WO2011068207A1 - Phosphorus-containing polyimide and method for producing same - Google Patents

Abstract

Disclosed are: a phosphorus-containing polyimide having a repeating unit represented by the belowmentioned general formula (II) (wherein R₁, R₂, and R₃ are as described in the specification and the patent claims); a phosphorus-containing tetracarboxylic dianhydride that is the starting material thereof; and a method for producing the phosphorus-containing polyimide. The phosphorus-containing polyimide has excellent flame retardant properties.

Description

Phosphorus-containing polyimide and method for producing the same

The present invention relates to a phosphorus-containing tetracarboxylic dianhydride, a phosphorus-containing polyimide produced using the same, and a method for producing the same. Furthermore, the present invention relates to various laminates produced using these phosphorus-containing polyimides or polyamic acid which is a precursor thereof, and electronic circuits such as flexible printed wiring boards produced using these laminates.

Generally, polyimide is excellent in flame retardancy, heat resistance, mechanical properties, electrical properties, etc., so it is widely used as a substrate material for flexible printed wiring boards, protective films for wiring and semiconductor elements, heat resistant adhesives, interlayer insulation materials, etc. in use.

In recent years, in order to meet the needs for light, thin and small electrical and electronic devices, it is desired to make polyimide thin films used for electrical and electronic devices. However, the flame retardancy of polyimide tends to decrease with decreasing polyimide film thickness. In recent years, with higher performance of components and elements used in electronic devices and CPUs, the amount of generated heat has increased remarkably and the average temperature in the devices has also increased, so a more advanced flame retardant technology is desired. ing. On the other hand, in order to impart flame retardancy required for electric and electronic products from the viewpoint of environmental problems, there is a demand for safer means in consideration of safety to the natural environment and the human body.

As a technique for imparting flame retardancy to a polyimide, a method of mixing a metal hydrate such as magnesium hydroxide with a siloxane-modified polyimide has been proposed (for example, see Patent Document 1). However, in this method, magnesium hydroxide must be separately subjected to a surface treatment with a phosphoric acid surfactant, and the process becomes complicated. In addition, in this method, a diamine having two or more hydroxyl groups in the molecule is recommended as a diamine component to be used for the base polymer, but such a diamine cannot be said to be easily available.

In addition, a method of expressing flame retardancy by using a specific polyimide resin containing a silicon unit and a specific epoxy resin containing a phosphorus element has been proposed (for example, see Patent Document 2). In this method, a phosphorus compound and an epoxy resin are reacted to obtain a target phosphorus-containing epoxy resin, but in order to have a function as an epoxy resin, the reaction is preferably performed so that two epoxy groups remain. The upper limit of the phosphorus content is only 5% by weight. Since the polyimide resin introduced with the silicon unit is flammable, in order to give sufficient flame retardancy to the polyimide resin composition obtained by this method, a lot of epoxy resin with low heat resistance must be mixed. Don't be.

Furthermore, as a method for imparting flame retardancy to a resin composition, a method of adding a phosphorus compound to the resin composition is known (for example, Non-Patent Document 1). However, in order to express flame retardancy with a conventionally known technique, it is necessary to add a large amount of a phosphorus compound.

JP 2008-63459 A JP 2009-29982 A

Flame retarding technology using non-halogen flame retardant materials (NTS), p. 28 (issued in 2001)

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a phosphorus-containing tetracarboxylic dianhydride; and a phosphorus-containing polyimide that is produced using the phosphorus-containing tetracarboxylic dianhydride and exhibits excellent flame retardancy, and a method for producing the same.

The present inventors use a phosphorus-containing tetracarboxylic dianhydride having a specific structure obtained by the reaction of a phosphorus compound having a specific structure with an acid dianhydride having a specific structure. The present invention has been completed by finding that the phosphorus-containing polyimide produced in this way has further excellent flame retardancy without impairing the properties of conventional polyimide. A first aspect of the present invention is the following general formula (I):

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is (It may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be connected to each other by a single bond)
The phosphorus containing tetracarboxylic dianhydride represented by these.

The second aspect of the present invention is the following general formula (II) produced using these phosphorus-containing tetracarboxylic dianhydrides:

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is May be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be bonded to each other by a single bond, R ₃ is a divalent organic group)
It relates to a phosphorus-containing polyimide having a repeating unit represented by:

The third aspect of the present invention is the following general formula (III):

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is May be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be bonded to each other by a single bond, R ₃ is a divalent organic group)
A phosphorus-containing polyamic acid having a repeating unit represented by the following general formula (II):

(Wherein R ₁ , R ₂ and R ₃ are as defined above)
The manufacturing method of the phosphorus containing polyimide which has a repeating unit represented by these.

Furthermore, the present inventors have found that a phosphorus-containing polyimide can be obtained by imidizing a polyamic acid having a benzophenone skeleton in the presence of a phosphorus compound having a specific structure, thereby completing the present invention. Therefore, the fourth aspect of the present invention is the following general formula (I ′):

(Wherein R ₃ is a divalent organic group)
A polyamic acid represented by the following general formula (1):

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is (It may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be connected to each other by a single bond)
It is related with the manufacturing method of the phosphorus containing polyimide characterized by imidating in presence of the phosphorus compound represented by these.

The phosphorus-containing tetracarboxylic dianhydride according to the first aspect of the present invention is useful as a raw material for phosphorus-containing polyimide having flame retardancy, or as a curing agent or modifier for epoxy resins. In addition, the flame-retardant phosphorus-containing polyimide produced using this phosphorus-containing tetracarboxylic dianhydride exhibits excellent flame-retardant properties, has a flame-retardant heat-resistant adhesive, and a flame-retardant electronic circuit It is useful as an insulating material for a substrate.

The method for producing a phosphorus-containing polyimide according to the fourth aspect of the present invention is a simple method of imidizing a polyamic acid having a benzophenone skeleton in the presence of a phosphorus compound. It is an excellent thing that can be done. The phosphorus-containing polyimide obtained by this production method also exhibits excellent flame retardancy and is useful as a heat-resistant adhesive having flame retardancy, an insulating material for electronic circuit boards having flame retardancy, and the like.

1 shows a ¹ H-NMR chart of the compound obtained in Example 1 (in the general formula (I), R ₁ and R ₂ are both phenyl groups). 1 shows a ¹³ C-NMR chart of the compound obtained in Example 1 (in the general formula (I), R ₁ and R ₂ are both phenyl groups). ₂ shows an FT-IR chart of the compound obtained in Example 1 (in the general formula (I), R ₁ and R ₂ are both phenyl groups).

Hereinafter, embodiments of the present invention will be described in detail.

