JP2844473B2 - Polybiphenylene ether ketone copolymer film - Google Patents

Description

The present invention relates to a novel polybiphenylene ether ketone copolymer film, and more particularly, to the field of electronics, electric and thermal insulation, and other general industrial fields. The present invention relates to a polybiphenylene ether ketone copolymer film that can be widely used for various applications.

[Problems to be Solved by Conventional Techniques and Inventions] In recent years, various types of resin films having excellent heat resistance and mechanical strength have been developed, and these have been widely used as materials for parts of electronic / electric devices and machines. Has been offered to.

On the other hand, as the range of application of the resin film expands, properties superior to those of the related art, that is, heat resistance,
There is an increasing demand for resin films having properties such as flame retardancy and mechanical strength.

However, even among polyetherketone resins, which are said to have the best performance among the resin films currently used, the glass transition temperature is low and the heat resistance is not sufficient. In addition, polyetherketone resins are liable to contain gels in the polymer due to severe production conditions, and therefore have difficulty in moldability and processability, and do not have satisfactory properties in all respects. In particular, the fact that the resin is easily included is a problem when these resins are formed into a film.

 The present invention has been made based on the above circumstances.

An object of the present invention is to provide a polybiphenylene ether having a high Tg (glass transition temperature), a good moldability because it does not contain any gel, and excellent mechanical strength, heat resistance, flame retardancy and solvent resistance. An object of the present invention is to provide a ketone copolymer film.

[Means for Solving the Problems] The invention according to claim 1 for achieving the above object has the following formula (I): And the following formula (II): Wherein the composition ratio of the repeating unit represented by the formula (I) is 0.15 to 0.40 mol and the melt viscosity at 400 ° C. is 3,000 to 100,000 poise. It is a polybiphenylene ether ketone copolymer film molded at a temperature higher by 10 to 100 ° C. than its crystal melting point, and the invention according to claim 2 is the polybiphenylene ether ketone copolymer film according to claim 1. Is a polybiphenylene ether ketone copolymer film obtained by heat-treating at a temperature between the crystallization temperature and the crystal melting point. The invention according to claim 3, wherein the polybiphenylene ether ketone copolymer film according to claim 1 is used. The polymer film is stretched in a uniaxial or biaxial direction at a temperature between the glass transition temperature and the crystal melting point of 1.5 to 10%. A polybiphenylene ether ketone copolymer film obtained by stretching the polybiphenylene ether ketone copolymer film according to claim 1, wherein the polybiphenylene ether ketone copolymer film has a glass transition temperature and a crystal melting point. At a temperature in between, after stretching in a uniaxial or biaxial direction at a draw ratio of 1.5 to 10 times, a polybiphenylene ether ketone copolymer film obtained by heat treatment at a temperature between the crystallization temperature and the crystal melting point. .

 The details will be described below.

—Polybiphenylene ether ketone copolymer— One of the important points in the polybiphenylene ether ketone copolymer film of the present invention is that the polybiphenylene ether ketone copolymer has a repeating unit represented by the formula (I). A repeating unit represented by the formula (II), wherein the repeating unit represented by the formula (II) has a composition ratio (molar ratio) of 0.15 to 0.40. Has a composition ratio (molar ratio) of 0.85 to 0.60.

When the composition ratio of the repeating unit represented by the formula (I) is 0.
If it is less than 15, the glass transition temperature of the polybiphenylene ether ketone copolymer will be low and the heat resistance will be lowered, or the melting point will be high and the moldability will be deteriorated. On the other hand, if it exceeds 0.60, the crystallinity of the polybiphenylene ether ketone copolymer is lost, and heat resistance and solvent resistance are reduced.

In the polybiphenylene ether ketone copolymer of the present invention, it is important that the melt viscosity (zero shear viscosity) at a temperature of 400 ° C. is 3,000 to 100,000 poise.

This is because a low molecular weight polybiphenylene ether ketone copolymer having a melt viscosity of less than 3,000 poise cannot achieve sufficient heat resistance and mechanical strength.

When the melt viscosity exceeds 100,000 poise, it becomes difficult to form a film.

The polybiphenylene ether ketone copolymer used in the present invention has, for example, a crystal melting point of about 330 to 400 ° C., has high crystallinity, has a sufficiently high molecular weight, shows sufficient heat resistance, and has high heat resistance. It is excellent in solvent properties and mechanical strength, and can be suitably used as a new material in, for example, electric / electronic equipment fields, mechanical fields, and the like.

