WO2005038825A1

WO2005038825A1 - Varnish for insulating film and insulating film

Info

Publication number: WO2005038825A1
Application number: PCT/JP2004/015212
Authority: WO
Inventors: Masahiro Tada; Mitsumoto Murayama
Original assignee: Sumitomo Bakelite Company, Ltd.
Priority date: 2003-10-17
Filing date: 2004-10-07
Publication date: 2005-04-28

Abstract

A varnish for insulating films, characterized by comprising (A) a polymer obtained by reacting a bisaminophenol compound having a bulky structure with a dicarboxylic acid compound and constituted mainly of a polybenzoxazole resin precursor and (B) an organic solvent in which the polymer (A) can be dissolved or dispersed. Also provided is an insulating film characterized by being an organic insulating film obtained from the varnish and comprising a resin layer constituted mainly of a polybenzoxazole resin obtained via dehydrating condensation reaction. The insulating film is excellent in electrical properties, thermal properties, mechanical properties, and physical properties, and in particular, has a low permittivity and excellent heat resistance.

Description

Description Varnish for insulating film

The present invention relates to a varnish for an insulating film and an insulating film. Background art

In semiconductor materials, talentless and paid materials are used in various parts depending on the required characteristics. For example, as an interlayer insulating film for a semiconductor, an inorganic oxide film such as silicon dioxide manufactured by a chemical vapor deposition method is used. However, with the recent increase in the speed and performance of semiconductors, there has been a problem that the inorganic oxide film as described above has a high relative dielectric constant. As one of the improvement measures, the application of oblique materials is being studied. As organic materials for semiconductors, polyimide resins having excellent heat resistance, electrical characteristics, and visual characteristics are cited. Ray, used for liquid crystal alignment films. However, polyimide resins generally have two carboxy groups on the imide ring, and thus have problems in water absorption and electrical properties. To solve these problems, attempts have been made to improve water absorption and electrical properties by introducing fluorine or a fluorine-containing group into an organic polymer, and some of them have been put to practical use.

In addition, there is a polybenzoxazole resin that exhibits better performance in terms of heat resistance, water absorption, and electrical properties than a polyimide resin, and its application to various fields has been attempted. For example, those having a structure consisting of 4,4,1-diamino-13,3'-dihydroxybiphenyl and terephthalanolic acid, consisting of 2,2-bis (3-amino-4-hydroxyphenylinoxy) hexafluoropropane and terephthalanolic acid Polybenzoxazole resin having a structure.

However, as semiconductor devices become more highly integrated and multi-layered, signals in the wiring of semiconductor devices are becoming increasingly important. As a measure to increase total power consumption, use 鲖 for the wiring metal and use a low dielectric constant for the interlayer insulating film. There is a demand for improvements in electrical properties, electrical properties, water absorption, and the like, and a material that satisfies all of these requirements has not yet been obtained. As one specific example,

Polybenzoxazole resins having a structure consisting of 4,4, diamino-1,3,3, dihydroxybiphenyl and terephthalic acid show excellent heat resistance, but their electrical properties such as dielectric constant are not sufficient. In addition, the introduction of fluorine into the polymer improves the electrical properties, but lowers the heat resistance and raises concerns about the generation of fluorine-based gas, which is a corrosive gas. — See No. 1,289,84.) Further, multi-layering: ^ has a problem in that the insulating film peels off due to the shearing force in the CMP process, so semiconductor applications such as interlayer insulating films, etching stopper films, and adhesion-imparting films (primer layers) In the case of applying a marginal fee to the insulating film of the above, it is required to have high level and high adhesion to the inorganic material produced by chemical vapor deposition / sputtering method and to the heterogeneous interface with the wiring metal. RU

Disclosure of Description ''

An object of the present invention is to provide a varnish for an insulating film which provides a film excellent in all of electrical characteristics, thermal characteristics and physical characteristics, and particularly excellent in heat resistance and adhesion, and an insulating film using the same. .

In view of such problems of the conventional materials for organic insulating films, the present inventors have made extensive studies and as a result, have found that a polyamino compound obtained by reacting a bisaminophenol compound having a specific structure with a dicarboxylic acid compound is obtained. Benzoxazole resin does not contain fluorine in the resin structure, has high heat resistance, and is synthesized from a monomer having a bulky structure, so that the resin can be highly formed without forming micropores in the resin. Low dielectric constant characteristics without lowering the heat resistance, and by reducing the oxygen element ratio in the resin to a specific range, the heat resistance and the low dielectric constant characteristics are reduced. Without doing so, it was found that an insulating film having higher adhesion could be obtained, and further improvement studies were advanced, and the present invention was completed.

That is, the present invention mainly comprises (A) a polybenzoxazole resin precursor obtainable by reacting a bisaminophenol compound represented by the formula (1) with a dicarboxylic acid compound represented by the formula (4). A varnish for an insulating film, characterized by comprising a polymer having a structure, and (B) an organic solvent capable of dissolving or dispersing the knitted polymer (A). An organic insulating film obtained by using the insulating film varnish, An insulating film comprising a resin layer having a main structure of polybenzoxazole resin prepared through a dehydration condensation reaction.

[In the formula (2), represents a divalent group selected from the groups represented by the formula (3), and on the benzene ring of the group represented by the formulas (2) and (3). Are hydrogen, methyl, ethyl, propyl, isopropyl, butylinole, isobutynole, t-butynole, cyclohexyl, phenyl, trimethinolesilinole, triethylsilyl, etc. It may be substituted with a monovalent organic group selected from adamantyl groups. ]

HOOC-Y-COOH (4)

[In Equation (4), Y is represented by Equation (5) — 1 and Equation (5) 1-2, Equation (6), Equation (7), Equation (8), Equation (9) ι and Equation (10). It represents a divalent group selected from the groups represented. ]

ZliSlO / ^ OOZdf X3d SJ88 £ 0 / S00Z OAV

[In the formula (5) — 1 and the formula (5) 1-2, represents a divalent group selected from the groups represented by the above formula (3), and these formulas (3) and (5) — The hydrogen atom on the benzene ring of the group represented by Formula 1 and Formula (5) -2 is methyl, ethylenol, propyl, isopropynole, butynole, isobutyl, t-butyl, cyclohexyl Or a phenyl group, a phenyl group, a trimethylsilyl group, a triethylsilyl group or an adamanchinole group, which may be substituted with a monovalent organic group. ]

Oozdf / e :) d

Sculpture OOZdf / e) d O

[The hydrogen atom on the carbon ring of the group represented by the formula (6), the formula (7), the formula (8), the formula (9), and the formula (10) is a methyl group, an ethyl group, a propyl group, It is substituted with a monovalent organic group selected from isopropyl, butyl, isobutyl, t-butynole, cyclohexyl, pheninole, trimethinolesilyl and triethylsilyl groups. Is also good. In the formula (8), R represents a monovalent organic group. ]

In the insulating varnish, the bisaminophenol conjugate represented by the formula (1) is preferably a compound having a fluorene skeleton. As a result, low dielectric constant characteristics can be obtained while maintaining the heat resistance of the insulating film, and the solubility of the polymer is improved when a varnish for an insulating film is produced. Compounds having a fluorene skeleton represented by the formula (1) include 9,9-bis [4- (4-amino-3-hydroxy) phenoxypheninole] phthalene / 9,9-bis (3 —Amino-4-hydroxyphenoleno) funolelene, more preferably 9,9-bis [2-methinole-5-cyclohexyl-4- (4-amino-3-hydroxy) phenoxyphenyl] fluorene, and others. Examples of the bisaminophenol compound represented by the above formula (1) include 2,2-bis [3-cyclohexyl 4- (4-amino-3-hydroxy) phenoxyphenyl / propane] and 1,1-bis [3-cyclohexyl ^^-4- (4-amino-3-hydroxy) phenoxyphenyl] cyclohexane is preferred.