I. Phosphorus-containing tetracarboxylic dianhydride First, the phosphorus-containing tetracarboxylic dianhydride, which is the first aspect of the present invention and is a raw material (acid component) of the phosphorus-containing polyimide of the present invention, and a method for producing the same To do.

"Phosphorus-containing tetracarboxylic dianhydride and method for producing the same"
The phosphorus-containing tetracarboxylic dianhydride represented by the general formula (I) of the present invention includes benzophenone tetracarboxylic dianhydride and the following general formula (1):

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is (It may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be connected to each other by a single bond)
It can obtain by making it react with the phosphorus compound represented by these.

Specific examples of the benzophenone tetracarboxylic dianhydride used here include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride. Anhydrides and 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride may be mentioned.

In the phosphorus compound represented by the general formula (1), R ₁ and R ₂ are both phenyl groups (wherein at least one of the hydrogen atoms on the benzene ring is an alkyl group or alkoxyl having 1 to 6 carbon atoms) (Which may be substituted with a group) is preferred, and specific examples include the following formula (1a):

で表わされるジフェニルホスフィンオキシド（ＤＰＯ）が挙げられる。

The diphenylphosphine oxide (DPO) represented by these is mentioned.

Similarly, as the phosphorus compound represented by the general formula (1), one of R ₁ and R ₂ is a phenyl group, the other is a phenoxy group, and one of the carbon atoms on each benzene ring is bonded to each other. Those bonded by a single bond (wherein at least one hydrogen atom on the benzene ring may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms) are preferred, and specific examples include: The following formula (1b):

で表わされる９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド（ＨＣＡ（登録商標））が挙げられる。

9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA (registered trademark)) represented by the formula:

By the reaction of benzophenone tetracarboxylic dianhydride with the phosphorus compound represented by the general formula (1), the general formula (I) of the present invention:

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is (It may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be connected to each other by a single bond)
The phosphorus-containing tetracarboxylic dianhydride represented by this can be obtained. Specific examples include the following general formula (Ia):

又は下記一般式（Ｉｂ）：

Or the following general formula (Ib):

（式中、Ｒ_１′及びＲ_２′は、同一であっても異なっていてもよく、水素、炭素数１～６のアルキル基又はアルコキシル基である）
で表わされるリン含有テトラカルボン酸二無水物を挙げることができる。

(In the formula, R ₁ ′ and R ₂ ′ may be the same or different and are hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group)
The phosphorus containing tetracarboxylic dianhydride represented by these can be mentioned.

This reaction is performed at a temperature of 40 to 250 ° C., preferably 50 to 200 ° C., more preferably 70 to 180 ° C. for 1 minute to 12 hours, preferably 5 minutes to 6 hours, more preferably 10 minutes to 3 hours. Can be done.

In this reaction, a solvent may be used. The solvent to be used is not particularly limited as long as it is an inert solvent for the reaction, and is appropriately selected according to the desired reaction temperature. You may use individually or in mixture of 2 or more types of solvents in arbitrary ratios. For example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, anisole, chlorobenzene, dichlorobenzene and trichlorobenzene, ether solvents such as tetrahydrofuran, diglyme and triglyme, N, N-dimethylformamide, N, N-dimethylacetamide An aprotic polar solvent such as N-methyl-2-pyrrolidone (NMP) or dimethyl sulfoxide (DMSO) can be used. The amount of the solvent used is 50 to 1000% by weight, preferably 100 to 500% by weight, based on benzophenonetetracarboxylic dianhydride.

After completion of the reaction, a crude product can be obtained by concentrating the reaction solution. The crude product can be purified by washing with a polar solvent such as acetonitrile, ethyl acetate, methyl isobutyl ketone. The washed crystal is separated by filtration and dried at a temperature of 40 to 250 ° C., preferably 80 to 200 ° C. under reduced pressure or normal pressure to obtain the desired product.

II. Phosphorus-containing polyimide and production method thereof Next, the phosphorus-containing polyimide and production method thereof, which are the second and third aspects of the present invention, will be described.

"Phosphorus-containing polyamic acid and method for producing the same"
The production of the phosphorus-containing polyimide of the present invention begins with the following general formula (III):

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is May be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be bonded to each other by a single bond, R ₃ is a divalent organic group)
The phosphorus containing polyamic acid which has a repeating unit represented by these is manufactured. The phosphorus-containing polyamic acid is produced by polymerizing the phosphorus-containing tetracarboxylic dianhydride obtained by the above method and a diamine component represented by the formula: H ₂ N—R ₃ —NH ₂ by a known method. Can be done by. Usually, the polymerization reaction is carried out in a solvent at a solute concentration of 5 to 80% by weight, preferably 10 to 50% by weight. After completion of the reaction, the reaction solution can be used as it is as a phosphorus-containing polyamic acid solution (varnish) in the subsequent imidization reaction. Alternatively, the phosphorus-containing polyamic acid solution may be prepared by isolating the phosphorus-containing polyamic acid from the reaction solution and then re-dissolving it in an appropriate solvent.

The diamine component represented by the formula: H ₂ N—R ₃ —NH ₂ may be an aromatic diamine, an aliphatic diamine or an alicyclic diamine, and as an example of R ₃ , A divalent group of a cyclic or condensed polycyclic aromatic compound (eg, phenylene, indenylene, naphthylene, fluorenylene), a divalent group of an aliphatic compound having 2 to 12 carbon atoms (eg, having 2 to 12 carbon atoms) Alkanediyl, alkenylene or alkynylene) or a divalent group of an alicyclic compound having 3 to 10 carbon atoms (eg, cycloalkylene or cycloalkenylene having 3 to 10 carbon atoms), or may be the same or different , two or more of the divalent groups, the direct or bridge member (here a bridge member, -O -, - CO -, - COO -, - OCO -, - SO 2 -, - S -, - _{H 2 -, - C (CH} 3) 2 - and -C _{(CF 3) 2} - is selected from the group consisting of) those which are connected to each other by (e.g., biphenyl-4,4'-diyl, diphenyl ether - 4,4'-diyl, diphenyl ether-3,4'-diyl, benzophenone-4,4'-diyl). These aromatic diamines, aliphatic diamines or alicyclic diamines have one or more substituents selected from alkyl groups having 1 to 6 carbon atoms, alkenyl groups, alkynyl groups or alkoxyl groups, or halogen atoms. It may be.

