JPH04283246A - Heat-resistant film - Google Patents

Abstract

PURPOSE:To prepare a heat-resistant film excellent in mechanical and chemical properties, profitability, and adhesion to an inorg. material by blending an arom. polyamide having specific diamine residues with a sol. resin. CONSTITUTION:A heat-resistant film is prepd. from a resin blend comprising 5-90wt.% arom. polyamide wherein 1-50mol% of all the diamine residues contain at least one kind of element selected from the group consisting of Si, Ge, and Sn and 10-95wt.% sol. resin. The film does not flow even above the softening point of the sol. resin, has a low thermal shrinkage and an excellent dimensional stability at high temp., has higher mechanical properties, such as tensile strength and elongation at break, than those of a film comprising the sol. resin alone, and hence can be easily handled in the secondary processing. Moreover, when the amt. blended of the sol. resin exceeds 50wt.%, the moisture absorption properties are improved.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant film, and more particularly to a heat-resistant film that is a blend of a soluble resin with low heat resistance and an aromatic polyamide.

0002

[Prior Art] Amorphous films represented by polycarbonate, polysulfone, polyetherimide, polyethersulfone, polysulfide sulfone, etc. are used as transparent conductive films for liquid crystals due to their excellent optical, electrical, and thermal properties. , printer ink ribbon, capacitor,
It is being used in a wide range of applications, including printed circuit boards and electrical insulation materials. However, a major drawback of these amorphous films, which are relatively inexpensive and have good humidity characteristics, is that they rapidly soften and flow at temperatures above the glass transition point, making them difficult to meet the demands of the market for highly heat-resistant materials. remains dissatisfied. Another major drawback is that the mechanical properties are poorer than that of crystalline films.

On the other hand, as heat-resistant films, films made of aromatic polyamides and aromatic polyimides are known, but although they have good heat resistance and mechanical properties, they are expensive due to poor productivity, and have poor humidity characteristics. It is worse than an amorphous film.

[0004] As a method of compensating for the drawbacks of these resins, molecular conjugation is also being investigated. For example, a high-strength film can be obtained by molecularly compositing polyparaphenylene terephthalamide (aromatic polyamide) with a rigid structure and nylon 6 (J. MACRMOL. SCI., PHY
S. , B17(4), 591-615 (1980)
), an example of a polymer composite obtained from a rigid reinforcing polymer and a matrix molecule with a flexible skeleton (Japanese Patent Publication No. 1
-36785) has been reported.

There is also a report that a heat-resistant film can be obtained by increasing the crystallinity of aromatic polyamide by blending a crystallization promoter such as amorphous polyether sulfone with aromatic polyamide having low crystallinity. Proceedings of the Molecular Society,
38(12), 4149-4154 (1989)).

[0006]

[Problems to be Solved by the Invention] However, for example, a molecular composite film of polyparaphenylene terephthalamide and nylon 6 can be prepared by dissolving it in concentrated sulfuric acid and adding a large amount of water, since polyparaphenylene terephthalamide is insoluble in organic solvents. It requires a very complicated production method of re-precipitation and heat compression at high temperatures to form a film, making it expensive even if it is industrialized, and the resulting film is only a brittle film with low elongation. In addition, in Japanese Patent Publication No. 1-36785, polyparaphenylenebenzbisthiazole, polyparaphenyleneterephthalamide, etc. are listed as rigid reinforcing polymers, but these polymers can also be dissolved in an acidic solvent to form a film. This makes it expensive, and the resulting film also has low elongation.

Furthermore, the method of blending an amorphous polymer with an aromatic polyamide with low crystallinity not only takes a long time for crystallization and has poor productivity, but also has poor mechanical properties of the resulting film, making it impractical for practical use. Not the point.

[0008] The present invention improves these problems and provides heat resistance that is excellent in mechanical properties, chemical properties (mainly moisture absorption properties), economical efficiency (cost), and has good adhesion to inorganic substances (particles, etc.). The purpose is to provide film.

[0009]

[Means for Solving the Problems] The present invention is a film made of a blend resin of an aromatic polyamide and a soluble resin, wherein the aromatic polyamide accounts for 5% by weight of the blend resin.
It is contained in a range of 90% by weight or more, and 1 mol% or more of the total diamine residues constituting the aromatic polyamide.
The heat-resistant film is characterized in that 0 mol% or less is composed of diamine residues containing at least one selected from silicon, germanium, and tin.

