JP2884665B2 - Aromatic polycarbonate / aromatic polyamide block copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an aromatic polycarbonate / aromatic polyamide block having both the characteristics of an aromatic polycarbonate and an aromatic polyamide, and having excellent heat resistance and humidity characteristics. It relates to a polymer composition.

[Prior art] Amorphous films typified by polycarbonate, polysulfone, polyetherimide, polyethersulfone, polysulfidesulfone, etc. are known for their excellent optical properties, electrical properties, and thermal properties. A wide range of applications such as films, printer ink ribbons, capacitors, printed circuit boards, and electrical insulating materials are being developed. However, one of the major drawbacks of these amorphous films, which are relatively inexpensive and have good humidity characteristics, is that the film rapidly softens and flows at a temperature higher than the glass transition point, and as a high heat-resistant material required by the market. Complains. Another major drawback is that the mechanical properties are poor compared to crystalline films.

On the other hand, as the heat-resistant film, a film made of an aromatic polyamide or an aromatic polyimide is known, but the heat resistance and mechanical properties are good, but the productivity is poor, so the cost is high, and the humidity property is also amorphous. Bad compared to film.

As a general method to make up for the disadvantages of these resins, 2
It is known to blend seed polymers. Also,
JP-A-1-252640 discloses a copolymer obtained by blocking two kinds of polymers.

[Problems to be Solved by the Invention] However, it is generally difficult to completely dissolve two kinds of polymers, and only a very limited combination is known. Since the combination of polycarbonate and aromatic polyamide is dissolved in a common solvent such as N-methyl-2-pyrrolidone, a completely compatible state is formed in the solution,
Although a fairly uniform film can be produced by forming a solution from this blend solution, phase separation still occurs on the order of submicrons, which is one of the causes that mechanical properties are not improved. Further, there is a drawback that after a long time at a high temperature, phase separation further progresses and mechanical properties are deteriorated. In JP-A-1-252640, a block copolymer of the above two types of polymers is prepared. However, even if one of the polymers is an aliphatic polycarbonate and has extremely poor heat resistance, even if an aromatic polyamide is blocked, the heat resistance is low. There is not much improvement.

The present invention solves this problem and provides a resin composition which is particularly preferable for a heat-resistant film excellent in mechanical properties, chemical properties (mainly, moisture absorption properties), economy (cost), and stability at high temperatures. The purpose is to do.

[Means for Solving the Problems] The present invention includes an aromatic polycarbonate / aromatic polyamide block copolymer comprising an aromatic polycarbonate segment and an aromatic polyamide segment in a range of 10% by weight or more and 100% by weight or less. The present invention relates to an aromatic polycarbonate / aromatic polyamide block copolymer composition characterized by the following.

The aromatic polycarbonate segment of the present invention preferably contains at least 50 mol% of a repeating unit represented by the following formula (I), more preferably at least 70 mol%. The aromatic polyamide segment is represented by the following formula (I
Those containing 50 mol% or more of the repeating unit represented by I) are preferable, and those containing 70 mol% or more are more preferable.

Here, Ar ₁ , Ar ₂ , and Ar ₃ have one or more structures containing at least one aromatic ring, and may have the same composition or different structures. Representative examples of these are as follows.

In addition, some of the hydrogens on these aromatic rings are halogen groups (especially chlorine and bromine), nitro groups, C _{1 to} C ₃ alkyl groups (especially methyl groups), and C _{1 to} C ₃ alkoxy groups. And those substituted with a substituent such as X is -O-,
—CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO— and the like. These are included in the form of homopolymer or copolymer.

As the aromatic polycarbonate segment, in terms of good compatibility with the aromatic polyamide, Having both the basic skeleton A and the structure of C = O are preferable. The basic skeleton A may have a substituent, for example, a halogen group.

