JPS6255552B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel aromatic polyamide-polyester composition, and more particularly to an aromatic polyamide-polyester composition with improved crystallization rate of polyethylene terephthalate. Polyester, such as polyethylene terephthalate, is used in various fields as a molding material, but its crystallization rate is very slow at the mold temperature used for normal molding, that is, 70 to 110°C, so it is not used as a molding material. There are technical and equipment issues that need to be resolved before it can be used as a fuel cell. For this reason, methods to promote the crystallization of polyethylene terephthalate have been by adding inorganic fine powders such as talc or graphite, or by combining sodium salts of carboxylic acids and low-molecular organic ester plasticizers. A method has been proposed in which crystal nucleation is promoted by using However, the former has a small effect of promoting crystallization, and the latter has too many limitations in terms of properties, so it cannot be said to be a very suitable method in practice. Therefore, when molding polyethylene terephthalate, special measures must be taken, such as heat treatment after molding to promote crystallization, or the use of a special high-temperature mold that can reach a mold temperature of 120 to 15°C. However, these methods could not be said to be satisfactory because they would require an increase in processing steps and equipment costs if they were to be implemented industrially. The present inventor has been conducting research on compositing aromatic polyamide with other resins for some time, and found that when a certain type of aromatic polyamide is composited with polyethylene terephthalate, the crystallization of polyethylene terephthalate is promoted. Based on this finding, the present invention was completed. That is, the present invention provides a composition comprising polyethylene terephthalate and an aromatic polyamide, wherein the aromatic polyamide has the general formula -NH-Ar ₁ -NH-...(1) (wherein Ar ₁ is divalent diamine residue represented by the general formula -CO-Ar ₂ -CO- ...(2) (Ar ₂ in the formula is a divalent aromatic group) Repeating units consisting of acid residues or repeating units consisting of aminocarboxylic acid residues represented by the general formula -NH-Ar ₃ -CO- ...(3) (Ar ₃ in the formula is a divalent aromatic group) Blocks and general formulas in which at least three repeating units or both repeating units are combined (R ₁ and R ₂ in the formula are divalent hydrocarbon groups) or an ester group represented by the general formula (R ₃ in the formula is a divalent hydrocarbon group) It is composed of a block in which at least three repeating units consisting of an ester group represented by the formula (R 3 is a divalent hydrocarbon group) or both are bonded, and the (a) block is connected to the component (A). against 0.01
-10% by weight, and the half width of the exothermic peak in the crystallization temperature range of polyethylene terephthalate is 10°C or less when measured using a differential scanning calorimeter. be. To explain in more detail, the composition of the present invention includes:
It is a mixture of (a) polyethylene terephthalate component and (B) aromatic polyamide component, and the aromatic polyamide component has the general formula (-NH- _Ar1 -NH-CO- _Ar2 -CO) _-n1 and (−NH—Ar ₃ —CO)−n ₂ (Ar ₁ , Ar ₂ and Ar ₃ in the formula have the same meanings as above, and n ₁ and n ₂ or n ₁ + n ₂ indicate an average degree of polymerization of 3 or more. A block consisting of one or both of the amide units represented by as well as (R ₁ , R ₂ and R ₃ in the formula have the same meanings as above,
m ₁ and m ₂ or m ₁ +m ₂ is a number representing an average degree of polymerization of 3 or more). In the composition of the present invention, it is necessary that the half width of the exothermic peak in the crystallization temperature range of 8 mg of polyethylene terephthalate in differential scanning calorimetry (DSC) be 10°C or less. The polyethylene terephthalate used as component (A) of the present invention can be arbitrarily selected from conventionally known polyethylene terephthalates, but usually the polyethylene terephthalate has a reduced specific viscosity (η
It is preferable to select a material with sp/c) of 0.3 or more depending on the purpose. Next, component (B) is a block copolymer consisting of an aromatic polyamide block and a polyester block.
Examples of Ar 1 , Ar ₂ and Ar 3 in (1), ( ₂ ) and ( ₃ ) include m-phenylene, 3,4'-biphenylene,
1,3-naphthylene, 1,6-naphthylene, 1,
7-naphthylene, 2,4-pyridylene,