Examples of the aromatic diamine component used here include those having one aromatic group: p-phenylenediamine, m-phenylenediamine, p-aminobenzylamine, m-aminobenzylamine, diaminotoluenes, diaminoxylene. , Diaminonaphthalenes, diaminoanthracenes, etc. having two aromatic groups: 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, o-tolidine, m- Tolidine, o-dianisidine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3 ' -Diaminodiphenyl ether, 4,4'-diamy Diphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 3, 4-diaminobenzophenone, 2,2-bis (4-aminophenoxy) propane, 2,2-bis (3-aminophenoxy) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, etc. Having three aromatic groups: 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, , 3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,4-bis Aromatic groups such as 3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,3-bis (3-aminobenzoyl) benzene, 9,9-bis (4-aminophenyl) fluorene Having two or more of: 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- ( 3-aminophenoxy) phenyl] ether, 4,4′-bis (4-aminophenoxy) benzophenone, 4,4′-bis (3-aminophen Noxy) benzophenone, 1,4-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] Benzene, 1,4-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 1,3-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] benzene, 4,4′-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] biphenyl, 4,4′-bis [3- (2-, 3- or -Aminophenoxy) benzoyl] biphenyl, 4,4'-bis [4- (2-, 3- or 4-aminophenoxy) benzoyl] diphenylsulfone, 4,4'-bis [3- (2-, 3- or 4-aminophenoxy) benzoyl] diphenylsulfone and the like. Further, the hydrogen atom on these aromatic rings may be substituted with one or more substituents selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group or an alkoxyl group, or a halogen atom. . In view of availability, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3- Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4 , 4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene is preferred.

Examples of aliphatic or alicyclic diamine components used herein include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diamino Pentane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4 -Diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, isophoronediamine and the like. Considering the availability, specifically, 1,6-diaminohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4 4,4'-diaminodicyclohexylmethane and isophoronediamine are preferably used.

The above diamine components may be used alone or in combination of two or more. Furthermore, the following general formula (IV):

(In the formula, m is an integer mixed value of 0 to 20, R ₄ represents a methyl, isopropyl, phenyl or vinyl group, R ₅ represents a divalent group of a hydrocarbon having 1 to 7 carbon atoms, for example, A siloxane diamine represented by (trimethylene, tetramethylene, phenylene, etc.) may be used in an amount in the range of 1 to 50 mol% of the diamine component.

Further, a monoamine compound or a dicarboxylic acid anhydride may be added for the purpose of adjusting the molecular weight. The monoamine compounds used are aniline, 4-aminophenol, 3-aminophenol, 4-aminobiphenyl, 4-phenoxyaniline, 3-aminophenylacetylene, 4-aminophenylacetylene, etc. Maleic anhydride, phthalic anhydride, 4-phenylethynyl phthalic anhydride, 4-ethynyl phthalic anhydride, trimellitic acid and the like. The amount of monoamine compound or dicarboxylic acid anhydride added varies depending on the molecular weight of the target phosphorus-containing polyimide, but it is usually 1.0 to several times the difference in the number of moles of all acid dianhydrides and diamine compounds used. The number of moles is preferably 1.5 to 4.0 times. When there are many acid dianhydrides, a monoamine compound is added, and when there are many diamine compounds, a dicarboxylic acid anhydride is added.

The solvent used in the production of the phosphorus-containing polyamic acid of the present invention is not particularly limited as long as it is an inert solvent. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Pyrrolidone, dimethyl sulfoxide, tetramethylurea, tetrahydrofuran and the like can be used alone or in a mixed form. Particularly preferred are N, N-dimethylacetamide and N-methyl-2-pyrrolidone. Further, these solvents may be used by mixing a solvent such as toluene, xylene, ethylbenzene, anisole, chlorobenzene, dichlorobenzene, trichlorobenzene, diglyme and triglyme in an arbitrary ratio. These solvents may also be used in preparing phosphorus-containing polyamic acid solutions by redissolving the isolated phosphorus-containing polyamic acid.

The phosphorus-containing polyamic acid having a repeating unit represented by the general formula (III) and the phosphorus-containing polyimide having a repeating unit represented by the general formula (II) are represented by the general formula (III). It does not mean only phosphorus-containing polyamic acid consisting only of repeating units and phosphorus-containing polyimide consisting only of repeating units represented by the general formula (II), but also includes those containing such repeating units as main constituent units. Means that. Accordingly, the purpose of the phosphorus-containing polyimide of the present invention and the reactivity of the phosphorus-containing polyamic acid that is a precursor thereof are represented by the above general formula (I) in the production of the phosphorus-containing polyamic acid. Tetracarboxylic dianhydrides other than phosphorus-containing tetracarboxylic dianhydrides can be partially used.

Examples of such tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3 ′, 3,4′-biphenyltetracarboxylic acid. Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, 3,3′-oxydiphthal Acid dianhydride, 4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,2,7,8-naphthalenetetracarboxylic dianhydride, and the like. In order to provide a phosphorus-containing polyimide having excellent flame retardancy, which is an object of the present invention, a phosphorus-containing tetracarboxylic dianhydride represented by the general formula (I) in the tetracarboxylic dianhydride component used It is preferable to use 30 mol% or more of the product, more preferably 50 mol% or more.

Furthermore, in the production of phosphorus-containing polyamic acid, the corresponding acid dianhydride isolation and purification steps as described above may be omitted. That is, a benzophenonetetracarboxylic dianhydride and a phosphorus compound represented by the general formula (1) in a solvent at 40 to 250 ° C., preferably 50 to 200 ° C., more preferably 70 to 180 ° C. for 1 minute to 12 hours. After cooling the solution containing phosphorus-containing tetracarboxylic dianhydride obtained by heating, preferably 5 minutes to 6 hours, more preferably 10 minutes to 3 hours, the desired diamine compound (the diamine compound is as described above) ) And a solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone as necessary, so that the solute concentration is 5 to 80% by weight, more preferably 10 to 50% by weight. Can be done by.

"Production method of phosphorus-containing polyimide"
The following general formula (III) obtained as described above:

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is May be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be bonded to each other by a single bond, R ₃ is a divalent organic group)
The phosphorus-containing polyamic acid having a repeating unit represented by the following general formula (II) of the present invention is thermally and / or chemically cyclized:

(Wherein R ₁ , R ₂ and R ₃ are as defined above)
The phosphorus containing polyimide which has a repeating unit represented by this can be obtained.

The phosphorus-containing polyimide of the present invention is produced by thermally and / or chemically ring-closing (that is, dehydrating) a phosphorus-containing polyamic acid by a known method. For example, a phosphorus-containing polyamic acid solution can be obtained by using a glass plate, a metal foil such as copper, aluminum, or stainless steel, or polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyimide, silicon resin, or fluorine. It is applied on a substrate such as a resin film such as a resin so that the thickness after drying is 0.1 to 250 μm, more preferably 1.0 to 100 μm, and 40 to 500 ° C., more preferably 70 to 350 ° C. The phosphorus-containing polyimide can be obtained by drying for 1 minute to 5 hours, more preferably 3 minutes to 3 hours. The obtained polyimide can be peeled off from the substrate and used as a film or as a laminate.

