JP2909644B2 - Polyetherketone copolymer film - Google Patents

Description

The present invention relates to a novel polyetherketone-based copolymer film, and more specifically, has high heat resistance and excellent dimensional stability at high temperatures, for example, The present invention relates to a polyetherketone-based copolymer film that can be widely used for various applications in the electric and electronic fields.

[Problems to be solved by the prior art and the invention] In recent years, in order to develop materials having excellent heat resistance, mechanical properties, and dimensional accuracy, polyamide, polyimide, polyester,
Various films such as polysulfone have been developed or are already commercially available, and they have been used for a wide range of applications as materials for components such as electronic / electric devices and machines.

Among these, aromatic ether ketone copolymers are extremely excellent in heat resistance, flame retardancy, chemical resistance, etc. Its application as a substrate is expected.

However, among these resin films, a film that sufficiently satisfies properties such as heat resistance, mechanical properties, and dimensional accuracy has not been found yet.

Even in polyetherketone resin, which is the thermoplastic resin film that is said to have the best performance among the resin films currently used, the glass transition temperature is low and the heat resistance is insufficient for practical use. is there.

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

An object of the present invention is to provide a thermoplastic resin film which has high heat resistance, has little heat shrinkage at high temperature, and has excellent dimensional accuracy.

[Means for Solving the Problems] In order to achieve the above object, the invention according to claim 1 has the following formula (I): And a repeating unit represented by the following formula (II): And a composition ratio of the repeating unit represented by the formula (I) [molar ratio, (I) / ｛(I)
+ (II)｝] is 0.15 to 0.40 and the temperature is 400 ° C.
A melt viscosity (zero shear viscosity) in the film of a polyetherketone copolymer having 3,000-100,000 poise, heat-treated at a temperature between the crystallization temperature and the crystal melting point of the polyetherketone copolymer, The invention according to claim 2, wherein the heat-treated film is a polyetherketone-based copolymer film obtained by re-heating at a temperature between the glass transition temperature and the crystal melting point of the polyetherketone-based copolymer. Stretches a film made of the polyetherketone copolymer having the repeating unit, composition and melt viscosity according to claim 1 in a uniaxial or biaxial direction at a draw ratio of 1.5 to 10 times, A heat treatment is performed at a temperature between the crystallization temperature and the crystal melting point of the ether ketone copolymer, and the heat-treated stretched film is treated with the polyether ketone. Polyether ketone copolymer film which had been re-heat-treated at a temperature between the glass transition temperature of the emission-based copolymer and the crystalline melting point.

 The details will be described below.

-Polyetherketone-based copolymer- One of important points in the polyetherketone-based copolymer film of the present invention is that the polyetherketone-based 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 polyetherketone-based copolymer will be low and the heat resistance will be lowered, or the melting point will be high and the moldability will be lowered. On the other hand, when it exceeds 0.40, the crystallinity of the polyetherketone copolymer is lost, and the heat resistance and the solvent resistance are reduced.

Further, in the polyetherketone-based copolymer of the present invention, it is important that the melt viscosity at a temperature of 400 ° C. (zero shear viscosity) is 3,000 to 100,000 poise.

This is because a low molecular weight polyetherketone-based 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 polyetherketone copolymer used in the present invention has a melt viscosity at 400 ° C. of 3,000 to 100,000 poise, a crystal melting point of about 330 to 400 ° C., and has high crystallinity and a sufficiently high melting point. It has a molecular weight, exhibits sufficient heat resistance, and is excellent in solvent resistance and mechanical strength, and can be suitably used as a new material in, for example, the electric / electronic equipment field and the mechanical field.

Such a polyetherketone-based copolymer can be produced as follows.

-Method for producing polyetherketone-based copolymer-Polyetherketone-based copolymer is prepared by dihalogenobenzonitrile, 4,4'-biphenol, and alkali metal compound at a specific use ratio in the presence of a neutral polar solvent. After the reaction, a copolymerization reaction of the reaction product with a specific amount of 4,4'-dihalogenobenzophenone can be carried out.