[Formula] (where X is -NH ₂ -, -O-, -NH-, -CO-, -SO ₂ -, -
OCH ₂ CH ₂ O-, etc.), but preferred are 4,4'-biphenylene,
1,4-naphthylene, 1,5-naphthylene, 2,
6-naphthylene, 2,5-pyridylene,

[Formula] (where X' is - CH ₂ CH ₂ -, -N=N-,

[Formula]

[Formula]-CH=N-),

[Formula] (where Y is -SO ₂ -, -CO-, -CH ₂ -), particularly preferred is p
-It is phenylene. These aromatic moieties may contain an inert group such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, or an alkoxycarbonyl group as a nuclear substituent. This aromatic polyamide block has the general formula
Diamine units of (1) and/or dicarboxylic acid units of general formula (2), diamine units of general formula (1), dicarboxylic acid units of general formula (2), and aminocarboxylic acid units of general formula (3), or It is formed only from aminocarboxylic acid units of the general formula (3), and the sum of the repeating numbers thereof may be at least 3, and may be selected as appropriate depending on the use of the composition of the present invention. For example, in the composition of the present invention,
If a reinforcing effect is expected from component (B), the larger the sum of the number of repetitions, the better the results will generally be obtained.If a highly finely dispersed state is required, the number of repetitions will be increased The smaller the sum, the better. Usually, an aromatic polyamide block having a sum of repeating numbers of 200 or less, preferably 100 or less, and a melting temperature of 220°C or higher, preferably 250°C or higher is used. The polyester block in component (B) is composed of the polyester group represented by the general formula (4) or the polyester group represented by the general formula (5), or both. The sum of the number of repeating units depends on the sum of the number of repeating units in the aromatic polyamide block, the intended use of the composition, the type of ester molecule, etc.
Selected within the range of at least 3. Organic residues R ₁ , R ₂ and
R ₃ is a divalent hydrocarbon group, which may be an aliphatic group or an aromatic group. Such examples include methylene, ethylene, trimethylene, tetramethylene, p-benzylene, 1,4-
Cyclohexylene, p-phenylene, m-phenylene, 4,4'-biphenylene, 1,4-naphthylene, 1,5-naphthylene, 2,6-naphthylene,