As the dicarboxylic acid compound represented by the formula (4), 、 represents a divalent group selected from the groups represented by the formulas (5) -1 and (5) -2 and the formula (6). And preferably has a divalent group selected from the groups represented by formulas (7), (8), (9) and (10). Is preferred. When Υ includes the groups represented by Formula (5) -1 and Formula (5) -12 and Formula (6), the adhesiveness becomes When the group represented by the formulas (7) to (10) is included, heat resistance such as a glass transition temperature and a modulus of elasticity during heating can be improved.

In addition, the terminal of the polybenzoxazole resin precursor obtained by reacting the bisaminophenol compound represented by the abominable formula (1) with the dicarboxylic acid compound represented by the formula (4) More preferably, it is sealed with a terminal blocking compound represented by the formula (11). Thereby, the heat resistance of the polybenzoxazole resin precursor can be improved, and the storage stability of the insulating film varnish can be improved.

[In the formula (11), R represents a monovalent organic group. Furthermore, the polybenzoxazole resin precursor obtained by reacting the bisaminophenol compound represented by the formula (1) with the dicarboxylic acid compound represented by the formula (4) is a 5- to 5-part polybenzoxazole resin precursor. It is preferable to have an oxygen element ratio of 10 mol%. Thereby, an insulating film having higher adhesion can be obtained without lowering the heat resistance and the low dielectric constant characteristics.

According to the present invention, electrical properties, thermal properties, mechanical properties and physical properties are all excellent, especially An insulating film having extremely low dielectric constant, high heat resistance, and excellent adhesion can be provided. BEST MODE FOR CARRYING OUT THE INVENTION

The polybenzoxazole resin precursor used in the present invention is prepared from a bisaminophenol compound represented by the formula (1) and a dicarboxylic acid compound represented by the formula (4) by a conventional acid chloride method and an active ester method. Method, a synthesis method by a condensation reaction in the presence of a dehydrating condensing agent such as dicyclohexylcarbodiimide polyphosphate and the like.

In the synthesis of the polybenzoxazole resin precursor used in the present invention, a reaction mole of a bisaminophenol compound (M mole) represented by the formula (1) and a dicarboxylic acid (N mole) represented by the formula (4) The ratio (M / N) is not particularly limited, but is preferably in the range of 0.5 to 2.0, more preferably in the range of 1.0 to 1.2. When the reaction molar ratio (M / N) is within the above range, a polymer having a higher molecular weight can be obtained with good reproducibility, the film forming property is good, and an insulating film having excellent mechanical and physical properties can be obtained.

Examples of the bisaminophenol compound represented by the formula (1) used in the present invention include, for example, 2,4-diaminoresorcinol, 2,4-diaminol 3-methylresorcinol, 4,6-diaminoresorcinol, , 6-diaminol 2-methylresorcinol, 2,2-bis (3-amino-4-hydroxy-7-nore) propane, 2,2-bis (3-amino-4-hydroxy-2-methylphenyl) propane, 2,2-bis (4-amino-3-hydroxyhydrinole) propane, 2,2-bis (4-amino-3-hydroxy-1-2-methynolephene) propane, 2,2-bis [3-cyclo Hexyl-1- (4-amino-3-hydroxy) phenoxyphene-propane, bis (3-amino-14-hydroxyphenolene) snorefone, bis (3-amino-1-hydroxy-2-methinolefe) Re) Snorefon, bis (4-amino-3-hydroxyhydrino), snorefon, bis (4-amino-3-hydroxy-2-methinolephenyl) sulfone, 3,3, diamino-1,4'-dihydroxy Biphenyl, 4,4,1-diamino-1,3,3-dihydroxybiphenyl, bis (3-amino-14-hydroxy-1 2-methynolephen), bis (4-amino-3-hydroxy-1 2) —Methinolepheninole), bis [(3-six-hexyl-2-l-methinole) -1 4- (4-amino-3-hydroxy) phenoxypheninole], 9,9-bis [4 _ (4-amino-1 3— (Hydroxy) phenoxyphenolene] fusololelen, 9,9-bis [4- (4-amino-3-hydroxy) phenoxy-1-3-methyl Norefue-nore] phneolelene, 9,9-bis- [4_ (4-amino3-hydroxy) phenoxy-1-3-pheninolepheninole] phnoleolene, 9,9-bis [4-1 (3-amino-4-hydroxy) phenoxyphene Nore] phneolelen, 9,9-bis [4- (3-amino-4-hydroxy) phenoxy-1-3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-4hydroxy) phenoxy 3-Fuyurphenyl] fluorene, 9,9-bis (4-amino-3-hydroxyphenole) funolelene, 9,9-bis (3-amino-4-hydroxyphenylene) funolelene, 9,9-bis [2-Methyl-5-cyclohexynole-1- (4-amino-13-hydroxy) phenoxyphenyl] fluorene, 3,3,1-diamino-4,4,1-dihydroxybiphenyl ether, 3,3, diamino- 4,4'-dihydroxy-1,2,1-dimethyl biphenyl ether, 4,4,1-diamino 3,3,1-hydroxybiphenyl ether, 4,4'-diamino 3,3,1-dihydroxy 1,2,2 , 1-dimethylbiphenyl ether, 1,1 '-[1,4-phenylene-bis (1-methylethylidene)] bis [(3-cyclohexyl-12-methylinole) -14- (4-amino- 3-hydroxy) phenoxyphenyl], 2,2-bis [3-cyclohexyl-1- 4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 1,1-bis [3-cyclohexane Xinole 4- (4-amino-3-hydroxy) phenoxyphenyl] cyclohexane and the like are not necessarily limited to these. Among these bisaminophenol compounds, compounds having a fluorene skeleton are preferred. As a result, low dielectric constant characteristics can be obtained while maintaining the heat resistance of the insulating film, and the solubility of the polymer is improved when a varnish for an insulating film is produced. Among the conjugates having a fluorene skeleton, 9,9-bis [4- (4-amino-3-hydroxy) phenoxyphene-nore] funolelene and 9,9-bis (3-amino-14-hydroxyphene) Compounds having a fluorene skeleton, such as nore) fluorene and 9,9-bis [2-methyl-15-cyclohexyl-4- (4-amino-3-hydroxy) phenoxyphenyl] fluorene, are more preferred. Further, in addition to the disulfide compound having a fluorene skeleton, 2,2-bis [3-cyclohexizolee 4- (4-amino-3-hydroxyphenoxy) pheninole] propane, 1,1- Bis [3-cyclohexylene 4- (4-amino-3-hydroxy) phenoxyphenyl] Cyclohexane is preferred. These can be used alone or in combination of two or more.