Further, a solvent azeotropic with water such as toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene is added to the phosphorus-containing polyamic acid solution, and the mixture is heated at 100 to 300 ° C, more preferably at 150 to 250 ° C. The phosphorus-containing polyimide can also be obtained by discharging water generated with imidization out of the system and performing thermal imidization. At this time, a nitrogen-containing heterocyclic compound such as pyridine, picoline or imidazole, or a tri-lower alkylamine such as triethylamine may be used. Alternatively, a dehydrating agent such as acetic anhydride, trifluoroacetic anhydride, N, N-dicyclohexylcarbodiimide and a nitrogen-containing heterocyclic compound such as pyridine, picoline or imidazole, or a tri-lower alkylamine such as triethylamine are added. Phosphorus-containing polyimide may be obtained by performing chemical imidation by dehydration at ˜200 ° C. for 1 to 24 hours. The solution that has been imidized thermally or chemically as described above is poured into a single solvent such as water, methanol, ethanol, isopropanol, acetone, toluene, xylene or a mixed solution thereof to precipitate crystals and filter. Separately, it can be dried and pulverized to obtain a powder form. The obtained polyimide can be used for injection molding or compression molding as it is. Separately, it can be dissolved in a solvent and used as a varnish, or it can be applied on the aforementioned substrate and dried to obtain a film form.

III. Method for Producing Phosphorus-Containing Polyimide A method for producing phosphorus-containing polyimide, which is the fourth aspect of the present invention, will be described.

"Production method of polyamic acid"
First, the phosphorus-containing polyimide of the present invention is produced by the general formula (I ′):

(Wherein R ₃ represents a divalent organic group)
Is produced.

The polyamic acid represented by the formula (I ′) is obtained by reacting a benzophenone tetracarboxylic dianhydride with a diamine component represented by the formula: H ₂ N—R ₃ —NH ₂ . This production method is not particularly limited and may be a known method, and is usually carried out in a solvent at a solute concentration of 5 to 80% by weight, preferably 10 to 50% by weight. After completion of the reaction, the reaction solution can be used as it is as a polyamic acid solution (varnish) in the subsequent imidization reaction. Alternatively, the phosphoric acid-containing polyamic acid solution may be prepared by isolating the polyamic acid from the reaction solution and then re-dissolving it in a suitable solvent.

The solvent used for the production of the polyamic acid is not particularly limited as long as it is inert to the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, Tetramethylurea, tetrahydrofuran and the like can be used alone or in a mixed form. Particularly preferred are N, N-dimethylacetamide and N-methyl-2-pyrrolidone. Further, these solvents may be used by mixing a solvent such as toluene, xylene, ethylbenzene, anisole, chlorobenzene, dichlorobenzene, trichlorobenzene, diglyme and triglyme in an arbitrary ratio. These solvents may also be used in preparing the polyamic acid solution by redissolving the isolated polyamic acid.

Specific examples of the benzophenone tetracarboxylic dianhydride used here include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride. Anhydrous, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride.

Formula used herein: diamine component represented by H _{2 N-R 3} -NH 2 is an aromatic diamine may be aliphatic diamine or alicyclic diamine, therefore as an example of R ₃ is 6 carbon atoms A divalent group of a monocyclic or condensed polycyclic aromatic compound of ˜14 (for example, phenylene, indenylene, naphthylene, fluorenylene), a divalent group of an aliphatic compound of 2 to 12 carbons (for example, carbon number) 2 to 12 alkanediyl, alkenylene or alkynylene) or a divalent group of an alicyclic compound having 3 to 10 carbon atoms (eg, cycloalkylene or cycloalkenylene having 3 to 10 carbon atoms), or the same or different The two or more divalent groups which may be present are directly or a cross-linking member (wherein the cross-linking member means —O—, —CO—, —COO—, —OCO—, —SO _2). Selected from the group consisting of —, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ — (eg, biphenyl-4, 4′-diyl, diphenyl ether-4,4′-diyl, diphenyl ether-3,4′-diyl, benzophenone-4,4′-diyl). These aromatic diamines, aliphatic diamines or alicyclic diamines have one or more substituents selected from alkyl groups having 1 to 6 carbon atoms, alkenyl groups, alkynyl groups or alkoxyl groups, or halogen atoms. It may be.

Examples of the aromatic diamine component, aliphatic or alicyclic diamine component are specific examples of the aromatic diamine component, aliphatic or alicyclic diamine component in the above section “II. Phosphorus-containing polyimide and production method thereof”. The same as each of the diamine compounds mentioned above.

The above diamine components may be used alone or in combination of two or more. Furthermore, the following general formula (IV):

(In the formula, m is an integer mixed value of 0 to 20, R ₄ represents a methyl, isopropyl, phenyl or vinyl group, R ₅ represents a divalent group of a hydrocarbon having 1 to 7 carbon atoms, for example, A siloxane diamine represented by (trimethylene, tetramethylene, phenylene, etc.) may be used in an amount in the range of 1 to 50 mol% of the diamine component.

The polyamic acid obtained by reacting the benzophenone tetracarboxylic dianhydride of the present invention with the diamine component does not mean only the polyamic acid consisting only of the repeating unit represented by the general formula (I ′). It is meant to include those containing a repeating unit as a main constituent unit. Therefore, in the production of the polyamic acid, the purpose of the phosphorus-containing polyimide of the present invention and the reactivity of the polyamic acid that is the precursor thereof are not affected. Things can be used in part.

Examples of such tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3 ′, 3,4′-biphenyltetracarboxylic acid. Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, 3,3′- Oxydiphthalic dianhydride, 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-di Carboxyphenyl) hexafluoropropane dianhydride, 1,2,7,8-naphthalene tetracarboxylic dianhydride and the like. In order to provide a phosphorus-containing polyimide having excellent flame retardancy, which is an object of the present invention, it is necessary to use 30 mol% or more of benzophenone tetracarboxylic dianhydride in the tetracarboxylic dianhydride component to be used. Preferably, it is more preferable to use 50 mol% or more.

Further, a monoamine compound or a dicarboxylic acid anhydride may be added for the purpose of adjusting the molecular weight. The monoamine compounds used are aniline, 4-aminophenol, 3-aminophenol, 4-aminobiphenyl, 4-phenoxyaniline, 3-aminophenylacetylene, 4-aminophenylacetylene, etc. Maleic anhydride, phthalic anhydride, 4-phenylethynyl phthalic anhydride, 4-ethynyl phthalic anhydride, trimellitic acid and the like. The amount of monoamine compound or dicarboxylic anhydride added varies depending on the molecular weight of the target polyimide, but it is usually 1.0 to several times the molar difference between the number of moles of all acid dianhydrides used and the diamine compound. The number is preferably 1.5 to 4.0 times. When there are many acid dianhydrides, a monoamine compound is added, and when there are many diamine compounds, a dicarboxylic acid anhydride is added.