Such a polybiphenylene ether ketone copolymer can be produced as follows.

-Method for producing polybiphenylene ether ketone copolymer-Polybiphenylene ether ketone copolymer is prepared by dihalogenobenzonitrile, 4,4'-biphenol, and an alkali metal compound at a specific use ratio in the presence of a neutral polar solvent. After the reaction, the reaction product and a certain amount of 4,
It can be produced by performing a copolymerization reaction with 4'-dihalogenobenzophenone.

Specific examples of the dihalogenobenzonitrile to be used include, for example, the following formula; (Wherein, X is a halogen atom.) 2,6-dihalogenobenzonitrile, 2,4-dihalogenobenzonitrile and the like.

Among these, preferred are 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4-dichlorobenzonitrile, and 2,4-difluorobenzonitrile, and particularly preferred is 2,6-dichlorobenzonitrile. Benzonitrile.

In the method of the present invention, the dihalogenobenzonitrile and the following formula: Is reacted in the presence of an alkali metal compound and a neutral polar solvent.

The alkali metal compound to be used is the 4,
Any material can be used as long as it can convert 4'-biphenol into an alkali metal salt, and there is no particular limitation. Preferred are an alkali metal carbonate and an alkali metal bicarbonate.

Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.

Among them, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal bicarbonate include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate.

Of these, preferred are sodium bicarbonate,
Potassium bicarbonate.

In the method of the present invention, sodium carbonate and potassium carbonate can be particularly preferably used among the above various alkali metal compounds.

Examples of the neutral polar solvent include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-
Dipropylacetamide, N, N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, Nn-propyl -2-pyrrolidone, Nn-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl -3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-
Piperidone, N-isopropyl-2-piperidone, N-
Methyl-6-methyl-2-piperidone, N-methyl-3
-Ethylpiperidone, dimethylsulfoxide, diethylsulfoxide, 1-methyl-1-oxosulfolane,
-Ethyl-1-oxosulfolane, 1-phenyl-1-
Oxosulfolane, N, N'-dimethylimidazolidinone, diphenylsulfone and the like.

In the method of the present invention, a reaction product obtained by reacting the dihalogenobenzonitrile with the 4,4′-biphenol in the presence of the alkali metal compound and the neutral polar solvent, React with 4'-dihalogenobenzophenone.

The 4,4′-dihalogenobenzophenone to be used has the following formula: (Where X has the same meaning as described above). In the method of the present invention,
4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone can be particularly preferably used.

In the production of the polybiphenylene ether ketone copolymer of the present invention, the ratio of the dihalogenobenzonitrile used is 2,6-dichlorobenzonitrile: 4,4'-dihalogenobenzophenone: 4,4'-biphenol: potassium carbonate Is 0.15 to 0.4: 0.85 to 0.6: 1: 1.2.

The molar ratio of the total amount of 2,6-dichlorobenzonitrile and 4,4'-dihalogenobenzophenone to the amount of the 4,4'-biphenol used is usually 0.98 to 1.02, preferably 1.00 to 1.01. is there. The molar ratio of potassium carbonate is usually 1.03 to 2.50, preferably 1.05 to 1.25.

The amount of the neutral polar solvent used is not particularly limited, but usually, the dihalogenobenzonitrile and the 4,4
It is selected in the range of 200 to 2,000 parts by weight per 100 parts by weight of the total of 4'-biphenol and the alkali metal compound.

To obtain a polybiphenylene ether ketone copolymer, for example, in the neutral polar solvent, the dihalogenobenzonitrile, the 4,4'-biphenol, and the alkali metal compound are added simultaneously, After the reaction between the dihalogenobenzonitrile and the 4,4'-biphenol, the 4,4'-dilogenobenzophenone is further added, usually at 150 to 380 ° C, preferably 180 ° C.
A series of reactions is performed at a temperature in the range of 330330 ° C. If the reaction temperature is lower than 150 ° C, the reaction rate is too slow to be practical, and if it exceeds 380 ° C, a side reaction may occur.

The reaction time of this series of reactions is usually 0.1 to 10
Time, preferably 1 hour to 5 hours.

After completion of the reaction, the polybiphenylene ether ketone copolymer is separated and purified from a neutral polar solvent solution containing the obtained polybiphenylene ether ketone copolymer according to a known method, thereby obtaining a polybiphenylene ether ketone copolymer. Coalescence can be obtained.