The dicarboxylic acid compound represented by the formula (4) used in the present invention is represented by the formula (5) 1, having a divalent group selected from the groups represented by formula (5) — 2, formula (6), formula (7), formula (8), formula (9), and formula (10) And the monovalent group R in the above formula (8) includes an alkyl group such as a methyl group, an ethyl group, an 'isopropyl group and a t-butyl group, and a group selected from a phenyl group and the like. Can be In the dicarboxylic acid compound represented by the formula (4), as the dicarboxylic acid compound having a divalent group represented by the formula (5) -1 and the formula (5) -2 as Y, for example, isophthalic acid , 4-methylisophthalic acid, 4-phenylenediisophthalenoic acid, 4_t-butylisophthalic acid, 4-trimethylsilylisophthalic acid, 4-adamantylisophthalic acid, 5-methylisophthalanolic acid, 5-phenylisolantanoleic acid, 5-t-butylisophthalic acid, 5-trimethylsilylisophthalanoic acid, 5-adamantinoleisophthalic acid, terephthalanolic acid, 2-methylinoterephthalic acid,

2-phenylterephthalic acid, 2-t-butynoleterephthalic acid, 2-trimethylsilylterephthalic acid, 2-adamantylterephthalic acid, 4,4, -biphenyldicarboxylic acid, 3,4, -biphenyldicarboxylic acid , 3,3-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4,1-sulfonylbisbenzoic acid, 3,4, Monosulfonylbisbenzoic acid, 3,3, -sulfonylbisbenzoic acid, 4,4, oxybisbenzoic acid, 3,4, oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2-bis (4-1 Carboxypheninole) propane, 2,2-bis (

3-potoxyphenyl) propane, 2, '2,1-dimethyl-1,4,4-biphenyldicarboxylic acid, 3,3,1-dimethyl-4,4, _biphenyldicarboxylic acid, 2,2,1-dimethyl-3, 3,1-Biphenyldicarboxylic acid, 9,9-bis [4- (· 4 lipoxyphenoxy) pheninole] fluorene, 9,9-bis [4- (3-carboxyphenoxy) ) Phenyl) fluorene, 4,4'-bis (4-force / repoxyphenoxy) biphenyl, 4,4,1-bis (3-canolepoxphenoxy) biphenyl, 3,4,1-bis (4-force-loxyphenoxy) biphenyl, 3,4,1-bis (3-force-loxyphenoxy) biphenyl, 3,3,1-bis (4-force-loxyphenoxy) biphenyl, 3,3'-bis (3-carboxyphenoxy) biphenyl, 4,4,1-bis (4-carboxyphenoxy) -ρ-terfeninole, 4,4, Bis (4-carboxyphenoxy) -1-m-phenyl, 3,4,1-bis (4-carboxyphenoxy) -p-terphenyl, 3,3,1-bis (4-canolepoxyphenoxy) 1) ρ-terfeninole, 3,4,1-bis (4-canolepoxif enoxy) 1m-terfeninole, 3,3'-bis (4-canolepoxifenoxy) 1m-turf Phenyl, 4,4, _bis (3-carboxyphenoxy) -1-ρ-terphenyl, 4,4,1-bis (3-canoleboxoxyphenoxy) -1m-terphenyl, 3,4,1-bis (3 —Carboxyphenoxy) -p-terpheninole, 3,3,1-bis (3-potassyloxyphenoxy) -p-terphenyl, 3,4,1-bis (3-carboxyphenoxy) 1-m-terfel, 3,3,1-bis (3-canoleboxyphenoxy) 1-m-terfenyl, 4,4,1-bis (2-t-butynole) pheno-resin carboxylic acid, 4,4 '1-bis (3-t-butyl) phenyldicarboxylic acid, 4,4,1-bis (2-trimethylsilyl) phenyldicarboxylic acid, 4,4,1-bis (3-trimethylsilyl) phenyldicarboxylic acid, 4 4,4,1-bis (2-adamantyl) phenyldicarboxylic acid, 4,4'-bis (3-adamantyl) phenyldicarboxylic acid, 6 Methynorenaphthalene-1,4-dicarbonic acid, 6-t-butylnaphthalene-1,4-dicarboxylic acid, 6-trimethylsilinorenaphthalene-1,4, dicanolevonic acid, 6-adamantinolenenaphthalene 1,4 Di-force / reponic acid, 4-methylnaphthalene-1,2,6-dicarboxylic acid, 4-tert-butylnaphthalene-1,2,6-dicarboxylic acid, 4-trimethylsilylnaphthalene-1,2,6-dicarboxylic acid, 4-adamantylnaphthalene Examples thereof include 1,2,6-dicarboxylic acid, but are not necessarily limited thereto. Of these, isophthalic acid, 5-methylisophthalic acid, 5-phenylisophthalic acid, 5-t-butylisophthalic acid, 5-trimethylsilylisophthalanoic acid, 5-adamantinoleisophthalic acid, 4,4'-oxybis Benzoic acid, 4,4'-sulfonylbisbenzoic acid, 9,9-bis [4- (4-carboxyphenoxy) phenyl] furylene are preferred. These can be used alone or in combination of two or more.

In the dicarboxylic acid compound represented by the formula (4) used in the present invention, Y represents the formula (

Examples of the dicarboxylic acid compound having a divalent group represented by 6) include, for example, 1,3-adamantanedicarboxylic acid, 2,5-dimethyladamantane_1,3-dicarboxylic acid, and 2,5-diphenyl ^ / Adamantane-1,3-dicarboxylic acid, 2,5-bis (t-butynole) adamantane-1,3-dicarboxylic acid, etc. The power is not limited to these. Of these, 1,3-adamantane dicarboxylic acid is preferred. These can be used alone or in combination of two or more.

Examples of the dicarboxylic acid compound having a divalent group represented by 7) include, for example, 3-ethini Luphthalenic acid, 4-ethynylphthalic acid, 2-ethynylisophthalic acid, 4-ethynylisophthalic acid, 5-ethynylisophthalanolic acid, 2-ethylurethanephthalic acid, 3-ethynylterephthalic acid, 5-ethynylterephthalic acid , 2-Ethynyl-1,5-naphthalenedicarboxylic acid, 3-ethynyl-1,5-naphthalenedicarboxylic acid, 4-ethynyl-1,5_naphthalenedicarboxylic acid, 1-ethynyl 2,6-naphthalenedicarboxylic acid , 3-ethynyl -2,6-naphthalenedicarboxylic acid, 4-ethyninolee 2,6-naphthalenedicarboxylic acid, 2-ethynyl-1,6-naphthalenedicarboxylic acid, 3-ethynyl-1,6-naphthalenedicarboxylic acid , 4-Ethyl-1,6-naphthalenedicarboxylic acid, 5-Ethynyl-1,6-naphthalenedicarboxylic acid, 7-Ethynyl-1,6-naphthalenedicarboxylic acid, 8-Ethylene 2,6-naphthalenedicarboxylic acid, 3,3'-Ethylene 2,2,2-biphenyldicarboxylic acid, 4,4,1-Jethinyl 2,2, -biphenyldicarboxylic acid, 5,5'-Jetinole-1,2,2-biphenyldicarboxylic acid, 6,6'-Jetini / lei 2,2,1-biphenyldicanolevonic acid, 2,2'-Jetinyl-1,3,3, 1,4-biphenyldicarboxylic acid, 4,4,1-diphenyl-1,3,3-biphenyldicarboxylic acid, 5,5,1-diethyl-1,3'-biphenyldicarboxylic acid, 6,6,1-diethyldicarboxylic acid 3,3'-Biphenyldicarboxylic acid, 2,2,1-diethyl-1,4,4-biphenyldicarboxylic acid, 3,3,1-Jetul-1,4,4'-Biphenyldicarboxylic acid, 2 , 2-bis (2-carboxy-3-ethynylphenyl) propane, 2,2-bis (2-hydroxypropyl 4-ethulhue) 2,2-bis (2-carboxy-5-ethynylphenyl) propane, 2,2-bis (2-carboxy-6-ethynii / refeninole) propane, 2,2-bis (3-caproloxy) _ 2-Ethynylphenyl) propane, 2,2-bis (3-carboxy-14-ethynylphenyl) propane, 2,2-bis (3-carboxy-1-5-ethynylphenyl) propane, 2,2-bis (3— Carboxy-6-ethynylphenyl) propane, 2,2-bis (4-carboxy-1-ethynylphenyl) propane, 2,2-bis (4-carboxy-3-ethynylphenyl) propane, 4-ethynyl 1, Examples include, but are not limited to, 3-dicarboxycyclopropane, 5-ethynyl-1,2,2-dicarboxycyclopropane, and the like. Of these, 2-ethynyl isophthalic acid, 4-ethyl isophthalic acid, 5-ethyl isophthalenoleic acid, 2,2-bis (4-carboxy-1-2-ethynylphenyl) propane, 2,2-bis (4-1 Carboxy-3-ethynylphenyl) propane is preferred. These may be used alone or in combination of two or more. Can be used.

