JP2752210B2 - Polyether copolymer film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyether copolymer film,
More specifically, polyether-based copolymers which are excellent in heat resistance, mechanical strength, solvent resistance, chemical resistance, flame retardancy, etc., and which can be suitably used as materials for electronic / electric devices, mechanical parts, etc. It relates to a polymer film.

[Conventional technology]

In recent years, various types of resin films having excellent heat resistance and mechanical strength have been developed and used for a wide variety of applications as materials for components such as electronic / electric devices and machines. When the field of application expands in this way, a resin film having more excellent properties is demanded.

Conventionally, films formed from various high-performance resins have been known. Among these, the most excellent heat resistance, even in the film made of polyetheretherketone resin, which is said to have mechanical strength, since the resin manufacturing conditions are severe, it is easy to include gel in the resin, enough No film having satisfactory film performance has been obtained.

[Problems to be solved by the invention]

 The present invention has been made in view of the above circumstances.

An object of the present invention is to solve the above-mentioned problems, have a sufficiently high glass transition temperature, excellent heat resistance, excellent mechanical properties such as mechanical strength, and solvent resistance, chemical resistance,
An object of the present invention is to provide a polyether copolymer film having advantages such as excellent flame retardancy.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, a specific polyether-based material having a sufficiently high glass transition temperature, excellent heat resistance, and excellent mechanical properties such as mechanical strength. Using a copolymer as a raw material resin, a film obtained by molding the resin under specific conditions, in particular, after forming into a film, stretching to a specific stretching ratio or a film obtained by heat treatment is an excellent film satisfying the above object. Thus, the present invention has been completed based on these findings.

That is, the present invention provides the following general formula [I] And the following formula [II] Represented by the formula [I] with respect to the sum of the content of the repeating unit represented by the formula [I] and the content of the repeating unit represented by the formula [II]. Of the repeating unit content (molar ratio ｛[I] /
([I] + [II])｝) is 0.1 to 0.5 and 40
A polyether copolymer film characterized by being formed by molding a polyether copolymer having a melt viscosity at 0 ° C of 1,000 poise or more at a temperature 10 to 100 ° C higher than its melting point. It is.

 Hereinafter, the present invention will be described in detail.

-Polyether-based copolymer- One of the important points in the polyether-based copolymer used as a raw material resin of the film of the present invention is that the repeating unit represented by the general formula (I) and the formula (II) And the proportion of these repeating units is in the specific range as described above.

Here, if the ratio of the repeating unit represented by the general formula [I] [that is, the molar ratio ｛[I] / ([I] +
When [II])｝) is less than 0.1, the melting point of the polymer becomes too high, the melt viscosity becomes high, and the moldability decreases. Further, when the proportion of the repeating unit represented by the general formula [I] exceeds 0.5, the degree of crystallinity is not sufficient, heat resistance is reduced, and mechanical strength and solvent resistance, chemical resistance This will lead to a decline.

The polyether-based copolymer may contain another repeating unit in a ratio that does not impair the object of the present invention.

As the polyether copolymer, those having a melt viscosity at 400 ° C. of 1,000 poise or more are used, but those having a melt viscosity of less than 1,000 poise have insufficient heat resistance. Preferably, those having a melt viscosity of 3,000 to 100,000 poise are used.

In the present invention, the above-mentioned various polyether-based copolymers may be used singly or may be used as desired.
More than one species may be used in combination as a mixture or a composition.

—Method for Producing Polyether Copolymer— The method for producing the polyether copolymer is not particularly limited, and can be produced according to various methods.

As a method for producing a polyether-based copolymer suitable for the present invention, for example, the following methods can be exemplified.

That is, an amount of dihalogenobenzonitrile corresponding to a molar ratio of 0.1 to 0.5 with respect to the total amount of dihalogenobenzonitrile and 1,4-bis (4-halobenzoyl) benzene is substantially equimolar to the total amount. After reacting an amount of 4,4'-biphenol (i.e., 4,4'-dihydroxybiphenyl) in the presence of an alkali metal compound and a neutral polar solvent, the resulting reaction product and said total amount It is produced by performing a copolymerization reaction with 1,4-bis (4-halobenzoyl) benzene in an amount corresponding to a molar ratio of 0.9 to 0.5.