Further, as the aromatic polyamide segment, from the viewpoint of improving heat resistance, which is one of the objects of the present invention, A
r ₂ and Ar ₃ are preferably mainly para-oriented and rigid structures,
Further, those having a substituent such as a halogen group or an alkyl group on the aromatic ring are more preferable because of high solubility in a solvent and compatibility with a polycarbonate and a soluble resin. Further, a halogen group is preferable because it improves the humidity characteristics of the obtained film. Further, solubility in solvents, from the viewpoint of compatibility with the soluble resin is _{high, -O -, - CH 2 -} , - SO 2 -, - S -, - CO- is two aromatic rings via a It is also preferable that the bonded structure is copolymerized, but if it is too large, the thermal characteristics, mechanical characteristics, and humidity characteristics are adversely affected.

Ar ₂ : (Ar ₄ ) _a (Ar ₅ ) _b (Ar ₆ ) _c Ar ₃ : (Ar ₇ ) _d (Ar ₈ ) _e where a + b + d + e ≧ 0.5 b + e ≧ 0.5 c <0.4 Ar ₄ , Ar ₇ : Ar ₅ , Ar ₈ : A group in which Ar ₄ and Ar ₇ are substituted with a nucleus (eg, halogen). Ar ₆ : Is preferable. Ar ₂ , Ar ₃
The groups other than Ar ₄ , Ar ₅ , Ar ₆ , Ar ₇ , and Ar ₈ constituting the above are not particularly limited as long as the above formula is satisfied.

For example, (Where p and q are integers from 1 to 4, p + q ≧ 1) (Where q is an integer of 0 to 4) and an aromatic polyamide / aromatic polycarbonate block copolymer having one or more aromatic polyamide segments represented by, for example, an aromatic polyamidese or a soluble resin. Is extremely stable even when stored for a long time, and the resulting film is tough and has excellent heat resistance and humidity characteristics.

The proportion of the aromatic polycarbonate / aromatic polyamide block copolymer constituting the aromatic polycarbonate / aromatic polyamide block copolymer composition of the present invention is at least 10% by weight, preferably at least 20% by weight, based on the composition. ,
It is more preferably at least 30% by weight, even more preferably at least 50% by weight, and needs to be at most 100% by weight. If the amount is less than 10% by weight, the effect of the aromatic polycarbonate / aromatic polyamide block copolymer as a compatibilizer is not sufficiently exhibited, and almost no improvement in mechanical properties is observed as compared with the case where it is not present.

The constituents of the block copolymer and the composition of the present invention are not limited, but the effect is more remarkable when two or more kinds of polymers are used. The best effect is obtained when the resin is made of an aromatic polyamide and a soluble resin. The aromatic polyamide herein may have the same composition as or a different composition from the aromatic polyamide segment, but the same composition is preferable because the compatibility between the polymers is high and the mechanical strength is easily improved. In addition, the soluble resin means one or more resins that dissolve 1% by weight or more in a solvent that dissolves the above-described block copolymer alone or in both of the aromatic polyamide and is not particularly limited. . As a common solvent for dissolving the aromatic polyamide, the block copolymer and the soluble resin, an organic solvent is preferable in consideration of ease of handling and the like, and N-methyl-
Examples include amide polar solvents such as 2-pyrrolidone, dimethylacetamide, hexamethylenephosphoramide, dimethylformamide, and dimethylimidazolidinone, and dimethyl sulfone. Particularly, N-methyl-2-pyrrolidone and N-methyl-2- Mixtures of pyrrolidone and other amide polar solvents are preferred. When using these solvents, in particular, polycarbonate, polyvinylidene fluoride,
Polymethyl methacrylate, polystyrene, polyvinyl alcohol, polyether sulfone, polysulfone,
Polyarylate, polysulfide sulfone, polyether imide and the like are preferable, and an amorphous resin excellent in improvement in mechanical properties at high temperature and excellent in humidity properties, for example, polycarbonate, polyether sulfone, polysulfone, polyarylate, polysulfide sulfone is preferred. More preferred. In particular, The resin having both the basic skeleton A and the structure of C ＝ O is very good in compatibility with the block copolymer or the aromatic polyamide. Therefore, the resin having at least one of the block copolymer and the soluble resin or the aromatic polyamide is preferred. It is more preferable because a blend solution obtained by dissolving either of them in the above-mentioned solvent is excellent in long-term storage stability, and a film excellent in mechanical properties and transparency is obtained. For example, polycarbonate, polyarylate and the like can be mentioned, and polycarbonate is more preferred from the viewpoint of economy. The basic skeleton A may have a substituent, for example, a halogen group. Further, in the composition of the block copolymer, the aromatic polyamide, and the soluble resin, another resin as the fourth component is preferably 30% by weight or less, more preferably 20% by weight or less of the block copolymer, and still more preferably. Is 15
% By weight. For example, when polycarbonate is used as a soluble resin, adding polyethersulfone, polysulfone, or the like thereto improves mechanical properties. In addition, in addition to the above solvents, good solvents for the soluble resin, for example, dioxane, tetrahydrofuran, methylene chloride, chloroform, 1,1,2-trichloroethane, tricrene, acetone, toluene, and the like, the soluble resin and the aromatic polyamide are compatible. If it is within a range that does not hinder the reaction, that is, within 20% by weight of the total solvent amount, preferably within 15% by weight, it may be used.

