JPH0428725A - Film, stretched film, heat treated film and heat retreated film - Google Patents

Abstract

PURPOSE:To obtain the subject film having a low linear expansion coefficient similar to a metal, having a high heat resistance and excellent in dimensional stability at high temperatures by blending a polyether copolymer having plural specified repeating units with an inorganic filler in a specified ratio. CONSTITUTION:An objective film produced by blending a polyether-based copolymer composed of repeating units represented by formulae I and II, having 0,15-0,40 composition ratio [molar ratio: formula I/(formula I+II)] of the repeating unit of formula I and showing 3000-100000 poise melting viscosity at 400 deg.C with an inorganic filler of 10-15wt.% based on the above-mentioned copolymer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a new film, a stretched film, a heat-treated film, and a reheat-treated film. It has the lowest heat resistance and excellent heat resistance.
Films of polyether copolymer resin compositions, stretched films thereof, heat-treated films thereof, and reheat-treated films thereof, which can be suitably used for electrical/electronic parts such as TAB base films and flexible printed circuit boards. Regarding.

[Prior art and the problem to be solved by the invention] In recent years,
In order to develop materials with excellent heat resistance, mechanical properties, and dimensional accuracy, various films such as polyamide, polyimide, polyester, and polysulfone have been developed or are already commercially available, and are used for parts of electronic and electrical equipment and machinery. It is used as a material for a wide range of purposes.

However, Kapton, which is said to be the most excellent boimide at present, has high hygroscopicity, but its film has poor dimensional stability.

In addition, polyetherketone polymer, which is a thermoplastic resin, is a material with excellent heat resistance, flame retardance, and chemical resistance, so it is used as a heat-resistant flexible material in the electrical and electronic fields. It is expected that it will be applied to printed circuit boards, etc.

However, even in this polyetherketone polymer, the glass transition temperature is low and the heat resistance is still insufficient for practical use.

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

The purpose of the present invention is to form a film of a polyether copolymer resin composition containing a polyether copolymer and a specific amount of inorganic filler, so that the coefficient of linear expansion is as low as that of metal, and it is heat resistant. The purpose of the present invention is to provide a film of a thermoplastic resin composition having high strength and excellent various properties.

[Means for solving the problem] To achieve the above object, # of the invention of claim 1 or,
It consists of a repeating unit represented by the following formula (T): and a repeating unit represented by the following formula HT)(r[), and the composition ratio [molar ratio (I)] of the repeating unit represented by the formula (1) is /((I)
+ (II) ) ] > 10.15 to 0.40, and the melt viscosity at 400°C is 1.000 to 10
(1, QO [l voids is 10 to 50% by weight based on the bodether copolymer and this polyether copolymer.
There is a film formed by forming a polyether copolymer resin composition containing an inorganic filler blended to have a content ratio of: A stretched film obtained by stretching a film in one or two axial directions at a stretching ratio of 1.2 to 3 times. The structure of the invention according to claim 4 is a heat-treated film obtained by heat-treating the stretched film according to claim 3 at a temperature between the delivery temperature and the crystal melting point of the polyether copolymer. This is a reheat-treated film obtained by reheating a heat-treated film obtained by reheating the film at a temperature between its glass transition temperature and the heat treatment temperature.

This will be explained in detail below.

-Botether copolymer Important points regarding the polyether copolymer which is the raw material for various films in the present invention) One is that the polyether copolymer is the repeating unit represented by the formula (1), and the repeating unit represented by the formula (1) is tO, (■), and the content ratio of the repeating unit represented by the above formula (1) "molar ratio, (I) / ((1) + (n))" or 0.15 ~0.4, and the composition ratio (molar ratio) of the repeating unit represented by formula (II) is 0.85 to 0.6
It is to be.

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 copolymer will be low, resulting in a decrease in heat resistance, or the melting point will be high, leading to deterioration in moldability. On the other hand, if it exceeds 0.4, the crystallinity of the polyether copolymer will be lost and the heat resistance and solvent resistance will decrease.

Furthermore, it is important that the polyether copolymer in the present invention has a melt viscosity (zero shear viscosity) of 1,000 to 100,000 voids at a temperature of 400°C.