【formula】

Examples include [Formula]. Usually, it is preferred that the polyester block has a melting temperature in the range of 120°C to 290°C. Particularly preferred is the case where R ₁ is ethylene or tetramethylene and R ₂ is p-phenylene in general formula (4). Component (B) used in the present invention can be produced according to a known method commonly used in the production of block copolymers. For example, a method in which an aromatic polyamide block part and a polyester block part are produced separately, and then they are directly reacted or bonded using a linking agent such as diisocyanate, dicarboxylic acid chloride, glycol, diamine, etc. A method in which an aromatic polyamide block part is first produced and then a polyester block part is produced in the reaction system, or a method in which a polyester block part is first produced and the aromatic polyamide block part is formed in its presence and simultaneously linked. Manufactured by etc. A preferred method for producing component (B) is:
Diamines represented by the general formula H ₂ N―Ar ₁ -NH ₂ (Ar ₁ in the formula has the same meaning as above) and general formula ClCO―Ar ₂ - COCl (Ar ₂ in the formula has the same meaning as above). dicarboxylic acid dichloride represented by ) with an organic solvent such as N,N-dimethylacetamide, N,
N,N',N'-tetramethylurea, hexamethylphosphoramide, N-methylcaprolactam, N
The aromatic polyamide block portion is produced by polymerization reaction in methyl-2-pyrrolidone, nitrobenzene, dimethyl sulfoxide, tetrahydrofuran, tetrachloroethane, chloroform, or a mixed solvent thereof, and is further produced in advance without isolation. react with a polyester block having a reactive end group such as a hydroxyl group or a carbonyl chloride group, or
Alternatively, in the reaction system in which the aromatic polyamide block part is produced as described above, a diol represented by the general formula HO―R ₁ -OH (R ₁ in the formula has the same meaning as above) and a general formula ClCO―R ₂ -COCl (R ₂ in the formula has the same meaning as above) is reacted with dicarboxylic acid dichloride to form a polyester block part and at the same time connect it with an aromatic polyamide block part. The molecular weight of the polyester portion of the thus obtained block copolymer can be adjusted, if necessary, by further melt polymerizing or transesterifying in the presence of a polyester-forming monomer or polyester. It is also advantageous to prepare the aromatic polyamide block part in advance as described above, add it to the polymerization reaction system of the polyester block part, and connect it to the aromatic polyamide block part while forming the polyester block part. It is. Regarding the ratio of the aromatic polyamide block part and the polyester block part in the component (B) used in the present invention, it is preferable to have a larger amount of polyester block because the compatibility with the component (A) will be greater. If the amount is too large, the average degree of polymerization of the entire composition tends to decrease, especially when the degree of polymerization of the polyester block is low, and the strength tends to decrease. Therefore, the ratio of the aromatic polyamide part to the polyester block part in component (B) is preferably selected within the range of 5:1 to 1:10, preferably 2:1 to 1:5. . The composition of the present invention is prepared by dispersing and compounding component (B) thus produced into component (A) by any means. Methods for this composite include a method of simply melt-mixing polyethylene terephthalate and a block copolymer, a method of dissolving or dispersing the polyethylene terephthalate in a solvent or dispersant, and mixing the two, or a method of mixing the two by dissolving or dispersing them in a solvent or dispersant, or before or during the polymerization process of polyethylene terephthalate. There are methods such as adding component (B) and mixing at the same time as forming polyethylene terephthalate, or preparing a high concentration mixture of component (B) and then adding polyethylene terephthalate thereto and melt-mixing. The mixing ratio of component (A) and component (B) in the present invention is (B)
The aromatic polyamide block in the component, i.e., the (a) block, is 0.01 to 10% by weight, preferably 0.02 to 10% by weight, based on the component (A), that is, polyethylene terephthalate.
The proportion is selected within a range of 5% by weight.
If the purpose is to have a reinforcing effect in addition to promoting crystallization, the amount can be increased depending on the application, but if the purpose is only to promote crystallization, 2% by weight or less is sufficient. The composition of the present invention must have a half-width at half maximum of an exothermic peak based on crystallization of polyethylene terephthalate of 10°C or less as measured by differential scanning calorimeter, that is, a differential scanning calorimeter. It is. This measurement can be carried out in a conventional manner using a commercially available device, such as a PerkinElmer DSC type device. For example, an 8 mg sample of polyethylene terephthalate is heated in a nitrogen atmosphere above the melting point of polyethylene terephthalate to completely melt the polyethylene terephthalate, and then cooled at a rate of 10°C/min to eliminate the exothermic peak associated with crystallization. This is done by recording. When polyethylene terephthalate is measured by differential scanning calorimetry in this manner, an exothermic peak in the crystallization temperature range appears in the range of 180 to 210°C. However, this exothermic peak is usually extremely wide, and when conventional inorganic powder is added as a nucleating agent, the half-width of the peak is usually around 20℃, as shown in Figure 1, even if it is small. 15℃
That's about it. When polyethylene terephthalate is molded using an ordinary mold, the cooling rate of the molten polyethylene terephthalate in the mold is 300 to 400%, especially in the parts that come into contact with the mold surface.