The amount of the aromatic polyamide segment of the present invention is preferably in the range of 5% by weight to 90% by weight of the block copolymer. If the amount of the aromatic polyamide segment is less than this range, the effect of improving the heat resistance may be lost, and the mechanical properties at high temperatures may be extremely deteriorated. Preferably 7% by weight or more, more preferably 10% by weight
That is all. On the other hand, if the amount of the aromatic polyamide is larger than this range, there is no economic merit and the humidity characteristics are deteriorated. It is preferably at most 70% by weight, more preferably at most 50% by weight.

As described above, or a block copolymer solution,
A film can be obtained by forming a solution of a composition comprising at least one of the aromatic polyamide and the soluble resin and the block copolymer into a solution.

The thermal dimensional change at 250 ° C. under a load (0.5 kg / mm ² ) in at least one direction of the film made of the block copolymer composition of the present invention is preferably 50% or less. If it is larger than 50%, it cannot be used in a case where tension is applied at a high temperature represented by thermal transfer applications. It is preferably at most 40%, more preferably at most 20%.

The heat shrinkage at 250 ° C. in at least one direction of the film comprising the block copolymer composition of the present invention is preferably 20% or less. More preferably 10% or less, further preferably 5%
It is as follows. If it is larger than 20%, the dimensional stability is poor, and for example, it cannot be put to practical use in the fields of thermal transfer applications, flexible circuit boards, and capacitors. The heat shrinkage at 200 ° C. in at least one direction is preferably 10% or less, more preferably 5% or less. 300 in at least one direction
The heat shrinkage at 30 ° C. is preferably 30% or less, more preferably 20% or less. Further, the coefficient of thermal expansion in at least one direction is 5
It is preferably at most 10 × 10 ⁻⁵ / ° C., more preferably at most 4 × 10 ⁻⁵ / ° C. If it exceeds 5 × 10 ^-5 / ° C, it cannot be used for flexible circuit boards.

The moisture absorption of the film comprising the block copolymer composition of the present invention is preferably 5% or less. It is more preferably at most 3%, further preferably at most 1%. If it is more than 5%, the dimensional change due to moisture absorption becomes large, and it is not practical. The coefficient of humidity expansion in at least one direction is 5 × 10 ₋₅ /%
RH or less is preferred. It is more preferably 4 × 10 ⁻⁵ /% RH or less.

The film comprising the block copolymer composition of the present invention preferably has an elongation at break in at least one direction of 10% or more. It is more preferably at least 15%, further preferably at least 20%. If it is less than 10%, the film will be broken during handling and processing of the film, which is not practical. The strength in at least one direction is preferably 5 kg / mm ² or more, more preferably 7 kg / mm ² or more, and further preferably 9 kg / mm ² or more. At least one direction of the Young's modulus is preferably 150 kg / mm ² or more, more preferably 200 kg / mm ^/ or. Further, the F-5 value (strength at an elongation of 5%) in at least one direction of the film is preferably 4 kg / mm ² or more, more preferably 6 kg / mm ² or more.