This is because a low molecular weight polyether copolymer having a melt viscosity of less than 3.000 voids cannot achieve sufficient heat resistance and mechanical strength.

Moreover, if 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 is resistant to solvents. Excellent strength and mechanical strength.
For example, it can be suitably used as a new material in the electric/electronic equipment field, machine making field, etc.

Such a polyether copolymer can be produced as follows.

-Production method of polyether copolymer-Polyether copolymer is produced by reacting dihalogenobenzonitrile, 4,4°-biphenol, and an alkali metal compound in the presence of a neutral polar solvent in a specific usage ratio. After that, it can be produced by carrying out a copolymerization reaction between the reaction product and a specific amount of 4,4'-dihalogenobenzophenone.

Specific examples of the dihalogenobenzonitrile that can be used include, for example, the linear formula.

(In the formula 1, X is a herogen atom.) Examples include 2,6-dihalogenobenzonitrile and 2,4-dihalogenobenzonitrile.

Among these, preferred are 2.6-dichlorobenzonitrile, 2.6-difluorobenzonitrile, and 2.4-dichlorobenzonitrile.
2.6-dichlorobenzonitrile is particularly preferred.

The dihalogenobenzonitrile and the following formula: 4
, 4'-biphenol in the presence of an alkali metal compound and a neutral polar solvent.

The alkali metal compound to be used is specified in @Note 4.4.
~ If there is something that can convert biphenol into an alkali metal salt, there are no particular restrictions, and the most dangerous ones are alkali metal carbonates and alkali metal hydrogen carbonates.

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

Among these, preferred are sodium carbonate and potassium carbonate.

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

Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N.

N-diethylacetamide, N,N-cypropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-
Isopropyl-2- and Loliton, N-inbutyl-2-
Pyrrolidone, N-n-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-3,4,5-1-rifthyl-2-pyrrolidone, N-
Methyl-2-piperidone N-ethyl-2-piperitone,
N-isopropyl-2-piperitone, N-methyl-6-
Methyl-2-piperitone, N-methyl-3-ethylpiperitone, dimethyl sulfoxide, diethyl sulfoxide, l-methyl-1-xosulfolane, 1-ethyl-1
-oxosulfolane, l-phenyl-1-oxosulfolane, N,N'-dimethylimidasisodinone, diphenylsulfone, and the like.

As an example of the production method, the 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 and the reaction product described in 4. React with 4°-dihalogenobenzophenone.

The 4.4°-dihalogenobenzophenone used has the following formula.

(Where, X has the same meaning as above.) In the method of the present invention), 4,4'-
Difluorobenzophenone 4.4°-Dichlorobenzophenone is 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 t,OS to 1.25.

There is no particular restriction on the amount of the neutral polar solvent used, but it is usually the same amount as the dihalogenobenzonitrile and 4.
The amount is selected in the range of 200 to 2.000 parts by weight based on 100% of the total weight of 4'-biphenol and the alkali metal compound.

In order to obtain a polyether copolymer, for example, the dihalogenobenzonitrile, the 4,4°-biphenol, and the alkali metal compound are simultaneously added to the neutral polar solvent, and the After reacting dihalogenobenzonitrile with the 4,4° biphenol,
Furthermore, the above-mentioned 4,4'-dihalogenobenzophenone is added, usually at 150-380°C, preferably at 180-330°C.
If the reaction temperature is less than 150°C, the reaction rate is too slow to be practical, and if it exceeds 380°C, side reactions may occur.

In addition, the reaction time of this series of reactions is usually 0.1 to 1
0 hours, preferably 0.5 hours to 5 hours.

After completion of the reaction, a polyether copolymer is obtained by separating and purifying the polyether copolymer from the resulting neutral polar solvent solution containing the polyether copolymer according to a known method. Something comes up.

In addition, the polyether copolymer used in the present invention is
It can also be obtained by simultaneously adding dihalogenobenzonitrile, biphenol, alkali gold salt, and dihalogenobenzophenone to a neutral polar solvent solution.