℃/min, the half-width of the exothermic peak in the crystallization temperature range in the differential scanning calorimeter measurement described above is
At about 20°C, the result is that the material is cooled and solidified with almost no crystallization on the mold surface. On the other hand, in the composition of the present invention, the temperature at the exothermic peak due to crystallization during the cooling process measured by differential scanning calorimetry is often 200 to 220°C.
℃, the crystallization temperature range is slightly shifted to the higher temperature side, and the exothermic peak is extremely acute. The half-width of this peak is at least 10°C or lower, preferably 8°C or lower, and 6°C or lower for those exhibiting particularly excellent properties. Therefore, in the case of the composition of the present invention, even if rapid cooling is performed in the mold, crystallization proceeds rapidly, and a molded product with homogeneous and good physical properties in which crystallization is sufficiently achieved can be obtained. is obtained. In addition to molded products, the composition of the present invention can be made into excellent products such as films and fibers. The composition of the present invention contains components (A) and (B) as essential components, but in addition to these, if desired, auxiliaries commonly used in polyester resins, polyamide resins, various films, and various fibers may be added. It may contain additives. Examples of such materials include glass fiber, asbestos fiber, poly-
p-phenylene terephthalamide fiber, carbon fiber, mica, aluminum silicate, glass beads,
Inorganic powders such as talc, coupling agents for these, ultraviolet stabilizers, mold release agents, antioxidants,
Examples include flame retardants, plasticizers, colorants, and other organic polymeric substances. There are no particular restrictions on the means of blending these auxiliary additives, and they may be mixed at the same time as components (A) and (B), or they may be added to either component (A) or component (B) in advance. It may be mixed and then mixed with the remaining ingredients. Furthermore, components (A) and (B) may be mixed and then added to the mixture. The composition of the present invention is suitable as a molding material, but can also be widely used as a material for films, fibers, etc. Next, the present invention will be explained in more detail with reference to Examples. The DSC measurement method, test piece molding, and evaluation method were as follows. (1) DSC measurement The sample was weighed and used in an amount equivalent to 8 mg of component (A), that is, even when glass fiber etc. was blended, the amount of component (A) was 8 mg. A DSC-type manufactured by Perkin-Elmer was used as the measuring device. The measurement was carried out in a nitrogen atmosphere, and the temperature was raised to 290℃, held for 5 minutes, and then cooled at a constant rate of 10℃/min. In this manner, the exothermic peak temperature (Tc) and the exothermic peak half width (ΔT) were determined. (2) Kneading using an extruder After mixing a predetermined amount of the sample in a rotating drum blender, it is mixed using an extruder.
It was extruded into pellets at 260-270°C. The obtained pellets were vacuum dried at 130°C for 5 hours. (3) Molding of test piece The pellets obtained in (2) above were molded using a molding machine (manufactured by Kawaguchi Iron Works).
KC-20). The molding conditions were a cylinder temperature of 270-275-280°C, a mold temperature set to a predetermined temperature, and a molding cycle of 25 seconds. (4) Mold releasability, appearance Mold releasability was determined by separation from the mold from the cavity and sprue during molding described in (3) above. In addition, the appearance was judged using the following symbols based on surface gloss and the presence or absence of avatars. ○: Good, △: Fairly good, ×: Poor (5) Measurement of tensile strength An ASTM No. 1 dumbbell test piece was molded using the method described in (3), and using this, the tensile strength was measured according to ASTMD638. Reference example 1 Reduced specific viscosity (ηsp/c) measured with a tetrachloroethane/phenol (4/6) mixed solvent is 0.61
Polyethylene terephthalate was dried, and the crystallization temperature range and half-width of its exothermic peak were determined by differential scanning calorimetry. That is, first, 8 mg of sample is
When the temperature was raised at a rate of 10°C/min, an endothermic peak at the melting point (T _n ) was observed at 255°C, so the temperature was further increased to 290°C and held at this temperature for 10 minutes. Cooling was performed at a rate of 10°C/min. The relationship between this temperature and the amount of heat generated is shown in FIG. 1 as a graph. To find the half-width of the exothermic peak from this figure, the peak height (h) of the temperature (Tc) at the exothermic peak based on crystallization at 181°C is (1/
Measure the width of the peak at the location corresponding to 2). As a result, it was found that the half width of the exothermic peak was 19°C. This polyethylene terephthalate was heated at 100℃ and 110℃.
When molded in a mold at 120°C and 120°C, the mold release properties were extremely poor (x), and the appearance of the molded product was poor (x) with no smoothness. Therefore, by setting the mold temperature to 150°C, we were finally able to obtain a mold that was almost satisfactory in terms of both mold releasability and appearance. Reference Example 2 Polyethylene terephthalate having an ηsp/c of 0.72 was mixed with 30% glass fiber (chopped strands having a length of 3 mm) using a single-screw extruder. Table 1 shows the results of molding this product. Reference examples 3, 4 2 kg of polyethylene terephthalate with ηsp/c of 0.61, 60 g of talc, and 30% amount of glass fiber (880
g) was kneaded using a single-screw extruder, molded, and evaluated. The results are shown in Table 1. Table 1 shows the results of a similar experiment using polyethylene terephthalate with ηsp/c of 0.72.