In the dicarboxylic acid compound represented by the formula (4) used in the present invention, examples of the dicarboxylic acid compound having a divalent group represented by the formula (8) as Y in the dicarboxylic acid compound represented by the formula (4) include, for example, , 3-phenylethynyl phthalic acid, 4-phenylethynyl phthalic acid, 2-phenyl ethynyl isophthalic acid, 4-phenyl / ethynyl isophthalic acid, 5-phenyl ethynyl isophthalanolic acid, 2 —Funelecetir terephthalenoleic acid, 3—Fuelechulterephthalinoleic acid, 2-Feninoleetininoleic acid 1,5,1-Naphthalenedicanoleponic acid, 3-Fenylechelel-1,5-Naphthalenediolenoic acid 1,4-phenylenetinol 1,5-naphthalenedicarboxylic acid, 1-phenylenethyninole-1,6-naphthalenediline rubonic acid, 3-phenylenyl-2,6-naphtha Dicarboxylic acids, 4-phenyl-1,2-naphthalenedicarboxylic acid, 2-phenylenediyl-1,6-naphthalene dicarboxylic acid, 3-phenylethynyl-1,6-naphthalenediolenoic acid, 4-1 1,6-naphthalenedinolenoic acid 1, 6-naphthalenedicanoleponic acid, 7-pheninolethinyl-1, 6-naphthalenedinolenoic acid, 8-phenylenetinyl-1,6-naphthalenedinolenic acid 6-naphthalenedicarboxylic acid, 3,3, diphenylethyl 2,2,1-biphenyldicarboxylic acid, 4,4'diphenylethyl-2,2,1-biphenyldicarboxylic acid, 5,5,1 Diphenyle-2,2'-biphenyldicarboxylic acid, 6,6'-Diphenyle-2,2'-biphenyleoleic acid, 2,2'-diphenylethynyl 3,3,1-biphenyldicarboxylic acid, 4,4'-diphenylethylcarboxylic acid 3,3,1-biphenyldicarboxylic acid, 5,5, diphenylethyl _3,3,1-biphenyldicarboxylic acid Acid, 6, 6, 1-diphenyl-2,3,3-biphenyldicarboxylic acid, 2,2,1-diphenyl-l-4,4'-biphenyldicarboxylic acid, 3,3,1-diphenyl Ethynyl-4,4, -biphenyl-dicarboxylic acid, 2,2-bis (2-potassium 3-propenyl) propane, 2,2-bis (2-potenoxy) (Phenylphenyl) propane, 2,2-bis (2-carboxy-1-5-phenylethylfurenyl) propane, 2,2-bis ((2-carboxy-1-6-phenylethylphenyl) propane , 2,2-bis (3-carboxy_2-pheninoleethynylphenyl) propane, 2,2- Bis (3-carboxy-4-phenylethynylphenyl) propane, 2,2-bis (3-capilloxy-5-phenylurchurphenyl) propane, 2,2-bis (3-carboxy-1-6-phenyl / lechulphen) 2,4-bis (4-carboxy-2-phenylethynylphenyl) propane, 2,2-bis (4,1-norreboxyl-13-pheninoleetinii / refeninole) propane. Ninoré Chenole 1, 3

5 1 2

2-dicarboxycyclopropane and the like.

Examples of the dicarboxylic acid compound represented by the formula (4) in which Y is Y and R in the dicarboxylic acid compound having a divalent group represented by the formula (8) is an alkyl group include: 3-hexylphthalanol Acid, 4-hexyl phthalic acid, 2-hexynyl isophthalic acid, 4-hexyl isophthalic acid, 5-hexyl isophthalanolic acid, 2-hexynyl terephthalic acid, 3-hexynyl terephthalic acid, 2- Hexchel 1,5-naphthalenedicarboxylic acid, 3-hexinolene 1,5-naphthalenedicarboxylic acid, 4-hexinolene 1,5-naphthalenedicarboxylic acid, 1-hexinolene 2,6-naphthalenedicarboxylic acid, 3 1-hexynyl _ 2,6-naphthalenedicarboxylic acid, 4-hexynyl-1,2,6-naphthalene dicarboxylic acid, 2-hexynyl-1,6-naphthalenedicarboxylic acid -1,3-hexyl-1,6-naphthalenedicarboxylic acid, 4-hexyl-1,6-naphthalenedicarboxylic acid, 5-hexyl-1,6-naphthalenedicarboxylic acid, 7-hexyl-1,6- Naphthalene dicarboxylic acid, 8-hexynyl-1,6-naphthalenedicarboxylic acid, 3,3'-dihexinoleno 2,2,1-biphenylinolecanoleponic acid, 4,4'-dihexinole 1 2,2, -biphenyldicarboxylic acid, 5,5'-dihexyl 2,2, -biphenyldicarboxylic acid, 6,6'_dihexynyl-2,2,2-biphenyldicarboxylic acid, 2,2, di Hexinyl-3,3,1-biphenyldicarboxylic acid, 4,4,1-dihexyl-3,3-biphenyldicarboxylic acid, 5,5'-dihexyl-3,3, -biphenyldicarboxylic acid , 6, 6, _dihexynyl-1,3,3'-biphenyldicarboxylic acid, 2, 2 1-dihexynyl-4,4, -biphenyldicarboxylic acid, 3,3, dihexynyl-4,4, _biphenyldicarboxylic acid, 2,2-bis (2-carboxy 3-hexyninolephene) Propane, 2,2-bis (2-nitrohexylphenyl) propane, 2,2-bis (2-carboxy_5-hexynylpheninole) propane, 2,2-bis (2-carboxy) One 6-hexylphenyl-2-propane, 2,2-bis (31-norhexoxy-2-hexynenorphenyl) propane, 2,2-bis (3_carboxy-14-hexynylphenyl) propane, 2, 2-bis (3-dipropoxy-5-hexylphenyl) propane, 2,2_bis (3-canolepoxy-1-6-hexnolephenyl) propane. 2,2-bis (4-hydroxyhexylinolephenoxy) propane, 2,2-bis (4-hexyloxy-3-hexynylpheninole) propane, 4-hexyl-1,3-dicarboxycyclo Propane, 5-ethynyl-2,2-dicarboxycyclopropane, 3-propynylphthalanolic acid, 4-propynylphthalic acid, 2-propynylisophthalanolic acid, 4-propynylisophthalic acid, 5-propynylisophthalanolic acid, 3 -Butyphthalic acid, 4-butyninolephthalic acid, 2-butynylisophthalic acid, 4-butynylisophthalenoic acid, 5-butynyl isophthalic acid, 3_isopropylethynylphthalanolic acid, 4_isopropylethynylphthalic acid, 2-Isopropylethynylisophthalenoic acid, 4 Sopropylethylusophthalic acid, 5-Isopropynoleethynylisophthalic acid, 3— Sopropylethyl isophthalic acid, 4-t-butyl ethyl phthalic acid, 2-t-butyl ethyl isophthalic acid, 4-t-butyl ethyl isophthalanolic acid, 5-t-butyl ethyl isophthalic acid, etc. However, the present invention is not limited to these.