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 is reacted with 4,4'-biphenol 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, among the above various alkali metal compounds, sodium carbonate and potassium carbonate can be suitably used for obtaining.

Examples of the neutral polar solvent include N, N-dimethylformamide, N, N-diethylformamide, N, N-zemethylacetamide, 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-peridone, N-methyl-6-methyl-2-piperidone, N-methyl-3-
Ethylpiperidone, dimethylsulfoxide, diethylsulfoxide, 1-methyl-1-oxosulfolane, 1-
Ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N, N′-dimethylimidazolidinone,
Diphenyl sulfone and the like.

In the present invention, the reaction product obtained by performing the reaction of the dihalogen benzonitrile with the 4,4'-biphenol in the presence of the alkali metal compound and the neutral polar solvent and the 4,4'- React with dihalogenobenzophenone. Alternatively, these raw materials can be added and reacted simultaneously.

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.

The molar ratio of the total amount of 2,6-dihalogenobenzonitrile and 4,4'-dihalogenobenzophenone to the amount of the 4,4'-biphenol used in the production of the polyetherketon copolymer of the present invention. However, it is usually from 0.98 to 1.02, preferably from 1.00 to 1.01. The molar ratio to potassium carbonate 4,4'-biphenol 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 polyetherketone copolymer, for example, in the neutral polar solvent, the dihalogenobennitrile, the 4,4'-biphenol, and the alkali metal compound are added simultaneously, After allowing the reaction between the dihalogenobenzonitrile and the 4,4'-biphenol, the 4,4'-dihalogenobenzophenone is further added, usually at 150 to 380C, preferably at 180 to 330C. A series of reactions is performed at a range of temperatures. Reaction temperature 15
Below 0 ° C, the reaction rate is too slow to be practical and 3
If it exceeds 80 ° C., a side reaction may occur.

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 polyetherketone copolymer is separated and purified from the neutral polar solvent solution containing the obtained polyetherketone copolymer according to a known method to obtain a polyetherketone copolymer. Coalescence can be obtained.

-Method for producing polyetherketone-based copolymer film-The polyetherketone-based copolymer film according to claim 1, wherein the polyetherketone-based copolymer is formed into a film, the film is heat-treated, and then heat-treated again. It is obtained by doing.

By forming the polyetherketone-based copolymer obtained as described above into a film, an unstretched film of the polyetherketone-based copolymer can be obtained.

The film is formed at a temperature 10 to 100 ° C. higher than the crystal melting point by using an ordinary method such as an extrusion molding method or a press molding method.
Preferably, it is performed at a temperature 30 to 70 ° C. higher than the crystal melting point, and quenched to obtain a highly transparent amorphous film.

For example, by feeding the polyetherketone-based copolymer to an extruder, setting the temperature of the polyetherketone-based copolymer to 350 to 400 ° C., extruding from a slit-shaped die in a molten state, and cooling and solidifying, An unstretched film of a polyetherketone-based copolymer can be produced.

Alternatively, an unstretched film of a polyetherketone-based copolymer can be obtained by forming a press film at a press temperature of 350 to 450 ° C. using a hot press machine and then quenching it.

Next, the amorphous film thus obtained is
By performing a heat treatment at a temperature between the crystallization temperature and the crystal melting point, a crystalline film can be obtained.

The heat treatment of the unstretched film is performed under tension, and the polyether ketone is heated to a crystallization temperature, that is, a temperature higher than a temperature at which the polymer in an amorphous state in the film formation crystallizes, but lower than a crystal melting point. This is achieved by heating the system copolymer.

The term "under tension" in the heat treatment of the present invention means that, when a polyetherketone-based copolymer film is fixed at a fixed length and heat-treated, a tension generated by shrinkage of the film accompanying the heat treatment is applied. Specifically, it refers to fixing the unstretched polyetherketone copolymer film with a metal frame or the like and applying the tension.

The heat treatment temperature is, for example, 190 to 370 ° C., and the heat treatment time is 1 to 600 seconds.

Examples of the heating method of the heat treatment include a method of passing through a heating furnace and a method of sandwiching between heating rolls.