[Table] Example 1 (1) A 1-volume reactor equipped with a high-speed stirrer was thoroughly dried by passing heated and dry nitrogen through it, cooled, and 100 ml of dried purified hexamethylphosphoramide, N- Charge 150ml of methyl-2-pyrrolidone and 8g of anhydrous lithium chloride,
Next, 2.25 g of p-phenylenediamine was added and completely dissolved. Next, this solution was cooled to 5 to 10°C, and while stirring vigorously, 4.27 g of terephthalic acid dichloride was added thereto, and after reacting for about 1 hour,
The temperature was raised to 30-40°C, and the reaction was further continued for 1 hour. A part of the produced poly-p-phenylene terephthalamide was taken out from the reaction system, separated by precipitation in water, washed repeatedly with warm water, dried, and the viscosity was measured. As a result, the relative viscosity (η _rel ) when dissolved in 97% concentrated sulfuric acid at a concentration of 0.2 g/100 ml and measured at 35° C. was 1.90, and the average degree of polymerization was about 80. Next, 6.47 g of ethylene glycol and 4.2 g of sodium hydride dispersion were added to the above reaction mixture, and after stirring for 1 hour, 21.1 g of terephthalic acid dichloride was added, and then 4.2 g of sodium hydride dispersion was added.
The reaction continued with vigorous stirring for an hour. The reaction mixture was then poured into a large amount of methanol to precipitate the product, which was separated. The filtered product was washed repeatedly with hot ethanol, further washed with warm water and acetone, and dried. In this way, 22.1 g of a product having a poly-p-phenylene terphthalamide content of approximately 23% by weight as determined from elemental analysis values was obtained. (2) To 10 g of the product obtained as described above, o-chlorophenol was added and heated to dissolve the soluble portion, and then filtered. This o-chlorophenol insoluble portion was further washed with o-chlorophenol, washed repeatedly with ethanol, and dried to obtain 3.4 g of solid content. Elemental analysis revealed that this was a block copolymer consisting of 50 repeating units of polyethylene terephthalate per 80 repeating units of poly-p-phenylene terephthalamide. In addition,
All of the o-chlorophenol soluble portion was polyethylene terephthalate. (3) 0.075 g of the o-chlorophenol-insoluble block copolymer obtained in (2) was added to a solution of 100 ml of hexamethylphosphoramide and 3 g of lithium chloride, heated and dissolved, and this was used in the reference example. The mixture was poured into a nitrobenzene solution containing 5 g of polyethylene terephthalate and stirred vigorously. Next, this was cooled, and a large amount of methanol was injected into it to precipitate and separate the polymer. Next, this polymer was separated, washed repeatedly with methanol, and dried to obtain a mixture of polyethylene terephthalate and block copolymer. This mixture contained about 1% by weight of the poly-p-phenylene terephthalamide block component, and had the results of differential scanning calorimetry measurements shown in FIG. 2 for 8 mg of the sample. As is clear from FIG. 2, the temperature (Tc) at the exothermic peak due to crystallization was 215°C, and at this temperature an extremely sharp exothermic peak was exhibited, with a half-width of 5.3°C. Example 2 Reaction product 1.1 obtained in the same manner as in Example 1 (1)
g (corresponding to about 0.37 g of o-chlorophenol-insoluble block copolymer) and 50 g of the same polyethylene terephthalate used in the reference example were heated at 260 to 280°C using a small kneading tester under a nitrogen atmosphere. The mixture was kneaded, taken out under a nitrogen atmosphere, and cooled. When this mixture was subjected to differential scanning calorimeter measurement in the same manner as in the reference example, the temperature at the exothermic peak due to crystallization was 213°C, and the half-width of the exothermic peak at that time was 5.5°C. In this case, the content of poly-p-phenylene terephthalamide block component relative to polyethylene terephthalate is approximately
It is 0.5% by weight. Example 3 Reaction product 2.2 obtained in the same manner as in Example 1 (1)
g, 50 g of the same polyethylene terephthalate used in the reference example, and 10 g of glass fiber were kneaded in the same manner as in Example 2, and 10 mg of the resulting mixture (8 mg as polyethylene terephthalate) was measured with a differential scanning calorimeter. . The temperature at the exothermic peak due to crystallization was 215°C, and the half width of the exothermic peak at that time was 5.3°C. In this case, the content of poly-p-phenylene terephthalamide block component to polyethylene phthalate is about 1
It was in weight%. Example 4 (1) 150 ml of N-methylpyrrolidone, 100 ml of N,N-dimethylacetamide, and 2.15 g of p-phenylenediamine were charged into the reactor used in Example 1 (1), dissolved, and then heated to 5 to 10°C. While stirring vigorously, 4.44 g of terephthalic acid dichloride was added thereto, and the mixture was allowed to react for 2 hours. A small amount of this reaction product was taken out in the same manner as in Example 1,
When the viscosity was measured, the relative viscosity (η _rel ) was
0.90, and the average degree of polymerization was about 10. (2) To the reaction mixture obtained in (1), 23 g of polyethylene terephthalate oligomer (low polymer of bishydroxyethyl terephthalate) with an average degree of polymerization of 10 and hydroxyl groups at both ends, N, N-