The aromatic polyamide of the present invention has the general formula

[
0011

[Chemical formula 1]

It is preferable that the repeating unit contained in the following formula is contained in an amount of 50 mol % or more, more preferably 70 mol % or more.

[0013] Here, Ar1 is the following (1), (2),
selected from (3), but not less than 1 mol% of Ar15
0 mol% or less is selected from (1), and 50 of Ar1
The mole % or more is selected from (2). A from the viewpoint of improving the compatibility between the polymer and particles when the polymer contains inorganic particles and the adhesion between the obtained film and metal etc.
It is desirable that 2 mol % or more, more preferably 3 mol % or more of r1 be selected from (1). Also, conversely (1)
If the amount is too large, the mechanical properties of the resulting film will deteriorate, so the amount is preferably 40 mol% or less, more preferably 30 mol% or less. The copolymerization component of Ar1 selected from (3) is preferably contained in a range of 40 mol% or less, more preferably 30 mol% or less, since too much of it will deteriorate the mechanical properties of the film.

Further, Ar2 is selected from the following (2) and (3), and 50 mol% or more of Ar2 is selected from (2). Furthermore, from the point of view of improving the mechanical properties of the obtained film, Ar2 is 60 mol% or more, more preferably 7
It is desirable that 0 mol% or more be selected from (2).

[0015]

[Case 2]

Furthermore, some of the hydrogen atoms on the aromatic rings in (1), (2), and (3) are halogen groups (especially chlorine), nitro groups, C1 to C3 alkyl groups (especially methyl basis)
, C1 to C3 alkoxy groups are more preferable because they have high solubility in solvents and high compatibility with soluble resins. Furthermore, halogen groups are preferred because they improve the humidity characteristics of the resulting film.

For example,

[0018]

[Chemical formula 3]

Examples include those containing 50 mol% or more of the following.

The soluble resin of the present invention refers to a resin that dissolves at least 1% by weight in the solvent that dissolves the aromatic polyamide described above. As the solvent for dissolving both the aromatic polyamide and the soluble resin, organic solvents are preferred from the viewpoint of ease of handling, such as N-methyl-2-pyrrolidone, dimethylacetamide, hexamethylphosphoramide, dimethylformamide, and dimethyl. Examples include amide polar solvents such as imidazolidinone, dimethyl sulfoxide, etc., and N-methyl-2-pyrrolidone and a mixture of N-methyl-2-pyrrolidone and other amide polar solvents are particularly preferred. When these solvents are used, particularly preferred are polycarbonate, polyvinylidene fluoride, polymethyl methacrylate, polystyrene, polyvinyl alcohol, polyether sulfone, polysulfone, polyarylate, polysulfide sulfone, polyetherimide, etc., which have good mechanical properties at high temperatures. Amorphous resins with remarkable improvement and excellent humidity characteristics, such as polycarbonate,
More preferred are polyether sulfone, polysulfone, polyarylate, and polysulfide sulfone. especially,

0
021]

[C4]

The basic skeleton Z of

[0023]

[C5]

Since the resin having both of the above structures has very good compatibility with the aromatic polyamide, the blended solution obtained by dissolving the aromatic polyamide and the soluble resin in the above solvent has excellent long-term storage stability. In addition, it is more preferred because a film with excellent mechanical properties and transparency can be obtained. Examples include polycarbonate and polyarylate, with polycarbonate being more preferred from the economic point of view. The basic skeleton Z may have a substituent, such as a halogen group. Further, another resin may be added to the blend resin of the aromatic polyamide and the soluble resin, preferably at most 40% by weight, more preferably at most 30% by weight, even more preferably at most 20% by weight of the soluble resin. For example, when polycarbonate is used as the soluble resin, mechanical properties are improved by adding polyethersulfone, polysulfone, or a third aromatic polyamide. In addition to the above solvents, good solvents for soluble resins such as dioxane, tetrahydrofuran, methylene chloride, chloroform, 1,1
, 2-trichloroethane, tricrene, acetone, toluene, etc., within a range that does not prevent the soluble resin and the aromatic polyamide from being compatible, preferably within 20% by weight of the total solvent amount, more preferably within 15% by weight. If so, it doesn't hurt to include it.