"Production method of phosphorus-containing polyimide"
The following general formula (I ′) obtained as described above:

（式中、Ｒ_３は二価の有機基を表す）
で表わされるポリアミド酸を、下記一般式（１）：

(Wherein R ₃ represents a divalent organic group)
A polyamic acid represented by the following general formula (1):

(Wherein R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group, wherein at least one hydrogen atom on each benzene ring of R ₁ and R ₂ is (It may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxyl group, and / or one of carbon atoms on each benzene ring of R ₁ and R ₂ may be connected to each other by a single bond)
In the presence of a phosphorus compound represented by Simultaneously with the imidization, the phosphorus compound represented by the general formula (1) is introduced into the polyimide skeleton to produce a phosphorus-containing polyimide.

In the phosphorus compound represented by the general formula (1), R ₁ and R ₂ are both phenyl groups (wherein at least one of the hydrogen atoms on the benzene ring is an alkyl group or alkoxyl having 1 to 6 carbon atoms) (Which may be substituted with a group) is preferred, and specific examples thereof include the following formula (1a):

で表わされるジフェニルホスフィンオキシド（ＤＰＯ）が挙げられる。

The diphenylphosphine oxide (DPO) represented by these is mentioned.

Similarly, as the phosphorus compound represented by the general formula (1), one of R ₁ and R ₂ is a phenyl group, the other is a phenoxy group, and one of the carbon atoms on each benzene ring is bonded to each other. Those bonded by a single bond (wherein at least one hydrogen atom on the benzene ring may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms) are preferred, and specific examples include: The following formula (1b):

で表わされる９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド（ＨＣＡ（登録商標））が挙げられる。

9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA (registered trademark)) represented by the formula:

The amount of the phosphorus compound represented by the general formula (1) is 0.5 to several times the number of moles of the benzophenonetetracarboxylic dianhydride used, preferably 0.8 to 4.0 times. Is a mole.

A phosphorus-containing polyimide can be produced by imidizing the polyamic acid obtained as described above in the presence of the phosphorus compound represented by the general formula (1). For example, imidation may be carried out after adding the phosphorus compound represented by the general formula (1) to the polyamic acid solution obtained as described above. Alternatively, a polyamic acid may be produced as described above from benzophenone tetracarboxylic dianhydride and a diamine component in a solvent to which a phosphorus compound represented by the general formula (1) has been added in advance, followed by imidization. Good.

The phosphorus compound represented by the general formula (1) may be directly added to the polyamic acid solution or the reaction solvent, but is inert to the reaction, for example, N, N-dimethylformamide, N, N-dimethylacetamide, 5 to 90% by weight in a solvent such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, tetrahydrofuran, toluene, xylene, ethylbenzene, anisole, chlorobenzene, dichlorobenzene, trichlorobenzene, diglyme and triglyme, preferably 10 to It may be added after dissolving at a solute concentration of 80% by weight.

Subsequently, the mixed solution of the polyamic acid and the phosphorus compound is a glass plate, a metal foil such as copper, aluminum, or stainless steel, or polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyimide, It is applied on a substrate such as a resin film such as a silicon resin or a fluororesin so that the thickness after drying is 0.1 to 250 μm, more preferably 1.0 to 100 μm, and more preferably 40 to 500 ° C. The phosphorus-containing polyimide can be obtained by drying at 70 to 350 ° C. for 1 minute to 5 hours, more preferably 3 minutes to 3 hours. The obtained phosphorus-containing polyimide can be peeled off from the substrate and used as a film form or as it is as a laminate.

Further, a solvent that azeotropes with water, such as toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene, is added to the mixed solution of the polyamic acid and the phosphorus compound, and 100 to 300 ° C, more preferably 150 to 250 ° C. It is possible to obtain phosphorus-containing polyimide by heating with, discharging water generated by imidization out of the system and performing thermal imidization. At this time, a nitrogen-containing heterocyclic compound such as pyridine, picoline or imidazole, or a tri-lower alkylamine such as triethylamine may be used. Alternatively, a dehydrating agent such as acetic anhydride, trifluoroacetic anhydride, N, N-dicyclohexylcarbodiimide and a nitrogen-containing heterocyclic compound such as pyridine, picoline or imidazole or a tri-lower alkylamine such as triethylamine are added. Phosphorus-containing polyimide can also be obtained by performing chemical imidation by dehydrating at ˜200 ° C. for 1 to 24 hours. The solution that has been imidized thermally or chemically as described above is poured into a single solvent such as water, methanol, ethanol, isopropanol, acetone, toluene, xylene or a mixed solution thereof to precipitate crystals and filter. Separately, it can be dried and pulverized to obtain a powder form. The obtained phosphorus-containing polyimide can be used for injection molding or compression molding as it is. Separately, it can be dissolved in a solvent and used as a varnish, or it can be applied on the aforementioned substrate and dried to obtain a film form.

IV. Various laminates and electronic circuits The metal laminate of the present invention is prepared by, for example, using a phosphorus-containing polyamic acid solution produced according to the description in the above section “II. Phosphorus-containing polyimide and its production method”, having a thickness of 0.5 to 400 μm, More preferably, it is applied to at least one surface of a metal foil such as copper, aluminum or stainless steel having a thickness of 1.0 to 200 μm so that the thickness after drying is 0.1 to 250 μm, more preferably 1.0 to 100 μm. , 40 to 500 ° C., more preferably 70 to 350 ° C., for 1 minute to 5 hours, more preferably 3 minutes to 3 hours.

Alternatively, on at least one side of the phosphorus-containing polyimide film obtained according to the description in the section of “II. Phosphorus-containing polyimide and production method thereof” or “III. Production method of phosphorus-containing polyimide”, an epoxy resin system, an acrylic resin system, It is laminated with a metal foil such as copper, aluminum, or stainless steel having a thickness of 0.5 to 400 μm, more preferably 1.0 to 200 μm through an adhesive such as a polyimide resin, and the layer is 100 under normal pressure or pressing conditions. It can be produced by processing at a temperature of ˜500 ° C., preferably 150 ° C. to 350 ° C.

The aromatic polymer laminate of the present invention has a thickness of 0.5 to 400 μm, more preferably 1 with a phosphorus-containing polyamic acid solution manufactured according to the description in the section “II. A thickness after drying of 0.1 to 200 μm on an aromatic polymer such as aromatic polyester, polyphenylene sulfide, aromatic polyimide, polyaryl ether ketone, aromatic polycarbonate, aromatic liquid crystal polymer, or polybenzoxazole is 0.1. It is manufactured by coating to a thickness of ˜250 μm, more preferably 1.0 to 100 μm, and drying at 40 to 500 ° C., more preferably 70 to 350 ° C. for 1 minute to 5 hours, more preferably 3 minutes to 3 hours. can do.