Examples of the dihalogenobenzonitrile to be used include 2,3-dihalogenobenzonitrile, 2,4-dihalogenobenzonitrile, 2,5-dihalogenobenzonitrile, 2,6
-Dihalogenobenzonitrile, 3,4-dihalogenobenzonitrile, 3,5-dihalogenobenzonitrile or a mixture of two or more thereof, but usually, for example, the following formula: (Where X is a halogen atom, and 2
The two Xs may be the same or different. 2,6-dihalogenobenzonitrile represented by the following formula: (In the formula, X has the same meaning as described above.) 2,4-dihalogenobenzonitrile and the like are preferably used.

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 addition, these may be used individually by 1 type, and may use 2 or more types together as needed.

The dihalogenobenzonitrile is represented by the following formula: Is reacted with 4,4'-biphenol represented by the formula (1) 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,
Cesium carbonate and the like.

Among them, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal bicarbonate include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate,
Rubidium hydrogen carbonate, cesium hydrogen carbonate and the like can be mentioned.

Of these, preferred are sodium bicarbonate,
Potassium bicarbonate.

Among the above various alkali metal compounds, sodium carbonate and potassium carbonate are particularly preferably used.

In addition, these may be used individually by 1 type, and may use 2 or more types together as needed.

Examples of the neutral polar solvent include, for example, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dipropylacetamide, N, N-dimethyl Benzoic acid amide, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, Nn-propyl-2-pyrrolidone, N -N-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, sulfolane, 1-methyl-
1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N, N'-
Dimethylimidazolidinone (DMI), diphenylsulfone and the like.

Preferred are NMP, DMI, sulfolane, diphenylsulfone and dimethylsulfoxide, particularly preferred is NMP.

These solvents may be used alone or in combination of two or more as needed. Also,
If necessary, for example, it can be used as a mixed solvent with another solvent such as an aromatic hydrocarbon solvent. For example, by using an aromatic hydrocarbon, such as toluene, which easily azeotropes with water in combination with the neutral polar solvent, water generated by condensation or the like during the polymerization reaction can be effectively removed from the reaction system.

The dihalogenobenzonitrile is used in a molar ratio relative to the total amount of dihalogenobenzonitrile and 1,4-bis (4-halobenzoyl) benzene, which is usually 0.1 to 0.5. And
The proportion of the alkali metal compound used is 4,4 ′.
-The amount is usually 1.01 to 2.50 equivalents, preferably 1.05 to 1.25 equivalents, per one hydroxyl group of biphenol.

The amount of the neutral polar solvent used is not particularly limited, but usually, the dihalogenobenzonitrile and the 1,4
-Bis (4-halobenzoyl) benzene and 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 biphenol and the alkali metal compound.

A reaction product obtained by performing a reaction between the dihalogenobenzonitrile and the 4,4′-biphenol in the presence of the alkali metal compound and the neutral polar solvent, and
1,4-bis (4-halobenzoyl) benzene is reacted. The 1,4-bis (4-halobenzoyl) benzene to be used is represented by the following formula: (Where Y is a halogen atom, and 2
The two Ys may be the same or different. ), Among which 1,4-bis (4-chlorobenzoyl) benzene and 1,4-bis (4-
Fluorobenzoyl) benzene and 1- (4-chlorobenzoyl) -4- (4-fluorobenzoyl) benzene are preferred, especially 1,4-bis (4-chlorobenzoyl)
Benzene and 1,4-bis (4-fluorobenzoyl) benzene are preferred.

In addition, these may be used individually by 1 type, and may use 2 or more types together as needed.

The 1,4-bis (4-halobenzoyl) benzene is
The molar ratio of the total amount of 1,4-bis (4-halobenzoyl) benzene and dihalogenobenzonitrile to the amount of the 4,4′-biphenol used is usually 0.98 to 1.02, preferably 1.00 to 1.01. Use in such proportions.

To obtain a polyether-based copolymer, for example, in the neutral polar solvent, the dihalogenobenzonitrile, the 4,4'-biphenol, and the alkali metal compound, simultaneously added, After the reaction of dihalogenobenzonitrile with the 4,4'-biphenol, the 1,4-bis (4-halobenzoyl) benzene is further added, usually at 150 to 380C, preferably 180 to 350C. A series of reactions is performed at a temperature in the range of ° C. Reaction temperature is 150 ℃
If it is less than 380, the reaction rate is too slow to be practical and 380
If the temperature exceeds ℃, a side reaction may be caused.