Next, the crystallized film obtained by the heat treatment is heat-treated again.

This reheat treatment is performed under tension or without tension as necessary, and is performed at a temperature between the glass transition temperature and the crystal melting point of the polyetherketone-based copolymer.

For example, at a temperature of 150 ° C. or more and the heat treatment temperature or less, further heat treatment is performed in a relaxed state, or further heat treatment is performed under limited shrinkage, constant length or slight elongation of 20% or less.

 The reheat treatment time is 1 to 600 seconds.

By this reheat treatment, the heat shrinkage of the film is reduced, and a film having excellent dimensional stability can be obtained.

In the present invention, in the invention of claim 1, the polyetherketone copolymer film to be subjected to the heat treatment is an unstretched film, and in the invention of claim 2, the polyetherketone to be subjected to the heat treatment The film of the system copolymer is a stretched film.

The stretching of the film of the polyetherketone copolymer is as follows:
The uniaxial or biaxial process is preferably performed at a temperature between the glass transition temperature and the crystal melting point. In the present invention, the polyetherketone-based copolymer film, a draw ratio of 1.5
Stretching is preferably performed at a draw ratio of up to 10 times, and particularly at a draw ratio of 2 to 5 times.
It is preferable to stretch the film by a factor of 2.

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

In the invention described in claim 2, the stretched film of the polyetherketone-based copolymer thus obtained is subjected to heat treatment and reheat treatment.

The operation or conditions of the heat treatment and the re-heat treatment are as described in the first aspect of the present invention.

The polyetherketone-based copolymer film according to claim 1 or claim 2 is: (1) In the field of electronics, a base film requiring a flexible printed board, a backing material for a flexible printed board, an electrode plate for a membrane, a backing material for a membrane, It can be used for base film for transparent electrode, 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 It can be used for insulating tapes (motors, generators, transformers), capacitors, electric wire coverings, shielding plates for microwave ovens and other thermal equipment, speaker diaphragms, lighting equipment covers, instrument display panels, etc. (3) In general industrial applications, such as overhead projector base paper, aircraft interior materials,
It can be used for nuclear power equipment, solar collector covers, ultrafiltration membranes, etc.

(4) In other cases, it can be used for composites such as heat-resistant labels, heat-resistant nameplates, aviation, vehicles, and defense-related products.

[Examples] Next, the present invention will be described more specifically based on examples.

Example 1 A reactor having an internal volume of 200 equipped with a Dein-Stark trap filled with toluene, a stirrer, and an argon gas blowing tube was charged with 1,548 g (9 mol) of 2,6-dichlorobenzonitrile, 4,4′-. 5,580 g (30 mol) of biphenol, 4,561 g (33 mol) of potassium carbonate and 50 of N-methylpyrrolidone
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.

Next, after performing a reaction at a temperature of 195 ° C. for 30 minutes,
4,582 g (21 mol) of 4'-difluorobenzophenone
A solution dissolved in -methylpyrrolidone 70 was added, and the reaction was further performed for 1 hour.

After the reaction is completed, the product is blended (Warning)
After washing with water and methanol in order,
After drying, 10.0 kg of white powder (98% yield) was obtained.

When the properties of this powdery product were measured, the melt viscosity (zero shear viscosity) at a temperature of 400 ° C. was 13,000 poise, the glass transition temperature was 185 ° C., the crystal melting point was 379 ° C., the crystallization temperature was 250 ° C., and the thermal decomposition onset temperature was The temperature was 562 ° C (5% weight loss in air).

According to IR spectrum analysis, this powdery product was a polyetherketone-based copolymer having the following repeating units.

Next, this polyetherketone-based copolymer was extruded at 390 ° C. using a twin-screw extruder (PCM-30, manufactured by Ikemi Tekko Co., Ltd.), and then pelletized.

The pellets were extruded into a film having a width of 25 cm using a T-die.

Fix the obtained film with a metal frame, and under tension
Heat treatment was performed at 300 ° C. for 180 seconds. The obtained heat-treated film had a thickness of 100 μm and had the following mechanical strength.