Also, an aromatic polyester, polyphenylene sulfide, aromatic polyimide, polyaryletherketone, aromatic polycarbonate, aromatic liquid crystal polymer, or polybenzoxazole having a thickness of 0.5 to 400 μm, more preferably 1.0 to 200 μm, etc. On one side of an aromatic polymer or a metal foil such as copper, aluminum, or stainless steel having a thickness of 0.5 to 400 μm, more preferably 1.0 to 200 μm, for example, the above-mentioned “II. Phosphorus-containing polyimide and The phosphorus-containing polyamic acid solution produced in accordance with the description of the “Production method” is applied, the other is overlaid on the coated surface, and then laminated or hot pressed, whereby the aromatic polymer metal via the phosphorus-containing polyimide of the present invention is used. A composite laminate can be produced.

A circuit pattern can be prepared by a known method on the metal laminate and aromatic polymer metal composite laminate produced as described above and used as an electronic circuit. The electronic circuit created using the phosphorus-containing polyimide of the present invention has excellent flame retardancy, and thus can provide a safe electrical / electronic device.

In order to clarify aspects of the present invention, examples and comparative examples are shown below, but the present invention is not limited to the examples shown here.

The solution viscosity, purity, melting point or glass transition temperature, NMR and infrared absorption spectrum measurement methods, and flame retardancy evaluation methods of the compounds obtained in the examples are as follows.

Solution viscosity: Measured at a temperature of 25 ° C. using a B-type viscometer (manufactured by Tokyo Keiki).

Purity: Measurement was performed using HPLC (manufactured by Shimadzu Corporation) and column (manufactured by Tosoh Corp. TSKgel ODS-80TM). The sample solution was prepared by dissolving or dispersing the sample in an acetonitrile / water mixture and then heating the solution at 60 ° C. for 15 minutes. The eluent used was an acetonitrile / water / phosphoric acid system, and the purity was calculated by area percentage.

Melting point or glass transition temperature: Measurement was carried out with a differential scanning calorimeter (manufactured by Shimadzu Corp. DSC-60) at a temperature of 10 ° C. per minute up to 40-400 ° C. The melting point or glass transition temperature was calculated from the extrapolation point of the DSCDSC curve by analysis software.

NMR: A solution in which a compound and heavy DMSO (containing DMSO-d ₆ 0.05% TMS manufactured by Cambrige Isotope Laboratories, Inc.) were mixed was prepared, and ¹ H-NMR measurement was performed using NMR (JNM-AL400 manufactured by JEOL Ltd.). And ¹³ C-NMR measurement was performed.

Infrared absorption spectrum: IR measurement device (Spectrum 100 FT-IR Spectrometer manufactured by Perkin Elmer Co., Ltd.) using the KBr method; or IR measurement device (Shimadzu Prestage® 21) using the ATR method. It was measured.

Evaluation of flame retardancy: The film was cut into a size of 200 mm × 50 mm to obtain a test piece. The test piece was wound in a cylindrical shape, fixed vertically to the clamp, and subjected to indirect flame twice for 3 seconds with a burner at the bottom of the sample.

Example 1
Synthesis of a phosphorus-containing tetracarboxylic dianhydride represented by the general formula (I) ( both R ₁ and R ₂ are phenyl groups) in a four-necked flask equipped with a stirrer, thermometer, nitrogen introduction tube and cooling tube 2.8 g (0.014 mol) of diphenylphosphine oxide (Aldrich), 3.5 g (0.011 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (manufactured by Daicel Chemical Industries) and 25 g of toluene And stirred at 110 ° C. for 4 hours under a nitrogen stream. After completion of the reaction, all the toluene was distilled off, and after cooling to 80 ° C., 10 g of acetonitrile was added. After cooling to room temperature, the precipitated solid was filtered off and washed with toluene and acetonitrile. The obtained solid was dried at 60 ° C. overnight to obtain 2.8 g of a crude product with a purity of 94.2%. This crude product was heated and washed with acetonitrile to obtain a purified product having a purity of 97.5% and a melting point of 151 ° C. FIG. 1 shows the ¹ H-NMR of the purified product, FIG. 2 shows the ¹³ C-NMR, and FIG. 3 shows the FT-IR chart (KBr method using Spectrum 100 FT-IR Spectrometer manufactured by Perkin Elmer).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 7.08 (d, J = 10 Hz, 1H), 7.48 (ddd, J = 7.6, 7.6, 3.6 Hz) , 4H), 7.59 (ddd, J = 7.6, 7.6, 1.2 Hz, 2H), 7.76 (ddd, J = 12.4, 7.5, 1.2 Hz, 4H), 8.06 (d, J = 8.0 Hz, 2H), 8.23 (dd, J = 8.0, 1.2 Hz, 2H), 8.29 (s, 2H).
¹³ C-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 75.0 (d, J = 16.4 Hz), 123.1, 125.8, 128.7 (d, J = 52.8 Hz) ), 130.7 (d, J = 537.6 Hz), 131.0, 131.2 (d, J = 39.6 Hz), 131.9, 132.5 (d, J = 13.2 Hz), 133 .9, 148.3 (d, J = 16.8 Hz), 162.5, 162.6.

Example 2
Synthesis thermometer of phosphorus-containing polyimide represented by the general formula (II) (R ₁ and R ₂ are both phenyl groups and R ₃ is diphenyl ether-4,4′-diyl), In a one-necked flask, 10.118 g (0.05 mol) of 4,4′-diaminodiphenyl ether (manufactured by Wakayama Seika Co., Ltd.), 26.2207 g (0.05 mol) of the phosphorus-containing tetracarboxylic dianhydride synthesized in Example 1 were used. Then, 205 g of NMP was charged and stirred at room temperature for 12 hours under a nitrogen stream to synthesize phosphorus-containing polyamic acid. The reaction solution (solute concentration 15%, viscosity (B-type viscometer: manufactured by Tokyo Keiki) 5,500 mPa · s) was used as it was as a phosphorus-containing polyamic acid solution. The obtained phosphorus-containing polyamic acid solution is coated on a glass plate so that the thickness after drying is 25 μm, dried at 90 ° C., 130 ° C., and 180 ° C. for 30 minutes, and then peeled off from the glass plate. It fixed to the metal frame and heat-processed at 200 degreeC and 250 degreeC each temperature for 1 hour. A phosphorus-containing polyimide in the form of a film having a thickness of 25 μm was obtained.