Among these, R is more preferably a phenyl group, and furthermore, 2-phenylethyleisophthalic acid, 4-phenylethynylisophthalenoleic acid, 5-phenylethynylisophthalic acid, 2,2-bis Preferred are (4-carboxy-1-phenylenethynylphenyl) propane and 2,2-bis (4-potassyl-3-phenyl / ethynylphenyl) propane. These can be used alone or in combination of two or more.

Examples of the dicarboxylic acid compound having a divalent group represented by 9) include, for example, 1,2-biphenylenediene / levonic acid, 1,3-biphenylenediene / reponic acid, and 1,4-biphenylenediate Nolevonic acid, 1,5-biphenylenedicarboxylic acid, 1,6-biphenylenedicarboxylic acid, 1,7-biphenylenedicarboxylic acid ^ ^ Bonic acid, 1,8-biphenylenedicarboxylic acid, 2, Examples include 3-biphenylenedicanoleponic acid, 2,6-biphenylenediolenoic acid, 2,7-biphenylenediolenoic acid, and the like. Benedicarboxylic acid and 2,7-biphenylenedicarboxylic acid are particularly preferred. These can be used alone or in combination of two or more.

Examples of the dicarboxylic acid compound having a divalent group represented by 10) include, for example, 4,4, transdicarboxylic acid, 3,4′-trandicarboxylic acid, 3,3′_trandicarboxylic acid, , 4'-Transdicarboxylic acid, 2,3'-transdicarboxylic acid, 2,2,1-transdicarboxylic acid, and the like. These can be used alone or in combination of two or more.

The dicarboxylic acid compound used in the present invention can be used in combination of two or more kinds. For example, as Y in the formula (4), a compound represented by the formula (5) -1 and the formula (5) -12 and the formula (6) A divalent group selected from groups represented by one or more groups selected from the groups represented by formulas (7), (8), (9) and (10) Can be used in combination. When the group represented by the formula (5) -1 and the formula (5) and the formula (6) is included, the adhesion is improved, and the group represented by the formula (7) to the formula (10) is included. As a result, the heat resistance such as the glass transition ^ i and the elastic modulus when heated is improved.

Further, a bisaminophenol compound and a dicarponic acid compound other than the bisaminophenol compound and the dicarponic acid compound may be used within a range that does not affect the properties of the insulating film of the present invention.

According to the present invention, in order to improve the storage stability of a polybenzoxazole resin precursor and a varnish for an insulating film containing the same, in the synthesis of a polybenzoxazole resin, a resin terminal is used. It is preferable that the end capping compound is reacted to perform end capping. Examples of the terminal blocking compound include: phthalic anhydride, phthalic anhydride such as 3-ethynyl-phthalic anhydride and 3-phthalene di-butanoic anhydride; and maleic anhydride and 5-norbornene-2. Acid anhydrides such as, 3-dicarboxylic anhydride; benzoic acid compounds such as benzoic acid, 4-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-phenylmethynylbenzoic acid and 3-phenylbenzoic acid Adamantyl carboxylic acid compounds such as 1-adamantyl carboxylic acid and 1-adamantyl ethynyl carboxylic acid; aniline, 4-ethyninolea-phosphorus, 3-ethyuraniline, 4-pheninoleethyninole Aryl compounds such as aniline and 3-phenylethynylaniline; 2-aminopheno-norre, 2-amino-5-ethyninolephenenole and 2-amino Aminophenol compounds such as over 5 Fueninoreechini Rufuenoru;, etc., and be used in combination either singly or 2 kinds accordance.

Examples of these conjugates include a group having a carbon-carbon double bond such as maleic anhydride-5-norpolene-1,2,3-dicarboxylic anhydride, and a ethul group or a ferulethane group. Compounds having a cross-linking group such as a group having a carbon-carbon triple bond such as a phenyl group are preferred. Thus, since the polybenzoxazole resin is calo-heated to generate a cross-linking reaction in a three-dimensional network, the heat resistance of the polybenzoxazole resin can be improved. Oxygen element ratio of polybenzoxazole O benzoxazole resin precursor used in the present invention is 5; preferably 1 0 mol%, 5. more preferably 5-9 mole ^_0/0, more preferably 6-8 mole ^_0/0 . When the oxygen element ratio is in the above range, an insulating film having higher adhesiveness can be obtained without lowering heat resistance and low dielectric constant. In obtaining such a polybenzoxazole resin precursor, in the bisaminophenol compound represented by the formula (1) and the dicarboxylic acid compound represented by the formula (4), X in the formula: Among the groups represented by the formula (3), those having a group containing an ether group, a sulfol group and a carboxy group are preferable. In particular, the dicarboxylic acid compound represented by the formula (4) is preferable. It is more preferable to have

As a method for producing the polybenzoxazole resin precursor used in the present invention, for example, in an acid chloride method, first, an acid chloride to be used is prepared. As an example, in the presence of a catalyst such as N, N_dimethylformamide, a dicarboxylic acid compound represented by the formula (4), for example, isophthalic acid, and an excess amount of chloridion thionyl are added at room temperature to 75 ° After reacting with C, excess thionyl chloride is distilled off by heating and reduced pressure, and the residue is recrystallized with a solvent such as hexane to obtain isophthalic chloride.

Next, a bisaminophenol compound represented by the formula (1), for example, 2,2-bis (3-amino-14-hydroxyphenyl) propane is usually treated with N-methyl-1-pyrrolidone, N, N —Dissolved in a polar solvent such as dimethylacetamide, and reacted with the previously prepared chloride compound of dicarboxylic acid in the presence of an acid acceptor such as triethylamine at room temperature at −30 ° C. Thereby, a polybenzoxazole resin precursor can be obtained.

Further, an acid sulfide compound of the terminal compound represented by the formula (11), for example, benzoic acid oxalate, prepared in advance in the same manner as the dicarboxylic acid compound, may be prepared by adding an acid acceptor such as triethylamine. By reacting at room temperature to −30 ° C. in the presence of the agent, a polybenzoxazole resin precursor having a terminal capped can be obtained.

Further, instead of the acid chloride compound, a dicarboxylic acid compound represented by the formula (4): By reacting the active ester compound with a bisaminophenol compound, a polybenzoxazole resin precursor can be obtained.

The varnish for an insulating film of the present invention generally comprises dissolving or dissolving the polybenzoxazole resin precursor obtained above in a solvent capable of dissolving or dispersing the polybenzoxazole resin precursor. It can be dispersed to obtain a varnish. Examples of the solvent include N-methyl-1-pyrrolidone, γ-butyrolactone, Ν, Ν-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycolone retinoleatene, diethyleneglyconelebutyate / leeteneole, Propylene glycol monomethyl ether, dipropylene glycol monomethinole ether, propylene glycol monomethinole ether acetate, methylinole lactate, ethyl lactate, butyrate lactate, methyl 1,3-butylene glycol acetate, 1,3_ Butylene glycol-3 monomonomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, cyclohexanone, etc., can be used alone or in combination of two or more. . The amount of the solvent used is not particularly limited, but is generally preferably about 5 to 100 times the weight of the polybenzoxazole resin precursor.

In addition, the varnish for an insulating film of the present invention may include a surfactant, a coupling agent, etc. as various additives, if necessary, to form an interlayer insulating film, a protective film, and an etching stopper film for a semiconductor. It can be used as an adhesion-imparting film, an interlayer insulating film of a multilayer circuit, a cover coat of a flexi-bonding board, a solder resist film, a liquid crystal alignment film and the like.

The insulating film of the present invention can be used as a photosensitive resin composition by using it together with a naphthoquinonediazide compound as a photosensitive agent.