The thickness of the film comprising the block copolymer composition of the present invention is preferably from 1 to 500 μm, more preferably from 2 to 200 μm. The density of the film is preferably 1.2~1.5g / cm ^3, more preferably 1.2~1.4g / cm ^3.

The dielectric constant (1 kHz) of the film comprising the block copolymer composition of the present invention is preferably from 3 to 7. The dielectric loss tangent (1 kHz) is preferably 3% or less. More preferably 2.5
% Or less.

The light transmittance of the film comprising the block copolymer composition of the present invention is preferably 50% or more. More preferably,
60% or more.

The average surface roughness (Ra) of the film comprising the block copolymer composition of the present invention is preferably from 10 to 500 nm, more preferably from 30 to 300 nm. Within this range, workability during processing and traveling performance during use are further improved, which is particularly desirable.
In order to achieve this surface roughness, it is effective to add inorganic and organic fine particles.

In addition, the film made of the block copolymer composition of the present invention preferably has a tear resistance in at least one direction of 0.01 kg / μm or more. If it is less than this, the film will be broken during handling and processing of the film, which is not practical.
More preferably, it is 0.1 kg / μm or more, and still more preferably 0.1 kg / μm.
3 kg / μm or more.

Next, a method for producing the block copolymer composition of the present invention will be described, but the present invention is not limited thereto.

The block copolymer of the present invention is a reaction between an aromatic polycarbonate having a phenolic hydroxyl group at both ends and an aromatic polyamide having an isocyanate group at both ends, an aromatic polycarbonate having a carboxylic acid at both ends and an amino at both ends. It is synthesized from a reaction with an aromatic polyamide having a group. Aromatic polyamide having isocyanate groups at both ends is obtained by reaction of diisocyanate with dicarboxylic acid, and aromatic polyamide having amino groups at both ends is obtained by reaction of diacid chloride with diamine or dicarboxylic diamine. The reaction between the diisocyanate and the dicarboxylic acid is carried out in an amide-based polar solvent in the presence of a catalyst, usually at a high temperature (50 to 200 ° C). In the case of using diacid chloride and diamine, it is synthesized by solution polymerization in an amide-based polar solvent such as N-methyl-2-pyrrolidone or dimethylacetamide, or by interfacial polymerization using an aqueous medium. Diacid chloride and diamine are mixed at low temperature (usually 50 ° C. or lower, preferably 30 ° C.) in a low moisture amide polar solvent.
℃ or less) and polymerized with stirring for 1 to 2 hours. The order of adding the monomers is not particularly limited. Hydrochloric acid generated after the polymerization is neutralized with an inorganic alkali or an organic neutralizing agent.
The reaction between the zirconic acid and the diamine is performed by a so-called direct polymerization method using an active phosphoric acid ester or the like in an amide-based polar solvent. The polymer solution obtained by these reactions may be used as it is as a stock solution for the next block reaction.For aromatic polyamides having amino groups at both ends, the polymer is isolated once and then redissolved in a solvent for blending. A stock solution may be prepared. When isolated, it is necessary to sufficiently purify and dry it before use in the next block reaction. In addition,
The intrinsic viscosity of the aromatic polyamide is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.0 or more in consideration of the mechanical properties of the finally obtained film. The upper limit is not particularly defined, but is preferably 10.0 or less.

In order to improve the mechanical properties of the resulting film, it is necessary to keep the molecular weight of the polymer above a certain level,
The average degree of polymerization m and n of (I) and (II) is preferably 3 or more, more preferably 10 or more. However, if the molecular weight is too high, the viscosity of the solution increases, which is not practical.
Is preferably 400 or less, more preferably 200 or less.