Tensile strength (ASTM D882) 9.5 kg / mm ² Tensile modulus (ASTM D882) 270 kg / mm ² Elongation at break (ASTM D882) 50% For 180 seconds.

About the re-heat treated film obtained in this way,
When held at 200 ° C for 30 minutes in a relaxed state, and at 250 ° C
The heat shrinkage when the sample was kept for 30 minutes was measured.

 The results were as follows.

 Maintained at 200 ° C for 30 minutes 0.10% Maintained at 250 ° C for 30 minutes 0.08%

Example 2 The heat-treated film obtained in Example 1 was heat-treated again at 200 ° C. for 300 seconds in a relaxed state.

About the re-heat treated film obtained in this way,
When held at 200 ° C for 30 minutes in a relaxed state and at 250 ° C
The heat shrinkage after holding for 30 minutes was measured.

 The results were as follows.

Maintained at 200 ° C. for 30 minutes 0.15% Maintained at 250 ° C. for 30 minutes 0.20% (Comparative Example 1) In Example 2, the heat shrinkage measured on the film before the reheat treatment was as follows.

 Hold at 200 ° C for 30 minutes 0.75% Hold at 250 ° C for 30 minutes 0.95% The results are shown in Table 1.

(Example 3) The amount of raw materials charged during the production of the copolymer in Example 1 was 2
Example 1 was changed except that 1290 g (7.5 mol) of -6-dichlorobenzonitrile, 4976 g (36 mol) of calcium carbonate, and 4910 g (22.5 mol) of 4,4'-difluorobenzophenone were used.
In the same manner as in the above, a polyetherketone-based copolymer having the following structure was produced.

This polyetherketone copolymer has a melt viscosity at 400 ° C. (zero shear viscosity) of 15,000 poise,
Glass transition temperature 182 ℃, melting point 380 ℃, crystallization temperature 24
The temperature at which the thermal decomposition started was 1 ° C. and 562 ° C.

Next, this copolymer was extruded and formed into a film in the same manner as in Example 1, and heat-treated to obtain a heat-treated film having a thickness of 100 µm. Its mechanical strength was as follows.

Tensile strength 10 kg / mm ² Tensile elastic modulus 290 kg / mm ² Elongation at break 40%
A reheat treatment was performed at 30 ° C. for 30 seconds. The results of measuring the heat shrinkage of the obtained reheat-treated film are described below.

 200 ° C, 30 minutes hold 0.05% 250 ° C, 30 minutes hold 0.08% The results are shown in Table 1.

Example 4 The heat-treated film obtained in Example 3 was re-heated at 280 ° C. for 60 seconds in a relaxed state.

 The heat shrinkage of the obtained reheat-treated film was measured.

 The results are shown below.

 200 ° C, 30 minutes 0.11% 250 ° C, 30 minutes 0.16% The results are shown in Table 1.

(Comparative Example 2) The heat-shrinkage rate measured for the heat-treated film obtained in Example 3, that is, the film before the re-heat treatment was as follows.

 Hold at 200 ° C for 30 minutes 0.65% Hold at 250 ° C for 30 minutes 0.88% The results are shown in Table 1.

(Example 5) The polyetherketone-based copolymer obtained in Example 1 was subjected to 390 using a twin-screw extruder (PCM-30, manufactured by Ikemi Tekko Co., Ltd.).
After extrusion at ℃, it was pelletized.

This pellet was used to form a film having a width of 25 cm using a T-die. Then, the film was stretched at a stretching speed of 1000% / minute by a biaxial stretching machine (manufactured by Toyo Seiki Seisakusho) at a stretching temperature of 188 ° C.
The film was biaxially stretched under the conditions of a stretching ratio of 3 × 3.

Next, the obtained stretched film was fixed to a metal frame, and heat-treated at 260 ° C for 30 seconds under a constant length.

Next, the heat-treated stretched film obtained above was fixed to a metal frame, and re-heat-treated at 200 ° C. for 30 seconds under a constant length.