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

After the completion of the reaction, the polyether copolymer is separated and purified from a neutral polar solvent solution containing the obtained polyether copolymer according to a known method to obtain a polyether copolymer. be able to.

In this way, a polyether-based copolymer can be efficiently produced by a simple process.

In addition, a powder of the polyether copolymer having a large bulk density can be obtained from the solution of the neutral polar solvent containing the polyether copolymer.

The polyether copolymer obtained as described above has excellent properties such as heat resistance and mechanical strength, and is used as a material for the polyether copolymer film of the present invention.

-Polyether-based copolymer film- The polyether-based copolymer film of the present invention (hereinafter, sometimes referred to as a copolymer film or a film) is the above-mentioned polyether-based copolymer (hereinafter, referred to as "polyether-based copolymer film"). Is sometimes referred to as a copolymer or a resin.) At its melting point (hereinafter, this melting point may be represented by _Tm in ° C.).
10 to 100 ° C. higher, that is, (T _m +10) ° C. to (T
_m + 100) ° C, preferably ( _Tm + 30) ° C to ( _Tm + 70) ° C
It is manufactured by molding at a temperature in the range of

Here, if the molding temperature is lower than (T _m +10) ° C., the moldability deteriorates. On the other hand, if it exceeds (T _m +100) ° C., the fluidity of the polymer during film formation becomes too high, which makes it difficult to process the film, or may cause inconvenience such as decomposition of the raw material.

The polyether-based copolymer is usually used alone for molding. However, if necessary, two or more kinds may be used in combination as a mixture or a composition.

The polyether-based copolymer can be subjected to molding, if desired, by appropriately containing other resins and additional components as long as the object of the present invention is not hindered.

Press molding and extrusion molding methods are used for film formation.
It can be performed by a usual molding method.

The polyether copolymer film of the present invention may be subjected to a post-treatment such as a stretching treatment and a heat treatment after being formed into a film. Generally, it is preferable to apply at least a stretching treatment.

This is because by performing an appropriate stretching treatment, the mechanical properties such as the mechanical strength of the obtained film can be further improved.

Usually, this stretching treatment is desirably performed in a uniaxial or biaxial direction at a temperature equal to or lower than the melting point of the resin (polyether copolymer) used.

If the stretching temperature is higher than the melting point, stable stretching may not be performed.

This stretching is desirably performed so that the stretching ratio is usually 1.5 to 10, preferably 2 to 5.

When the stretching ratio is less than 1.5, a sufficient stretching effect cannot be obtained, and in particular, improvement in mechanical properties such as tensile strength becomes insufficient.

Further, after this stretching, it is desirable to appropriately subject the stretched film to a heat treatment.

This heat treatment is usually performed at a temperature within a temperature range higher than the crystallization temperature of the resin (polyether-based copolymer) and lower than the melting point, with or without tension, as necessary.

By subjecting the stretched film to a heat treatment as described above, the strength of the film can be further improved.
When the unstretched film is heat-treated, it is preferable that the heat treatment be performed at a temperature slightly higher than the crystallization temperature of the resin (polyether copolymer) used.

The polyether copolymer film obtained in this way has the advantages of excellent heat resistance, mechanical properties such as tensile strength, solvent resistance, chemical resistance, and flame retardancy. It can be suitably used in the fields of electronic / electric equipment, mechanical parts, and the like, for example.

〔Example〕

Next, the present invention will be described more specifically with reference to examples and comparative examples of the present invention, but the present invention is not limited to these examples.

Production Example 1 38.70 g (0.225 mol) of 2,6-dichlorobenzonitrile and 139.66 of 4,4'-biphenol were placed in a 5 L reactor equipped with a Dein-Stark trap filled with toluene, a stirrer, and an argon gas inlet tube. g (0.75 mol), 124.39 g (0.9 mol) of potassium carbonate and 1.5 l of N-methyl-2-pyrrolidone were added, and the temperature was raised from room temperature to 195 ° C. over 1 hour while blowing in argon gas.