The polyether copolymer used in the present invention is 40
The melt viscosity at 0°C is 3,000 to 100,000 voids, and the crystal melting point is 330 to 400°C.

The polyether copolymer resin composition according to claim 1, wherein the polyether copolymer and the inorganic filler are mixed in a specific proportion or at a content ratio of the inorganic filler to the polyether copolymer. It is manufactured from a polyether-based copolymer resin composition that is blended so as to have the following properties.

Examples of the inorganic filler in this invention include carbonates such as calcium carbonate, magnesium carbonate, and tolomite, sulfates such as calcium sulfate and magnesium sulfate, sulfites such as calcium sulfite, talc, clay, mica, asbestos, and glass fibers. , glass peas, silicates such as calcium silicate, montmorillonite, and bentonite, silicon dioxide, metal powders such as alumina, iron, zinc, and aluminum, ceramics such as silicon carbide, silicon nitride, and their whiskers, carbon black, and graphite. , carbon fiber, etc. Among the various inorganic fillers, for example, calcium carbonate, silicon dioxide, alumina, clay (kaolin, bentonite,
Shirato etc.).

Talc, metal oxides (MgO, ZnO1Ti02), etc. are preferable.

The inorganic filler may be in the form of a single particle, a plate, or a fiber, but in this invention, the particle size is 5 pm or less.
It is sufficient if the size is smaller than that, and preferably a finer one is used.

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

An important point in the polyether copolymer composition used in the present invention is the blending ratio of the inorganic filler to the polyether copolymer, 10 to 50% by weight, preferably 15 to 40% by weight. It is a certain thing.

If the blending ratio of the inorganic filler is less than 10% by weight, the expansion coefficient becomes large and the difference from metal becomes large. Moreover, if it exceeds 50% by weight, moldability may deteriorate.

The polyether copolymer resin composition was prepared by mixing and blending an appropriately selected inorganic filler at a ratio of 10 to 50% by weight with the polyether copolymer powder obtained by the above-mentioned manufacturing method. After that, it can be obtained by kneading it in an extruder and forming it into pellets.

Alternatively, a method of producing a polyether copolymer in the presence of an inorganic filler may be adopted.

However, if the mixing ratio of the inorganic filler exceeds 50% by weight, the moldability deteriorates, making it difficult to form into a film.

-Production method of film, stretched film, heat-treated film, and reheat-treated film- The film according to claim 1 can be obtained by forming the obtained polyether copolymer resin composition into a film. .

Forming into a film is carried out using a conventional method such as extrusion molding or press molding at a temperature of 10 to +00"C higher than the crystal melting point, preferably 30 to 70"C higher than the crystal melting point, followed by rapid cooling. By this method, a non-grade film with good transparency can be obtained.

For example, the Botether copolymer resin composition is fed to an extruder, the resin temperature is set at 350 to 450°C,
By extruding the molten material through a slit-shaped die, cooling and solidifying it, an unstretched, non-quality film of the polyether copolymer resin assembly Jt can be produced.

Or press at a temperature of 350 to 450 using a heat press machine.
By producing a press film at ℃, it is possible to obtain an unstretched, unstretched film of the Botether copolymer resin composition.

Then, the stretched film according to claim 2 can be produced by orienting these unstretched films by uniaxial stretching or two-wheel stretching.

The stretching method may be either two-wheel simultaneous or one-axis sequential.

The stretching temperature is a temperature between the glass transition temperature and the crystal melting point,
For example, it is carried out at 180 to 250°C.

The stretching ratio is preferably 1.2 to 3 times, especially 1
．． It is preferable that it is 3 to 2.5 times.

If the stretching ratio is less than 1.2 times, a sufficient stretching effect (improving effect on film properties such as tensile strength and tensile modulus) may not be achieved; The effect may not improve further.

Furthermore, by heat-treating the film before stretching or the stretched film after stretching, it is possible to obtain a heat-treated film with significantly improved heat resistance.

Heat treatment is carried out by heating at a temperature between the crystallization temperature and the crystal melting point, resulting in a crystallized film.