150 ml of dimethylacetamide was added, followed by 1 g of sodium hydride dispersion, and the reaction system was heated to 80-100°C and reacted for 2 hours. After the reaction was completed, the cooled reaction mixture was poured into a large amount of methanol, and the precipitated product was first washed with methanol, then with ethanol, water, and acetone, and dried to obtain 24.3 g of block copolymer. I got it. As a result of elemental analysis, the content of poly-p-phenylene terephthalamide block component in this product was about 19%. (3) Two types of compositions were prepared by melt-mixing 4 g and 8 g of the block copolymers obtained in (2) with 50 g of polyethylene terephthalate, respectively. The content of the block component of poly-p-phenylene terephthalamide in these compositions was about 1.5% and about 3%, respectively, and the heat generation due to crystallization was determined by differential scanning calorimeter measurement conducted in the same manner as in the reference example. The temperature at the peak and the half width of the exothermic peak at that time are 5.7°C at 210°C and 6.5°C at 208°C, respectively.
It was hot. Example 5 10 mg of antimony oxide and 20 mg of triphenyl phosphite were added to 10 g of the reaction product obtained in Example 4 (2),
While raising the temperature under vacuum, the temperature was finally raised to 280°C to carry out polymerization. The solution viscosity of the o-chlorophenol soluble portion of the obtained polymer was 0.58. Further, the content of poly-p-phenylene terephthalamide block component in the polymer was found to be about 19.5% based on elemental analysis. Next, as a result of differential scanning calorimeter measurement of 8 mg of a composition obtained by melt-kneading 2 g of this polymer and 50 g of polyethylene terephthalate, the temperature at the exothermic peak due to crystallization was 212°C, and the half-width of the exothermic peak at this temperature was It was 5.9℃. Example 6 In place of p-phenylenediamine in (1) of Example 1, a mixture of 80 mol% of p-phenylenediamine and 20 mol% of 4,4'-diaminodiphenyl was used. The reaction was carried out in the same manner as in 1).
22.3 g of product having an aromatic polyamide block component content of approximately 23% were thus obtained. 2g of this product and polyethylene terephthalate
The results of differential scanning calorimeter measurement of 8 mg of the mixture with 50 g of the mixture showed that the temperature at the exothermic peak due to crystallization was 216°C,
The half width of the exothermic peak at this temperature was 5.7°C. Example 7 The same experiment as in Example 1 (1) was repeated on a 10 times larger scale. The resulting product had a poly-p-phenylene terephthalamide content of 24%. this
70g of polyethylene terephthalate (0.82ηsp/
c) After kneading 1.5 kg with a twin-screw extruder, glass fiber was further kneaded with a single-screw extruder to give a concentration of 30% by weight. The obtained resin was molded at a predetermined mold temperature. The results are shown in Table 2. In addition, when the product kneaded using a twin-screw extruder was molded as it was in molds at 120°C and 110°C, molded products with good mold releasability and appearance were obtained in both cases. Example 8 The experiments of Example 4 (1) and (2) were repeated on a 5-fold scale. However, 500g of nitrobenzene is used as a solvent for bishydroxyterephthalate oligomer.
was added and used. The resulting product contains approximately 20% polyparaphenylene terephthalamide component.
It contained. This 100g, polyethylene terephthalate (ηsp/c is 0.82) 1.5Kg, glass fiber
The resulting resin was kneaded in a single-screw extruder, and the resulting resin was molded and evaluated. The results are shown in Table 2. Example 9 An experiment similar to Example 5 (1) was carried out on a 20 times larger scale, and the poly-p-phenylene terephthalamide block component in the resulting product was 22%. This and polyethylene terephthalate (ηsp/c is
0.72) in a twin-screw extruder, and then 30% of glass fiber was blended and kneaded in a single-screw extruder. The results of molding the obtained resin are shown in Table 2. Furthermore, when the product was simply kneaded using a twin-screw extruder and molded in a mold at 110°C, both the mold releasability and the appearance of the molded product were good (〇). Example 10 An experiment similar to Example 6 (1) was carried out on a 10 times larger scale, and then 100 g of the obtained product (containing about 23% as an aromatic polyamide block component) and polyethylene terephthalate (ηsp/c is 0.78) Kneading and molding were performed in the same manner as in Example 7 using 1.5 kg and glass fiber. The results are shown in Table 2. Example 11 Hexamethylphosphoramide 1 as solvent,
Using 1.5 g of N-methylpyrrolidone, 75 g of lithium chloride, 10.81 g of m-phenylenediamine as a diamine, and 21.11 g of terephthalic acid dichloride as a dicarboxylic acid component were added, and the reaction was carried out in the same manner as in Example 1 (1). Next, 100 g of polyethylene terephthalate/sebacate (molar ratio of terephthalic acid to sebacic acid is 70:30, ηsp/c is 0.38) as a polyester for copolymerization is added to this solution, and 20 g of sodium hydride dispersion is added.
g was added thereto, and the reaction was carried out for one day. Then this 200
After adding ml of methanol, the mixture was poured into a large amount of water, and the resulting precipitate was separated, washed, and dried.
This contains approximately 24% aromatic polyamide component. This is polyethylene terephthalate (η
sp/c is 0.76) 1.5 kg was kneaded in a twin-screw extruder, and then kneaded with 30% amount of glass fiber in a single-screw extruder. Table 2 shows the results of molding the obtained resin (in a mold at 110°C). Example 12 A reaction similar to Example 11 was carried out using 38.21 g of an aminocarboxylic acid component, ie, p-aminobenzoyl chloride hydrochloride, instead of reacting the diamine component with the dicarboxylic acid component. The results are shown in Table 2. Example 13 A similar experiment was conducted using 19.11 g of p-aminobenzoyl chloride hydrochloride and 19.11 g of m-aminobenzoyl chloride hydrochloride instead of p-aminobenzoyl chloride hydrochloride in Example 12. The results are shown in Table 2.