In the method of manufacturing the insulating film of the present invention, first, the varnish for an insulating film of the present invention is applied to a suitable support, for example, a glass, metal, silicon wafer, ceramic substrate, or the like, to form a coating film. . Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, the coating film thus obtained is subjected to a calo-heat treatment and converted into a resin by a dehydration condensation reaction to obtain an insulating film comprising a resin layer having a polybenzoxazole resin as a main structure. preferable. " Insulation according to the present invention is an interlayer insulating film for semiconductors, a protective film, an etching stopper film, an adhesion-imparting film, an interlayer insulating film for a hard mask multi-layer circuit, a flexipno, a cover coat for a coaxial board, a solder resist film, and a liquid crystal. It can be used for an alignment film or the like. Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the contents of the examples. For property evaluation, the dielectric constant, heat resistance, and density were measured using the films prepared in Examples and Comparative Examples. The measurement conditions for each characteristic were as follows, and the measurement results are summarized in Table 1. Hereinafter, “parts” indicates “parts by weight”.

1. Dielectric constant

The measurement was performed at a measurement frequency of 1 MHz using a Hewlett-Packard anne HP-4284A Precision LCR meter.

2. Heat resistance ''

Using TG / DTA220 manufactured by Seiko Instruments Inc., the temperature at which the weight loss reached 5% was measured under a nitrogen gas flow at a heating rate of 10 ° C / min.

3. Adhesion (tape test)

After 100 squares of lmmX 1mm were cross cut, a peeling test was carried out using a Scotch tape manufactured by Sumitomo 3LEM, and the number of peeled squares in the 100 squares was measured.

4. Adhesion (stud pull test)

A stud bin is attached vertically to the top surface of the resin film with an epoxy adhesive, and the stud bin is pulled perpendicular to the resin film using a Quadruple Sebastian V-type strength tester. (Stud pull strength) was measured. Example 1

9,9-bis [2-methynoleic 5-cyclohexyl 4- (4-amino-3-hydroxy) phenoxyphenyl] fluorene 7.25 parts (l Ommol), 40 parts dried under dry nitrogen atmosphere Bruno was dissolved in N- methyl-2-pyrrolidone, in which the 5 ° C, solid 2.46 parts of 5-t-Puchiruisofutaru acid dichloride ⁽⁹ .5mmo 1) ', 30 minutes Kaketeyu I made it. Subsequently, the temperature was returned to room temperature and the room temperature was removed for 1 hour. Thereafter, at 5 ° C., 2.45 parts (22 mmo 1) of triethylamine was added dropwise over 30 minutes. After completion of the dropwise addition, the temperature was returned to room temperature, and the mixture was stirred and reacted at room temperature for 3 hours to obtain a polybenzoxazole resin precursor having an oxygen element ratio of 5.8 mol%. The resulting Poribenzookisa tetrazole resin precursor using a Tosoh Corp. GPC, was determined the number average molecular weight in terms of polystyrene with (Mn), 7.0x 10 ^3, a weight average molecular weight (Mw) 1.36X It was 1 0 ^4.

10 g of this polybenzoxazole resin precursor was dissolved in N-methyl-2-pyrrolidone to form a 20% solution, which was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a varnish. The varnish was applied to a silicon wafer and a silicon wafer using a spin coater on a SiC substrate having a 10 nm thick SiC film. After application, dried on a hot plate at 90 ° C for 240 seconds, nitrogen was introduced, and the oxygen concentration was controlled to 100 ppm or less using an oven, 250 ° C / 60 minutes, 350 ° C The resin was heated in the order of / 60 minutes and converted to a polybenzoxazole resin by a dehydration condensation reaction to obtain a resin film for an insulating film. Various characteristics were evaluated using the obtained film.

Example 2

In Example 1, 9,25-bis [2-methyl-5-cyclohexyl-1- (4-amino-3-hydroxy) phenoxyphenyl] fluorene was added to 7.25 parts (lOmmol). Instead of using Example 2, except that 6.08 parts (1 Ommo 1) of 2,2-bis [3-cyclohexyl 4- (4-amino-13-hydroxy) phenoxyphenyl] propane was used instead. Similarly, a polybenzoxazole resin precursor having an oxygen element ratio of 5.2 mol% was synthesized. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 7.0 × 10 ³ and the weight average molecular weight (Mw) was 1.36 × 10 ⁴ in terms of polystyrene. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 3

In Example 1, 9,9-bis [2-methyl-1-5-cyclohexyl-1- (4-amino-3-hydroxy) phenoxyphenyl] fluorene 7.25 parts (l Ommol) ) Example 1 except that 6.41 parts (1 Ommo 1) of 1,1-bis [3-cyclohexyl 4- (4-amino-13-hydroxy) phenoxycyclophenyl] cyclohexane was used. Similarly, a polybenzoxazole resin precursor having an oxygen element ratio of 5.2 mol% was synthesized. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 7.0 × 10 ³ and the weight average molecular weight (Mw) was 1.36 × 10 ⁴ in terms of polystyrene. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 4

In Example 1, 9,9-bis [2-methyl-1-5-cyclohexyl-1- (4-amino-3-hydroxy) phenoxyphenyl] fluorene 7.25 parts (1 Ommo 1 ) Was replaced by 5.65 parts (10 mmo 1) of 9,9-bis [4- (4-amino-13-hydroxy) phenoxypheninole] funolene, all in the same manner as in Example 1. Thus, a polybenzoxazole resin precursor having an oxygen element ratio of 6.3 mol% was synthesized. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 7.0 × 10 ³ and the weight average molecular weight (Mw) was 1.30 × 10 ⁴ in terms of polystyrene. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 5

In Example 1, 9.25 parts (1 Ommo 1) were replaced with 9,9-bis [2-methynole-5-cyclohexyl 4- (4-amino-3-hydroxy) phenoxyphenyl] fluorene. 4,9,9-Bis (3-amino-4-hydroxyphenyl) fluorene 3.80 parts (10 mmo 1) were replaced with 2.46 parts (9.5 mmo 1) of 5-t-butyl isophthalic dichloride solid, and 4,4 Except for using 2.80 parts (9.5 mmo 1) of solid, monooxybisbenzoic acid dichloride, all in the same manner as in Example 1 and the oxygen element ratio was 6.9 mol. / _{0 A} polybenzoxazole resin precursor was synthesized. The molecular weight was measured by GPC, the number average molecular weight in terms of polystyrene (Mn) is 8.0 XI 0 ^3, weight average molecular weight (Mw) of 1.80 X 10 ^4. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 6

In Example 1, 2.46 parts of solid of 5-t-butylisophthalic acid dichloride (9. 5 mmo 1) was replaced with 1,3-adamantane dicarboxylic chloride solid, 2.03 parts (9.5 mm ο 1) in the same manner as in Example 1 except that the oxygen element ratio was 5.6 mol%. A polybenzoxazole resin precursor was synthesized. The molecular weight was measured by GPC, the number average molecular weight in polystyrene bell (Mn) is 4.0X 10 ^3, a weight average molecular weight (Mw) of 1.25 X 10 ^4. Thereafter, a glass was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 7

In Example 1, instead of 2.46 parts (9.5 mmo 1) of 5_t-butyl isophthalic acid dichloride solid, 2.88 parts (9.5 mm mm) of solid of 5-ferruetinyl isophthalanolic acid chloride was used. Except for using o 1), the same procedure as in Example 1 was carried out except that the oxygen element ratio was 5.8 mol ⁰ /. The synthesis of a polybenzoxazole resin precursor was performed. When the molecular weight was measured by GPC, polystyrene had a number average molecular weight (Mn) of 6.0 × 10 ³ and a weight average molecular weight ( _Mw ) of 1.31 × 10 ⁴ . Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 8

In Example 1, 9,9-bis [2-methyl-1-5-cyclohexyl-1- (4-amino-3-hydroxy) phenoxyphenyl] fluorene 7.25 parts (1 Ommo 1 ) Is replaced by 3.80 parts (10 mm o 1) of 9,9-bis (3-amino-4-pidroxyphenyl) fluorene and 2.46 parts (9.5 mm) of 5-t-butylisophthalic acid dichloride solid o In the same manner as in Example 1, except that 2.62 parts (9.5 mMol) of 2,7-biphenylenedicarboxylic acid chloride solid was used instead of 1), the oxygen element ratio was 5.8 mol%. A certain polybenzoxazole resin precursor was synthesized. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 7.5 × 10 ³ and the weight average molecular weight (Mw) was 1.53 × 10 ⁴ in terms of polystyrene. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was removed and evaluated.