The heat shrinkage of the stretched film obtained after the reheat treatment was measured. The measurement of the heat shrinkage rate is in the relaxed state of the stretched film at 200 ° C. for 30 minutes and at 250 ° C.
For 30 minutes.

 The results were as follows.

 Maintain at 200 ° C for 30 minutes 0.15% Maintain at 250 ° C for 30 minutes 0.12% The results are shown in Table 2.

(Example 6) The reheat condition was set to 250 ° C. while the stretched film was in a relaxed state.
Was carried out in the same manner as in Example 6, except that the time was changed to 180 seconds.
The heat shrinkage of the obtained reheat-stretched stretched film was as follows.

 Hold at 200 ° C for 30 minutes 0.18% Hold at 250 ° C for 30 minutes 0.25% The results are shown in Table 2.

(Example 7) The conditions of the reheat treatment were as follows.
The procedure was the same as in Example 6, except that the time was 0 seconds. The heat shrinkage of the obtained reheat-stretched stretched film was as follows.

200 ° C., 30 minutes hold 0.01% 250 ° C., 30 minutes hold 0.02% (Comparative Example 3) In Example 5, the stretched film heat-treated,
The heat shrinkage of the heat-treated stretched film before the re-heat treatment was as follows.

 Hold at 200 ° C for 30 minutes 0.90% Hold at 250 ° C for 30 minutes 1.15% The results are shown in Table 2.

(Example 8) The polyetherketone copolymer obtained in Example 3 was formed into a biaxially stretched film having a stretch ratio of 3x3 in the same manner as in Example 5, and heat-treated under the same conditions. .

Next, the heat-treated stretched film was fixed to a metal frame, and re-heat treated at a constant length of 300 ° C. for 30 seconds. The heat shrinkage measured for the stretched film obtained after the reheat treatment was as follows.

200 ° C, Hold for 30 minutes 0.00% 250 ° C, Hold for 30 minutes 0.01% (Example 9)
The procedure was the same as Example 8 except that the temperature was 60 ° C. for 60 seconds. The heat shrinkage of the obtained reheat-stretched stretched film was as follows.

 200 ° C, 30 minutes hold 0.01% 250 ° C, 30 minutes hold 0.02% The results are shown in Table 2.

(Comparative Example 4) The heat-shrinkage rate of the stretched film heat-treated in Example 8, that is, the heat-treated stretched film before the reheat treatment was as follows.

 Hold at 200 ° C for 30 minutes 0.85% Hold at 250 ° C for 30 minutes 1.02% The results are shown in Table 2.

[Effects of the Invention] In the present invention, since the polyetherketone copolymer film is subjected to heat treatment and re-heat treatment, the polyetherketone copolymer film of the present invention has high heat resistance and high temperature. Excellent dimensional stability.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08J 5/00-5/02 C08J 5/12-5/22

Claims (2)

(57) [Claims] (1) The following formula (I): And a repeating unit represented by the following formula (II): And a composition ratio of the repeating unit represented by the formula (I) [molar ratio, (I) / ｛(I)
+ (II)｝] is 0.15 to 0.40 and the temperature is 400 ° C.
A melt viscosity (zero shear rate) in the film of the polyetherketone copolymer having 3,000-100,000 poise, heat treatment at a temperature between the crystallization temperature and the crystal melting point of the polyetherketone copolymer, A polyetherketone-based copolymer film obtained by re-heating the heat-treated film at a temperature between the glass transition temperature and the crystal melting point of the polyetherketone-based copolymer. 2. A film comprising a polyetherketone copolymer having a repeating unit, a composition ratio and a melt viscosity according to claim 1 is stretched in a uniaxial or biaxial direction by 1.5 to 1%.
It is stretched to 0 times, the stretched film is heat-treated at a temperature between the crystallization temperature and the crystal melting point of the polyetherketone-based copolymer, and the heat-treated stretched film is made of glass of the polyetherketone-based copolymer. A polyetherketone-based copolymer film reheat-treated at a temperature between the transition temperature and the crystal melting point.