A film made of the blend resin can be obtained by solution casting the blend solution described above.

The amount of aromatic polyamide in the film of the present invention must be in the range of 5% to 90% by weight of the total blended resin in the film. When the amount of aromatic polyamide is less than this range, the effect of improving heat resistance is no longer observed, and the mechanical properties at high temperatures are extremely deteriorated. Preferably 10% by weight or more, more preferably 20% by weight
That's all. Furthermore, if the amount of aromatic polyamide is greater than this range, there will be no economic advantage. Preferably 7
It is 0% by weight or less, more preferably 50% by weight or less.

The thermal dimensional change rate of the film of the present invention at 250° C. under a load (0.5 kg/mm 2 ) in at least one direction is 50% or less. If it is greater than 50%, it cannot withstand use in situations where tension is applied at high temperatures. Preferably it is 40% or less, more preferably 20% or less.

[0028] The heat shrinkage rate of the film obtained in the present invention at 250°C in at least one direction is preferably 20% or less. More preferably 10% or less, even more preferably 5%
It is as follows. If it exceeds 20%, the dimensional stability will be poor and it will not be practical in the fields of thermal transfer applications, flexible circuit boards, and capacitor applications, for example. Further, the heat shrinkage rate at 200° C. in at least one direction is preferably 10% or less, more preferably 5% or less. Further, the heat shrinkage rate at 300° C. in at least one direction is preferably 30% or less, more preferably 20% or less, even more preferably 15% or less. Further, the coefficient of thermal expansion in at least one direction is 5×
It is preferably 10-5/°C or less, more preferably 4×10-5/°C or less.

[0029] The moisture absorption rate of the film is preferably 5% or less,
More preferably it is 3% or less, and still more preferably 1% or less. If it is more than 5%, the dimensional change due to moisture absorption becomes large and it is not suitable for practical use. Further, the humidity expansion coefficient in at least one direction is preferably 5 x 10-5/%RH or less, and 4 x 1
0-5/%RH or less is more preferable. 3×10-5/%
RH or less is more preferable.

[0030] Furthermore, the elongation at break in at least one direction of the obtained film is preferably 10% or more. More preferably it is 15% or more, and still more preferably 20% or more. 10
If it is less than %, the film will break during handling or processing, making it unsuitable for practical use. Further, the strength in at least one direction is preferably 5 kg/mm2 or more, more preferably 7 kg/mm2 or more, and even more preferably 9 kg/mm2.
/mm2 or more. The Young's modulus in at least one direction is preferably 150 kg/mm 2 or more, more preferably 200 kg/mm 2 or more. Furthermore, the F-5 value (strength at 5% elongation) of the film of the present invention in at least one direction is preferably 4 kg/mm2 or more, and 6 kg/m2.
m2 or more is more preferable.

[0031] The thickness of the film of the present invention is 0.2 to 200
The thickness is preferably μm, and more preferably 1 to 50 μm. More preferably, it is 2 to 40 μm. In addition, the density of this film is preferably 1.0 to 1.5 g/cm3, and preferably 1.1 to 1.5 g/cm3.
1.4 g/cm3 is more preferable.

The dielectric constant (1kHz) of the film is 2~
7 is preferable, and 3 to 7 are more preferable. Further, the dielectric loss tangent (1 kHz) is preferably 3% or less. More preferably, it is 2% or less.

[0033] The light transmittance of the film obtained by the present invention is preferably 50% or more. More preferably, it is 60% or more.

Furthermore, the average surface roughness (Ra) of the film is preferably 10 to 500 nm, more preferably 30 to 500 nm.
It is 300 nm. This range is particularly desirable since workability during processing and runnability during use will be even better. Note that in order to achieve this surface roughness, it is effective to add inorganic or organic fine particles.

[0035] Furthermore, the end tear resistance of the film of the present invention in at least one direction is preferably 0.05 kg/μm or more. If it is less than this, the film will break during handling or processing, making it unsuitable for practical use. More preferably 0.1 kg/μm or more, even more preferably 0.3 k
g/μm or more.

Next, the method for producing a heat-resistant film of the present invention will be explained, but the method is not limited thereto.