A two-terminal reactive aromatic polyamide obtained as described above and an aromatic polycarbonate having a phenolic hydroxyl group or a carboxylic acid at both terminals, in an amide solvent,
The reaction is carried out using a catalyst corresponding to each reaction to obtain a target block copolymer. This reaction solution may be used as it is in the following stock solution for blending or film formation, or may be once isolated by reprecipitation or the like. These stock solutions include
In some cases, an inorganic salt such as calcium chloride or magnesium chloride is added as a dissolution aid. This blocking reaction is a reaction between polymers, and 100% is unlikely to occur. Therefore, when only a block copolymer is required, it is described in Chapter 3 of the book “Polymer Solution” (Kyoritsu Shuppan). Separation and separation can be performed by any method. Moreover, you may use it as it is as mentioned below.

As a method for producing a block copolymer composition comprising at least one of an aromatic polyamide and a soluble resin and a block copolymer, an aromatic polyamide or a soluble resin is added to a solution of the amide solvent of the block copolymer. Is dissolved, or blended with a solution in which aromatic polyamide or soluble resin is dissolved in advance, or aromatic polyamide and soluble resin are separately prepared as raw stock solutions, and the stock solutions are blended with each other or the soluble resin is dissolved. By adjusting the amide-based polar solvent and performing the above-mentioned polymerization of the aromatic polyamide in the polymerization and simultaneously performing the polymerization and the blending, the film from the solution obtained by further blending with the blended solution and the block copolymer solution can be used. It is obtained by molding into. When synthesizing the block copolymer, a homopolymer which is not blocked may be used without separation. The apparent intrinsic viscosity obtained from the stock solution for film formation thus obtained is preferably 0.1 to 8.0, more preferably 0.2 to 5.0. The solution viscosity can be freely selected, but is preferably 5 to 50,000 poise / 30 ° C., more preferably 10 to 20,000 poise from the viewpoint of castability. The polymer concentration is preferably 1 to 50%, more preferably 5 to 30%.

This stock solution for forming a film is formed into a film by the following method. First, a dry-wet method is used. The film is cast on a support in the form of a film using a doctor knife, a mouthpiece, or the like, and dried at a temperature usually in the range of 50 to 250 ° C, more preferably 60 to 200 ° C, for a certain time. If the temperature is lower than 50 ° C., the evaporation rate of the solvent is slow, and if it exceeds 250 ° C., bumping of the solvent occurs, resulting in deterioration of the film quality. The dried film is peeled from the support, and immersed in or sprayed with an aqueous medium to extract the inorganic salt and the solvent. The aqueous medium is a liquid containing water as a main component and is a poor solvent for polymers, but a liquid having an affinity for inorganic salts and amide polar solvents.
For example, water alone, a mixture of water and an amide-based polar solvent constituting a stock solution, water and ethylene glycol, acetone,
A mixture with a lower alcohol may be mentioned, but at least 50% or more of water is desirable in consideration of the desalting / desolvation rate and solvent recovery. The temperature of the wet bath is usually 5 to 5.
90 ° C is appropriate. In the wet process, an inorganic salt serving as a dissolution aid and an amide-based polar solvent are extracted. In the film immediately after the completion of the wet process, the residual amount of the inorganic salt is 3% or less per polymer, more preferably 1%. The following is good. The residual ratio of the amide polar solvent is not particularly limited, but it is advantageous to extract as much as possible in consideration of solvent recovery. Since the film in the wet process is in a state of swelling with an aqueous medium, it can be easily stretched in the wet temperature range, and the mechanical properties of the final film have been improved.In general, the film is stretched in the longitudinal direction 1.01 to 5.0 times in the process. You. The film after the wet process is subjected to a heat treatment for evaporating the aqueous medium and evaporating the amide polar solvent.
In this heating step, finally 100 ℃ or more, preferably 200 ℃
The treatment is carried out at a temperature of at least 500 ° C., but once the moisture is dried at 50 to 100 ° C. (the amount of moisture is up to 20% by weight or less based on the weight of the film), and then the heat treatment is carried out at the above temperature. This is preferable because a film having characteristics can be easily obtained. In the heating step, the film is stretched 1.01 to 5.0 times in the transverse direction. Also, there is no problem if relaxing is performed as needed.