Example 3
Phosphorus-containing compounds represented by the general formula (II) (R ₁ and R ₂ are both phenyl groups, and R ₃ is 1,4-phenyleneoxy-biphenyl-4,4′-diyloxy-1,4-phenylene) In a four-necked flask equipped with a polyimide thermometer and a nitrogen inlet tube, 8.5602 g (0.027 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, diphenylphosphine oxide (DPO) 5.313 g (0.027 mol) and 47.4 g of diglyme were charged and heated at 160 ° C. for 3 hours to synthesize phosphorus-containing tetracarboxylic dianhydride. The solution containing the acid dianhydride was cooled to room temperature, charged with 9.7766 g (0.027 mol) of 4,4′-bis (4-aminophenoxy) biphenyl (BAPB) and 47.4 g of NMP, and under a nitrogen stream at room temperature. The mixture was stirred for 12 hours to synthesize phosphorus-containing polyamic acid. The reaction solution (solute concentration 20%, viscosity (B-type viscometer: manufactured by Tokyo Keiki Co., Ltd., 8,000 mPa · s)) was directly used as a phosphorus-containing polyamic acid solution. Application to a glass plate, drying and heat treatment were carried out in the same manner as in Example 2 to obtain a phosphorus-containing polyimide in the form of a film having a thickness of 20 μm.

Comparative Example 1
In a four-necked flask equipped with a thermometer and a nitrogen inlet tube, 16.1113 g (0.05 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether were used. 0118 g (0.05 mol) and 148 g of NMP were charged and stirred at room temperature for 12 hours under a nitrogen stream to synthesize phosphorus-containing polyamic acid. The reaction solution (solute concentration 15%, viscosity (B-type viscometer: manufactured by Tokyo Keiki) 12,000 mPa · s) was used as it was as the polyamic acid solution. Application to a glass plate, drying and heat treatment were carried out in the same manner as in Example 2 to obtain a polyimide containing no phosphorus in the form of a film having a thickness of 20 μm.

Comparative Example 2
Except for changing the diamine compound to 4,4′-bis (4-aminophenoxy) biphenyl (BAPB) 18.4214 g (0.05 mol), the same operation as in Comparative Example 1 was performed, and phosphorus in the form of a film having a thickness of 20 μm was obtained. The polyimide which does not contain was obtained.

Evaluation of flame retardancy The polyimides obtained in Examples 2 and 3 and Comparative Examples 1 and 2 were evaluated. The results are shown in Table 1.

Example 4
Production of Metal Laminate The phosphorus-containing polyamic acid solution produced in Example 2 was placed on a 18 μm thick copper foil (manufactured by Mitsui Kinzoku Co., Ltd., 3EC-VLP) so that the resin thickness after drying would be 25 μm. After applying and drying at 90 ° C., 130 ° C., and 180 ° C. for 30 minutes, heat treatment was performed at 250 ° C. for 1 hour in a vacuum dryer to obtain a phosphorus-containing polyimide / metal laminate.

Example 5
Production of Aromatic Polymer Laminate The phosphorus-containing polyamic acid solution produced in Example 2 was dried on a 25 μm thick aromatic polyimide film (manufactured by DuPont, Kapton (registered trademark) H). Is applied at a temperature of 90 ° C, 130 ° C, 180 ° C for 30 minutes, and then heat-treated at 250 ° C for 1 hour in a dryer to form a phosphorus-containing polyimide / aromatic polymer laminate. Got the body.

Example 6
Production of aromatic polymer metal composite laminate The phosphorus-containing polyamic acid solution produced in Example 2 was dried on a copper foil having a thickness of 18 μm (manufactured by Mitsui Kinzoku Co., Ltd., 3EC-VLP) with a resin thickness after drying of 5 μm. Then, the coating was performed and dried at a temperature of 160 ° C. for 3 minutes. Next, an aromatic polyimide film having a thickness of 40 μm (manufactured by DuPont, Kapton (registered trademark) EN) was stacked on the coated surface, and lamination was performed at a temperature of 200 ° C. The obtained laminate was heat-treated at a temperature of 350 ° C. to obtain a metal / phosphorus-containing polyimide / aromatic polymer composite laminate.

Example 7
Synthesis of phosphorus-containing polyimide (production method according to the fourth aspect of the present invention)
In a four-necked flask equipped with a thermometer and a nitrogen introduction tube, in a nitrogen stream, 4,4′-diaminodiphenyl ether (4-ODA) (manufactured by Wakayama Seika Co., Ltd.) 10.118 g (0.05 mol), 9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA (registered trademark)) (manufactured by Sanko Co., Ltd.) 10.8086 g (0.05 mol), N-methyl-2-pyrrolidone (NMP) 148. 0 g was charged and dissolved. Then, 3,113 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) (manufactured by Daicel Chemical) was charged with 16.11313 g (0.05 mol), stirred at room temperature for 12 hours, A mixed solution of polyamic acid and a phosphorus compound having a 000 mPa · s and a solute concentration of 20% was obtained. The obtained mixed solution is coated on a glass plate so that the thickness after drying is 20 μm, dried at 90 ° C., 130 ° C., and 180 ° C. for 30 minutes, and then peeled off from the glass plate to form a metal frame. After fixing, heat treatment was performed at 200 ° C. and 250 ° C. for 1 hour to obtain a polyimide film containing 4.4% (theoretical value) of phosphorus atoms in the repeating unit. When the IR of the polyimide film (ATR method by Prestage 21 manufactured by Shimadzu Corporation) was measured, the absorption of the carbonyl stretching vibration of benzophenone at 1670 cm ⁻¹ disappeared. The glass transition temperature of the film was 255 ° C., and the flame retardancy evaluation was ○.

Comparative Example 3
In a four-necked flask equipped with a thermometer and a nitrogen inlet tube, in a nitrogen stream, 4,4′-diaminodiphenyl ether (4-ODA) (manufactured by Wakayama Seika Co., Ltd.), 10.118 g (0.05 mol), N-methyl 148.0 g of -2-pyrrolidone (NMP) was charged and dissolved. Subsequently, 3,113 ′, 4,4′-biphenyltetracarboxylic dianhydride (BTDA) (manufactured by Daicel Chemical) was charged with 16.113 g (0.05 mol) and stirred at room temperature for 12 hours. A polyamic acid solution having 500 mPa · s and a solute concentration of 15% was obtained. The obtained polyamic acid solution was coated on a glass plate so that the thickness after drying was 20 μm, dried at 90 ° C., 130 ° C., and 180 ° C. for 30 minutes, and then peeled off from the glass plate. The polyimide film containing no phosphorus was obtained by heat treatment at 200 ° C. and 250 ° C. for 1 hour. The glass transition temperature of the film was 263 ° C., and the flame retardancy evaluation was x.