—Method for Producing Polybiphenylene Ether Ketone Copolymer Film— The polybiphenylene ether ketone copolymer film according to claim 1 is obtained by forming the polybiphenylene ether ketone copolymer into a film.

The film is formed by a usual method such as a press molding method or an extrusion molding method, at a temperature 10 to 100 ° C. higher than the crystal melting point, preferably at a temperature 30 to 70 ° C. higher than the crystal melting point, and by quenching. Thus, an amorphous film having good transparency can be obtained.

By subjecting the thus obtained amorphous film to a heat treatment at a temperature between its crystallization temperature and the crystal melting point, a crystalline film can be obtained.

The stretching film is formed uniaxially or biaxially and at a temperature between Tg (glass transition temperature) and Tm (crystal melting point).

Further, the heat treatment of the stretched film is performed under tension or no tension as necessary, and Tcc [crystallization temperature: a temperature at which the polymer which has been made amorphous by the above film formation crystallizes by heat treatment (heating)]. It is performed at a temperature higher than Tm (crystal melting point).

In the present invention, the polybiphenylene ether ketone copolymer film is stretched by the stretching method described above.
It is preferable to stretch 1.5 to 10 times, especially stretching ratio 2
It is preferable to stretch the film up to 5 times.

If the draw ratio is less than 1.5 times, a sufficient draw effect (effect of improving film properties such as tensile strength and tensile elasticity) may not be achieved, and even if the draw ratio exceeds 10 times, the draw effect is not sufficient. Furthermore, it may not improve.

The polybiphenylene ether ketone copolymer film thus obtained can be used in the field of electronics for: (1) base film for flexible printed circuit board, backing material for flexible printed circuit board, electrode plate for membrane, backing material for membrane, transparent electrode It can be used for base film, film cell for liquid crystal, IC carrier tape, optical card, base film for perpendicular magnetization, etc. (2) In the field of electric and thermal insulation, sheet heating element base and surface cover film, insulating tape (Motors, generators, transformers), condensers, electric wire coverings, shielding plates for microwave ovens and other thermal equipment, speaker diaphragms, lighting equipment covers, instrument display panels, etc. (3) General industrial use In overhead projector base paper, aircraft interior ,
It can be used for nuclear related equipment, solar collector cover, ultrafiltration membrane, etc. (4) In addition, it can be used for heat-resistant labels, heat-resistant nameplates, composites for aviation, vehicles, defense, etc.

[Examples] (Production Example 1) A reactor having an inner volume of 5 equipped with a Dein-Stark trap filled with toluene, a stirrer, and an argon gas blowing tube was charged with 32.34 g (0.188 mol) of 2,6-dichlorobenzonitrile, 4 139.66 g (0.75 mol) of 4,4'-biphenol, 124.39 g (0.9 mol) of potassium carbonate and 1.5 of N-methylpyrrolidone were added, and the temperature was raised from room temperature to 195 ° C. over 1 hour while blowing argon gas.

After the temperature was raised, a small amount of toluene was added and water generated was removed by azeotropic distillation.

Next, after performing a reaction at a temperature of 195 ° C. for 30 minutes,
122.85 g of 4'-difluorobenzophenone (0.563 mol)
Was dissolved in N-methylpyrrolidone 1.5, and the mixture was further reacted for 1 hour.

After the reaction is completed, the product is blended (Warning)
And washed with acetone, methanol, water and acetone in this order, and then dried to obtain 259.36 g (98% yield) of a white powdery copolymer having a bulk density of 0.12 g / cm ³ . .

When the properties of this polybiphenylene ether ketone copolymer were measured, the melt viscosity at 400 ° C (Gero shear viscosity) was 13,000 poise, the glass transition temperature was 182 ° C, the crystal melting point was 379 ° C, the crystallization temperature was 241 ° C, The decomposition onset temperature was 562 ° C (5% weight loss in air).

(Production Examples 2 to 6) The same operation as in Production Example 1 was carried out, except that the charging ratio of each raw material and the reaction conditions were partially changed, to obtain polybiphenylene ether ketones having various properties shown in Table 1. A polymer was produced.

Table 1 shows the content of the repeating unit, the melt viscosity, the glass transition temperature, the crystal melting point, and the crystallization temperature of each polymer.

Example 1 The copolymer produced in Production Example 1 was press-molded at 400 ° C., and then poured into water and quenched to obtain a transparent amorphous film.

