JP3038486B2 - Resin composition film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel resin composition film, and more specifically, has excellent slipperiness, high heat resistance, and excellent dimensional stability at high temperatures. For example, the present invention relates to a resin composition 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, polyamides, polyimides, polyesters,
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, polyetherketone-based polymers are extremely excellent in heat resistance, flame retardancy, chemical resistance, etc. Films are also used as heat insulating flexible printed circuit boards in the electrical and electronic fields. Its application as a material is expected.

However, even this polyetherketone-based polymer has a low glass transition temperature, and the heat resistance is practically insufficient.

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

An object of the present invention is to form a resin composition in which a specific amount of an inorganic filler is blended with a polyether-based copolymer to form a film, which has good slipperiness and high heat resistance, and is excellent in various properties. It is to provide a resin film.

[Means for Solving the Problems] To achieve the above object, the configuration of the invention of claim 1 is represented by the following formula (I); And a repeating unit represented by the following formula (II): And the content of the repeating unit represented by the formula (I) [molar ratio, (I) /
{(I) + (II)}] is from 0.15 to 0.4, and the melt viscosity (zero shear viscosity) at a temperature of 400 ° C. is from 3,000 to
For a polyether copolymer that is 100,000 poise,
A resin composition film formed by extrusion molding or press molding a polyether-based copolymer composition in which an inorganic filler is blended so that the content ratio thereof is 0.001% by weight or more and less than 10% by weight. A second aspect of the present invention is a resin composition film obtained by heat-treating the resin composition film of the first aspect at a temperature between a crystallization temperature and a crystal melting point. The resin composition film according to claim 1, a stretching ratio of 1.5 to 10 at 180 to 250 ° C.
A resin composition film stretched by a factor of two, and then heat-treated at a temperature between the crystallization temperature and the crystal melting point, wherein the resin composition film according to claim 2 or 3 is And a resin composition film obtained by reheating at a temperature between the glass transition temperature and the heat treatment temperature.

 The details will be described below.

-Polyether-based copolymer- One of the important points in the polyether-based copolymer used as a raw material of the resin composition film of the present invention is that the polyether-based copolymer is represented by the formula (I). And the repeating unit represented by the formula (II), and the content of the repeating unit represented by the formula (I) [molar ratio, (I) / {(I) + (II)}]. Is 0.
It is in the range of 15 to 0.4, and the composition ratio (molar ratio) of the repeating unit represented by the formula (II) is 0.85 to 0.6.

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 polyether-based copolymer will be low and the heat resistance will be lowered, or the melting point will be high and the moldability will be degraded. On the other hand, if it exceeds 0.4, the crystallinity of the polyether-based copolymer is lost, and heat resistance and solvent resistance are reduced.

Further, the polyether copolymer in the present invention has a melt viscosity (zero shear viscosity) at a temperature of 400 ° C.
It is important that it is between 3,000 and 100,000 poise.

This is because a low molecular weight polyether 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 polyether 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, exhibits sufficient heat resistance, and has solvent resistance. It is excellent in 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 polyether-based copolymer can be produced as follows.

-Method for producing polyether copolymer-The polyether copolymer reacts dihalogenobenzonitrile, 4,4'-biphenol, and an alkali metal compound at a specific ratio in the presence of a neutral polar solvent. After the reaction, a reaction product and a specific amount of 4,4'-dihalogenobenzophenone can be subjected to a copolymerization reaction to produce the compound.

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.

Said 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,
There is no particular limitation as long as 4'-biphenol can be converted into an alkali metal salt, and 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.

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.

As an example of the production method, the reaction product obtained by performing the reaction of the dihalogenobenzonitrile and 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.

The molar ratio of the total amount of dihalogenobenzonitrile and 4,4'-dihalogenobenzophenone to the amount of 4,4'-biphenol used is usually 0.98 to 1.02, preferably 1.00 to 1.01. The molar ratio of the alkali metal compound 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 polyether copolymer, for example, in the neutral polar solvent, the dihalogenobenzonitrile,
The 4,4′-biphenol and the alkali metal compound are added simultaneously to allow the dihalogenobenzonitrile to react with the 4,4′-biphenol,
Further, the above 4,4'-dihalogenobenzophenone is added, and a series of reactions is carried out usually at a temperature in the range of 150 to 380C, preferably 180 to 330C. Reaction temperature 150
Below ℃, the reaction rate is too slow to be practical and 38
When the temperature exceeds 0 ° C., a side reaction may be caused.

The reaction time of this series of reactions is usually 0.1 to 10
Hours, preferably 0.5 hours 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.

The polyether copolymer used in the present invention can also be obtained by simultaneously adding dihalogenobenzonitrile, biphenol, an alkali metal salt, and dihalogenobenzophenone to a neutral polar solvent solution.

The polyetherketone-based copolymer used in the present invention has a melt viscosity at 400 ° C of 3,000 to 100,000 poise and a crystal melting point of 330 to 400 ° C.

-Polyether-based copolymer composition- The resin composition film according to claim 1, wherein the polyether-based copolymer and the inorganic filler are blended in a specific blending ratio. Produced from the composition.