The aromatic polyamide used in the present invention can be obtained by reacting a diisocyanate with a dicarboxylic acid, or a diacid chloride with a diamine. In the case of diacid chloride and diamine, it is synthesized by solution polymerization in an amide polar solvent such as N-methyl-2-pyrrolidone or dimethylacetamide, or by interfacial polymerization using an aqueous medium. The diacid chloride and the diamine are stirred in a low-moisture amide polar solvent at a low temperature (usually 50°C or lower, preferably 30°C or lower) for 1 to 2 hours to polymerize. The order of adding the monomers is not particularly limited. Hydrochloric acid generated after polymerization is neutralized with an inorganic alkali or organic neutralizing agent. Furthermore, the reaction between diisocyanate and dicarboxylic acid is carried out in an amide polar solvent in the presence of a catalyst, usually at a high temperature (50 to 200°C).
). These polymer solutions may be used as they are as a stock solution for blending, or the polymer may be isolated once and then redissolved in a solvent to prepare a stock solution for blending. Inorganic salts such as calcium chloride, magnesium chloride, etc. may be added to the blending stock solution as a solubilizing agent.

[0038] In order to improve the mechanical properties of a heat-resistant film, it is necessary to keep the molecular weight of the polymer above a certain level, and this is conveniently expressed in terms of intrinsic viscosity (ηinh). That is, when the intrinsic viscosity is dissolved in N-methyl-2-pyrrolidone, preferably 1.
It is 0 to 10.0, more preferably 1.5 to 7.0.

Methods for blending the aromatic polyamide and the soluble resin include a method in which stock solutions of the aromatic polyamide and the soluble resin are prepared separately and blended together, and a method in which the stock solutions of the aromatic polyamide and the soluble resin are prepared separately, and a method in which the stock solutions of the aromatic polyamide and the soluble resin are blended together. Examples include a method in which aromatic polyamide is polymerized in the polymerized polymer, and polymerization and blending are performed simultaneously. The apparent intrinsic viscosity obtained from the film-forming stock solution thus obtained is preferably 0.1 to 8.0, more preferably 0.2 to 8.0.
It is 5.0. The solution viscosity can be freely selected, but from the viewpoint of flowability, it is preferably 5 to 50,000 poise/30°C, and 10 to
20,000 poise is more desirable. Resin concentration is 1-50
%, more preferably 5 to 30%.

[0040] This film-forming stock solution is made into a film by the following method.

First, in the dry-wet method, a film is cast onto a support using a doctor knife, a nozzle, etc.
Drying is carried out at a temperature in the range of 0 to 250°C, more preferably in the range of 60 to 200°C for a certain period of time. If it is less than 50°C, the evaporation rate of the solvent is slow, and if it exceeds 250°C, bumping of the solvent occurs, resulting in a decrease in film quality. The dried film is peeled off from the support and immersed in or sprayed with an aqueous medium to extract the inorganic salt and solvent. What is an aqueous medium?
A liquid whose main component is water, which is a poor solvent for polymers, but has an affinity for inorganic salts and amide polar solvents. Examples include water alone, a mixture of water and an amide polar solvent constituting the stock solution, and a mixture of water and ethylene glycol, acetone, or lower alcohol, but at least 50% of the water is desalted or
This is desirable in consideration of desolvation speed and solvent recovery. Further, the temperature of the wet bath is usually 5 to 90°C. In the wet process, inorganic salts and amide polar solvents that serve as solubilizing agents are extracted, and the amount of inorganic salts remaining in the film immediately after the wet process is 3% or less, more preferably 1% based on the polymer.
The following is good. Although the residual rate of the amide polar solvent is not particularly defined, it is advantageous to extract as much as possible in consideration of solvent recovery. During the wet process, the film is swollen with an aqueous medium, making it easy to stretch in the wet temperature range.
．． 01 to 5.0 times in the longitudinal direction. After the wet process, the film is heated to evaporate the aqueous medium and amide polar solvent. In this heating step, the final temperature is 100°C or higher, preferably 200°C or higher and 500°C or lower. In addition, in the heating process, 1
．． 01 to 5.0 times. There is no problem in relaxing if necessary.