Next, the wet method is a method of directly extruding from a die into an aqueous medium (which may contain 0 to 100% by weight of an alcohol such as methanol or ethanol) without a dry step in the dry-wet method. Because it contains a large amount of amide-based polar solvents, etc., the rapid replacement of inorganic salts and amide-based polar solvents in aqueous media is likely to cause the generation of voids or roughening of the film in the final film. An inorganic salt such as calcium chloride, lithium chloride, or lithium bromide is contained in the aqueous medium to control the substitution rate as necessary, or the water tank is multi-staged, and water and an amide polar solvent / inorganic are used. For example, a mixture of salts has a concentration gradient. Like the dry-wet method, the film may be stretched 1.01 to 5 times in the machine direction in this step. The film after the wet process is subjected to heat treatment (200-500 ° C) and transverse stretching (1.01
~ 5.0 times). Before the heating, it is preferable to dry the water once at 50 to 100 ° C., and the drying is performed by a hot roll or hot air, and in some cases, the longitudinal stretching of 1.01 to 5 times is also performed.

Next, a dry method is used. This method is a process in which the extraction step is omitted, contrary to the wet method, and is a method that can be performed only by using an organic solvent and not containing an inorganic salt as a dissolution aid in a stock solution for film formation. The undiluted solution cast on the support from a doctor knife or mouthpiece is dried and peeled off from the support in the same manner as the wet-wet method, and 1.
Stretched 01 to 5.0 times. The film subjected to the dry process is subjected to the same heat treatment and stretching as in the dry-wet process. As described above, a heat-resistant film can be obtained.

A film comprising the composition of the present invention thus obtained is a thermal transfer ribbon, a printed circuit board, a capacitor,
There are applications such as electrical insulation materials, especially thermal transfer ribbons,
Printed circuit boards and capacitor applications are desirable.

[Examples] Next, embodiments of the present invention will be described based on examples, but the present invention is not limited thereto. In addition, the measuring method of the characteristic in an Example is as follows.

Intrinsic viscosity (ηinh) The intrinsic viscosity was measured using an Ubbelohde viscometer under the conditions of 0.5 g / 100 ml and 30 ° C. using N-methyl-2-pyrrolidone as a solvent according to the following equation.

Solution Viscosity (Poise) Measured at a temperature of 30 ° C. using a rotary B-type viscometer (Tokyo Keiki).

Tensile elongation, Young's modulus, F-5 value 10mm width, 50mm length, pulling speed 3 with TRS type tensile tester
It was measured under the condition of 00 mm / min.

Heat shrinkage (%) The sample was placed in an oven without load at a predetermined temperature for 10 minutes, returned to room temperature, measured for dimensions, and calculated by the following formula.

Moisture absorption (%) The film weight was measured after absolute drying at 150 ° C. for 60 minutes and after standing in 75% RH for 48 hours, and was calculated by the following formula.

Moisture absorption = (75% RH, film weight after standing for 48 hours−film weight when absolutely dry) / film weight when absolutely dry × 100
(%) Coefficient of thermal expansion (α) To eliminate the effect of moisture absorption and desorption on thermal shrinkage,
It calculated from the dimensional change in the 80-150 degreeC area | region at the time of heating to ℃ and gradually cooling. The dimensional change was measured by a thermomechanical analyzer (TMA).

Humidity expansion coefficient (β) Dehumidification (about 30% RH) and humidification (about 80%)
% RH), the film length at the time of equilibrium was read, and the difference (elongation) was obtained from the following equation.

[Delta] H: humidification time and humidity difference when dehumidification (% RH) 10 minutes at a temperature 250 ° C. over a thermal dimensional change rate load 0.5 kg / mm ² under load, placed in an oven, measure the dimensions returned to room temperature , Calculated by the following formula.

Dielectric constant, tan δ Measured according to ASTM-D-150-81.

Light transmittance was measured according to ASTM D-1003.

Tear resistance was measured according to JIS-C-2318, and was converted per 1 μm thickness.