Examples of the inorganic filler compounded in the polyether copolymer include calcium carbonate, silicon dioxide, alumina, clay (kaolin, bentonite, clay, etc.), talc, and metal oxides (MgO, ZnO, TiO _2). ) And the like.

These inorganic fillers may be used alone or in a combination of two or more.

The inorganic filler may have a particle size of 5 μm or less, but preferably a finer one is used.

An important point in the polyether-based copolymer composition used in the present invention is that the mixing ratio of the inorganic filler to the polyether-based copolymer is 0.001% by weight or more and 10% or more.
% By weight, preferably 0.005% by weight or more and less than 5% by weight.

If the blending ratio of the inorganic filler is less than 0.001% by weight, the effect of the film slip property may not be exhibited.
On the other hand, when the compounding ratio exceeds 10% by weight, the tear strength of the obtained polyether-based copolymer composition is reduced, and the stretchability may be reduced.

The polyether copolymer composition is mixed with a predetermined ratio of an inorganic filler appropriately selected to the polyether copolymer powder obtained by the above-described method for producing a polyether copolymer, and blended. After that, it can be obtained by kneading with an extruder.

Further, a method of producing a copolymer in the presence of an inorganic filler may be employed.

-Method for Producing Resin Composition Film-The resin composition film of the present invention can be obtained by forming the obtained polyether-based copolymer composition into a film.

Film formation is carried out 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, by a usual extrusion molding method or press molding method, and by rapid cooling, good transparency is obtained. An amorphous film is obtained.

For example, by feeding the polyether copolymer composition to an extruder, setting the resin temperature to 350 to 450 ° C., extruding from a slit-shaped die in a molten state, and cooling and solidifying, the polyether copolymer is obtained. An amorphous film of the composition can be made.

Alternatively, an amorphous film of the polyether-based copolymer composition can be obtained by producing a press film at a press temperature of 350 to 450 ° C. using a hot press machine.

The amorphous film thus obtained can be made into a crystalline film by heat-treating it at a temperature between its crystallization temperature and the crystal melting point.

Next, these amorphous films are oriented by uniaxial stretching or biaxial stretching.

The stretching method may be any of two-axis simultaneous or one-axis sequential.

The stretching is performed at a temperature between the glass transition temperature and the crystal melting point, for example, 180 to 250 ° C.

The stretching ratio is preferably 1.5 to 10 times, particularly 2 to
Preferably it is 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. It may not improve further.

In addition, heat treatment of the resin composition film before or after stretching can significantly improve the heat resistance of the film.

Regardless of the stretching, the heat treatment of the resin composition film is performed under tension, and the crystallization temperature, that is, the temperature at which the polymer that has been made amorphous by the above film formation crystallizes by the heat treatment (heating), Temperature below the melting point, for example 19
Perform at 0-370 ° C.

As a preferred example, the stretched resin composition film is fixed with a metal frame or the like, and under tension, 190 to 370 ° C.,
Heat treatment is performed for 1 to 600 seconds.

There are no particular restrictions on the heating method, and various means can be adopted.

Further, the heat-treated film obtained by this heat treatment is again subjected to a heat treatment at a temperature near the heat treatment temperature.

This reheat treatment is performed under tension or no tension as needed, and is performed at a temperature between the glass transition temperature of the polyether copolymer composition and the heat treatment temperature.

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

The resin composition film thus obtained is used in the field of electronics as: (1) base film for flexible printed circuit board, backing material for flexible printed circuit board, electrode plate for membrane, backing material for membrane, base film for transparent electrode, liquid crystal Film cell, IC carrier tape (base film for TAB), 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, Insulation tapes (motors, generators, transformers), condensers, wire coatings, shielding plates for microwave ovens and other thermal equipment, speaker diaphragms, lighting equipment covers, instrument display panels, base films for thermal transfer recording media, magnetic recording (3) General industrial use In the process, overhead projector base paper, aircraft interior materials,
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] Next, the present invention will be described more specifically based on examples.

(Example 1) 1,548 g (9 mol) of 2,6-dichlorobenzonitrile, 4,4'- were placed in a reactor having an inner volume of 200 L equipped with a Dein-Stark trap filled with toluene, a stirrer, and an argon gas blowing tube. 5,580 g (30 mol) of biphenol, 4,561 g (33 mol) of potassium carbonate, and N-methyl-2-pyrrolidone 50 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 conducting the reaction at a temperature of 195 ° C. for 30 minutes, a solution of 4,582 g (21 mol) of 4,4′-difluorobenzophenone dissolved in N-methyl-2-pyrrolidone 70 was added thereto, and further added for 1 hour. The reaction was performed.

After the completion of the reaction, the mixture is washed with water and methanol in that order and then dried to obtain 10.0 kg of a white powdery copolymer (yield 98%).
%).

When the properties of this copolymer were measured, the temperature was 40
The melt viscosity at 0 ° C (zero shear viscosity) was 13,000 poise, the glass transition temperature was 185 ° C, the crystal melting point was 379 ° C, and the thermal decomposition onset temperature was 562 ° C (5% weight loss in air).