Next, in the wet method, the material is introduced into an aqueous medium (containing alcohol such as methanol or ethanol, or only alcohol) directly from the die or once formed into a film on a support. This is the way to do it. Because it contains a large amount of amide-based polar solvents, inorganic salts and amide-based polar solvents are rapidly replaced in the aqueous medium, which tends to cause voids or surface roughness in the final film. Inorganic salts such as calcium chloride, lithium chloride, lithium bromide, etc. may be contained in the aqueous medium to control the substitution rate as necessary, or water and amide polar solvents/inorganic salts may be added to the water tank in multiple stages. to create a concentration gradient in a mixture of Similar to the wet-dry method, the film may be stretched 1.01 to 5 times in the longitudinal direction in this step. After the wet process, the film is heated (
200-500℃) and transverse stretching (1.01-5.0
times) will be carried out.

Next is the dry method. This method is the opposite of the wet method, in that it omits the extraction step, and is only possible when an organic solvent is used and the membrane forming stock solution does not contain an inorganic salt as a solubilizing agent. The stock solution cast onto the support using a doctor knife or die is dried and peeled off from the support in the same manner as the dry-wet method, and stretched 1.01 to 5.0 times in the longitudinal direction between the support and the heating process. Ru. After completing the dry process, the film is heated and stretched in the same manner as in the wet-dry process. The heat-resistant film of the present invention can be obtained in the manner described above.

Applications of the heat-resistant film of the present invention thus obtained include ribbons for thermal transfer, flexible printed circuit boards, capacitors, and electrical insulation materials.

[0045]

EXAMPLES Next, embodiments of the present invention will be described based on examples, but the invention is not limited thereto. In addition, the method of measuring the characteristics in the examples is as follows.

(1) Intrinsic viscosity (ηinh) According to the following formula,
0.5g/1 using N-methyl-2-pyrrolidone as a solvent
Measurement was performed using an Ubbelohde viscometer under conditions of 00ml and 30°C.

[0047]

[Formula 1]

[0048]

(2) Solution viscosity (poise) Measured at a temperature of 30° C. using a rotating B-type viscometer (Tokyo Keiki).

(3) Elongation at break, strength, Young's modulus, F-5
Measurement was performed using a TRS type tensile tester under conditions of width 10 mm, length 50 mm, and tensile speed 300 mm/min.

(4) Thermal shrinkage rate (%) After heating for 10 minutes in an oven set at a predetermined temperature without any load, the product was returned to room temperature, the dimensions were measured, and the calculation was calculated using the following formula.

[0052]

[Formula 2]

[0053]

(5) Moisture absorption rate (%) The weight of the film was measured after being completely dried at 150° C. for 60 minutes and after being left in 75% RH for 48 hours, and calculated using the following formula.

Moisture absorption rate = (75% RH, weight of film after standing for 48 hours - weight of film when completely dry) / (weight of film when completely dry) x 10
0 (%) (6) Coefficient of thermal expansion (α) To eliminate the effects of heat shrinkage and moisture absorption and desorption, the film was heated to 150%
80-150 when heated to ℃ and gradually cooled
Calculated from dimensional changes in the °C range. The amount of dimensional change was measured by a thermomechanical analyzer (TMA).

(7) Humidity expansion coefficient (β) In a constant temperature and humidity chamber, read the film length when equilibrium is reached during dehumidification (approximately 30% RH) and humidification (approximately 80% RH). Using the difference (amount of elongation), it was calculated from the formula below.

[0057]

[Formula 3]

[0058]

(8) Thermal dimensional change rate under load Load 0.5k
g/mm2, placed in an oven at 250°C for 10 minutes, returned to room temperature, measured dimensions, and calculated using the formula below.

[0060]

[Formula 4]

[0061]

(9) Dielectric constant, tanδ According to ASTM-D-150-81.

(10) Light transmittance Measured in accordance with ASTM D-1003.

(11) Average surface roughness (Ra) Measured using a high precision thin film step measuring instrument ET-10 manufactured by Kosaka Institute. The conditions were as follows, and the average value of 20 times was taken as the value.

・Stylus tip radius: 0.5 μm ・Stylus load: 5 mg ・Measurement length: 0.5 mm ・Cutoff value: 0.08 mm ``Measurement and Evaluation Methods'' (Sogo Technological Center, 1983).

(12) End tear resistance (kg/μm) JIS-
It was measured in accordance with C-2318 and converted into a value per 1 μm of thickness.