Molecular weight, molecular weight distribution, degree of polymerization Measure the absolute molecular weight distribution by GPC-LALLS method using NMP as a solvent (including 0.01M LiCl), find the number average molecular weight, and divide by the molecular weight of the monomer unit using this to polymerize I asked for degrees.

Average surface roughness (Ra) It was measured using a high-precision thin film step measuring device ET-10 manufactured by Kosaka Laboratory. The conditions are as follows, and the value was determined by averaging 20 times.

・ Stylus tip radius: 0.5 μm ・ Stylus load: 5 mg ・ Measurement length: 1 mm ・ Cutoff value: 0.08 mm The definition of Ra can be found, for example, in Jiro Nara, “Method of measuring and evaluating surface roughness” (General Technology Center, 1983).

All parts used in the following examples are parts by weight.

Example 1 75 mol% of 2-chloroparaphenylenediamine (hereinafter C
PA) and 25 mol% of 4,4'-diaminodiphenyl ether (hereinafter abbreviated as 4,4'-DAE), 97 mol% of 2-chloroterephthalic chloride (hereinafter abbreviated as CTPC) and N-methyl-2- The reaction was carried out at 20 ° C. or lower in pyrrolidone (hereinafter abbreviated as NMP) to obtain an NMP solution of an aromatic polyamide having a number average molecular weight of 15,000 (degree of polymerization: about 50). This solution was poured into a large amount of water, purified after reprecipitation, and dried sufficiently to obtain a powdery polymer. The intrinsic viscosity was 2.4. 20 parts of this polymer and a polycarbonate having a carboxylic acid at both ends (number average molecular weight
20 parts of 20000, bisphenol A type) were dissolved in 200 parts of NMP, and 1.0 part of triphenyl phosphite, 0.5 part of pyridine and 0.17 part of cetyltrimethylammonium chloride were added, and reacted at 110 ° C. for 3 hours. After the reaction, the precipitate was purified by reprecipitation in a large amount of methanol, and the GPC was measured after drying.As a result, it was observed that the peak was shifted to the high molecular weight side, and there were some shoulders. Part of the polycarbonate was extracted. After extraction, GPC was measured again. However, since there was still a shoulder based on the unreacted aromatic polyamide on the low molecular weight side, fractionation was performed using large-capacity GPC to obtain an almost pure block copolymer.

10 parts of this block copolymer was dissolved in 70 parts of NMP, uniformly cast on a glass plate using an applicator, dried in an oven at 130 ° C. for 7 minutes, and then heat-treated at 300 ° C. for 1 minute to a thickness of 10 μm. The final film was obtained. The obtained film has a tensile elongation of 32%, a tensile strength of 14 kg / mm ² , and a Young's modulus of 435 k.
g / mm ² , F-5 value 12 kg / mm ² , end crack resistance 0.58 kg / μm, heat shrinkage at 250 ° C. for 10 minutes 0.5%, load under 250 ° C. (0.5 kg / mm ² ) 17% thermal dimensional change, thermal expansion coefficient (α)
Is 1.9 × 10 ^-5 / ° C, the moisture absorption is 0.9%, and it is tough and has humidity characteristics.
The film had excellent heat resistance.

Example 2 100 mol of 3,4'-diphenyl ether diisocyanate
% And terephthalic acid 98 mol% are dissolved in NMP and reacted at 120 ° C. for 2 hours using terephthalic acid monosodium salt as a catalyst.
An aromatic polyamide having isocyanate groups at both ends was obtained. After the polymerization is completed, a small amount of a sample for GPC measurement is collected, and has a phenolic hydroxyl group at both ends and a number average molecular weight of 25.
000 polycarbonate (bisphenol A type) was added in an amount of 20 parts to 10 parts of the aromatic polyamide.
The reaction was carried out at 2 ° C. for 2 hours. After completion of the reaction, the precipitate was reprecipitated in a large amount of methanol and dried. According to GPC, the number average molecular weight of the aromatic polyamide before adding the polycarbonate was 17,000. Also, the polymer finally obtained from GPC was found to be a composition consisting of a block copolymer, an aromatic polyamide and a polycarbonate, and their weight ratio from the amount extracted with methylene chloride was 40:15. : 45.