Example 9

In Example 1, 9,9-bis [2-methynoleic 5-hexylhexyl 4- (4-amino-3-hydroxy) phenoxypheninole] funolelene 7.25 parts (lOmmol) was replaced with 9,9-bis Monobis [4 -— (4-amino-3-hydroxy) phenoxypheninole] funolelene 5.65 parts (1 Ommo 1) is replaced with 2.46 parts (9.5 mmo 1) of 5-t-butylisophthalic acid dichloride solid, and 5.17 parts (9.5 mmo 1) of 5-ethynyl-isophthalenoyl chloride solid Except for using, all in the same manner as in Example 1 and the oxygen element ratio was 7.1 mol. /. Was synthesized. Measurement of the molecular weight by GPC, the number average molecular weight in terms of polystyrene (Mn) is 8.5x 10 ^3, a weight average molecular weight (Mw) of 1.70 X 10 ^4. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 10

In Example 1, instead of 9,25-bis [2-methinole 5-six-hexoxyl 4- (4-amino-3-hydroxy) phenoxyphenyl] fluorene 7.25 parts (lOmmol), 9 4,4,1 transcript was obtained by replacing 3.80 parts (10 mmo 1) of, 9_bis (3-amino-4-hydroxyphenyl) fluorene with 2.46 parts (9.5 mmo 1) of 5-t-butylisophthalic dichloride solid. A polybenzoxazole resin precursor having an oxygen element ratio of 5.5 mol% was synthesized in the same manner as in Example 1 except that 2.88 parts (9.5 mmo 1) of a solid of dicarboxylic acid chloride was used. And rollers were measured molecular weight by GPC, the number average molecular weight in polystyrene fireman's standard (Mn) is 8.3 XI 0 ^3, weight average molecular weight (Mw) of 1.53 X 10 ^4. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 11

In Example 1, 9,9-bis [2-methyl-5-cyclohexyl-14- (4-amino-3-hydroxy) phenoxyphenyl] fluorene instead of 7.25 parts (l Ommol) was replaced with 9 Instead of 3.80 parts (10 mmo 1) of 1,9-bis (3-amino-4-hydroxyphenyl) fluorene, 2.46 parts (9.5 mmo 1) of 5-t-butylisophthalenoleic dichloride was replaced with 5-t- Except that 1.92 parts (7.6 mmo 1) of butyl isophthalic acid dichloride solid and 0.43 part (1.9 mmo 1) of 5-ethynyl-isophthalic chloride solid were used, the same procedure as in Example 1 was carried out. 5.7 mol% of a polybenzoxazole resin precursor was synthesized. The molecular weight was measured by GPC, the number average molecular weight in the port polystyrene Fuji (Mn) is 6.8 XI 0 ^3, weight average molecular weight (Mw) of 1.45 X 10 ^4. Then, a varnish was prepared in the same manner as in Example 1 and used for an insulating film. The evaluation was performed using a resin film.

Example 12

In Example 1, 9,9-bis [2-methyl-1-5-cyclohexyl-4- (4-amino-3-hydroxy) phenoxyphenyl] fluorene 7.25 parts (1 Ommo 1 ) Is replaced with 3.80 parts (10 mmo 1) of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene and 2.46 parts (9.5 mmo 1) of 5-t-butylisophthalic dichloride solid. , 4,4,1-Oxybisbenzoic acid dichloride solids, 2.24 parts (7.6 mmo, 1) and 5-phenylenephthaloisophthalic acid solids, 0.58 parts (1.9 mmo 1), were used. In the same manner as in Example 1, a polybenzoxazole resin precursor having an oxygen element ratio of 6.65 mol% was synthesized. The molecular weight was measured by GPC, the number average molecular weight in terms of polystyrene (Mn) is 8.3 XI 0 ^3, weight average molecular weight (Mw) of 1.81 X 10 ^4. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 13

Dissolve 3.80 parts (10 mMol) of 9,9-bis (3-amino-4-hydroxy-1-phenyl) fluorene in 40 parts of dry N-methyl-1-pyrrolidone under a dry nitrogen atmosphere; Then, at 5 ° C, 2.80 parts (9.5 mm o 1) of 4,4, -oxybisbenzoic dichloride was slowly added over 30 minutes. Subsequently, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 1 hour. Thereafter, 2.45 parts (22 mmol) of triethylamine was added dropwise at 5 ° C for 30 minutes. After the completion of the dropwise addition, the temperature was returned to room temperature, and the mixture was stirred and reacted at room temperature for 3 hours. Thereafter, at 5 ° C., 0.16 parts (0.1 mmo 1) of 5-norbornene-1,2,3-dicanoleponic anhydride was added. After the addition was completed, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 3 hours to react, thereby obtaining a polybenzoxazole resin precursor having an oxygen element ratio of 6.94 mol% and having a terminal capped. The obtained polybenzoxazole resin precursor was used to determine the number average molecular weight (Mn) in terms of polystyrene using GPC manufactured by Tosoh Corporation. As a result, 8.5 × 10 ³ and weight average molecular weight (Mw) of 2.5 × 10 ^{Was 4} . Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Example 14

Example 13! / ,,, 4, 4, mono-oxybisbenzoic acid dichloride 2 80 parts (9.5mm Instead of o 1), add 2.24 parts (7.6 mm o 1) of 4,4, mono-oxybisbenzoic dichloride solid and 0.58 part (1.9 mmo 1) of 5-phenylene diisophthalic acid solid. Instead of using 0.1 part (O.lmmo1) of 0.1 part (O.lmmol) of 1,5-norpolonene-1,2,3-dicarboxylic anhydride, 0.13 part (O.lmmo1) of 4-phenylenedicarboxylic acid chloride was used. In the same manner as in Example 13, a polybenzoxazole resin precursor having an oxygen element ratio of 6.65 mol% and a sealed end was synthesized. Measurement of the molecular weight by GPC, the number average molecular weight in terms of polystyrene (Mn) is 8.6 XI 0 ^3, weight average molecular weight (Mw) of 1.78 X 10 ^4. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Comparative Example 1

In a separable flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel, 14.65 parts (40 mmo 1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After dissolving in 200 parts of dried dimethylacetamide and adding 7.92 parts of pyridine (20 Ommo 1), 100 g of dimethinoleacetamide was added at 100 ° C under dry nitrogen at 15 ° C. 'A solution of 16.92 g (4 Ommo 1) of isopropylidene biphenyl dicarboxylic acid dichloride at the end of a hexanophthalone mouth was added dropwise over 30 minutes, and the precipitate was collected and dried, and the oxygen element ratio was 5.7 mol. % Of a polybenzoxazole resin precursor powder was obtained. When the molecular weight was measured by GPC, the number average molecular weight Mn was 3.8 × 10 ⁴ and Mw was 8.03 × 10 ⁴ in terms of styrene. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Comparative Example 2