This copolymer has the following repeating units.

(I) / {(I) + (II)} = 0.3 Talc (FF-R, average particle diameter 0.7 μm) manufactured by Asada Flour Milling Co., Ltd. was added to this polyether copolymer at a content of 0.0
The mixture was blended so as to be 1% by weight, extruded at 390 ° C. using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.), and then pelletized.

Using the pellets, extrusion molding with a T-die,
A resin composition film having a width of 25 cm was obtained.

When the physical properties of this resin composition film were measured, the tensile strength was 8 kg / mm ² (according to ASTM D882) and the tensile modulus was 260
Kg / mm ² (according to ASTM D882), elongation at break 110% (ASTM D882)
882).

Next, this resin composition film was stretched at a stretching speed of 1,000% / min.
Then, the film was biaxially stretched three times vertically and three times horizontally, then fixed to a metal frame, and heat-treated at 260 ° C. for 30 seconds under a constant length to obtain a biaxially oriented film having a thickness of 25 μm.

The mechanical strength of the stretched resin composition film has a tensile strength of 13 kg / mm ^2, tensile modulus 350 Kg / mm ^2, elongation at break 25
%Met.

The coefficient of friction of the stretched resin composition film was measured using a surface property measuring device (HEIDON-14, manufactured by Shin-Toyo Kagaku Co., Ltd.). Measurement conditions: ball indenter: SUSφ10mm, speed: 300mm
/ min, weight: 200 g.

 The results are shown in Table 1.

(Example 2) The procedure of Example 1 was repeated, except that the blending ratio of talc was changed to 0.5%.

 Table 1 shows the evaluation results.

(Example 3) The procedure of Example 1 was repeated, except that the blending ratio of talc was changed to 5.0% by weight.

 Table 1 shows the evaluation results for the coefficient of friction.

(Example 4) The amount of raw materials charged in the production of the copolymer in Example 1 was 2,
In the same manner as in Example 1 except that 1290 g (7.5 mol) of 6-dichlorobenzonitrile, 4976 g (36 mol) of potassium carbonate, and 4910 g (22.5 mol) of 4,4′-difluorobenzophenone were used, the following structural units were used. Was obtained.

(I) / {(I) + (II)} = 0.25 This polyether-based copolymer has a melt viscosity at 400 ° C. (zero shear viscosity) of 15,000 poise, a glass transition temperature of 182 ° C. and a melting point of 380. ° C, thermal decomposition onset temperature is 562
° C.

The talc was blended with this copolymer so that the content ratio was 0.5% by weight, and a stretched resin composition film was obtained in the same manner as in Example 1.

Table 1 shows the results of evaluating the coefficient of friction of the obtained stretched resin composition film.

(Example 5) The procedure of Example 4 was repeated, except that titania was blended as an inorganic filler so that the content ratio was 0.5% by weight.

Table 1 shows the evaluation results of the coefficient of friction of the stretched resin composition film.

(Examples 6 to 10) Each of the heat-treated films obtained in Examples 1 to 5 was heat-treated again at 250 ° C for 30 seconds. The heat shrinkage of the obtained reheat-treated film was measured in accordance with JIS C-2318.

 The results are shown in Table 2.

(Comparative Example 1) A stretched resin composition film was obtained in the same manner as in Example 1 except that the polyether-based copolymer produced in Example 1 was used and no inorganic filler was added. .

The coefficient of friction of the stretched resin composition film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

The heat shrinkage of the films of Comparative Example 2 and Comparative Example 1 was measured. The results are shown in Table 2.

[Effects of the Invention] According to the present invention, it is possible to provide a resin composition film having good sliding properties and excellent heat resistance.

In addition, the stretched resin composition film has excellent mechanical properties.

Furthermore, the resin composition film obtained by the heat treatment has excellent dimensional stability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // B29K 71:00 B29L 7:00 (56) References JP-A-4-28725 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08J 5/00-5/02 C08J 5/12-5/22 C08L 71/10 B29C 71/02

Claims (4)

(57) [Claims] (1) The following formula (I): And a repeating unit represented by the following formula (II); And the content of the repeating unit represented by the formula (I) [molar ratio, (I) / ｛(I) +
(II)｝] is 0.15 to 0.4, and the content of the inorganic filler is 0.001% by weight with respect to the polyether copolymer having a melt viscosity (zero shear viscosity) at a temperature of 400 ° C. of 3,000 to 100,000 poise. %. A resin composition film formed by extrusion molding or press molding a polyether-based copolymer composition blended to be at least 10% by weight. 2. A resin composition film obtained by subjecting the resin composition film according to claim 1 to a heat treatment at a temperature between the crystallization temperature and the crystal melting point. 3. The resin composition film according to claim 1, which is stretched at 180 to 250 ° C. at a stretching ratio of 1.5 to 10 times, and then heat-treated at a temperature between its crystallization temperature and the crystal melting point. Resin composition film. 4. A resin composition film obtained by subjecting the resin composition film according to (2) or (3) to a heat treatment at a temperature between the glass transition temperature and the heat treatment temperature.