[0067] All parts used in the following examples represent parts by weight.

Example 1 95 mol% of 2-chloroparaphenylenediamine (hereinafter abbreviated as CPA) and 5 mol% of bis(3-aminopropyl)tetramethyldisiloxane (hereinafter abbreviated as SiDA) were mixed with 100 mol% of 2-chloroparaphenylenediamine (hereinafter abbreviated as CPA). Terephthalic acid chloride (hereinafter abbreviated as CTPC) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were reacted at 20°C or lower to obtain an NMP solution of aromatic polyamide. This solution was poured into a large amount of water, reprecipitated and dried to obtain a powdery polymer. 30 parts of this polymer was dissolved in 200 parts of NMP, and NMP containing 30 parts of polycarbonate, which had been prepared separately, was dissolved in 200 parts of NMP.
200 parts of MP solution was added to obtain a blend solution. The intrinsic viscosity was 1.9 and the solution viscosity was 1500 poise.

[0069] This film-forming stock solution was uniformly cast onto a glass plate using an applicator, and heated in an oven at 120°C for 8 hours.
After drying for a minute, it was peeled off from the glass plate, immersed in running water for 10 minutes, and then heated at 300° C. for 1 minute to obtain a final film with a thickness of 19 μm. The elongation at break of the obtained film was 30
%, tensile strength 23kg/mm2, Young's modulus 750k
g/mm2, F-5 value 17kg/mm2, end tear resistance 0.85kg/μm, heat shrinkage rate at 250℃ for 10 minutes is 0.5%, under load at 250℃ (0.5kg/mm
m2) has a thermal dimensional change of 1.0%, a coefficient of thermal expansion (α) of 1.7 x 10-5/°C, a moisture absorption rate of 1.0%, and an average surface roughness of 80 nm, making it tough, moisture-resistant, and heat-resistant. The film had excellent properties and workability.

Example 2 CPA 80 mol%, 4,4'-diaminodiphenyl ether (hereinafter abbreviated as DAE) 10 mol%, SiDA1
After reaction of 0 mol % with 50 mol % of CTPC and 50 mol % of terephthalic acid chloride (hereinafter abbreviated as TPC), the mixture was isolated to obtain an aromatic polyamide. This aromatic polyamide 3
Blend a solution of 0 parts dissolved in 300 parts of NMP and 400 parts of an NMP solution containing 70 parts of polycarbonate,
This blend solution was cast on a glass plate and heated to 150°C.
After drying for 4 minutes at 230°C for an additional 30 seconds. This film was stretched 1.2 times in both length and width at 250°C using a stretcher, and then further heated at 280°C. The obtained film had excellent properties as shown in Table 1.

Example 3 CPA60mol%, DAE30mol%, SiDA1
An aromatic polyamide was obtained from 0 mol% and 100 mol% of CTPC. 30 parts of aromatic polyamide isolated after the reaction,
An NMP solution blended with 70 parts of polyether sulfone was uniformly cast onto a glass plate using an applicator.
When immersed in running water, it will naturally peel off from the glass plate. After further immersing for 10 minutes to remove the solvent, the film was heated at 300° C. for 1 minute to obtain a final film with a thickness of 10 μm. The film had very excellent properties as shown in Table 1.

Example 4 40 parts of the aromatic polyamide of Example 1 was mixed with polyarylate 6
A film was prepared in the same manner as in Example 1. The film had very excellent properties as shown in Table 1.

Example 5 CPA 60 mol%, 4,4'-diaminodiphenylsulfone 30 mol%, bis(4-aminophenyl)tetramethyldisiloxane 10 mol% and TPC 100m
A film was produced from a blend solution consisting of 70 parts of aromatic polyamide obtained from OL% and 30 parts of polycarbonate. The film was stretched 1.2 times both in the length and width directions, and as shown in Table 1, a film with very excellent properties was obtained.

Example 6 A film was produced in exactly the same manner as in Example 3 except that polyether sulfone was replaced with polycarbonate. The film had very excellent properties as shown in Table 1.

Comparative Example 1 An NMP solution of polycarbonate was cast onto a glass plate,
The properties of the film made only of polycarbonate obtained by drying at 120°C for 6 minutes and then heating to 210°C were very poor in thermal properties, as shown in Table 1.

