¹ = 4-valent organic group; R ² = 2-valent organic group; k = 5 to 10,000 integer; W ¹ = T ^1, -OH or actinic functionality,; T ¹ = An atomic group containing a tetrazole group represented by the formula (1). Embedded image In the formula (1), P ¹ = —NH—, —NR— (R = alkyl group having 1 to 3 carbon atoms), —SO ₂ —, —SO ₂ O—, —O—, or —S
-; Q = single bond, or a divalent organic group; R ₁ = hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms,
A cyclic aliphatic group having 3 to 6 carbon atoms, a phenyl group, a substituted phenyl group represented by the formula (2), [In the formula (2), n = an integer of 1 to 3; X = an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, -NR'R "(R ', R" = each independently A hydrogen atom, a methyl group, an ethyl group, an acetyl group, or an ethylcarbonyl group; provided that both are not hydrogen atoms.), —COOCH ₃ , —NO ₂ , —SH,
Or -SCH ₃ ] or a substituted alkyl group represented by the formula (3). Embedded image [In the formula (3), m = 1 to 10; Y = —NR′R ″ (R ′, R ″ = each independently a hydrogen atom, a methyl group, an ethyl group, an acetyl group, or an ethylcarbonyl group) However, unless both are hydrogen atoms), a phenyl group, or a substituted phenyl group represented by the above formula (2). ] 3. The method according to claim 1, wherein the polyimide resin (A) has the formula (II)
Polyimide resin composition according to claim 1, wherein the in represented by the polyamic acid (A _2). Embedded image Wherein (II), R ¹ = 4-valent organic group; R ² = 2-valent organic group; k = 5 to 10,000 integer; W ² = T ^2, -OH or actinic functionality,; T ² = An atomic group containing a tetrazole group represented by the formula (4). Embedded image Wherein (4), P ² = single bond, -CO -, - COO -, - SO 2 -, or -SO ₂ O-; Q = single bond, or a divalent organic group; R ₁ = hydrogen atom, An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms,
A cyclic aliphatic group having 3 to 6 carbon atoms, a phenyl group, a substituted phenyl group represented by the formula (2), or the formula (3);
A substituted alkyl group represented by 4. In addition to the polyamide resin (A), at least one polyimide resin selected from the group consisting of polyamic acid, solvent-soluble polyimide, photosensitive polyamic acid, photosensitive polyamic acid ester, and photosensitive polyimide ( The polyimide resin composition according to any one of claims 1 to 3, further comprising (C). 5. The polyimide resin (A) according to claim 1, wherein the polyimide resin (A) is contained in such a proportion that the weight ratio of the tetrazole group is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin component. Or the polyimide-based resin composition according to item 1. 6. The composition according to claim 1, further comprising at least one additive selected from the group consisting of a photopolymerization initiator (D) and a photosensitizer (E) having a photopolymerizable functional group.
The polyimide resin composition according to any one of the above. 7. A method for producing a polyamic acid by reacting a diamine compound with a tetracarboxylic acid or an acid anhydride thereof in a polar organic solvent, wherein the reaction system comprises a diamine compound and a tetracarboxylic acid or an acid anhydride thereof together with a diamine compound. The presence of a compound (a) having a functional group capable of reacting with an amino group or a carboxyl group and a tetrazole group, thereby producing a polyamic acid having a tetrazole group introduced into at least one end. A method for producing a modified polyimide resin. 8. By reacting a polyimide resin having an amino group or a carboxyl group at at least one end with a compound (a) having a functional group capable of reacting with an amino group or a carboxyl group and a tetrazole group, A method for producing a terminal-modified polyimide resin, comprising producing a polyimide resin having a tetrazole group introduced into at least one terminal. 9. Compound (a) having a functional group capable of reacting with an amino group or a carboxyl group and a tetrazole group
Is a tetrazole group-containing compound represented by the formula (III). Embedded image In the formula (III), P = —COX [X = hydrogen atom, halogen atom, —OH,
Or -OR (R = alkyl group having 1 to 3 carbon atoms)],-
SO ₂ X [X = halogen atom or —OH)], halogen atom, —OH, —SH, —NH ₂ , —NHR (R =
An alkyl group having 1 to 3 carbon atoms) or -SH; Q = a single bond or a divalent organic group; R ₁ = a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, An allyl group having 3 to 10 carbon atoms,
A cyclic aliphatic group having 3 to 6 carbon atoms, a phenyl group, a substituted phenyl group represented by the formula (2), or the formula (3);
A substituted alkyl group represented by