 The thickness of the obtained film was 200 μm.

When the physical properties of this film were measured, the tensile strength was 9 k.
g / mm ² , tensile modulus 210 kg / mm ² , elongation at break 210% (A,
The oxygen index was 31.5% (according to ASTM D2863).

Example 2 The polymer produced in Production Example 1 was press-formed at 400 ° C. and poured into ice water to obtain a transparent amorphous film. The thickness of the film was 200 μm. This film was heat-treated at 250 ° C. for 1 minute to produce a crystallized film.

When the physical properties of this film were measured, the tensile strength was 11
kg / mm ² , the tensile modulus was 250 kg / mm ² , and the breaking elongation was 130%. Next, when the oxygen index of this film was measured, it was 31.5% and was excellent in flame retardancy.

In addition, this crystallized film swells when immersed in concentrated sulfuric acid for a long time, but hydrochloric acid, nitric acid, dichloroacetic acid,
Attacks against strong acids such as trifluoroacetic acid, strong alkalis such as caustic soda and potassium hydroxide, organic solvents such as acetone, dimethyl ether, methyl ethyl ketone, benzene, toluene, ethyl acetate, dimethylformamide, N-methylpyrrolidone and methylene chloride, and hot water. Without being
It was quite stable.

(Comparative Example 1) A film was prepared from polyetherketone [PEEK450G manufactured by ICI] under the same conditions as in Example 1, and the physical properties were measured in the same manner.

The tensile strength of the film was 9 kg / cm ² , the tensile modulus was 210 kg / mm ² , the elongation at break was 170%, and the oxygen index was 23.5%.

In addition, this film was dissolved in p-chlorophenol, dichloroacetic acid and the like in addition to concentrated sulfuric acid, and a little craze occurred in acetone.

Example 3 The polymer produced in Production Example 1 was press-molded at 400 ° C. and poured into ice water to obtain a transparent amorphous film.

 The thickness of the film was 200 μm.

This film was stretched by a uniaxial stretching machine (manufactured by Shibata Machine Co., Ltd.) and a biaxial stretching machine (manufactured by Toyo Seiki Seisakusho) under the molding conditions shown in Table 2 (stretching speed: 1000% /
Minutes).

Table 2 shows the properties of the obtained stretched film. In addition,
ASTM D882 was used for the measurement method.

(Examples 4 to 6) Stretched films were produced using the amorphous films of Production Examples 4, 5, and 6 under the stretching conditions and heat setting conditions shown in Table 2.

 Table 2 shows the properties of the obtained film.

(Examples 7 and 8) Using the amorphous film of Production Example 4, stretched films were produced under different stretching ratios and heat setting conditions from those of Example 3.

 Table 2 shows the properties of the stretched film.

(Comparative Example 2) A stretched film was prepared from polyether ketone [PEEK 450G manufactured by ICI] under the stretching conditions and heat setting conditions shown in Table 2.

 Table 2 shows the properties of the obtained stretched film.

[Effects of the Invention] Since the film of the present invention uses a copolymer having a high glass transition temperature and no gel component as a raw material resin, it has good moldability, and has excellent mechanical strength and heat resistance. Has flame resistance, flame retardancy and solvent resistance.

Claims (4)

(57) [Claims] (1) The following formula (I): And a repeating unit represented by the following formula (II): Wherein the composition ratio of the repeating unit represented by the formula (I) is 0.15 to 0.40 mol and the melt viscosity at 400 ° C. is 3000 to 100,000 poise. A polybiphenylene ether ketone copolymer film formed by molding a copolymer at a temperature 10 to 100 ° C. higher than its crystalline melting point. 2. The polybiphenylene ether ketone copolymer film according to claim 1, wherein the polybiphenylene ether ketone copolymer film is heat-treated at a temperature between the crystallization temperature and the crystal melting point. 3. The stretching ratio of the polybiphenylene ether ketone copolymer film according to claim 1 in a uniaxial or biaxial direction between its glass transition temperature and crystal melting point.
A polybiphenylene ether ketone copolymer film stretched 1.5 to 10 times. 4. The stretching ratio of the polybiphenylene ether ketone copolymer film according to claim 1 in a uniaxial or biaxial direction between its glass transition temperature and crystal melting point.
A polybiphenylene ether ketone copolymer film stretched 1.5 to 10 times and then heat-treated between its crystallization temperature and its crystallization melting point.