Comparative Example 2 A film was prepared in the same manner as in Example 3 except that the amount of aromatic polyamide was changed to 1 part.
At ℃, it melted and no film was obtained. Therefore, a film was obtained by changing the heating temperature to 210°C, but as shown in Table 1, the thermal properties were very poor.

Comparative Example 3 A film consisting of 95 parts of aromatic polyamide obtained from the reaction of 100 mol% of 4,4'-diaminodiphenylmethane and 100 mol% of TPC and 5 parts of polycarbonate was prepared in the same manner as in Example 1. The film had poor humidity characteristics.

As described above, films outside the scope of the present invention were inferior in either thermal properties or humidity properties.

Example 7 Paraphenylene diamine 50 mol%, DAE 20 mo
A membrane-forming stock solution was prepared by blending 30 parts of an aromatic polyamide obtained from 1% SiDA, 30 mol% SiDA, 60 mol% TPC, and 40 mol% isophthalic acid dichloride, 50 parts polycarbonate, and 20 parts polyethersulfone. This blended stock solution was continuously extruded into water through a nozzle with a width of 450 mm and a slit of 0.2 mm, and vertically 1.
A long film was obtained by stretching 1.2 times in the transverse direction at 300°C. The mechanical properties of the obtained film include: elongation at break of 35%, tensile strength of 15 kg/mm2,
Young's modulus 420kg/mm2, end tear resistance 0.66k
g/μm, and the heat shrinkage rate at 250°C for 10 minutes is 0.
4%, thermal dimensional change under load (0.5 kg/mm2) at 250°C is 15%, moisture absorption rate is 0.4%, humidity expansion coefficient (
β) was 2.1×10 −5 /%RH, which was a tough film with excellent humidity characteristics and heat resistance. Also, ε is 3.6, t
It has excellent electrical properties with an δ of 0.5% and a light transmittance of 7.
At 5%, the optical properties were also excellent. Furthermore, the average height of protrusions on the surface was 120 nm, and the film had good smoothness.

Example 8 CPA 97 mol%, bis(4-aminophenyl)dimethylgermanium 3 mol%, CTPC 100 mol%
When a blend solution consisting of 30 parts of the aromatic polyamide obtained from the above and 70 parts of polycarbonate was formed into a film by the method of Example 3, a film with excellent properties was obtained.

Example 9 A film was prepared in exactly the same manner as in Example 1 except that SiDA was changed to bis(4-aminophenyl)dimethyltin, and a film having the characteristics shown in Table 1 was obtained.

[0082]

[Table 1]

[0083]

Effects of the invention: The film made of the blended resin of aromatic polyamide and soluble resin obtained by the present invention does not flow even at temperatures above the softening pour point of the soluble resin, and has low thermal shrinkage at high temperatures and is dimensionally stable. Excellent. In addition, it has better mechanical properties, especially tensile elongation and tensile strength, than a single film of soluble resin, and is easier to handle during processing. Furthermore, the soluble resin accounts for 5% of the total resin in the film.
When it exceeds 0% by weight, the humidity properties (especially hygroscopicity) of the film are improved.

Furthermore, since the aromatic polyamide of the present invention and the soluble resin have very good compatibility, the blend solution has excellent long-term stability, and the polymer is easily finely dispersed in the obtained film, suppressing the generation of microvoids at the interface. It has excellent mechanical properties and transparency. In particular, since aromatic polyamide contains silicon, germanium, tin, etc., its affinity with inorganic particles and the like is improved, so even if a large amount of inorganic particles and the like are added to the polymer, there is little deterioration in mechanical properties. Also, when made into a film, it has good adhesion to metals and the like.

Furthermore, since a relatively inexpensive soluble resin is used, it is possible to reduce the manufacturing cost of the film.

Claims (1)

[Claims] 1. A film made of a blend resin of an aromatic polyamide and a soluble resin, wherein the aromatic polyamide is contained in an amount of 5% to 90% by weight of the blend resin, and the aromatic polyamide is further contained in a range of 5% to 90% by weight of the blended resin. 1 mol% or more and 50 mol% or less of all the constituting diamine residues are silicon,
A heat-resistant film comprising a diamine residue containing at least one selected from germanium and tin.