The undiluted solution for film formation was uniformly cast on a glass plate using an applicator, and dried in an oven at 120 ° C. for 8 minutes.
It was peeled off from the glass plate and immersed in running water for 10 minutes. Once dried in an oven at 100 ° C under tension,
Heat treatment was performed at 00 ° C. to obtain a final film having a thickness of 9 μm. The resulting film has a tensile elongation of 28% and a tensile strength of 22 kg / m.
m ² , Young's modulus 380 kg / mm ² , F-5 value 18 kg / mm ² , end crack resistance 0.44 kg / μm, heat shrinkage at 250 ° C. for 10 minutes is 2.3
%, Thermal dimensional change under load of 250 ℃ (0.5kg / mm ² ) is 15%,
The coefficient of humidity expansion (β) is 1.6 × 10 ^-5 / ° C, the moisture absorption is 1.0%,
The average surface roughness was 75 nm, which was tough and excellent in humidity characteristics, heat resistance and workability.

Example 3 A composition comprising 10 parts of a block copolymer obtained in the same manner as in Example 1, 25 parts of an aromatic polyamide obtained from 100 mol% of 4,4'-DAE and 100 mol% of CTPC, and 65 parts of polyether sulfone Thus, a film was produced in the same manner as in Example 1. Elongation at break of the obtained film is 25% and strength is 10 kg / m.
m ² , Young's modulus 285 kg / mm ² , end crack resistance 0.51 kg / μm, thermal shrinkage at 250 ° C for 10 minutes 1.2%, thermal dimensional change under load at 250 ° C (0.5 kg / mm ² ) Was 18% and the moisture absorption was 0.8%, which was tough and excellent in humidity characteristics and heat resistance.

[Effects of the Invention] The present invention provides a composition containing a predetermined amount of a specific aromatic polycarbonate / aromatic polyamide block copolymer, so that, for example, a film made of the composition has a softening pour point of an aromatic polycarbonate resin. It does not flow even at the above temperature, it has a small heat shrinkage at high temperature and has excellent dimensional stability, and it is suitable for a single film of aromatic polycarbonate resin or a film made of a blend resin of aromatic polyamide and aromatic polycarbonate resin. Mechanical properties,
In particular, it is excellent in elongation at break and strength, which facilitates handling and handling during processing. Furthermore, the humidity characteristics (particularly, hygroscopicity), which is said to be the greatest drawback of the aromatic polyamide, are improved.

In addition, the aromatic polycarbonate / aromatic polyamide block copolymer of the present invention and the aromatic polyamide or the aromatic polycarbonate resin have very good compatibility, so that the solution of the composition has excellent long-term stability, and Since the block copolymer functions as a compatibilizer, two types of polymers are easily finely dispersed in the obtained film, and the generation of microvoids at the interface is suppressed, so that the film is excellent in mechanical properties and transparency.

Furthermore, a relatively inexpensive aromatic polycarbonate resin is block-copolymerized with an aromatic polyamide, so that the production cost of the film can be reduced.

In addition, when the composition of the present invention is used not only as a film but also as a fiber or a molded article, a composition excellent in mechanical strength, impact resistance and the like can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 81/00 C08L 69/00 C08L 77/10 C08G 64/18 C08G 69/00-69/42

Claims (3)

(57) [Claims] 1. An aromatic polycarbonate comprising an aromatic polycarbonate / aromatic polyamide block copolymer comprising an aromatic polycarbonate segment and an aromatic polyamide segment in a range of 10% by weight or more and 100% by weight or less. Aromatic polyamide block copolymer composition. 2. An aromatic polycarbonate / aromatic polyamide block copolymer comprising at least one of an aromatic polyamide and a soluble resin, and an aromatic polycarbonate segment and an aromatic polyamide segment. The aromatic polycarbonate / aromatic polyamide block copolymer composition according to (1). 3. The aromatic polycarbonate / aromatic polyamide block copolymer composition according to claim 2, wherein the soluble resin is an aromatic polycarbonate.