Regardless of whether or not the stretching is carried out, the heat treatment is performed under tension, and the crystallization temperature is higher than the temperature at which the film-formed and amorphous polymer is crystallized by heat treatment (temperature elevation) and lower than the crystal melting point. For example, it is carried out at 190 to 370°C.

As a preferred example, the stretched film is fixed to a metal frame or the like, heated under tension to 190 to 370°C, and then heat-treated for 1 to 600 seconds.

There are no particular restrictions on the heating method, and various means may be employed.

Furthermore, the heat-treated film obtained by this heat treatment is
A reheat-treated film can be produced by performing reheat treatment again at around the heat treatment temperature.

This reheat treatment is preferably carried out under tension or without tension as required, and at a temperature between the glass transition temperature of the polyether copolymer resin composition and the heat treatment temperature.

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

The films, stretched films, heat-treated films and reheat-treated films obtained in this way are:

(1) In the electronics field, base films for flexible printed circuit boards, backing materials for flexible printed circuit boards, electrode plates for membranes, backing materials for membranes, base films for transparent electrodes, film cells for liquid crystals, IC carrier tapes (base films for TAB) (2) In the electrical and thermal insulation fields, it can be used for sheet heating element bases, surface cover films, insulating tapes (motors,
(generators, transformers), capacitors, wire coatings, shielding plates for microwave ovens and other heat equipment, speaker diaphragms, lighting equipment covers, instrument faceplates, base films for thermal transfer recording media, base films for magnetic recording media It can be used for etc.

(3) In general industrial applications, it can be used for Oherhentbroschictor base paper, aircraft interior materials, nuclear power related equipment, solar collector covers, ultrafiltration membranes, etc.; (4) In other applications, it can be used for heat-resistant labels, heat-resistant nameplates, etc. It can be used for components such as aviation, vehicles, and defense.

[Examples] Next, the present invention will be described in more detail based on Examples.

(Example 1) 1,548 g of 2,6-cyclopenzonitrile was placed in a reactor with an internal volume of 200 g, equipped with a Dean-Starck trap filled with toluene, a stirring device, and an argon gas blowing tube.
g (9 mol), 4.4'-biphenol S, 580
g (:10 mol), potassium carbonate 4.551 g
(33 mol) and 50 moles of N-methyl-2-pyrrolidone were added, and the temperature was raised from room temperature to 195°C over 1 hour while blowing argon gas.

After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy.

Next, after carrying out a reaction at a temperature of 195°C for 30 minutes, 4.4°-difluorobenzophenone 4.582
g (21 mol) to N-methyl-2-pyrrolidone 70
The dissolved solution was added to the solution, and the reaction was continued for an additional hour.

After the reaction is completed, the polyether copolymer 10 in the form of a white powder is obtained by washing with water and methanol in that order and drying.
．． 0 kg (yield 98%) was obtained.

When the properties of this polyether copolymer were measured, the melt viscosity (zero shear viscosity) at a temperature of 400°C was 16,000 poise, and the glass transition temperature was 185
℃, the crystal melting point was 348℃, and the thermal decomposition onset temperature was 560℃ (5% weight loss in air).

According to infrared absorption spectrum analysis, this polyether copolymer had the following repeating units.

(I) (II) (z)/((r)+(n))=0.3 To this polyether copolymer, talc (FF-R1 average particle size 0.74 m) manufactured by Asada Seifun ■ was added. Blend so that the content is 20% by weight.

Two-wheel extruder (manufactured by Ikegai Iron Works: PCM-3) at 390℃
0) to form a pellet.

Using this pellet, extrusion molding was performed using a T-die to obtain a film with a diameter of 2Sc-.

When the physical properties of this film were measured, the tensile strength was 8.
kg/-1" (ASTM D882 compliant), tensile modulus 260 kg/-" (ASTM 08g
2), and the elongation at break was 60% (based on ASTM D882).

Next, this unstretched film was biaxially stretched 15 times vertically and 1.5 times horizontally at a stretching speed of 500%/min at 190° C. using a two-wheel stretching machine (manufactured by Toyo Seiki Seisakusho) to obtain a stretched film. Obtained.