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

Then, after reacting at a temperature of 195 ° C. for 30 minutes, 1,4-
169.2 g of bis (4-fluorobenzoyl) benzene (0.52
(5 mol) in 1.5 l of N-methylpyrrolidone was added, and the mixture was further reacted for 1 hour.

After the completion of the reaction, the product was washed several times with pure water to completely remove the salt, and dried to obtain 304.0 g of a white powdery copolymer (yield: 98%).
%).

The structure of the obtained copolymer is represented by the following repeating unit [I] And the next repeating unit [II] And a repeating unit [I] and a repeating unit [II]
Was a polyether copolymer having a molar ratio of 0.30: 0.70.

Also, when the properties of this copolymer were measured,
Melt viscosity η _m (zero shear viscosity) at a temperature of 400 ° C is 13,0
The glass transition temperature T _g is 190 ° C., the crystal melting point T _m is 384 ° C., and the thermal decomposition onset temperature T _d is 565 ° C. (5% in air).
Weight loss) and showed high heat resistance.

The crystallization temperature _Tc was 230 ° C.

Production Examples 2 to 5 Polyether copolymers were produced in the same manner as in Production Example 1, except that the proportions of the raw materials were changed. Table 1 shows the content of the repeating unit represented by the formula [I], η _m , T _g , T _m , T _d and T _c (crystallization temperature) of each copolymer.

Example 1 The polyether copolymer produced in Production Example 1 was used
Press molding was performed at 400 ° C., which was 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.
5 kg / mm ² , tensile modulus 220 kg / mm ² , elongation at break 150% (all based on ASTM D882), and oxygen index 35.5 (based on ASTM D2863).

Example 2 The polyether copolymer produced in Production Example 1 was used
Press molding was performed at 400 ° C., which was then put into ice water and quenched to obtain a transparent amorphous film. The thickness of the film was 200 μm. This film was heat-treated at 230 ° C. for 1 minute to produce a crystallized film.

When the physical properties of this film were measured, the tensile strength was 12
kg / mm ² , tensile modulus 250 kg / mm ² , elongation at break 90%
Met. Next, when the oxygen index of this film was measured, it was 35.5 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 Polyetheretherketone [ICI: PEEK 450G]
Was prepared under the same conditions as in Example 1, and the physical properties were measured in the same manner.

This film had a tensile strength of 9 kg / mm ² , a tensile modulus of 210 kg / mm ² , an elongation at break of 170%, and an oxygen index of 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 this 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% / min).

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

Examples 4 and 5 Stretched films were produced using the amorphous films of Production Examples 3 and 4 under the stretching conditions and heat setting conditions shown in Table 2.

 Table 2 shows the properties of the obtained film.

Examples 6 and 7 Using the amorphous film of Production Example 1, stretched films were produced under different stretching ratios and heat-setting conditions from Example 3 shown in Table 2.

 Table 2 shows the properties of the stretched film.

Comparative Example 2 A stretched film was prepared from polyetheretherketone (PEEK450G, 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] According to the present invention, a specific polyether-based copolymer is molded under specific conditions to form a film, and particularly after the molding, is stretched at a specific stretching ratio to form a film. Therefore, it has excellent heat resistance and, for example, remarkably excellent mechanical properties such as mechanical strength even when compared with a film made of a conventional engineering resin such as a conventional polyetheretherketone, and further has a solvent resistance and a chemical resistance. And a film having advantages such as excellent flame retardancy and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71:00

Claims (3)

(57) [Claims] 1. The following general formula [I] And the following formula [II] Represented by the formula [I] with respect to the total of the content of the repeating unit represented by the formula [I] and the content of the repeating unit represented by the formula [II]. Of the repeating unit content (molar ratio ｛[I] /
([I] + [II])｝) is 0.1 to 0.5 and 40
A polyether copolymer film obtained by molding a polyether copolymer having a melt viscosity at 0 ° C of 1,000 poise or more at a temperature 10 to 100 ° C higher than its melting point. 2. The polyether copolymer film according to claim 1, which is stretched 1.5 to 10 times in a uniaxial or biaxial direction at a temperature not higher than its melting point. Polymer film. 3. A polyether copolymer film obtained by subjecting the polyether copolymer film according to claim 1 or 2 to a heat treatment at a temperature between a crystallization temperature and a melting point. United film.