[Table] Examples 14 to 18 The same experiment as in Example 11 was carried out by changing the diamine, dicarboxylic acid component, and polyester for copolymerization. The results are shown in Table 3.

【table】

【table】 [Brief explanation of the drawing]

Figure 1 is an explanatory diagram showing an example of calculating the crystallization temperature of polyethylene terephthalate and the half-width of the exothermic peak at that temperature from the results of differential scanning calorimetry measurements. Figure 2 is an illustration of poly-p-phenylene terephthalamide and polyethylene terephthalamide. 2 is a graph showing the temperature at the exothermic peak and the half width of the exothermic peak based on crystallization for a composition with terephthalate.

Claims (1)

[Claims] 1 Consisting of (A) polyethylene terephthalate and (B) aromatic polyamide, the aromatic polyamide has (a) the general formula -NH-Ar ₁ -NH- (wherein Ar ₁ is a divalent is an aromatic group) and a dicarboxylic acid residue is represented by the general formula -CO-Ar ₂ -CO- (where Ar ₂ is a divalent aromatic group). At least 3 repeating units consisting of an aminocarboxylic acid residue or both repeating units represented by the unit or general formula -NH-Ar ₃ -CO- (Ar ₃ in the formula is a divalent aromatic group) Combined blocks and (b) general formula (R ₁ and R ₂ in the formula are divalent hydrocarbon groups) or an ester group represented by the general formula (R ₃ in the formula is a divalent hydrocarbon group) It is composed of a block in which at least three repeating units consisting of an ester group represented by the formula (R 3 is a divalent hydrocarbon group) or both are bonded, and the (a) block is connected to the component (A). against 0.01
-10% by weight, and the half width of the exothermic peak in the crystallization temperature range of polyethylene terephthalate is 10°C or less when measured using a differential scanning calorimeter. 2. The composition according to claim 1, wherein the (a) block has an amide group derived from p-phenylenediamine and terephthalic acid as a repeating unit. 3. The composition according to claim 1, wherein the block (b) has an ester group derived from ethylene glycol or tetramethylene glycol and terephthalic acid as a repeating unit.