In Example 1, instead of 7.25 parts (lOmmol) of 9,9-bis [2-methyl-15-cyclohexyl-14- (4-amino-3-hydroxy) phenoxyphenyl] fluorene 9,80-bis (3-amino-4-hydroxyphenyl) fluorene to 3.80 parts (10 mmo'l), 5-t-butylisophthalic acid dichloride solid 2.46 parts (9.5 mmo 1) Example 1 was repeated except that instead of using 4,4,-[1,4-phenylenebis (1-methylethylidene) dibenzoic acid diclotide 'solid 4.28 parts (9.5 mmo 1), Similarly to the above, a polybenzoxazole resin precursor having an oxygen element ratio of 3.6 mol% was synthesized. When the molecular weight was measured by GPC, the number average molecular weight in terms of polystyrene ( Mn) was 5.2 × 10 ³ and the weight average molecular weight (Mw) was 1.25 × 10 ⁴ . Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

Comparative Example 3

In Example 1, instead of 9,9-bis [2-methyl-15-cyclohexynoleic 4- (4-amino-3-hydroxy) phenoxyphenyl] fluorene 7.25 咅 (1 Ommo 1) Then, instead of 2,40-diaminoresorcinol 1.40 parts (lOmmol) with 2.46 parts (9.5 mmol 1) of 5-t-butyl isophthalic dichloride solid, 4,4,1- (oxyphenylenedioxy) 2 A polybenzoxazole resin precursor having an oxygen element ratio of 11.1 mol% was synthesized in the same manner as in Example 1 except that 4.54 parts (9.5 mmol) of benzoic dichloride solid was used. The molecular weight was measured by GPC, the number average molecular weight in terms of polystyrene (Mn) is 5.0 XI 0 ^3, weight average molecular weight (Mw) of 1.15 X 10 ^4. Thereafter, a varnish was prepared in the same manner as in Example 1, and a resin film for an insulating film was prepared and evaluated.

1 table

As is clear from the results summarized in Table 1, all of the insulating film resin films produced using the insulating film varnish of the present invention have a low dielectric constant of less than 3.0 and have a fluorine-containing group. The same dielectric constant as that of the comparative example was obtained, the heat resistance was 450 ° C. or higher, and the adhesiveness was 60 MPa or higher, showing good and balanced properties. On the other hand, in Comparative Example 1, the dielectric constant was low, but the adhesion was weak, and corrosive gas was generated during curing. In Comparative Example 2, the adhesion to the silicon wafer was good, but the adhesion to the highly hydrophobic SiC substrate was weak. Comparative Example 3 exhibited excellent adhesion, but had a dielectric constant exceeding 3.0. Industrial availability '14

According to the present invention, it is possible to provide an insulating film having excellent electrical properties, thermal properties, mechanical properties, and physical properties, particularly having an extremely low dielectric constant, high heat resistance, and excellent adhesion. Various fields that require an insulating film to have, for example, interlayer insulating films for semiconductors, protective films It can be applied as an etch stopper film, an adhesion-imparting film, a hard mask, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible / H tonnage plate, a solder resist film, a liquid crystal alignment film, and the like. Therefore, it has industrial applicability.

Claims

The scope of the claims

1. (Α) Polybenzoxazole resin precursor obtainable by reacting a bisaminophenol compound represented by the formula (1) with a dicarboxylic acid compound represented by the formula (4) A varnish for an insulating film, comprising: a polymer having a main structure of: and (B) an organic solvent capable of dissolving or dispersing the polymer (A).

[In the formula (2), Xi represents a divalent group selected from the groups represented by the formula (3), and these groups represented by the formulas (2) and (3) on the benzene ring Hydrogen atoms include methyl, ethyl, propyl, isopropyl, pentinole, isobutyl, t-butyl, cyclohexyl, phenyl, trimethinolesilyl, triethylsilyl, and adamantyl. It may be substituted with a monovalent organic group selected from among them. ]

HOOC-Y-COOH (4)

[In Equation (4), Y is represented by Equations (5) -1 and (5) _2, (6), (7), (8), (9), and (10). Represents a divalent group selected from the following groups: ]

Ġ Ĩ5) -1

[In the formulas (5) — 1 and (5) -12, Xi represents a divalent group selected from the groups represented by the above formula (3). The hydrogen atom on the benzene ring of the group represented by is a methynole group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptinole group, a t-pentynole group, a cyclohexyl group, a feninole group, a trimethylsilyl group, It may be substituted with a monovalent organic group selected from a triethylsilyl group and an adamantyl group. ]

/ VD mss OSId

Sculpture OOZdf / e) d O

[The hydrogen atom on the carbon ring of the group represented by the formula (6), the formula (7), the formula (8), the formula (9), and the formula (10) is a methyl group, an ethylene group, a propyl group, or an isopropyl group. May be substituted with a monovalent organic group selected from a group, a butyl group, an isobutyl group, a t-butyl group, a cyclohexyl group, a phenyl group, a trimethylsilyl group and a triethylsilyl group. In the formula (8), R represents a monovalent organic group. ]

2. The varnish for an insulating film according to claim 1, wherein the bisaminophenol compound represented by the formula (1) has a fluorene skeleton.

3. The bisaminophenol compound represented by the formula (1) is 9,9-bis [4- (4-amino-3-hydroxy) phenyloxyfluorene] fluorene, which is described in claim 2. Insulation varnish for S. .

4. The varnish for an insulating film according to claim 2, wherein the bisaminophenol compound represented by the formula (1) is 9,9_bis (3-amino-4-hydroxyphenyl) fluorene.

5. The bisaminophenol compound represented by the formula (1) is converted to 9,9_bis [2-methyl-5-cyclohexanol_4_ (4-amino-13-hydroxy) phenoxyphenyl] fluorene. 3. The varnish for an insulating film according to claim 2.

6. The bisaminophenol compound represented by the formula (1) is 2,2-bis [3-cyclohexyl-14- (4-amino-13-hydroxy) phenoxyphenyl] propane. The varnish for an insulating film according to claim 1.

7. The bisaminophenol compound represented by the formula (1) is converted to 1,1-bis [3-cyclohexyl

2. The varnish for an insulating film according to claim 1, wherein the varnish is 4- (4-amino-3-hydroxy) phenoxyphenylecyclohexane.

8. The dicarboxylic acid compound represented by the formula (4) is represented by the formula (5) -1 and the formula (5) as Y. The varnish for an insulating film according to any one of claims 1 to 7, which has a divalent group selected from the groups represented by 2 and the formula (6).

9. The dicarboxylic acid compound represented by the formula (4) is a divalent group selected from the groups represented by the formulas (7), (8), (9) and (10) as Y. The varnish for an insulating film according to any one of claims 1 to 7, wherein the varnish for an insulating film has:

10. The varnish for an insulating film according to any one of claims 1 to 9, wherein the organic group R in the formula (8) is a phenol group.

1 1. What can be achieved by reacting the bisaminophenol compound represented by the formula (1) with the dicarboxylic acid compound represented by the formula (4) using the terminal blocking compound represented by the formula (11) The varnish for an insulating film according to any one of claims 1 to 10, wherein a terminal of the polybenzoxazole resin precursor capable of forming is sealed.

[In the formula (11), R represents a monovalent organic group. ]

12. The oxygen element of the polybenzoxazole resin precursor obtained by reacting the bisaminophenol compound represented by the formula (1) with the dicarboxylic acid compound represented by the formula (4) The insulating varnish according to any one of claims 1 to 11, wherein the ratio is ⁵ to 10 mol%.

13. A varnish for an insulating film according to any one of claims 1 to 12 is used. An organic insulating film obtained by a dehydration-condensation reaction and comprising a resin layer having a polybenzoxazole resin as a main structure.