Comparative Example 4
A four-necked flask equipped with a thermometer and a nitrogen inlet tube was charged with 10.118 g (0.05 mol) of 4,4′-diaminodiphenyl ether (4-ODA), 9,10-dihydro-9-oxa-acid in a nitrogen stream. 21.6172 g (0.10 mol) of 10-phosphaphenanthrene-10-oxide (HCA (registered trademark)) (manufactured by Sanko Co., Ltd.) and 188.6 g of N-methyl-2-pyrrolidone (NMP) were charged and dissolved. . Thereafter, 15.5107 g (0.05 mol) (manac Co., Ltd.) of 4,4′-oxydiphthalic dianhydride was charged and stirred at room temperature for 12 hours to give a polyamide having a solution viscosity of 7,800 mPa · s and a solute concentration of 20%. A mixture of an acid solution and a phosphorus compound was obtained. The obtained mixture is applied onto a glass plate so that the thickness after drying is 20 μm, dried at 90 ° C., 130 ° C., and 180 ° C. for 30 minutes, and then peeled off from the glass plate and fixed to a metal frame. Then, heat treatment was performed at 200 ° C. and 250 ° C. for 1 hour to obtain a polyimide film. When the IR of the polyimide film (ATR method by Prestage 21 manufactured by Shimadzu Corporation) was measured, the presence of phosphorus was not observed. The glass transition temperature of the film was 228 ° C., and the flame retardancy evaluation was x.

Examples 8 to 10, Comparative Example 5
In the same manner as in Example 7, various components were changed to prepare a polyimide film. The composition and results are shown in Table 2.

The abbreviations in the table indicate the following.
BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride APB: 1,3-bis (3-amino Phenoxy) benzene BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane BAPS: bis [4- (4-aminophenoxy) phenyl] sulfone HCA®: 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide DPO: Diphenylphosphine oxide (Aldrich)

The phosphorus-containing polyimide produced by using the phosphorus-containing tetracarboxylic dianhydride of the present invention exhibits excellent flame resistance and physical properties equivalent to those of conventional polyimide, and also exhibits good heat resistance even when it becomes a thin film. It is possible to meet the needs for light, thin, and small devices such as electrical and electronic equipment. Moreover, since the use of the flame-retardant phosphorus-containing polyimide of the present invention can avoid or reduce the addition of a further flame retardant, it is a flame-retarding technique with higher safety in the natural environment and the human body.

Particularly, by using the method for producing a phosphorus-containing polyimide described in the fourth aspect of the present invention, the phosphorus-containing polyimide can be produced by a simple method without requiring any special equipment or process. The phosphorus-containing polyimide produced by using this production method is very useful as a heat-resistant adhesive, an insulating material for an electronic circuit board, and the like that are required to be thinned and flame-retardant.

Claims (14)

The following general formula (II):

(Where
R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group,
Here, at least one hydrogen atom on the benzene ring of each of R ₁ and R ₂ may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms, and / or benzene of each of R ₁ and R ₂ One of the carbon atoms on the ring may be connected to each other by a single bond,
R ₃ is a divalent organic group)
The phosphorus containing polyimide which has a repeating unit represented by these. In the general formula (II), R ₁ and R ₂ are both phenyl groups, or _one of R ₁ and R ₂ is a phenyl group and the other is a phenoxy group, and the carbon on each benzene ring One of the atoms is bonded to each other by a single bond (wherein at least one hydrogen atom on the benzene ring may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms), The phosphorus-containing polyimide according to 1. The following general formula (I):

(Where
R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group,
Here, at least one hydrogen atom on the benzene ring of each of R ₁ and R ₂ may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms, and / or each of R ₁ and R ₂ (One of the carbon atoms on the benzene ring may be connected to each other by a single bond)
The phosphorus containing tetracarboxylic dianhydride represented by these. In the general formula (I), R ₁ and R ₂ are both phenyl groups, or _one of R ₁ and R ₂ is a phenyl group and the other is a phenoxy group, and the carbon on each benzene ring One of the atoms is bonded to each other by a single bond (wherein at least one hydrogen atom on the benzene ring may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms), 4. The phosphorus-containing tetracarboxylic dianhydride according to 3. The following formula (Ia):

And the following formula (Ib):

(In the formula, R ₁ ′ and R ₂ ′ may be the same or different and are hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group)
The phosphorus-containing tetracarboxylic dianhydride according to claim 3 or 4, which is selected from the group consisting of: The following general formula (III):

(Where
R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group,
Here, at least one hydrogen atom on the benzene ring of each of R ₁ and R ₂ may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms, and / or benzene of each of R ₁ and R ₂ One of the carbon atoms on the ring may be connected to each other by a single bond,
R ₃ is a divalent organic group)
A phosphorus-containing polyamic acid having a repeating unit represented by the following general formula (II):

(Wherein R ₁ , R ₂ and R ₃ are as defined above)
The manufacturing method of a phosphorus containing polyimide which has a repeating unit represented by these. Formula (I ′) below:

(Wherein R ₃ is a divalent organic group)
A polyamic acid represented by the following general formula (1):

(Where
R ₁ and R ₂ may be the same or different and are a phenyl group or a phenoxy group,
Here, at least one hydrogen atom on the benzene ring of each of R ₁ and R ₂ may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms, and / or benzene of each of R ₁ and R ₂ One of the carbon atoms on the ring may be connected to each other by a single bond)
A method for producing a phosphorus-containing polyimide, wherein imidization is performed in the presence of a phosphorus compound represented by formula (1). In the phosphorus compound of the general formula (1), R ₁ and R ₂ are both phenyl groups, or _one of R ₁ and R ₂ is a phenyl group and the other is a phenoxy group, and each benzene One of the carbon atoms on the ring is connected to each other by a single bond (wherein at least one of the hydrogen atoms on the benzene ring may be substituted with an alkyl group or alkoxyl group having 1 to 6 carbon atoms). The manufacturing method of Claim 7 which is a thing. The phosphorus compound described in the general formula (1) is represented by the following formula (1a):

And / or the following formula (1b)

The manufacturing method of Claim 7 or 8 which is. A metal laminate obtained by laminating a metal foil on at least one side of the phosphorus-containing polyimide according to claim 1 or 2. An aromatic polymer laminate obtained by laminating an aromatic polymer on at least one surface of the phosphorus-containing polyimide according to claim 1 or 2. An aromatic polymer metal composite laminate obtained by laminating a metal foil and an aromatic polymer through the phosphorus-containing polyimide according to claim 1 or 2. An electronic circuit comprising the metal laminate according to claim 10. An electronic circuit comprising the metal composite laminate according to claim 12.

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