Thereafter, these unstretched and stretched films were each fixed to a metal frame and heat-treated at 300° C. for 60 seconds under one foot length to obtain a biaxially oriented heat-treated film having a thickness of 751 Lm.

Furthermore, these heat-treated films were heated for 30 minutes in a relaxed state.
Heat treatment was performed at 0° C. for 60 seconds to obtain a reheat-treated film.

Among these, when the physical properties of the unstretched reheat-treated film were measured, the tensile strength was 10 kg/ms" (A S
TM 0882 compliant), tensile modulus 300kg/-
12 (based on ASTM D882), elongation at break 15%
(based on ASTM D882).

Furthermore, the coefficient of linear expansion of these reheat-treated films was measured using TMA 100 manufactured by SEI KO Electronics.

The results are shown in Table 1.

In addition, the solder heat resistance tester (manufactured by Tabai Co., Ltd.) was used at 300°.
C. A soldering heat resistance test was conducted for 2 seconds.

The results are shown in Table 1.

(Example 2) Filming, heat treatment, and reheat treatment were performed in accordance with Example 1, except that the blending ratio of talc was adjusted to 30%, and biaxial stretching was not performed. was conducted under the same conditions.

The evaluation results are shown in Table 1.

(Example 3) Film formation, heat treatment, and reheat treatment were performed under the same conditions as in Example 1, except that the synthesized polymer was filled with the inorganic material shown in Table 1 and two-wheel stretching was not performed. I did it.

The evaluation results are shown in Table 1.

(Examples 4 and 5) The amount of raw materials charged during copolymer production in Example 1 was changed to 2.
6-cyclobenzonitrile 1,290 g (7.5 mol), potassium carbonate 4,976 g (36 mol), 4
, 4°-difluorobenzophenone 4.910 g (
A polyether copolymer consisting of the following structural unit was obtained in the same manner as in Example 1, except that the amount was changed to 22.5 mol).

(I) (■) (I)/((1)+([1))=0. This polyether copolymer has a melt viscosity (zero shear viscosity) of 11,000 poise at 400°C, a glass transition temperature of 182°C, a crystal melting point of 379°C, and a thermal decomposition onset temperature of 562°C. Ta.

The inorganic fillers shown in Table 1 were blended into this polyether copolymer, and then film formation, biaxial stretching, heat treatment, and reheat treatment were performed under the same conditions in accordance with Example 1.2.

The linear expansion coefficient and soldering heat resistance of this film were measured under the same conditions as in Example 1.

The evaluation results are shown in Table 1.

(Comparative Example 1) The same procedure as that of Example 1 was used except that the polyether copolymer produced in Example 1 was used and no S-based filler was added.
It is made into a film in the same way, heat treated and reheated,
The coefficient of linear expansion was measured.

The evaluation results are shown in Table 1.

(Hereinafter, blank space) Table ※※ ◎: No change at all [Optical effect] According to the present invention, it has a low coefficient of linear expansion comparable to that of metal, and has high heat resistance and stability at high temperatures. It is also possible to provide a soaked resin composition film.

Further, the resin composition film of the present invention can be used for electrical/electronic parts such as TAB base films and flexible printed circuit boards.

Claims (4)

[Claims] (1) The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼The repeating unit represented by (I) and the following formula (II); ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ (II) Consisting of repeating units represented by formula (I), composition ratio of repeating units represented by formula (I) [molar ratio: (I)/{(
I)+(II)}] is 0.15 to 0.40, and the melt viscosity at 400°C is 3,000 to 100,
A polyether copolymer resin containing a polyether copolymer having a poise of 0.000 poise and an inorganic filler blended at a content ratio of 10 to 50% by weight with respect to the polyether copolymer. A film formed by forming a composition. (2) The film according to claim 1 is stretched at a stretching ratio of 1.2 to
A stretched film that is uniaxially or biaxially stretched three times. (3) A heat-treated film obtained by heat-treating the film according to claim 1 or the stretched film according to claim 2 at a temperature between the crystallization temperature and the melting point of the polyether copolymer. (4) A reheat-treated film obtained by reheating the heat-treated film according to claim 3 at a temperature between the glass transition temperature of the polyether copolymer and the heat treatment temperature.